WO2018072140A1 - 一种制备丙烯和c4烃类的方法及其装置 - Google Patents
一种制备丙烯和c4烃类的方法及其装置 Download PDFInfo
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- WO2018072140A1 WO2018072140A1 PCT/CN2016/102561 CN2016102561W WO2018072140A1 WO 2018072140 A1 WO2018072140 A1 WO 2018072140A1 CN 2016102561 W CN2016102561 W CN 2016102561W WO 2018072140 A1 WO2018072140 A1 WO 2018072140A1
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 103
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 103
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 120
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 60
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000005336 cracking Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 117
- 239000003054 catalyst Substances 0.000 claims description 105
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 96
- 238000011069 regeneration method Methods 0.000 claims description 94
- 230000008929 regeneration Effects 0.000 claims description 91
- 239000007787 solid Substances 0.000 claims description 84
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 60
- 239000000047 product Substances 0.000 claims description 40
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 239000005977 Ethylene Substances 0.000 claims description 26
- 150000001336 alkenes Chemical class 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 19
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 18
- 239000001294 propane Substances 0.000 claims description 15
- 239000003546 flue gas Substances 0.000 claims description 13
- 230000001172 regenerating effect Effects 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000006227 byproduct Substances 0.000 claims description 12
- 241000269350 Anura Species 0.000 claims description 10
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 abstract description 24
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 13
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- -1 ethylene, propylene Chemical group 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 101000723939 Mus musculus Transcription factor HIVEP3 Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
Images
Classifications
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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
-
- 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
- C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J38/30—Treating with free oxygen-containing gas in gaseous suspension, e.g. fluidised bed
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/06—Propene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/12—Alkadienes
- C07C11/16—Alkadienes with four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C9/00—Aliphatic saturated hydrocarbons
- C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
- C07C9/10—Aliphatic saturated hydrocarbons with one to four carbon atoms with four carbon atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1872—Details of the fluidised bed reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- 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
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- 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
Definitions
- the invention relates to the field of chemical catalysis, in particular to a method for preparing propylene and C4 hydrocarbons from an oxygen-containing compound and a device thereof.
- Propylene and butadiene are important chemical raw materials, generally obtained from naphtha cracking and steam cracking.
- the main source of propylene is ethylene co-produced propylene and refinery by-product propylene, while the main source of butadiene is obtained by further processing of C4 by-products from the ethylene cracking process.
- the DMTO technology developed by Dalian Chemicals Co., Ltd. uses SAPO molecular sieve as catalyst, using dense phase circulating fluidized bed reactor, using methanol aqueous solution as raw material, the yield of ethylene and propylene in the product is about 80%, and C4 hydrocarbons are produced by more than 10% by-product. class.
- Patent CN104098429A discloses a process for preparing propylene and C4 hydrocarbons from methanol by using a circulating fluidized bed, which adopts a ZSM-5 catalyst, and the process is characterized in that the raw materials methanol and most of the C1, C2 and C5 hydrocarbons in the product enter together.
- a circulating fluidized bed reactor, propylene, C4 hydrocarbons, C6 or higher hydrocarbons and by-products are recovered as final products.
- Patent CN101177374B discloses a process for the preparation of olefins from methanol or dimethyl ether.
- the process comprises a methanol or dimethyl ether conversion reaction, an alkylation reaction of ethylene and methanol, and a catalytic cracking reaction of a C4 or more recombinant component.
- C4 or more Recombinant catalytic cracking reaction using Catalyst 2 to complete the reaction in another reactor.
- the methods disclosed in the patents CN104098429A and CN101177374B have a common feature of increasing the selectivity of the target products (propylene and C4) by refining light components (hydrocarbons having a carbon number of not more than 2).
- the main reaction of the above light component refining reaction is the alkylation reaction of ethylene with methanol.
- Both the MTO reaction and the olefin alkylation reaction can employ an acidic molecular sieve catalyst, but the MTO reaction rate is much higher than the olefin alkylation reaction.
- the fresh SAPO catalyst has high activity and is more favorable for the alkylation reaction of olefin. After carbon deposition of the catalyst, the alkylation rate of olefin will decrease rapidly.
- Methanol is both a raw material for the olefin alkylation reaction and a raw material for the MTO reaction. Therefore, the olefin alkylation reaction is inevitably accompanied by the MTO reaction.
- the MTO reaction causes the catalyst to deposit carbon and reduce the activity, which inhibits the olefin alkylation reaction. Increasing the rate of olefin alkylation can reduce the amount of light components in the product gas, thereby increasing the capacity per unit volume of the reactor.
- the methods disclosed in the patents CN104098429A and CN101177374B do not relate to the reactor structure, nor do they define the manner of catalyst flow in the reactor, the flow of the raw materials, the manner in which the raw materials are distributed, and the like.
- the method disclosed in the patent CN101177374B uses a SAPO catalyst, and the embodiment shows that the mass ratio of methanol to light component is 1:10-20, thereby showing that the light component content is extremely high and the reactor unit volume capacity is extremely low.
- the method disclosed in the patent CN104098429A uses a ZSM-5 catalyst, and the product has a higher hydrocarbon content of C6 or higher, and the content of the light component in the product gas is not disclosed in the method.
- hydrocarbons above C5 can be converted into ethylene, propylene, C4 hydrocarbons, etc., thereby improving the selectivity of propylene and C4 hydrocarbons.
