method for storing or increasing the energy content of a reaction mixture and system for capturing o

专利摘要:
"METHODS AND COMPONENTS FOR THERMAL ENERGY STORAGE". The present invention relates generally to a method of storing thermal energy or heat pump using reversible chemical reactions. Within a reversible cycle, inorganic oxoacid compounds and / or their salts, oxyacid or nitrogen, sulfur or phosphorus, or their corresponding salt, are hydrolyzed and condensed or polymerized in order to release and capture heat. It is therefore a first aspect of the present invention to provide for the use of inorganic esters in a method of storing thermal energy, specifically using inorganic phosphoric acids and / or their salts. The invention further provides a method for storing thermal energy, said method comprising a polymerization of inorganic oxyacids using an external heat source. In a further aspect the invention provides a method for releasing thermal energy from said heat storage which comprises an exothermic hydrolyzation step of the inorganic oxyacids and / or their salt. If no cooling occurs between the polymerization and the hydrolyzation step, a heat pump can be created. Such a heat pump could be extremely useful in improving the industry's waste heat to a higher level more (...).
公开号:BR112013019055B1
申请号:R112013019055-8
申请日:2012-01-24
公开日:2020-07-21
发明作者:Wouter Ducheyne；Christian STEVENS
申请人:Technology For Renewable Energy Systems (Tfres) Bvba；Universiteit Gent；
IPC主号:

专利说明:

