Energy 152 (2018) 985e1010

Contents lists available at ScienceDirect

Energy
journal homepage: www.elsevier.com/locate/energy

Review

High temperature heat pumps: Market overview, state of the art,

research status, refrigerants, and application potentials
Cordin Arpagaus a, *, Fre

de

ric Bless a, Michael Uhlmann a, Jürg Schiffmann b,
Stefan S. Bertsch a
a
NTB University of Applied Sciences of Technology Buchs, Institute for Energy Systems, Werdenbergstrasse 4, 9471 Buchs, Switzerland
b
Ecole Polytechnique F

ed
erale de Lausanne, Laboratory for Applied Mechanical Design, Rue de la Maladiere 71b, 2002 Neucha^tel, Switzerland

a r t i c l e i n f o a b s t r a c t

Article history: This study reviews the current state of the art and the current research activities of high temperature
Received 16 December 2017 heat pumps (HTHPs) with heat sink temperatures in the range of 90 to 160
C. The focus is on the analysis
Received in revised form of the heat pump cycles and the suitable refrigerants. More than 20 HTHPs from 13 manufacturers have
23 March 2018
been identified on the market that are able to provide heat sink temperatures of at least 90
C. Large
Accepted 30 March 2018
application potentials have been recognized particularly in the food, paper, metal and chemical in-
Available online 31 March 2018
dustries. The heating capacities range from about 20 kW to 20 MW. Most cycles are single-stage and
differ primarily in the refrigerant (e.g. R245fa, R717, R744, R134a or R1234ze(E)) and compressor type
Keywords:
High temperature heat pump
used. The COPs range from 2.4 to 5.8 at a temperature lift of 95 to 40 K. Several research projects push the
Market overview limits of the achievable COPs and heat sink temperatures to higher levels. COPs of about 5.7 to 6.5 (at
State of the art 30 K lift) and 2.2 and 2.8 (70 K) are achieved at a sink temperature of 120
C. The refrigerants investigated
Research status are mainly R1336mzz(Z), R718, R245fa, R1234ze(Z), R600, and R601. R1336mzz(Z) enables to achieve
COP exceptionally high heat sink temperatures of up to 160
C.
Refrigerant © 2018 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 986
1.1. Terminology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 986
1.2. Application potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 986
1.3. Industrial processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 988
1.4. Barriers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 989
1.5. Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 989
2. Market overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991
2.1. Heat pump products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 991
2.2. Cycles and COPs of HTHPs available on the market . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 993
2.3. New heat pump technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 993
3. Research status . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 993
3.1. Publications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 993
3.2. Research projects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 993
4. Refrigerants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 999
4.1. Selection properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 999
4.2. Hydrofluorocarbons (HFCs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 999
4.3. Hydrofluoroolefins (HFOs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 999
4.4. Hydrochlorofluoroolefins (HCFOs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1002
4.5. Natural refrigerants and hydrocarbons (HCs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1002

* Corresponding author.
E-mail address: [email protected] (C. Arpagaus).

https://doi.org/10.1016/j.energy.2018.03.166
0360-5442/© 2018 Elsevier Ltd. All rights reserved.
986 C. Arpagaus et al. / Energy 152 (2018) 985e1010

4.6. Novec 649 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1002

4.7. Thermodynamic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1002
5. Simulation of system performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1003
6. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1005
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1006
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1006
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1007

1. Introduction glides in the sink and source. Zeotropic working fluids (e.g.
ammonia-water) and an internal liquid circulation are applied. For
1.1. Terminology more information on these subjects, the reader is referred to the
mentioned references above.
The term high temperature heat pump (HTHP) is frequently
used in connection with industrial heat pumps, mainly for waste
heat recovery in process heat supply [1]. However, the terminology 1.2. Application potential
for the temperature level of a HTHP is not consistent in the litera-
ture. Bauder [2] described the application of a HTHP with heat sink From an exergetic point of view, industrial waste heat repre-
temperatures generally above 100
C. Jakobs [3] defined the term sents a very valuable heat source for heat pumps thanks to the
industrial heat pump as a heat pump with sink temperatures of up relatively high temperature level of about 30 to 70
C, which is
to 150
C for heat recovery and upgrading in industrial processes, significantly higher than outdoor air, ground heat, or ground water
but also for heating, cooling and air conditioning in commercial and [1,14]. Industrial waste heat accumulates in the form of e.g. cooling
industrial buildings. Peureux and Bobelin [4e8] introduced the liquid in chillers, waste water, warm compressed air, or moist
term very high temperature heat pump (VHTHP) with heat sink exhaust air [19].
temperatures between 100 and 140
C. Fig. 1 visualizes the devel- An ideal Carnot heat pump cycle represents the highest theo-
opment perspectives of the temperature levels in industrial heat retical performance at constant heat source and sink temperatures.
pumps for heat recovery [4e8]. A Lorenz cycle is the theoretical limit considering a temperature
This review article assumes 100
C as a boundary for classifying glide on the heat source and sink sides (logarithmic mean tem-
a HTHP. The article will not distinguish between HTHP and VHTHP. peratures), and is equivalent to an infinite multi-stage Carnot cycle.
Focus is on closed-cycle compression heat pumps (Fig. 2), as this The temperature glide of the heat source and the heat sink can vary
type is most widely used and available in a large variety of sizes for significantly depending on the industrial application. For example,
different applications [9]. drying and steam generation processes are closer to Carnot, while
Thermally driven sorption cycles [1,10e14] or hybrid other applications like high temperature networks have higher
absorption-compression heat pumps [15e18] based on the Osen- temperature glides and the Lorenz COP is more appropriate.
brück cycle are other relevant technologies for high temperature Fig. 3 compares the achievable Carnot COP and Lorenz COP
heat supply in industrial applications. The hybrid systems are values as a function of the heat source and heat sink temperatures.
especially useful for high sink temperatures and high temperature The calculation of the COP Lorenz assumes a 30 K temperature glide
on the source and sink sides. For a constant heat sink temperature,
a higher heating COP is achieved with a higher heat source tem-
perature. For a constant temperature lift (e.g. 70 K and 50 K), the
temperature of the heat sink has only a minor influence on the COP
compared to the temperature lift. The minor increase in COP is
related to the increasing temperature of the heat source and
increased exergy of the source. This almost linear increase high-
lights the potential of using industrial heat pumps for waste heat
recovery. Thus, the use of heat pumps represents a large untapped
potential for waste heat utilization and a significant contribution to
reducing CO2 emissions. In this regard, industrial heat pumps can
make an important contribution to improving efficiency in
industry.
According to a study of the International Energy Agency (IEA)
[20], industry is the largest heat-consuming final sector with 79 EJ
in 2011, accounting for nearly 46% of the world total energy use for
heat in that year. This was up from 61 EJ in 2000, reflecting an
average growth of 1.7 EJ/year.
Beside space heat and hot water, there is a great demand for
process heat in industry for the production, the processing, or the
finishing of products. Generally, process heat is supplied above
80
C [1]. The theoretical application potential for the use of heat
pumps in industrial processes can be estimated by evaluating the
Fig. 1. Development of temperature levels for compression heat pumps, HP: conven-
heat demand of each industrial sector and the temperature levels of
tional heat pump, HTHP: high temperature heat pump, VHTHP: very high temperature the applied processes. Fig. 4 illustrates some distributions of the
heat pump, adapted from Peureux and Bobelin [4e8]. industrial heat demand in Switzerland [21,22], Germany [5,23e26],
 C. Arpagaus et al. / Energy 152 (2018) 985e1010 987

Fig. 2. Classification of heat pumps, adapted from Nellissen and Wolf [9].

Fig. 3. COP Carnot (left) and COP Lorenz (right) as a function of the heat source and heat sink temperatures. The marked values are at the same temperature lift of 70 K and 30 K
illustrating an almost linear COP increase with the heat source temperature. The calculation of the COP Lorenz assumes a temperature glide of 30 K on the heat source and heat sink
sides.

France [5,7,27,28], and the U.S [34]. In the Swiss industry (Fig. 4 (a)), states þ Norway, Switzerland, and Iceland) for industrial processes
process heat accounts for about 54% of the total heat demand in 2012 was estimated by Rehfeldt et al. [30] to be 30726, 20 542 and
(84.9 PJ of 156 PJ in 2015) [21,22]. 821 PJ at the temperature levels > 500
C (e. g. iron and steel pro-
Germany's industry consumed 10909 PJ for process heat, space duction), 100 to 500
C (e. g. steam consumption in the paper, food
heating and hot water production in 2012. This corresponded to and chemical industries), and <100
C (e. g. food industry). These
about 74% of the total industrial heat demand of 20 587 PJ [29]. Fig. 4 figures were derived by using a bottom-up approach to disaggre-
(b) indicates that about 272 PJ of heat could be provided by today's gate the Eurostat's energy balance into the dimensions of temper-
heat pump technology up to 80
C. This equals 16% of the industrial ature level and end-use. Other estimates of the European industrial
heat demand. If the sink temperature of the heat pumps could be heat demand showed similar temperature distribution patterns for
increased to 100
C, 165 PJ are added to a total of 437 PJ, in particular most industrial subsectors [31,32]. Naegler et al. [31] estimated the
because of a significant contribution from the paper industry. With total final energy demand for process heat in the EU28 industry on
the introduction of HTHPs delivering temperatures of up to 140
C the order of 80 500 PJ in 2012 and evaluated the process heat de-
another 172 PJ heat could be added to a total of 612 PJ, which is 32% mands of 20 077 PJ (<100
C), 20 214 PJ (100 to 400
C), and 30 859 PJ
of the industrial heat demand [23]. The additional potential is (>400
C). The breakdown of the heat quality was in line with the
mainly in the food and chemical industries. three temperature intervals defined in Ecoheat & Power [33]. Pardo
The process heat demand in France between 60 and 140
C was et al. [32] estimated the useful heat demand of the EU27 industry
estimated to be 119 PJ in 2009 [5,7,27,28]. Food & beverages, sugar, for 2009 to be 40 434 PJ taking into account energy conversion losses
dairy and transport equipments industries require heat primilarly during transformation and distribution. Around 58% of the heat
at 60 to 100
C. On the other hand, heat at 100 to 140
C is mainly demand was consumed in the high range of temperatures
required in the pulp & paper, iron/steel/ferro-alloys, rubber & (>400
C), 20% in the medium range (100 to 400
C), and 22% in the
plastic, and cement/lime/plaster industries. All over Europe, the low range (<100
C). Most of the useful heat came from direct
final heat demand of the EU28 þ 3 countries (28 member combustion of fuels, with natural gas as the main contributor,
988 C. Arpagaus et al. / Energy 152 (2018) 985e1010

Fig. 4. Theoretical potential for HTHPs in various industrial sectors divided by temperature ranges of process heat accessible with industrial heat pumps. (a) Switzerland [21,22], (b)
Germany [5,23e26], (c) France [5,7,27,28], (d) U.S [34].