- the main reaction for preparing propylene and C4 hydrocarbons from methanol is MTO reaction and olefin alkylation. Therefore, the key to improving the selectivity of propylene and C4 hydrocarbons lies in catalyst design and reactor design. It is one of the important methods to improve the economics of methanol to produce propylene and C4 hydrocarbons by optimizing the reactor design to avoid the MTO reaction inhibiting the olefin alkylation reaction.
- the invention aims at a low rate of ethylene alkylation reaction in the process of preparing propylene and C4 hydrocarbons from methanol, and provides a novel method and device for increasing the alkylation reaction rate of ethylene.
- This method is used In the production of propylene and C4 hydrocarbons from oxygenates, it has the advantages of high yield of propylene and C4 hydrocarbons and good process economy.
- the present invention provides an apparatus for the preparation of propylene and C4 hydrocarbons using an oxygenate, the apparatus comprising:
- a) turbulent fluidized bed reactor (1) comprising a reactor shell (2), n reactor feed distributors (3-1 to 3-n) , reactor gas-solid separator 1 (4), reactor gas-solid separator 2 (5), reactor heat extractor (6), product gas outlet (7) and reactor stripper (8), wherein
- the lower part of the fluidized bed reactor (1) is the reaction zone
- the upper part of the turbulent fluidized bed reactor (1) is the settling zone
- the n reactor feed distributors (3-1 to 3-n) are placed.
- Reaction zone (preferably n reactor feed distributors are placed in the reaction zone from bottom to top, 0 ⁇ n ⁇ 10), reactor heat extractor (6) is placed in the reaction zone, and reactor gas-solid separator 1 (4) And the reactor gas-solid separator 2 (5) is placed outside the settling zone or the reactor casing (2), and the inlet of the reactor gas-solid separator 1 (4) is connected to the regeneration riser (24), and the reactor is gas-solid
- the catalyst outlet of separator 1 (4) is placed at the bottom of the reaction zone, the gas outlet of reactor gas-solid separator 1 (4) is placed in the settling zone, and the inlet of reactor gas-solid separator 2 (5) is placed in the settling zone.
- the catalyst outlet of the reactor gas-solid separator 2 (5) is placed in the reaction zone, and the gas of the reactor gas-solid separator 2 (5)
- the body outlet is connected to the product gas outlet (7), and the reactor stripper (8) passes through the reactor housing (2) from the outside to the bottom of the turbulent fluidized bed reactor (1) and is open to the turbulent flow
- the reaction zone of the chemical bed reactor (1) (preferably the level of the opening of the reactor stripper inside the reactor shell is higher than the height of the 1/10 reaction zone);
- catalytic cracking riser 28
- the bottom of the catalytic cracking riser (28) is connected to the outlet of the catalytic cracking inclined pipe (26) and is provided with a C5 or higher hydrocarbon inlet (29), a catalytic cracking riser (28)
- the outlet is connected to the settling zone of the turbulent fluidized bed reactor (1);
- a fluidized bed regenerator (14) comprising a regenerator housing (15), a regenerator feed distributor (16), a regenerator gas-solid separator (17), a regenerator heat extractor (18), a flue gas outlet (19) and a regenerator stripper (20), wherein a lower portion of the fluidized bed regenerator (14) is a regeneration zone, an upper portion of the fluidized bed regenerator (14) Is the settling zone, the regenerator feed distributor (16) is placed at the bottom of the regeneration zone, the regenerator heat extractor (18) is placed in the regeneration zone, and the regenerator gas-solids separator (17) is placed in the settling zone or regenerator shell Outside the body (15), the inlet of the regenerator gas-solids separator (17) is placed in the settling zone, and the catalyst outlet of the regenerator gas-solids separator (17) is placed in the regeneration zone.
- a gas outlet of the biomass gas-solid separator (17) is connected to the flue gas outlet (19), and a regenerator stripper (20) is opened at the bottom of the regenerator housing
- the bottom of the reactor stripper (8) is provided with a reactor stripping gas inlet (9), and the bottom of the reactor stripper (8) is connected to the inlet of the inclined tube (10), and the inclined tube is to be produced.
- (10) is provided with a standby slide valve (11), the outlet of the inclined tube (10) is connected to the inlet of the waiting riser (12), and the bottom of the waiting riser (12) is provided with a rising gas inlet ( 13), the outlet of the standby riser (12) is connected to the settling section of the fluidized bed regenerator (14);
- the regenerator stripper (20) is provided with a regenerator stripping gas inlet (21) at the bottom, and the bottom of the regenerator stripper (20) is connected to the inlet of the regenerative inclined tube (22), and the regenerative inclined tube (22)
- There is a regeneration slide valve (23) the outlet of the regeneration inclined pipe (22) is connected to the inlet of the regeneration riser (24), and the regeneration lift pipe (24) is provided with a regeneration lift gas inlet (25) at the bottom of the regeneration riser (24).
- An outlet of the tube (24) is connected to the inlet of the reactor gas-solid separator 1 (4);
- the bottom of the regenerator stripper (20) is also connected to the inlet of the catalytic cracking inclined pipe (26), and the catalytic cracking inclined pipe is provided with a catalytic cracking slide valve (27).
