NZ613505B2 - Methods and components for thermal energy storage - Google Patents

Abstract

Method to store or increase the energy content of a reaction mixture by means of an endothermic condensation reaction is disclosed. The reaction mixture comprises an inorganic oxoacid compound and/or its salt and water. The reaction is enabled by the heat input from a heat source distinct from the reaction mixture. The inorganic oxoacid compound and/or its salt can be an oxoacid of nitrogen, sulphur or phosphorus, or its corresponding salt. Further disclosed is a system for capturing or storing energy, comprising capture means for capturing energy and storage means for storing captured energy. The capture and storage means comprise at least one reaction vessel at least partially filled with a reaction mixture comprising an inorganic oxoacid compound and/or its salt and water, suitable for having an endothermic condensation reaction performed on the reaction mixture, and comprising a heating element in thermal communication with the vessel. reaction mixture. The inorganic oxoacid compound and/or its salt can be an oxoacid of nitrogen, sulphur or phosphorus, or its corresponding salt. Further disclosed is a system for capturing or storing energy, comprising capture means for capturing energy and storage means for storing captured energy. The capture and storage means comprise at least one reaction vessel at least partially filled with a reaction mixture comprising an inorganic oxoacid compound and/or its salt and water, suitable for having an endothermic condensation reaction performed on the reaction mixture, and comprising a heating element in thermal communication with the vessel.

Description

METHODS AND COMPONENTS FOR TH'TRMAT. *ZNilRGY STORAGIL‘LJ Field 0: the Invention This invention relates generally to a method o_ thermal energy storage or heat pump, i.e. increase the thermal energy from an external heat source, using reversible chemical reactions. Within a ible cycle, a mixture comprising inorganic oxoacid compounds and/or its salt and water such as e.g. nitrate—, sulfate— phosphate— and sulfonate—esters, are depolymerized by means of an ethhermic ysation reaCtion and polymerized by neans of an endothermic condensation reaction in order to release and capture heat. It is accordingly a jirst aspect o: the present invention. to provide the use 0; inorganic d compounds and/or its salts and water in a method 0: thermal energy storage and / or in a method to increase the thermal energy from an external heat source, hereina‘ter a'so re‘erred to as a heat pump, in particular using' nic phosphorus oxoacid. nds and/or its salts, such as e.g. polyphosphoric acid.

The invention r provides a method to store thermal energy, said method comprising condensation reaction 0; a reaction. mixture comprising inorganic oxoacid compounds and/or its salts and water using an external heat source.

In a further aspect the inventior provides a method to release thermal energy from said heat e comprising an exothermic hydrolysation step 0: the inorganic oxoacid compounds or its salts.

Using the methods and components of the t invention it is le to store thermal energy at ambient circumstances in a transportable medium. As a consequence it allows converting a continuous heat generation process into a discontinuous and even dislocated ption. Moreover it is possible to pump up heat from ambient heat or low temperature heat sources, e.g. 80-200°C, to higher temperature levels with low specific electricity consumption, i.e. to use the method of the present invention as a heat pump.

Background to the Invention Any discussion of the prior art hout the specification should in no way be considered as an ion that such prior art is widely known or forms part of common general knowledge in the field.

Thermal energy storage is very important in many applications d to the use of waste heat from industrial processes, renewable energies or from different other sources. Moreover heat recuperation is receiving wide spread attention as a means of reducing the demand on fossil fuels and as means of reducing the exhaust of Kyoto gases.

Several heat capturing systems already exist. Heat can be ted from solar or heat sinks, or other sources including sun, geothermal, rest heat or other heat sources.

Examples of heat capturing systems can generally be divided in 3 categories: I. Sensible heat <500MJ/m3):  Water systems  Thermal oil Latent heat by phase change in materials 3: 0 Materials using there phase change as a means to store or release heat. Example is the use 0: Na— acetate crystallization. (theoretical heat y 300—800 GJ/m3) ° Using absorption heat 0: water on silica gel.

Reaction heat by reversible chemical reac:ions 0 Using the mixing heat 0' sul‘uric acid and water.

° Using the on heat 0: hydrogen and metals like Magnesium. (theoretical heat density 3GJ/m3) ° Salt Hydrates Most o: the proposed alternative energy is using the sun or wind as an energy source. Due to the process cal cycle) 0: the present invention, another heat source can be used with more easiness then nowadays: waste heat. Lots o: waste heat (also called rest heat) are generated in industry and released into the environment as non usable or "urther energy utilization, more specific electricity generation, this due to the low exergy state. However the use 0: rest heat makes sense for instance in residential areas for heating houses or flats and in industrial areas to heat process streams. d. 0: using conventional energy sources with high exergy, as e.g. natural gas or other combustibles 0: others, one could use as well the low exergetic rest heat. It prohibits using high caloric energy sources for low caloric applications. One 0: the mayor obstructions to use rest heat for these purposes is the jacL that rest heat in industry is used continuously versts the discontiruous usage 0: residential heat and moreover the fact that the heat producing industry is d quite ar ”rom ntial areas. The energy bu""ering capacity, the easiness 0: transport and the possibilities to use this chemical cycle as a heat pump or what is claimed below, forces a breakthrough for the use 0: rest heat and opens a new way for reducing Kyoto gases.

The use 0: cheap and low COzgenerating transport such as e.g. bulk or container shipments by boat and nes form an alternative “or intensive C02 generating road trucks.

In the method described ‘urther in this text, heat is used to form rs 0" inorganic oxoacid compounds or its salts by a (poly) condensation reaction 0: inorganic mo'ecules or molecu'es containing inorganic stb molecules with polyoxoacid compounds or its salts. Proton concentrations, catalysts, membranes etc. are used to promote the synthesis (condensation reaction) and hydrolysis reaction. -—| «.g. mono phosphoric acid and poly phosphoric acids are r polymerized by means 0; adding heat and by removing water nsation). The hydrolysis reaction by adding the water again, generates the exothermic depolymerization heat.

Moreover the method and components can be used as a reversible heat pump enabling to generate cold from rest heat, or to increase the thermal energy 0: a heat sources, with very low ic consumption, typically l-lO%. It according'y clearly di""ers ‘rom existing heat pump systems such as; A. Organic Rankine Cyclus (ORC) g up heat from low temperature sources to higher temperature levels or using the ORC to produce electricity trom rest heat.

Typically their realistic thermal e "iciency or COP is a heat to power ratio 0: about 3—5. a . Using LithiumRromid. or water/NH3 and rest heat as a heat pump to produce cold by absorbing heat due to the dissolution 0t Td—Rr in water under vacuum conditions.

In US 6,177,025B1, and JP01161082 this process is further optimized, with an improved e "iciency, by means 0“ a crystallization inribiting additive C . tic systems such as :or e bed in CN101168481A, see whole document and WP: abstract acc.no 2008—114900 [46] and CAS abstract acc.no. 2008:53869’. "n this document ATP is used to realize storage and release 0: high energy. This is done by use o: a secretory gland, and consequently di "ers "rom the reversible hydrolysation reaction. of the present invention. :3. Crystallization ses that release heat with a phase transition to form a so'id or solid lline form. 0 JP 58060198A; Matsushita electric works ltd; Nomura Kazuo; Heat accumulating material. In this patent the a sodium phosphate; Na2HPO4 is used to store heat by :means 0: crystallization. or phase transition, by means 0: specific nucleus agent. 0 GB 1396292 A ; Randall; 10 Feb. 1971; Improvements in or relating to heat storage units. In this patent the use of a crystallization reat o; phosphates is used to store heat.

L*.i . Using dissolution heat such as after bringing after bringing sulfur oxide and sulfuric acid in contact with water‘ or burning' heat by Ibringing' S in contact with air, as described in the 2 s below: 0 US 4,421,734; Norman Dec 20, 1983; Sulfuric Acid— sulfur heat storage cycle. In this patent the heat 0: the ution O' sulfurdioxyde or highly concentrated sulfuric acid in water, acting as a solvent, to form. low concertrated. sulfuric acid w and the burning o sul"ur with oxygen are used to produce heat. To realize heat storage, the highly trated sulfuric acid and sulfur need to be stored. This storage enables leveling' heat from the sun during longer period. 0 US 4,532,778; Clark et al ,1985 ; chemical heat pump and chemical energy storage system. In This US patent the dissolution heat is o sul"uric acid is used to store heat or to realize a heat pump to upgrade the temperature 'evel (or increase the l energy) 0: waste heat.

EH Further systems using' dissolution. heat, are based. on the application 0: salt hydrates, like e.g.

Mg(OH)2 Ca(OH)2, Sodium. carbonate and. water, to use the mixing heat 0: the salts in water.

C) Recent patents on engineering, 2008, 2,208—216.

Review 0: recent patents on chemical heat pump.

Cheng Warg, Peng Zhang and Ruzhu Wang. The thermal potential transformation ible reaction in chemical heat pump mainly includes liquid—gas absorption, solid—gas reaction and solid adsorption. o Possibility of al heat pump technologies by Yukitaka Kato, 31St Jan, 2011, High density thermal energy storage workshop, Arlington, Virginia, USA.

Description o_ sLaLe o_ Lke art chemical heat pumps :mainly Ibased. on she finding‘ that :metallic oxydes & chloride reac:ions are till then best available techniques for chemical heat pumps.