[0001] [0001] The present invention relates generally to a method of storage of thermal energy or heat pump, that is, it increases the thermal energy of an external heat source, using reversible chemical reactions. Within a reversible cycle, a mixture comprising inorganic oxoacid compounds and / or their salts and water such as, for example, nitrate, sulphate, phosphate and sulphonate esters, is depolymerised by means of an exothermic hydrolyzation reaction and polymerized by through an endothermic condensation reaction to release and capture heat. It is therefore a first aspect of the present invention to provide for the use of inorganic oxoacid compounds and / or their salts and water in a method of thermal energy storage and / or in a method of increasing the thermal energy of an external heat source, hence hereinafter also referred to as a heat pump, specifically using inorganic phosphorus oxoacid compounds and / or their salts, such as, for example, polyphosphoric acid.
[0002] [0002] The invention further provides a method for storing thermal energy, said method comprising a condensation reaction of a reaction mixture comprising inorganic oxoacid compounds and / or their salts and water using an external heat source. In a further aspect the invention provides a method for releasing thermal energy from said heat storage which comprises a step of exothermic hydrolysation of the inorganic oxoacid compounds or their salts.
[0003] [0003] Using the methods and components of the present invention it is possible to store thermal energy in ambient circumstances in a transportable medium. As a consequence this allows to convert a process of continuous heat generation into a discontinuous and even displaced consumption. Furthermore, it is possible to pump heat from a source of ambient or low-temperature heat, for example, 80-200 ° C, to higher temperature levels with specific low electricity consumption, that is, using the method of the present invention as a heat pump. Background of the Invention
[0004] [0004] Thermal energy storage is very important in many applications related to the use of waste heat from industrial processes, renewable energies or from different other sources. Furthermore, heat recovery is receiving widespread attention as a means to reduce demand on fossil fuels and as a means to reduce the discharge of Kyoto gases.
[0005] [0005] Several heat capture systems already exist. Heat can be generated from solar or heat sinks, or other sources that include the sun, geothermal, remaining heat or other sources of heat.
[0006] - Sistemas de água - Óleo térmico II. Calor latente por mudança de fase em materiais <1 MJ/m3: - Materiais que utilizando mudança de fase como um meio para armazenar ou liberar calor. Um exemplo é a utilização de cristalização de acetato de Na. (densidade de calor teórica 300-800 GJ/m3) - Utilizar calor de absorção de água em sílica gel. III. Calor de reação por reações químicas reversíveis <3 GJ/m3: - Utilizar o calor de mistura de ácido sulfúrico e água. - Utilizar o calor de reação de hidrogênio e metais como o Magnésio. (Densidade de calor teórica 3 GJ/m3) - Hidratos de sal [0006] Examples of heat capture systems can generally be divided into 3 categories: I. Sensitive heat <500 MJ / m3: - Water systems - Thermal oil II. Latent heat due to phase change in materials <1 MJ / m3: - Materials that use phase change as a means to store or release heat. An example is the use of Na acetate crystallization. (theoretical heat density 300-800 GJ / m3) - Use silica gel water-absorbing heat. III. Reaction heat by reversible chemical reactions <3 GJ / m3: - Use the mixture heat of sulfuric acid and water. - Use the heat of reaction of hydrogen and metals such as magnesium. (Theoretical heat density 3 GJ / m3) - Salt hydrates
[0007] [0007] Most of the proposed alternative energy is using the sun or the wind as an energy source. Due to the process (chemical cycle) of the present invention, another heat source can be used more easily than today: waste heat. Large amounts of waste heat (also called remaining heat) are generated in industry and released into the environment as unusable for the use of additional energy, more specifically electricity generation, due to the low state of exergy. However, the use of remaining heat makes sense, for example, in residential areas to heat houses or apartments and in industrial areas to heat process flows. Instead of using conventional energy sources with high exergy, such as, for example, natural gas or other fuels, one can also use the remaining low energy heat. This prohibits the use of high sources of caloric energy for low caloric applications. One of the main obstacles to the use of the remaining heat for these purposes is the fact that the heat remaining in the industry is used continuously versus the discontinued use of residential heat and even more so the fact that the heat production industry is located quite far from residential areas. . The energy storage capacity, the ease of transport and the possibilities of using this chemical cycle as a heat pump than the one claimed below, forces a breakthrough for the use of remaining heat and opens a new way to reduce Kyoto gases. The use of cheap and low CO2 generation transport, such as, for example, gross or containerized cargo by boats and pipelines, forms an alternative to CO2-intensive road trucks.
[0008] [0008] In the method further described in this text, heat is used to form polymers of inorganic oxoacid compounds or their salts by a (poly) condensation reaction of inorganic molecules or molecules that contain inorganic submolecules with polyoxoacid compounds or their salts. Proton concentrations, catalysts, membranes, etc. are used to promote synthesis (condensation reaction) and hydrolysis reaction. For example, mono phosphoric acid and poly phosphoric acids are further polymerized by adding heat and removing water (condensation). The hydrolysis reaction by adding water again, generates heat from exothermic depolymerization.
[0009] - JP 58060198A; Matsushita electric works ltd; Nomura Kazuo; Material de acumulação de calor. Nesta patente o fosfato de sódio; Na2HP04 é utilizado para armazenar calor por meio de cristalização ou transição de fase, por meio de um agente de núcleo específico. - GB 1396292 A; Randall; 10 Fev. 1971; Aperfeiçoamentos em ou relativos a unidades de armazenamento de calor. Nesta patente a utilização de um calor de cristalização de fosfatos é utilizada para armazenar calor. E. Utilizar calor de dissolução tal como após colocar óxido de enxofre e ácido sulfúrico em contato com água ou calor de queima colocando S em contato com o ar, como descrito nas 2 patentes abaixo: - US 4.421.734; Norman 20 de Dezembro de 1983; Ciclo de armazenamento de calor Ácido Sulfúrico - enxofre. Nesta patente o calor da dissolução de dióxido de enxofre ou ácido sulfúrico altamente concentrado em água, atuando como um solvente, para formar ácido sulfúrico de baixa concentração e a queima de enxofre com oxigênio são utilizados para produzir calor. Para realizar o armazenamento de calor, o ácido sulfúrico altamente concentrado e o enxofre precisam ser armazenados. Este armazenamento permite a nivelação de calor do sol durante um período mais longo. - US 4.532.778; Clark et al 06 de Agosto de 1985; bomba de calor química e sistema de armazenamento de energia química. Nesta patente US o calor de dissolução de ácido sulfúrico é utilizado para armazenar calor ou para realizar uma bomba de calor para aumentar o nível de temperatura (ou aumentar a energia térmica) de calor de refugo. F. Sistemas adicionais que utilizam calor de dissolução estão baseados na aplicação de hidratos de sal, como, por exemplo, MgCl2, Mg(OH)2 Ca(OH)2, carbonato de sódio e água, para utilizar o calor de mistura dos sais em água. - Patentes recentes de engenharia, 2008, 2.208-216. Revisão de patentes recentes sobre bomba de calor química. Cheng Wang, Peng Zhang e Ruzhu Wang. A reação reversível de transformação de potencial térmico em bomba de calor química principalmente inclui absorção de líquido - gás, reação de sólido - gás e adsorção de sólido. - Possibilidade de tecnologias de bomba de calor química por Yukitaka Kato, 31 de Janeiro, 2011, Seminário de armazenamento de energia térmica de alta densidade, Arlington, Virginia, USA. Descrição de bombas de calor químicas da melhor técnica moderna principalmente baseado na descoberta que as reações de óxidos metálicos & cloro são até então as melhores técnicas disponíveis para as bombas de calor químicas. G. Outros sistemas para explorar ATP como uma molécula com alta densidade de energia, podem simplesmente utilizar estes compostos como um melhorador para desempenho de bateria ou motor; por exemplo - US20070218345 A; Sakai et al; uma célula de combustível, dispositivo eletrônico, corpo móvel, sistema de cogeração de sistema de geração de energia. - US20020083710A1; Schneider, Thomas; Motor molecular com utilização de ATP, actina & miosina para girar cilindros para produzir trabalho. - EP 1089372A1; Camus et al. 28 Set., 1999; Sistema de geração de energia e armazenamento independente e autossustentável. Especialmente os parágrafos 0006 e 0056 e a Figura 7 onde ATP é utilizado. Nesta patente um método para armazenamento elétrico está descrito em que o ATP é utilizado para aperfeiçoar o desempenho de bateria. [0009] Furthermore, the method and components can be used as a reversible heat pump that allows to generate remaining heat cold, or to increase the thermal energy of heat sources, with a very low electrical consumption, typically 1-10% . This consequently clearly differs from existing heat pump systems such as; A. Organic Rankine Cycle (ORC) that pumps heat from low temperature sources to higher temperature levels or using ORC to produce electricity from remaining heat. Typically its realistic thermal efficiency or COP is a heat to energy ratio of approximately 3-5. B. Use Lithium Bromide or water / NH3 and remaining heat as a heat pump to produce cold by absorbing heat due to the dissolution of Li-Br in water under vacuum conditions. In US 6,177,025 B1, and JP01161082 this process is further optimized, with an improved efficiency, through a crystallization inhibiting additive. C. Enzyme systems as, for example, described in CN101168481A, see complete document and summary of WPI account number 2008-H14900 [46] and CAS summary account number 2008: 538691. In this document ATP is used to perform high energy storage and release. This is done by using a secretory gland, and therefore differs from the reversible hydrolyzation reaction of the present invention. D. Crystallization processes that release heat with a phase transition to form a solid or solid crystalline form. - JP 58060198A; Matsushita electric works ltd; Nomura Kazuo; Heat accumulation material. In this patent, sodium phosphate; Na2HP04 is used to store heat through crystallization or phase transition, using a specific core agent. - GB 1396292 A; Randall; 10 Feb. 1971; Improvements in or relating to heat storage units. In this patent the use of a phosphate crystallization heat is used to store heat. E. Use heat of dissolution such as after placing sulfur oxide and sulfuric acid in contact with water or burning heat by placing S in contact with air, as described in the 2 patents below: - US 4,421,734; Norman December 20, 1983; Heat storage cycle Sulfuric Acid - sulfur. In this patent the heat of dissolving sulfur dioxide or highly concentrated sulfuric acid in water, acting as a solvent, to form low concentration sulfuric acid and burning sulfur with oxygen are used to produce heat. To perform heat storage, highly concentrated sulfuric acid and sulfur must be stored. This storage allows the heat leveling of the sun to be leveled over a longer period. - US 4,532,778; Clark et al August 6, 1985; chemical heat pump and chemical energy storage system. In this US patent the sulfuric acid dissolving heat is used to store heat or to make a heat pump to increase the temperature level (or increase the thermal energy) of waste heat. F. Additional systems that use heat of dissolution are based on the application of salt hydrates, such as, for example, MgCl2, Mg (OH) 2 Ca (OH) 2, sodium carbonate and water, to use the heat of mixing the salts in water. - Recent engineering patents, 2008, 2,208-216. Review of recent patents on chemical heat pump. Cheng Wang, Peng Zhang and Ruzhu Wang. The reversible reaction of transforming thermal potential into a chemical heat pump mainly includes absorption of liquid - gas, reaction of solid - gas and adsorption of solid. - Possibility of chemical heat pump technologies by Yukitaka Kato, January 31, 2011, High density thermal energy storage seminar, Arlington, Virginia, USA. Description of chemical heat pumps of the best modern technique mainly based on the discovery that the reactions of metal oxides & chlorine are the best techniques available until now for chemical heat pumps. G. Other systems to explore ATP as a molecule with a high energy density, can simply use these compounds as an enhancer for battery or engine performance; for example - US20070218345 A; Sakai et al; a fuel cell, electronic device, mobile body, power generation system cogeneration system. - US20020083710A1; Schneider, Thomas; Molecular engine using ATP, actin & myosin to rotate cylinders to produce work. - EP 1089372A1; Camus et al. 28 Sep., 1999; Independent and self-sustaining energy generation and storage system. Especially paragraphs 0006 and 0056 and Figure 7 where ATP is used. In this patent a method for electrical storage is described in which ATP is used to improve battery performance.
[0010] [00010] But they are not based on a reversible hydrolyzation reaction as in the present case. Instead, ATP synthesis will be activated enzymatically (see CN101168481A above) or by photosynthesis, for example, Nature materials, 2005, Vol 4 (3); Luo et al pp 220-224; Photoinduced proton gradients and ATP biosynthesis produced by vesicles encapsulated in a silica matrix. SUMMARY OF THE INVENTION
[0011] [00011] As already explained above, the present invention is based on the discovery that inorganic oxoacid compounds and / or their salts and water can be used in a reversible hydrolyzation reaction to store and / or increase the thermal energy of a source of heat.
[0012] [00012] To store thermal energy, the heat is converted to molecular reaction heat by means of a condensation reaction triggered by the removal of water (dehydrolysis) from the reaction medium with the formation of high energy covalent ester bonds in the compounds of inorganic oxoacids and / or their salts of the present invention.
[0013] [00013] To release thermal energy, such as, for example, in a method to increase the thermal energy of a heat source, from the high energy covalent ester bonds, the inorganic oxoacid compounds of the present invention are subjected to a hydrolyzation reaction by adding water to the reaction medium comprising said oxoacid compounds or their salts.
[0014] [00014] Thus in one aspect the present invention provides for the use of inorganic oxoacid compounds and their salts and water in a method for storing and / or increasing the thermal energy of a heat source.
[0015] [00015] In said use the thermal energy of the heat source is stored through a condensation reaction with the removal of water from the reaction solution and the formation of polyorganic oxoacid compounds and / or their salts.
[0016] [00016] In said use the thermal energy of the heat source is increased by means of a hydrolysation reaction of inorganic oxoacid compounds and / or their salts, through the addition of water to a reaction solution.
[0017] - a energia térmica da fonte de calor é armazenada por meio de uma reação de condensação com a remoção de água da solução de reação e a formação de compostos de oxoácido poli inorgânicos e/ou seus sais; e em que - a energia térmica da fonte de calor é aumentada por meio de uma reação de hidrolisação de compostos de oxoácido inorgânicos e/ou seus sais, através da adição de água a uma solução de reação que compreende os ditos ésteres inorgânicos. [00017] In other words, the present invention provides for the use of inorganic oxoacid compounds and / or their salts and water in a method for storing and / or increasing the thermal energy of a heat source, characterized by the fact that; - the thermal energy of the heat source is stored through a condensation reaction with the removal of water from the reaction solution and the formation of polyorganic oxoacid compounds and / or their salts; and in what - the thermal energy of the heat source is increased by means of a hydrolysation reaction of inorganic oxoacid compounds and / or their salts, by adding water to a reaction solution comprising said inorganic esters.
[0018] [00018] The inorganic oxo acid compounds and / or their salts in the above mentioned uses or used in the methods of the present invention are oxy acid or nitrogen, sulfur, or phosphorus or its corresponding salt.
[0019] [00019] In one aspect of the present invention the inorganic oxoacid compounds and / or their salts used are represented by the general formula (I) R-Op - ((OnX (OQ) mO) y) -R '(I) on what; Z represents - (OnX (OQ) mO) yR "; R represents hydrogen, a hydrocarbon or Z; R 'and R "are each independently hydrogen, a hydrocarbon or a metal cation, specifically a monovalent metal cation, even more specifically K or Na; X represents Sulfur (S), Nitrogen (N) or Phosphorus (P); specifically X represents P; n = 1 or 2; m = 0 or 1; p = 0 or 1; y = at least 1; specifically 1 to 100; more specifically 1 to 10; even more specifically 1 to 4; alternatively y is 1 to 3; and each Q independently represents a hydrogen, a hydrocarbon or a metal cation, specifically a monovalent metal cation, even more specifically K or Na.
