EP2256406B1 - Procédé pour utiliser la chaleur dissipée d'und réaction chimique - Google Patents

Procédé pour utiliser la chaleur dissipée d'und réaction chimique Download PDF

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Publication number
EP2256406B1
EP2256406B1 EP09405103.4A EP09405103A EP2256406B1 EP 2256406 B1 EP2256406 B1 EP 2256406B1 EP 09405103 A EP09405103 A EP 09405103A EP 2256406 B1 EP2256406 B1 EP 2256406B1
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Prior art keywords
water
reaction
steam
temperature
bar
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EP09405103.4A
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German (de)
English (en)
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EP2256406A3 (fr
EP2256406A2 (fr
Inventor
Heinz Baumann
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Dr W Kolb AG
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Dr W Kolb AG
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K1/00—Steam accumulators
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K3/00—Plants characterised by the use of steam or heat accumulators, or intermediate steam heaters, therein
    • F01K3/004—Accumulation in the liquid branch of the circuit
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K3/00—Plants characterised by the use of steam or heat accumulators, or intermediate steam heaters, therein
    • F01K3/18—Plants characterised by the use of steam or heat accumulators, or intermediate steam heaters, therein having heaters
    • F01K3/188—Plants characterised by the use of steam or heat accumulators, or intermediate steam heaters, therein having heaters using heat from a specified chemical reaction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B33/00—Steam-generation plants, e.g. comprising steam boilers of different types in mutual association
    • F22B33/18—Combinations of steam boilers with other apparatus
    • F22B33/185—Combinations of steam boilers with other apparatus in combination with a steam accumulator
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22D—PREHEATING, OR ACCUMULATING PREHEATED, FEED-WATER FOR STEAM GENERATION; FEED-WATER SUPPLY FOR STEAM GENERATION; CONTROLLING WATER LEVEL FOR STEAM GENERATION; AUXILIARY DEVICES FOR PROMOTING WATER CIRCULATION WITHIN STEAM BOILERS
    • F22D3/00—Accumulators for preheated water
    • F22D3/06—Accumulators for preheated water directly connected to boilers

