CN116004278B - Method for increasing yield of low-carbon olefin - Google Patents
Method for increasing yield of low-carbon olefin Download PDFInfo
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- CN116004278B CN116004278B CN202111231764.8A CN202111231764A CN116004278B CN 116004278 B CN116004278 B CN 116004278B CN 202111231764 A CN202111231764 A CN 202111231764A CN 116004278 B CN116004278 B CN 116004278B
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- 238000000034 method Methods 0.000 title claims abstract description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 237
- 239000003054 catalyst Substances 0.000 claims abstract description 87
- 239000002808 molecular sieve Substances 0.000 claims abstract description 63
- 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 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000000295 fuel oil Substances 0.000 claims abstract description 39
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 31
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims description 73
- 230000008569 process Effects 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000003795 desorption Methods 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 125000005842 heteroatom Chemical group 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 description 19
- 239000002149 hierarchical pore Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- QOTAEASRCGCJDN-UHFFFAOYSA-N [C].CO Chemical compound [C].CO QOTAEASRCGCJDN-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- GZGREZWGCWVAEE-UHFFFAOYSA-N chloro-dimethyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(C)Cl GZGREZWGCWVAEE-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- LWSYSCQGRROTHV-UHFFFAOYSA-N ethane;propane Chemical compound CC.CCC LWSYSCQGRROTHV-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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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
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method for increasing yield of low-carbon olefin is characterized in that methanol and naphtha and/or heavy oil enter a catalytic cracking reaction device together, a molecular sieve with eight-membered ring crystal pore canal is used as an auxiliary agent of a catalytic cracking catalyst, the molecular sieve with eight-membered ring crystal pore canal at least contains 1-2 nm of intragranular ultra-micropores and 2-50 nm of mesopores, the volume of the mesopores is 0.01-0.36 cm 3/g, and the grain size is 50-10000 nm.
Description
Technical Field
The invention relates to a method for increasing yield of low-carbon olefin, in particular to a method for increasing yield of low-carbon olefin by catalytic cracking (decomposition).
Background
The low-carbon olefin is an important basic chemical raw material, and the production process mainly comprises catalytic cracking (pyrolysis), steam cracking, olefin preparation from methanol, dehydrogenation of ethane (propane) and the like. Although the processes of the traditional petroleum processing routes such as catalytic cracking (pyrolysis) and steam cracking are mature and stable, the economy of the traditional petroleum processing routes is limited by petroleum price, and the defects of high difficulty in increasing the yield of low-carbon olefin and the like exist. Although the process for preparing olefin from methanol has the advantage of high yield of low-carbon olefin, the investment for device construction is large. Based on the recognition of the similarity of the catalytic cracking (solution) process and the methanol-to-olefin process, the integrated research of the methanol-to-olefin process and the catalytic cracking (solution) process is utilized, and the existing catalytic cracking (solution) industrial device is one of the development directions for improving the low-carbon olefin yield of the catalytic cracking (solution) process and the economy of the methanol-to-olefin process.
Chang Fuxiang et al (petrochemical, 2005, z1, 108-111.) have shown that the mechanism study of methanol and n-hexane coupling reactions under the action of ZSM-5, ZSM-35, Y and Beta molecular sieves: the methanol can change the activation mode of the n-hexane and improve the yield of the low-carbon olefin. Panyu et al (chemical engineering journal, 2006,57,785-790.) under the action of a conventional catalytic cracking catalyst, methanol is used as part of the reaction feed of a catalytic cracking unit, the hydrocarbon yield of methanol conversion reaches 26.3-28.1% by mass, and low-carbon olefins account for 66.5-67.8% by mass of hydrocarbon composition. However, the preparation of olefin from methanol is usually carried out by a hydrocarbon pool mechanism, the efficient and high-selectivity conversion of methanol is carried out on the premise of generating a polymethyl aromatic intermediate, the reaction rate of the preparation of olefin from methanol is far lower than that of the conventional catalytic cracking (de) reaction, and the content of dimethyl ether in the product can still reach more than 5 percent by mass. CN102816589a discloses that adding group IVB element or aluminum modified octamembered ring silicoaluminophosphate SRM molecular sieve as a co-catalyst to FCC catalyst and improving FCC ethylene and propylene yields by introducing methanol and ethanol in the stripping section. However, the introduction of the SRM molecular sieve has a certain influence on oil conversion, the carbon deposition of the catalyst is obviously improved, and the yields of heavy oil and diesel oil are also increased to a certain extent, which is probably that the hydrogen transfer activity of the catalytic material is enhanced by the modulation of the group IVB element. In summary, it is known that the conversion of methanol to prepare low-carbon olefins under FCC conditions and change the cracking process of naphtha to a certain extent, but how to reduce the induction period of the reaction of preparing olefins from methanol, increase the rate of generating polyaromatic hydrocarbons, and further increase the macromolecule cracking activity of the catalytic material is one of the key problems to be solved in improving the conversion efficiency of methanol under catalytic cracking (decomposition) conditions.