followed by petroleum products and coal products. In fact, these appear particularly attractive.
three fuels represented around 83% of the primary energy con- Although the data presented here have been derived for a spe-
sumption [32]. cific geographical region, e.g. Europe and the U.S., most data are
For the European heat pump market, Nellissen and Wolf [9] considered representative for the corresponding industrial sub-
have evaluated a technical potential of about 626 PJ (174 TWh) at sectors around the world. However, in order to assess the potential
temperatures up to 150
C, which would be accessible with heat for HTHPs in industrial processes, more data on the global indus-
pumps (Fig. 5). About 113 PJ or 19% of the potential heat demand trial heat demand with proportions of the temperature levels and
lies between 100 and 150
C and is argued to be particularly final end-use are required.
reachable by industrial HTHPs. The temperature range above 150
C
remains for the time being inaccessible for heat pump technology. 1.3. Industrial processes
The assessment revealed in particular a realistic potential of HTHP
applications in the food and tobacco, the chemical, and the paper Fig. 6 gives an overview of industrial processes in different in-
industries (see shaded bars in Fig. 5). The technical potential would dustrial sectors identified as suitable for the integration of HTHPs.
be much larger, but practical reasons it is often not possible to fully The process temperatures between 20 and 200
C have been
exploit it. compiled and verified with various literature data
Fox et al. [34] performed a detailed analysis of the U.S. energy [1,13,23,25,35e45]. In addition, the temperature band widths are
consumption for 2008 in industry where steam at temperature marked according to the available heat pump technology readiness
below 260
C is heavily used. The industrial subsectors included level (TRL).
paper and pulp, chemicals, food, petroleum and coal, and primary Overall, great application potential for HTHPs has been identi-
metals, which is in line with the major main natural gas consumers. fied in the food, paper, and chemical industries, in particular in
The distribution of the steam energy temperature is shown drying processes, as well as in pasteurizing, sterilizing, evaporation,
Fig. 4(d). The corresponding data source [34] was reduced to 40 to and distillation.
200
C temperature ranges and classified by industry. The analysis In the temperature range of up to 100
C, there are many
showed a total process heat demand of 30 416 PJ between 40 and possible applications like drying, pre-heating, boiling, pasteurisa-
200
C. All subsectors use steam in a temperature ranges suitable tion, or even laundering or coloring. These industrial processes can
for HTHPs. The paper and pulp, chemical, and food industries already be supplied with today's heat pump technology.
 C. Arpagaus et al. / Energy 152 (2018) 985e1010 989

Fig. 5. Technical market potential of process heat in Europe accessible with industrial heat pumps distributed by temperature and industrial sectors (based on Eurostat data from
2012 of 33 countries, data adapted from Nellissen and Wolf [9]).

From 100
C on, prototypes of HTHPs are under development Its main goal is to overcome existing difficulties and barriers for the
and from 140
C on laboratory systems are in research status. In larger scale market introduction of industrial heat pumps.
particular, there is great industrial interest to expand the spectrum
of the heat sink temperature of compression heat pumps to over 1.5. Objectives
120
C for the production of low-pressure process steam [45,46].
Research activities in this area have increased in recent years. HTHPs are featured in a variety of publications related to in-
dustrial applications. Some of these publications refer to the topic
1.4. Barriers of this paper and will be discussed shortly. Brunin et al. [55]
compared the working domains of compression heat pumps using
Despite the great ecological potential, there are some barriers to different fluids. The modeled operating ranges were represented as
the wider spread of industrial HTHPs. Among others, the following a function of the heat sink outlet temperature versus the temper-
barriers are reported [3,5,14,26,37,47e53]: ature difference between the heat sink outlet and the heat source
inlet. The fields of application were defined by limiting values for
 Low level of awareness of the technical possibilities and the COP, volumetric heating capacity, low and high pressure. Van de Bor
economically feasible application potentials of HTHPs among et al. [56] proposed an approach to predict the economic perfor-
users, consultants, investors, plant designers, producers, and mance of different types of industrial heat pumps (e.g. mechanical,
installers. heat driven absorption, and vapor compression) based on the lift to
 Lack of knowledge about the integration of HTHPs in industrial sink temperature ratio for the process fluids. The proposed per-
processes. Tailor-made designs lead to cost-intensive integra- formance maps can be used for heat pump selection. Ommen et al.
tion into existing processes. [57] investigated possible technical and economic working do-
 Long payback periods over 3 years, which is larger than for gas mains of industrial heat pumps for several natural refrigerants
or oil fired boilers (required payback < 3 years). when considering variations in temperature lift and sink temper-
 Competing heating technologies generating high temperature atures. Common single-stage vapor compression heat pumps with
using fossil fuels at low energy prices (depends on the respec- heat sink temperatures of up to 115
C and temperature lifts up to
tive electricity to gas price ratio). 40 K were compared using both economic and technical con-
 Lack of available refrigerants in the high temperature range with straints. Jensen et al. [16] evaluated the economic feasible working
low global warming potential. domain of an ammonia-water hybrid absorption-compression heat
 Lack of pilot and demonstration systems. pump. Heat sink temperatures up to 150
C and temperature lifts
 Lack of training and events additionally supporting the spread of up to 60 K could be attained with commercially available compo-
HTHP knowledge. nents and with economic benefits compared to gas combustion.
Recently, Bamigbetan et al. [58] provided a review on vapor
In order to overcome these obstacles, the International Energy compression heat pumps for high temperature heating up to 120
C
Agency (IEA) has already conducted several programs on the sub- using natural working fluids (e.g. hydrocarbons, ammonia, water,
ject of industrial heat pumps. These were the completed Annex 9 CO2). Different challenges from fluid selection, component devel-
program in 1990 on High Temperature Industrial Heat Pumps, the opment to system optimization were discussed.
Annex 21 from 1992 to 1996 on Global Environmental Benefits of Overall, the screening of the open literature revealed that there
Industrial Heat Pumps [54], and the Annex 35 from 2010 to 2014 on is still a limited number of studies comparing different vapor
the Application of Industrial Heat Pumps [5]. The Annex 48 from compression HTHPs. Most of the research studies focus on one
2016 to 2019 on Industrial Heat Pumps (Second Phase) is ongoing. specific vapor compression HTHP system. There is a lack of a
990 C. Arpagaus et al. / Energy 152 (2018) 985e1010

Fig. 6. Overview of processes in different industrial sectors structured by typical temperature ranges and Technology Readiness Level (TRL) of heat pumps, data compiled from
various literature data [1,13,23,25,26,35e43].
 C. Arpagaus et al. / Energy 152 (2018) 985e1010 991

comprehensive comparison of those studies. Therefore, the objec- hours at temperatures of up to 200
C before half-life maintenance.
tives of this review paper are: R1336mzz(Z) is used as working fluid with a suitable polyolester
(POE) oil. Further research is ongoing to achieve even higher
(1) Thorough state of the art review of commercially available heating temperatures and optimise performance [63].
HTHP systems on the market focusing on suitable cycle Ochsner builds HTHPs with screw compressors and sink tem-
concepts, applied refrigerants, and current limits of peratures from 95 up to 130
C [43,81]. Waste heat is used as heat
operation. source at 35 to 55
C (one-stage economizer cycle) or 8 to 25
C
(2) Systematic comparison of experimental and theoretical (two-stage cascade cycle). The heating capacity ranges from 170 to
studies on HTHPs in research status with an evaluation of the 750 kW. Higher capacities can also be achieved by connecting
heat pump cycles, used refrigerants, and achieved sink several machines (e.g. twin-units 1.5 MW) [66].
temperatures and COPs. The hybrid heat pump developed by Hybrid Energy AS is a
(3) Identification of a set of unified design guidelines for HTHPs combination of an absorption and compression heat pump oper-
with suggestions for future research areas. ating according to the Osenbrück cycle [5]. The heat pump is
typically operated with an ammonia/water mixture. As the mixture
The paper is structured into four parts and follows the following is a non-azeotrope working fluid, the boiling and condensation take
road map. place with gliding temperatures. Up to 120
C are possible with
First, the market for available HTHPs with sink temperatures standard components. At the operating point of 40
C/100
C a COP
above 90
C is evaluated and the application limits and perfor- of about 4.5 is achieved [16,17].
mances are summarized. Second, an overview of the research ac- Japan is well known for transcritical CO2 (R744) heat pumps
tivity in the area of HTHP is presented. The operating ranges of heat [1,82]. The Eco Sirocco from Mayekawa provides hot air at 100 to
pumps in research status are described in detail. The third part is 120
C [5,13,70]. The transcricial process reaches a COP value of 2.9
devoted to the refrigerants and their selection criteria for HTHP when using waste water at 25
C and supplying hot air of 120
C (at
applications. The general focus is on the examination of possible 20
C air inlet temperature). The heat pump achieves a heating
heat pump cycles and suitable refrigerants for use at sink temper- capacity of about 90 kW [5].
atures above 120
C. In the fourth part, the thermodynamic effi- The thermeco2 product line of Dürr thermea runs with heat
ciency of the selected refrigerants is compared by means of a source temperatures of 8 to 40
C and reaches heat sink tempera-
simplified system simulation in an idealized heat pump cycle. tures of up to 110
C. The product line covers heating capacities
from 51 kW to 2.2 MW. Depending on the requested capacity up to
2. Market overview 6 piston compressors are connected in parallel. The thermeco2
HHR1000 heat pump achieves a COP of 3.9 at a sink temperature of
2.1. Heat pump products 80
C (at 20
C inlet) with a source temperature of 20
C (60 K lift)
[5,72,73].
The range of heat pump models on the market with high heat The Kobelco HEM-90A model uses a semi hermetic inverter
capacities and sink temperatures has grown steadily in recent years twin-screw compressor and delivers up to 90
C hot water from
[23,24,50]. Over 20 heat pump models from 13 manufacturers have ambient air for applications in the food, beverage, automotive, and
been identified worldwide, which are able to supply at least 90
C chemical industries [61,83]. The refrigerant used is a mixture of
heat [59,60] (Table 1). R134a and R245fa. With 10
C to þ40
C air as a source, heating
The companies Kobe Steel [5,13,61,62], Viking Heat Engine SA capacities of approx. 70 to 230 kW are achieved. The COPs are in the
[63,64], Ochsner Energie Technik GmbH [43,66e68], Mayekawa range of 1.7 to 3.0 [83].
[5,13,70], Hybrid Energy AS [16,17,69], Combitherm [71], and Dürr Fig. 7 shows the industrial HTHPs available on the market sorted
Thermea GmbH [5,72,73] show pioneering developments with according to their maximum heat sink temperature and heating
their HTHPs. capacity. The heating capacities range from about 20 kW to 20 MW.
The products Kobelco SGH 120, HeatBooster, Eco Sirocco, For high temperature applications and high lifts, the compres-
IWWDS, HWW 245fa, and thermeco2 represent the industrial sors must be able to overcome high pressure ratios [84]. Nearly all
benchmark with heat sink temperature of 110 to 150
C. The of the compressor manufacturers offer optimized designs for spe-
maximum attainable sink temperature is primarily determined by cial applications. Mainly single-screw (Emerson, Ochsner) or twin-
the selection of the refrigerant, the cycle design and the choice of screw compressors (GEA Refrigeration, Kobelco), two-stage turbo
the compressor type [2]. Water, brine, exhaust air or wastewater is compressors (Friotherm, Mitsubishi) and parallel-connected piston
typically used as a heat source with a temperature range between compressors (Combitherm, Viessmann, Dürr thermea) are used. In
17 and 65
C. most cases, turbo and screw compressors are implemented for
Kobe Steel has been marketing the steam grow heat pumps large heating capacities over 10 MW [2].
SGH120 and SGH165 since 2001 under the brand Kobelco. The In general, the oil in piston and screw compressors is selected to
SGH165 model is able to generate steam at 165
C from process fit the properties of the working fluid. In addition to the compati-
waste heat of 35 to 70
C and by recompressing 120
C steam to bility and viscosity, the thermal stability of the oil is also considered
165
C (6 bar) [1,5,13,61,62,80]. Preferred application fields are the at high temperatures. Coking of the oil at high gas temperatures has
sterilization of food and beverages, the concentration of liquids and to be prevented [84]. Typically, POE lubricants are used [63,64].
juices, drying processes, and the distillation of alcohol [5]. The In turbo compressors, the attainable pressure lift is proportional
semi-hermetic twin-screw compressor has been specially devel- to the vapor density and the square of the peripheral impeller
oped for high pressure and temperature. An amount of 890 kg/h of speed [85]. In order to generate high pressure lifts the peripheral
steam at 165
C is generated with a heating COP of 2.5 when using speed of the impeller and the molecular weight molar of the
waste heat of 70
C [5]. refrigerant need to be as high as possible. Speeds between 40 000
The HeatBooster of Viking has been developed in collaboration and 250 000 rpm are state of the art. Extreme values go up to
with AVL Schrick [63e65]. This HTHP produces heat up to 150
C 900 000 rpm [85]. The Turbocor TG310 from Danfoss is a twin-
from waste heat with a capacity of about 200 kW. The heat pump turbine centrifugal compressor and has been on the market since
incorporates a piston compressor designed for 40’000 operating April 2012 [86,87]. Its magnetic bearings enable oil-free refrigerant
992 C. Arpagaus et al. / Energy 152 (2018) 985e1010