[0020] [00020] In another aspect of the present invention the inorganic oxoacid compounds and / or their salts used are polyphosphoric acids. It is therefore an object of the present invention to provide the use of polyphosphoric acids in a method for storing and / or increasing the thermal energy of a heat source.
[0021] - a energia térmica da fonte de calor é armazenada por meio de uma reação de desidrolisação (reação de condensação) de ácidos fosfóricos (incluindo os ácidos mono e polifosfóricos); e em que - a energia térmica da fonte de calor é aumentada por meio de uma reação de hidrolisação de ácidos polifosfóricos, através da adição de água a uma solução de reação que compreende os ditos ácidos polifosfóricos. [00021] Specifically, the use of polyphosphoric acids in a method to store and / or increase the thermal energy of a heat source, characterized by the fact that: - the thermal energy of the heat source is stored through a dehydrolysation reaction (condensation reaction) of phosphoric acids (including mono and polyphosphoric acids); and in what - the thermal energy of the heat source is increased by means of a hydrolyzation reaction of polyphosphoric acids, by adding water to a reaction solution comprising said polyphosphoric acids.
[0022] [00022] In another aspect of the present invention the inorganic oxo acid compounds and / or their salts used are polyphosphoric acids and / or their salts represented by the general formula (Ia) RO - ((OP (OQ) mO) y -R '(Ia) on what R represents hydrogen, a hydrocarbon or a metal cation, specifically a monovalent metal cation, even more specifically K or Na; R 'represents hydrogen, a hydrocarbon or a metal cation, specifically a monovalent metal cation, even more specifically K or Na; m = 0 or 1; y = at least 1; specifically 1 to 100; more specifically 1 to 10; even more specifically 1 to 4; alternatively y is 1 to 3; and each Q represents a hydrogen, a hydrocarbon or a metal cation, specifically a monovalent metal cation, even more specifically K or Na.
[0023] [00023] In still a further aspect of the present invention the polyphosphoric acids and / or their salts used are; pure inorganic linear polyphosphoric acids and / or their salts represented by the following formula: Mn + 2PnO (3n + 1) (Ib) with n = at least 2; specifically 1 to 10E6; more specifically 2 to 5; M is H + or a metal cation, specifically a monovalent metal cation, even more specifically K or Na; pure inorganic cyclic polyphosphoric acids and / or their salts represented by the following formula: MnPnO3n (Ic) with n = at least 3; specifically 1 to 12; more specifically 3, 4, 5 or 6; M is H + or a metal cation, specifically a monovalent metal cation, even more specifically K or Na; pure inorganic branched polyphosphoric acids and / or their salts, specifically a monovalent metal cation salt, even more specifically K or Na; or their combinations.
[0024] [00024] In a specific aspect of the present invention the polyphosphoric acids and / or their salts used are selected from the group consisting of Phosphophenolpyruvate, Glyceratel, 3 bi phosphate, Formyl phosphate, Acetyl phosphate, Propionyl phosphate, Butyryl phosphate or other carboxyl phosphates , Phospho-creatine, Phospho-arginine, Glucose phosphates (1 or 6-phosphate), fructose phosphates, Glycerol-3-phosphate, Nicotine amide adenine dinucleotide phosphate (NADP), dihydroxyacetone phosphate, glyceraldehyde phosphates, phosphate phosphate, xyldehyde phosphates, -heptulosphosphate, erythrosphosphate, ribulosphosphate, phospho-serine, aspartphosphate and adenosinophosphate.
[0025] [00025] Based on the above, the present invention further provides a method for storing or increasing the energy content of a reaction mixture, said reaction mixture comprising an inorganic oxoacid compound and / or its salt and water, said reaction being enabled by the heat inserted from a heat source other than said reaction mixture.
[0026] [00026] The present invention further provides a method, in which the heat source distinct from said reaction mixture is either heat remaining 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 of the uses or methods of the present invention. In principle, any heat source can be used, including heat captured or obtained from solar energy, geothermal energy, wind energy, electricity, remaining heat from industry and the like.
[0027] [00027] The present invention further provides a method, in which water and / or the inorganic oxoacid compound and / or its salt is removed from the reaction mixture.
[0028] [00028] The present invention further provides a method, further comprising the step of releasing the respective increased energy content, stored from the reaction mixture in a subsequent process step through the exothermic hydrolysation of the reaction products of said reaction mixture.
[0029] [00029] The present invention further provides a method, wherein the inorganic oxoacid compound and / or its salt is an oxoacid or nitrogen, sulfur or phosphorus, or its corresponding salt.
[0030] [00030] The present invention further provides a method, in which the inorganic oxoacid compound and / or its salt is represented by the general formula (I) R-Op - ((OnX (OQ) mO) y) -R '(I) on what; R represents hydrogen, a hydrocarbon or Z (as described below); X represents sulfur, nitrogen or phosphorus; Z represents - (OnX (OQ) mO) yR "; R 'and R "each independently represents hydrogen, a hydrocarbon or a metal cation; n = 1 or 2; m = 0 or 1; p = 0 or 1; y = at least 1; and Q each independently represents a hydrogen, a hydrocarbon or a metal cation.
[0031] [00031] The present invention further comprises a method, in which the inorganic oxoacid compound and / or its salt are polyphosphoric acids and / or their salts, specifically represented by the general formula (Ia) RO - ((OP (OQ) mO) y -R '(Ia) on what R and R 'each independently represents hydrogen, a hydrocarbon or a metal cation; m = 0 or 1; y = at least 1; and each Q represents a hydrogen, a hydrocarbon or a metal cation. The present invention further provides a method, in which polyphosphoric acids and / or their salts are; The. pure inorganic linear polyphosphoric acids or their salts represented by the following formula: Mn + 2PnO (3n + 1) (Ib) with n = at least 2; M is H + or a metallic cation; B. pure inorganic cyclic polyphosphoric acids or their salts represented by the following formula: ΜnΡnO3n (Ic) with n = at least 3; M is H + or a metallic cation; ç. branched; or d. their combinations.
[0032] [00032] The present invention further provides a method, in which the metal cation is a monovalent metal cation, even more specifically K or Na.
[0033] [00033] The present invention further provides a method, in which y is within the range of 1 to 100; more specifically within the range of 1 to 10; even more specifically within the range of 1 to 3.
[0034] [00034] The present invention further provides a method, in which the phosphoric acid salts are selected from the group containing Phosphophenolpyruvate, Glyceratel, 3 bi phosphate, Formyl phosphate, Acetyl phosphate, Propionyl phosphate, Butyryl phosphate or other carboxyl phosphates, Phospho -creatin, Phospho-arginine, Glucose phosphates (1 or 6-phosphate), fructose phosphates, Glycerol-3-phosphate, Nicotine amide adenine dinucleotide phosphate (NADP), dihydroxyacetonephosphate, glyceraldeidophosphates, xylosphosphosphates , Erythrosephosphate, ribulosphosphate, phospho-serine, Aspartyl phosphate and adenosinophosphate.
[0035] [00035] The present invention further provides a method, in which the endothermic condensation reaction is represented by the following formula: HOXOn (OH) mOR '+ R-Op- ((XOn (OH) m-0) y-1) -H -> R-Op- ((XOn (OH) m-0) y) -R '+ H2O
[0036] - um meio de captura para capturar energia; - um meio de armazenamento para armazenar a energia capturada, em que os meios de captura e armazenamento compreendem pelo menos um vaso de reação pelo menos parcialmente cheio com uma mistura de reação que compreende um composto de oxoácido inorgânico e/ou seu sal e água, adequada para ter uma reação de condensação endotérmica executada sobre a dita mistura de reação, e compreendendo um elemento de aquecimento em comunicação térmica com o dito vaso. [00036] The present invention further provides a system for capturing or storing energy, which comprises - a means of capture to capture energy; - a storage medium for storing captured energy, wherein 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 carried out on said reaction mixture, and comprising a heating element in thermal communication with said vessel.
[0037] [00037] The present invention further provides a system, additionally characterized by the fact that it comprises a release means to release the captured energy and stored in a subsequent exothermic hydrolysis step.
[0038] [00038] The present invention further provides a system, further characterized by the fact that the reaction mixture comprises an inorganic oxoacid compound and / or its salt.
[0039] [00039] As hereinafter provided in more detail, the reaction solution may further comprise conditioning components to optimize the reaction conditions for the esterification / hydrolyzation reactions, such as catalysts to catalyze the condensation / hydrolyzation reaction. BRIEF DESCRIPTION OF THE DRAWINGS
[0040] [00040] Figure 1 A. General reaction scheme.
[0041] [00041] B. CHEMENERGY cycle block diagram.
[0042] [00042] Figure 2: CHEMENERGY cycle with inorganic phosphate / polyphosphate esters.
[0043] [00043] Figures 3 - 11: Different possible applications for the CHEMENERGY cycle in increasing the thermal energy of a heat source. Details on the elements in the flowcharts for each of the applications can be found in Table 3 below.
[0044] [00044] Figure 12: General flowchart for the recurring elements in the practical exploration of the CHEMENERGY cycle. Storage tanks, both the heat storage tank (s) and the component storage tank (s), are optional. DESCRIPTION OF THE INVENTION
[0045] [00045] The present invention is based on the findings that inorganic oxoacid compounds and / or their salt, such as, for example, nitrate, sulfate, phosphate and sulfonate esters, can be used in a method of thermal energy storage exploring the reversible chemical hydrolysis and condensation reaction which are exo and endothermic, respectively.
[0046] [00046] It is therefore a first objective of the present invention to provide the use of inorganic oxoacid compounds and / or their salt in a method of storing thermal energy.
[0047] [00047] The inorganic oxoacid compounds and / or their salt as used herein are selected from the group of inorganic oxoacid compounds and / or their salt with an oxoacid or nitrogen, sulfur or phosphorus, or their corresponding salt; and specifically inorganic oxoacid or its salt refers to phosphorus oxyacid and / or its salt such as phosphorylated hydrocarbons and inorganic (poly) phosphoric acids and their salts.
[0048] [00048] As is generally known in the art, polymerization refers to the attachment of organic groups (esterification) to phosphorus (P), nitrogen (N), or sulfur (S) via oxygen linkers or refers to polymerization of inorganic oxoacid compounds or their salts or of nitrogen, sulfur or phosphorus, with the generation of H2O or water, through an endothermic condensation reaction using an alcoholic precursor of said organic group or a hydroxyl group of said inorganic oxyacids. A general representation of said esterification is provided in step (2) of Figure 1.
[0049] [00049] The inorganic oxoacid compound and / or its salt as used in the methods of the present invention, are represented by the general formula (I) R-Op - ((OnX (OQ) mO) y) -R '(I) on what; Z represents - (OnX (OQ) mO) yR "; R represents hydrogen, a hydrocarbon or Z; R 'and R "are each independently hydrogen, a hydrocarbon or a metal cation, specifically a monovalent metal cation, even more specifically K or Na; X represents Sulfur (S), Nitrogen (N) or Phosphorus (P); specifically X represents P; n = 1 or 2; m = 0 or 1; p = 0 or 1; y = at least 1; specifically 1 to 100; more specifically 1 to 10; even more specifically 1 to 4; and each Q independently represents a hydrogen, a hydrocarbon or a metal cation, specifically a monovalent metal cation, even more specifically K or Na.
[0050] [00050] In a specific embodiment of the present invention the inorganic oxoacid compound and / or its salt are polyphosphoric acids and / or their salts, represented by the general formula (Ia) RO - ((OP (OQ) mO) y -R '(Ia) on what R represents hydrogen, a hydrocarbon or a metal cation, specifically a monovalent metal cation, even more specifically K or Na; R 'represents hydrogen, a hydrocarbon or a metal cation, specifically a monovalent metal cation, even more specifically K or Na; m = 0 or 1; y = at least 1; specifically 1 to 100; more specifically 1 to 10; even more specifically 1 to 4; and each Q represents a hydrogen, a hydrocarbon or a metal cation, specifically a monovalent metal cation, even more specifically K or Na.
[0051] [00051] The remainder of the hydrocarbon in any of the aforementioned formulas can be any organic compound comprising a hydroxyl group such as, for example, alcohols, carboxylic acids, esters, etc., or it can be any of sugars and bases that form nucleotides and nucleic acids or any organic molecule that ends in a hydroxyl group; wherein said hydroxyl group is capable of forming an inorganic ester with a phosphate, polyphosphate, nitrate, sulfate or sulfonic acid. Specifically with a phosphate or polyphosphate.
[0052] - Como bases poderia, por exemplo, tomar Purina, Pirimidina, Adenina, Guanina, Timina, Citosina, Uracila, Hipoxantina, 5-metilcitosina, N6-metiladenina, di-hidrouracila, 1-metilguanina, ribotimidimina, pseudouridina, ou 1-metiliosina. - Como açúcares (pentose) se poderia, por exemplo, tomar frutose, ribose, D-ribofuranose, ou 2-deoxi-D-ribofuranose. [00052] Nucleotides have a well-known meaning in the art and consist of any combination of different nitrogenous bases and different sugars (pentoses) and can have mono, di and tri phosphate (s) as a phosphoryl group:
[0053] [00053] Nucleic acids have a well-known meaning in the art and can consist of any combination of different nucleotides. The nucleotides are linked in poly nucleotides or nucleic acids through a column made of sugars and phosphate groups joined by ester bonds.
[0054] [00054] In one embodiment of the present invention, inorganic esters comprise or consist of a 'polyphosphate'. Polyphosphates are anionic phosphate polymers bonded between hydroxyl groups and hydrogen atoms. The polymerization that takes place is known as a condensation reaction. Chemical phosphate bonds are typically high-energy covalent bonds, which means that energy is available when such bonds break in spontaneous or enzyme-catalyzed reactions. In said embodiment, a specific group of inorganic phosphate esters consists of, but is not limited to, Phosphophenolpyruvate, Glyceratel, 3 bi phosphate, Formyl phosphate, Acetyl phosphate, Propionyl phosphate, Butyryl phosphate or other carboxyl phosphates, Phospho-creatine, Phospho-creatine arginine, Glucose phosphates (1 or 6-phosphate), fructose phosphates, Glycerol-3-phosphate, Nicotine amide adenine dinucleotide phosphate (NADP), dihydroxyacetonephosphate, glyceraldehyde phosphates, xylulosphosphates, ribosphosphates, phosphosphosphates, ribosphosphates phospho-serine, Aspartyl phosphate and adenosin phosphate.
[0055] [00055] One of the main advantages of these molecules is the fact that they are already available in nature and that the environmental impact is already known. These molecules form, as long as there is life on earth, one of the most important structures to ensure the storage / energy supply of all living cells. The fact that these components are used in living cells ensures that they are suitable for moderate temperatures, pressure and pH.
[0056] [00056] These properties make them suitable for heat processes in ambient circumstances as provided in the different embodiments of the present invention.
[0057] [00057] In another embodiment of the present invention, linear polyphosphoric acids and / or their salts are represented by the following formula: Mn + 2PnO (3n + 1) (Ib) with n = at least 2; specifically 1 to 10E6; more specifically 2 to 5; M is H + or a metal cation, specifically a monovalent metal cation, even more specifically K or Na; In another embodiment of the present invention, cyclic polyphosphoric acids and / or their salts are represented by the following formula: MnPnO3n (Ic) with n = at least 3; specifically 1 to 12; more specifically 3, 4, 5 or 6; M is H + or a metal cation, specifically a monovalent metal cation, even more specifically K or Na; In the methods of the present invention, the reaction products can be a mixture comprising any combination of the products described above.
[0058] [00058] In the thermal energy storage method, reversible chemical hydrolysis and condensation reaction which are exo and endothermic, respectively, are combined with heat capture / storage, heat transport and heat generation processes to explore the storage / energy supply capacity of the aforementioned molecules.