G.0ther sys:ems to exploit ATP as a molecule with a high energy density, may simply 'use this compounds as an enhancer for battery or mo:or performance; e.g. o USZOO70218345 A; Sakai et al; A fuel cell, electronic device, movable body, power generation system congeneration system. (3 US20020083710A1; Schneider, Thomas; Molecular motor with use 0: ATP, actin & myosin to rotate cylinders to e work. 0 EP 1089372A1 ; Camus et a;. Sept 28,1999 ; Independent and self—sustainable power gereration and storage . Tspecially paragraphs 0006 and 0056 and figure 7 where ATP is used. In this patent a method for ical storage is described n ATP is used to improve the battery performance.

But do not rely on a reversible ysation reaction as in the t case. Instead ATP synthesis will be driven tically (see CN101168481A above) or by photosynthesis, e.g. Nature materials, 2005, Vol4(3); Luo et a1 pp220—224; Photo induced proton gradients and ATP biosynthesis produced by vesicles encapsulated in a silica matrix.

It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to e a useful alternative.

Summary of the Invention As y explained hereinbefore, the present invention is based on the finding that inorganic oxoacid compounds and/or their salts and water can be used in a ible hydrolysation reaction to store and/or increase the l energy of a heat .

To store the thermal energy, the heat is converted into molecular reaction heat by means of a condensation reaction driven by the removal from water (dehydrolysis ) from the reaction medium with the formation of high-energy covalent ester bounds in the inorganic oxoacid compounds and/or their salts of the present invention.

To release the thermal energy, such as for example in a method to increase the l energy of an heat source, from the high-energy covalent ester bounds, the inorganic oxoacid compounds of the present invention are subjected to a hydrolysation reaction by adding water to the reaction medium comprising said d compounds or their salts.

According to a first aspect, the present invention provides a method to store or increase the energy content of a on mixture by means of an endothermic condensation reaction, said on mixture comprising an inorganic oxoacid compound and/or its salt and water, said on being enabled by the heat input from a heat source distinct from said reaction mixture.

According to a second , the t invention provides a system for capturing and storing energy, comprising: capture means for capturing energy; and storage means for storing captured energy, wherein the capture and storage means comprise at least one reaction vessel at least partially filled with a reaction mixture sing an inorganic oxoacid compound and/or its salt and water, suitable for having an endothermic condensation reaction performed on said reaction mixture, and comprising a heating t in thermal communication with said vessel.

Unless the context clearly requires otherwise, throughout the description and the claims, the words “comprise”, “comprising”, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”. - 8a - Thus in one aspect the present invention provides the use of inorganic oxoacid compounds and their salts and water in a method to store and/or increase the thermal energy from a heat source.

In said use the thermal energy of the heat source is stored by means of a sation reaction with the removal of water from the reaction solution and the formation of poly inorganic oxoacid compounds and/or their 2012/051025 salts.

In said. use the thermal energy 0: the heat source is increased by means 0: a hydro'ysation reaction 0; inorganic oxoacid compounds and/or its salts, through the addition 0: water to a reaction solution In other words, the present invention provides the use or nic oxoacid compounds and/or its salts and water in a method to store and/or increase the l energy from a heat source, characterized in that; — the thermal energy 0: the heat source is stored by means an sation reaction with the removal o_ water jrom the reaction solution and the ‘ormation O“ poly inorganic oxoacid compounds and/or its salts; and in that — the thermal energy 0: the heat source is increased by means 0: a hydrolysation reaction inorganic oxoacid compounds and/or its salts, through the addition 0: water to a reaction solution comprising said inorganic esters.

The inorganic oxoacid. nds and/or its saltsin the aforementioned uses or used in the methods 0: the present invention. is an oxoacid. 0“ either nitrogen, sulfur or phosphorus or its corresponding salt In an aspect o: the present invention the inorganic d nds and/or its salts us d ar r pr s nt d by general ‘ormula (") R_Op_ ( (OnX (0Q)m_o) y) _R, (:Z) wherein; Z represents —(CmX(OQ)m—O)y—R”; R represents hydrogen, a hydrocarbon or Z; R' and R' ' are each independently hydrogen, a hydrocarbon or a metal cation, in particular a monovalent metal cation, even more in particular K or Na; X represents Sulfur (S), Nitrogen (N) or Phosphorus (P) ; in particular X ents P; n = 1 or 2; m = 0 or 1; p = 0 or 1; y = at least 1; in particular 1 to 100; more in particular 1 to 10; even more in particular 1 to 4; alternatively y is 1 to 3; and each Q independently represents a hydrogen, a hydrocarbon or a metal cation, in particular a monovalent metal cation, even more in particular K or Na .

In r aspect of the present invention the inorganic oxoacid compounds and/or their salts used are polyphosphoric acids. Accordingly, the present invention relates to the use of polyphosphoric acids in a method to store and/or increase the thermal energy from a heat source.

In particular, the present ion relates to the use of polyphosphoric acids in a method to store and/or increase the thermal energy from a heat , characterized in that; - the thermal energy of the heat source is stored by means of a dehydrolysation on (condensation reaction) of phosphoric acids (including mono and poly phosphoric acids) ; and in that - the thermal energy of the heat source is increased by means of a hydrolysation reaction of polyphosphoric acids, through the on of water to a reaction solution sing said polyphosphoric acids.

In another aspect of the present invention the inorganic oxoacid compounds and/or their salts used are polyphosphoric acids and/or their salts represented by general formula (la) R-O-((OP(OQ)m-O)Y)-R' (Ia) wherein: R represents hydrogen, a hydrocarbon or a metal cation, in particular a monovalent metal cation, even more in particular K or Na; R' represents en, a hydrocarbon or a metal cation, in particular a monovalent metal , even more in particular K or Na; m = 0 or 1; y = at least 1; in particular 1 to 100; more in particular 1 to 10; even more in particular 1 to 4; alternatively y is 1 to 3; and each Q represents a hydrogen, a hydrocarbon or a metal cation, in particular a monovalent metal cation, even more in particular K or Na.

In an even further aspect of the present invention the polyphosphoric acids and/or their salts used are: pure inorganic linear osphoric acids and/or their salts represented by the following formula: Mn+2PnO(3n+1) (lb) with n = at least 2; in particular 2 to 10E6; more in particular 2 to 5; M is H+ or a metal , in particular a monovalent metal cation, even more in particular K or Na; or pure inorganic cyclic polyphosphoric acids and/or their salts represented by the following formula: n (Ic) with n = at least 3; in particular 3 to 12; more in particular 3,4,5 or 6; M is H+ or a metal cation, in. particular‘ a :monovalent metal cation, even more in particular K or Na; pure inorganic branched poly phosphoric acids and/or its, in ular a monovalent metal cation salt, even more in particular K or Na;or combinations thereor.I) In a particular aspect o: the t invention the polyphosphoric acids and/or its salts used are seleCted from the group ting o: Phosphoenolpyruvate, Glyceratel,3 bi phosphate,Formyl phosphate, Acetyl phosphate,Propionyl phosphate,3utyryl phosphate or other carboxyl phosphates, Phospho—creatine, Phospho—arginine, Glucose phosphates (l or 6—phosphate), fructose phosphates, Glycerol—3—phosphate, Nicotine amide adenine dinucleotide phosphate (NADP), dihydroxyacetonephosphate, glyceraldehydephosphates, sephosphate, ribosephosphates, sedoheptulosephosphate, Erythrosephosphate, ribuloseophosphate phospho—serine, Aspartylphosphate and adenosinephosphate.

Based on the forgoing, the present invention jurther provides a method to store or increase the energy content or a on mixture by means or an endothermic sation reaction, said reaction mixture comprising an inorganic oxoacid compound and/or its salt and water, said reaction being d. by the heat input from. a heat source distinct from said reaction mixture.

The present invention ‘urther provides a , wherein the heat source distirct from. said. reaction. mixture is either rest heat from industrial processes, or heat derived from natural resources such as solar or wind energy. In other words, there is no limitation to the heat source in any one of the uses or methods 0: she present invention. In principle any heat source can be used, including heat captured or obtained from solar , geothermal energy, wind energy, electricity, rest heat from industry and the like.

The t invention ‘urther provides a method, wherein water and/or the inorganic oxoacid. nd and/or its salt is removed from the reaction mixture.

The present invention ‘urther provides a method, further comprising the step of ing the stored, resp. increased. energy content of the reaction. mixture in a subsequent process step through the exothermic ysation of the reaction products of said reaction mixture.

The present invention ‘urther provides a method, wherein the inorganic oxoacid compound and/or its salt is an oxoacid 0‘ either nitrogen, sulfur or phosphorus, or its corresponding salt.

The present invention ‘urther provides a , wherein the inorganic oxoacid compound and/or its salt is represented by l ‘ormula (") R_Op_ ( (OnX (0Q) m—O) y) _R, (I wherein; R represents hydrogen, a hydrocarbon or Z(as bed hereinbelow); X represents sulfur, nitrogen or phosphorus; Z represents —(CmX(OQ)m—O)y—R”; R’ and R” each independently represent hydrogen, a hydrocarbon or a metal cation; n = l or 2; m = O or 1; p = O or 1; y = at least 1; and Q each independently ent hydrogen, arbon or a metal cation.

The present ion further es a method, wherein the inorganic oxoacid compound and/or its salt are polyphosphoric acids and/or their salts, in particular represented by general formula ("a) R—O—((OP(OQ)m—O)y —R’ (Ia) wherein R and R’ each independently represent hydrogen, a hydrocarbon or a metal cation; m = O or l;y = at least l;and each Q ents hydrogen, arbon or a Hetal cation.