Definitions

  • the present invention relates to a method for using waste heat of an exothermic chemical reaction or for heat recovery.
  • the EP 0 158 747 A1 describes a method for using waste heat from a continuous chemical reaction, namely the production of phthalic anhydride, or maleic anhydride, wherein the waste heat of the reaction is first converted into high-pressure steam and then released in this form to a steam reservoir.
  • the vapor storage By using the vapor storage, the water vapor discharged from the reactor can be kept relatively constant.
  • steam storage is fed with steam from a boiler which generates steam in a fluctuating manner. From the steam storage then steam is provided to other facilities for further use.
  • pressurized water is stored in a steam accumulator. Reducing the pressure of water stored at its saturation point results in an excess of energy in the water, causing some of the water to turn into steam (so-called "flashing").
  • flashing In the steam storage water is kept as a saturated liquid at elevated pressure and elevated temperature.
  • WO2006 / 128311A2 discloses a heat powered vehicle with external power generation in which the energy is generated in stationary incinerators such as waste incinerators.
  • the invention is therefore based on the object to provide a system for the efficient use of heat of reaction of an alkoxylation reaction, in which the disadvantages of the prior art are overcome.
  • the solution to this problem is achieved in that a method for using the heat of reaction in a reaction vessel discontinuously conducted exothermic chemical reaction is presented, in which the heat of reaction supplied water of a first, lower temperature in a heat exchanger at least indirectly to a second, higher Temperature heats up, and this water the second, higher temperature is fed to a vapor storage, characterized in that the chemical reaction is conducted in a batch process and that the chemical reaction is an alkoxylation reaction.
  • the alkoxylation reaction is an ethoxylation reaction or a propoxylation reaction or a butoxylation reaction or a mixed form of such reactions.
  • These are so-called “batch reactions” or “batch processes”, i. at least partially discontinuous reactions.
  • a batch process is to be understood as meaning a process in which (compared to purely continuously conducted reactions in which all reagents are added continuously, ie successively) at least one reagent (starting material or raw material) is batchwise or presented in a thrust.
  • so-called “semi-batch processes” in which at least one starting material (for example alcohol) is introduced as a batch and at least one further starting material (for example epoxide) is metered successively into the reaction vessel can also be encompassed by this term.
  • the reaction vessel is filled batchwise with at least one starting material and in certain reactions also with the optionally necessary solvents, etc., and the chemical reaction starts, at least one further reagent, if necessary, being added (continuously). After completion of the reaction, the contents are taken with the products and the remaining educts.
  • Typical alkoxylation reactions with reaction enthalpies of (-100) - (-200) kJ / mol produce 2000-4000 kWh for recycling on a 25t scale.
  • the heat of reaction or waste heat of such discontinuous reactions is thus also discontinuous, or not constant, ie delivered variably.
  • a memory preferably a steam accumulator (called “steam accumulator") is provided, in front of the device in which the steam is used, such as a boiler, or other possible uses.
  • water is understood as a chemical compound (H 2 O). Possibly. may be added to the water additives, and it may, for example, small amounts of salts, etc. are present dissolved.
  • water is always used here for the liquid state of matter.
  • steam in connection with the steam area in the steam accumulator, for example.
  • the heat of reaction is thus supplied to the steam reservoir as water in the liquid state of aggregation, namely as water of the second, higher temperature.
  • the steam storage is steamed. If it is not about steam from a boiler, but the recovery of waste heat from a chemical reaction, so must be interposed between the heat exchanger and the steam storage still an evaporation step, which is not necessary here.
  • the medium exiting the heat exchanger namely hot / hot water, is used directly to feed the vapor storage without any vaporization between them.
  • Water supplied in the heat exchanger of the first, lower temperature is water in the liquid state of aggregation, which if necessary is treated, ie, for example, decalcified, deionized, or degassed.
  • the water supplied to the heat exchanger of the first, lower temperature comes at least partially, but possibly also completely, from a condensate tank, ie it is preferably at least partially recirculated, ie recycled or recycled water.
  • the condensate tank is refilled directly by the amount of water which is withdrawn from the condensate tank and is no longer returned there in the form of possibly treated fresh water.
  • the heat exchanger at least partly directly with fresh water, which if necessary prepared, ie for example decalcified, deionized, or degassed, is fed and so the condensate tank is replenished indirectly via the steam storage path.
  • the water delivered by the heat exchanger to the steam reservoir has, according to a preferred embodiment of the invention, a pressure of in the range of 2-6 bar, preferably about 4-5 bar and a temperature of about 130-160 degrees Celsius, preferably about 140- 150 degrees Celsius.
  • the heat of reaction is transferred via the reaction solution or the reaction mixture to the supplied water of the first temperature.
  • the waste heat of the chemical reaction is preferably transferred to the water by using at least part of the reaction mixture or the reaction solution as a heat transfer fluid for heat transfer from the reaction vessel to a heat exchanger.