[0059] [00059] Thus in an additional embodiment, the present invention provides a method for storing thermal energy, said method comprising the condensation reaction as represented in step (2) of Figure 1, hereinafter also referred to as a polymerization of inorganic oxyacids. and / or its salts, using an external heat source.
[0060] [00060] Any available heat source can be used in the methods of the present invention. A typical heat source includes heat captured from solar radiation, and heat remaining from the industry. Through the polymerization reaction of inorganic oxyacids and / or their salts, the thermal energy of the heat source is transformed into molecular reaction heat, that is, in a high energy covalent bond, as found in inorganic oxyacids and / or their salts formulas (I), (Ia), (Ib) and (Ic); also referred to as 'polymerized compounds'.
[0061] [00061] The high energy bonds bound in inorganic - oxygen - covalent inorganic and specifically the bonds of phosphorus -oxygen - high energy phosphorus provide a storage of thermal energy in a molecular form with an energy density of approximately 400 kJ / kg - See table 1. In table 1 the heat of solution is not incorporated, in case, for example, an inorganic oxoacid or polyphosphoric acid is used, the heat of solution comes above said reaction heats. For example, in the case of polyphosphoric acids, the energy density can be> 1 GJ / m3 depending on the degree of polymerization and temperature levels.
[0062] [00062] In the said high energy molecular form, a previous continuous heat flow can be stored / transported under ambient circumstances. This consequently generates a method to store a continuous heat generation process in a discontinuous or displaced consumption. This can, for example, be implemented to store wind energy on a stormy night with electrical resistance in captured heat and release heat at the peak of the morning generating steam or ORC as presented in applications 7 & 9.
[0063] [00063] In the aforementioned method of storing thermal energy, the 'polymerized compounds' are optionally removed from the aqueous reaction solution and stored. The aqueous reaction solution used in the methods of the present invention is determined by, among others, the nature of the components used to catalyze the transformation, hereinafter also referred to as the transformation components or conditioning components, and known to those skilled in the art. For example, when enzymes are used to catalyze the transformation, the aqueous reaction solution will be an appropriate buffering solution, such as, for example, the use of a solution with 5 mg / l of dephosphorylase extracted from Escherichia coli; when living cells are used to catalyze the transformation, an appropriate cell culture medium will be used instead. The living cells used to catalyze the transformation typically consist of microorganisms such as, for example, bacteria, for example, salmonella, legionella or Escherichia coli, known to absorb heat by dehydrolysing inorganic phosphate and being phosphorylated compounds.
[0064] [00064] Changes in the concentration of the solvent, that is, changes in the concentration of water in the case of an aqueous solution, or of components present in the solvent, for example, but not limited to metal ions, or of increasing concentration of the reaction components, such as evaporation in the case of an aqueous solution or extraction of the water with organic solvents such that the solvent is first evaporated together with the water and secondly condensed, to be separated in a third stage of solvent by, for example, a gravimetric liquid for liquid phase separation, to influence, trigger, catalyze or inhibit the reaction.
[0065] [00065] Alternatively, changes in the concentration of protons can also be used to catalyze the transformation of thermal energy in the aforementioned high-energy covalent bonds. The proton concentration can be influenced by chemicals, for example, specially designed acids and / or bases, compounds that contain steric acid - base functions, or by the use of semipermeable membranes.
[0066] [00066] Typical examples include, for example, HCl as a chemical (for example, commercially available at 30-40% by weight in water) to increase the concentration of protons.
[0067] [00067] As proton membranes, one can take a PEM or "commercially available proton exchange membranes", for example used in hydrogen fuel cells, which include, but are not limited to, one of the following membranes: Nafion®; Solopor®, Toyota PEM, 3M PEM ..., and the like.
[0068] [00068] The removal of the polymerized compounds from the reaction solution can be done in different process steps, including, for example, a membrane separation step based on the size of the molecules. In said embodiment, the transformation components are preferably much larger than the polymerized compounds and can easily be separated from each other. For example, when enzymes are used to catalyze the transformation, ultrafiltration membranes or nanofiltration membranes, respectively with a mesh size of approximately 10-100 nm and 1-10 nm, are used. For a very large complex structure, microfiltration can also be used (> 100 nm). The mesh size of the membranes are dependent on the structure and / or molecular weight of the enzyme. Depending on the products used and the reaction circumstances, different types of commercially available membranes can be chosen. See table 2 for different possible examples.
[0069] [00069] In addition to the membrane filtration separation technique as described above under nanometer and microfiltration, other means for separating the polymerized compounds from the reaction solution are known to those skilled in the art and include, for example, property-based separation techniques electrical or magnetic, for example, large (enzyme) complexes to separate in an electric / magnetic field, separation techniques based on density by centrifugal forces or by sedimentation, based on precipitation, or phase transition from liquid to solid followed by solid liquid separation, or by sticking products to gels, evaporating water from the reaction solution and more.
[0070] [00070] It is therefore an additional object of the present invention to provide the use of 'polymerized compounds', to store / transport thermal energy at room temperature. This consequently generates the use of 'polymerized compounds' in a method to store a process of continuous heat generation in a discontinuous consumption.
[0071] [00071] As the objective is to provide an alternative energy source, that is, to convert a continuous heat generation process into a discontinuous heat release system, the present invention still provides the means to release the heat from the polymerized compounds , said method comprising the hydrolysation reaction as represented in step (1) of Figure 1, hereinafter also referred to as a hydrolysation of inorganic oxyacids and / or their salts, and using the thermal energy released by said exothermic reaction as a source of heat.
[0072] [00072] As for the polymerization reaction, above, the reaction conditions for the hydrolyzation reaction will be determined, among others, by the nature of the components used to catalyze the transformation (transformation components) and are known to those skilled in the art, in other words and as apparent from the examples hereinafter, there is a conditional flow of feed 21 to optimize the reaction conditions for the hydrolyzation reaction. For example; when enzymes are used to catalyze the transformation, an appropriate buffering solution, such as, for example, the use of a solution with 5 mg / l of 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. The living cells used to catalyze the transformation, typically consist of microorganisms such as, for example, bacteria, for example, salmonella, legionella or Escherichia coli. The cells generate heat by hydrolyzing phosphorylated compounds.
[0073] [00073] Changes in the concentration of the solvent can be used, that is, changes in the concentration of water in the case of an aqueous solution, or of components present in the solvent such as, for example, but not limited to metal ions, cells, enzymes, etc., or by increasing the concentration of the reaction components, such as evaporation in the case of an aqueous solution or extracting the water with organic solvents such that the solvent is first evaporated together with the water and secondly condensed, to be separated in a third stage of the solvent by, for example, a gravimetric liquid for liquid phase separation, to influence, activate, catalyze or inhibit the reaction.
[0074] [00074] Alternatively, chemicals and proton exchange membranes can also be used to catalyze the transformation of thermal energy in the aforementioned high-energy covalent bonds. The concentration of protons can be influenced by chemicals, or by the use of semipermeable membranes.
[0075] [00075] Typical examples include, for example, NaOH as a chemical (for example, commercially available at 50% by weight in water) to decrease the concentration of protons.
[0076] [00076] As proton membranes, one can take a PEM or "Proton exchange membranes", commercially available, for example, used in hydrogen fuel cells, which include, but are not limited to, one of the following membranes: Nafion®; Solopor®, Toyota PEM, 3M PEM ..., and the like.
[0077] [00077] Again the polymerized compounds are optionally removed from the reaction medium using procedures known in the art, as provided for the polymerized compounds above. In said form, hydrolyzed compounds, that is, which comprise the hydroxyl group capable of forming inorganic polyoxoacid compounds or their salts or nitrogen, sulfur or phosphorus can be used as the source material in the dehydrolysis reaction (supra) .
[0078] [00078] Of course, the systems (installations) that use the CHEMENERGY cycle as described here, are also within the scope of this application. In a first aspect, such systems can be systems for capturing or storing energy, characterized by comprising a capture means for capturing energy from a heat source using the polymerization reaction (condensation) as described here (represented as A in the applications below); and a storage medium for storing the captured energy in the form of the reaction products of said condensation reaction. Said heat-trapping means includes 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 endothermic condensation reaction carried out on said mixture of reaction, and comprising a heating element in thermal communication with said vessel.
[0079] [00079] In a second aspect, such systems could be systems to release the thermal energy stored in the reaction products of the condensation reaction according to the present invention, characterized by the fact that it comprises a release means to release the captured energy and stored in the reaction products of the condensation reaction according to the present invention by means of an exothermic hydrolysis step (represented as C in the applications below). Said means for releasing energy includes at least one reaction vessel for a reaction mixture comprising an inorganic oxoacid compound and / or its salt as described herein, suitable for having an exothermic hydrolysation reaction and comprising a heating element in thermal communication with said vessel.
[0080] [00080] In an additional aspect the system includes both a means to capture energy from a heat source using the polymerization reaction (condensation) as described here (represented as A in the applications below) and a means to release the captured and stored energy in the reaction products of the condensation reaction according to the present invention, by means of an exothermic hydrolysis step (represented as C in the applications below). Such a system that has both means (A) and (C) allows heat with a low exergy status and used to trigger the endothermic condensation reaction (A) to be pumped to a higher exergy status in the exothermic hydrolyzation reaction. (C), that is, in the establishment of a heat pump using the CHEMENERGY cycle of the present invention.
[0081] [00081] In a specific embodiment, the systems for releasing thermal energy from the reaction products of the condensation reaction of the present invention, may also comprise a heat exchanger (represented as B in the applications below). This heat exchanger will be used to increase the temperature of the reaction products of the condensation reaction fed to the reaction mixture used in the exothermic hydrolyzation reaction (C). Without being limited to this, the temperatures used vary from approximately 60 ° -500 ° C; typically approximately 120 - 500 ° C, and more specifically approximately 150 - 300 ° C.
[0082] [00082] This invention will be better understood with reference to the Experimental Details which follows, but those skilled in the art will readily appreciate that these are only illustrative of the invention as more fully described in the claims which follow later. In addition, throughout this request, several publications are cited. The description of these publications is hereby incorporated by reference in this application to more fully describe the modern best practice to which this invention belongs. EXAMPLE
[0083] [00083] Example 1 - phosphate / polyphosphate esters Energy Density
[0084] [00084] The hydrolysis of a phosphorus compound has a reaction energy of approximately 150-500 kJ / kg depending on the reaction conditions. Typically, the proposed components have an energy density of 400-1000 MJ / m3. When higher temperature sources, such as the sun, are used, it is possible, for example, to condense (dehydrolyze) the phosphoric acid until dry P2O5 is achieved, which has an energy density of approximately 3000 MJ / m3 .
[0085] [00085] Compared to other heat storage materials, the heat capacity of the polymerized compounds claimed here is substantially higher. For example, the paraffin phase change reaction provides 20-90 kJ / kg depending on the reaction conditions (copyright @ 2002 John Wiley & Sons, Ltd.). Dissolving sulfuric acid in water provides a reaction heat of 300-400 kJ / kg depending on the reaction conditions (Chemical and engineering thermodynamics Stanley I. Sandler copyright @ 1989 John Wiley & Sons, Ltd.). The only exception being the crystallization of Na acetate which provides 400 MJ / m3, but requires a phase transition during heat conversion. Products Used
[0086] [00086] The cycle described here has its energy derived from chemical energy: CHEMENERGY. It uses molecules that can be phosphorylated, nitrolyzed or sulfonized or hydrocarbons (PHs) or inorganic (poly) phosphates (IPs), poly phosphoric acids, or inorganic oxoacid compounds and / or their salts of or nitrogen, sulfur, 1. Nucleotides: consist of any combination of different nitrogenous bases and different sugars (pentoses) and can have mono-, di- and tri-phosphate (s) as a phosphoryl group.
[0087] [00087] As bases one could take: Purine, Pyrimidine, Adenine, Guanine, Thymine, Cytosine, Uracil, Hypoxanthine, 5-methylcytosine, N6-methyladenine, dihydrouracil, 1-methylguanine, ribotimidimine, pseudouridine, 1-methyliosine,. ..
[0088] [00088] As sugars (pentose) one could take fructose, ribose, D-ribofuranosis, 2-deoxy-D-ribofuranosis, ... 2. Nucleic acids: these can consist of any combination of different nucleotides. The nucleotides are linked by phosphate bonds between 2 bases in the nucleic acids. 3. Most of the energy molecules found in all living cells: Phosphophenolpyruvate, Glyceratel, 3 bi phosphate, Formyl phosphate, Acetyl phosphate, Propionyl phosphate, Butyryl phosphate or other carboxyl phosphates, Phospho-creatine, Phospho-arginine, Phosphates of glucose (1 or 6-phosphate), fructose phosphates, Glycerol-3-phosphate, Nicotine amide adenine dinucleotide phosphate (NADP), dihydroxyacetonephosphate, glyceraldehyde phosphate, xylulosphosphate, ribosphosphate phosphate, serosephosphate Aspartyl phosphate and adenosin phosphate. 4. Inorganic polyphosphoric acids and their salts. 5. Inorganic (poly) nitrates such as cellulose, ... 6. (Poly) sulfates and inorganic sulfonates.
[0089] [00089] It is not the Phosphorylation process or the condensation or polymerization process as such or the esterification process in living cells that is claimed, but the condensation and specifically the condensation process of phosphoric acid and / or polyphosphoric acids and / or its salts in combination with heat storage, heat pump, transport and generation processes in industrial applications which is called the "Chemenergy cycle".