The present invention further provides a method, wherein the polyphosphoric acids or their salts are; a. pure inorganic linear polyphosphoric acids or their salts represented by the following formula: ngPngm4)(Ib) with n= at least 2; M is H+ or a metal cation; b. pure inorganic cyclic polyphosphoric acids or their salts represented by the following formula: 2012/051025 n (I C) with n= at least 3; M is H+ or a metal cation; branched; or d. combinations thereor.I) The present invention ‘urther provides a method, wherein the metal cation is a Hwnovalent metal cation, more in particular K or Na.

The present invention urcher provides a method, wherein y is within the range o_ l ,o 100, more in particular within the range 0: l to 10, still more in particu'ar within the range 0: l to 3.

The t invention ‘urther provides a method, wherein the salts o: phosphoric acids are selected from the group containing Phosphoenolpyruvate, Glyceratel,3 bi phosphate,Formyl phosphate, Acetyl phosphate,Propionyl phosphace,3ucyryl ate or other carboxyl ates, Phospho—creatine, o—arginine, Glucose phosphates (l or 6—phosprate), fructose phosphates, Glycerol—3— phosphate, Nicotine amide adenine dinucleotide phosphate (NADP), dihydroxyacetonephosphate,glyceraldehydephosphates, xylulosephosphate,ribosephosphates,sedoheptulosephosphate, Erythrosephosphate, ribuloseophosphate o—serine, Aspartylphosphate and adenosinephosphate.

The present ir vention ‘urther provides a method, wherein :he endothermi c condensation reaction is represented by she "ollowing ‘ormula 2012/051025 HOXOn(OH)mOR’ + R—op—((xon(OH)m—O)y,1)—H —> R-Op-((XOn(OH)m-O)y)—R' + H20 The present invention ‘urther provides a system :or capturing or storing energy, comprising — capture means for capturing energy; — storage means for storing captured energy, wherein the capture and s:orage means comprise at least one reaction vessel at least partia'ly ‘illed with a reaction H) mixture comprising‘ an nic oxoacid. compound. and/or its salt and. water, suitable for having' an endothermic condensation reaction performed on said reaction mixture, and comprising a heating element in thermal communication with said vessel.

The present invention r es a system, further characterized. in that it comprises a release means :or releasing the energy captured and stored in a subsequent exothermic hydrolysis s:ep.

The present ion ‘urther provides a system, further characterized in that the reaction mixture comprises an inorganic oxoacid compound and/or its salt.

As ed in more detail hereinafter, the reaction solution may further comprise corditioning components to optimize the reaction conditions for the esterification / ysation reactions, such as sts to catalyze the sation / hydrolysation reaction.

Brief Description of the Drawings Figure 1: A. General reaction scheme B. Block Diagram CHEMENERGY cycle.

Figure 2: CHEMENERGY cycle with inorganic phosphate / osphate esters.

Figures 3 - 11: Different possible ations for the CHEMENERGY cycle in increasing the thermal energy of a heat source. Details on the ts in the flow diagrams for each of the applications can be found in Table 3 below .

Figure 12: General flow m for the reoccurring elements in the practical exploitation of the CHEMENERGY cycle. The storage tanks, both the heat storage tank(s) and the component storage tank(s), are optional.

Description of the Invention The present invention is based on the findings that inorganic oxoacid compounds and/or their salts, such as, e.g. nitrate-, sulfate-, phosphate- and sulfonate-esters, can be used in a method of thermal energy storage, exploiting the reversible chemical hydrolysis and condensation reaction which are exo- and endothermic, respectively.

Accordingly, the present invention relates to the use of nic oxoacid compounds and/or their salts in a method of l energy storage.

The inorganic oxoacid compounds and/or its salt as used herein are selected from the group o:: inorganic oxoacid compounds and/or its salt with an oxoacid 0: either nitrogen, sulfur or phosphorus, or its corresponding salt; and in partic ilar the nic oxoacid or its salt refer to oxoacids o: phosphorus and/or its salt such as phosphorylated tydrocarbons and inorganic (poly)phosphoric acids and its salts.

As is generally known in the art, polymerization re"ers to the attachment of organic groups (esterification) to phosphorus (P), nitrogen (N), or Sulfur (S) through oxygen s, or refers to the polymerization of inorganic oxoacid nds or their salts of either nitrogen, sulfur or phosphorus, with the generation of H20 or water, by means of an endothermic condensation reaction using an alcoholic precursor O“ said organic group or‘ a hydroxy; group O: said nic oxoacids. A general representation 0: said fication is provided in step (2) of Fig. l.

The inorganic oxoacid compound and/or its salt as used in the methods of the present invention, are represented by general formu'a V1 R_Op_ ( (Onx (0Q) m_O) y) _R, (I) wherein Z ents —(CmX(OQ)m—O)y—R”; R represents hydrogen, a hydrocarbon or Z; R’ and R” are each independently hydrogen, a arbon or a metal cation, in particular a monovalent metal cation, even more in particular K or Na; X represents Sul:Ill]: (S), Nitrogen (N) or Phosphorus (P); in particular X represents P; n = 1 or 2 ; m = 0 or 1; p = 0 or 1; y = at least 1; in particular 1 to 100; more in particular 1 to 10; even more in particular 1 to 4; each Q independently represents a hydrogen, a hydrocarbon or a metal cation; in particular a monovalent metal cation; even more in particular K or Na.

In a particular embodiment of the present invention, the inorganic d compound and/or their salts are polyphosphoric acids and/or their salts, represented by general formula (la) R((OP O)Y)–R’ (Ia) wherein: R represents hydrogen, a hydrocarbon or a metal cation, in particular a monovalent metal cation, even more in particular K or Na; R' represents hydrogen, a arbon or a metal cation, in particular a monovalent metal cation, even more in particular K or Na; m = 0 or 1; y = at least 1; in particular 1 to 100; more in particular 1 to 10; even more in particular 1 to 4; each Q represents a hydrogen, a arbon or a metal cation, in particular a monovalent metal cation, even more in particular K or Na .

The arbon rest in anyone of the aforementioned formula can be any organic compound comprising a hydroxyl group like for instance ls, carboxylic acids, esters etc, or can be any O: sugars and bases forming nucleotides and. nucleic acids or any organic mo lecule ending' on a hydroxyl group; wherein said hydroxyl group is capable in forming an inorganic ester Wl':h a ate, polyphosphate, e, sulphate or sulfonic acid. In particular with a phosphate or po lyphosphate.

Nucleo:ides have a well—known meaning in the art and c " o_ any combination 0 di""eren L nitrogenous bases and di" "erent sugars (pentoses) ard can have mono, di and tri phosphate(s) as a phosphoryl group: I3ase ( Sugar —Phosphate) - As bases one could for example take Purine, Pyrimidine, Adenine, Guanine, Thymine, ne, Uracil, Hypoxanthine, 5—methylcyto sine, N6— adenine, dihydrouracil, l—methylguanine, ribo:hymidine, pseidouridine, or 1 —methyliosine.

— As sugars (pentoseV one cou'd ‘or example take jruccose, , D—ribofuranose, or 2—deoxy—D— ribofuranose.

Nucleic acids have a well—known meaning in the art and can consist out o: any combination 0 idi, "erent nucleotides.

The nucleotides are linked into poi_ynucleotides or nucleic acids through. a backbone made O: sugars and phosphate groups joined by ester bonds.

I3ase —(— Sugar —Phosphate)n 2012/051025 In one embodiment o: the present invention the inorganic eSters comprise or consist o; a ‘polyphosphate’.

Polyphosphates are anionic phosphate polymers linked between hydroxyl groups and hydrogen atoms. The polymerization that takes place is known as a condensation reaction. Phosphate chemical bonds are typically high— energy covalent bonds, which means that energy is available upon ng such bonds in spontaneous or enzyme catalyzed reactions. In said embodiment, a particular group o: inorganic phosphate esters consist o; but is not d to Phosphoenolpyruvate, Glyceratel,3 bi phosphate, Formyl phosphate, Acetyl phosphate, Propionyl phosphaoe,3uoyryl phosphate or other carboxyl ates, Phospho—creatine, Phospho—arginine, Glucose phosphates (l or 6—phosptate), fructose phosphates, Glycerol—3— phosphate, ne amide e eotide phosphate (NADP), dihydroxyacetonephosphate, glyceraldehydephosphates, sephosphate, ribosephosphates, sedoheptulosephosphate, Erythrosephosphate, ribuloseophosphate phospho—serine Aspartylphosphate and adenosinephosphate.

One ol ohe major advantages ol ohese molecules is the fact that they are already available in nature and that the environmental impact is already known. These molecules form, since life is on earth, one of the most important structures to ensure energy storage / supply 0‘ all 'iving ce"s. The fact that these components are used in living ce"s ensures that they are suitable ‘or mild temperatures, pressure and pH.

These properties makes them adequate for heat processes on ambient circumstances, such as provided in the di "erent embodiments of the present invention.

In another particular embodiment of the present invention, the linear poly phosphoric acids and/or their salts are represented by the ing formula: Mn+2PnO(3n+1) (Ib) with n = at least 2; in particular 2 to 10E6; more in particular 2 to 5; and M is H+ or a metal cation, in particular a monovalent metal cation, even more in particular K or Na .

