CN117326910A - Method for increasing propylene yield by olefin pyrolysis, propylene yield increasing system and application - Google Patents
Method for increasing propylene yield by olefin pyrolysis, propylene yield increasing system and application Download PDFInfo
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 137
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 94
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000000197 pyrolysis Methods 0.000 title description 3
- 239000002994 raw material Substances 0.000 claims abstract description 96
- 239000000463 material Substances 0.000 claims abstract description 80
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- 239000002808 molecular sieve Substances 0.000 claims abstract description 70
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000005336 cracking Methods 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- 230000005496 eutectics Effects 0.000 claims description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 230000000638 stimulation Effects 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 51
- 238000007599 discharging Methods 0.000 description 16
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- 230000008569 process Effects 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000004523 catalytic cracking Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
-
- 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
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0496—Heating or cooling the reactor
-
- 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
-
- 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
- C07C2529/80—Mixtures of different zeolites
-
- 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
Abstract
The invention provides a method and a system for increasing propylene yield, comprising the steps of obtaining a light material flow rich in propylene, a material flow in C4-C6 and heavy material flows above C7 through a multi-section bed olefin cracking reactor, wherein a first section layer, a second section layer and a third section layer in the multi-section bed are filled with different silicon-aluminum molecular sieve catalysts. Aiming at the reaction characteristics of different beds in the multi-stage bed olefin cracking reactor, the method of filling olefin cracking catalysts with different catalytic properties in each stage of beds is used, so that the utilization efficiency of olefin-rich raw materials in different beds is improved.
Description
Technical Field
The invention belongs to the technical field of propylene preparation, and particularly relates to a method for increasing propylene yield by olefin pyrolysis, a system for increasing propylene yield and application thereof.
Background
Propylene is one of important basic organic chemical raw materials, and is mainly used for producing a plurality of products such as polypropylene, isopropylbenzene, acrylonitrile, acrylic acid and the like. In recent years, the demand for propylene has grown more than ethylene in the market due to the strong demand for propylene derivatives, with polypropylene and alkylaromatic compounds being the fastest growing propylene derivatives.
At present, propylene production is mainly carried out by a line of ethylene unit byproducts and refinery byproducts, and about 70% of propylene in the world comes from the byproducts of steam cracking units and the conventional catalytic cracking units of refineries. However, there is limited space to continue to increase propylene production through both processes. The new technology for increasing the yield of propylene mainly comprises the technologies of propane dehydrogenation, olefin disproportionation, olefin cracking, olefin preparation from methanol, propylene preparation from methanol and the like. The propane dehydrogenation technology limits the production of propylene due to raw material sources and cost, and the olefin disproportionation technology has long process route and large investment, so that the production cost is high.
In the processes of steam cracking, catalytic cracking and olefin production from methanol, a certain amount of C4 and above fractions can be produced by the production of main products of ethylene and propylene, and the C4 and above fractions are rich in olefin components, so that the efficient utilization of the C4 and above fractions has become a great subject faced by petrochemical enterprises.
The traditional utilization of C4 hydrocarbon comprises two aspects of fuel utilization and chemical utilization, wherein the fuel utilization is mainly used for liquefied gas, MTBE, alkylated oil and the like, and the chemical utilization is mainly used for producing various related derivatives by utilizing separable components in C4 fractions. In addition, in order to improve the added value of the C4 and above fractions, new technologies, such as olefin cracking propylene yield increasing technology, are developed, and the technologies not only improve the added value of the C4 fraction, but also meet the increasing requirement of the market on propylene.
The catalytic cracking technology for propylene is a technological process for utilizing catalyst with unique shape selectivity and acidity to implement catalytic cracking to raise propylene yield, and its advantages are flexible raw material range, and can adopt by-product C4 and above olefines from FCC unit, steam cracking unit or MTO unit. Olefin cracking technology has become an important bridge between connecting petroleum, coal resources and propylene products in petrochemical and coal industries.
Chinese patent CN1274342a reports a process for producing ethylene and propylene from an olefin feedstock by catalytic conversion, wherein the catalyst employs a medium pore zeolite having SiO 2 /Al 2 O 3 The molar ratio is 200-5000, but it is a molecular sieve which is essentially proton-free, and at the same time requires modification of the catalyst with at least one metal selected from group IB elements.