[0090] - Um exemplo de uma grande escala pode ser uma grande rede industrial ou residencial de vizinhanças (cidade) ou apartamentos conectados no mesmo sistema de aquecimento que obtém calor de calor de desperdício industrial armazenado com o ciclo chemenergy, transportado por tubulações e cargas brutas. - Um exemplo de uma pequena escala pode ser a utilização dentro de uma casa/fazenda com pequenas capacidades de geração de calor, como, por exemplo, sistema solar/esterqueira/fossa, e um pequeno patim de Chemenergy para aperfeiçoar o desempenho de calor. O Processo Geral do Processo de "CHEMENERGY" (Figura 1)Armazenamento de Calor 1. Armazenamento 1.1 de componentes hidrolisados 2. Seção de condicionamento 1: adicionar enzimas, íons, células, substâncias frescas. 3. Armazenamento 1.2 de produtos de condicionamento. 4. Seção de reação 1: utilização de calor térmico para polimerizar os componentes pela, mas não limitado a, remoção, extração ou evaporação de água da solução. 5. Seção de separação 1: utilização de diferentes técnicas e etapas de separação para separar os componentes polimerizados dos produtos de condicionamento, refugo, enzimas, agentes de separação de enzima e solventes (ou especificamente água). 6. Armazenamento 1.3 de componentes polimerizados. Liberação de Calor 1. Armazenamento 2.1 de componentes polimerizados 2. Seção de condicionamento 2: adicionar enzimas, íons, células, substâncias frescas, água. 3. Armazenamento 2.2 de produtos de condicionamento. 4. Seção de reação 2: utilização de dissipador de calor (demanda de calor) para hidrolisar os componentes pela, mas não limitado a, adição de pequenas quantidades, por exemplo, 1-10% de água (solução de condicionamento) ou na fase líquida ou de vapor. 5. Seção de separação 2: utilização de diferentes técnicas e etapas de separação para separar os componentes polimerizados dos produtos de condicionamento, refugo, enzimas, agentes de separação de enzima e solventes (ou especificamente água). 6. Armazenamento 2.3 de componentes hidrolisados. O PROCESSO DE "CHEMENERGY" COM COMPOSTOS FOSFORILADOS (Figura 2)Loop de Captura de Calor1. Armazenamento de fluxos de alimentação.2. Condicionamento dos fluxos de alimentação adicionando de armazenamento de tamponamento. Fatores importantes para influenciar as reações são entre outros pH, concentração de íons (Ca2+, Mg2+, K, Na, Cl-, Pi, ácidos, ....) enzimas, células, água, solventes, temperatura & muitos outros.3. Reação: reação de condensação para formar ácido polifosfórico ou seu sal absorvendo calor, por exemplo, mas não limitado a, diminuindo a concentração de água, tal como, por exemplo, extraindo, removendo e/ou evaporando a água.4. Separação de componentes: a separação pode ser feita em diferentes etapas de processo. Uma técnica de separação específica é a separação de membrana, com base no tamanho e/ou polaridade das moléculas. Por exemplo, os componentes maiores não podem passar pela membrana, os componentes menores podem. - Separação de membrana 1a: Ultrafiltração, ATPase (ou parte de ATPase) e agentes de separação AT(D)P são separados do restante. (tabela 2, MWCO < 2000, pH < 7). - Separação de membrana 1b: Ultrafiltração, separação de agentes de separação de ATP de ATPase ou parte desta enzima. (tabela 2, MWCO < 100.000, pH < 7) - Separação de membrana 2: Nanofiltração, separação de água. (tabela 2, MWCO < 100, pH < 7). - Separação de membrana 3: Membrana de troca de íons, separação de íons. (tabela 2, MWCO < 500.000, pH < 7). 5. Armazenamento e transporte sob circunstâncias ambientes.[00090] All modes can be used on a large scale or on a very small scale. - An example of a large scale can be a large industrial or residential network of neighborhoods (city) or apartments connected in the same heating system that obtains heat from industrial waste heat stored with the chemenergy cycle, transported by pipes and gross loads. - An example of a small scale could be the use inside a house / farm with small heat generation capacities, such as, for example, solar / dung / pit system, and a small Chemenergy skid to improve the heat performance. The General Process of the "CHEMENERGY" Process (Figure 1) Heat Storage 1. Storage 1.1 of hydrolyzed components 2. Conditioning section 1: add enzymes, ions, cells, fresh substances. 3. Storage 1.2 of conditioning products. 4. Reaction section 1: use of thermal heat to polymerize components by, but not limited to, removing, extracting or evaporating water from the solution. 5. Separation section 1: use of different separation techniques and steps to separate the polymerized components from conditioning products, refuse, enzymes, enzyme separation agents and solvents (or specifically water). 6. Storage 1.3 of polymerized components.Heat Release 1. Storage 2.1 of polymerized components 2. Conditioning section 2: add enzymes, ions, cells, fresh substances, water. 3. Storage 2.2 of conditioning products. 4. Reaction section 2: use of heatsink (heat demand) to hydrolyze components by, but not limited to, adding small amounts, for example, 1-10% water (conditioning solution) or in the phase liquid or steam. 5. Separation section 2: use of different separation techniques and steps to separate the polymerized components from conditioning products, scrap, enzymes, enzyme separation agents and solvents (or specifically water). 6. Storage 2.3 of hydrolyzed components.THE "CHEMENERGY" PROCESS WITH PHOSPHORILATED COMPOUNDS (Figure 2) Heat Capture Loop 1. Storage of feed streams. 2. Conditioning of feed streams by adding buffering storage. Important factors to influence the reactions are, among others, pH, ion concentration (Ca2 +, Mg2 +, K, Na, Cl-, Pi, acids, ...) enzymes, cells, water, solvents, temperature & many others. 3. Reaction: condensation reaction to form polyphosphoric acid or its salt by absorbing heat, for example, but not limited to, decreasing the water concentration, such as, for example, extracting, removing and / or evaporating water. 4. Separation of components: separation can be done in different process steps. A specific separation technique is membrane separation, based on the size and / or polarity of the molecules. For example, the larger components cannot pass through the membrane, the smaller components can. - Membrane separation 1a: Ultrafiltration, ATPase (or part of ATPase) and AT (D) P separation agents are separated from the rest. (table 2, MWCO <2000, pH <7). - Membrane separation 1b: Ultrafiltration, separation of ATP separation agents from ATPase or part of this enzyme. (table 2, MWCO <100,000, pH <7) - Membrane separation 2: Nanofiltration, water separation. (table 2, MWCO <100, pH <7). - Membrane separation 3: Ion exchange membrane, ion separation. (table 2, MWCO <500,000, pH <7). 5. Storage and transportation under ambient conditions.
[0091] [00091] In some applications, steps 2 & 3 of the loop described above can be done simultaneously, for example, the concentration increase and the heat absorption reaction phase both using heat respectively to evaporate the solvent and to polymerize the components hydrolyzed.
[0092] - Separação de membrana 4a: Ultrafiltração, ATPhidrolase (ou parte de ATPhidrolase) e agentes de separação AD(T)P são separados do restante. (tabela 2, MWCO < 2000, pH > 7). - Separação de membrana 4b: Ultrafiltração, ATPhidrolase (ou parte de ATPhidrolase) separados de agentes de separação AD(T)P. (tabela 2, MWCO < 100.000, pH > 7). - Separação de membrana 5: Nanofiltração, separação de água. (tabela 2, MWCO < 100, pH > 7). - Separação de membrana 6: Membrana de troca de íons, separação de íons. (tabela 2, MWCO < 500.000, pH > 7). - Outras sequências de etapas de separação podem ser feitas com o mesmo efeito. 5. Armazenamento e transporte sob circunstâncias ambientes.[00092] Even more so in some applications where water is separated from the solution, steps 3 & 4 are combined in order to trigger the reaction towards the polymerized components. The separation technique can be, but is not limited to, evaporation of water; or an organic solvent together with small fractions of water and then condensed to be separated from the solvent by gravimetric liquid for liquid extraction. Heat release process loop: 1. Storage of feed streams. 2. Conditioning of feed streams by adding buffering storage. Important factors to influence the reactions are, among others, pH, ion concentration (Ca2 +, Mg2 +, K, Na, Cl-, Pi, acids, ...) enzymes, cells, water, solvents, temperature & many others. 3. Reaction: Hydrolysis with heat release adding water or other hydrolysing agents, either in the liquid or vapor phase. 4. Separation of components: separation can be done in different process steps. A specific separation technique is membrane separation, based on the size and / or polarity of the molecules. For example, the larger components cannot pass through the membrane, the smaller components can. - Membrane separation 4a: Ultrafiltration, ATPhydrolase (or part of ATPhydrolase) and AD (T) P separation agents are separated from the rest. (table 2, MWCO <2000, pH> 7). - Membrane separation 4b: Ultrafiltration, ATPhydrolase (or part of ATPhydrolase) separated from AD (T) P separation agents. (table 2, MWCO <100,000, pH> 7). - Membrane separation 5: Nanofiltration, water separation. (table 2, MWCO <100, pH> 7). - Membrane separation 6: Ion exchange membrane, ion separation. (table 2, MWCO <500,000, pH> 7). - Other sequences of separation steps can be done with the same effect. 5. Storage and transportation under ambient conditions.
[0093] [00093] In some applications, steps 2 & 3 of the loop described above can be done simultaneously, for example, conditioning of, for example, pH could be necessary to keep the reaction going. In the case where the second hydrolyzation component is water, separation of the components will not be necessary.
[0094] 1.1 Produto de reação de temperaturas 1 em: 20°C (armazenamento ambiente) 1.2. Entrada de calor de reação de temperaturas 1 > 50°C e de preferência > 70°C: especificamente > 80°-100°C; mais especificamente > 140°C: vindo de calor de refugo industrial disponível. 1.3. Produto de reação de temperaturas 2 em: pelo menos 20°C (armazenamento ambiente ou temperaturas mais altas. 1.4 Saída de calor de reação de temperaturas 2 > 40°C: servida de um sistema de aquecimento central 2. Concentração de reação 1 em pH < ou > 7 + íons na água a 80°C e concentração de água, por exemplo < 30% e de preferência < 10%; especificamente < 15% e mais especificamente < 5-10% ou menor.3. Concentração de reação 2 em pH > ou < 7 + íons na água a 90°C e concentração de água, por exemplo, > 30%. Nem todos os subcomponentes como a AMP, Pirofosfato, íons etc., são aqui mostrados.4. Como ATP e ADP todos os outros tipos de fosfatos ou polifosfatos dos componentes descritos nesta invenção podem ser utilizados também; especificamente, os hidrocarbonetos fosforilados, oxiácido inorgânicos de fósforo ou ácidos polifosfóricos mais específicos e/ou seus sais.5. Nem todos os fluxos de interconexão estão mostrados, mas as principais conexões mostradas são suficientes para mostrar a funcionalidade para alguém versado na técnica.6. Bombas, Válvulas, tubulações e outras especificações de equipamento de processamento padrão não estão indicadas.7. Pressões dependendo de queda de pressão sobre membranas e quedas de pressão de tubulação. A serem projetadas dependendo do tamanho e geometria.8. Materiais de equipamento a serem escolhidos com atenção para as circunstâncias de meio (principalmente acionado por pH). Materiais de equipamento & tubulação de Hastelloy ou duplex são adequados para a aplicação aqui descrita. Outros materiais (aço carbono, aço inoxidável ou outras ligas), que resistem às circunstâncias de meio, a serem tomados em função de presos de material e vida útil desejada.[00094] Additional details in Figure 2 can be specifically: 1. At the following temperatures the cycle was operated: 1.1 Temperature reaction product 1 in: 20 ° C (ambient storage) 1.2. Reaction heat input from temperatures 1> 50 ° C and preferably> 70 ° C: specifically> 80 ° -100 ° C; more specifically> 140 ° C: coming from available industrial waste heat. 1.3. Temperature reaction product 2 in: at least 20 ° C (ambient storage or higher temperatures. 1.4 Reaction heat output from temperatures 2> 40 ° C: served by a central heating system 2. Reaction concentration 1 at pH <or> 7 + ions in water at 80 ° C and water concentration, for example <30% and preferably <10%; specifically <15% and more specifically <5-10% or less. 3. Reaction concentration 2 at pH> or <7 + ions in water at 90 ° C and water concentration, for example,> 30%. Not all subcomponents like AMP, Pyrophosphate, ions, etc. are shown here. 4. As ATP and ADP all other types of phosphates or polyphosphates of the components described in this invention can be used as well; specifically, phosphorylated hydrocarbons, inorganic phosphorus oxyacids or more specific polyphosphoric acids and / or their salts. 5. Not all interconnection flows are shown, but the main connections shown are sufficient to show functionality to someone skilled in the art. 6. Pumps, valves, piping and other specifications of standard processing equipment are not indicated. 7. Pressures depending on pressure drop on membranes and pipeline pressure drops. To be designed depending on size and geometry. 8. Equipment materials to be chosen with attention to the medium circumstances (mainly pH driven). Hastelloy or duplex piping & equipment materials are suitable for the application described here. Other materials (carbon steel, stainless steel or other alloys), which withstand the circumstances of the medium, to be taken due to the material stuck and desired life.
[0095] - Muitos dos materiais utilizados tem rotas sendo arquivadas por, por exemplo, companhias farmacêuticas utilizando os PHs para testar medicamentos in vitro em ATP ou outros nucleotídeos. Estes processos são principalmente para uma produção de pequena escala e, por exemplo, aplicação de ciclo de calor de unidade única. - Existem também materiais que podem ser criados combinando produtos químicos comercialmente disponíveis como, por exemplo, Ácido Acético e Ácido Fosfórico para produzir acetilfosfato. Estas matérias primais podem ser utilizada para ciclos de calor de grande escala. - Utilização de ácido (poli)fosfórico comercialmente disponível, de preferência de qualidade quimicamente pura, tipicamente 70% - 85% de H3PO4. [00095] The raw materials for this process can be produced in different ways. One could extract the biomass or chemical components available and available chemical reaction routes. - Many of the materials used have routes being filed by, for example, pharmaceutical companies using PHs to test drugs in vitro on ATP or other nucleotides. These processes are mainly for small scale production and, for example, single unit heat cycle application. - There are also materials that can be created by combining commercially available chemicals such as Acetic Acid and Phosphoric Acid to produce acetylphosphate. These raw materials can be used for large-scale heat cycles. - Use of commercially available (poly) phosphoric acid, preferably of chemically pure quality, typically 70% - 85% H3PO4.
[0096] [00096] Specific to this cycle is the use of phosphorylated hydrocarbons or inorganic (poly) phosphoric acids and / or their salts. PH regulation
[0097] 1. Misturar água e ácido Polifosfórico a 20°C e pressão ambiente. Com base no balanço de calor abaixo detalhado, a temperatura aumentará para aproximadamente 95°C, agitar a mistura. 2. Estabelecer um vácuo acima da mistura quente, manter a mistura quente com resistência elétrica e remover a água evaporada com um condensador de ar. A duração desta etapa de evaporação (separação) será dependente da quantidade de água a ser removida, mas é provável durar por aproximadamente 1 hora. 3. Resfriar a mistura de polifosfato com ar ambiente para 25°C. Retornar para a etapa 1 e o loop está fechado. [00097] In the Chemenergy cycle, the conditioning of feed flows for both the Heat Storage and Heat Release part, includes pH regulation. Any known method for regulating the pH in a feed stream can be used, and includes, for example, the application of a "proton exchange membrane" (PEM), such as, for example, the commercially available Nafion®; Solopor®, the Toyota PEM or 3M PEM. Said membranes transport protons unidirectionally and selectively to the cathode (negative side) of the membrane. Alternatively, the pH is regulated using specific acid / base complexes or chemicals as a pH regulator, and includes, for example, the application of HCl or NaOH. EXAMPLE 2 - LABORATORY TEST OF THE CHEMENERGY PROCESS IN DIFFERENT STARTING CONDITIONS 2.1. Starting with the heat release process loop at room temperature 1. Mix water and polyphosphoric acid at 20 ° C and ambient pressure. Based on the heat balance detailed below, the temperature will rise to approximately 95 ° C, stir the mixture. 2. Establish a vacuum above the hot mixture, keep the mixture hot with electrical resistance and remove evaporated water with an air condenser. The duration of this evaporation step (separation) will depend on the amount of water to be removed, but it is likely to last for approximately 1 hour. 3. Cool the polyphosphate mixture with room air to 25 ° C. Return to step 1 and the loop is closed.
[0098] [00098] If the mass% of the mixture is 90% polyphosphoric acid mixed with 10% water, a reaction heat of 300 kJ / kg and a total average mixing heat capacity (Cp) of 1.5 kJ / kgK , Delta T, can be calculated from a simple heat balance as follows; Heat of Reaction = (Mass) x (Cp) x (Delta T). With this, Delta T = (Reaction Heat) / [(Cp) x (Mass)]
[0099] [00099] Using the Reaction Heat, Cp and Mass mentioned above, the change in temperature / kg will be 75 ° C. In other words, the mixture will increase from 25 ° C to just under 100 ° C. 2.1.1. Conclusion to the CHEMENERGY process when starting at room temperature