In another particular embodiment of the present ion, the cyclic polyphosphoric acids and/or their salts are represented by the following formula: MnPnO3n (Ic) with n = at least 3; in ular 3 to 12; more in particular 3, 4, 5 or 6; and M is H+ or a metal cation, in particular a monovalent metal cation, even more in particular K or In the methods of the present ion, the reaction ts can be a mixture comprising any combination of the products described above.

In the method of thermal energy storage, the reversible chemical hydrolysis and sation reaction which are exo- and endothermic respectively, are combined with heat capture/storage, heat transportation and heat generation processes to exploit the energy storage/supply capacity of the aforementioned molecules.

Thus in a further embodiment, the present invention provides a method to store thermal , said method comprising the sation reaction as represented in step (2) of Fig. l, hereinafter‘ also referred. to as a polymerization o: inorganic oxoacids and/or its salts, using an external heat .

Any available heat source can be used in the methods OT the present invention. Typical heat source include heat captured from sun radiation, and rest heat from industry.

Through the polymerization reaction o_ the inorganic oxoacids and/or its salts, the thermal erergy of the heat source is transformed into molecular reaction heat, i.e. into a high—energy covalent bound, as found in the inorganic ds and/or its salts o" "ormulas ( ),( a),( b)and. (2c); also referred. to as ‘polymerized compounds’.

The high—energy covalent inorganic—oxygen—inorganic linked bounds and in ular the nergy phosphorus— oxygen—phosphorus bounds, provide storage o_ thermal energy in a lar form with an energy density 0: about 400kJ/kg - See table 1. In table 1 the solution heat is not incorporated, in. case 0 or instance ar inorganic oxoacid or polyphosphoric acid is used, the solution heat comes above tte said reaction heats. For example, in case o: Polyphosphoric acids, the energy density can go > lGJ/m3 depending on the degree 0: polymerization and temperature levels.

In said high—energy lar form, a previously continuous heat stream can stored / transported at ambient circumstances. It accordingly yields a method to bu er a continuous heat generation process into a discontinuous or dislocated consumption. This can e.g. be implemented to store wind energy on a stormy night with electrical resistance into captured. heat and release the heat on morning peak by generating steam or ORC as depicted in application 7 & 9.

Table l —lI-kJ/kgkcaI/kg keel/mol- _--—_48812 _--_-42015 _-—--84118 _--—_17488 Volledige hydrolyse ATP -- 61,44- 499,12 cetyl phosphate --73,37- 154,01 N—Phosphoenolpyruvate 89,69- 165,02 NPhosphoenoIpyruvate 98,09- 875,75 In the entioned method of thermal energy storage, H) ‘the polymerized. compounds’ are optionally removed. from the aqueous reaction. on. and. stored. The aqueous reaction solution used in the methods of the present invention is determined by, t others, the nature of the components used to catalyze the transformation, hereina"ter also referred to as the transformation components or ioning components, and known to the skilled n. For exampl ; wh n nzym s ar us d to catalyze the transformation, the aqueous reaction solution will be an appropriate bu""er solution, such as for example the use of a solutior with 5mg/l dephosphorylase extracted from 'ischerichia coli; when living cells are used to catalyze the transformation, an riate cell e medium will be used instead. Living cells used to catalyze the ormation, typically consist Cl microorganisms such as for example bacteria, e.g. salmonella, legionella or ?scherichia coli, known to absorb heat by dehydrolisation 0“ inorganic phosphate and the to be phosphorilised compounds.

One can use ctanges in the concentration ol the solvent, i.e. change the water concentration in case 0: an aqueous solution, or 0: components present in the solvent like for instance but not limited to metallic ions, or 0; up concentration of the reaCtion components, like e.g.. evaporation in case 0: an aqueous solution or extracting the water with organic solvents in such a way that first the solvent is evaporated together with the water and secondly condensed, to be separated in a third step from the solvent by for instance gravimetric liquid to liquid phase separation, to nce, drive, ze or inhibit the reaction.

Alternatively, cranges in the proton concentration can also be used. to catalyze the ormation. 0“ thermal energy into the aforementioned high—energy covalent bonds.

Proton concentration can be nced by chemicals, e.g. lly ed acids and/or bases, compounds containing al acid—base functions, or by use 0: semi permeable membranes.

Typical es include for ce HCl as chemical (e.g. commercial available 30—40 wght% in water) to increase proton concentration.

As proton membranes one can take commercial available P?M or “Proton exchange membranes”, for instance used in hydrogen fuel cells, including but not limited to, one o; the following membranes: Nafion®; Solopor®, Toyota PEM, 3M PEM , and the like.

Removal 0: the polymerized compounds 0: the reaction solution can be done in di "erent process steps, including for example a membrane separation step based on the size 0: the molecules. In said embodiment, the transformation components are preferably much larger than the rized compounds and can easily be separated from one another.

For example, when s are used to catalyze the oransformation, ultra filtration membranes or nano filtration. membranes, with. a respectively mesh size or about lO—lOOnm and l—lOnm are used. For very large complex struc:ure micro "iioration can be used as well (>100 nm).

The mesh size of the membranes are depending on the struc:ure and/or the molecular weight 0: the enzyme.

Depending on the used products and reaction circumstances, di""erenL types 0: commercial ble membranes can be chosen. See table 9 for di "erent possible examples. 23esides the membrane filtration. separation techrique as described above under nano—, ultra— and micro— filoration, other means to separate the polymerized compounds from the on solution are known to the person d in :he art and include for example separation techniques based on elec:rical or ical properties 0 "or instance large (enzyme)complexes to separate in an electrical / magnetic field, separation ques based on density by centrifugal forces or by ntation, based on percipitation, on phase transition from liquid to solid 'o'lowed by liquid solid separation, or by adhesing the products to gels, by evaporating water from the reaction solution and many more.

Table 2: Commercially available membranes for nano-, ultra- & microfiltration from 2 manufacturers (source www.sterlitech.com) Nanofiltration (NF) Designation Manufacturer Polymer Pore Size 25C Ph Range CK GE Osmonics Cellulose Acetate 0 MWCO 2 - 8 DK GE Osmonics TF (Thin Film) 0 MWCO 2 - 8 DL GE Osmonics TF (Thin Film) 0 MWCO 2 - 8 HL GE Osmonics TF (Thin Film) 0 MWCO 3 - 9 3 Koch Membrane TF (Thin Film) com 200 MWCO 4 - 10 TFC-SR2 Koch Membrane Proprietary 350 MWCO 4 - 9 SelRO MPF-34 Koch Membrane Proprietary 200 MWCO 0 - 14 SelRO MPF-44 Koch Membrane Proprietary 250 MWCO 3 - 10 SelRO MPF-36 Koch ne etary 1000 MWCO 1 - 13 Ultrafiltration (UF) CQ GE Osmonics CA (Cellulose Acetate) 20000 MWCO 2 - 9 GE GE Osmonics Composite Polyamide 2 - 11 GH GE Osmonics TF (Thin Film) 1000 MWCO 2 - 11 GK GE Osmonics TF (Thin Film) 2000 MWCO 2 - 11 GM GE Osmonics TF (Thin Film) 4000 MWCO 2 - 11 ER GE Osmonics Polysulfone 30000 MWCO 0.5 - 13 EW GE Osmonics ersulfone 60000 MWCO 0.5 - 13 PT GE Osmonics PES 5000 MWCO (Polyethersulfone) PW GE Osmonics PES 20000 MWCO 2 - 11 (Polyethersulfone) JW GE cs PVDF 30000 MWCO 1 - 11 MW GE Osmonics Ultrafilic 100000 MWCO 1 - 10 SelRO MPF-U20-S Koch Membrane Proprietary 20000 MWCO 3 - 11 SelRO MPF-U20-T Koch Membrane Proprietary 20000 MWCO 0 - 14 SelRO MPF-U20-P Koch Membrane Polyethersulfone 25000 MWCO 0 - 14 8 Koch Membrane lfone 5000 MWCO 2 - 10 HFK-131 Koch Membrane Polysulfone 10000 MWCO 2 - 10 HFK-141 Koch Membrane Polysulfone 30000 MWCO 2 - 10 HFM-100 Koch Membrane PVDF 50000 MWCO 2 - 10 HFM-116 Koch Membrane PVDF 50000 MWCO 2 - 10 HFM-180 Koch Membrane PVDF 100000 MWCO 2 - 10 HFM-183 Koch Membrane PVDF 100000 MWCO 2 - 10 HFP-707 Koch Membrane PVDF 120000 MWCO 2 - 10 Microfiltration (MF) JX GE Osmonics PVDF 0.3 micron 2 - 11 HFK-618 Koch Membrane Polysulfone 0.1 micron 2 - 10 Accordingly the present invention s to the use of erized compounds” to store/transport thermal energy at ambient temperature. As such, it relates to the use of “polymerized compounds” in a method to buffer a continuous heat generation process into a discontinuous consumption.

As the invention relates to ion of an alternative energy source, i.e. to convert a continuous heat generation process into a discontinuous heat release system, the present invention further provides the means to release heat from the polymerized nds, said method comprising the hydrolysation reaction as represented in step (1) of Fig. 1, hereinafter also ed to as a hydrolysation of inorganic oxoacids and/or their salts, and using the thermal energy released by said exothermic reaction as a heat source.

As for the rization reaction, supra, the reaction conditions for the hydrolysation on will be determined by, amongst others, the nature of the components used to catalyze the transformation (transformation components) and are known to the skilled artisan, in other words and as apparent from the examples hereinafter, there is a conditioning of the feed stream (21) to optimize the on conditions for the hydrolysation reaction. For example; when enzymes are used to catalyze the transformation, an appropriate buffer solution, such as for example, a solution with 5mg/l phosphorylase extracted from Escherichia coli will be used; when living cells are used to catalyze the transformation, an appropriate cell culture medium will be used instead. Living cells used to catalyze the transformation, typically consist of microorganisms such as for example bacteria, e.g. salmonella, ella or Escherichia coli.