Chinese patent CN103030501A discloses a method for producing propylene by using olefin with four or more carbon atoms as raw material and producing propylene on catalyst, wherein the catalyst comprises 48-89 parts by weight of SiO 2 /Al 2 O 3 The molecular sieve comprises, by mole, 200-800 parts of HZSM-5 molecular sieve, 0.1-2 parts of at least one of elements of group VIII of the periodic table of elements, and 10-50 parts of at least one binder selected from silicon oxide or aluminum oxide. The preparation conditions and the catalytic performance of the molecular sieve catalyst are described in detail in the patent, but the filling mode of the catalyst in the reactor is not mentioned, and the propylene yield cannot meet the increasing propylene product demand.
Chinese patent CN1915929a discloses a method for preparing propylene by cracking olefins having four or more carbon atoms, by passing an olefin feedstock through a fixed bed reactor comprising at least two catalyst beds to form an effluent containing propylene, the reactor comprising a feed pipe, a gas distributor, a first catalyst bed, an intermediate heat exchanger, a second catalyst bed, and an outlet pipe. The first section and the second section of the reactor adopt ZSM-5 molecular sieve catalysts, and an intermediate heat exchanger is arranged in the reactor, so that the purposes of maximizing propylene yield and prolonging the catalyst stability period are achieved. However, the reactor designed in this patent is relatively complex, and at the same time, the propylene yield is relatively low, which is only in the range of 21.0 to 23.0%.
At present, a single-bed fixed bed reactor is generally used in the olefin catalytic cracking technology, and the reaction flow mainly comprises the steps that raw material olefin is heated into high-temperature gas-phase olefin through a feeding and discharging heat exchanger and then enters the fixed bed reactor to contact with a catalyst for reaction. The gas phase product enters a compressor after being cooled by a feeding and discharging heat exchanger, and enters a product separation system after being compressed.
Disclosure of Invention
The invention aims to solve the technical problems of low yield of propylene which is a target product in the reaction of producing propylene by catalytic cracking of olefins with four or more carbon atoms in the prior art, and provides a method for increasing propylene yield by olefin cracking.
One of the purposes of the invention is to provide a method for increasing propylene yield, which comprises the steps of passing an olefin raw material through a multi-stage bed olefin cracking reactor to obtain a light material flow containing propylene, a material flow in C4-C6 and a heavy material flow containing C7 and more than C7, wherein a first stage bed layer, a second stage bed layer and a third stage bed layer in the multi-stage bed olefin cracking reactor are filled with different silicon-aluminum molecular sieve catalysts.
In the invention, the multi-stage bed olefin cracking reactor is filled with olefin cracking catalysts with different catalytic properties from a first stage bed, a second stage bed and a third stage bed in the feeding direction. In a preferred embodiment, the SiO of the aluminosilicate molecular sieve catalyst is 2 /Al 2 O 3 The molar ratio is 20-800, preferably 50-500; the silicon-aluminum molecular sieve catalysts of the first section bed layer, the second section bed layer and the third section bed layer are respectively selected from ZSM-5 molecular sieve, ZSM-11 molecular sieve or ZSM-5/ZSM-11 eutectic molecular sieve; in a more preferred embodiment, the silica alumina molecular sieve catalyst of the first and third stage beds is selected from a ZSM-5 molecular sieve or a ZSM-11 molecular sieve; the silicon-aluminum molecular sieve catalyst of the second section bed layer is ZSM-5/ZSM-11 eutectic molecular sieve.
In a preferred embodiment, the method for increasing propylene yield comprises the following steps: after the olefin raw material is heated, the olefin raw material enters a multi-stage bed olefin cracking reactor to react under the action of a catalyst, the olefin raw material at the inlet of the feeding side line of each stage of bed layer and the olefin raw material at the inlet of the feeding side line of the next stage of bed layer enter the next stage of bed layer to continue to react in the reaction process until the last stage of bed layer, the product obtained by the last stage of bed layer reaction is separated to obtain a light material flow containing propylene, a material flow in C4-C6 and heavy material flows above C7 and C7, and the material flow in C4-C6 returns to the inlet of the olefin raw material flow of the first stage of bed layer to be mixed into the olefin raw material to continue to react.
According to one embodiment of the invention, the method for increasing propylene production comprises the following steps: the multi-stage bed olefin cracking reactor is adopted, the multi-stage bed reactor comprises an olefin raw material first-stage bed inlet, an olefin raw material second-stage bed inlet and an olefin raw material third-stage bed inlet, a first olefin raw material entering from the first-stage bed inlet is reacted in the first-stage bed, a material obtained by the first-stage bed reaction and a second olefin raw material entering from the second-stage bed inlet are converged and enter into the second-stage bed reaction, a material obtained by the second-stage bed reaction and a third olefin raw material entering from the third-stage bed inlet are converged and enter into the third-stage bed reaction, a material obtained by the third-stage bed reaction flows out of the olefin cracking reactor, olefin cracking catalysts with different catalytic properties are filled in the first-stage bed, the second-stage bed and the third-stage bed are separated to obtain a light material flow rich in propylene, a C4-C6 medium material flow and a heavy material flow above C7 and C7, and a material flow obtained by the reaction, and the medium material flow obtained by the C4-C6 returns to the olefin raw material first-stage bed inlet of the reactor.