Table 1
Selection of industrial HTHPs with heat sink temperatures above 90
C (extended from Refs. [59,60]).

Manufacturer Product Refrigerant Max. heat sink temperature Heating capacity Compressor type References

Kobe Steel SGH 165 R134a/R245fa 165
C 70 to 660 kW Twin screw [5,13,61,62]
(Kobelco steam grow heat pump) SGH 120 R245fa 120
C 70 to 370 kW
HEM-HR90,-90A R134a/R245fa 90
C 70 to 230 kW

Vicking Heating Engines AS HeatBooster S4 R1336mzz(Z) 150
C 28 to 188 kW Piston [63e65]

R245fa

Ochsner IWWDSS R2R3b €

R134a/OKO1 130
C 170 to 750 kW Screw [43,66e68]
IWWDS ER3b €
OKO (R245fa) 130
C 170 to 750 kW
IWWHS ER3b €
OKO (R245fa) 95
C 60 to 850 kW

Hybrid Energy Hybrid Heat Pump R717/R718 120
C 0.25 to 2.5 MW Piston [16,17,69]
(NH3/H2O)

Mayekawa Eco Sirocco R744 (CO2) 120
C 65 to 90 kW Screw [5,13,70]

Eco Cute Unimo R744 (CO2) 90
C 45 to 110 kW

Combitherm HWW 245fa R245fa 120
C 62 to 252 kW Piston [23,24,71]

HWW R1234ze R1234ze(E) 95
C 85 to 1301 kW

Dürr thermea thermeco2 R744 (CO2) 110
C 51 to 2‘200 kW Piston (up to 6 in parallel) [5,72,73]

Friotherm Unitop 22 R1234ze(E) 95
C 0.6 to 3.6 MW Turbo (two-stage) [74,75]

Unitop 50 R134a 90
C 9 to 20 MW

Star Refrigeration Neatpump R717 (NH3) 90
C 0.35 to 15 MW Screw (Vilter VSSH 76 bar) [76]

GEA Refrigeration GEA Grasso R717 (NH3) 90
C 2 to 4.5 MW Twin screw (63 bar) [77]
FX P 63 bar

Johnson Controls HeatPAC HPX R717 (NH3) 90
C 326 to 1‘324 kW Piston (60 bar) [78]
HeatPAC Screw R717 (NH3) 90
C 230 to 1‘315 kW Screw
Titan OM R134a 90
C 5 to 20 MW Turbo

Mitsubishi ETW-L R134a 90
C 340 to 600 kW Turbo (two-stage) [5,13]

Viessmann Vitocal 350-HT Pro R1234ze(E) 90
C 148 to 390 kW Piston (2e3 in parallel) [79]

temperature of 165.5
C [88].

Combitherm GmbH offers HTHPs (HWW R245fa series) with up
to 120
C sink temperature and 62 to 252 kW heating capacity. The
systems cover 30
C source and 70
C sink temperature and run
with piston compressors [71,84]. In a cooperation project with Dürr
Ecoclean GmbH a HTHP prototype with refrigerant R245fa has been
designed [24]. The developed HTHP achieved a heating capacity of
45 kW and used waste heat from a workpiece washing plant for the
evaporation of aqueous cleaning solution at 100
C [44]. During
operation the HTHP reached a COP of 3.4 (water source tempera-
ture 50
C, water sink temperature 100
C, 50 K lift, W50/W50)
[4,23].
Star Refrigeration, GEA Grasso, and Johnson Controls use NH3
(R717) with optimized high-pressure compressors. Ammonia offers
a wide operating range and beneficial thermodynamic properties
with a critical temperature of 133
C [89].
The heat pump (Neatpump) from Star Refrigeration is producing
hot water at up to 90
C with heating capacities from 380 kW to
2.6 MW [76,80]. The incorporated Vilter single-screw compressor
Fig. 7. Commercially available industrial HTHPs sorted by maximum heat sink tem-
technology (VSSH series) with special steel cast design holds
perature and heating capacity. The implemented compressor types are color-coded
(black: screw, grey: piston, white: turbo compressor).
pressures of up to 76 bar [90]. COPs of about 4 are achieved at 50
C/
90
C [76,80].
The latest generation of the GEA Grasso twin-screw compressor
circuits. In particular, with refrigerant R1234ze(E) the turbo allows pressures of up to 63 bar and thus sink temperatures of up to
compressor delivers a nominal capacity of 65 to 310 kW [86]. 90
C [5,77]. At a source temperature of 35
C and a sink tempera-
The Unitop series from Friotherm AG are designed for operating ture of 80
C, a COP of 5.0 is achieved with a heat output of 14 MW
temperatures from 40 to 90
C using two-stage turbo compressors [77].
[74]. Very high heat capacities of up to 20 MW are achieved with The piston compressor applied in the single-stage Sabroe
the Unitop 50. Such large heat pumps are usually customized [75]. HeatPAC HPX heat pumps from Johnson Controls [78] enables
One of the largest heat pumps has been constructed for the pressures of up to 60 bar. Depending on the heat pump size, 326 to
Stockholm district heating network with 6 parallel Unitop 50FY 1‘324 kW of heat can be supplied with a COP of 4.0 at 39
C source
units [23]. To reach even higher temperatures, Friotherm would use and 90
C sink temperature. Other heat pumps from the brands
the low-pressure refrigerant R1233zd(E) having a critical York and Sabroe, the HeatPAC Screw, Titan OM and HeatPAC
 C. Arpagaus et al. / Energy 152 (2018) 985e1010 993

Custom can deliver maximum heat sink temperatures of 90
C [91]. 2.3. New heat pump technologies
The Vitocal 350-HT Pro series delivers heat outputs from 148 to
390 kW and a considerable COP of up to 3.4 at 50
C source and In addition, there are new promising heat pump technologies
90
C sink temperature [79] and 3.1 at 40
C/90
C [92]. The heat close to market launch, such as the ROTATION HEAT PUMP K7 from
pump works with the refrigerant R1234ze(E). ecop Technologies GmbH with 400 to 700 kW heating capacity
According to Wolf et al. [23,52] the specific investment costs for [96,97] or the industrial SPP HighLift heat pumps from Olvono
industrial heat pumps with a heat capacity above 500 kW are be- Technology AS with a typical heat output of 500 kW [98e101]. Both
tween 250 and 700 Euro per kW. Fleckl et al. [50] have evaluated technologies make use of a working medium staying in the gas
similar investment costs of about 300 to 800 Euro per kW for use in phase during the whole cycle offering high temperature flexibility.
heat recovery in industrial processes. For comparison, in China, the The SPP HighLift heat pump is based on the Stirling cycle using
investment costs for 300 kW heat pump systems are around 170 helium (R704) and reaches a maximum temperature of 195
C at
Euros per kW [93]. high efficiency, e.g. waste heat recycling at 45
C and hot water
production at 120
C with a heating COP of 2.2 [99].
The ROTATION HEAT PUMP uses centrifugal forces for
compression and subsequent temperature increase that allows
2.2. Cycles and COPs of HTHPs available on the market realizing an efficient Joule process (also known as Brayton cycle)
[97]. Compared to a two phase cycle heat transfer at sink and source
Table 2 shows the cycle diagrams together with the achieved are sensible and the process is flexible in temperature levels. A
COPs of the various HTHPs on the market described in Table 1. Most natural inert gas mixture (ECOP Fluid 1, extracted from air and
circuits are one-stage and differ especially in the applied refrigerant containing Argon, Helium, and Krypton) is used as working gas.
and compressor type. Two-stage cycles are applied by Friotherm Temperatures of up to 150
C are possible. Detailed calculations in
[74,75], Mitsubishi [5,13,94], and Ochsner [43,66,68,81,95]. Frio- combination with measurements yield COPs of 5.5 at 60
C heat
therm optimized the two-stage R1234ze(E) circuit of the Unitop source (30 K glide) and 100
C sink temperatures (40 K glide)
heat pumps with an open-flash economizer. A heating COP of 3.5 [96,97].
was experimentally measured at an operating point of 33.8
C
source and 95
C sink temperature [75]. The two-stage cascade of 3. Research status
Ochsner [43,66,68,81,95] uses R134a in the first stage and OKO1 €
(contains R245fa) in the second stage. At the operating point 45
C 3.1. Publications
source and 90
C sink temperature a COP of about 4.0 is achieved
[43,81]. Fig. 9 illustrates the number of publications in the SCOPUS and
Several parallel-connected piston compressors are used by Web of Science online databases with the search keyword “high
Viessmann [79,92] and Dürr thermea [5,72,73] to achieve higher temperature heat pump”. Historically, the trend of publications
heating capacities. Internal heat exchangers (IHX) are installed e.g. follows the level of energy prices, especially the oil price [102]. The
by Viessmann [79,92], Mayekawa [5,13,70], Ochsner oil price shock in the 1970s led to a boom in energy research and
[43,66,68,81,95], and Viking [63,64], in order to ensure sufficient the development of heat pumps received considerable interest.
overheating of the working fluid in the suction line upstream of the Energy research groups have been set up and a large number of
compressor. Efficiency increases of 10 to 25% are reported for CO2 research projects in the field of heat pumps started [5]. The number
transcritical cycles [1]. of scientific publications reached a peak in the early 1980s. As an
Mayekawa and Dürr thermea rely on the natural refrigerant CO2. example, in 1982, the promotion of heat pump research reached
Due to the transcritical cycle and the high temperature glide pre- also an all-time high in Germany [23]. With declining energy prices
sent in the gas cooler with minimal temperature difference be- in the 1980s and 1990s heat pumps were somewhat out of focus,
tween refrigerant and supplying fluid, CO2 heat pumps are especially also HTHPs. Since 2007 there has been a marked increase
particularly efficient for hot water generation. in publications again due to the support of activities on renewable
Friotherm and Viessmann apply the low GWP refrigerant energies and climate change. Today's research on HTHPs has shifted
R1234ze(E), which is regarded as a potential replacement refrig- more towards industrial and large scale applications [23]. Between
erant for R134a. 2008 and 2016, on average about 12 papers on HTHPs have been
Mitsubishi Heavy Industries optimized the R134a cycle of the published annually.
compact ETW-L hot water heat pump with a closed economizer
and two-stage turbo compressor with intermediate injection. Hot 3.2. Research projects
water of up to 90
C can be generated from waste heat of approx-
imately 10 to 50
C [94]. The heat output is 547 kW at 50
C source There are various research projects ongoing worldwide in the
and 90
C sink temperature, which results in a COP of 4.1. The ETW- field of HTHPs with sink temperatures greater than 100
C. Table 3
L is controlled by the blade position of the first compressor stage, gives an overview of the most relevant experimental research
the motor speed and a hot gas bypass [5,13,94]. projects sorted according to the maximum achieved sink temper-
Fig. 8 shows the COP values given in Table 2 for the various in- atures. Table 4 shows the corresponding heat pump cycles and the
dustrial HTHPs as a function of the respective temperature lift. The achieved COPs for a given temperature lift. In the following, the
COP values range between 1.6 and 5.8 with a temperature lift of 130 main results of these research projects will be discussed shortly.
to 25 K, respectively. The mean COP of this data composition is Helminger et al. [103] from the Austrian Institute of Technology
about 3.3 at an average temperature lift of 61 K. Also plotted are the (AIT) investigated a single-stage HTHP cycle with IHX using
COP Carnot curves at 140
C sink temperature. Most experimental R1336mzz(Z) and pushed the sink temperature close to 160
C.
data range between 40 and 60% Carnot efficiency (Second Law ef- Market available components and minor modifications to the
ficiency, h2nd). compressor were applied in order to meet the high temperature
Transcritical CO2 cycles (Mayekawa Eco Sirocco, Thermeco2) are requirements. A COP of 2.7 was measured at 109
C source and
not displayed in Fig. 8 since the efficiencies mostly depend on the 156
C sink temperatures. As stated, the use of an IHX in the cycle
return temperatures in the gas cooler. significantly increased the COP by 4% up to 47% compared to a
Table 2
Heating COPs and cycles of industrial HTHPs available on the market (TLT: heat source temperature [
C], THT: heat sink temperature [
C], DT: temperature lift [K], Compressor
types.
 C. Arpagaus et al. / Energy 152 (2018) 985e1010 995

