CN114453030A - Regeneration system and method of cellulose biomass catalytic cracking hydrogen production catalyst - Google Patents
Regeneration system and method of cellulose biomass catalytic cracking hydrogen production catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 177
- 238000011069 regeneration method Methods 0.000 title claims abstract description 67
- 230000008929 regeneration Effects 0.000 title claims abstract description 62
- 239000002028 Biomass Substances 0.000 title claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 36
- 239000001257 hydrogen Substances 0.000 title claims abstract description 36
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 34
- 229920002678 cellulose Polymers 0.000 title claims abstract description 34
- 239000001913 cellulose Substances 0.000 title claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title abstract description 29
- 238000004939 coking Methods 0.000 claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000571 coke Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 22
- 239000003546 flue gas Substances 0.000 claims description 22
- 238000002485 combustion reaction Methods 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 4
- 230000002779 inactivation Effects 0.000 claims description 3
- 238000007233 catalytic pyrolysis Methods 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 18
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- 239000002808 molecular sieve Substances 0.000 description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 7
- 230000005587 bubbling Effects 0.000 description 6
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- 238000006555 catalytic reaction Methods 0.000 description 4
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- 230000009471 action Effects 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 238000005262 decarbonization Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
- B01D45/02—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by utilising gravity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
- B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
Abstract
The invention relates to the field of catalyst regeneration systems, in particular to a regeneration system and a method of a cellulose biomass catalytic cracking hydrogen production catalyst, wherein the system comprises the following components: the system comprises a quick coke burning tank, a low linear speed settler, a descending external heat collector and an ash collection system; the lower part of the quick coking tank is provided with a main air inlet, a regenerated catalyst lifting inlet and a regenerated catalyst outlet, the middle part of the quick coking tank is provided with an inactivated catalyst inlet, and the middle upper part of the quick coking tank is provided with a high-temperature regenerated catalyst outlet; the low linear speed settler is connected with the fast coking tank; the upper part of the low linear speed settler is connected to an ash collection system; the descending external heat collector is connected with the quick coke burning tank. The regeneration system is suitable for the condition that a large amount of carbon residue is generated in the catalytic cracking process of cellulose biomass, can effectively ensure the regeneration temperature and the regeneration effect of the deactivated catalyst, and can efficiently separate the regenerated catalyst and ash particles.
Description
Technical Field
The invention relates to the field of catalyst regeneration systems, in particular to a regeneration system and method for a cellulose biomass catalytic cracking hydrogen production catalyst.
Background
The molecular sieve catalyst has good catalytic activity in the process of hydrogen production by biomass cracking, the application of the molecular sieve catalyst enables reaction conditions in the catalytic reaction process to be mild, the conversion rate of raw materials to be high, the selectivity of target products to be high, and although the service performance is good, the rapid inactivation of the catalyst is one of the main problems which restrict the popularization of the cellulose biomass hydrogen production technology. This phenomenon is mainly caused by the formation of carbon deposits in the micropores of the molecular sieve surface area, the main hazard of carbon deposits is to cover active sites or to block the channels, and the rate of formation is influenced by the pore structure, acidity and reaction operating conditions of the molecular sieve. Through analysis of the formation process of the carbon deposit component, a model in the form of the carbon deposit, methods for limiting carbon deposit inactivation of the molecular sieve catalyst and an optimized regeneration condition can be obtained, high-temperature combustion treatment is needed for removing the carbon deposit from the inactivated catalyst, and phenomena such as dealumination and collapse of a molecular sieve framework, load metal sintering and the like are easily caused if the operation process is improperly designed, so that the regeneration and the use of the catalyst are influenced.
The catalyst regeneration system is an important component of a biomass cracking hydrogen production system, carbon deposition is removed by a high-temperature combustion method, a regenerated catalyst with stable performance is provided for a reaction system, and the catalytic reaction is maintained to be stably carried out.