  • a portion of the reaction solution can be removed from the reaction vessel and passed into the heat exchanger.
  • the reaction mixture or the reaction solution or even the reaction product is cooled in the heat exchanger and flows back to the reaction vessel, to react further, and to remove heat again.
  • the reaction solution is conveyed or circulated by a pump from the reaction vessel into the heat exchanger and / or from there back into the reaction vessel.
  • the reaction mixture thus transfers the heat of reaction to the water supplied in the heat exchanger.
  • the waste heat produced in the reaction vessel is transferred to the water, whereby the water is heated.
  • the heated water then exits the heat exchanger and is directed into the steam reservoir.
  • the water of a first temperature which is either supplied as treated fresh water or comes from the condensate tank, on the way to the steam storage through a arranged in the reaction vessel heat exchanger, or eg is passed through a kind of "cooling coil", wherein the water receives there heat of reaction, and thus simultaneously the reaction or the reaction solution is cooled in the reaction vessel.
  • the heated water of the second temperature then exits the heat exchanger again and is supplied in heated form to the steam storage.
  • a secondary circuit such as e.g. a molten salt cycle, be interposed between the heat exchanger and the reaction vessel.
  • the entering into the steam reservoir water has a pressure of preferably about 4-5 bar and a temperature of preferably about 140-150 ° C.
  • the temperature in the steam accumulator is preferably about 120-135 ° C at a pressure of about 2-3 bar, and after loading the steam battery with water about 150-155 ° C at a pressure of about 5-6 bar.
  • the steam accumulator has an upper area in which hot steam is located and a lower area in which hot water is located. At phase equilibrium in the steam accumulator, the temperature of the steam corresponds to the temperature of the water and the pressure of the steam corresponds to the pressure of the water.
  • the steam storage is filled at the initial start-up for the initial load with recycled water from the condensate tank, which has a temperature of about 100 degrees Celsius.
  • the condensate tank may be either directly, i. regardless of the operating state of the heat recovery system with possibly treated fresh water are filled, or indirectly during operation of the heat recovery system with fresh water or recycled water after passing through the heat exchanger and the steam accumulator.
  • steam ie "water” in the gaseous state of aggregation, as well as water in the liquid state of aggregation, are supplied from the steam reservoir to other uses.
  • steam ie "water” in the gaseous state of aggregation, as well as water in the liquid state of aggregation
  • another advantage of the invention compared to the prior art is that not only steam is taken from the steam reservoir, but also hot water, which can be used for various purposes.
  • At least a portion of the water discharged from the vapor storage is, in a next preferred embodiment, used to heat raw materials, i. Educts used for the chemical reaction.
  • At least a portion of the water discharged from the steam reservoir is used to feed a boiler.
  • a boiler preferably so-called "high-quality" steam is generated, which has a pressure of about 5-9 bar, preferably about 6-8 bar, and a temperature of about 160-170 degrees Celsius. (about 25-30 m 3 per 24 h, average about 1.2 m 3 per h).
  • steam is emitted from the steam reservoir, which has a pressure of about 2-5 bar, preferably about 2-4 bar and a temperature of about 120-150 degrees Celsius, preferably about 130-140 degrees Celsius having.
  • Modern boilers or water tanks are very efficient when properly loaded, and they respond quickly to charge fluctuations.
  • ordinary "shell boilers” can not adequately cover large peak demands and should be protected from large fluctuations in the cargo.
  • the present method allows a stable charging pattern for boilers or other uses to avoid the negative effects of large charge variations.
  • steam from the boiler can be immediately made available to meet peak demand.
  • the steam storage is thus to a certain extent an "expansion" of the energy storage capacity of the boiler.
  • water discharged from the steam storage to the boiler or other uses is replaced intermittently by supplying hot water from the heat exchanger or by the water heated by the waste heat of the chemical reaction.
  • the working cycle ("duty cycle") of the discontinuous reaction or the recovery device according to the invention is preferably characterized in that, while preferably approx. 30-60 min heat of reaction and transferred to the water, followed by a period of preferably about 2 hours, in which no heat release takes place.
  • a temperature and / or pressure drop takes place in the steam accumulator, typically from about 150 ° C to about 133 ° C and 120 ° C and from about 5 bar to about 2 bar.
  • further vapor is used for further chemical reactions, e.g. for preheating other raw materials derived from the steam storage.
  • the characteristics of the present invention reduce the energy requirement of the production plant. At the same time, the CO 2 - or GHG emissions ("greenhouse gas”) and thus the environmental and energy costs can be reduced.
  • the system for utilizing the waste heat of the chemical reaction has at least one control and / or control mechanism.
  • FIGS. 1 and 2 in each case a scheme according to a first or a second embodiment of a system for using heat of reaction from an alkoxylation reaction is shown.
  • the system for using the heat of reaction has a reaction vessel 2 in which an exothermic alkoxylation reaction takes place.
  • the alkoxylation reaction is a discontinuously conducted reaction, preferably a so-called "batch process".
  • the empty reactor is filled with the starting materials and any necessary solvents and the chemical reaction starts.
  • the contents are taken with the products and any remaining educts.