- the present invention provides an oxygenate-containing process for the preparation of propylene and C4 hydrocarbons, comprising:
- the oxygenate-containing feedstock is passed from the n reactor feed distributors (3-1 to 3-n) to the reaction zone of the turbulent fluidized bed reactor (1) to contact the catalyst to form propylene. And C4 hydrocarbon product streams and carbon-containing catalysts;
- the catalyst to be produced is regenerated by the fluidized bed regenerator (14) to form a regenerated catalyst, and a part of the regenerated catalyst is separated into the turbulent fluidized bed reactor by gas-solid separation of the reactor gas-solid separator 1 (4) (1) At the bottom of the reaction zone, another portion of the regenerated catalyst passes through the catalytic cracking inclined tube (26) into the catalytic cracking riser (28);
- the process of the invention is carried out using a device for the preparation of propylene and C4 hydrocarbons for oxygenates according to the first aspect, wherein
- the spent catalyst passes through the reactor stripper (8), the inclined tube (10), the standby slide valve (11) and the waiting riser (12) into the settling section of the fluidized bed regenerator (14);
- the regeneration medium is passed from the regenerator feed distributor (16) to the regeneration zone of the fluidized bed regenerator (14), and the regeneration medium and the catalyst to be produced undergo a charring reaction to generate flue gas containing CO and CO 2 and a regenerated catalyst.
- the flue gas is discharged after being removed by the regenerator gas-solid separator (17);
- a part of the regenerated catalyst passes through the regenerator stripper (20), the regeneration inclined pipe (22), the regeneration slide valve (23) and the regeneration riser pipe (24) to enter the inlet of the reactor gas-solid separator 1 (4), after gas-solid separation
- the regenerated catalyst enters the bottom of the reaction zone in the turbulent fluidized bed reactor (1); the other part of the regenerated catalyst passes through the regenerator stripper (20), the catalytic cracking inclined pipe (26), and the catalytic cracking slide valve (27).
- the reactor stripping gas enters the reactor stripper (8) from the reactor stripping gas inlet (9) and is in countercurrent contact with the catalyst to be produced, and then enters the turbulent fluidized bed reactor (1);
- the raw lift gas inlet (13) enters the standby riser (12) and is in contact with the catalyst to be produced, and then enters the settling section of the fluidized bed regenerator (14);
- regenerator stripping gas is fed from the regenerator stripping gas inlet (21) into the regenerator stripper (20) in countercurrent contact with the regenerated catalyst and then into the fluidized bed regenerator (14); the regenerating propellant gas is passed from the regenerating ascending gas inlet ( 25) Entering the regeneration riser (24) and the regenerated catalyst in downstream contact, and then entering the inlet of the reactor gas-solid separator 1 (4).
- the main feature of the turbulent fluidized bed reactor of the present invention is that the light component is introduced from the lowermost reactor feed distributor, the oxygenates are separately introduced by the n reactor feed distributors, and the regenerated catalyst directly enters the reaction.
- the bottom of the area On the one hand, in the lower part of the reaction zone, the catalyst activity is high, which is favorable for the alkylation reaction of ethylene, propylene and methanol; on the other hand, due to the use of oxygenates
- the multi-stage feeding method avoids most of the conversion reaction of oxygenates in a small part of the reaction zone, so that the oxygen concentration in the reaction zone is relatively uniform in most of the reaction zone, which weakens the MTO reaction to the olefin alkyl group. Inhibition of the reaction. Therefore, the turbulent fluidized bed reactor of the present invention can effectively increase the alkylation reaction rate of the olefin, and the reactor has a high volume per unit volume.
- the main feature of the catalytic cracking riser in the present invention is that its outlet is directly connected to the settling zone of the turbulent fluidized bed reactor, and the turbulent fluidized bed reactor shares the gas-solid separator 2.
- the fluidized bed regenerator of the present invention is preferably a turbulent fluidized bed regenerator.
- the reactor gas-solid separator 1, the reactor gas-solid separator 2, and the regenerator gas-solid separator in the present invention are preferably cyclones.
- the MTO reaction produces products such as ethylene and propylene
- the olefin alkylation reaction consumes ethylene and propylene, etc.
- the ethylene alkylation reaction rate is high, and the light component content of the product gas is low, and the light component is recycled.
- Low volume In the method of the present invention, the light component circulation amount is 5-40 wt.% of the oxygenate feed amount.
- hydrocarbons above C5 are circulated in the system, and the amount of hydrocarbons above C5 is 2-20 wt.% of the oxygenate feed amount.
- the composition of the product gas is 20-50wt.% propylene, 15-40wt.% C4 hydrocarbons, 10-45wt.% light components, 0-5wt.% propane and 5-20wt.% C5 or more hydrocarbons. class.
- the light component contains more than 90% by weight, for example >95% by weight of ethylene, and the other components are methane, ethane, hydrogen, CO and CO 2 and the like.
- the catalyst contains a SAPO molecular sieve which simultaneously functions as a methanol to olefin, an olefin alkylation, and a catalytic cracking.
- the regenerated catalyst has a carbon content of ⁇ 2 wt.%, and more preferably, the regenerated catalyst has a carbon content of ⁇ 0.5 wt.%.
- the carbon content of the catalyst to be produced is 5-12 wt.%, and further preferably, the carbon content of the catalyst to be produced is 5-10 wt.%.
- the reaction conditions of the reaction zone of the turbulent fluidized bed reactor (1) are: an apparent linear velocity of gas of 0.1-2 m/s, a reaction temperature of 300-550 ° C, and a reaction pressure of 100- 500 kPa, the bed density is 200-1200 kg/m 3 .
- the catalytic cracking riser (28) has a reaction condition of an apparent gas velocity of 2.0-10.0 m/s, a reaction temperature of 400-750 ° C, and a reaction pressure of 100-500 kPa.
- the density is 30-300 kg/m 3 .