[0100] [000100] Notwithstanding the fact that in this case the reaction loop is closed, thermodynamically this does not make sense due to the fact that the heat generated in step 1, is counterbalanced by the energy required to evaporate the water from the mixture in step 2. For reasons, and as explained herein, the CHEMENERGY process of the present invention is specifically useful in combination with an external heat source, such as, for example, waste heat from industrial processes. Under these circumstances and as explained in 2.3. Below, the heat release process loop can start at, for example, the remaining industrial heat level, for example, between 50 ° C - 200 ° C and more specifically between 80 - 150 ° C, but you can also start with higher temperatures, such as 300 ° C, if desired. 2.2. Starting with the heat release process loop at the remaining industrial heat temperature
[0101] 1. Misturar água e Polifosfatos a 90°C sob uma pressão de 600 KPa (6 bar). Em analogia com 2.1 acima um Delta T de 75°C era esperado e a temperatura subiu para aproximadamente 165°C enquanto agitando a mistura continuamente. 2. A mistura foi resfriada com ar ambiente para aproximadamente 90°C. Isto deve ser comparado com a liberação na direção de um processo. 3. A pressão acima da mistura quente foi liberada até que a água evaporou, enquanto mantendo a mistura quente com água de 90°C e removendo a água evaporada com um condensador de ar. A duração desta etapa de evaporação (separação) será dependente da quantidade de água a ser removida, mas durou por aproximadamente 1 hora. 4. A mistura foi pressurizada até 600KPa (6 bar), e a água evaporada é reutilizada na etapa 1, fechando o loop do processo de CHEMENERGY. O aumento de temperatura foi de aproximadamente 30-50°C. [000101] With this experiment the objective was to pump heat from a temperature level to a higher level. The temperature level of step one in test 1 was 90 ° C, this is the average temperature level which is referred to in the waste heat industry, namely 60 - 120 ° C. For example, the oil cooling level for a diesel engine is approximately 90 ° C. Steps 1-4 were tested 10 times one after another to prove cyclicity and / or reversibility. 1. Mix water and polyphosphates at 90 ° C under a pressure of 600 KPa (6 bar). In analogy with 2.1 above a Delta T of 75 ° C was expected and the temperature rose to approximately 165 ° C while stirring the mixture continuously. 2. The mixture was cooled with room air to approximately 90 ° C. This must be compared to the release in the direction of a process. 3. The pressure above the hot mixture was released until the water evaporated, keeping the mixture hot with water at 90 ° C and removing the evaporated water with an air condenser. The duration of this evaporation step (separation) will depend on the amount of water to be removed, but it lasted for approximately 1 hour. 4. The mixture was pressurized to 600KPa (6 bar), and the evaporated water is reused in step 1, closing the CHEMENERGY process loop. The temperature increase was approximately 30-50 ° C.
[0102] [000102] In this second case, as the remaining heat is used for the evaporation step, only a limited amount of additional energy is required to pressurize the mixture. Consequently, part of the remaining heat with a low exergy status (at 90 ° C) is pumped to a higher exergy status of approximately 165 ° C. In this laboratory configuration, the experiment only served to pump hot water from 90 ° C to hot air of 165 ° C. But one can imagine that if we use other fluids, and / or heat sources, the present cycle allows the creation of heat pumps to generate or enhance the remaining heat in the direction of energy and / or useful heat. For example, the CHEMENERGY process of the present invention could be used to trigger chemical reactions in a chemical plant at 120-130 ° C which are now triggered by high temperature steam, for example, 600-1000 KPa (6-10 bar), using remaining steam of 100-200 KPa (1-2 bar) instead.
[0103] [000103] This is the combination of the increase in temperature, caused by the hydrolysis reaction of inorganic oxyacids and / or their salts, specifically inorganic polyphosphoric acids and / or their salts, with the presence of a heat source; energy that can give rise to much higher temperature increases, for example,> 200 ° C, thus resulting in a total increase in thermal energy. As will be apparent from the following exemplary applications of the CHEMENERGY cycle in different environments, the heat source is on the one hand used to remove water 20 from reaction product 14 from the hydrolyzation reaction (C), that is, in other words to trigger the polymerization reaction (condensation) (A); and on the other hand, to increase the thermal energy of the condensed (polymerized) components 10 used in the hydrolyzation reaction (C).
[0104] [000104] In the list below 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 10 of general formula Ib and Ic above (polymer lengths are generally> 1, and typically approximately 2-7), by removing water 20 under the influence of the heat / energy source. The water obtained from this polymerization (condensation reaction) can be (re) used in the reverse reaction, that is, in the hydrolysis reaction, possibly after conditioning with conditioning components 21 or blown into the atmosphere. Depending on the energy source, the polymerization reaction is carried out under vacuum, near vacuum or a small overpressure. For heat sources starting at approximately 140 ° C a small overpressure is desired, typically 10-50 KPa (0.1 -0.5 barg), but sometimes higher due to specific operating demands. For heat sources up to approximately 80 ° C, a sub-pressure is desired, typically> 2.5 KPa (0.025 bar) or less. For heat sources between and approximately 80 ° C to 140 ° C, the pressure ranges from a slight underpressure of ± 2.5 KPa (0.025 bar) to plus or minus 1 atm. Of course, from the above and as part of the CHEMENERGY cycle, the polymerization reaction is carried out at lower temperatures ranging from approximately 80 - 200 ° C, but typically from 90 -120 ° C.
[0105] [000105] In the reverse reaction, that is, the hydrolysis reaction (C), said liquid mixture of polyphosphoric acids 10 is used as a hydrolyzed polymer (addition of water) under pressure in the direction of phosphoric acid 14 and some remains of acids polyphosphoric in an exothermic reaction with the release of heat raising the initial remaining heat to a higher energy level. Again, the phosphoric acid can be (re) used as a feed stream in the condensation reaction (A) mentioned above, thus closing the CHEMENERGY cycle according to the present invention. In the hydrolyzation reaction, water can be added as hot water, or as a liquid or vapor. When in the form of steam, this gives an extra boost to the hydrolysis reaction due to the extra added condensation heat when mixing the steam with the polyphosphoric acids. In principle, the hydrolyzation reaction can be carried out at ambient temperatures, but when used as a temperature increase (heat pump) to increase the thermal energy of a source, it is carried out at higher temperatures, for example, but not limited to 60 ° -500 ° C; typically 120-500 ° C, and more specifically approximately 150 - 300 ° C. In this case, and as previously explained here, the heat / energy source will also be used to increase the thermal energy of the condensed (polymerized) components (10) used in the hydrolysis reaction (C).
[0106] [000106] Evidently, the core in the aforementioned CHEMENERGY process is the reversibility of the hydrolyzation reaction of polyphosphoric acids versus phosphoric acids. So in principle phosphoric acids can be used in a closed cycle, but as some irreversible side reactions could occur, some spillage (waste) and a new feed of phosphoric acids could be needed to maintain optimum performance. Consequently, the concentrations of phosphoric acid are quite stable throughout the cycle with concentrations ranging from approximately 80 - 90%; specifically approximately 84 - 94% after hydrolysis and approximately 90 - 100%; specifically approximately 94 - 100% before hydrolysis.
[0107] - Aplicação 1 (Figura 3): bomba de calor para valorizar o calor restante, em aquecimento/resfriamento de processo, armazéns, áreas residenciais, supermercados, etc., utilizando calor restante de outro processo, ambiente, sol, vento, e similares, - Aplicação 2 (Figura 4): bomba de calor entre redes de calor, para aumentar a energia térmica de um nível de temperatura/pressão de fluido de calor como, por exemplo, vapor, água, óleo térmico, ..., para um nível de temperatura/pressão mais alto de um fluido de calor como, por exemplo, vapor, água, óleo térmico, ..., - Aplicação 5 (Figura 5): utilização de tecnologia de bomba de calor para gerar frio, com, por exemplo, altas temperaturas ambientes, para o resfriamento de processos industriais, armazéns, supermercados, refrigeradores, casas, áreas residenciais etc., com calor restante de processos, ambiente, sol, vento, energia térmica combinada, vizinhança ou outros, - Aplicação 6 (Figura 6): transformar o calor restante de processos, sol, vento, energia térmica combinada, etc., através de uma bomba de calor para geração de vapor para expandir o vapor sobre uma turbina na geração de eletricidade, - Aplicação 7 (Figura 7): bombear o calor restante de processos, sol, vento, energia térmica combinada, etc... e transformar com uma turbina de 'Ciclo Rankine Orgânico' (ORC) em eletricidade, - Aplicação 8 (Figura 8) transformar o calor solar em eletricidade, utilizando mais ou menos o mesmo esquema que para a Aplicação 7, somente diferindo em que o calor solar é utilizado como fonte de calor ao invés. Nesta aplicação específica, o calor solar pode ser utilizado para desidrolisar totalmente parte 14b ou todo o ácido fosfórico líquido 14 na reação de polimerização (condensação), gerando P2O5 puro (sólido) ou quase puro (pasta). Neste caso uma densidade de energia muito alta é alcançada (até 3 GJ/m3) e o sistema deve ser projetado para manipular este material. Isto pode, por exemplo, ser feito aquecendo um ácido fosfórico que não flui em um contentor (contenção isolada) constantemente aquecido por luz solar direta ou indireta e escapamentos de vapor de água de ácido fosfórico até que somente um pó seco ou uma pasta de P2O5 sólido reste. - Aplicação 9 (Figura 9): no armazenamento de eletricidade alimentada por vento. Nesta aplicação o calor é gerado por resistência elétrica, este calor é utilizado através de uma bomba de calor para geração de vapor para expandir o vapor sobre uma turbina e gerar eletricidade. Este pode ser utilizado para armazenar eletricidade gerada pelo vento durante as reduções na rede de eletricidade e economizá-la para mais tarde durante os picos na rede de eletricidade; descontínua, por exemplo. - Aplicação 3 (Figura 10): no armazenamento de calor ou energia (calor restante, calor solar, energia eólica, vapor, etc....) com um tanque de armazenamento de calor. Nesta aplicação o calor restante de processos, sol, vento e outros é utilizado para bombear e armazenar calor. Este pode, por exemplo, ser utilizado para conectar um produtor de calor descontínuo a um consumidor de calor contínuo, vice versa, ou para conectar uma produção de calor descontínua com um consumo de calor descontínuo; - Aplicação 4 (Figura 11): em transporte de calor, que difere do acima em que o calor restante é realmente convertido e capturado em uma forma transportável permitindo por um lado o transporte de 'calor restante' por navio de carga, contentores, caminhões, tubulações para outro local do rio, docas, canal, cidade, área industrial ou residencial...para consumidor(es) de calor ou sua rede, e por outro lado permitindo a conversão de calor restante de seu motor de meio de transporte, como, por exemplo, o calor de motor de um carro, ônibus, barco, caminhão e outros, transportado e valorizado em certas localizações como, por exemplo, em casa, no trabalho ...; ou suas combinações (Aplicação 10).[000107] Depending on the application, the cycle is either continuous (continuous flow of feed flows between reactions (A) and (C)), for example: - Application 1 (Figure 3): heat pump to recover the remaining heat, in process heating / cooling, warehouses, residential areas, supermarkets, etc., using remaining heat from another process, environment, sun, wind, and the like, - Application 2 (Figure 4): heat pump between heat networks, to increase the thermal energy from a heat fluid temperature / pressure level, such as steam, water, thermal oil, ..., to a highest temperature / pressure level of a heat fluid such as steam, water, thermal oil, ..., - Application 5 (Figure 5): use of heat pump technology to generate cold, with, for example, high ambient temperatures, for the cooling of industrial processes, warehouses, supermarkets, refrigerators, houses, residential areas etc., with heat remaining processes, environment, sun, wind, combined thermal energy, neighborhood or others, - Application 6 (Figure 6): transform the remaining heat from processes, sun, wind, combined thermal energy, etc., through a heat pump to generate steam to expand the steam over a turbine to generate electricity, - Application 7 (Figure 7): pump the remaining heat from processes, sun, wind, combined thermal energy, etc ... and transform it with an 'Organic Rankine Cycle' (ORC) turbine into electricity, - Application 8 (Figure 8) transform solar heat into electricity, using more or less the same scheme as for Application 7, only differing in that solar heat is used as a heat source instead. In this specific application, solar heat can be used to fully dehydrate part 14b or all of the liquid phosphoric acid 14 in the polymerization reaction (condensation), generating pure (solid) or almost pure P2O5 (paste). In this case a very high energy density is achieved (up to 3 GJ / m3) and the system must be designed to handle this material. This can, for example, be done by heating a phosphoric acid that does not flow into a container (isolated containment) constantly heated by direct or indirect sunlight and steam escapes from phosphoric acid until only a dry powder or a paste of P2O5 solid remains. - Application 9 (Figure 9): in the storage of electricity powered by wind. In this application the heat is generated by electrical resistance, this heat is used through a heat pump to generate steam to expand the steam over a turbine and generate electricity. This can be used to store electricity generated by the wind during reductions in the electricity grid and save it for later during peaks in the electricity grid; discontinuous, for example. - Application 3 (Figure 10): in the storage of heat or energy (remaining heat, solar heat, wind energy, steam, etc ...) with a heat storage tank. In this application the remaining heat from processes, sun, wind and others is used to pump and store heat. This can, for example, be used to connect a batch heat producer to a continuous heat consumer, vice versa, or to connect a batch heat production with a batch heat consumption; - Application 4 (Figure 11): in heat transport, which differs from the above in that the remaining heat is actually converted and captured in a transportable form allowing on the one hand the transport of 'remaining heat' by cargo ship, containers, trucks , pipes to another location on the river, docks, canal, city, industrial or residential area ... for heat consumer (s) or its network, and on the other hand allowing the conversion of the remaining heat from your means of transport engine, as, for example, the engine heat of a car, bus, boat, truck and others, transported and valued in certain locations, such as at home, at work ...; or their combinations (Application 10).
[0108] [000108] Where the above can create the impression that the continuous or discontinuous operation of the CHEMENERGY cycle is dependent on the absence or presence of storage tanks in the above applications only refers to a continuous or discontinuous energy conversion. Whether or not tanks are used to store the reaction solutions, all processes 1-9 can be operated continuously or discontinuously. Consequently, in the general flow diagram (Figure 12) that represents the reocurrent flow in each of the above applications, storage tanks are optional.
[0109] - de uma pequena aplicação, por exemplo, doméstica até uma grande escala industrial. - sobre patins, pequena escala, grande escala. - em contentores ou outras plataformas móveis. [000109] Details about the elements in the flowcharts for each of the above applications can be found in Table 3 below.
[0110] [000110] In each of the possible applications the cycle can be controlled with a simple temperature, pressure, flow or other sensors that regulate valves and systems, or projected from something between a simple electrical & instrumentation project and / or a highly sophisticated electrical & instrumentation design, fully automated installations with an optimizer connected to the Internet, mobile phone or others to operate at maximum economic efficiency 24 hours a day. The optimizer could work on demand, at room temperature, wind or other circumstances determining the installation's economy or performance.
[0111] [000111] Based on industry standardized safety reviews, such as HAZOP, facilities are designed with high safety standards that contain or an intrinsic safe design (such as, for example, vacuum and maximum operating pressure +10 %), pressure valves, or automated safety integrity function systems (SIF or SIL) or a combination of these design criteria. The installations are controlled with alarms and trips in order to keep the installation in the safe operating range. The basic equipment design depends on the process design but the detailed equipment design may be different in order to meet PED, ASME or other local design codes or local modern best technology technology.

