CN115490566A - Fixed bed reaction system and application thereof, and reaction regeneration method for preparing low-carbon olefin by converting oxygen-containing compound water material - Google Patents
Fixed bed reaction system and application thereof, and reaction regeneration method for preparing low-carbon olefin by converting oxygen-containing compound water material Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 170
- 150000001875 compounds Chemical class 0.000 title claims abstract description 74
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000001301 oxygen Substances 0.000 title claims abstract description 73
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 73
- 238000011069 regeneration method Methods 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 163
- 230000008929 regeneration Effects 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 150000001336 alkenes Chemical class 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 26
- 239000002808 molecular sieve Substances 0.000 claims description 26
- 238000000926 separation method Methods 0.000 claims description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000003546 flue gas Substances 0.000 claims description 14
- 150000002576 ketones Chemical class 0.000 claims description 14
- 150000001299 aldehydes Chemical class 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000000047 product Substances 0.000 description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 239000005977 Ethylene Substances 0.000 description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 22
- -1 carbon olefins Chemical class 0.000 description 21
- 230000000694 effects Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000004523 catalytic cracking Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
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- 239000003345 natural gas Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000003034 coal gas Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
- B01J38/14—Treating with free oxygen-containing gas with control of oxygen content in oxidation gas
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
The invention provides a fixed bed reaction system and an application and reaction regeneration method thereof, wherein the system comprises: the device comprises a fixed bed reactor and a plurality of sections of catalyst bed layers arranged in the fixed bed reactor, wherein each section of catalyst bed layer is respectively arranged to be capable of independently controlling temperature, and each section of catalyst bed layer is provided with a material feeding hole and a material discharging hole; the catalyst bed layers at all sections are connected in parallel during reaction; the catalyst bed layers of all the sections are connected in series when in regeneration; the method comprises the following steps: feeding materials from a section of catalyst bed layer in the reactor to contact with the catalyst to generate a product material flow containing low-carbon olefin, starting other catalyst bed layer sections to react after the reaction of the section is finished, finishing the reaction process of the fixed bed reactor after the catalyst bed layer sections are all started to react for at least one time, and starting the regeneration process of the fixed bed reactor. The method of the invention has the advantages of capability of processing the raw material with high water content, high conversion rate of the oxygen-containing compound, high yield of olefin and long reaction regeneration period.
Description
Technical Field
The invention relates to a fixed bed reaction system, application thereof in low-carbon olefin preparation through conversion of an oxygen-containing compound water material and a reaction regeneration method for low-carbon olefin preparation through conversion of the oxygen-containing compound water material.
Background
The demand for lower olefins, defined herein as ethylene and propylene, is increasing as two important basic chemical feedstocks are being developed. Ethylene and propylene have traditionally been produced mainly through petroleum routes, but the cost of producing ethylene and propylene from petroleum resources has been increasing due to the limited supply and high price of petroleum resources. In recent years, alternative energy conversion technologies, such as a process for preparing olefin (OTO) by converting an oxygen-containing compound, including methanol, ethanol, dimethyl ether, methyl ethyl ether, etc., have been vigorously developed. There are many technologies available for producing oxygenates and feedstocks including coal, natural gas, biomass, and the like. Such as methanol, can be made from coal or natural gas, the process is fully mature, and production scales of millions of tons can be realized. Due to the wide range of oxygenate sources, coupled with the economics of the conversion to lower olefins processes, processes for the conversion of Oxygenates To Olefins (OTO), particularly the conversion of Methanol To Olefins (MTO), are receiving increasing attention.
The oxygen-containing compound is mainly methanol, and the by-products of the oxygen-containing compounds such as ketone, aldehyde, ether and the like are inevitably produced in the catalytic conversion process. The partial oxygen-containing compounds are generally primarily separated in the form of aqueous solution mixtures, and because the components are complex and the concentration is not high, the recovery difficulty and the cost are high, and the partial oxygen-containing compounds are generally treated as hazardous wastes. In recent years, with the increasing treatment cost, how to effectively recycle the part of the oxygen-containing compounds and improve the resource utilization of production wastes gradually becomes a difficult problem to be solved urgently in the industrial process of preparing low-carbon olefins from the oxygen-containing compounds.
CN103752229 discloses a method for coupling the reaction of propylene/ethylene preparation by catalytic cracking of olefin and the reaction of propylene/ethylene preparation by oxygen-containing compounds in a reactor, wherein 2-9 catalyst beds are arranged in the reactor from top to bottom in sequence, an intersegmental feeding mixing distributor is arranged between each catalyst bed, the reaction temperature is 400.0-650.0 ℃, and the oxygen-containing compounds are selected from methanol, dimethyl ether and the mixture thereof, but the reaction cracking of aldehyde ketone oxygen-containing compounds is not involved.
CN102276408 discloses a radial fixed bed reactor, which solves the problem of reaction heat release, reduces bed pressure drop, and can improve the overall olefin yield and the long-term stability of a catalyst.
CN102325741 and CN102227393 disclose a method for producing olefin by direct reaction of ketone and hydrogen in the presence of a hydrogenation catalyst containing Cu and a solid acid substance by using a fixed bed reactor, wherein the reaction temperature is 50-300 ℃. It was not determined whether the feed contained water or not.
Disclosure of Invention
The invention aims to solve the technical problems of low olefin yield and short reaction regeneration period in the preparation of low-carbon olefin by using an oxygen-containing compound in the prior art, and provides a fixed bed reaction system, application thereof and a reaction regeneration method for preparing low-carbon olefin by converting an oxygen-containing compound water material.