- reaction conditions of the regeneration zone of the fluidized bed regenerator (14) are: an apparent apparent linear velocity of 0.1-2 m/s, a regeneration temperature of 500-750 ° C, and a regeneration pressure of 100-500 kPa.
- the bed density is 200-1200 kg/m 3 .
- the oxygenate is methanol and/or dimethyl ether; and/or the regeneration medium is any one or a mixture of any of air, oxygen-depleted air or water vapor; / or the reactor stripping gas, the regenerator stripping gas, the raw lifting gas and the regeneration lifting gas are water vapor or nitrogen.
- FIG. 1 is a schematic view of an apparatus for producing propylene and C4 hydrocarbons in an oxygen-containing compound according to an embodiment of the present invention.
- the method for preparing propylene and C4 hydrocarbons from an oxygen-containing compound according to the present invention and a schematic diagram thereof are shown in FIG. 1 , and the device comprises:
- a turbulent fluidized bed reactor (1) comprising a reactor shell (2), n reactor feed distributors (3-1 to 3-n), and a reactor gas-solid separator 1 (4) ), reactor gas-solid separator 2 (5), reactor heat extractor (6), product gas outlet (7) and reactor stripper (8), wherein the turbulent flow
- the lower part of the chemical bed reactor (1) is the reaction zone
- the upper part of the turbulent fluidized bed reactor (1) is the settling zone
- the n reactor feed distributors (3-1 ⁇ 3-n) are arranged from bottom to top.
- the reactor heat extractor (6) is placed in the reaction zone, the reactor gas-solid separator 1 (4) and the reactor gas-solid separator 2 (5) are placed in the settling zone or Outside the reactor housing (2), the inlet of the reactor gas-solids separator 1 (4) is connected to a regeneration riser (24), and the catalyst outlet of the reactor gas-solid separator 1 (4) is placed at the bottom of the reaction zone.
- the gas outlet of the reactor gas-solids separator 1 (4) is placed in the settling zone, the inlet of the reactor gas-solids separator 2 (5) is placed in the settling zone, and the catalyst outlet of the reactor gas-solids separator 2 (5) is placed In the reaction zone, the gas outlet of the reactor gas-solid separator 2 (5) is connected to the product gas outlet (7), and the inlet of the reactor stripper (8) is in the reaction zone of the turbulent fluidized bed reactor (1) , whose level is higher than the height of the 1/10 reaction zone;
- catalytic cracking riser (28) with a C5 or higher hydrocarbon inlet (29) at the bottom, and an outlet of the catalytic cracking riser (28) connected to the settling zone of the turbulent fluidized bed reactor (1); catalytic cracking
- the inlet of the riser (28) is connected to the outlet of the catalytic cracking inclined pipe (26), and the catalytic cracking inclined pipe (26) is provided with a catalytic cracking slide valve (27), and the inlet of the catalytic cracking inclined pipe (26) is connected to the regenerator Stripper (20).
- a fluidized bed regenerator (14) comprising a regenerator housing (15), a regenerator feed distributor (16), a regenerator gas-solid separator (17), a regenerator heat extractor (18), a flue gas outlet (19) and a regenerator stripper (20), wherein a lower portion of the fluidized bed regenerator (14) is a regeneration zone, and an upper portion of the fluidized bed regenerator (14) is a settling zone, and the regenerator feed distribution
- the device (16) is placed at the bottom of the regeneration zone, the regenerator heat extractor (18) is placed in the regeneration zone, and the regenerator gas-solids separator (17) is placed outside the settling zone or the regenerator housing (15), the regenerator gas
- the inlet of the solid separator (17) is placed in the settling zone, the catalyst outlet of the regenerator gas-solids separator (17) is placed in the regeneration zone, and the gas outlet of the regenerator gas-solid separator (17) is connected to the flue gas outlet (19)
- the inlet of the regenerator stripper (20) is connected to
- the bottom of the reactor stripper (8) is provided with a reactor stripping gas inlet (9), and the bottom of the reactor stripper (8) is connected to the inlet of the inclined tube (10), and the inclined tube is to be produced.
- (10) is provided with a standby slide valve (11), the outlet of the inclined tube (10) is connected to the inlet of the waiting riser (12), and the bottom of the waiting riser (12) is provided with a rising gas inlet ( 13), the outlet of the standby riser (12) is connected to the settling section of the fluidized bed regenerator (14);
- the bottom of the regenerator stripper (20) is provided with a regenerator stripping gas inlet (21), a regenerator
- the bottom of the stripper (20) is connected to the inlet of the regeneration inclined pipe (22), the regeneration inclined pipe (22) is provided with a regeneration slide valve (23), and the outlet of the regeneration inclined pipe (22) is connected to the regeneration riser (24).
- the inlet of the regeneration riser (24) is provided with a regeneration lift gas inlet (25), and the outlet of the regeneration riser (24) is connected to the inlet of the reactor gas-solid separator 1 (4).
- the fluidized bed regenerator (14) may be a turbulent fluidized bed regenerator; the reactor gas solids separator 1 (4), the reactor gas solids separator 2 (5), and the regenerator gas solids.
- the separator (17) may be a cyclone separator.