The deactivated catalyst in the catalytic cracking hydrogen production process of cellulose biomass can carry a large amount of residual carbon to enter a regeneration system, and is different from the deactivated catalyst in the conventional petroleum catalytic cracking process, the part of residual carbon can generate inorganic metal residues mainly containing potassium and silicon after combustion, the surface carbon deposition is removed by combustion in the catalyst regeneration process, the part of residual carbon can be combusted simultaneously, a large amount of heat can be emitted in the catalyst regeneration process, the temperature is too high after the catalyst is regenerated, the requirement of the reaction system is not met, and therefore the regeneration temperature needs to be stably controlled and the heat is taken in time. Moreover, the carbon residue combustion products need to be separated from the regeneration system to ensure that the regenerated catalyst returned to the reaction system does not carry the metal residues, thereby influencing the catalytic reaction effect. The existing catalyst regeneration systems, such as a coke burning tank, a circulating fluidized bed and the like, can not solve the problems of regeneration and ash removal at the same time. The technical problems of catalyst structure damage and catalytic performance reduction caused by the existing molecular sieve catalyst regeneration technology and difficult ash separation are solved. Therefore, the development of an environment-friendly and efficient regeneration system special for the molecular sieve catalyst for catalytic cracking of cellulose biomass to produce hydrogen is urgently needed.
Disclosure of Invention
In order to solve the technical problem, the invention provides a regeneration system and a method of a cellulose biomass catalytic cracking hydrogen production catalyst. The catalyst regeneration system is suitable for the special condition that a large amount of carbon residue is generated in the catalytic cracking process of cellulose biomass, and compared with the existing catalyst regeneration system, the catalyst regeneration system not only can effectively ensure the regeneration temperature and the regeneration effect of the deactivated catalyst, but also can efficiently separate the regenerated catalyst and ash particles.
In a first aspect, the present invention provides a regeneration system of a catalyst for catalytic cracking of cellulose biomass to produce hydrogen, comprising: the system comprises a quick coking tank 1, a low linear speed settler 2, a descending external heat collector 5 and an ash collection system; the lower part of the quick coking tank 1 is provided with a main air inlet, a regenerated catalyst lifting inlet and a regenerated catalyst outlet, the middle part of the quick coking tank 1 is provided with an inactivated catalyst inlet, and the middle upper part of the quick coking tank 1 is provided with a high-temperature regenerated catalyst outlet; the low linear speed settler 2 is connected with the fast coking tank 1; the upper part of the low linear velocity settler 2 is connected to the ash collection system; the descending external heat collector 5 is connected with the rapid coking tank 1.
The environment-friendly efficient regeneration system provided by the invention is mature and reliable, is convenient to operate and maintain, can ensure efficient decarbonization and regeneration of the deactivated catalyst and efficient separation of residual carbon combustion products by aiming at the special regeneration process of the molecular sieve catalyst for preparing hydrogen by catalytic cracking of cellulose biomass, and can also control the temperature of the regenerated catalyst, thereby ensuring that the catalyst returned to the reaction system meets the requirements of catalytic reaction.
Preferably, the fast-coking tank 1 is a bubbling-type combustion bed reactor.
Further preferably, the rapid-coking tank is a bubbling type combustion bed reactor with high coking strength. The term "high scorch strength" means a scorch strength of 200 to 350 kg/t.h. According to the invention, the bubbling type combustion bed reactor can efficiently realize a coking process, so that the catalyst can be regenerated at high speed and high efficiency.
According to the regeneration system of the cellulose biomass catalytic cracking hydrogen production catalyst provided by the invention, the low linear speed settler 2 is positioned above the fast coking tank 1, and the height of the low linear speed settler 2 is 3-12 m. According to the invention, the design mode of the settler can improve the separation effect of the catalyst, reduce the loss of the catalyst and realize the efficient separation of the catalyst and the plant ash particles.
Preferably, the height of the low linear velocity settler 2 is 5 to 10m, more preferably 7 to 8m, and in the examples, 7.5m or the like is used.
Preferably, the low linear velocity settler 2 is used for returning a small amount of regenerated catalyst particles to the fast coking tank 1 by gravity natural settling separation during the process of flue gas carrying away.
In the invention, the low linear speed settler 2 is a container with an operating linear speed higher than the entrainment speed of ash particles and lower than the entrainment speed of catalyst particles, the low linear speed settler 2 meets the requirement of natural settling separation height of catalyst particles, the catalyst particles settle in the low linear speed settler 2 and return to the fast coking retort 1, and flue gas entrained ash particles are discharged to an ash collection system from the upper part of the low linear speed settler 2.