According to a first aspect of the present invention, there is provided a fixed bed reaction system comprising:
the device comprises a fixed bed reactor and a plurality of sections of catalyst bed layers arranged in the fixed bed reactor, wherein each section of catalyst bed layer is respectively arranged to be capable of independently controlling the temperature, and each section of catalyst bed layer is provided with a material feeding hole and a material discharging hole.
Preferably, the system further comprises: the separation unit is connected with the material discharge hole and used for separating reaction materials, and comprises one or more of a gas-liquid separation unit, a gas-gas separation unit and a liquid-liquid separation unit; and/or a raw material supply unit connected with the material feeding port; preferably, the raw material supply unit comprises a material storage unit and a supply pipeline; preferably, the feeding pipelines comprise a first-stage pipeline, a second-stage pipeline and a third-stage pipeline which are connected in series, and the first-stage pipeline comprises 2-5 pipelines which are connected in parallel and connected with the material storage unit; the third stage pipeline comprises 2-10 pipelines connected with the fixed bed reactor in parallel.
Preferably, the system comprises a plurality of said fixed bed reactors, preferably 1-3 of said fixed bed reactors; and/or the catalyst bed layer is 2-10 sections, preferably 3-5 sections; and/or the catalyst bed layers are connected in parallel during reaction.
Preferably, the catalyst beds in the sections are connected in series during regeneration; and/or each pipeline arranged in the system is provided with an opening and closing valve; and/or a transition zone is arranged between the catalyst beds for distributing raw materials, gathering products and separating the temperature of the catalyst beds.
According to a second aspect of the invention, the invention provides the use of the reaction system of the invention for the conversion of an oxygenate water feed to lower olefins.
According to a third aspect of the present invention, the present invention provides a reaction regeneration method for converting an oxygen-containing compound water material into low carbon olefins, which is performed in the fixed bed reaction system of the present invention, and the system comprises: the device comprises a fixed bed reactor and a plurality of sections of catalyst bed layers arranged in the fixed bed reactor, wherein each section of catalyst bed layer is independently arranged to be capable of controlling temperature, and each section of catalyst bed layer is provided with a material feeding hole and a material discharging hole; the catalyst bed layers at all sections are connected in parallel during reaction; the catalyst bed layers of all the sections are connected in series when in regeneration;
the method comprises the following steps:
a) Feeding a material containing an oxygen-containing compound and water from one section of a catalyst bed layer in the fixed bed reactor to contact with the catalyst to generate a product material flow containing low-carbon olefin, wherein the catalyst bed layer section contacted with the section is used as a reaction section, and the rest catalyst bed layer sections which are not started are constant-temperature sections; after the reaction of the section is finished, cutting off the material feeding containing the oxygen-containing compound and the water of the section, starting other catalyst bed sections to react, and repeating the steps until the catalyst bed sections are all started for at least one reaction, finishing the reaction process of the fixed bed reactor, and starting the regeneration process of the fixed bed reactor.
Preferably, the method comprises:
selecting catalyst beds of the fixed bed reactors from top to bottom in sequence as reaction sections, and selecting each section of catalyst bed as a reaction section only once in a reaction regeneration period;
preferably, the temperature of the catalyst bed layer in the reaction section is 400-550 ℃, and the temperature of the catalyst bed layer in the constant temperature section is 200-400 ℃;
more preferably, the temperature of the catalyst bed layer in the reaction section is 450-500 ℃, and the temperature of the catalyst bed layer in the constant temperature section is 250-350 ℃.
Preferably, when the conversion rate of the outlet oxygen-containing compound of each section of the catalyst bed layer serving as the reaction section is less than 50%, the switching between the reaction section and the constant-temperature section is carried out.
Preferably, the method further comprises:
b) After the product flow containing the low-carbon olefin enters a gas-liquid separator for gas-liquid separation, a gas-phase product containing the low-carbon olefin is subjected to a light hydrocarbon separation process, and a liquid-phase product is subjected to an oxygen-containing compound recovery process;
c) After the fixed bed reactor is purged by nitrogen, air is introduced to regenerate the catalyst, and the regenerated flue gas is used for removing the flue gas.
Preferably the oxygenate comprises at least one of an alcohol, an aldehyde and a ketone, preferably the oxygenate comprises at least one of methanol, ethanol, acetaldehyde, propionaldehyde, acetone and butanone.
Preferably, the ketone accounts for not less than 20% of the mass of the oxygen-containing compound, and the aldehyde accounts for not more than 10% of the mass of the oxygen-containing compound.
Preferably, the catalyst is a molecular sieve, preferably the molecular sieve is selected from at least one of ZSM-5, ZSM-11 and ZSM-34; more preferably, the silica to alumina ratio of the molecular sieve is greater than 80, and preferably the silica to alumina ratio of the molecular sieve is greater than 200.
Preferably, the reaction pressure of the fixed bed reactor is 0 to 0.6MPa, preferably 0.05 to 0.3MPa, in terms of gauge pressure.