simple circuit with 45 K temperature lifts (see data in Table 4). demonstrated. Latest studies are heading in the direction of
In former studies with a simple single-stage cycle, Fleckl et al. compressor improvements with higher efficiency for high pressure
[50,104] achieved a COP of 2.4 at a sink temperature of 150
C (70 K ratios and expansion valves for higher temperatures.
temperature lift). COPs of 4.3 to 5.8 could be reached at 35 K tem- In the national research project PACO [5,6,8,28] the technical
perature lift and between 2.1 and 2.5 at 70 K lift, respectively. The feasibility of a water (R718) HTHP was demonstrated up to 140
C
secondary efficiencies (h2nd ¼ COP/COPCarnot) ranged between 39% sink temperature. Chamoun et al. [107,108,110] built a pilot plant
and 50%. In order to prevent compression into the 2-phase region of using a twin-screw compressor with modified sealing and water
the R1336mzz(Z) refrigerant (see log(p)-h diagram in Section 4), vapor injection. Waste heat of 85 to 95
C was used as source and
about 10 K superheat was necessary at a temperature lift of 35 K, water was condensed at about 145
C providing a heat output of
and about 20 K superheat at 70 K lift, respectively [104]. In another more than 300 kW. Water vapor was generated in a flash tank at
project with the company Ochsner, Wilk et al. [105] reported sink 0.6 bar and 83
C [107] and was fed into the suction chamber of the
temperatures of up to 130
C and a heating capacity between 250 twin-screw compressor. Water was additionally injected to avoid
and 400 kW with a one-stage economizer cycle running with a compressor overheating and lower the hot-gas temperature. After
screw compressor and the refrigerant OKO1. € The measured COP condensation, the water was collected in an accumulator and was
values were between 2.1 and 2.3 at a temperature lift of 70 K (45 to expanded to low pressure. In the flash tank, the water liquid
60
C heat source and 115 to 130
C sink temperatures). separated from the vapor. The liquid water was pumped through
In Germany, Noack [37] developed a laboratory heat pump the evaporator absorbing heat and re-entered the flash tank, which
providing sink temperatures of up to 140
C from 60 to 90
C heat in turn generated steam. At 94
C source and 121
C sink temper-
source while using a low GWP refrigerant with working name HT ature, a COP of about 5.5 was measured [108]. This corresponded to
125 (safety class A1, non-toxic, ODP ¼ 0). All components used were a secondary efficiency of about 38%. At 75
C source and 130
C sink
standard components without modification. A COP of 4.5 was temperature a COP of 3.6 and 49% efficiency were evaluated.
achieved at 120
C sink and 80
C source temperature (40 K lift). Already in 1985, the Japanese researchers Yamazaki and Kubo
Reibner [106] described a way to determine the minimum [112] presented a 400 kW heat pump running with pentane (R601)
necessary superheat for a particular refrigerant based on its phys- providing condensation temperatures of up to 135
C. The heat
ical properties. The superheat is proportional to the inverse slope of pump generated low-pressure steam of 130
C using waste heat of
the saturation line in the pressure-enthalpy diagram, and thus 90
C as heat source. A variable-capacity screw compressor was
approximately linear to the isochoric heat capacity and the molar used with a motor power of 75 kW. A COP of 4.5 was reached at
mass of the particular refrigerant. Accordingly, R1233zd, R245fa, 80
C source and 135
C sink temperatures [112,123]. The thermal
R114 and R236ea require less than 10 K minimum superheat, which properties of R601 and a polyglycol-based lubricating oil were
is possible to achieve in an evaporator of a simple heat pump cycle. evaluated in a 15 kW laboratory heat pump. In a scaled-up pilot
In contrast, fluids like LG6 and R1336mzz(Z) require more than 15 K plant, the suitable liquid combination was successfully tested over
superheat and thus a modified heat pump cycle with an IHX, 10500 operating hours [3,112,123].
additional heating, or a by-pass system to provide the required More recently, Fukuda et al. [114], from the Kyushu University
overheating. experimentally tested the low GWP refrigerant R1234ze(Z) in a
In the experimental setup, Reibner et al. [89,106,111] applied an single-stage HTHP with 1.8 kW heating capacity. A two-stage rotary
IHX and an electric heating band to control the superheat at the compressor with two roller pistons developed for R410A was
compressor outlet. A coaxial twin tube heat exchanger was applied using polyolester oil as lubricant. The COP increased with
installed as evaporator and plate heat exchangers for the condenser higher sink temperature at a constant lift of 30 K from 5.4 at 45
C/
and the IHX. The refrigerants with designation DR-2 and LG6 were 75
C, to 6.3 at 70
C/100
C and 6.6 at 90
C/120
C source/sink
applied [5,89]. Condensation temperatures of up to 140
C with a temperatures. The basic suitability of R1234ze(Z) for the use in
COP of 3.7 with 50 K lift could be achieved, as well as a COP of 4.8 at HTHPs could be demonstrated.
130
C condensation and 40 K lift. In Norway, the project HeatUp [58,124] aims to extend the
In France, Johnson Controls (JCI), Clauger and Electricite
de temperature range for heat pumps beyond 200
C by using natural
France (EDF) are the main drivers in the development of HTHPs working fluids like butane (R600), ammonia (NH3), and water
[1,4e6]. In a cooperation project with JCI and EDF, a HTHP was (H2O). As part of this research project, Bamigbetan et al. [118]
tested with R245fa using an economizer circuit with IHX presented early test results of a 20 kW propane/butane (R290/
[5,6,87,122]. To cover the entire heating capacity range of 900 to R600) heat pump designed in a cascade configuration with R290 in
1'200 kW a twin-screw compressor and a centrifugal compressor the low and R600 in the high temperature stage. The laboratory
with magnetic bearings were developed. Both compressor tech- system is able to lift heat from about 30
C source up to 120
C sink
nologies were tested up to 120
C sink temperature [6]. The HTHP temperature. The hydrocarbon charges were minimized for safety
reached a COP of 5 to 6 at 60
C source and 100
C sink temperature and the design parameters were adjusted for compressor protec-
[5]. tion and best performance [119]. The HTHP runs with a modified
In the AlterECO project (Analysis Low Temperature Energy reciprocating compressor in the high temperature stage that per-
Recovering ECOnomy), Peureux and Bobelin [5,7,8] designed a mits up to 80
C suction and 160
C discharge temperature. Addi-
HTHP capable of operating at 140
C condensation temperature and tional thermal protection was installed and an appropriate
200 kW heat output. ECO3, a refrigerant mixture containing R245fa lubrication oil was selected for high temperatures. The test rig also
was used [7]. The heat pump operated with two parallel scroll allows a large temperature glide from about 30
C to over 100
C in
compressors of 75 kW power each. Test campaigns were run for the heat sink. Heating COPs of 2.1 to 2.6 were measured for 70 K
more than 1’000 h under industry-like conditions to demonstrate temperature lifts [118].
reliability [5,7]. The condensation temperature was steadily Wemmers et al. [115] in the Netherlands, designed a pilot R600
increased from 80 to 125
C at an evaporation temperature of 35 to heat pump able to deliver low pressure steam of up to 2.4 bar
60
C. COPs of 6 to 7 were achieved at 55
C source and 90
C sink (125
C) from 60
C waste heat at a COP of 1.9. The HTHP was
temperature. At a condensation temperature of 125
C (evaporation developed from commercially available components to ensure
at 50 to 60
C) a COP of 2 to 3 was reached. For 140
C sink tem- quick market introduction. The heat pump configuration also in-
perature, the basic technological feasibility could also be cludes a subcooler in order to heat process water at 70
C
996 C. Arpagaus et al. / Energy 152 (2018) 985e1010

Fig. 8. COP of various industrial HTHPs as a function of the temperature lift. Data from literature: Kobelco SGH 120/165 [5,13,61,62], Kobelco HEM-HR90 [5,13,61,62], HeatBooster S4
[63e65], Ochsner [43,66e68], Hybrid Heat Pump [16,17,69], Unitop 22/22 [74,75], Combitherm [23,24,71], GEA Grasso FX P [77], Star Refrigeration Neatpump [76], SABROE HeatPAC
HPX [78], Vitocal 350-HT Pro [79], Mitsubishi ETW-L [5,13].