In a further preferred embodiment:
the above-mentioned aluminosilicate molecular sieve catalyst can be selected from aluminosilicate molecular sieve catalysts commonly used in the art in the silica-alumina ratio range, preferably SiO of said aluminosilicate molecular sieve catalyst 2 /Al 2 O 3 The molar ratio is 20 to 800, more preferably 50 to 500;
the olefin raw material is at least one selected from C4 and above fractions produced by an FCC device, C4 and above fractions produced by an MTO device and C4 and above fractions produced by an ethylene device;
the heating of the olefin raw material comprises heating the olefin raw material sequentially through a heat exchanger and a heating furnace, and preferably, the temperature of the olefin raw material is 50-60 ℃; the temperature of the heated olefin raw material is 450-650 ℃, preferably 500-600 ℃;
the multi-section bed olefin cracking reactor is an adiabatic fixed bed reactor,
the multi-stage bed olefin cracking reactor comprises at least 3 stages of beds, preferably 3-5 stages; the catalyst in the 4 th to 5 th stages except 1 to 3 th stages in the reactor is not particularly limited, and an optional silica-alumina molecular sieve catalyst may be used;
in the multi-stage bed olefin cracking reactor, the reaction process conditions of each stage of bed layer are that the reaction temperature is 500-600 ℃ and the weight airspeed of the reaction gas is 2-40 h -1 The pressure drop of the catalyst bed layer is 0-0.2 MPa;
the product obtained by the final bed reaction is subjected to cooling and compression and then component separation.
It is a second object of the present invention to provide a propylene stimulation system for carrying out the propylene stimulation method described above.
Specifically, the system comprises a raw material storage tank, a heat exchanger, a heating furnace, a multi-stage bed olefin cracking reactor and a separation system which are sequentially connected by material pipelines, wherein the separation system is provided with a light material flow pipeline rich in propylene, a material flow pipeline in C4-C6 and heavy material flow pipelines above C7 and C7, and the material flow pipeline in C4-C6 is connected with a raw material input pipeline of the heat exchanger.
Further, the multi-stage bed olefin cracking reactor is an adiabatic fixed bed reactor;
the multi-stage bed olefin cracking reactor comprises at least 3 stages of reaction beds which are vertically arranged, and preferably 3 to 5 stages; from the feeding direction, a first section of bed layer, a second section of bed layer and a third section of bed layer … … are sequentially arranged, wherein the first section of bed layer, the second section of bed layer and the third section of bed layer are filled with different silicon-aluminum molecular sieve catalysts, and preferably, the silicon-aluminum molecular sieve catalysts of the first section of bed layer, the second section of bed layer and the third section of bed layer are independently selected from ZSM-5 molecular sieve, ZSM-11 molecular sieve or ZSM-5/ZSM-11 eutectic molecular sieves, more preferably, the silica-alumina molecular sieve catalyst of the first section bed layer and the third section bed layer is selected from ZSM-5 molecular sieves or ZSM-11 molecular sieves, and the silica-alumina molecular sieve catalyst of the second section bed layer is ZSM-5/ZSM-11 eutectic molecular sieves; wherein, the SiO of the silicon-aluminum molecular sieve catalyst 2 /Al 2 O 3 The molar ratio is 20-800, preferably 50-500;
in the multi-stage bed olefin cracking reactor, each bed except the first bed is provided with a feeding side inlet, and the feeding side inlet is connected with a raw material output pipeline of a heating furnace; and a heat exchanger and a compressor are arranged between the multi-section bed olefin cracking reactor and the separation system.
The third object of the present invention is to apply the propylene yield increasing method or the propylene yield increasing system to propylene yield increasing by olefin cracking.