Cells generate heat by hydrolysation of WO 01110 phosphorilised compounds.

One can use ctanges in the concentration ol the t, i.e. change the water concentration in case 0: an aqueous solution, or of ents present in the solvent like for instance btt not limited to metallic ions, cells, enzymes etc., or 0: up concentration 0; the reaction ents, like e.g. evaporation in case 0: an aqueous solution or extracting the water with organic solvents in such a way that first the solvent is evaporated. together‘ with. the water and secondly condensed, to be separated in a third step from the solvent by for instance gravimetric liquid to liquid phase separation, to influence, drive, catalyze or inhibit the on.

Alternatively, chemical_s and pro:on exchange membranes can also be used. to catalyze the crans "ormation 0“ thermal energy into the aforementioned nergy covalent bonds.

Proton concentration can be influenced by chemicals or by use Ol semi permeable membranes.

Typical examples include for instance NaOH as chemical (e.g. commercial available 50 wght% in water) to decrease the proton concentration As proton membranes one can take commercial available P?M or “Proton exchange membranes”, for instance used in hydrogen fuel cells, including but not limited to, one of the following membranes: Nafion®; Solopor®, Toyota PEM, 3M PEM , and the like.

Again, the hydrolysed compounds are optionally d from the on medium using art known procedures, such as provided for the polymerized compounds above. In said WO 01110 2012/051025 form, the hydrolysed compounds; i.e. sing the hydroxyl group capable in forming an nic poly d nds or their salts 0: either nitrogen, sulfur or phosphorus can be used as sonrce material in the dehydrolysis reaction (supra).

Evidently, systems (installations) using the CHfiMfiNfiRGY cycle as described herein, are also within the scope o; the present application. 211 a first aspect such systems could be systems for capturing or storing energy, characterized. in comprising' capture means for ing energy from a heat source using the polymerization (condensation) reaction as (described herein (represented as A in the applications below); and storage means for storing captured energy in the "orm 0' the reaction ts 0: said condensation reaCtion. Said means for capturing teat include at least one reaction vessel for a reaction mixture comprising an inorganic oxoacid compound and/or its salt as described herein and water, suitable for having an ermic condensation reaction performed on said reaction mixture, and comprising a heating element in thermal communication with said vessel.

In a second aspect, such systems could be systems to release the thermal energy stored in the reaction produCts o: the condensation reaction according to the present invention, characterized ill that ii: comprises a. release means for releasing the energy captured and stored in the on products 0: the condensation reaction according to the present invention, by means or an exothermic hydrolysis step (represented as C in the applications below). Said means for releasing the energy include at least one reaction vessel :or a reaction mixture comprising an inorganic oxoacid compound and/or its salt as described. herein, suitable for having an rmic hydrolysation reaction and comprising a heating element in thermal communication with said vessel.

In a further aspect, the system includes both means :or ing energy from a heat source using the polymerization (condensation) reaCtion as described herein represented as A in the applications below); and means :or releasing the energy captured and stored in the reaCtion ts 0: the condensation reaction according to the present invention, by means or an rmic ysis step (represented as C in the applications below . Such system having both means (A) and (C) allow that the heat with a low exergy status and used in driving the endothermic condensation reaction (A) is —up to a. higher exergy status in the exothermic hydrolysation reaction (C), i.e. in establishing a heat—pump making use 0: the CHfiMfiNfiRGY cycle 0: the present invention.

In. a particular embodiment the systems to release the thermal energy from the reaction products o_ the condensation reaction or the present invention, may further comprise a heat—exchanger (represented as 3 in the applications below). This heat—exchanger will be used to increase the temperature 0: the reaction products of the condensation reaction ted into the reaction e used in the rmic hydrolysation reaction (C). Without being limited thereto, temperatures used range from about 60O — 500°C; typica'ly ‘rom about 120-500°C, ard more in particular from about 150 — 300°C. -3 2- This invention will be better understood by reference to the Sixperimental iDetails that “ol'ow, but those skilled. in the art will readily appreciate that these are only illustrative of the ion as described more fully in the claims that fo'low thereafter.

Additionally, throughout this ation, various publications are cited. The disclosure of these publications is hereby incorporated by reference into this application to describe more fully the state of the art to which this invention pertains.

EXAMPLE S Example 1 — phosphate / polyphosphate esters Energy density The ysis o: a phosphor compound has a reaction energy 0: approximately 150—500 kJ/kg depending‘ on the reaction conditions. Typically the proposed components have an energy density of OOMJ/m3. When higher temperature sources like e.g. sun are used, one can e.g. condense (dehydrolyse) phosphoric acid. till dry P205 is d, which has an energy density 0: about BOOOMJ/m3 Comparing to other heat storing materials, the heat ty 0: the polymerized. components here claimed is substantially higher. E.g. The phase change on or para "in delivers 20—90 kJ/kg depending on the reaction conditions (copyright@2002 John Wiley & Sons, Ltd.).

Solving sulfuric acid in water gives a reaction heat or 300—400 kJ/kg depending on reaction conditions (Chemical and engineering thermodynamics y I. Sandler copyright@l989 John Wiley & Sons, Ltd.). The sole exception being the llization of Na—acetate that delivers 4OOMJ/m3, but requires a phase transition during the heat conversion.

Products used The here—described cycle has its energy derived from chemical energy: CPfiMfiNfiRGY. It uses molecules that can be phosphorilised, nitrolised or sulfonised or hydrocarbons (PHs) or inorganic (poly)phosphates(ZPs), poly phosphoric acids, or inorganic oxoacid compounds and/or their salts of either en, sulfur l” Nucleotides: consist out 0: any combination 0; ent niLrogenuous bases and di "erent sugars ses) and can have mono, di and tri phosphate(s) as a phosphoryl group.

As bases one could take: Purine, Pyrimidine, Adenine, Guanine, Thymine, Cytosine, Uracil, Hypoxanthine, 5—methylcytosine, N6—methyladenine, ouracil,l—methylguanine, ribothymidine, pseudouridine, l—methyliosine....

As sugars (pentose) one could take fructose, ribose, D—ribofuranose, 2—deoxy—D— ribofuranose,.... 2.Nucleic acids: they can consist out 0; any combination of di""erent nucleotides. The nucleotides are linked by ate links between 2 bases in the nucleic acids. 3.Most found energy molecules in all living cells: oenolpyruvate Glycerate;,3 bi phosphate,Formyl phosphate, Acetyl phosphate, Propionyl phosphate,3utyryl phosphate or other carboxyl phosphates, Phospho— creatine, Phospho—arginine, Glucose phosphates (l or 6—phosphate), fructose phosphates, Glycerol— 3—phosphate, Nicotine amide adenine dinucleotide phosphate (NADP), dihydroxyacetonephosphate, aldehydephosphates, xylulosephosphate, phosphates, sedoheptulosephosphate, Erythrosephosphate, ribuloseophosphate o— serine, Aspartylphosphate, adenosine phosphate 4.:norganic polyphosphoric acids and their salts 5.:norganic (poly)nitrates like :or instance cellulose,... 6.:norganic sulfates and sulfonates It is not the Phosphorilation s or the condensation or polymerization s as such or the esterijication process in living cells that is claimed but the condensation and in particular the s 0: condensation o: phosphoric acid and/or polyphosphoric acids and/or their salts in combination with a heat storage, heat pump, transportation and generation processes in industrial applications which is called the “Chemenergy cycle”.

All embodiments can be used on a large scale or on very small scale.

D 1xample O“ a large scale can be a big industrial or residential network 0: neighborhoods (city) or ' ats connected to the same heat system getting heat from industrial waste heat bu""ered with the chemenergy cycle, transported by pipelines and bulk nts.

D 1xample 0“ a small scale can. be the use . a house/farn with small heat generation capabilities, like e.g. solar system/dunghill/cesspool, and a small Chemenergy skid to improve heat performance.

The “CHEMENERGY” process general process (Figure 1) Heat storage l.Storage 1.1 0“ hydrolysed components. 2.Conditioning n 1: adding s, ions, cells, fresh substances. 3.Storage 1.2 o: conditioning prodtcts 4.Reaction section 1: usage of thermal heat to polymerize components by e.g., but not limited to, removing, extracting‘ or atirg‘ the water from the solution. 5.Separation sectior l: usage 0" di""erent separation techniques and steps to separate the polymerized components from the conditioning products, waste, nzym s, nzym. s paration. agents and solvents (or in particular water). 6.Storage l.3 O“ polymerized components.

Heat release l.Storage 2.l ot polymerized components. 2.Conditioning section 2: adding s, ions, cells, fresh substances, water. age 2.2 o: conditioning products 4.?eaction section 2: usage 0: heat sink (heat demand) to hydrolyse components by e.g. but not limited to, -3 6- adding small amounts, e.g. 1—10% of water (conditioning solution) either in the liquid or vapor phase.

.Separation section 2: usage 0" dfi""erent tion techniques and steps to separate the polymerized components from the conditioning ts, waste nzym s, nzym. s paration. agents and solvents (or in ular water). 6.Storage 7.3 0“ hydrolysed components.