According to the regeneration system of the catalyst for catalytic cracking of cellulose biomass to produce hydrogen, provided by the invention, the ash collection system comprises the cyclone separator 3 and the ash collector 4, and the cyclone separator 3 is connected with the ash collector 4.
According to the invention, the high-temperature flue gas carrying ash particles and a very small amount of catalyst particles is discharged from the upper part of the low linear velocity settler 2 to the cyclone separator 3, the separated and purified flue gas is discharged from the top of the cyclone separator 3, and the ash and the catalyst particles are collected in the ash collector 4 at the lower part of the cyclone separator 3.
Preferably, the descending external heat remover 5 is used for exchanging part of the heat of the regenerated catalyst, and the heat exchange medium and the regenerated catalyst flow in opposite directions.
Further preferably, the upper part of the descending external heat remover 5 is connected to the high-temperature regenerated catalyst outlet, and the lower part of the descending external heat remover 5 is connected to the regenerated catalyst lifting inlet of the fast coke-burning tank 1.
According to the invention, the descending external heat collector 5 is used for collecting partial heat of the regenerated catalyst, preferably, the descending external heat collector 5 is used for cooling the regenerated high-temperature catalyst to a temperature index suitable for the requirement of the reaction system, the descending external heat collector 5 exchanges heat for the regenerated catalyst with overhigh temperature and cools the regenerated catalyst to meet the requirement of the reaction system, and the heat collection amount can be flexibly adjusted by controlling the flow of the regenerated catalyst and the flow of a heat exchange medium.
Further preferably, the system further comprises a catalyst circulation pipe, and the lower part of the descending external heat collector 5 is connected with the deactivated catalyst inlet through the catalyst circulation pipe.
Further preferably, a heat exchange medium inlet is arranged at the lower part of the descending external heat collector 5, and a heat exchange medium outlet is arranged at the upper part of the descending external heat collector 5.
Preferably, the descending external heat remover 5 adopts boiler desalted water as heat exchange medium.
In a second aspect, the present invention provides a regeneration method of the regeneration system of the catalyst for hydrogen production by catalytic cracking of cellulosic biomass, including: the method comprises the steps that an inactivated catalyst and residual carbon enter the middle of a quick coking tank 1, the lower portion of the quick coking tank 1 is mixed with main air to be combusted, a regenerated catalyst and flue gas are obtained, the regenerated catalyst is separated from the flue gas in a low linear velocity settler 2, the separated regenerated catalyst enters a descending external heat collector 5, the regenerated catalyst enters the lower portion of the quick coking tank 1 after being cooled, and then the regenerated catalyst enters a reaction system from the lower portion of the quick coking tank 1. The deactivated catalyst and the residual carbon are provided by a reaction system for preparing aromatic hydrocarbon by biomass cracking.
Preferably, the deactivated catalyst discharged from the reaction system for producing hydrogen by catalytic cracking of cellulose biomass and the residual carbon generated by the reaction are introduced into the middle of the fast coking tank 1 for bubbling combustion to remove carbon. The flue gas carries partial regenerated catalyst to flow to 2 tops of low linear speed settler, controls certain linear speed in the low linear speed settler 2, has both satisfied this part catalyst that smugglies secretly and can subside through self gravity, satisfies again that the bulk density index is less than the ash content granule of catalyst and can enter into ash content collection system along with flue gas discharge low linear speed settler 2, carries out high-efficient separation with the gas-solid phase of dusty flue gas by cyclone's mode. Meanwhile, at the upper part of the fast coking tank 1, the regenerated catalyst is firstly introduced into an external heat collector for cooling, the heat collector adopts a descending design, the flow direction of heat exchange medium desalted water is opposite to that of the catalyst, the catalyst after heat extraction is returned to the lower part of the fast coking tank 1, the whole regeneration process is completed, the requirement of a reaction system on the temperature of the regenerated catalyst is met, and then the regenerated catalyst is led out to the reaction system from the lower part of the fast coking tank 1.