Aiming at the reaction characteristics of different beds in the multi-stage bed olefin cracking reactor, the invention ensures that the proceeding degree of various reactions in each stage of bed is different along with the composition difference of reactants and an optimized catalyst is required to be adapted. After entering a first bed reactor, olefin raw materials are contacted with a bed filled with ZSM-5 catalyst, olefin cracking reaction is carried out to generate hydrocarbons with different carbon numbers, and the hydrocarbons enter a second bed as reaction products; the reaction is an endothermic reaction, the temperature of the product after the reaction is reduced, the product is mixed with a second olefin raw material in a second bed layer and reacts with the second olefin raw material, a part of the second olefin raw material is subjected to self-cracking reaction, and a part of the second olefin raw material is subjected to polymerization reaction with a product in a previous bed layer, and the ZSM-5/ZSM-11 eutectic molecular sieve which is simultaneously provided with two structures is used in the second bed layer due to the reduction of the reaction temperature and more reaction types, so that a synergistic effect can be exerted, and two types of reactions are promoted to be more carried out to produce a reaction path of propylene; the generated product enters a third bed layer to be contacted with a third olefin raw material, and the ZSM-11 main catalytic raw material is used for carrying out polymerization and cracking reaction with the product of the previous bed layer, so that the content of hydrocarbon with other carbon numbers is further reduced, the generation of propylene is promoted, and the service life of the catalyst is prolonged. Different catalysts are used, and a eutectic molecular sieve is used as an intermediate bed layer, so that the effects of synergy and transition are achieved in a structure gradual change mode, and the occurrence of uncontrollable reaction caused by structural mutation is reduced.
Compared with the traditional multi-section bed reactor, the invention adopts the multi-section bed olefin cracking reactor with unique design, thereby not only improving the service life of the catalyst, but also obviously improving the yield of propylene. The invention utilizes a multi-stage bed olefin cracking reactor and a mode of filling olefin cracking catalysts with different catalytic properties in each stage of bed layer, can effectively increase propylene yield, can improve raw material throughput, and plays a role in enlightening the device in large scale; the yield-increasing propylene system provided by the invention is simple in design, safe and reliable, and well solves the problem of higher requirement on propylene yield in actual production.
Drawings
FIG. 1 shows a method for increasing propylene yield by olefin cracking. In the figure: the device comprises an A feeding and discharging heat exchanger, a B heating furnace, a C multi-section bed olefin cracking reactor, a D compressor, an E separation system and an F raw material storage tank; a main olefin raw material feeding pipeline 1, a main olefin raw material feeding pipeline 2, a hot end outlet pipeline of a heat exchanger 3, a first stage olefin raw material bed inlet pipeline 4, a second stage olefin raw material bed inlet pipeline 5, a third stage olefin raw material bed inlet pipeline 6, a reactor outlet pipeline 7, a cold end outlet pipeline 8, a compressor outlet pipeline 9, a material flow pipeline in 10C 4-C6, a propylene product pipeline 11 and other product pipelines 12.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In one embodiment of the present invention, the specific process for propylene stimulation using the system shown in FIG. 1 is as follows:
50-60 ℃ olefin-rich raw material enters a boundary zone through a 1-olefin raw material feeding main pipeline, is mixed with a circulating material flow (material flow in C4-C6) 10 from an E separation system and flows into a 2-raw material feeding main pipeline, then enters an A-feeding and discharging heat exchanger, passes through a B heating furnace, heats the raw material to reach a reaction temperature, then enters a C multi-stage olefin cracking reactor through pipelines 4, 5 and 6 respectively through flow control, enters the reactor through the pipeline 4 and the upper part of a first stage bed filled with one molecular sieve catalyst, enters the reactor through the pipeline 5 from the upper part of a second stage bed filled with another eutectic molecular sieve catalyst, and enters the reactor through the pipeline 6 from the upper part of a third stage bed filled with another molecular sieve catalyst. The feedstock from line 5 is contacted with the reaction product from the first stage bed and reacted in the second stage bed, and the resulting product is contacted with the olefin-rich feedstock from line 6 before passing through the third stage bed. The total product is cooled by an outlet pipeline of the reactor 7 through an inlet-outlet heat exchanger A, enters a compressor D for boosting, enters an E separation system, and a C4-C6 medium material flow is returned to a main raw material feeding pipeline 2 as a circulating material flow, a light material flow rich in propylene is discharged from a propylene product pipeline 11, and heavy material flows above C7 and C7 are discharged from other product pipelines 12.