Preferably, the mass space velocity of each section of catalyst bed layer of the fixed bed reactor is 0.01-40.0 h- 1 Preferably 0.5-10.0 h- 1 。
Preferably, the conditions for regeneration of the fixed bed reactor include: the regeneration temperature is 350-600 ℃, the regeneration pressure is 0-0.5 MPa in terms of gauge pressure, and the mass airspeed of the regeneration air is 0.01-50.0 h in terms of the total mass of the molecular sieve catalyst in the reactor 1 。
Preferably, the conditions for regeneration of the fixed bed reactor include: the regeneration temperature is 400-550 ℃, the regeneration pressure is 0.1-0.3 MPa by gauge pressure, and the mass airspeed of the regeneration air is 0.05-5.0 h by the total mass of the molecular sieve catalyst in the reactor 1 。
The method of the invention has the advantages of capability of processing high water content raw materials, high conversion rate of oxygen-containing compounds, high olefin yield and long reaction regeneration period.
Drawings
FIG. 1 is a schematic diagram of a process and system for producing lower olefins from oxygenates in accordance with the present invention.
Description of the reference numerals
1-fixed bed reactor, 2-gas-liquid separator;
3-mixture raw material, 4-inert gas;
5-regeneration gas, 6-gas-liquid separator feed valve;
7-flue gas, 8-gas phase product containing low carbon olefin;
9-liquid phase product, 10, 11, 12, 13, 14-feed valve of fixed bed reactor;
15. 16, 17, 18 and 19-discharge valves of fixed bed reactors.
Detailed Description
The following describes the embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention provides a fixed bed reaction system comprising:
the device comprises a fixed bed reactor and a plurality of sections of catalyst beds arranged in the fixed bed reactor, wherein each section of catalyst bed is respectively arranged to be capable of independently controlling the temperature, and each section of catalyst bed is provided with a material feeding hole and a material discharging hole. Through the setting, can realize that each section catalyst bed can react independently, mutual noninterference.
According to a preferred embodiment of the invention, the system further comprises: and the separation unit is connected with the material discharge hole and is used for separating reaction materials, and preferably comprises one or more of a gas-liquid separation unit, a gas-gas separation unit and a liquid-liquid separation unit.
According to a preferred embodiment of the present invention, a raw material supply unit connected to the material feed port; preferably, the raw material supply unit comprises a material storage unit and a supply pipeline.
According to the invention, no special requirement is required on the feeding pipeline, and aiming at the invention, the feeding pipeline preferably comprises a first-stage pipeline, a second-stage pipeline and a third-stage pipeline which are connected in series, wherein the first-stage pipeline comprises 2-5 pipelines which are connected with the material storage unit in parallel and are used for switching different raw materials; the third-stage pipeline comprises 2-10 pipelines which are connected with the fixed bed reactor in parallel and used for switching different catalyst bed layers. The second-stage pipeline is used for mixing the materials in the first-stage pipeline.
According to a preferred embodiment of the present invention, preferably, the system comprises a plurality of the fixed bed reactors, preferably 1 to 3 of the fixed bed reactors. Specifically, the selection can be performed according to the reaction requirement, for example, two reactors can be switched at any time, and when the first reactor is used for reaction, the second reactor is reserved; when the first reactor finishes the reaction operation, the second reactor can be switched immediately for the reaction operation, and the first reactor is subjected to inert gas purging and catalyst regeneration procedures to ensure continuous conversion of the oxygen-containing compound water material.
According to a preferred embodiment of the present invention, preferably, the catalyst bed is in 2 to 10 stages, more preferably 3 to 5 stages. When the loading of the catalyst is the same, the multi-section bed layer is adopted, so that the bed layer thickness of the single-section catalyst can be properly reduced, and although the active reaction running time of the single-section bed layer is reduced, the superposition of the multi-section bed layers can increase the total reaction running time.
According to the preferred embodiment of the present invention, preferably, the catalyst beds are connected in parallel during the reaction. Thereby realizing that catalyst beds at all sections are not interfered with each other, reducing the influence of the deactivated catalyst on the conversion of the oxygen-containing compound as much as possible and improving the yield of the low-carbon olefin.
According to the preferred embodiment of the present invention, it is preferred that the catalyst beds are regenerated in series. Thereby realizing simple and convenient catalyst regeneration operation and improving the efficiency.
According to a preferred embodiment of the present invention, preferably, a switching valve is provided on each of the pipes provided in the system. Thereby realizing the independent control of each section of catalyst bed layer.
According to the preferred embodiment of the present invention, preferably, a transition zone is arranged between each section of the catalyst bed for separating the distribution of raw materials, the accumulation of products and the temperature of the catalyst bed.
The system is suitable for various reaction systems, such as fixed bed catalytic reaction with rapid inactivation, butylene cracking, methanol-to-propylene, toluene-methanol alkylation and the like. The invention particularly provides application of the reaction system in the conversion of an oxygen-containing compound water material to prepare low-carbon olefin.
According to a preferred embodiment of the present invention, there is provided a method for regenerating a reaction for converting an oxygen-containing compound water feed into lower olefins, the method being performed in a fixed-bed reaction system according to the present invention, the system comprising: the device comprises a fixed bed reactor and a plurality of sections of catalyst bed layers arranged in the fixed bed reactor, wherein each section of catalyst bed layer is independently arranged to be capable of controlling temperature, and each section of catalyst bed layer is provided with a material feeding hole and a material discharging hole; the catalyst bed layers at all sections are connected in parallel during reaction; the catalyst bed layers of all the sections are connected in series when in regeneration;
the method comprises the following steps:
a) Feeding a material containing an oxygen-containing compound and water from one section of a catalyst bed layer in the fixed bed reactor to contact with the catalyst to generate a product stream containing low-carbon olefins, wherein the catalyst bed layer section contacted with the section is used as a reaction section, and the rest catalyst bed layer sections which are not started are constant-temperature sections; after the reaction of the section is finished, cutting off the material feeding containing the oxygen-containing compound and the water of the section, starting other catalyst bed sections to react, and repeating the steps until the catalyst bed sections are all started for at least one reaction, finishing the reaction process of the fixed bed reactor, and starting the regeneration process of the fixed bed reactor.