- the method for preparing propylene, C4 hydrocarbons from an oxygenate according to the present invention comprises:
- the oxygenate-containing feedstock is passed from the n reactor feed distributors (3-1 to 3-n) to the reaction zone of the turbulent fluidized bed reactor (1) to contact the catalyst to form propylene. And C4 hydrocarbon product streams and carbon-containing catalysts;
- the C5 or higher hydrocarbon inlet (29) enters the catalytic cracking riser (28), and the regenerated catalyst from the catalytic cracking inclined tube (26) is in downstream contact a cracking reaction occurs to form a stream containing propylene, a C4 hydrocarbon, and a carbon-containing catalyst, and then a stream containing propylene, a C4 hydrocarbon, and a carbon-containing catalyst enter the turbulent fluidization via the outlet of the catalytic cracking riser (28).
- the settling zone of the bed reactor (1) less than 20 wt.% of C5 or more hydrocarbons are recovered as by-products;
- a part of the regenerated catalyst passes through the regenerator stripper (20), the regeneration inclined tube (22), the regeneration slide valve (23) and the regeneration riser (24) into the inlet of the reactor gas-solid separator 1 (4), gas-solid After separation, the regenerated catalyst enters the bottom of the reaction zone in the turbulent fluidized bed reactor (1); the other part of the regenerated catalyst passes through the regenerator stripper (20), the catalytic cracking inclined pipe (26), and the catalytic cracking slide valve (27). Entering the catalytic cracking riser (28);
- the reactor stripping gas is fed into the reactor stripper (8) from the reactor stripping gas inlet (9) in countercurrent contact with the catalyst to be produced, and then enters the turbulent fluidized bed reactor (1); Entering the standby riser (12) from the waiting riser inlet (13) and the catalyst to be produced in downstream flow, and then entering the settling section of the fluidized bed regenerator (14);
- regenerator stripping gas is fed into the regenerator stripper (20) from the regenerator stripping gas inlet (21) in countercurrent contact with the regenerated catalyst, and then enters the fluidized bed regenerator (14); the regeneration propellant gas is regenerated by the regeneration gas.
- the inlet (25) enters the regeneration riser (24) in in-stream contact with the regenerated catalyst and then enters the inlet of the reactor gas-solid separator 1 (4).
- This case is a comparative case, using the device shown in Figure 1, but the reactor fluidized bed reactor (1) does not contain the reactor gas-solid separator 1 (4), the regeneration riser (24) is directly connected to the turbulence The settling zone of the fluidized bed reactor (1).
- the turbulent fluidized bed reactor (1) contains three reactor feed distributors (3-1 to 3-3), and the reactor gas-solid separator 1 (4) is placed outside the reactor casing (2).
- the level of the inlet of the reactor stripper (8) is at the height of the 1/2 reaction zone.
- the reaction conditions of the turbulent fluidized bed reactor (1) are: the apparent linear velocity of the gas is about 1.0 m/s, the reaction temperature is about 450 ° C, the reaction pressure is about 150 kPa, and the bed density is about 350 kg/m 3 . .
- the catalytic cracking riser (28) has a reaction condition of an apparent linear velocity of about 5.0 m/s, a reaction temperature of about 600 ° C, a reaction pressure of about 150 kPa, and a bed density of about 50 kg/m 3 .
- the reaction conditions of the fluidized bed regenerator (14) regeneration zone are: the apparent apparent linear velocity of the gas is about 1.0 m/s, the regeneration temperature is about 650 ° C, the regeneration pressure is about 150 kPa, and the bed density is about 350 kg/m 3 .
- the catalyst contains SAPO molecular sieve, the carbon content of the catalyst to be produced is about 7%, and the carbon content of the regenerated catalyst is about 0.2 wt.%.
- the oxygenate is methanol
- the regeneration medium is air
- the reactor stripping gas, the regenerator stripping gas, the waiting lift gas and the regeneration lift gas are water vapor.
- the light component recycle amount was 20 wt.% of the methanol feed amount, and 71 wt.% of the light components were circulated in the system.
- the hydrocarbon recycle amount above C5 is 12 wt.% of the methanol feed amount, and 92 wt.% of the C5 or higher hydrocarbons are circulated in the system.
- the composition of the product gas discharged from the turbulent fluidized bed reactor (1) is: 31 wt.% propylene, 19 wt.% C4 hydrocarbons, 29 wt.% light components, 2 wt.% propane, and 19 wt.% C5 or more hydrocarbons. .
- the light component contains 98 wt.% of ethylene, and 2 wt.% of methane, ethane, hydrogen, CO, CO 2 and the like.
- composition of the product gas discharged from the separation system is: 50 wt.% propylene, 31 wt.% C4 hydrocarbons, 14 wt.% light components, 3 wt.% propane, and 2 wt.% C5 or more hydrocarbons.
- the turbulent fluidized bed reactor (1) contains three reactor feed distributors (3-1 to 3-3), and the reactor gas-solid separator 1 (4) is placed in the reaction. Outside the housing (2), the level of the inlet of the reactor stripper (8) is at the height of the 1/2 reaction zone.
- the reaction conditions of the turbulent fluidized bed reactor (1) are: the apparent linear velocity of the gas is about 1.0 m/s, the reaction temperature is about 450 ° C, the reaction pressure is about 150 kPa, and the bed density is about 350 kg/m 3 . .
- the catalytic cracking riser (28) has a reaction condition of an apparent linear velocity of about 5.0 m/s, a reaction temperature of about 600 ° C, a reaction pressure of about 150 kPa, and a bed density of about 50 kg/m 3 .
- the reaction conditions of the fluidized bed regenerator (14) regeneration zone are: the apparent apparent linear velocity of the gas is about 1.0 m/s, the regeneration temperature is about 650 ° C, the regeneration pressure is about 150 kPa, and the bed density is about 350 kg/m 3 .