Further preferably, deactivated catalyst and carbon residue from a reaction system for preparing aromatic hydrocarbon by biomass cracking are conveyed to the lower part of the rapid coking tank 1 through an inclined pipe to be mixed and combusted with main air, the regeneration temperature is too high due to the combustion of the carbon residue carried by the deactivated catalyst, a downlink external heat collector 5 is started to take away excess heat, and the regeneration temperature is maintained; if the sampling finds that the carbon content of the regenerated catalyst does not reach the standard or the burning depth of the carbon residue is insufficient, the regenerated catalyst with the carbon content not reaching the standard and the incompletely burnt carbon residue are returned to the quick coking tank 1 through the catalyst circulating pipe and contacted with the main air again and burned at the lower part of the quick coking tank 1. In the invention, after the combustion products are subjected to gas-solid phase separation, the flue gas leaves a regeneration system; the solid phase contains a regenerated catalyst and plant ash particles, the plant ash is separately collected after the two are separated, and the clean regenerated catalyst is returned to the reaction system for recycling.
Preferably, the operating temperature of the rapid coking tank 1 is 600-1000 ℃; the operation gas speed is 2-6 m/s; the scorching strength is 200-350 kg/t.h; the top pressure of the low linear speed settler 2 is 0.2-0.4 MPa; the operation gas velocity is less than 0.1 m/s. The invention has better effect by adopting parameters and can better realize the high-efficiency separation of the catalyst and the plant ash particles.
In the invention, the better operation conditions of the main process equipment of the cellulose biomass catalytic cracking hydrogen production catalyst regeneration system are as follows: fast-coking tank 1: the operation temperature is 600-1000 ℃; the operation gas speed is 2-6 m/s; the scorching strength is 200-350 kg/t.h; low linear velocity settler 2: the top pressure was 0.3MPa (gauge pressure); the operation gas velocity is less than 0.1 m/s. Further preferably, the optimized operating parameters are: fast-coking tank 1: the operating temperature is 850 ℃; the operating gas velocity is 1.5 m/s; the scorch strength is 300 kg/t.h; low linear velocity settler 2: the top pressure was 0.3MPa (gauge pressure) and the operating gas velocity was 0.08 m/s.
The invention has the beneficial effects that: the regeneration system of the molecular sieve catalyst can ensure an efficient carbon removal regeneration process and fully burn a large amount of residual carbon generated in the catalytic cracking hydrogen production process of cellulose biomass. The regenerated catalyst has little leakage with the smoke and can not cause structural collapse due to high linear speed combustion. The descending external heat collector can conveniently take away the redundant heat, and the regenerated catalyst can meet the temperature requirement of the reaction system. The regenerated catalyst and ash particles of the carbon residue combustion product can be efficiently separated and do not return to a reaction system.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic diagram of a cellulose-based biomass catalytic cracking hydrogen production molecular sieve catalyst regeneration system in an embodiment of the invention;
description of reference numerals:
1-a rapid coking tank, 2-a low linear velocity settler, 3-a cyclone separator, 4-an ash collector and 5-a descending external heat collector.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and the following embodiments are used for illustrating the present invention and are not intended to limit the scope of the present invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from normal commercial vendors, not indicated by the manufacturer.
The embodiment of the invention provides a regeneration system of a cellulose biomass catalytic cracking hydrogen production catalyst, which comprises: the system comprises a quick coking tank 1, a low linear speed settler 2, a descending external heat collector 5 and an ash collection system; the lower part of the quick coking tank 1 is provided with a main air inlet, a regenerated catalyst lifting inlet and a regenerated catalyst outlet, the middle part of the quick coking tank 1 is provided with an inactivated catalyst inlet, and the middle upper part of the quick coking tank 1 is provided with a high-temperature regenerated catalyst outlet; the low linear speed settler 2 is connected with the rapid coking tank 1; the upper part of the low linear velocity settler 2 is connected to the ash collection system; the descending external heat collector 5 is connected with the rapid coking tank 1. The rapid coking tank 1 is a bubbling type combustion bed reactor with high coking strength. The low linear speed settler 2 is located above the fast coking tank 1, and the height of the low linear speed settler 2 is 3-12 m. The ash collection system comprises a cyclone 3 and an ash collector 4, and the cyclone 3 and the ash collector 4 are connected. The descending external heat collector 5 is used for exchanging part of heat of the regenerated catalyst, and the flow direction of the heat exchange medium is opposite to that of the regenerated catalyst. The upper part of the descending external heat remover 5 is connected with the high-temperature regenerated catalyst outlet, and the lower part of the descending external heat remover 5 is connected with the regenerated catalyst lifting inlet of the rapid coking tank 1. The lower part of the descending external heat collector 5 is provided with a heat exchange medium inlet, and the upper part of the descending external heat collector 5 is provided with a heat exchange medium outlet. The descending external heat collector 5 adopts heat exchange medium as boiler desalted water.