Example 1:
a schematic of a process flow employing a three stage bed feed is shown in figure 1. 50 ℃ olefin-rich raw material enters a boundary zone through a 1 olefin raw material feeding main pipeline, is mixed with a material flow 10 in C4-C6 from an E separation system and flows into a 2 raw material feeding main pipeline, then enters an A feeding and discharging heat exchanger, passes through a B heating furnace, heats the raw material to 560 ℃, and respectively enters a C multi-section bed olefin cracking reactor from pipelines 4, 5 and 6, and the weight airspeed of each section bed is controlled to be 25h -1 A pressure drop of 0.15MPa, the feed flowing in via line 4 and a catalyst packed with ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 Molar ratio = 200) into the reactor from the upper part of the first bed, the feed flowing in via line 5 was fed from a bed packed with ZSM-5/ZSM-11 eutectic molecular sieve catalyst (SiO 2 /Al 2 O 3 Molar ratio = 200) of the second bed into the reactor, the feed flowing in via line 6 was catalyzed by a ZSM-11 molecular sieve packedAgent (SiO) 2 /Al 2 O 3 Molar ratio = 200) into the reactor. The feedstock from line 5 is contacted with the reaction product from the first bed and reacted at 545 c in the second bed and the resulting product is contacted with the olefin-rich feedstock from line 6 and passed through the third bed and reacted at 530 c in the third bed. The total product is cooled by an outlet pipeline of the reactor 7 through an inlet-outlet heat exchanger A, enters a compressor D for boosting, enters an E separation system, and a C4-C6 medium material flow is returned to a raw material feeding main pipeline 2 as a circulating material flow 10, a propylene-rich light material flow is discharged by a propylene product pipeline 11, and heavy material flows above C7 and C7 are discharged by other product pipelines 12. The propylene yield was 56%.
Example 2:
a schematic of a process flow employing a three stage bed feed is shown in figure 1. 50 ℃ olefin-rich raw material enters a boundary zone through a 1 olefin raw material feeding main pipeline, is mixed with a material flow 10 in C4-C6 from an E separation system and flows into a 2 raw material feeding main pipeline, then enters an A feeding and discharging heat exchanger, passes through a B heating furnace, heats the raw material to 560 ℃, and respectively enters a C multi-section bed olefin cracking reactor from pipelines 4, 5 and 6, and the weight airspeed of each section bed is controlled to be 25h -1 A pressure drop of 0.15MPa, the feed flowing in via line 4 and a catalyst packed with ZSM-11 molecular sieve (SiO 2 /Al 2 O 3 Molar ratio = 200) into the reactor from the upper part of the first bed, the feed flowing in via line 5 was fed from a bed packed with ZSM-5/ZSM-11 eutectic molecular sieve catalyst (SiO 2 /Al 2 O 3 Molar ratio = 200) of the second bed into the reactor, the feed flowing in via line 6 was fed from a bed of ZSM-5 molecular sieve catalyst (SiO 2 /Al 2 O 3 Molar ratio = 200) into the reactor. The feedstock from line 5 is contacted with the reaction product from the first bed and reacted at 545 c in the second bed and the resulting product is contacted with the olefin-rich feedstock from line 6 and passed through the third bed and reacted at 530 c in the third bed. The total product is cooled by an A feeding and discharging heat exchanger from an outlet pipeline of the 7 reactor, enters a D compressor for boosting, enters an E separation system, and a C4-C6 medium material flow returns as a circulating material flow 10To the main feed line 2, a light stream rich in propylene is withdrawn from the 11 propylene product line and heavy streams of C7 and above C7 are withdrawn from the 12 other product lines. The propylene yield was 53%.
Example 3:
a schematic of a process flow employing a three stage bed feed is shown in figure 1. 50 ℃ olefin-rich raw material enters a boundary zone through a 1 olefin raw material feeding main pipeline, is mixed with a material flow 10 in C4-C6 from an E separation system and flows into a 2 raw material feeding main pipeline, then enters an A feeding and discharging heat exchanger, passes through a B heating furnace, heats the raw material to 560 ℃, and respectively enters a C multi-section bed olefin cracking reactor from pipelines 4, 5 and 6, and the weight airspeed of each section bed is controlled to be 25h -1 A pressure drop of 0.15MPa, the feed flowing in via line 4 and a catalyst packed with ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 Molar ratio = 360) into the reactor from the upper part of the first bed, the feed flowing in via line 5 was fed from a bed packed with ZSM-5/ZSM-11 eutectic molecular sieve catalyst (SiO 2 /Al 2 O 3 Molar ratio = 200) of the second bed into the reactor, the feed flowing in via line 6 was fed from a bed of ZSM-11 molecular sieve catalyst (SiO 2 /Al 2 O 3 Molar ratio = 200) into the reactor. The feedstock from line 5 is contacted with the reaction product from the first bed and reacted at 545 c in the second bed and the resulting product is contacted with the olefin-rich feedstock from line 6 and passed through the third bed and reacted at 530 c in the third bed. The total product is cooled by an outlet pipeline of the reactor 7 through an inlet-outlet heat exchanger A, enters a compressor D for boosting, enters an E separation system, and a C4-C6 medium material flow is returned to a raw material feeding main pipeline 2 as a circulating material flow 10, a propylene-rich light material flow is discharged by a propylene product pipeline 11, and heavy material flows above C7 and C7 are discharged by other product pipelines 12. The propylene yield was 54%.