- the catalyst contains SAPO molecular sieve, the carbon content of the catalyst to be produced is about 7%, and the carbon content of the regenerated catalyst is about 0.2 wt.%.
- the oxygenate is methanol
- the regeneration medium is air
- the reactor stripping gas, the regenerator stripping gas, the waiting lift gas and the regeneration lift gas are water vapor.
- the light component recycle amount was 15 wt.% of the methanol feed amount, and 98 wt.% of the light components were circulated in the system.
- the hydrocarbon recycle amount above C5 is 12 wt.% of the methanol feed amount, and 92 wt.% of the C5 or higher hydrocarbons are circulated in the system.
- the composition of the product gas discharged from the turbulent fluidized bed reactor (1) is: 35 wt.% propylene, 23 wt.% C4 hydrocarbons, 21 wt.% light components, 2 wt.% propane, and 19 wt.% C5 or more hydrocarbons. .
- the light component contains 97 wt.% of ethylene, and 3 wt.% of methane, ethane, hydrogen, CO, CO 2 and the like.
- composition of the product gas discharged from the separation system is: 57 wt.% propylene, 37 wt.% C4 hydrocarbons, 1 wt.% light component, 3 wt.% propane, and 2 wt.% C5 or more hydrocarbons.
- This case differs from Example 1 (comparative case) only in that the regenerated catalyst enters the bottom of the turbulent fluidized bed reactor, first in contact with the light component, while the regenerated catalyst in Example 1 enters the turbulent fluidized bed reactor. Settling zone. Comparing this case with Example 1, it can be seen that the first contact of the catalyst with the light component can greatly improve the conversion rate of the light component. In this case, the light component discharged from the separation system is only 7% of the comparative case, and therefore, the present invention The device effectively increases the rate of ethylene alkylation reaction.
- This case is a comparative case using the apparatus shown in Figure 1, but does not include a catalytic cracking ramp (26), a catalytic cracking spool (27), and a catalytic cracking riser (28). Hydrocarbons above C5 are not recycled and are directly recovered as by-products.
- the turbulent fluidized bed reactor (1) contains four reactor feed distributors (3-1 to 3-4), the reactor gas-solid separator 1 (4) is placed in the settling zone, and the reactor stripper ( 8) The level of the inlet is at the height of the 3/4 reaction zone.
- the reaction conditions of the turbulent fluidized bed reactor (1) are: the apparent linear velocity of the gas is about 1.2 m/s, the reaction temperature is about 360 ° C, the reaction pressure is about 200 kPa, and the bed density is about 300 kg/m 3 . .
- the reaction conditions of the fluidized bed regenerator (14) regeneration zone are: the apparent apparent linear velocity of the gas is about 1.2 m/s, the regeneration temperature is about 700 ° C, the regeneration pressure is about 200 kPa, and the bed density is about 300 kg/m 3 .
- the catalyst contains SAPO molecular sieve, the carbon content of the catalyst to be produced is about 8%, and the carbon content of the regenerated catalyst is about 0.1 wt.%.
- the oxygenate is methanol
- the regeneration medium is air
- the reactor stripping gas, the regenerator stripping gas, the waiting lift gas and the regeneration lift gas are water vapor.
- the light component recycle amount was 16 wt.% of the methanol feed amount, and 90 wt.% of the light components were circulated in the system.
- the composition of the product gas discharged from the turbulent fluidized bed reactor (1) is: 39 wt.% propylene, 25 wt.% C4 hydrocarbons, 29 wt.% light components, 2 wt.% propane, and 5 wt.% C5 or more hydrocarbons. .
- the light component contains 96 wt.% of ethylene, and 4 wt.% of methane, ethane, hydrogen, CO, CO 2 and the like.
- composition of the product gas discharged from the separation system is: 53 wt.% propylene, 33 wt.% C4 hydrocarbons, 4 wt.% light components, 3 wt.% propane, and 7 wt.% C5 or more hydrocarbons.
- the turbulent fluidized bed reactor (1) contains four reactor feed distributors (3-1 to 3-4), and the reactor gas-solid separator 1 (4) is placed in sedimentation.
- the level of the inlet of the reactor stripper (8) is at the height of the 3/4 reaction zone.
- the reaction conditions of the turbulent fluidized bed reactor (1) are: the apparent linear velocity of the gas is about 1.2 m/s, the reaction temperature is about 360 ° C, the reaction pressure is about 200 kPa, and the bed density is about 300 kg/m 3 . .
- the catalytic cracking riser (28) has a reaction gas velocity of about 7.0 m/s, a reaction temperature of about 650 ° C, a reaction pressure of about 200 kPa, and a bed density of about 40 kg/m 3 .
- the reaction conditions of the fluidized bed regenerator (14) regeneration zone are: the apparent apparent linear velocity of the gas is about 1.2 m/s, the regeneration temperature is about 700 ° C, the regeneration pressure is about 200 kPa, and the bed density is about 300 kg/m 3 .
- the catalyst contains SAPO molecular sieve, the carbon content of the catalyst to be produced is about 8%, and the carbon content of the regenerated catalyst is about 0.1 wt.%.
- the oxygenate is methanol
- the regeneration medium is air
- the reactor stripping gas, the regenerator stripping gas, the waiting lift gas and the regeneration lift gas are water vapor.
- the light component recycle amount was 16 wt.% of the methanol feed amount, and 90 wt.% of the light components were circulated in the system.