The embodiment of the invention provides a regeneration method of a catalyst regeneration system for hydrogen production by catalytic cracking of cellulose biomass, which comprises the following steps: the method comprises the steps that an inactivated catalyst and residual carbon enter the middle of a quick coking tank 1, the lower portion of the quick coking tank 1 is mixed with main air to be combusted, a regenerated catalyst and flue gas are obtained, the regenerated catalyst is separated from the flue gas in a low linear velocity settler 2, the separated regenerated catalyst enters a descending external heat collector 5, the regenerated catalyst enters the lower portion of the quick coking tank 1 after being cooled, and then the regenerated catalyst enters a reaction system from the lower portion of the quick coking tank 1. Preferably, the deactivated catalyst discharged from the reaction system for hydrogen production by catalytic cracking of cellulose biomass and the residual carbon generated by the reaction enter the middle part of the rapid coking tank 1 together for bubbling combustion to remove carbon. The flue gas carries partial regenerated catalyst to flow to 2 tops of low linear velocity settler, controls certain linear velocity in the low linear velocity settler 2, has both satisfied this part catalyst smugglied secretly and can subside through self gravity, satisfies again that the bulk density index is less than the ash content granule of catalyst and can enter into ash content collection system along with flue gas discharge low linear velocity settler 2, carries out high-efficient separation with the gas-solid phase of dusty flue gas by cyclone's mode. Meanwhile, at the upper part of the fast coking tank 1, the regenerated catalyst is firstly introduced into an external heat collector for cooling, the heat collector adopts a descending design, the flow direction of heat exchange medium desalted water is opposite to that of the catalyst, the catalyst after heat extraction is returned to the lower part of the fast coking tank 1, the whole regeneration process is completed, the requirement of a reaction system on the temperature of the regenerated catalyst is met, and then the regenerated catalyst is led out to the reaction system from the lower part of the fast coking tank 1.
The embodiment of the invention provides a regeneration method of a catalyst regeneration system for catalytic cracking of cellulose biomass to produce hydrogen, inactivated catalyst and carbon residue from a reaction system for producing aromatic hydrocarbon by cracking of biomass are conveyed to the lower part of a rapid coking burning tank 1 through an inclined tube to be mixed and burned with main air, the carbon residue carried by the inactivated catalyst is burned to cause overhigh regeneration temperature, a descending external heat collector 5 is started to take away excessive heat and maintain the regeneration temperature; if the sampling finds that the carbon content of the regenerated catalyst does not reach the standard or the burning depth of the carbon residue is insufficient, the regenerated catalyst with the carbon content not reaching the standard and the incompletely burnt carbon residue are returned to the quick coking tank 1 through the catalyst circulating pipe and contacted with the main air again and burned at the lower part of the quick coking tank 1. The operation conditions of the main process equipment of the cellulose biomass catalytic cracking hydrogen production catalyst regeneration system are as follows: fast-coking tank 1: the operation temperature is 600-1000 ℃; the operation gas speed is 2-6 m/s; the scorching strength is 200-350 kg/t.h; low linear velocity settler 2: the top pressure was 0.3MPa (gauge pressure); the operation gas velocity is less than 0.1 m/s. Further preferably, the optimized operating parameters are: fast-coking tank 1: the operating temperature is 850 ℃; the operating gas velocity (linear velocity) was 1.5 m/s; the burning intensity is 200-300 kg/t.h; low linear velocity settler 2: the top pressure was 0.3MPa (gauge pressure) and the operating gas velocity was 0.08 m/s.