  • the alkoxylation reaction is an exothermic reaction such as, for example, an ethoxylation, propoxylation or butoxylation reaction.
  • a fatty alcohol and an epoxide react with one another to form at least one reaction product 16, which can be removed from the reaction vessel 2.
  • FIG. 1 are three raw materials 6a-c shown, with less, or even more starting materials are possible.
  • the reaction vessel 2 preferably has a typical volume in the range of about 10 m 3 to 50 m 3 .
  • the delivery rate is preferably about 2000-4000 kWh per batch, i. per 25 t.
  • the heat of reaction is transferred in the heat exchanger 19 to supplied water 5 and 15 respectively.
  • This has a first, low temperature T1 of in the range of about 100 degrees Celsius and a first pressure p1 of in the range of about 0 bar.
  • the water 5, 15 supplied to the heat exchanger 19 can either be cold fresh water 5, which may have previously been treated in a conditioner 13, eg a deionizer or a descaling agent or a degasser. It can also be quite or partially recycled, ie recycled water 15 from a condensate tank 3, ie condensate, which was optionally also processed.
  • a switching point 14 is arranged in the system, at the fresh water supply to the water cycle, and / or vice versa, can be switched. It is also possible that a mixture of fresh water 5 and recycled water 15 is supplied to the heat exchanger 19.
  • the water 5/15 is then heated to a second temperature T2 of in the range of about 140 to 160 degrees Celsius at a second pressure p2 in the range of about 3 bar to 5 bar.
  • a first temperature T1 'to the supplied water 5/15 a first temperature T1 transmitted.
  • at least part of the reaction solution 2a is branched out of the reaction vessel 2 and passed into a heat exchanger 19 arranged outside the reaction vessel 2, and then passed through the heat exchanger 19 before the reaction solution 2a is returned to the reaction vessel 2 again.
  • This circulation is preferably achieved by a pump (not shown).
  • the reaction solution 2b leaving the heat exchanger 19 again has a second, lower temperature T2 'than the reaction solution 2a conducted from the reaction vessel 2 to the heat exchanger 19, since the water 5/15 "cools" the reaction solution 2a in the heat exchanger 19.
  • the reaction heat is transferred to the supplied water 5/15 a first temperature T1 as an alternative to the above heat exchange by circulation of the reaction solution by the supplied water 5/15 by a arranged in the reaction vessel 2 "heat exchanger" 19, eg a cooling coil or arranged in the reaction vessel 2 other cooling device is guided.
  • the water leaving the heat exchanger 19 5 'here also has a second temperature T2 of about 140 to about 160 degrees Celsius and a second pressure p2 of about 3-5 bar.
  • the water exiting from the heat exchanger 19 5 'in the liquid state of aggregation is fed to a steam reservoir 1.
  • the steam accumulator 1 is usually made of a cylindrical pressure vessel, which is partially filled with water, preferably to 50% -90%. It typically has a volume in the range of about 50 m 3 to 200 m 3 .
  • the steam reservoir 1 has in its interior an upper steam region 1a and a lower water region 1b, the water surface of the water region 1b being the interface with the steam region 1a, ie these two regions 1a, 1b are not separated by a wall, the two aggregate states essentially in phase equilibrium.
  • the water preferably occurs and as shown in FIG Fig. 1 and 2 via a water pipe 1c with inlet openings or
  • Nozzles in the water area 1 b of the steam accumulator 1 a are preferably in the phase equilibrium.
  • the temperature prevailing in the steam storage temperature T8, T9 is preferably in the range of about 120 degrees Celsius to 150 degrees Celsius, at a pressure p8, p9 of in the range of about 2 bar to 5 bar.
  • Steam 10a-10c at a temperature T4 of about 120 to 150 degrees Celsius at a pressure p4 in the range of about 2 to 5 bar, ie preferably so-called "low-grade steam", can be withdrawn from the steam region 1a.
  • This vapor 10a-10c may be supplied to multiple uses 11a-11c, such as e.g. heating a mobile container 11a, preferably a swap body, and / or the steam 10b may react with other chemical reactions 11b e.g. be fed to the preheating of raw materials.
  • Other uses 11c are alternatively or additionally possible.
  • Water 8a-8c, 9a-9b may be withdrawn from the water region 1b at a temperature T3 of in the range of about 120 degrees Celsius to about 150 degrees Celsius and a pressure of in the range of about 2 to 5 bar, and various uses. 6c, 4, 12 are supplied.
  • raw materials 6a-6c for the said chemical reaction can be preheated with the water 8a-8c, preferably via heat exchangers 20a-20c, so that they can be supplied to the reaction vessel 2 as preheated educts 6a'-6c '. It is also possible that the preheating of the educts 6a-6c via closed circuits in combination with a heat exchanger takes place (not shown).
  • a Condensate tank 3 are supplied. This preferably has a volume of in the range of 50 m 3 up to 200 m 3 .
  • this condensate tank 3 can deliver water 15 for recycling, which has a temperature T6 of in the range of approximately 100 degrees Celsius and a pressure p6 of approximately 0 bar. This water 15 is then according to the embodiments in Fig.
  • fresh water 5 which has been treated in a conditioner 13 may also be supplied directly to the condensate tank 3 in order to replace the amount of water 15 which is withdrawn therefrom and does not flow back there again.
  • hot water 9a, 9b can also be supplied to other uses.
  • a portion 9a of the water which preferably has a temperature T3 of in the range of about 120 to 150 degrees Celsius and a pressure p3 of in the range of about 2 to 5 bar, are fed to a boiler 4, in which the water 9a is further heated and converted into steam.
  • the boiler provides this so-called "high quality" steam 18 to other uses, preferably at a temperature T5 of in the range of about 160 degrees Celsius to 180 degrees Celsius and a pressure P5 of in the range of about 6 to about 10 bar ,