According to the present invention, there is no special requirement for the regeneration process, nor for the regeneration means.
According to a preferred embodiment of the present invention, preferably, the method comprises: the catalyst bed layers of the fixed bed reactor are selected from top to bottom in sequence as reaction sections, and each section of catalyst bed layer is selected as a reaction section only once in a reaction regeneration period, so that the high-efficiency utilization rate of the catalyst is realized.
According to a preferred embodiment of the invention, the temperature of the catalyst bed layer in the reaction section is 400-550 ℃, and the temperature of the catalyst bed layer in the constant temperature section is 200-400 ℃. The device has the advantages of preventing material condensation and saving energy consumption.
According to a preferred embodiment of the present invention, more preferably, the temperature of the catalyst bed layer in the reaction section is 450 to 500 ℃, and the temperature of the catalyst bed layer in the constant temperature section is 250 to 350 ℃. Therefore, the method has the advantage of improving the yield of the low-carbon olefin.
According to a preferred embodiment of the present invention, the switching between the reaction section and the constant temperature section is preferably performed when the conversion rate of the outlet oxygen-containing compound of each section of the catalyst bed layer as the reaction section is less than 50%. This arrangement has the advantage of a combined increase in oxygenate conversion and catalyst activity time.
According to a preferred embodiment of the present invention, preferably, the method further comprises:
b) After the product flow containing the low-carbon olefin enters a gas-liquid separator for gas-liquid separation, a gas-phase product containing the low-carbon olefin is subjected to a light hydrocarbon separation process, and a liquid-phase product is subjected to an oxygen-containing compound recovery process;
c) After the fixed bed reactor is purged by nitrogen, air is introduced to regenerate the catalyst, and the regenerated flue gas is used for removing the flue gas.
The present invention does not specifically require the oxygen-containing compound, and according to a preferred embodiment of the present invention, preferably the oxygen-containing compound includes at least one of alcohol, aldehyde, and ketone, and more preferably, the oxygen-containing compound includes at least one of methanol, ethanol, acetaldehyde, propionaldehyde, acetone, and butanone. According to the present invention, preferably the oxygenate is a mixture of methanol, acetaldehyde and acetone.
According to a preferred embodiment of the present invention, preferably, the ketone accounts for not less than 20% by mass of the oxygen-containing compound, and the aldehyde accounts for not more than 10% by mass of the oxygen-containing compound. This has the advantage of increasing the catalyst activation time.
According to the present invention, it is preferable that the ketone accounts for 20 to 60% by weight of the oxygen-containing compound and the aldehyde accounts for 1 to 10% by weight of the oxygen-containing compound.
According to a preferred embodiment of the present invention, the oxygenate is a mixture of methanol, acetaldehyde and acetone, the acetone is present in an amount of 20 to 60 wt% based on the mass of the oxygenate, the acetaldehyde is present in an amount of 1 to 10 wt% based on the mass of the oxygenate, and the methanol is present in an amount of 30 to 70 wt% based on the mass of the oxygenate.
According to a preferred embodiment of the present invention, the oxygen-containing compound accounts for 10 to 70% by mass of the total material; preferably, the oxygen-containing compound accounts for 20-50% of the total material by mass. Thereby having the advantage of handling high water content materials.
The catalyst is not particularly required by the present invention, and according to a preferred embodiment of the present invention, the catalyst is a molecular sieve, more preferably the molecular sieve is at least one selected from the group consisting of ZSM-5, ZSM-11 and ZSM-34; it is further preferred that the silica to alumina ratio of the molecular sieve is greater than 80, and it is preferred that the silica to alumina ratio of the molecular sieve is greater than 200. Thereby having the advantage of improving the yield of the low-carbon olefin.
According to a preferred embodiment of the present invention, preferably the molecular sieve is a ZSM-5 molecular sieve.
According to a preferred embodiment of the present invention, the reaction pressure of the fixed bed reactor is 0 to 0.6MPa, preferably 0.05 to 0.3MPa, in gauge pressure.