Example 1
As shown in fig. 1, this embodiment provides a regeneration system of a catalyst for catalytic cracking of cellulosic biomass to produce hydrogen. The method comprises the following steps: the system comprises a quick coke burning tank 1, a low linear speed settler 2, a cyclone separator 3, an ash collector 4 and a descending external heat collector 5. The lower part of the quick coking tank 1 is provided with a main air inlet, a regenerated catalyst lifting inlet and a regenerated catalyst outlet, the middle part of the quick coking tank 1 is provided with an inactivated catalyst inlet, and the middle upper part of the quick coking tank 1 is provided with a high-temperature regenerated catalyst outlet; the low linear speed settler 2 is connected with the fast coking tank 1; the upper part of the low linear velocity settler 2 is connected to the ash collection system; the descending external heat collector 5 is connected with the rapid coking tank 1. The rapid coking tank 1 is a bubbling type combustion bed reactor with high coking strength. The low linear speed settler 2 is positioned above the fast coking tank 1, and the height of the low linear speed settler 2 is 7.5 m. The ash collection system comprises a cyclone 3 and an ash collector 4, and the cyclone 3 and the ash collector 4 are connected.
The descending external heat collector 5 is used for exchanging part of heat of the regenerated catalyst, and the flow direction of the heat exchange medium is opposite to that of the regenerated catalyst. The upper part of the descending external heat remover 5 is connected with the high-temperature regenerated catalyst outlet, and the lower part of the descending external heat remover 5 is connected with the regenerated catalyst lifting inlet of the rapid coking tank 1. The lower part of the descending external heat collector 5 is provided with a heat exchange medium inlet, and the upper part of the descending external heat collector 5 is provided with a heat exchange medium outlet. The descending external heat collector 5 adopts heat exchange medium as boiler desalted water.
The present embodiment provides an operation method for performing a deactivated catalyst regeneration process by using the regeneration system, which includes the following steps:
spent catalyst and carbon residue C1 from a cellulose biomass catalytic cracking hydrogen production reaction system enter from the middle part of a quick coking tank 1 and are mixed and combusted with main air L1 (air) from the lower part, the coking strength of the quick coking tank 1 is 300 kg/t.h, the operating temperature is 850 ℃, and the operating pressure is 0.35MPa (gauge pressure).
The deactivated catalyst is regenerated after burning and decarbonizing, simultaneously, the carbon residue of one of the entrained reaction products is burnt into ash particles, the carbon residue and the ash particles are lifted upwards by flue gas, most of the regenerated catalyst is separated at the bottom of the low linear velocity settler 2 due to the action of gravity, a small amount of particles and the ash particles are brought into the low linear velocity settler 2 by the flue gas, the top pressure of the low linear velocity settler 2 is 0.3MPa (gauge pressure), the operating linear velocity in the low linear velocity settler 2 is 0.1m/s, the value is lower than the entrainment velocity of the catalyst and higher than the entrainment velocity of the ash particles, so that part of the catalyst particles entrained so far are settled downwards again under the action of gravity, the flue gas and ash particle material flow G1 is discharged to the cyclone separator 3 through the top of the low linear velocity settler 2, the ash particles are separated from the flue gas under the action of centrifugal force, and the flue gas G2 is discharged to a post-system from the top of the cyclone separator 3, the ash particles are discharged to an ash collector 4.
The temperature of the regenerated catalyst after being coked is 850 ℃, the temperature requirement of a reaction system on a circulating catalyst is not met, and the temperature needs to be reduced through heat exchange, so that the regenerated catalyst C2 after being coked firstly enters a downlink external heat collector 5 to exchange heat with desalted water W1 to reduce the temperature to 650 plus 700 ℃ to generate steam W2, the cooled catalyst C3 is lifted to the lower part of the quick coking tank 1 through lifting air L2 (air), and the regenerated and heated catalyst C4 after being coked is conveyed to the reaction system through the lower part of the quick coking tank 1. If the sampling finds that the carbon content of the regenerated catalyst does not reach the standard or the burning depth of the carbon residue is insufficient, the regenerated catalyst with the carbon content not reaching the standard and the incompletely burnt carbon residue are returned to the lower part of the fast coke burning tank 1 to be contacted with the main air for burning again through the catalyst circulating pipe.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A regeneration system of a cellulose biomass catalytic cracking hydrogen production catalyst is characterized by comprising: the system comprises a quick coking tank (1), a low linear speed settler (2), a descending external heat collector (5) and an ash collection system; the lower part of the quick coking tank (1) is provided with a main air inlet, a regenerated catalyst lifting inlet and a regenerated catalyst outlet, the middle part of the quick coking tank (1) is provided with an inactivated catalyst inlet, and the middle upper part of the quick coking tank (1) is provided with a high-temperature regenerated catalyst outlet; the low linear speed settler (2) is connected with the fast coking tank (1); the upper part of the low linear velocity settler (2) is connected to the ash collection system; the descending external heat collector (5) is connected with the quick coke burning tank (1).