Example 4:
a schematic of a process flow employing a three stage bed feed is shown in figure 1. The 50 ℃ olefin-rich raw material enters the boundary zone through a 1 olefin raw material feeding main pipeline, is mixed with a C4-C6 medium material flow 10 from an E separation system and flows into a 2 raw material feeding main pipeline, and then enters a feeding and discharging materialThe heat exchanger is used for heating the raw material to 560 ℃ through a heating furnace B, the raw material respectively enters a C multi-section bed olefin cracking reactor from pipelines 4, 5 and 6, and the weight airspeed of each section of bed layer is controlled to be 25h -1 A pressure drop of 0.15MPa, the feed flowing in via line 4 and a catalyst packed with ZSM-5 molecular sieve (SiO 2 /Al 2 O 3 Molar ratio = 200) into the reactor from the upper part of the first bed, the feed flowing in via line 5 was fed from a bed packed with ZSM-5/ZSM-11 eutectic molecular sieve catalyst (SiO 2 /Al 2 O 3 Molar ratio = 100) of the second bed into the reactor, the feed flowing in via line 6 was fed from a bed of ZSM-11 molecular sieve catalyst (SiO 2 /Al 2 O 3 Molar ratio = 200) into the reactor. The feedstock from line 5 is contacted with the reaction product from the first bed and reacted at 545 c in the second bed and the resulting product is contacted with the olefin-rich feedstock from line 6 and passed through the third bed and reacted at 530 c in the third bed. The total product is cooled by an outlet pipeline of the reactor 7 through an inlet-outlet heat exchanger A, enters a compressor D for boosting, enters an E separation system, and a C4-C6 medium material flow is returned to a raw material feeding main pipeline 2 as a circulating material flow 10, a propylene-rich light material flow is discharged by a propylene product pipeline 11, and heavy material flows above C7 and C7 are discharged by other product pipelines 12. The propylene yield was 54%.
Comparative example 1:
a schematic diagram of a process flow of feeding by adopting three sections of beds is shown in FIG. 1, and SiO of a ZSM-5 molecular sieve catalyst used by each section of bed is shown in the schematic diagram 2 /Al 2 O 3 The molar ratio was 200. 50 ℃ olefin-rich raw material enters a boundary zone through a feeding main pipeline of the 1 olefin-rich raw material, is mixed with 10 circulating material flows, enters a feeding and discharging heat exchanger A through a feeding main pipeline of the 2 olefin-rich raw material, then passes through a heating furnace B, reaches 560 ℃ after being heated twice, enters a reactor from the upper part of each section of bed layer of a C multi-section bed layer olefin reactor through pipelines 4, 5 and 6, and controls the weight space velocity of each section of bed layer to be 25h -1 The pressure drop is 0.15MPa, the temperatures of the second bed layer and the third bed layer are 545 ℃ and 530 ℃, and olefin cracking occurs when the second bed layer and the third bed layer are contacted with the beds each filled with the same ZSM-5 molecular sieve catalystAnd (3) cooling the total product from an outlet pipeline of the reactor 7 through an inlet-outlet heat exchanger A, pressurizing the total product in a compressor D, introducing the total product into an E separation system, returning a C4-C6 medium material flow as a circulating material flow to a main raw material feeding pipeline 2, discharging a propylene-rich light material flow from a propylene product pipeline 11, and discharging heavy material flows above C7 and C7 from other product pipelines 12. The propylene yield was 47%.