According to a preferred embodiment of the invention, the mass space velocity of each section of the catalyst bed layer of the fixed bed reactor is 0.01-40.0 h- 1 Preferably 0.5-10.0 h- 1 。
According to a preferred embodiment of the present invention, the conditions for the regeneration of the fixed bed reactor comprise: the regeneration temperature is 350-600 ℃, the regeneration pressure is 0-0.5 MPa in terms of gauge pressure, and the mass airspeed of the regenerated air is 0.01-50.0 h in terms of the total mass of the molecular sieve catalyst in the reactor 1 。
According to a more preferred embodiment of the present invention, preferably, the conditions of regeneration of the fixed bed reactor comprise: the regeneration temperature is 400-550 ℃, the regeneration pressure is 0.1-0.3 MPa by gauge pressure, and the mass airspeed of the regeneration air is 0.05-5.0 h by the total mass of the molecular sieve catalyst in the reactor 1 。
According to a preferred embodiment of the present invention, the present invention provides a reaction regeneration method for converting an oxygen-containing compound water material into low-carbon olefins, which mainly comprises the following steps: a) Contacting a material containing an oxygen-containing compound and water with a molecular sieve catalyst in a fixed bed reactor to generate a product stream containing low-carbon olefins; b) After the product flow enters a gas-liquid separator for gas-liquid separation, a light hydrocarbon separation procedure is carried out on a gas phase product containing low-carbon olefin, and an oxygen-containing compound recovery procedure is carried out on a liquid phase product; c) Cutting off materials containing oxygen compounds and water, purging the fixed bed reactor with nitrogen, introducing air to regenerate the molecular sieve catalyst, and removing the flue gas from the regenerated flue gas system; the fixed bed reactor is internally provided with a plurality of sections of catalyst bed layers, the catalyst bed layers are connected in parallel during reaction, materials are contacted with the catalyst bed layers in sequence and only contacted with one of the catalyst bed layers during reaction, the catalyst bed layers are connected in series during regeneration, and transition regions are arranged among the catalyst bed layers.
Embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 shows a process flow diagram for the conversion of an oxygenate water feed to lower olefins in accordance with one embodiment of the present invention.
The system of fig. 1 comprises: the device comprises a fixed bed reactor 1 and a gas-liquid separation system, wherein the fixed bed reactor is communicated with the gas-liquid separation system; the fixed bed reactor is provided with a plurality of catalyst bed reaction sections from top to bottom, and the temperature of each reaction section can be independently adjusted.
When the system of fig. 1 is adopted to prepare the low-carbon olefin, the feed valve 10 of the fixed bed reactor and the discharge valve 15 of the fixed bed reactor can be firstly opened, the feed valves 11, 12, 13 and 14 of the fixed bed reactor and the discharge valves 16, 17, 18 and 19 of the fixed bed reactor are closed, the catalyst bed layer at the uppermost part of the fixed bed reactor is used as a reaction section for reaction, the mixture raw material 3 of the oxygenated compounds and the water is sequentially subjected to catalytic cracking reaction through the fixed bed reactor 1, the product is separated through the gas-liquid separator 2, the obtained gas-phase product 8 containing the low-carbon olefin can enter a subsequent separation process from the upper part of the gas-liquid separator 2, and the liquid-phase product 9 enters the subsequent separation process from the lower part of the gas-liquid separator 2. The rest catalyst bed layers are constant temperature sections, and transition regions are respectively arranged among the catalyst bed layers.
In the reaction process, when the conversion rate of the oxygen-containing compound in the cracked product at the outlet of the reaction section is less than 50%, adjusting the temperature of a constant-temperature section at the next stage of the reaction section to the reaction temperature to obtain a new reaction section; and adjusting the temperature of the reaction section to a constant temperature to obtain a new constant temperature section.
Then the feed valve 11 of the fixed bed reactor and the discharge valve 16 of the fixed bed reactor are opened, the feed valves 10, 12, 13 and 14 of the fixed bed reactor and the discharge valves 15, 17, 18 and 19 of the fixed bed reactor are closed, and the reaction is continued by using a new reaction section.
When the catalyst is regenerated, the catalyst can be regenerated by blowing the fixed bed reactor 1 with the inert gas 4, then introducing the regeneration gas 5, and introducing the regenerated flue gas 9 into a flue gas system.
Example 1
Example 1 proposes a reaction regeneration method for converting an oxygen-containing compound water material into low-carbon olefins, as shown in figure 1,
1-fixed bed reactor, 2-gas-liquid separator;
3-mixture raw material, 4-inert gas;
5-regeneration gas, 6-gas-liquid separator feed valve;
7-flue gas, 8-gas phase product containing low carbon olefin;
9-liquid phase product, 10, 11, 12, 13, 14-feed valve of fixed bed reactor;
15. 16, 17, 18 and 19-discharge valves of the fixed bed reactors.
The method comprises the following steps:
1. firstly, opening a feed valve 10 of a fixed bed reactor and a discharge valve 15 of the fixed bed reactor, closing feed valves 11, 12, 13 and 14 of the fixed bed reactor and discharge valves 16, 17, 18 and 19 of the fixed bed reactor, reacting by using a catalyst bed layer at the uppermost part of the fixed bed reactor as a reaction section, performing catalytic cracking reaction on a mixture raw material 3 containing an oxygen-containing compound and water sequentially through the fixed bed reactor 1, separating the product through a gas-liquid separator 2, allowing the obtained gas-phase product 8 containing low-carbon olefin to enter a subsequent separation process from the upper part of the gas-liquid separator 2, and allowing the liquid-phase product 9 to enter the subsequent separation process from the lower part of the gas-liquid separator 2. The rest 4 sections of catalyst bed layers are constant temperature sections, and transition zones are respectively arranged among the catalyst bed layers.
In the mixture, the mass ratio of the oxygen-containing compound to the water is 1:1. the oxygen-containing compounds are alcohol, aldehyde and ketone oxygen-containing compounds, and based on the mass of the oxygen-containing compounds, the mass percentage of the alcohol compounds is 40%, the mass percentage of the aldehyde compounds is 10%, and the mass percentage of the ketone compounds is 50%. Wherein, the alcohol compound is methanol, the aldehyde compound is acetaldehyde, and the ketone compound is acetone according to the mass ratio.