compressor and a refrigerant with the designation BY-4 (near-

azeotropic refrigerant mixture). COP values of 2.8e3.6 were eval-
uated at a temperature lift of 40 K in the range of 90e110
C sink
temperatures. Zhang et al. [113] investigated a new binary, near-
azeotropic mixture called BY-5 in a single-stage HTHP with scroll
compressor, liquid receiver, and gas-liquid separator. The heat
pump provided a heating capacity of 16 to 19 kW with sink tem-
peratures of up to 130
C. A COP of about 2.2 was achieved at 80
C
source and 130
C sink temperature. The BY-5 refrigerant has been
designed to be environmentally friendly, although the GWP of 800
is still relatively high. Huang et al. [117] investigated the perfor-
mance of a single-stage heat pump system using a constant speed
scroll compressor and R245fa as refrigerant. The outlet temperature
of pressurized water could be heated up to 114
C, and a COP of up
to 5.18 was reached with a condensation temperature of 120
C and
a temperature lift of 49 K.
The Korean researchers Lee et al. [116] designed a HTHP for low
pressure steam generation using R245fa as refrigerant. In order to
Fig. 9. Number of publications with the search keyword "high temperature heat
ensure superheating, an IHX was implemented in the heat pump
pump" in the online databases SCOPUS (www.scopus.com) and Web of Science (www. circuit. The produced heat was transferred to circulating pressur-
webofknowledge.com) (accessed on September 25, 2017). Crude oil price in US dollar ized water. By flashing the heated water to the two-phase region, a
per barrel (2016 deflated using the US consumer price index, source: BP Statistical portion of water was converted to steam. A steam reservoir sepa-
Review of World Energy 2017 [102]).
rated the steam and the water. In open loop configuration addi-
tional water was supplied to the flash tank. With this set-up steam
(maximum is 100
C). In this way, up to 160 kW heat is extracted temperatures of 104e123
C (1.2e2.2 bar) could be reached. At
from the heat pump without the need to supply more work to the 60
C source and 105
C steam temperature a COP of about 3.5 was
compressor. reached.
Moisi et al. [120] from the Graz University of Technology in To sum up, it can be stated that there is a high experimental
Austria developed a R600 heat pump prototype with a heating research activity in the area of HTHPs. The main research goals are
capacity of 40 kW using a modified, inverter-driven separating increasing heat pump efficiency, testing new environmental-
hood piston compressor. First experimental tests showed stable friendly refrigerants and achieving high heat sink temperatures.
operation at the design conditions of 60
C source and 110
C sink Experimental research on HTHPs is being driven mainly by research
temperature with a COP of 3.5. A superheat of 18 K was set to avoid groups in Austria [50,103e105,120,125,126], France [5,7,107e110],
cutting the saturation curve during compression. Germany [37,89,106,111], Japan [112,114], Norway [58,118,119,124],
In China, Huang et al. [117], Zhang et al. [113], and Yu et al. [121] The Netherlands [115], Switzerland [46,59,60], Korea [116], and
reported about experimental studies on HTHPs with sink temper- China [113,117,121]. At least 17 experimental research projects with
atures above 100
C. Yu et al. [121] tested the performance of a HTHPs have been identified to reach heat sink temperatures of
HTHP with 65e120 kW heating capacity using a double scroll above 100
C. Heat sink temperatures above 120
C were reported
 C. Arpagaus et al. / Energy 152 (2018) 985e1010 997

Table 3
Research projects of HTHPs sorted by the heat sink temperature. Further information is given on the organization, project partners, heat pump cycle, compressor type,
refrigerant, and heating capacity.

by several authors [7,37,50,89,103e116]. The refrigerants used were higher sink temperature. This phenomenon is related to the situ-
mainly R1336mzz(Z) [50,103,104], R718 [107e110], R245fa ation close to the critical point of the refrigerant, where the
[5e7,87,116,117,122], R1234ze(Z) [114], R600 [115,118,120,125,126], condensation enthalpy decreases gradually with higher tempera-
and R601 [112], as well as fluids with no further published infor- ture in relation to the compression enthalpy, whereby the COP
mation on the chemical composition, such as LG6 [89,106,111], decreases.
€
OKO1 [105], ECO3 [5,7], HT125 [37], BY-4 [121], or BY-5 [113]. In the case of Wilk et al. [105], the refrigerant used was OKO1 €
The heating capacities of the functional models and laboratory (containing R245fa) and the COP remained relatively constant be-
prototypes presented range from 1.8 to 12 kW. Larger prototypes tween 3.6 and 3.9. Noack [37] used the refrigerant HT125 with
are capable of producing several 100 kW heat. Piston compressors unknown chemical composition on account of secrecy.
are mainly used in the laboratory scale systems. The state of the art results of commercial available HTHPs are
Most of the studied cycles are single-stage and partly contain an displayed as shaded area in Fig. 10. The area has been determined
IHX [89,103,106,111] and/or an economizer [5,6,87,105,122] with from data presented in Fig. 8. As can be seen, several research
intermediate vapor injection into the compressor. There are a few projects push the limits of the achievable COPs and sink tempera-
experimental examples on two-stage cycles [118] and studies with tures to higher levels compared to the commercial available heat
additional subcoolers/heat exchangers for combined water heating pumps. More R&D efforts are dedicated to increase the techno-
[7,115]. The highest sink temperature reported was almost 160
C logical readiness level and efficiency of HTHPs.
using a single-stage cycle with an IHX and R1336mzz(Z) [103]. Numerous theoretical studies have been carried out to assess
Fig. 10 shows the experimentally achieved COPs of the different the efficiency of a simple single-stage heat pump cycle with various
research projects as a function of the heat sink temperature, and refrigerants assuming different temperature lifts (30 to 80 K),
the respective temperature lifts (DTlift) in the range from 20 to 70 K. superheating (3 to 20 K), subcooling (5 to 60 K) and compressor
The COPs tend to increase with higher sink temperature and lower isentropic efficiency (0.7 to 1.0) [7,89,106,114,127e134]. Table 5
temperature lift. The band widths of the COPs at 120
C sink tem- summarizes these theoretical studies and the data are sorted by
perature are in the ranges of about 5.7 to 6.5 at 30 K temperature lift the temperature lift of the heat pump. Also shown are the respec-
and 2.2 to 2.8 at 70 K, respectively. Helminger et al. [103] achieved tive bandwidth of the condensation temperatures and the calcu-
the highest sink temperature of 155
C with a COP of 2.7, temper- lated COPs. For example, Kondou and Koyama [131] revealed a
ature lift of 45 K, and refrigerant R1336mzz(Z). Fleckl et al. [50,104] remarkable COP of 5.3 with R1233zd(E) and an 80 K temperature
reached 150
C with a COP of 2.4 and a considerable temperature lift (70
C/150
C), similar to that of R245fa, due to the large amount
lift of 70 K. of subcooling.
Some curves reach a COP maximum and decline slightly with
998 C. Arpagaus et al. / Energy 152 (2018) 985e1010

Table 4
Cyles and achieved heating COPs of experimental research studies on HTHPs (TLT: source temperature [
C], THT: sink temperature [
C], DTlift: temperature lift [K], COP: Heating
coefficient of performance [], Second Law efficiency h2nd ¼ COP/COPCarnot).
 C. Arpagaus et al. / Energy 152 (2018) 985e1010 999

4. Refrigerants Furthermore, the refrigerant must be safe to the environment.

Ozone depleting substances (ODS) like chlorofluorocarbons (CFCs)
4.1. Selection properties and hydrochlorofluorocarbons (HCFCs) have been used as heat
pump working fluids in the past [153] but are phased out of pro-
The selection of the refrigerant is a key element in the design of duction under the Montreal Protocol [139] on a global scale. The EU
HTHPs. The requirements for the refrigerant are manifold as regulation (EC) No 1005/2009 prohibits the use of ODS.
described by several authors [1,84,89,103,135e138]. Table 6 sum- Hydrofluorocarbons (HFCs) were designated as greenhouse
marizes the most essential evaluation criteria for the application in gases under the Kyoto Protocol [154] and are subjected to phase
HTHPs, which are grouped into the categories thermal suitability, down (production and consumption) in most developed countries
environmental compatibitly, safety, efficiency, availability, and under the Kigali amendment [155] to the Montreal protocol. In
other factors. Europe, the F-Gas regulation (EU) No 517/2014 [141] foresees the
Table 7 compares the properties of a selection of working fluids phase down of HFCs. By 2022 only refrigerants with a GWP smaller
for HTHP application. Listed are the chemical composition, the than 150 may be used in new refrigerators and freezers for com-
critical pressure and temperature, the ozone depletion potential mercial use. Consequently, the GWP should be as low as possible for
(ODP), the global warming potential (GWP), the normal boiling future-proof usage in HTHPs.
point (NBP), the safety group classification, the molecular weight, One of the most important thermodynamic parameters is the
and the current price relative to CO2. achievable COP of a working fluid in a heat pump cycle. The volu-
The fluids are classified by type and critical temperature. metric heating capacity (VHC) is important for the compressor
Marked in grey are refrigerants, which have a GWP higher than 150, design as it determines its size and cost, and it influences the
a non-zero ODP (except R1233zd(E) and R1224yd(Z)), a critical achievable experimental COP. Section 5 is dedicated to asses the
temperature below 150
C, or are rated at safety group A3. COP, the VHC, and the pressure ratio of different refrigerants in a
The upper temperature limit of subcritical heat pump cycles is basic heat pump cycle. Other decision criteria for refrigerant se-
determined by the critical temperature of the refrigerant. A tem- lection are its availability on the market and its price. For example,
perature gap of about 10 to 15 K from the desired condensation the low GWP refrigerant R1234yf (sales price 120 EUR/kg) is
temperature has to be maintained to ensure subcritical heat pump currently about 12 times more expensive than R134a (10 EUR/kg).
operation [2]. The closer the condensation temperature to the R1233zd(E) costs about 55 EUR/kg, which is comparable to R245fa
critical point, the smaller the condensation enthalpy and the (57 EUR/kg) or Novec 649 (59 EUR/kg).
heating COP [89,106,114,127e130,132,134]. Transcritical or super-
critical heat pump cycles are also applied e.g. with R744 4.2. Hydrofluorocarbons (HFCs)
[5,13,70,72,73]. In these processes, the heat transferred to the sink
is sensible and a large temperature glide is required, which is In the past, industrial HTHPs mainly used the chlorinated hy-
suitable for hot water heating. drocarbon R114 [156,157], as it allowed condensating temperatures
The pressure level of the heat pump system determines the of up to 130
C [158,159]. Due to their high ODP, CFCs were replaced
material efforts of the equipments. The higher pressure should be by fluorinated hydrocarbons in the 1990s. R245fa, R245ca, and
kept below a practical value of about 25 bar [130,149], although R365mfc offer zero ODP and relatively high critical temperatures of
compressors are available for R32 and R410A which can withstand 154.0, 174.4, and 186.9
C at moderate pressures of 36.4, 39.3, and
up to 50 bar. The lower pressure should not be below one atmo- 32.7 bar [7,160]. R365mfc was originally developed as foaming
sphere at standstill to avoid foreign gas entry [37,103]. To minimize agent for high temperature applications. However, its GWP of 804 is
compressor power the pressure ratio should be as low as possible. rather high, and it is flammable (A2). To overcome the flammability,
The thermal stability of the refrigerant-oil mixture limits the R365mfc is sometimes mixed with perfluoropolyether (PFPE) or
compression discharge temperature. A properly selected refriger- R227ea. Solkatherm SES36 [144] from Solvay contains e.g. 35% PFPE
ation oil ensures tightness, lubricity and temperature stability. as a blend component. It is an azeotrope with a critical temperature
With today's technology, the compression end temperature (e.g. in of 177.6
C. But the GWP of SES36 is 30126 [145]. Two zeotropic
a piston head) should not exceed about 150
C [150]. A too high mixtures containing R365mfc and R227ea have also been devel-
compressor discharge temperature could pose challenges in the oped. They have critical temperatures of 177.1
C and 181.6
C, and
compressor heat management and the selection of lubricants and are offered under the trade names Solkatherm SES24 [161] and
polymeric materials of equipment construction [151]. It can lead to SES30 [162]. Their GWPs are about 10110 [163].
a loss of lubricity and oil tightness up to chemical decomposition However, with regard to the increasing restrictions imposed by
and coking of oil [84]. In addition, the working fluids need to be the Kyoto Protocol [154] and the F-Gas regulation [141], R365mfc,
chemically compatible (no degradation) with metal materials like R227ea, R245fa, and R134a will be phased down in the foreseeable
aluminum, steel and copper, as well as with polymers [127,128,152]. future due to their high GWP. This drives research and industry
For safety reasons, flammability and toxicity should be avoided towards the evaluation of alternative refrigerants with lower GWP
or be as low as possible. International safety standards (e.g. EN 378) [49].
regulate the usage of heat pump systems filled with flammable
working fluids. The allowed charge limit depends on several as- 4.3. Hydrofluoroolefins (HFOs)
pects like type of location, type of person presence and room vol-
ume. According to the Regulation (EC) No 1272/2008, a fluid is Hydrofluoroolefin (HFO) refrigerants are considered as envi-
denominated as toxic if it exhibits at least one of the following ronmentally friendly (low GWP) alternatives to replace HFCs.
health hazard classifications; skin or eye irritation, acute toxicity, R1234yf (Honeywell Solstice®yf, Chemours Opteon™YF) and
carcinogenicity, germ cell mutagenicity, or aspiration hazard. Re- R1234ze(E) (Solstice®ze) are regarded as substitutes for R134a
frigerants with lower and no flammability (A1 or A2) reduce the [13,164]. The critical temperatures and pressures are comparable.
complexity of the safety devices and thus the costs. The major application areas are automotive air conditioners, re-
Fig. 11 classifies the most promising refrigerants according to frigerators and freezers. They could also serve as refrigerants for a
their flammability and toxicity in the safety groups according to first stage of a two-stage HTHP cascade.
DIN EN 378-1 [142] and ASHRAE [143]. R1336mzz(Z) and R1234ze(Z) are attractive replacements for
1000 C. Arpagaus et al. / Energy 152 (2018) 985e1010