The “CHEMENERGY” process with phosphorilated nts (Figure 2) Heat capturing loop l.Storage o "eed streams. 2. Conditioning o_ the Seed streams by adding from bu""er storage. Important factors to influence reactions are among o:hers pH, ion concentration ( Ca2", Mg2+, K, Na, C;—, Pi, acids, ....) enzymes, cells, water ,solvents, temperature & many others. 3. Reaction: condensation reaction to form polyphosphoric acid or its salt by absorbing heat by e.g., but not limited to, diminishing the water concentration, such as for example by extracting, removing and/or evaporating the water. 4.Separation 0: components: separation can be done in di""erent process steps. A partic1lar separation que is membrane separation, based on the size and or polarity 0: she nwlecules. E.g. the larger WO 01110 components cannot pass the membrane, the smaller components can.

O Membrane separation la: UltrajilLraLion, ATPase (or part 0: ATPase) and AT(D)P separation agents are ted from rest. (table 2, MWCO < 2000, pH < 7 ) O Membrane tion lb: ilLraLion, separation 0: ATP separation agents from ATPase or part of this enzyme. (table 2, MWCO < 100,000, pH <7) O Membrane separation 2: Nanofiltration, separation of water. (table 2, MWCO < 100, pH < 7 ) O Membrane separation 3: Ion exchange membrane, separation 0: ions. (table 2, MWCO < 500,000, pH < 7) .Storage and transport under ambient circumstances.

In some applications, steps 2 & 3 of the above described loop can be done simultaneously e.g. the up concentration and heat ing reaction phase using both heat respectively to evaporate the solvent and to rize the hydrolyzed components.

Moreover in some applications where water is separated from the solution, steps 3 & 4 are combined in order to drive the reaction towards the polymerized components. The separation technique can be, but not limited to, by evaporating' water; or an organic solvent together with small fractions 0: water and later condensed to be separated Irom the solvent by gravimetric liquid to liquid extraCtion.

Heat releasing process loop: l.Storage o "eed streams. 2. Conditioning o_ Lhe Seed Streams by adding from bu""er sLorage. ImporoanL jacLors Lo injluence reactions are among Others pH, ion concentration ( Ca2+, Mg2", K, Na, Cl—, Pi, ....) enzymes, cells, water ,solvents, temperature & many others. 3.Reaction: Hydrolysis with release of heat by adding water or other hydrolyzing agents, either in the liquid or vapor phase. 4.Separation 0: components: separation can be done in di""erenL process steps. A particular tion technique is membrane separation, based on the size and or polarity o: the les. m .g. the larger components cannot pass the membrane, the smaller ents can.

O Membrane separation 4a: Ultrafiltration, ATPhydrolase (or part 0: ATPhydrolase) and AD(T)P separation agents are separated from rest.(table 2, MWCO < 2000, pH >7) O Membrane separation 4b: Ultrafiltration, ATPhydrolase (or part 0: ATPhydrolase) separated from AD(T)P separation agents.(table 2, MWCO < 0, pH >7) O Membrane separation 5: Nanofiltration, separation of (table 2, MWCO <100, pH >7) O Membrane separation 6: Ion exchange membrane, separation 0: ions. (table2 MWCO < 500,000, pH >7) O Other tion step sequences can be made with same e ecL.

.Storage and ort under ambient circumstances.

In some applications, steps 2 & 3 o_ the above described loop can be done simultaneously e.g. the conditioning o; e.g. the pH could be ary to maintain the reaction going. In case the second hydrolyzing component is water a tion o: the components will not be necessary.

Further details to figure 2 can be in particular: 1” At following temperatures cycle was operated: 1.1. Temperatures reaction_ 1 product in: 20°C (ambient storage). 1.2. atures reaction 1 heat input > 50°C and preferable > 70°C: in particular > 80°— 100°C; nore in particular > 140°C: coming from available industrial waste heat. 1.3. Temperatures reaction 2 product in: at least 20°C (ambient storage or higher temperatures). 1.4. Temperatures reaction 2 heat output > 40°C: served for a central heating system. 2.Reaction 1 concentration at pH < or > 7 + ions in water at 80°C and water concentration e.g. < 30% and pre‘erab1e < 10%; in particu1ar < 15% and more in particular < 5—10% or lower. 3.Reaction 2 tration at pH > or < 7 + ions in water at 90°C and water concentration e.g. > 30% No: all subcomponents as AMP, Pyrophosphate, ions etc are shown rere. 4. As ATP and ADP all other kinds phosphates or polyphosphates o: the in this invention described components can be used as well; in particular the orylated. hydrocarbons,inorganic oxoacids o; phosphorus or more specific polyphosphoric acids and/or their salts. 5. Not all interconnection flows are shown. but the principle shown connections are enough to show onality ‘or a skilled artisan 6.Pumps, Valves, piping ard other standard processing equipment specijicacions not ted. 7. Pressures depending on pressure drop over nes and piping pressure drops. To be engineered depending on size and geometry. 8. Equipment materials to be chosen. with attention for the medium circumstances (mainly pH driven).

Hastelloy CH: duplex equipment & piping materials are suited for here described application. Other materials (carbon steel, stainless steel or Other alloys), resisting the medium circumstances, to be ta<en in function 0: al prices and desired life time.

Feed stocks and raw materials.

Raw materials ‘or this process can be produced in di""erenL ways. One could extract the components from biomass or out 0: available chemicals and available chemicals reaction routes.

D Many o: the used materials have routes being "l ed by e.g. pharmaceutical ies using the PHs :or testing medicaments in vitro on ATP or other tides. These processes are mainly for a small scale production and e.g. unit wise heat cycle application.

D There are also als that can. be created. :rom combining commercially available chemicals like :or inStance Acetic acid and Phosphoric acid to produce acetylphosphate. These feed stocks can be used :or large scale heat cycles D Use 0: commercially available (poly)phosphoric acid, preferably chemically pure quality , typically 70%— 85% H3PO4.

Speci 1c or this cycle is the use of Phosporilated hydrocarbons or inorganic (poly)phosphoric acids and/or their salts. pH regulation In the ergy cycle, conditioning o_ the Seed streams for both the Heat Storage and {eat Release part, ircludes pH tion. Any known method to regulate the pi in a feed stream. can be used, and include :or example the ation 0: a “proton exchange membrane” (PEM), such as for‘ e the commercial available Nafion®; Solopor®, the Toyota PEM or 3M PEM. Said membranes unidirectional and seleCtively transport protons to the cathode (negative side) o_ the membrane. Alternatively, the pH is regulated using specific bases complexes or chemicals as pH regulator, and include for example the application 0: HCL or NaOT.

Example 2 — Laboratory Testing of the CHEMENERGY process at different starting conditions 2.1. Starting’ with the heat releasing process loop at ambient temperature 1.Mix water and Polyphosphoric acid at 20°C and ambient pressure. Based on the teat balance detailed below, temperature will raise to about 95°C, agitate the mixture. 2. Establish vacuum. above the warm. mixture, keep the mixture warm. with. icai resistance and. remove the evaporated water with an air ser. Duration of this evaporation (separation) step will be dependent on the amount 0: water to be removed, but is Likely to last for about 1 hour. 3.Coo; the polyphosphate mixture with ambient air to °C. Go back to Step 1 and the loop is closed.

Calculation 0: change in ature (Delta T): " the HBSS% (I: the mixture is 90% polyphosphoric acid mixed up with 10% water, a reaction heat 0: 300kJ/kg and an overall average mixture heat capacity (Cp) 0: 1.5 kJ/kgK, the Delta T, can be calculated from a simple heat e as follows; Reaction Heat = (Mass) x (Cp) x (Delta T).

Hence, Delta T = (Reaction Heat) / [(Cp) x (Mass)] Using the entioned Reaction Heat, Cp and Mass, the change in temperatire/kg will be 75°C. In other words the mixture wi'l rise ‘rom 75°C to something less then 100°C. 2.1.1. Conclusion for the ERGY process when starting at t temperture Notwithstanding the fact that in this case the reaction loop is , thermodynamically it doesn’t make sense due to the fact the heat generated in step 1, is counterbalanced by the energy required to evaporate water from the ndxture in step 2. For said reasons, and as explained herein, the CHfiMfiNfiRGY process 0: the present invention is particularly iseful in combination with an external heat source, such as for example waste heat from industrial processes. Under said stances and as explained in 2.3. below, the heat releasing process loop can start at for example industrial r st h at l v l, .g. between 50°C — 200°C and more specific between 80—150°C but can also start from. higher temperatures, like e.g. 300°C, if desired. 2.2. Starting' with the heat releasing process loop at industrial rest heat temperature With this experiment it was the objective to pump up heat or one tenperature level to a higher level. The ature 'evel 0“ step one in test 1 was 90°C, this is the e temperature level which is cal'ed in industry waste heat, namely between 60 —120°C. E.g. the oil cooling 'evel ot diesel motor is about 90°C. Steps 1—4 were tested L0 times after each other to prove cyclicity and/or reversibility. 2012/051025 1.Mix water and Polyphosphates at 90°C under a pressure o: 6 bar. In analogy with 2.1 above a Delta T o: 75°C was to be expected and temperature did rise to about 165°C while agitating the mixture continuously. 2.The mixture was cooled with ambient air to about 90°C.