Comparative example 2:
a schematic diagram of a process flow of feeding by adopting three sections of beds is shown in FIG. 1, and SiO of a ZSM-11 molecular sieve catalyst used by each section of bed is shown in the schematic diagram 2 /Al 2 O 3 The molar ratio was 200. 50 ℃ olefin-rich raw material enters a boundary zone through a feeding main pipeline of the 1 olefin-rich raw material, is mixed with 10 circulating material flows, enters a feeding and discharging heat exchanger A through a feeding main pipeline of the 2 olefin-rich raw material, then passes through a heating furnace B, reaches 560 ℃ after being heated twice, enters a reactor from the upper part of each section of bed layer of a C multi-section bed layer olefin reactor through pipelines 4, 5 and 6, and controls the weight space velocity of each section of bed layer to be 25h -1 The pressure drop is 0.15MPa, the temperatures of the second bed layer and the third bed layer are 545 ℃ and 530 ℃, the second bed layer and the third bed layer are respectively contacted with beds filled with the same ZSM-11 molecular sieve catalyst for olefin cracking reaction, the total product is cooled by an outlet pipeline of the 7 reactor through an A feeding and discharging heat exchanger and then enters a D compressor for boosting, then enters an E separation system, a C4-C6 medium material flow is returned to a 2 raw material feeding main pipeline as a circulating material flow, a propylene-rich light material flow is discharged from an 11 propylene product pipeline, and heavy material flows above C7 and C7 are discharged from 12 other product pipelines. The propylene yield was 37%.
Comparative example 3:
a schematic diagram of a process flow of feeding by adopting three sections of beds is shown in figure 1, and SiO of a ZSM-5/ZSM-11 eutectic molecular sieve catalyst used by each section of beds is shown in the formula 2 /Al 2 O 3 The molar ratio was 200. The 50 ℃ olefin-rich raw material enters a boundary zone through a feeding main pipeline of the 1 olefin-rich raw material, is mixed with 10 circulating material flows, enters an A feeding and discharging heat exchanger through a feeding main pipeline of the 2 olefin-rich raw material, then passes through a B heating furnace, reaches 560 ℃ after being heated twice, and enters a reverse reactor from the upper part of each section of bed layer of the C multi-section bed layer olefin reactor through pipelines 4, 5 and 6 respectivelyThe reactor controls the weight airspeed of each section of bed layer to be 25h -1 The pressure drop is 0.15MPa, the temperatures of the second bed layer and the third bed layer are 545 ℃ and 530 ℃, the second bed layer and the third bed layer are respectively contacted with beds filled with the same ZSM-5/ZSM-11 eutectic molecular sieve catalyst in each section to generate olefin cracking reaction, total products are cooled by an inlet and outlet heat exchanger of a reactor 7 and then enter a compressor D to be boosted and enter an E separation system, a C4-C6 medium material flow is used as a circulating material flow to return to a raw material feeding main pipeline 2, a light material flow rich in propylene is discharged from a propylene product pipeline 11, and heavy material flows above C7 and C7 are discharged from other product pipelines 12. The propylene yield was 40%.
Comparative example 4:
the process flow using three stage bed feed is similar to that shown in figure 1, with no lines 5, 6. 50 ℃ olefin-rich raw material enters a boundary zone through a 1 olefin raw material feeding main pipeline, is mixed with a material flow 10 in C4-C6 from an E separation system and flows into a 2 raw material feeding main pipeline, then enters an A feeding and discharging heat exchanger, passes through a B heating furnace, heats the raw material to 560 ℃, enters a C multi-stage bed olefin cracking reactor from a pipeline 4, and controls the weight space velocity of each stage of bed layer to be 25h -1 The feed flowing in via line 4, having a pressure drop of 0.15MPa, enters the reactor from the upper portion of the first bed and is charged with ZSM-5 molecular sieve catalyst (SiO 2 /Al 2 O 3 The first bed layer contact with the mole ratio=200) reacts, and then the first bed layer contact is sequentially subjected to the reaction of the first bed layer contact with the ZSM-5/ZSM-11 eutectic molecular sieve catalyst (SiO) 2 /Al 2 O 3 Molar ratio = 200) and a second bed packed with ZSM-11 molecular sieve catalyst (SiO 2 /Al 2 O 3 Molar ratio = 200). The reaction product from the first bed reacts at 545 c in the second bed and the resulting product passes through the third bed where it reacts at 530 c. The total product is cooled by an outlet pipeline of the reactor 7 through an inlet-outlet heat exchanger A, enters a compressor D for boosting, enters an E separation system, and a C4-C6 medium material flow is returned to a raw material feeding main pipeline 2 as a circulating material flow 10, a propylene-rich light material flow is discharged by a propylene product pipeline 11, and heavy material flows above C7 and C7 are discharged by other product pipelines 12. The propylene yield was 25%.
TABLE 1 types of catalysts used in examples 1 to 4 and comparative examples 1 to 9 and propylene yields
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art who is skilled in the art to which the present invention pertains should make equivalent substitutions or modifications according to the technical scheme and the inventive concept disclosed herein, and should be covered by the scope of the present invention.