Fig. 10. Experimentally achieved COPs of HTHPs in research status as a function of the sink temperature at different temperature lifts (20 to 70 K). Data from literature: Huang et al.
[117], Bobelin et al. [5,7], EDF/JCI [5,6,87,122], Fukuda et al. [114], Helminger et al. [103], Reibner et al. [89,106,111], Fleckl et al. [50,104], Chamoun et al. [107e110], Yamazaki and
Kubo [112], Wilk et al. [105], Noack [37], Moisi et al. [120], Yu et al. [121]. Shaded area: The state of the art of commercial available HTHPs (according to Fig. 8) is indicated at 120
C
heat sink temperature with a COP of up to 3.5 and about 6 at 60 to 90
C.

R245fa and R365mfc, as several studies have shown have shown that the material compatibility relative to copper and
[5,127,128,130,140,152,156,157,165e167]. steel is similar to those of R245fa, which is widely used in high
The advantages of R1336mmz(Z) are the high critical tempera- temperature applications and shows no material problems [130].
ture of 171.3
C at a rather low pressure of 29.0 bar. It is safety class The fluid remained transparent and the metal surfaces clean. There
A1 [168], has a GWP of 2 [130,140], zero ODP and an atmospheric are only mild interactions between R1336mzz(Z) and common
life of 22 days [140,152,165e167]. Chemours is about to commer- plastics and elastomers [128,171]. As lubricant, polyolester oil (POE)
cialize R1336mzz(Z) (previously referred to as DR-2 with high viscosity is recommended as it is fully miscible over wide
[127,128,151,169]) under the brand Opteon™MZ, which can ranges of temperatures and compositions [169]. The negligible
deliver sink temperatures above 160
C [130]. It is stable up to temperature glide makes the refrigerant also suitable for large heat
250
C for organic rankine cycles (ORC), waste heat recovery ap- pumps (and chillers) with flooded evaporators. R1336mzz(Z) is
plications [170,171], and steam generation [130]. Laboratory tests liquid at room temperature (at 1 atm) and has a molecular weight

Table 5
Theoretical comparison of the efficiency (COP) of a single-stage heat pump cycle with different refrigerants at different temperature lifts DTlift (30 to 80 K) and assumptions for
superheating DTSH (3 to 20 K), subcooling DTSC (5 to 60 K), and compressor isentropic efficiency his (0.7 to 1.0).
 C. Arpagaus et al. / Energy 152 (2018) 985e1010 1001

Table 6
Selection criteria of refrigerants for application in HTHPs [1,84,89,103,135e138].

Category Required properties

Thermal suitability  High critical temperature (>150
C) allowing subcritical heat pump cycles
 Low critical pressure (<30 bar)
 Pressure at standstill >1 atm
 Low pressure ratio
Environmental compatibility  ODP ¼ 0 (no ozone depletion)
 GWP < 10 (low global warming)
 Future-proof according to regulations
Safety  Non-toxicity
 No or only low flammability
Efficiency  High efficiency (COP) at high temperature lifts
 Minimal superheat to prevent liquid compression
 High volumetric heating capacity (VHC)
Availability  Available on the market
 Low price
Other factors  Satisfactory solubility in oil
 Thermal stability of the refrigerant-oil mixture
 Lubricating properties at high temperatures
 Material compatibility with aluminum, steel and copper

of 164.1 g/mol. As shown in Section 2 and 3, experimental evidence heat from various sources. The VHC is comparable to R245fa and
with R1336mzz(Z) in HTHPs has already been demonstrated in about 54% higher than for R1336mzz(Z) at 130
C condensation
several studies [45,50,63e65,103,104]. temperature and 50 K temperature lift [132].
Its isomer R1336mzz(E) is a novel, non-flammable working fluid Relatively little information is available on the isomer
with a GWP of 18 and a critical temperature of 137.7
C [132]. It has R1234ze(Z) [1,134,156,157,172,173]. Its critical temperature and
zero ODP and a favorable toxicity profile based on testing to date. It pressure are 150.1
C and 35.3 bar [134], which allows subcritical
could be used in HTHPs and ORC technology platforms to recover cycle operations at high temperatures. The flammability is rated

Table 7
Comparative properties of refrigerants for HTHP application. CFC: Chlorofluorocarbons, HCFC: Hydrochlorofluorocarbons, HFC: Hydrofluorocarbons, HFO: Hydrofluoroolefins,
HCFO: Hydrochlorofluoroolefins, HC: Hydrocarbons, Tc: Critical temperature, pc: Critical pressure, ODP: Ozone Depletion Potential (basis R11 ¼1.0 [139]), GWP: Global
Warming Potential for 100-year time horizon (basis CO2 ¼ 1.0, values from IPCC 5th assessment report [140] and F-Gas regulation (EU) No 517/2014 [141]), SG: Safety group
classification (DIN EN 378 [142] and ASHRAE Standard 34 [143]), NBP: Normal boiling point at 1.013 bar, M: molecular weight, Approximate sales price in Euro per kg
refrigerant relative to CO2 with 9 EUR/kg (based on a 10 kg container, excl. VAT, transport, rent, prices from PanGas AG, Climalife, TEGA, Sigma-Aldrich, Solkatherm, and 3M,
October 2017), n.a.: not yet available but close to market or very high prices (>10000 EUR/kg). Marked in grey are refrigerants with GWP > 150, ODP > 0.001, safety group A3,
and Tc < 150
C, *refrigerants selected for further cycle efficiency evaluation in section 5, aSolkane®365mfc from Solvay, bSolkatherm®SES36 from Solvay [144], cLewandowski
et al. [145], davailable from Linde or Honeywell (Genetron® 245fa), eOpteon™ MZ from Chemours, fFukuda et al. [114], gJuhasz [132], hSolstice®zd from Honeywell [88,146,174],
i
AMOLEA® 1224yd from AGC Chemicals [147], jNovecTM 649 from 3M [148], kMolecular biology reagent quality.
1002 C. Arpagaus et al. / Energy 152 (2018) 985e1010