The pressure of the reaction in the fixed bed reactor was 0.2MPa. The temperature of the reaction section is 480 ℃, and the temperature of the constant temperature section is 300 ℃. ZSM-5 molecular sieve catalysts are respectively filled in each section, and the silica-alumina ratio of the catalysts is 250.
The mass space velocity of the mixture in the first reaction zone was 5.0h based on the mass of the oxygenate -1 。
2. In the reaction process, when the conversion rate of the oxygen-containing compound in the cracked product at the outlet of the reaction section is less than 50 percent, regulating the temperature of a constant temperature section at the next stage of the reaction section to the reaction temperature to obtain a new reaction section; and adjusting the temperature of the reaction section to a constant temperature to obtain a new constant temperature section. Then the feed valve 11 of the fixed bed reactor and the discharge valve 16 of the fixed bed reactor are opened, the feed valves 10, 12, 13 and 14 of the fixed bed reactor and the discharge valves 15, 17, 18 and 19 of the fixed bed reactor are closed, and the reaction is continued by using a new reaction section. The reaction was carried out until all beds had switched.
3. After the reaction is finished, the catalyst is regenerated, the fixed bed reactor 1 is firstly swept by nitrogen inert gas 4, the catalyst is regenerated by introducing regeneration gas air 5, and the regenerated flue gas 7 is introduced into a flue gas system.
The regeneration temperature is 500 ℃, the regeneration pressure is 0.2MPa, and the catalyst is based on the mass of the catalystMeter, mass space velocity of regenerated gas is 5.0h -1 。
The average conversion of the feed of example 1 was calculated to be 82.5%, the average selectivity (ethylene + propylene) was calculated to be 73.7%, and the total activity time of each catalyst stage was calculated to be 920h.
Example 2
Example 2 differs from example 1 only in that the temperature in the reaction section of example 2 was 500 ℃ and the temperature in the constant temperature section was 200 ℃, all other steps and parameters being the same.
The average conversion of the feed of example 2 was calculated to be 83.0%, the average selectivity of (ethylene + propylene) was calculated to be 70.7%, and the total activity time of each stage of the catalyst was 892h.
Example 3
Example 3 differs from example 1 only in that the temperature in the reaction zone of example 3 was 450 c and the temperature in the thermostatic zone was 350 c, the remaining steps and parameters being identical.
The average conversion of the feed of example 3 was calculated to be 81.8% and the average selectivity (ethylene + propylene) was calculated to be 72.0%, the total activity time of each catalyst stage being 910h.
Example 4
Example 4 differs from example 1 only in that the temperature in the reaction zone of example 4 was 400 c and the temperature in the thermostatic zone was 250 c, the remaining steps and parameters being identical.
The average conversion of the feed of example 4 was calculated to be 74.8%, the average selectivity (ethylene + propylene) was calculated to be 59.3%, and the total activity time of each catalyst stage was calculated to be 860h.
Example 5
Example 5 differs from example 1 only in that the temperature in the reaction zone of example 5 was 550 c and the temperature in the thermostatic zone was 400 c, the remaining steps and parameters being identical.
The average conversion of the feed of example 5 was calculated to be 84.2%, the average selectivity of (ethylene + propylene) was calculated to be 66.1%, and the total activity time of each stage of the catalyst was calculated to be 705h.
Example 6
Example 6 differs from example 1 only in that the mass ratio of oxygenate to water in the mixture feed of example 6 is 1:7. the oxygen-containing compounds are alcohol, aldehyde and ketone oxygen-containing compounds, and based on the mass of the oxygen-containing compounds, the mass percentage of the alcohol compounds is 20%, the mass percentage of the aldehyde compounds is 20%, and the mass percentage of the ketone compounds is 60%. Wherein, the alcohol compound is methanol and ethanol with the mass ratio of 3.
The average conversion of the feed of example 6 was calculated to be 71.6%, the average selectivity (ethylene + propylene) was calculated to be 60.7%, and the total activity time of each catalyst stage was calculated to be 495h.
Example 7
Example 7 differs from example 1 only in that the mass ratio of oxygenate to water in the mixture feed of example 7 is 3:2. the oxygen-containing compounds are alcohol, aldehyde and ketone oxygen-containing compounds, and based on the mass of the oxygen-containing compounds, the mass percentage of the alcohol compounds is 15%, the mass percentage of the aldehyde compounds is 5%, and the mass percentage of the ketone compounds is 80%. Wherein, the alcohol compound is ethanol, the aldehyde compound is propionaldehyde, and the ketone compound is acetone and butanone with the mass ratio of 3.
The average conversion of the feed of example 7 was calculated to be 78.4%, the average selectivity (ethylene + propylene) was calculated to be 65.7%, and the total activity time of each catalyst stage was calculated to be 801h.
Example 8
Example 8 differs from example 1 only in that the mass ratio of oxygenate to water in the mixture feed of example 8 is 2:3. the oxygen-containing compounds are alcohol, aldehyde and ketone oxygen-containing compounds, and based on the mass of the oxygen-containing compounds, the mass percentage of the alcohol compounds is 89%, the mass percentage of the aldehyde compounds is 1%, and the mass percentage of the ketone compounds is 10%. Wherein, the alcohol compound is methanol, the aldehyde compound is acetaldehyde, and the ketone compound is acetone according to the mass ratio.