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Processing Of Solid Wastes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (12)

  1. Procédé pour utiliser la chaleur de réaction d'une réaction chimique exotherme effectuée de manière discontinue dans une cuve de réaction (2) où la chaleur de réaction chauffe de l'eau (5, 15) fournie et ayant une première température plus basse (T1) au moins indirectement à une deuxième température plus haute (T2) dans un échangeur de chaleur (19), et que celle-ci est fournie à un réservoir de vapeur (1), caractérisé en ce que la réaction est effectuée en procédé par lots et que la réaction chimique est une réaction d'alcoxylation.
  2. Procédé selon la revendication 1, caractérisé en ce que la chaleur de réaction est fournie au réservoir de vapeur (1) sous forme d'eau (5') dans l'état liquide, préférablement sous forme d'eau ayant une deuxième température plus haute (T2).
  3. Procédé selon la revendication 2, caractérisé en ce que l'eau (5') fournie au réservoir de vapeur (1) par l'échangeur de chaleur (19) présente une pression (p2) dans la plage de 2 à 6 bars, préférablement d'environ 4 à 5 bars, et une température d'environ 130 à 160 degrés Celsius, préférablement d'environ 140 à 150 degrés Celsius.
  4. Procédé selon une des revendications précédentes, caractérisé en ce que au moins une partie de la solution de réaction (2a) est déviée hors de la cuve de réaction (2) et est circulée entre la cuve de réaction (2) et un échangeur de chaleur (19) disposé à l'extérieur de la cuve de réaction (2), où la circulation est préférablement entraînée par une pompe.
  5. Procédé selon une des revendications 1 à 3, caractérisé en ce que l'eau fournie (5, 15) est guidée à travers un échangeur de chaleur (19) disposé dans la cuve de réaction (2), avant que celle-ci est fournie au réservoir de vapeur.
  6. Procédé selon une des revendications précédentes, caractérisé en ce que de la vapeur (10a-10c) ayant une pression (p4) dans la plage d'environ 2 à 5 bars, préférablement d'environ 2 à 4 bars et présentant une température (T4) dans la plage d'environ 120 à 150 degrés Celsius, préférablement dans la plage d'environ 130 à 140 degrés Celsius, ainsi que de l'eau (8a-8c, 9a-9c) dans l'état liquide ayant une pression (p3) d'environ 2 à 5 bars, préférablement dans la plage d'environ 2 à 4 bars et présentant une température (T3) dans la plage d'environ 120 à 150 degrés Celsius, préférablement d'environ 130 à 140 degrés Celsius, sont fournies à d'autres utilisations (4, 6a-6c, 11a-11c, 12) à partir du réservoir de vapeur (1).
  7. Procédé selon la revendication 6, caractérisé en ce que au moins une partie de l'eau fournie à partir du réservoir de vapeur (1) est utilisée pour le chauffage de matériaux de départ (6a-6c) pour la réaction chimique.
  8. Procédé selon la revendication 6 ou 7, caractérisé en ce que au moins une partie de l'eau (9a) fournie à partir du réservoir de vapeur (1) est utilisée pour l'alimentation d'un boiler (4), où de la vapeur à haute qualité (18) présentant une pression (p5) d'environ 5 à 9 bars, préférablement d'environ 6 à 10 bars et une température (T5) d'environ 160 à 180 degrés Celsius est produite dans le boiler (4).
  9. Procédé selon une des revendications précédentes, caractérisé en ce que de la vapeur (10a à 10c) est fournie à partir du réservoir de vapeur (1), où au moins une partie de la vapeur (10a) fournie à partir du réservoir de vapeur (1) est utilisée pour le chauffage d'au moins une cuve mobile (11a), préférablement d'une cuve à support alternant.
  10. Procédé selon une des revendications précédentes, caractérisé en ce que l'eau fournie (5) ayant une première température plus basse (T1) est au moins partiellement, préférablement entièrement de l'eau fraiche dans l'état liquide, laquelle est éventuellement purifiée.
  11. Procédé selon une des revendications précédentes, caractérisé en ce que l'eau fournie (15) ayant une première température plus basse (T1) provient au moins partiellement d'une cuve de de condensation (3).
  12. Procédé selon une des revendications précédentes, caractérisé en ce que la réaction chimique est une réaction d'éthoxylation ou une réaction de propoxylation ou une réaction de butoxylation ou une forme mixte de ces réactions.
EP09405103.4A 2008-06-20 2009-06-18 Procédé pour utiliser la chaleur dissipée d'und réaction chimique Active EP2256406B1 (fr)

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DE102018004987B4 (de) * 2018-06-20 2022-08-25 Singulus Technologies Ag Verfahren und Vorrichtung zur Bereitstellung von Dampf
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WO2026052840A1 (fr) * 2024-09-09 2026-03-12 Basf Se Appareil et procédé d'utilisation de chaleur perdue
WO2026052841A1 (fr) * 2024-09-09 2026-03-12 Basf Se Appareil et procédé d'utilisation de chaleur perdue

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EP2256406A2 (fr) 2010-12-01

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