2. The regeneration system of cellulose biomass catalytic cracking hydrogen production catalyst according to claim 1, wherein the fast-burning coke tank (1) is a bubbling-type combustion bed reactor.
3. The regeneration system of the catalyst for catalytic pyrolysis of cellulose biomass to produce hydrogen according to claim 1, wherein the low linear velocity settler (2) is located above the fast coking tank (1), and the height of the low linear velocity settler (2) is 3-12 m.
4. The regeneration system of cellulose biomass catalytic cracking hydrogen production catalyst according to any one of claims 1 to 3, wherein the ash collection system comprises a cyclone separator (3) and an ash collector (4), and the cyclone separator (3) and the ash collector (4) are connected.
5. The regeneration system of cellulose biomass catalytic cracking hydrogen production catalyst according to claim 1, wherein the descending external heat collector (5) is used for exchanging part of heat of the regenerated catalyst, and the heat exchange medium and the regenerated catalyst flow in opposite directions.
6. The regeneration system of cellulose biomass catalytic cracking hydrogen production catalyst according to claim 5, wherein the upper part of the downward external heat collector (5) is connected to the high temperature regenerated catalyst outlet, and the lower part of the downward external heat collector (5) is connected to the regenerated catalyst lifting inlet of the fast coke-burning tank (1).
7. The regeneration system of cellulose biomass catalytic cracking hydrogen production catalyst according to claim 6, wherein the lower part of the downward external heat collector (5) is provided with a heat exchange medium inlet, and the upper part of the downward external heat collector (5) is provided with a heat exchange medium outlet.
8. The regeneration system of cellulose biomass catalytic cracking hydrogen production catalyst according to claim 7, wherein the downward external heat collector (5) adopts a heat exchange medium to remove salt water from the boiler.
9. The regeneration method of the regeneration system of the cellulose biomass catalytic cracking hydrogen production catalyst according to claims 1 to 7, characterized by comprising: inactivation catalyst and residual carbon get into fast burning coke jar (1) middle part, in fast burning coke jar (1) lower part and main air mixed combustion obtain regenerated catalyst and flue gas, regenerated catalyst is in low linear velocity settler (2) with the flue gas separation, after the separation regenerated catalyst gets into down outer heat collector (5), gets into after the cooling fast burning coke jar (1) lower part, again by fast burning coke jar (1) lower part gets into reaction system.
10. The regeneration method of the regeneration system of the catalyst for catalytic pyrolysis of cellulose biomass to produce hydrogen according to claim 9, wherein the operating temperature of the fast-burning coke tank (1) is 600-1000 ℃; the operation gas speed is 2-6 m/s; the scorching strength is 200-350 kg/t.h; the top pressure of the low linear speed settler (2) is 0.2-0.4 MPa; the operation gas velocity is less than 0.1 m/s.
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| US20160304799A1 (en) * | 2009-11-18 | 2016-10-20 | G4 Insights Inc. | Method and system for biomass hydrogasification |
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| CN108114721A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of continuous production method of catalyst and biomass preparing synthetic gas |
| CN217248979U (en) * | 2022-02-08 | 2022-08-23 | 中节能工程技术研究院有限公司 | Regeneration system of catalyst for cellulose biomass catalytic cracking hydrogen production |
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Patent Citations (4)
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| US20160304799A1 (en) * | 2009-11-18 | 2016-10-20 | G4 Insights Inc. | Method and system for biomass hydrogasification |
| CN108114721A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of continuous production method of catalyst and biomass preparing synthetic gas |
| CN106552667A (en) * | 2016-12-01 | 2017-04-05 | 北京禾生新源科技有限公司 | A kind of regenerative system and renovation process of molecular sieve catalyst being applied in biomass cracking aromatic hydrocarbons |
| CN217248979U (en) * | 2022-02-08 | 2022-08-23 | 中节能工程技术研究院有限公司 | Regeneration system of catalyst for cellulose biomass catalytic cracking hydrogen production |
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