The average conversion of the feed of example 8 was calculated to be 86.2% and the average selectivity (ethylene + propylene) was calculated to be 63.3%, for a total activity time of 770h for each catalyst stage.
Example 9
Example 9 differs from example 3 only in that in example 9, the reaction zone of the fixed bed reactor is a ZSM-34 molecular sieve catalyst having a silica to alumina ratio of 200. The remaining steps and parameters were the same.
The average conversion of the feed of example 9 was calculated to be 76.0% and the average selectivity (ethylene + propylene) to 60.6%, the total activity time of each stage of the catalyst being 745h.
Example 10
Example 10 differs from example 1 only in that in example 10 the regeneration temperature is 550 ℃, the regeneration pressure is 0.1MPa, and the mass space velocity of the regeneration gas is 30.0h based on the mass of the catalyst -1 . The remaining steps and parameters were the same.
The results of the reaction after regeneration in example 1 were calculated: the average conversion of the raw materials is 82.3 percent, the average selectivity of (ethylene + propylene) is 73.6 percent, and the total activity time of each catalyst is 916h. The reaction results after regeneration in example 10 were calculated: the average conversion of the raw materials is 81.1 percent, the average selectivity of the (ethylene + propylene) is 70.9 percent, and the total activity time of each catalyst is 905h.
Comparative example 1
Comparative example 1 is different from example 1 only in that the temperature of the reaction section and the constant temperature section of comparative example 1 is 480 ℃ and the remaining steps and parameters are the same.
The average conversion of the feed of comparative example 1 was calculated to be 80.3%, the average selectivity of the (ethylene + propylene) was calculated to be 70.1%, and the total activity time of each stage of the catalyst was calculated to be 830h.
Comparative example 2
Comparative example 2 differs from example 1 only in that the temperature of the reaction zone and the constant-temperature zone of comparative example 2 is 400 ℃ and the remaining steps and parameters are the same.
The average conversion of the feed of comparative example 2 was calculated to be 66.1%, the average selectivity (ethylene + propylene) was calculated to be 53.2%, and the total activity time of each stage of the catalyst was calculated to be 780h.
Comparative example 3
Comparative example 3 differs from example 1 only in that the catalyst bed of comparative example 3 is not staged, the reactor is filled with the same amount of catalyst as in example 1, and the remaining steps and parameters are the same.
The average conversion of the feed of comparative example 3 was calculated to be 75.9%, the average selectivity (ethylene + propylene) was calculated to be 44.7%, and the total activity time of each catalyst stage was calculated to be 480h.
The above examples and comparative examples were tested or calculated using the following methods:
average conversion of feedstock = (total mass of oxygenate in feedstock-total mass of oxygenate in reaction product)/total mass of oxygenate in feedstock x 100%;
average selectivity of (ethylene + propylene) = total mass of ethylene and propylene in the reaction product/total mass without water in the reaction product x 100%;
the catalyst activity time is the reaction time from the charge to the end of all reaction zones when switching to regeneration.
The experimental results show that the reaction regeneration method for preparing the low-carbon olefin by converting the oxygen-containing compound water material in the embodiment of the invention has the advantages that the conversion rate of most raw materials can reach more than 80 percent, the average selectivity of ethylene and propylene is more than 70 percent, the activity time of the catalyst is obviously prolonged relative to a comparative example, and even can reach 920h, which shows that the method can greatly prolong the service life of the catalyst while obtaining better low-carbon olefin yield.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the individual specific technical features in any suitable way. The invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (10)
1. A fixed bed reaction system, comprising:
the device comprises a fixed bed reactor and a plurality of sections of catalyst bed layers arranged in the fixed bed reactor, wherein each section of catalyst bed layer is respectively arranged to be capable of independently controlling the temperature, and each section of catalyst bed layer is provided with a material feeding hole and a material discharging hole.
2. The reaction system of claim 1, wherein the system further comprises:
the separation unit is connected with the material discharge hole and used for separating reaction materials, and comprises one or more of a gas-liquid separation unit, a gas-gas separation unit and a liquid-liquid separation unit; and/or
The raw material supply unit is connected with the material feeding port;
preferably, the raw material supply unit comprises a material storage unit and a supply pipeline; preferably, the feeding pipelines comprise a first-stage pipeline, a second-stage pipeline and a third-stage pipeline which are connected in series, and the first-stage pipeline comprises 2-5 pipelines which are connected in parallel and connected with the material storage unit; the third stage pipeline comprises 2-10 pipelines connected in parallel with the fixed bed reactor.
3. The reaction system according to claim 1 or 2, wherein,
the system comprises a plurality of the fixed bed reactors, preferably 1-3 of the fixed bed reactors; and/or
The catalyst bed layer is 2-10 sections, preferably 3-5 sections; and/or
The catalyst bed layers at all sections are connected in parallel during reaction; and/or
The catalyst bed layers of all the sections are connected in series when in regeneration; and/or
Opening and closing valves are respectively arranged on all pipelines arranged in the system; and/or
Transition zones are arranged among the catalyst beds of each section and used for distributing raw materials, gathering products and separating the temperature of the catalyst beds.
4. Use of the reaction system of any one of claims 1 to 3 for the conversion of an oxygenate water feed to lower olefins.