with A2L [114]. The thermodynamic properties appear promising. 50
C (0.1 bar) to steam at 150
C (5 bar) the pressure ratio is about
Its GWP is smaller than 1 [140]. R1234ze(Z) is assessed as suitable 50. In order to keep the discharge temperature to a tolerable level,
drop-in substitute for R114 in HTHP applications [156,172] and several compression stages are required with intermediate cooling
promising as an alternative to R245fa [5,114,172]. [46,176]. Typically, water vapor recompression systems are oper-
ated using large compressors or high-speed oil-free turbo com-
4.4. Hydrochlorofluoroolefins (HCFOs) pressors with high flow rate and low-pressure ratio to compensate
for the low density of the water vapor [46,58].
The HCFO R1233zd(E) with a critical temperature and pressure CO2 heat pumps are common in smaller sizes [5,13,70]. They
of 165.5
C and 35.7 bar, and safety class A1 is available from have also been commercialised in the larger range [5,72,73]. In spite
Honeywell under the brand name Solstice®zd and it is recom- of the low critical temperature of 31
C and high critical pressure of
mended as a refrigerant for HTHP applications [146,174]. Although 73.6 bar, CO2 heat pumps also achieve sink temperatures of 90 to
R1233zd(E) contains chlorine, its ODP is extremely small (0.00034) 120
C in transcritical cycles. R744 is feasible as an HTHP fluid if the
due to the very short atmospheric lifetime of 40.4 days [166,175]. inlet temperature of the heat sink is not too far above the critical
On the other hand, thermal studies to copper and steel showed temperature. The high transcritical temperature glide in the gas
turbidity and discoloration of steel after 7 days at 250
C [128,171]. cooler makes R744 a particularly suitable refrigerant for domestic
Moreover, the vapor pressure at ambient temperature is only hot water heating and other processes with very large temperature
1.079 bar (20
C). This could lead to air infiltration into the heat differences in the sink.
pump circuit in downtimes at lower ambient temperatures, even Ammonia is widely used in industrial heat pumps up to about
though a heat pump is subjected to a leak test before 90
C heat sink temperature [76e78]. Beneficial is its high VHC
commissioning. compared to other refrigerants [177]. For higher temperatures,
In October 2017, the Japanese refrigerant manufacturer AGC existing compressor technology is limited due to high discharge
Asahi Glass has obtained ASHRAE certification for its new low GWP pressures [7]. With special cast steel construction, NH3 compres-
HCFO refrigerant R1224yd(Z) [147]. It is an A1 non-flammable sors are able to withstand pressures of up to 76 bar and 110
C [90].
refrigerant designed mainly for use in centrifugal chillers and However, certain safety precautions must be implemented due to
waste heat recovery heat pumps. AGC will market the refrigerant as the toxicity of ammonia (B2L).
Amolea® 1224yd with commercial production beginning in early The hydrocarbons n-butane (R600) and pentane (R601) are re-
2018. With an almost zero ODP (atmospheric lifetime of 21 days) frigerants without ODP and very low GWP. They are relatively cheap
and an GWP value under 1, R1244yd(Z) has little impact on the (18 and 49 CHF per kg) and have high critical temperatures of
environment. Its physical properties are stated to be very close to 152
C and 196.6
C at 38.0 and 33.7 bar, respectively. R600 is
R245fa and R1233zd(E). Furthermore, it has also good compatibility considered as a suitable medium in HTHPs with liquefaction tem-
with most commonly used metals, plastics, and elastomers, and it is peratures up to 120
C. These temperatures can be achieved in
miscible with synthetic oils such as POEs. standard compressors [87,149]. On the other hand, due to the high
flammability (A3), special safety measures have to be implemented
and HCs are therefore recommended for small systems with small
4.5. Natural refrigerants and hydrocarbons (HCs) charging volumes [158]. According to EN 378 [142], the maximum
capacity of HCs for laboratory equipment is limited to 150 g, for
Natural refrigerants suitable for high temperature applications supervised commercial systems with corresponding explosion
are R718 (water), R744 (CO2), R717 (ammonia), and hydrocarbons. protection up to 2.5 kg.
When using water, the major part of the heat pump cycle is below
atmospheric pressure because of the high normal boiling point of 4.6. Novec 649
100
C. The latent heat of water is about 15 times larger than that of
R134a at 50
C [176]. This property makes water very attractive for 3M™ Novec™ 649 [148] is another refrigerant with favorable
temperatures above 150
C [153]. However, due to the low water thermodynamic properties for use in HTHPs. Novec 649 has been
vapor density, the required swept volume and pressure ratio are designed as replacement for compounds with high ODPs and
very high. For example, to increase the water temperature from GWPs, such as sulfur hexafluoride (SF6) and HFCs like R134a and
R245fa. The fluid has a fairly high critical temperature of 168.6
C
and a molar mass of 316 g/mol. It is an effective heat transfer fluid
particularly used for electronics cooling applications.

4.7. Thermodynamic properties

Fig. 12 compares the thermodynamic properties of the re-

frigerants R365mfc, R245fa, SES36, R1234ze(Z), R1233zd(E),
R1336mzz(Z), R1224yd(Z), R600, R601, and Novec 649, which have
a critical temperature above 150
C and are suitable for HTHP
application. Fig. 12 (a) shows the vapor pressure curves of the re-
frigerants. At 130
C the vapor pressures of R1234ze(Z), R245fa and
R600 are at about 25 bar. R1336mzz(Z) is roughly equivalent to
R365mfc, SES36, and R601 at around 12 bar. The pressures of
R1224yd(Z) and R1233zd(E) are in between, at approx. 20 bar and
Novec 649 below at about 10 bar. Generally, lower vapor pressures
allow higher condensing temperatures without exceeding the
Fig. 11. Safety group classification, according to DIN EN 378-1 [142] and ASHRAE [143],
A: lower toxicity, B: higher toxicity, 1: no flame propagation, 2: lower flammability (2L:
operation limits of commonly available large centrifugal compres-
“mildly flammable” with a maximum burning velocity of 10 cm/s), 3: higher sors [151].
flammability. Fig. 12 (b) shows the p-h and Fig. 12 (c) the T-s diagrams for
 C. Arpagaus et al. / Energy 152 (2018) 985e1010 1003

Fig. 12. Comparison of p-T (a), p-h (b), and T-s (c) curves of working fluids selected for HTHPs. The enthalpy and entropy values are referenced to 200 kJ/kg and 1 kJ/kg-K for
saturated liquid at 0
C (273.15 K) (standard reference state for IIR).

these fluids. Characteristic are the saturated vapor curves with a Table 8 lists the basic equations and the applied assumptions.
positive slope (dT/ds > 0) [106,125,126,151,160,178,179]. The two- The cycle was modeled assuming isobaric condensation and
phase regions of the fluids are significant leaned over to the right, evaporation, isenthalpic expansion, and compression with a con-
which can be recognized from the shapes of the p-h and T-s plots. stant isentropic efficiency of 0.7, which is common for theoretical
As a result, special superheating control is needed to prevent wet calculations [7,133]. The thermodynamic properties of the re-
fluid compression and compressor damage [126]. A sufficiently frigerants were obtained from the EES fluid database, except
high superheating is necessary to ensure a dry compression with R1224yd(Z), whose values were taken from literature [147].
high temperature lifts [128]. The temperature lift between the condensation and the evap-
The minimum superheat depends on the refrigerant, the oration temperature was fixed at 70 K, as an example for high
condensation and evaporation temperatures, and the isentropic temperature application. For simplification of the paper, the sim-
compressor efficiency. It can vary between 0 and 35 K [125,126]. For ulations were performed with a constant subcooling of 5 K in the
R600, it lies in the range of 5 K (at 0
C evaporation and 50
C condenser, which implies a low heat sink temperature difference,
condensation temperature) to 18 K (0
/125
C) [125]. At least 14 K as is typically the case in drying and steam generation applications.
minimum superheat is necessary to avoid cutting the saturation A pinch temperature approach for adapting the subcooling to the
curve during compression at 40
C evaporation and 125
C sink temperature would be more feasible with variable tempera-
condensation temperature based on isentropic compression ture differences. Within the IHX, a minimum temperature differ-
(his ¼ 1). R1233zd(E) and R245fa require less than 10 K minimum ence of 5 K between the state points 6 and 4 was assumed (see
superheat, which is possible to achieve in an evaporator of a simple Fig. 13).
heat pump cycle. In contrast, fluids like R1336mzz(Z) that require To ensure dry compression with such a high temperature lift,
more than 11 K superheat (for a 40 K lift) require a modified heat two groups of refrigerants were formed to control the superheat:
pump cycle [128]. A simple concept for the realization of the
required superheat is the use of an IHX, which simultaneously  Group I (SES36, R1233zd(E), R1234ze(Z), R245fa, R600): Su-
heats the suction gas and subcools the liquid after condensation perheat control at compressor inlet (suction gas DTSH;I ¼ 5 K)
[106,125,126]. Furthermore, a single stage cycle with IHX is most (Eq. (3) active, (7) disabled),
favorable as a tradeoff between cycle complexity and efficiency  Group II (R601, R365mfc, R1336mzz(Z), Novec 649,
[125]. R1224yd(Z)): Superheat control at compressor outlet (discharge
gas DTSH;II ¼ 5 K) (Eq. (7) active, (3) disabled).
5. Simulation of system performance
Fig. 14 shows the simulated COPs (a), VHCs (b), and pressure
In order to compare the thermodynamic efficiency of the ratios (c) of the heat pump cycle with the different refrigerants as a
selected refrigerants (see Fig. 12), a system simulation was per- function of the condensation temperature at a constant tempera-
formed for an idealized heat pump cycle with IHX. The different ture lift of 70 K. The COPs rise to an optimum with higher
thermodynamic states are illustrated in Fig. 13. This heat pump condensation temperature, as other studies have also shown
cycle offers a simple configuration, subcritical operation and re- [89,106,114,129,131,132]. The falling branches of the curves are
quires only a minimum number of equipment components. associated with the narrowing of the two-phase region and the
The natural refrigerants R718 and R744 have been excluded in endpoint corresponds to the critical temperature of the respective
the theoretical analysis as they require special cycle designs with fluid.
multi-stage recompression or transcritical operation. The optimum COP is refrigerant dependent and its condensation
The simulation model was developed in Engineering Equation temperature lies about 40 to 60 K below the critical temperature
Solver (EES) software (Version 10.268 [180]) to calculate the COP, (e.g. R1336mzz(Z); optimum condensation at 120
C, critical tem-
the VHC and the pressure levels (i.e. pratio ) for a condensation perature at 171
C, 51 K difference). The optimum condensation
temperature range between 60 and 200
C. The VHC describes the temperatures for R1234ze(Z), R1224yd(Z), R1234zd(E), and Novec
generated heat capacity per processed volume of refrigerant suc- 649 are about 100 to 120
C, respectively. SES36, R601, and
tion vapor and it gives an idea of the compressor size. It is derived R365mfc are most efficient in the range of 130 to 160
C, as illus-
from the product of the enthalpy difference ðh2  h3 Þ supplied to trated by the grey shaded area in Fig. 14 (a). SES36 provides the
the heat sink and the suction vapor density (r1 ). highest COP over the entire temperature range with a maximum of
1004 C. Arpagaus et al. / Energy 152 (2018) 985e1010

Fig. 13. Heat pump cycle and log(p)-h diagrams at 60
C evaporation and 130
C condensation temperature (70 K lift) with his ¼ 0.7, isenthalpic expansion, DTSC ¼ 5 K, DTIHX ¼ 5 K
illustrating the superheat control of group I refrigerants (e.g. R1233zd(E)) with DTSH,I ¼ 5 K at compressor inlet, and group II refrigerants (e.g. R1336mmz(Z)) with DTSH,II ¼ 5 K at
compressor outlet.

about 3.5. R601 reaches an optimal COP of around 3.3, and R365mfc and Novec 649 the lowest VHC among the investigated refrigerants.
of 3.2. At 130
C, R245fa and R600 have the lowest COPs of all R1234ze(Z), R600, R1224yd(Z), R245fa, and R1233zd(E) appear
refrigerants. most promising with VHC values ranging from 20 500 to 30 400 kJ/
The cycle efficiency for the HFO refrigerants R1234ze(Z), m3.
R1233zd(E), and R1336mzz(Z), increases relative to R245fa with At 130
C, the VHC of R1336mzz(Z) is about 58% lower than
condensing temperatures above 100
C, which is highly promising R245fa resulting in a larger compressor. This is in agreement with
for HTHP applications. Besides, HFOs are non-combustible, non- other simulation studies where the decrease was about 65% [130]
toxic, and have the lowest GWPs among the investigated refrig- and 41% [133] at slightly different assumptions of superheating
erant candidates. (20 K [130,133]), subcooling (10 K [133]), and compressor efficiency
Fig. 14 (b) compares the different VHCs for the selected re- (0.8 [130]). R1336mzz(Z), SES36, R601, R365mfc, as well as Novec
frigerants. The VHC curves increase with condensation tempera- 649 show similar VHC values in a range of around 10100 to 10800 kJ/
ture, which is equivalent to a higher evaporation pressure (at a m3.
fixed temperature lift), and thus higher suction vapor density Table 9 lists the values of the discharge gas temperature (T2 ), the
[127,181]. Close to the critical point, the VHCs tend to flatten due to pressure ratio, and the pressure levels at 60
C evaporation and
the decreasing latent heat in the condenser. 130
C condensation temperature. To mitigate the effects of the
A higher VHC is advantageous for positive displacement com- relatively high compressor discharge temperatures (130 to 150
C),
pressors (e.g. reciprocating pistons and screws) as it requires a some equipment modifications would probably be required. Fig. 14
smaller swept volume at a given capacity [2], and thus smaller size (c) shows a decrease of the pressure ratio with higher condensation
and investment costs. Common VHC values in heat pump appli- temperature due to the increasing evaporation pressure. Pressure
cations are between 30 000 and 60 000 kJ/m3 [106]. The lower prac- ratios in the order of 4 to 6 are reached between 130 and 160
C
tical limit depends on the compressor type and is about 10000 kJ/m3 condensation temperatures, which can be achieved with common
[89]. positive displacement compressors.
For temperatures above 130
C, R1234ze(Z) enables the highest Fig. 15 compares the calculated VHCs and COPs of the different

Table 8
Equations and assumptions used to model the heat pump cycle in EES software (V10.268 [180]).
 