This is to be compared with the release towards a process. 3.Pressure above the warm mixture was released till water m evaporated, whilst keeping the mixture warm with water or 90°C and removing the evaporated water with an air condenser. Duration 0: this evaporatior (separation) step will be dependent on the amount 0: water to be removed, but lasted for about 1 hour. 4. The mixture was pressurized up to 6 bar, and the ated water are reused in step 1, closing the loop 0: the ERGY process. Temperature lift was about —50°C. 2.2.1. Conclusion for the CHEMENERGY process when starting at rest hcat tcmpcrturc In this second case, since rest heat is used for the evaporation step, only a limited amount 0: additional energy is required to pressurize the mixture.

Consequently, part 0: the rest heat with. a low exergy status (a: 90°C) is pumped—up to a higher exergy status or about 165°C. In this laboratory set up, the experiment only served to pump up warm water 0: 90°C into hot air 0; 165°C. But one can imagine that i: we use other fluida, and/or heat s, the present cycle allows the creation 0: heat pumps to generate or ze rest heat towards useful energy and/or heat. E.g. The CHfiMfiNfiRGY process 0: the present invention could. be used to drive chemical ons in a chemical plant at LZO—lBOOC that are now driven by high temperature steam o: e.g. 6—10 bar, using rest steam o: 1—2 bar d.

It is thus the ation 0: the temperature lift, caused by the hydrolysis reaction 0: the inorganic oxo acids and/or their salts,in particular inorganic polyphosphoric acids and/or their salts, with the presence 0: a heat / energy source that can give rise to mtch higher ature lifts, e.g. > 200°C, thus resulting in an overall increase 0: thermal energy. As will become apparenc from the following exemplary applications 0: the CHfiMfiNfiRGY cycle in di "erent environments, the heat SOJICG is on the one hand used to remove water (20) from the reaction product (14) (If the hydrolysation reac:ion (C), i.e. in other words to drive the polymerization ( condensation) reaction (A); and on the other hand to se the thermal energy or the condensed ( polymerized) components (10) used in the hydrolysation reaction (C).

In the below list of possible applications, as an example, liquid phosphoric acid (14) was used as a monomer to be polymerized (condensation reaction (A ) towards a liquid mixture of polyphosphoric acids (lO) of l formula "b and EC above (polymer lengths are generally >1, and typically fron about 2—7), through the removal 0: water (20) under influence CL- che heat // energy source. The water ed from this polymerization (condensation reaction) can be (re)used in the reverse reaction, i .e. the hydrolysation on, eventually after ioning with ioning components (21) or blown into the atmosphere. iDepending on the energy source the polymerization reaction is run under vacuum, near vac1um or small overpressure. For heat sources ng at about 140°C a small overpressure is desired, typically 0,1 — 0,5 barg, but sometimes higher in function of specific operational demands. For heat sources up to about 80°C under pressure is desired, typically >0,025 bar or lower.

For heat sources between and about 80°C to 1—0°C, pressure varies from a slight under pressure + 0,095 bar to more or less 1 atm. ?vidently, "rom the foregoing and as part or the CHfiMfiNfiRGY cycle, the polymerization reaction is performed at lower temperatures ranging from about 80 — 200°C, but typically from 90 — 120°C.

In the e reaction, i.e. the ysation reaction C), said liquid mixture of po'yphosphoric acids (10) is used as polymer hydrolysed (adding of water) under pressure towards the phosphoric acid (14) ard some rests o: osphoric acids in an exothermic reaCtion with the release 0: heat elevating the initial reSt heat to a higher energy level. Again, the phosphoric acid car be (re)used as feed stream in the aforementioned condensation reaction (A), thus closing the CHfiMfiNfiRGY cycle according to the present invention. In the hydrolysation. reaction, the water‘ may’ be added. as warm water, either in liquid. or vapor form. When. in vapor form, this gives an extra boost to the hydrolysis on due to the extra added condensation heat when mixing the vapor‘ with. the polyphosphoric acids. In. principle the hydrolysation reaction can be run at ambient temperatures, but when used as temperature lift (heat pump) to se the thermal energy 0: a , it is run at higher temperatures like e.g. but not limited to 600 — 500°C; typically from 120—500°C, and more in particular from about 150 — 300°C. In said instance, and as already n d h r inb for , th h at / energy source will also be ised to se the thermal energy 0: the condensed (polymerized) components (10) used. in the hydrolysation reaction (C).

Evidently, the core in the aforementioned CHfiMfiNfiRGY process is the reversibility o: the ysation reaCtion o: Polyphosphoric acids versus phosphoric acids. Thus in principle the phosphoric acids can be used in a Closed cycle, but since some irreversible side reactions might occur, some spill (waste) and new feed 0: phosphoric acids might be needed to keep performance optimal.

Consequently, phosphoric acid concentrations are fair'y stable throughout the cycle with corcentrations ranging from about 80 — 90 %; in particular from about 84 — 94% after hydrolysis and from about 90 — 100%; in ular from about 94 — 100% before hydrolysis.

Depending on the application, the cycle is either continuous (continuous flow ol the feed streams between the reactions (A) and (C ), e.g.; — Application l (Fig 3) : heat pump to valorize rest heat, in heating/cooling from processes, warehouses, residential areas, supermarkets, etc, using rest heat from another process, environment, sun, wind, and the like, — Application 2 (Fig 4): heat pump between heat networ<s, to increase the thermal energy from. one heat fluidum temperature/pressure level like e.g. steam, water, l oilpu to a higher temperature/pressure level of a heat fluidum. like e.g. steam, water, thermal oil, , — ation 5 (Fig 5): use 0: heat pump technology to generate cold. with. e.g. high. ambient temperatures, for Cooling of industrial processes, warehouses, supermarkets , refrigerators, houses, residential areas etc. with rest heat from processes, environment, sun, wind, combined heat power, neighborhood or , — Application 6 (Fig 6): transforming rest heat from ses, sun, wind, combined heat power, etc. via a heat pump for steam generation to expand steam over a turbine in the generation 0“ electricity, — Application 7 (Fig 7): g' up rest heat from processes, sun, wind, ed heat power, etc m and transforming' with. an ‘Organic Ranking‘ Cycle’ (ORC) turbine towards electricity, — Application 8 (Fig 8): transforming solar heat towards electricity, using more or less the same scheme as for Application 7, only di "ering in that solar heat is used as heat source instead. In this particular ation, the solar heat can be ised to fully dehydrolyse some (l4b) or all 0: the liquid phosphoric acid (14) in the polymerization (condensation) reaction, yielding pure (solid) or m almost pure (slurry) Pfik. In this case a very high energy density is reached (up to 3GJ/m3) and the system must be designed to handle this material. This can e.g. be done by heating up a non flowing phosphoric acid in a container(insulated nment )constantly heated by direct or indirect sunlight and water vapor escapes from. the phosphoric acid till only a dry powder or slurry 0“ solid P905 is le‘t.

— Application 9 (Fig 9): in bu "ering wind powered electricity. In this application. the heat is generated by electric resistance, this heat is used via a heat pump for steam generation to expand steam over a turbine and generating electricity. "t can be used ‘or bu "ering eleCtricity generated by wind during dips in the electricity network and save it for later during peaks in the electricity network; discontinuous, e.g.

- Application 3 (Fig 10): in bu "ering heat or energy (rest heat, solar heat, wird , steam, etc m) with a heat storage tank. In this application rest heat Irom. processes, sur, wind and others is used to pump up and store heat. This can. e.g. be 'used :fin: connecting a. discontinuous heat producer to a continuous heat consumer, vice versa or to link discontinuous heat produCtion with tintous heat consumption; — Application. 4 (Fig 11): in. heat ort, that di""ers "rom the Ioregoing in that the rest heat is indeed converted and captured in a transportab'e ‘orm enabling on the one hand transport ol ‘rest heat’ by bulk ship, containers, trucks, pipelines to another place 0: river, docks, canal, town, rial or ntial aream to a heat consumer(s) or its network, and on the other hand enabling the conversiono: rest heat 0: transport media its engine, like e.g. motor heat of car, bus, boat, truck and others, transported and valorized at certain locations like e.g. at home, a: work... ; or combinations thereof (Application 10).

Where the foregoing may create the sion that continuous or discontinuous operation. of che CHfiMfiNfiRGY cycle is ent on the absence or presence 0" bu""er tan <s, in the foregoing applications it on'y refers to a COD:inuous or discontinuous erergy conversion. Whether or not tanks are used to bu""er reaction solutions all processes l—9 can be operated continuously or discontinuously. Consequently, in the genera' flow diagram. (Fig. 12) representing' the reoccurring flow in each of the foregoing applications, the storage tanks are Details on the elements in the flow diagrams for each of the ing applications can be found in Table 3 below. 2012/051025 L :3 viééiersér ‘L =52 7 7 L“. and ‘ L. g I: 575577 . 7757;777:7777 , heat Heat57.7777575577775577775774757775‘ 57777 ,6 tag/576$ $1 intc 7-565775757775555héatfiumpi 5577575755575 .07 storage .7“ g setarhaattomrds 577573777 hgjwith ‘ .3. 7 resthéat Wind 775777777777; 577771575 75.