- the hydrocarbon recycle amount above C5 is 4 wt.% of the methanol feed amount, and 95 wt.% of the C5 or higher hydrocarbons are circulated in the system.
- the composition of the product gas discharged from the turbulent fluidized bed reactor (1) is: 34 wt.% propylene, 23 wt.% C4 hydrocarbons, 25 wt.% light components, 2 wt.% propane, and 16 wt.% C5 or more hydrocarbons. .
- the light component contains 96 wt.% of ethylene, and 4 wt.% of methane, ethane, hydrogen, CO, CO 2 and the like.
- composition of the product gas discharged from the separation system is: 55 wt.% propylene, 37 wt.% C4 hydrocarbons, 4 wt.% light components, 3 wt.% propane, and 1 wt.% C5 or more hydrocarbons.
- Example 3 comparative case
- Example 3 Comparing this case with Example 3, it can be seen that the hydrocarbons of C5 and above discharged by the separation system in this case are only 14% of the comparative cases. Therefore, the device of the present invention can effectively promote the hydrocarbons above C5.
- the cleavage is propylene and C4 hydrocarbons.
- the turbulent fluidized bed reactor (1) contains six reactor feed distributors (3-1 to 3-6), and the reactor gas-solid separator 1 (4) is placed in sedimentation.
- the level of the inlet of the reactor stripper (8) is at the height of the 5/6 reaction zone.
- the reaction conditions of the turbulent fluidized bed reactor (1) are: the apparent linear velocity of the gas is about 1.5 m/s, the reaction temperature is about 420 ° C, the reaction pressure is about 250 kPa, and the bed density is about 250 kg/m 3 . .
- the catalytic cracking riser (28) has a reaction condition of an apparent linear velocity of about 7.0 m/s, a reaction temperature of about 700 ° C, a reaction pressure of about 250 kPa, and a bed density of about 40 kg/m 3 .
- the reaction conditions of the fluidized bed regenerator (14) regeneration zone are: the apparent apparent linear velocity of the gas is about 1.5 m/s, the regeneration temperature is about 700 ° C, the regeneration pressure is about 250 kPa, and the bed density is about 250 kg/m 3 .
- the catalyst contains SAPO molecular sieve, the carbon content of the catalyst to be produced is about 9%, and the carbon content of the regenerated catalyst is about 0.05 wt.%.
- the oxygenate is dimethyl ether
- the regeneration medium is oxygen-depleted air
- the reactor stripping gas, the regenerator stripping gas, the waiting lift gas and the regeneration lift gas are nitrogen.
- the light component recycle amount was 19 wt.% of the dimethyl ether feed amount, and 85 wt.% of the light components were circulated in the system.
- the amount of hydrocarbons above C5 is 14 wt.% of the amount of dimethyl ether fed, and 90 wt.% of C5 or more hydrocarbons are circulated in the system.
- the composition of the product gas discharged from the turbulent fluidized bed reactor (1) is: 35 wt.% propylene, 23 wt.% C4 hydrocarbons, 23 wt.% light components, 3 wt.% propane, and 16 wt.% C5 or more hydrocarbons. .
- the light component contains 96 wt.% of ethylene, and 4 wt.% of methane, ethane, hydrogen, CO, CO 2 and the like.