Claims (10)
1. A method for increasing yield of propylene comprises the steps of passing an olefin raw material through a multi-stage bed olefin cracking reactor to obtain a light material flow containing propylene, a material flow in C4-C6 and a heavy material flow containing C7 and more than C7, wherein a first stage bed layer, a second stage bed layer and a third stage bed layer in the multi-stage bed olefin cracking reactor are filled with different silicon-aluminum molecular sieve catalysts.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
SiO of the silicon-aluminum molecular sieve catalyst 2 /Al 2 O 3 The molar ratio is 20-800, preferably 50-500; and/or the number of the groups of groups,
the silica-alumina molecular sieve catalyst of the first section bed layer, the second section bed layer and the third section bed layer is independently selected from ZSM-5 molecular sieve, ZSM-11 molecular sieve or ZSM-5/ZSM-11 eutectic molecular sieve.
3. The method of claim 2, wherein the step of determining the position of the substrate comprises,
the silicon-aluminum molecular sieve catalyst of the first section bed layer and the third section bed layer is selected from ZSM-5 molecular sieve or ZSM-11 molecular sieve;
the silicon-aluminum molecular sieve catalyst of the second section bed layer is ZSM-5/ZSM-11 eutectic molecular sieve.
4. A method according to any one of claims 1-3, characterized in that the method comprises in particular the following steps: after the olefin raw material is heated, the olefin raw material enters a multi-stage bed olefin cracking reactor to react under the action of a silicon-aluminum molecular sieve catalyst, in the reaction process, the product of each stage of bed layer and the olefin raw material at the inlet of the feeding side line of the next stage of bed layer enter the next stage of bed layer together to continue to react until the last stage of bed layer, the product obtained by the last stage of bed layer reaction is separated to obtain a propylene-containing light material flow, C4-C6 medium material flows and heavy material flows above C7 and C7, and the C4-C6 medium material flows are returned to the olefin raw material flow inlet of the first stage of bed layer to be mixed with the olefin raw material to continue to react.
5. The method of claim 4, wherein the step of determining the position of the first electrode is performed,
the olefin raw material is at least one selected from C4 and above fractions produced by an FCC device, C4 and above fractions produced by an MTO device and C4 and above fractions produced by an ethylene device; and/or the number of the groups of groups,
the olefin raw material heating comprises the steps of heating the olefin raw material sequentially through a heat exchanger and a heating furnace; preferably, the temperature of the olefin feedstock is 50 to 60 ℃, and the temperature of the olefin feedstock after heating is 450 to 650 ℃, preferably 500 to 600 ℃.
6. The method of claim 4, wherein the step of determining the position of the first electrode is performed,
the multi-stage bed olefin cracking reactor comprises at least 3 stages of beds, preferably 3-5 stages; and/or the number of the groups of groups,
in the multi-stage bed olefin cracking reactor, the reaction process conditions of each stage of bed layer are respectively as follows: the reaction temperature is 500-600 ℃, and the weight space velocity of the reaction gas is 2-40 h -1 The pressure drop of the catalyst bed layer is 0-0.2 MPa; and/or the number of the groups of groups,
the product obtained by the final bed reaction is subjected to cooling and compression and then component separation.
7. A propylene stimulation system for carrying out the propylene stimulation method of any one of claims 1 to 6.
8. The system of claim 7, wherein the system comprises a raw material storage tank, a heat exchanger, a heating furnace, a multi-stage bed olefin cracking reactor and a separation system which are sequentially connected by material pipelines, wherein the separation system is provided with a light material flow pipeline containing propylene, a material flow pipeline in C4-C6 and heavy material flow pipelines above C7 and C7, and the material flow pipeline in C4-C6 is connected with a raw material input pipeline of the heat exchanger.
9. The system of claim 8, wherein the system further comprises a controller configured to control the controller,
the multi-section bed olefin cracking reactor is an adiabatic fixed bed reactor; and/or the number of the groups of groups,
the multi-section bed olefin cracking reactor comprises at least 3 sections of reaction beds which are vertically arranged, and preferably 3-5 sections; and/or the number of the groups of groups,
in the multi-stage bed olefin cracking reactor, each bed except the first stage of bed is provided with a feeding side inlet, and the feeding side inlet is connected with a raw material output pipeline of a heating furnace; and/or the number of the groups of groups,
and a heat exchanger and a compressor are arranged between the multi-section bed olefin cracking reactor and the separation system.
10. Use of the method for propylene yield increase according to any one of claims 1 to 6 or the system for propylene yield increase according to any one of claims 7 to 9 for olefin cracking propylene yield increase.
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