Input parameters & assumptions: Tevap ¼ 10 to 130
C, Tcond ¼ 60 to 200
C, DTlift ¼ 70 K , TSC ¼ 5 K, D
TSH;I ¼ DTSH;II ¼ 5 K, DTIHX ¼ T6 ­T4 ¼ 5 K (for refrigerants without
temperature glide)

Pressures pevap ¼ pðTevap ; x ¼ 1Þ (1)

pcond ¼ pðTcond ; x ¼ 0Þ (2)
State point 1 h1 ¼ hðpevap ; Tðx¼1Þ þ DTSH;I Þ I: (3)
s1 ¼ sðpevap ; h1 Þ (4)
State point 2 h2s ¼ hðpcond ; s1 Þ (5)
h2 ¼ h1 þ ðh2s  h1 Þ=his (6)
h2 ¼ hðpcond ; Tðx¼1Þ þ DTSH;II Þ II: (7)
State point 3 h3 ¼ hðpcond ; Tðx¼0Þ  DTSC Þ (8)
State point 4 h4 ¼ hðpcond ; T6 þ DTIHX Þ (9)
State point 5 h5 ¼ h4 (10)
State point 6 h6 ¼ h4 þ h1  h3 T6 ¼ Tðpevap ; x ¼ 1Þ (11)
Results COP ¼ ðh2  h3 Þ=ðh2  h1 Þ (12)
VHC ¼ ðh2  h3 Þr1 (13)
p ¼ pevap =pcond (14)
 C. Arpagaus et al. / Energy 152 (2018) 985e1010 1005

would be R1336mzz(Z), whose COP and VHC are nearly identical

(approximately 3% lower COP and 16% higher VHC). R1224yd(Z),
R1234ze(Z) and R1233zd(E) are closest to R245fa, although their
COPs are about 3% lower respectively 9% higher than the corre-
sponding R245fa value. The cycle analysis suggests that it is not
possible to simultaneously achieve a high COP and a high VHC with
one refrigerant. There is an efficiency/capacity tradeoff between the
working fluids when selecting a refrigerant for HTHP application.
This tradeoff was also observed and discussed by Brown [172] when
it came to replacing HFCs by HFOs refrigerants possessing low
GWPs and condensation temperatures of 85
C maximum.

6. Conclusions

The market analysis of this state of the art review provides the
following major findings:

 High temperature heat pumps (HTHPs) are suitable systems for

waste heat recovery in various industrial processes such as
drying, sterilization, evaporation, papermaking, or food
preparation.
 For the European heat pump market, a technical potential of
about 113 PJ of process heat between 100 and 150
C can be
assumed realizable with industrial HTHPs.
 More than 20 HTHPs from 13 manufacturers have been identi-
fied on the market, which can provide heat sink temperatures of
at least 90
C. Only a few products are able to supply tempera-
tures of up to 120
C. Benchmark is the HeatBooster from Vick-
ing with 150
C, followed by the HTHPs from Ochsner with
130
C. Kobelco SGH120, Mayekawa Eco Sirocco and Hybrid
Energy Heat Pump deliver up to 120
C.
 The heating capacities of the commercial HTHPs range from
about 20 kW to 20 MW.
 The COP values range betwee about 2.4 and 5.8 with a tem-
perature lift of 95 to 40 K, respectively. Most experimental data
range between 40 and 60% Second Law efficiency (h2nd ¼ COP/
COPCarnot).
 Generally, single-stage heat pump cycle concepts are applied.
Cycle optimizations are achieved by implementing an internal
heat exchanger (IHX) between suction gas and subcooling
liquid, parallel compressors, economizer circuits with interme-
diate vapor injection into the compressor, or two-stage
cascades.
 The main applied refrigerants in commercial HTHPs are R245fa,
R717, R744, R134a, and R1234ze(E).
 The major market barriers for a wider spread of today's HTHP
technology in the industrial sectors are insufficient knowledge
about the integration of HTHPs in industrial processes, the lack
of available refrigerants in the high temperature range with low
GWP, and the high price ratio of electricity to fossil fuels.

Several R&D projects are currently running on an international

level to push the limits of the achievable COPs and heat sink tem-
peratures to higher levels compared to the state of the art results of
commercially available HTHPs.

 At least 17 experimental research projects with HTHPs have

Fig. 14. Simulated COPs, VHCs, and pressure ratios for the heat pump cycle with been identified that reach heat sink temperature of more than
different refrigerants as a function of the condensation temperature at fixed temper- 100
C. Several experimental studies report about heat sink
ature lift of 70 K. The temperature range of 130 to 160
C is illustrated by the grey
temperatures above 120
C. The highest heat sink temperatures
shaded area.
of close to 160
C were achieved with the refrigerant
R1336mzz(Z).
refrigerants. Considering the HFOs, the graphic shows that the  The heat pump cycles applied are mainly single-stage, or are
closest “drop-in” replacement for R365mfc in HTHP applications additionally equipped with an IHX and/or an economizer with
intermediate injection into the compressor.
1006 C. Arpagaus et al. / Energy 152 (2018) 985e1010

Table 9  
Simulation results of the heat pump cycle at fixed conditions: Tevap ¼ 60
C, Tcond ¼ 130
C, DTlift ¼ 70 K , DTSC ¼ 5 K, DTIHX ¼ 5 K, his ¼ 0:7.

Refrigerant COP [] VHC [kJ/m3] pratio [] pevap [bar] pcond [bar] DTSH;I [K] DTSH;II [K] T2 [
C]

Group I: DTSH;I ¼ 5 K
SES36 3.47 1810 5.5 2.2 12.0 5 8.6 138.6
R1233zd(E) 3.07 2594 4.9 3.9 19.1 5 6.2 136.2
R1234ze(Z) 3.06 3426 4.8 5.2 24.6 5 21.2 151.2
R245fa 2.82 2808 5.1 4.6 23.4 5 3.0 133.0
R600 2.76 3284 4.1 6.4 26.3 5 2.8 132.8
Group II: DTSH;II ¼ 5 K
R601 3.27 1604 5.1 2.1 11.0 18.6 5 135
R365mfc 3.21 1536 5.8 2.0 11.4 21.1 5 135
R1336mzz(Z) 3.11 1779 5.5 2.4 13.5 20.9 5 135
Novec 649 3.03 1064 6.0 1.5 8.8 40.9 5 135
R1224yd(Z) 2.91 3247 4.8 4.4 21.1 6.4 5 135

 The heating capacities range from laboratory-scale in the order promising.

of 10 kW up to larger prototypes with more than 100 kW. As an outlook, there is a strong presumption that HTHPs with
 Piston compressors are mainly used in the laboratory systems, heat sink temperatures of 160
C will reach market maturity in the
while screws are applied in larger test systems. coming years. Various research and demonstration projects are in
 At a heat sink temperature of 120
C, experimental COPs of progress or in the concept phase. The higher heat sink tempera-
about 5.7 to 6.5 (at 30 K temperature lift) and 2.2 and 2.8 (70 K) tures will open up new areas of application, in particular drying
are achieved, respectively. processes in the paper and food industry, and process heat to serve
 There is significant research towards testing new low-pressure steam networks. The future research activities are
environmental-friendly refrigerants with low GWP for use in mainly directed towards the following areas:
HTHPs. R1336mzz(Z), R718, R245fa, R1234ze(Z), R600, and
R601, as well as fluids without any other published information  Optimization and development of heat pump components and
€
on the chemical composition, such as LG6, OKO1, ECO3, HT125, systems (e.g. heat exchangers and compressors, reduction of
BY-4, or BY-5 are intensively investigated. heat losses, selection of lubricants) to resist higher
temperatures.
A comparative simulation study in a single-stage cycle reveals  Increasing cycle efficiency, e.g. through multi-stage circuits and
that an optimum COP is reached depending on the refrigerant and the combination with oil-free turbo compressors.
its condensation temperature. A tradeoff between the COP and the  Scale-up of functional models to industrial scale.
volumetric heating capacity (VHC) needs to be found when  Development of environmentally friendly synthetic refrigerants
selecting a refrigerant for a HTHP application. R1336mzz(Z) would with low GWP and use of natural refrigerants, such as hydro-
be the closest drop-in replacement for R365mfc, and R1224yd(Z), carbons or water.
R1234ze(Z) and R1233zd(E) for R245fa, whose COPs and VHCs are
nearly identical. Characteristic for these refrigerants is a positive Acknowledgment
slope (dT/ds > 0) of the saturated vapor curves. In order to ensure
dry compression at high temperature lifts, a minimum superheat This research project is part of the Swiss Competence Center for
must be ensured. A cycle design with an IHX seems to be most Energy Research SCCER EIP of the Swiss Innovation Agency
Innosuisse.

Nomenclature

c critical
CFC chlorofluorocarbon
cond condensation
COP coefficient of performance
evap evaporation
h2nd Second Law efficiency (COP/COPCarnot)
GWP global warming potential
h enthalpy [kJ kg1]
HC hydrocarbon
HCFC hydrochlorofluorocarbon
HCFO hydrochlorofluoroolefin
HFC hydrofluorocarbon
HFO hydrofluoroolefin
HT high temperature, sink temperature
HTHP high temperature heat pump
IHX internal heat exchanger
in inlet
Fig. 15. Volumetric heating capacity (VHC) versus COP of different refrigerants forthe
out outlet

HTHP application at fixed conditions: Tevap ¼ 60
C, Tcond ¼ 130
C, DTlift ¼ 70 K , D ODP ozone depletion potential
TSC ¼ 5 K, DTIHX ¼ 5 K, his ¼ 0:7. ODS ozone depleating substance
 C. Arpagaus et al. / Energy 152 (2018) 985e1010 1007

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