权利要求:
Claims (16)
[0001]
Method for storing or increasing the energy content of a reaction mixture, said reaction being enabled by the heat inserted from a heat source other than said reaction mixture, characterized by the fact that the energy content of the reaction mixture is stored or increased by means of an endothermic condensation reaction, said reaction mixture comprising an inorganic oxoacid compound and / or its salt and water.
[0002]
Method according to claim 1, characterized in that the heat source other than said reaction mixture is either heat remaining from industrial processes, or heat derived from natural resources such as solar or wind energy.
[0003]
Method according to claim 1 or 2, characterized in that the water and / or the inorganic oxoacid compound and / or its salt is removed from the reaction mixture.
[0004]
Method according to any one of claims 1 to 3, characterized in that it further comprises the step of releasing the respective increased energy content, stored in the reaction mixture in a subsequent process step through the exothermic hydrolysation of the reaction products of the said reaction mixture.
[0005]
Method according to any one of claims 1 to 3, characterized in that the inorganic oxoacid compound and / or its salt is an oxoacid or nitrogen, sulfur or phosphorus, or its corresponding salt.
[0006]
Method according to claim 5, characterized in that the inorganic oxoacid compound and / or its salt is represented by the general formula (I): R-Op - ((OnX (OQ) mO) y) -R '(I) on what; R represents hydrogen, a hydrocarbon or Z; X represents sulfur, nitrogen or phosphorus; Z represents - (OnX (OQ) mO) yR "; R 'and R "each independently represents hydrogen, a hydrocarbon or a metal cation; n = 1 or 2; m = 0 or 1; p = 0 or 1; y = at least 1; and Q each independently represents a hydrogen, a hydrocarbon or a metal cation.
[0007]
Method according to claim 5, characterized by the fact that the inorganic oxoacid compound and / or its salt are polyphosphoric acids and / or their salts, represented by the general formula (Ia): RO - ((OP (OQ) mO) y -R '(Ia) on what R and R 'each independently represents hydrogen, a hydrocarbon or a metal cation; m = 0 or 1; y = at least 1; and each Q represents a hydrogen, a hydrocarbon or a metal cation.
[0008]
Method according to claim 5, characterized by the fact that polyphosphoric acids and / or their salts are; (a) pure inorganic linear polyphosphoric acids or their salts represented by the following formula: Mn + 2PnO (3n + 1) (Ib) with n = at least 2; M is H + or a metallic cation; (b) pure inorganic cyclic polyphosphoric acids or their salts represented by the following formula: MnPnO3n (Ic) with n = at least 3; M is H + or a metallic cation; (c) branched; or (d) combinations thereof.
[0009]
Method according to any of claims 6 to 8, characterized in that the metal cation is a monovalent metal cation, more specifically K or Na.
[0010]
Method according to claim 6 or 7, characterized by the fact that y is within the range of 1 to 100; more specifically within the range of 1 to 10; even more specifically within the range of 1 to 3.
[0011]
Method according to claim 7, characterized in that the phosphoric acid salts are selected from the group containing Phosphophenolpyruvate, Glyceratel, 3 bi phosphate, Formyl phosphate, Acetyl phosphate, Propionyl phosphate, Butyryl phosphate or other carboxyl phosphates, Phospho -creatin, Phospho-arginine, Glucose phosphates (1 or 6-phosphate), fructose phosphates, Glycerol-3-phosphate, Nicotine amide adenine dinucleotide phosphate (NADP), dihydroxyacetonephosphate, glyceraldeidophosphates, xylosphosphosphates , Erythrosephosphate, ribulosphosphate, phospho-serine, Aspartyl phosphate and adenosinophosphate.
[0012]
Method according to any one of claims 1 to 6, characterized in that the endothermic condensation reaction is represented by the following formula: HOXOn (OH) mOR '+ R-Op- ((XOn (OH) m-0) y-1) -H -> R-Op- ((XOn (OH) m-0) y) -R '+ H2O
[0013]
Method according to claim 12, characterized by the fact that X represents phosphorus.
[0014]
System to capture or store energy, comprising: - a means of capture to capture energy; - a storage medium for storing captured energy, wherein the capture and storage means comprise at least one reaction vessel at least partially filled with a reaction mixture and comprising a heating element in thermal communication with said vessel, characterized by the fact that the reaction mixture comprises an inorganic oxoacid compound and / or its salt and water, suitable for having an endothermic condensation reaction carried out on said reaction mixture.
[0015]
System according to claim 14, characterized by the fact that it also comprises a release means to release the captured and stored energy in a subsequent exothermic hydrolysis step.
[0016]
System according to claim 14, characterized in that the reaction mixture comprises an inorganic oxoacid compound and / or its salt as defined in any one of claims 6 to 11.