- composition of the product gas discharged from the separation system is: 53 wt.% propylene, 35 wt.% C4 hydrocarbons, 5 wt.% light components, 5 wt.% propane, and 2 wt.% C5 or more hydrocarbons.
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Abstract
Description
Claims (14)
- 一种用于含氧化合物制备丙烯和C4烃类的装置,所述装置包含:湍动流化床反应器,所述湍动流化床反应器包含反应器壳体、n个反应器进料分布器、反应器气固分离器1、反应器气固分离器2、反应器取热器、产品气出口和反应器汽提器,其中湍动流化床反应器的下部是反应区,湍动流化床反应器的上部是沉降区,n个反应器进料分布器置于反应区,反应器取热器置于反应区,反应器气固分离器1和反应器气固分离器2置于沉降区或反应器壳体外部,反应器气固分离器1的入口连接于再生提升管,反应器气固分离器1的催化剂出口置于反应区的底部,反应器气固分离器1的气体出口置于沉降区,反应器气固分离器2的入口置于沉降区,反应器气固分离器2的催化剂出口置于反应区,反应器气固分离器2的气体出口连接于产品气出口,反应器汽提器在湍动流化床反应器的底部由外向内穿过反应器壳体并且开口于湍动流化床反应器的反应区内;催化裂解提升管,所述催化裂解提升管的底部连接于催化裂解斜管的出口并设有C5以上烃类入口,其出口连接于湍动流化床反应器的沉降区;流化床再生器,所述流化床再生器包含再生器壳体、再生器进料分布器、再生器气固分离器、再生器取热器、烟气出口和再生器汽提器,其中流化床再生器的下部是再生区,流化床再生器的上部是沉降区,再生器进料分布器置于再生区的底部,再生器取热器置于再生区,再生器气固分离器置于沉降区或再生器壳体外部,再生器气固分离器的入口置于沉降区,再生器气固分离器的催化剂出口置于再生区,再生器气固分离器的气体出口连接于烟气出口,再生器汽提器开口于再生器壳体的底部;其中,反应器汽提器的底部设有反应器汽提气入口,反应器汽提器的底部连接于待生斜管的入口,待生斜管中设有待生滑阀,待生斜管的出口连接于待生提升管的入口,待生提升管的底部设有待生提升气入口,待生提升管的出口连接于流化床再生器的沉降段;再生器汽提器的底部设有再生器汽提气入口,再生器汽提器的底部连接于再生斜管的入口,再生斜管中设有再生滑阀,再生斜管的出口连接于再生提升管的入口,再生提升管的底部设有再生提升气入口,再生提升管 的出口连接于反应器气固分离器1的入口;再生器汽提器的底部还连接于催化裂解斜管的入口,催化裂解斜管中设有催化裂解滑阀。
- 根据权利要求1所述的装置,其中所述n个反应器进料分布器由下至上置于反应区,0<n<10。
- 根据权利要求1所述的装置,其中所述反应器汽提器在反应器壳体内部的开口的水平高度高于1/10反应区的高度。
- 根据权利要求1所述的装置,其中所述催化裂解提升管和所述湍动流化床反应器共用气固分离器2。
- 根据权利要求1所述的装置,其中所述流化床再生器是湍动流化床再生器。
- 根据权利要求1所述的装置,其中所述反应器气固分离器1、反应器气固分离器2和再生器气固分离器是旋风分离器。
- 一种含氧化合物制备丙烯和C4烃类的方法,包括:将含有含氧化合物的原料从n个反应器进料分布器通入湍动流化床反应器的反应区,与催化剂接触,生成含有丙烯和C4烃类产品的物流和含碳的待生催化剂;待生催化剂经流化床再生器再生,形成再生催化剂,一部分再生催化剂经反应器气固分离器1的气固分离后,进入湍动流化床反应器中反应区的底部,另一部分再生催化剂经过催化裂解斜管进入催化裂解提升管;将由湍动流化床反应器流出的含有丙烯和C4烃类产品的物流送入产品分离系统,经分离获得丙烯、C4烃类、轻组分、丙烷、C5以上烃类,轻组分包含超过90wt%的乙烯,还包含少量的甲烷、乙烷、氢气、CO和CO2,70wt.%以上的轻组分由湍动流化床反应器最下方的反应器进料分布器返回湍动流化床反应器的反应区,乙烯和含氧化合物在催化剂的作用下发生烷基化反应,生成包含丙烯的产物,低于30wt.%的轻组分作为副产物被回收;80wt.%以上的由分离系统而来C5以上烃类由C5以上烃类入口进入催化裂解提升管,和来自于催化裂解斜管的再生催化剂顺流接触,发生裂解反应,生成含有丙烯、C4烃类的物流和含碳的催化剂,随后,含有丙 烯、C4烃类的物流和含碳的催化剂经由催化裂解提升管的出口进入湍动流化床反应器的沉降区,低于20wt.%的C5以上烃类作为副产物被回收。
- 根据权利要求7所述的方法,其使用根据权利要求1至6中任一项所述的装置进行,其中待生催化剂经过反应器汽提器、待生斜管、待生滑阀和待生提升管进入流化床再生器的沉降段;再生介质从再生器进料分布器通入流化床再生器的再生区,再生介质和待生催化剂发生烧炭反应,生成含有CO、CO2的烟气和再生催化剂,烟气经过再生器气固分离器除尘后排放;一部分再生催化剂经过再生器汽提器、再生斜管、再生滑阀和再生提升管进入反应器气固分离器1入口,气固分离后,再生催化剂进入湍动流化床反应器中反应区的底部;另一部分再生催化剂经过再生器汽提器、催化裂解斜管、催化裂解滑阀进入催化裂解提升管;反应器汽提气由反应器汽提气入口进入反应器汽提器和待生催化剂逆流接触,然后进入湍动流化床反应器;待生提升气由待生提升气入口进入待生提升管和待生催化剂顺流接触,然后进入流化床再生器的沉降段;再生器汽提气由再生器汽提气入口进入再生器汽提器和再生催化剂逆流接触,然后进入流化床再生器;再生提升气由再生提升气入口进入再生提升管和再生催化剂顺流接触,然后进入反应器气固分离器1的入口。
- 根据权利要求7所述的方法,其中所述催化剂含有SAPO分子筛。
- 根据权利要求7所述的方法,其中轻组分循环量为含氧化合物进料量的5-40wt.%。
- 根据权利要求7所述的方法,其中C5以上烃类循环量为含氧化合物进料量的2-20wt.%。
- 根据权利要求7所述的方法,其中所述待生催化剂碳含量为5-12wt.%,并且所述再生催化剂碳含量<2wt.%。
- 根据权利要求7所述的方法,其中所述含氧化合物为甲醇和/或二甲醚;和/或所述再生介质为空气、贫氧空气或水蒸气中的任意一种或任意几种的混合物;和/或所述反应器汽提气、再生器汽提气、待生提升气和再生提升气为水蒸气或氮气。
- 根据权利要求7所述的方法,其中所述湍动流化床反应器反应区反应条件为:气体表观线速度为0.1-2m/s,反应温度为300-550℃,反应压力为100-500kPa,床层密度为200-1200kg/m3;和/或所述催化裂解提升管反应条件为:气体表观线速度为2.0-10.0m/s,反应温度为400-750℃,反应压力为100-500kPa,床层密度为30-300kg/m3;和/或所述流化床再生器再生区反应条件为:气体表观线速度为0.1-2m/s,再生温度为500-750℃,再生压力为100-500kPa,床层密度为200-1200kg/m3。
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CN108786672B (zh) * | 2017-04-27 | 2021-01-26 | 中国科学院大连化学物理研究所 | 甲醇和/或二甲醚与苯制对二甲苯联产低碳烯烃的方法 |
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