Heat 7735 H557 77777570777775 -: L“: 0777775 'Trénsformihg fiybfidéppiicatim Stréam‘number’ .75 .7» ‘5 mL (.17 7‘55 L15 , CtasaicaI $51577th watersy5tem7 >< 7 55137777573557! 57 dehydrdtysad product-LL , >< , -, _ polymerise Dr :15 775737555pry-7.7M 775m 1737; , 7 55757 752757257 0577 X X _, , , 1975557777555 57§$5557715hydmtysed , pmctuL'ct ' I _‘ , x x x x x x x x x x _7 55771777577555 or 55531575737555 5roctu5t7755755’Lj 12 ‘L ‘ L. Lwith 077775757‘ CL‘ 7 7, x x x x x x x x x x - ~ _ ,7 7555577355 53757577755557 _ L_L.L 13L depaiymerisact product L L’ - X x x X X x x x x X 7 _' 555756772775557777555hydrolysed or ,' , , ,1 L177 ' 555579777575555 5755775! _'y ' , L! ., .L' x x x x x x x x x x ' 67577377570in5 5757757 757775755 5575777555757 , 737555777755 y-n ysLe or 7, dapgtymerisw product 77,5777 7577K L. x X , _--’ 775577 5013577577555]57 dehydrotysed product _ x x ><>< ' L,L 7 fresh 775775571 ordehydmtysed pmduct -_ pressurised, for 55778557170 storage 72.77777 x x ’ water V5557 {75m reactor550555 ' J ,' ' x x X X X X water vapor fmm 55157 r 55717 . 50775577557 55777575755757.7755 ' ‘ ‘ 7 19 MW _ 4,5 , y‘ ’ ’ 7 (35777275775575 .- 7 Condensate pressurised Cand5r7$ate 1755775727 with 5775,:orC . XXXJ 7 _' , V3557 7575355 vacuum or, 575557777555! 35777 b-‘XXX HXXX 30 31 Xxxxx h><><>< ><><><><><><>< XXXXX ><><><><X><><>< MW Extrasteam 57077 777 75mm: to boost, 7..) .4 O X x X X MW _, temperatureLand heat 5577757 Extramnéensate_ L , x x x x x X X 7 pane-55775713575 at 5777vacuum 7.5 ,vapor ' x ' Condensed7715507 at Vacuum ' _- 7 7 x ><>< 7 P7557573 77757775 7‘57 heat 5531577757 {or n5t’)LLL 75555573715177 5575‘ 577575777577 - MW ’ pressurised heated precinct (737 7750 >< _7 , 'Heatlelenmt: usage£75777 er 23 33 33 1 2,3 2,3 0,1 x MW , 5507571 757 tram heat 75557577757 ><U1><>< ><><><><>< xx xx xx xx , 775577 55777757155775 from 7757‘ ' 57555775355 fresh condensate " ‘ 557773555575 fromreaction55577577 75 Law pressure steam ><><><>< >< ><><><><><><><>< , ,7, XXXX 7557155575 55 775 5777 p7essu75 5755777, _ praduetian 7 7 , 7 ,_ ,_ x X x Back up high 575557775stream ' ‘- 7, , x ><>< 7' - 7 77372707775777 ORG _- Expansmn turbiné ORG 7 7 7 7, 7 ‘ $55755 7/5557 77557757077 577277777577 (DEC (35555775575 ORG 77755777771 _ [ 53775357777556 tsquid ORC Medium ><><><><>< xxxxxxx 55777557755757; 19595707 55.571577 ‘ ‘ - 42 64 67 2 42 10 1 55 MW Plate H5577 exchanger: '7 " y- 12 18 16 0,5 12 3 0,3 20 MW , , , Hydrolysafion reaetmn $550577 7 24 36 36 1 24 6 __ 0,6 30 MW Expansiaq 7777575355575 P577757 ‘ 7 ', 2,3 2,3 0,1 3 MW [27557775 55537777755577 - '7 . 240 360 360 10 240 6 10000 kW _ 57,1 ,~' H5515) er(MWHEiecmcfiyWW) 96 92 92 100 % _ ,, , ,575579557) ' , 57577575177537 7 5% 23% 11% - - ‘7 7 55777799577577 otcatatysté 5775WeL y streams, notdepicted 5775755555 flaw5759mm ' 7472751 but, 5,77 P&iD ~ ’ No valves, 77575775773775577 on FFDL‘ 7 Heat 755577577775771775755 and transport 5597557571, ijYPFD ,7 , WO 01110 Depending on the applications, the cycle can be build ° from small e.g. ic application to a big industrial scale. ° on skids, small scale big scale. ° in containers or other movable platforms.

In each 0: the possible applications the cycle can be controlled with simple temperature, pressure I flow or other sensors regulating valves and systems, or designed from something between simple electrical & instrumentation design and/or highly sophisticated electrical & instrumentation design, fully ted installations with optimizer connected to internet, mobile phone or others 'ZO run. on. maximum. economical output 24h a day. zer might run on , ambient temperature, wind or other circumstance determining the economics or performance 0; the installation.

Based on industry standardized safety reviews, like e.g.

{AZOP, lations are designed to high safety standards containing wrether intrinsic safe desigr (like e.g. vacuum and maximum operating presstre nlO%), pressure valves, or automated safety irLegriLy "unction (S"F or S"L) systems or a combination of these design criteria. "nstallations are controlled with alarms and trips in order to keep the lation in the safe operating range. Basic design 0; equipment depends on the process design but the detailed equipment design can be di""erenL in order to meet P33, ASME or other local design codes or local state O: the art technology.

Claims (18)

1. A method to store or increase the energy content of a reaction mixture by means of an endothermic condensation reaction, said reaction mixture comprising an inorganic oxoacid compound and/or its salt and water, said reaction being enabled by the heat input from a heat source distinct from said reaction mixture.

2. The method according to claim 1, wherein the heat source ct from said reaction mixture is either rest heat from industrial processes, or heat derived from natural resources such as solar or wind energy.

3. The method according to claim 1 or claim 2, wherein water and/or the inorganic oxoacid compound and/or its salt is removed from the reaction mixture.

4. The method according to any one of the preceding claims, further comprising the step of releasing the stored or increased energy content of the reaction mixture in a subsequent process step through the exothermic hydrolysation of a reaction product of said reaction mixture.

5. The method according to any one of claims 1 to 3, wherein the nic oxoacid compound and/or its salt is an oxoacid of either nitrogen, sulfur or phosphorus, or its corresponding salt.

6. The method according to claim 5, n the nic oxoacid compound and/or its salt is ented by general formula (I) (OnX(OQ)m-0)y)-R' (I) wherein; R represents hydrogen, a hydrocarbon or Z (as described below); X represents , nitrogen or phosphorus; Z represents -(OnX(OQ)m-0)y–R’’; R’ and R’’ each independently represent hydrogen, a hydrocarbon or a metal cation; n = 1 or 2; m = 0 or 1; p = 0 or 1; y = at least 1; and each Q independently represents hydrogen, hydrocarbon or a metal cation.

7. The method ing to claim 5, wherein the inorganic oxoacid compound and/or its salt is a polyphosphoric acid and/or its salt, represented by general formula (la) R-O-((OP(OQ)m-O)Y)–R’ (la) R and R’ each independently represent hydrogen, a hydrocarbon or a metal cation; m = 0 or 1; y = at least 1; and each Q independently ents hydrogen, hydrocarbon or a metal cation.

8. The method according to claim 5, wherein the polyphosphoric acid or its salt is: a. a pure inorganic linear polyphosphoric acid or its salt represented by the following formula: Mn+2PnO(3n+1) (lb) with n = at least 2; M is H+ or a metal cation; b. a pure inorganic cyclic polyphosphoric acid or its salt represented by the following formula: n (Ic) with n = at least 3; M is H+ or a metal cation; c. branched; or d. a combination thereof.

9. The method according to any one of claims 6 to 8, wherein the metal cation is a monovalent metal cation, more in particular K or Na.

10. The method according to claim 6 or claim 7, wherein y is within the range of 1 to 100, more in particular within the range of 1 to 10, still more in particular within the range of 1 to 3.

11. The method according to claim 7, wherein the salt of oric acid is selected from phosphoenolpyruvate, glycerate 1,3-biphosphate, formyl phosphate, acetyl phosphate, propionyl phosphate, butyryl phosphate or any other carboxyl phosphate, phospho-creatine, phospho-arginine, a glucose phosphate (1- or 6-phosphate), se phosphate, glycerolphosphate, nicotinamide adenine dinucleotide phosphate (NADP) , dihydroxyacetonephosphate, a glyceraldehydephosphate , xylulosephosphate, a phosphate, sedoheptulosephosphate, osephosphate, ribulosephosphate, phospho-serine, aspartylphosphate and adenosinephosphate.

12. The method according to any one of claims 1 to 6, wherein the endothermic condensation reaction is represented by the following formula: HOXOn(OH)mOR' + R-Op-((XOn(OH)m-O)y-1)-H -> R-Op- ((XOn(OH)m-O)y)-R' + H2O

13. The method according to claim 12, wherein X represents phosphorus.

14. A system for ing and storing energy, comprising: e means for capturing energy; and storage means for storing captured energy, wherein the capture and storage means comprise at least one reaction vessel at least partially filled with a reaction mixture sing an inorganic oxoacid compound and/or its salt and water, suitable for having an endothermic condensation reaction performed on said reaction mixture, and comprising a heating element in thermal communication with said .

15. The system according to claim 14, further comprising a release means for releasing the energy captured and stored in a subsequent exothermic hydrolysis step.

16. The system ing to claim 14 or claim 15, wherein the reaction mixture ses an inorganic oxoacid compound and/or its salt, as set forth in any one of claims 6 to 11.

17. A method according to claim 1, substantially as herein described with reference to any one or more of the examples but excluding comparative examples.

18. A system according to claim 14, substantially as herein described with reference to any one or more of the examples but excluding ative examples.