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同族专利:

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公开号 | 公开日

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MY164107A|2017-11-30|

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US20130306268A1|2013-11-21|

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BR112013019055A2|2016-10-04|

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EP2668459A1|2013-12-04|

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DK2668459T3|2016-01-25|

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PT2668459E|2016-02-17|

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PL2668459T3|2016-04-29|

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EP2668459B1|2015-10-28|

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ZA201305627B|2014-04-30|

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HUE026609T2|2016-06-28|

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JP2014503786A|2014-02-13|

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EA026677B9|2017-08-31|

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CA2825467A1|2012-08-02|

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EP2995895A1|2016-03-16|

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RS54534B1|2016-06-30|

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AU2012210610B2|2016-10-27|

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CN103384809A|2013-11-06|

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SMT201600030B|2016-02-25|

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KR101885825B1|2018-08-06|

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JP5925810B2|2016-05-25|

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US9163868B2|2015-10-20|

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WO2012101110A1|2012-08-02|

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CY1117256T1|2017-04-26|

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EA201370167A1|2014-01-30|

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GB201101337D0|2011-03-09|

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HRP20160021T1|2016-03-11|

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EA026677B1|2017-05-31|

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SI2668459T1|2016-04-29|

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ES2559019T3|2016-02-10|

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CA2825467C|2016-10-11|

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CN103384809B|2016-01-20|

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KR20140040114A|2014-04-02|

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NZ613505A|2015-02-27|

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法律状态:
2018-12-18| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-06-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-07-21| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/01/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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GBGB1101337.2A|GB201101337D0|2011-01-26|2011-01-26|Methods and components for thermal energy storage|

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GB1101337.2|2011-01-26|

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PCT/EP2012/051025|WO2012101110A1|2011-01-26|2012-01-24|Methods and components for thermal energy storage|

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