5. A reaction regeneration method for converting an oxygen-containing compound water material to prepare low-carbon olefin, which is characterized in that the method is carried out in a fixed bed reaction system of any one of claims 1 to 3, and the system comprises: the system comprises a fixed bed reactor and a plurality of sections of catalyst bed layers arranged in the fixed bed reactor, wherein each section of catalyst bed layer is respectively arranged to be capable of independently controlling the temperature, and each section of catalyst bed layer is provided with a material feeding hole and a material discharging hole; the catalyst bed layers at all sections are connected in parallel during reaction; when the catalyst bed layers of all the sections are regenerated, the catalyst bed layers are connected in series;
the method comprises the following steps:
a) Feeding a material containing an oxygen-containing compound and water from one section of a catalyst bed layer in the fixed bed reactor to contact with the catalyst to generate a product stream containing low-carbon olefins, wherein the catalyst bed layer section contacted with the section is used as a reaction section, and the rest catalyst bed layer sections which are not started are constant-temperature sections; after the reaction of the section is finished, cutting off the material feeding of the section containing the oxygen-containing compound and the water, starting other catalyst bed sections for reaction, and repeating the steps until the catalyst bed sections all start at least one reaction, ending the reaction process of the fixed bed reactor, and starting the regeneration process of the fixed bed reactor.
6. The method of claim 5, wherein the method comprises:
selecting catalyst bed layers of the fixed bed reactor as reaction sections from top to bottom in sequence, and selecting each section of catalyst bed layer as a reaction section only once in a reaction regeneration period;
preferably, the temperature of the catalyst bed layer in the reaction section is 400-550 ℃, and the temperature of the catalyst bed layer in the constant temperature section is 200-400 ℃;
more preferably, the temperature of the catalyst bed layer in the reaction section is 450-500 ℃, and the temperature of the catalyst bed layer in the constant temperature section is 250-350 ℃.
7. The method as claimed in claim 5 or 6, wherein the switching between the reaction section and the constant temperature section is performed when the conversion rate of the outlet oxygen-containing compound of each catalyst bed as the reaction section is less than 50%.
8. The method of any of claims 5-7, wherein the method further comprises:
b) After the product flow containing the low-carbon olefin enters a gas-liquid separator for gas-liquid separation, a gas-phase product containing the low-carbon olefin is subjected to a light hydrocarbon separation process, and a liquid-phase product is subjected to an oxygen-containing compound recovery process;
c) After the fixed bed reactor is purged by nitrogen, air is introduced to regenerate the catalyst, and the regenerated flue gas is removed to a flue gas system.
9. The method according to any one of claims 5 to 8,
the oxygenate comprises at least one of alcohol, aldehyde and ketone, preferably the oxygenate comprises at least one of methanol, ethanol, acetaldehyde, propionaldehyde, acetone and butanone;
more preferably, the ketone accounts for not less than 20% of the mass of the oxygen-containing compound, and the aldehyde accounts for not more than 10% of the mass of the oxygen-containing compound; and/or
The oxygen-containing compound accounts for 10 to 70 percent of the total mass of the materials; preferably, the oxygen-containing compound accounts for 20-50% of the total material by mass;
the catalyst is a molecular sieve, preferably the molecular sieve is at least one selected from ZSM-5, ZSM-11 and ZSM-34, preferably the molecular sieve is a ZSM-5 molecular sieve; more preferably, the silica to alumina ratio of the molecular sieve is greater than 80, and preferably the silica to alumina ratio of the molecular sieve is greater than 200.
10. The method according to any one of claims 5-9,
the reaction pressure of the fixed bed reactor is 0-0.6 MPa, preferably 0.05-0.3 MPa in gauge pressure; and/or
The mass space velocity of each section of catalyst bed layer of the fixed bed reactor is 0.01 to 40.0h in terms of oxygen-containing compound -1 Preferably, it is0.5～10.0h -1 (ii) a And/or
The conditions for regeneration of the fixed bed reactor include: the regeneration temperature is 350-600 ℃, the regeneration pressure is 0-0.5 MPa in terms of gauge pressure, and the mass airspeed of the regenerated air is 0.01-50.0 h in terms of the total mass of the molecular sieve catalyst in the reactor -1 ；
Preferably, the conditions for regeneration of the fixed bed reactor include: the regeneration temperature is 400-550 ℃, the regeneration pressure is 0.1-0.3 MPa in terms of gauge pressure, and the mass airspeed of the regenerated air is 0.05-5.0 h in terms of the total mass of the molecular sieve catalyst in the reactor -1 。
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| CN1172688A (en) * | 1996-08-02 | 1998-02-11 | 中国石油化工总公司 | Fixed bed catalytic reaction method of multistage series step-by-step change and its device |
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| CN104437268A (en) * | 2014-11-06 | 2015-03-25 | 南京大学 | Multistage parallel intensified fixed bed reactor and using method thereof |
| CN211988534U (en) * | 2020-03-23 | 2020-11-24 | 宁波巨化化工科技有限公司 | Sectional independent control type fixed bed reactor |
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| CN1172688A (en) * | 1996-08-02 | 1998-02-11 | 中国石油化工总公司 | Fixed bed catalytic reaction method of multistage series step-by-step change and its device |
| CN103752229A (en) * | 2014-01-26 | 2014-04-30 | 惠生工程（中国）有限公司 | Fixed bed reactor for preparing olefin by oxygen-contained compound |
| CN104248940A (en) * | 2014-09-24 | 2014-12-31 | 浙江大学 | Multistage radial stationary bed reaction system and method for producing propylene from oxy-compound as raw material |
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