On the other hand, the raw materials of the catalytic cracking (decomposition) process have short residence time in the reaction device, and the catalyst is completely regenerated; the process for preparing olefin from methanol generally requires longer reaction time, and the catalyst is partially regenerated in order to improve the effective utilization rate of methanol carbon. Therefore, under the condition of catalytic cracking (decomposition), how to effectively regulate the reaction path of the active center of the reaction for preparing olefin from methanol to the generation of the active intermediate of the polymethyl arene is a key problem to be solved for improving the effective utilization rate of methanol carbon in the reaction process.
Disclosure of Invention
The invention aims at solving the technical problem of how to improve the effective utilization rate of methanol carbon in the reaction process in the prior art, and provides a method for increasing the yield of low-carbon olefin by combining a catalytic cracking (decomposition) process.
The invention provides a method for increasing yield of low-carbon olefin, which is characterized by comprising the following steps: methanol and naphtha and/or heavy oil enter a catalytic cracking reaction device together, a molecular sieve with eight-membered ring crystal pore canals is used as an auxiliary agent of a catalytic cracking catalyst, and the molecular sieve with eight-membered ring crystal pore canals at least contains 1-2 nm of intracrystalline ultra-micropores and 2-50 nm of mesopores, and the volume of the mesopores is 0.01-0.36 cm 3/g; the grain size is 50-10000 nm.
Aiming at the technical problem to be solved, the inventor adopts multistage pore characteristics from the viewpoint of improving the accessibility of the active center of the eight-membered ring channel active component, namely, molecular sieves which at least contain 1-2 nm of intragranular ultra-micropores and 2-50 nm of mesopores, have the mesopore volume of 0.01-0.36 cm 3/g and the grain size of 50-10000 nm are used as auxiliary agents, the molecular sieve auxiliary agents also have certain activity in the catalytic cracking (decomposition) reaction of macromolecules (namely, molecules with the kinetic diameter larger than the eight-membered ring channel size) in naphtha and/or heavy oil raw materials, and can promote the cracking (decomposition) of small molecular oil components (including straight-chain alkanes and straight-chain alkenes) to generate light olefins and/or alkanes, and particularly, the molecular sieve auxiliary agents can also efficiently catalyze the conversion of methanol to generate the light olefins.
According to the invention, the catalytic cracking (decomposition) and the process for preparing the olefin from the methanol are integrated, and the selectivity of the low-carbon olefin in the catalytic cracking (decomposition) is improved by modulating the reactive components of the reaction feed and the catalyst in a methanol co-feed mode so as to increase the yield of the low-carbon olefin.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The invention provides a method for increasing yield of low-carbon olefin, which is characterized by comprising the following steps: methanol and naphtha and/or heavy oil enter a catalytic cracking reaction device together, a molecular sieve with eight-membered ring crystal pore canals is used as an auxiliary agent of a catalytic cracking catalyst, and the molecular sieve with eight-membered ring crystal pore canals at least contains 1-2 nm of intracrystalline ultra-micropores and 2-50 nm of mesopores, and the volume of the mesopores is 0.01-0.36 cm 3/g; the grain size is 50-10000 nm.
According to the invention, the molecular sieve with eight-membered ring crystal pore canal has multi-level pore structure characteristics, namely comprises at least intragranular ultra-micropores (1-2 nm), mesopores (2-50 nm), or further comprises macropores (> 50 nm), wherein the volume of the mesopores is 0.01-0.36 cm 3/g, preferably 0.05-0.36 cm 3/g, such as 0.05, 0.13, 0.16, 0.18, 0.24, 0.27, 0.36cm 3/g and the like.
According to the invention, the molecular sieve with eight-membered ring crystal channels has a grain size of 50-10000 nm, preferably 200-3000 nm, for example 1000-2000 nm, 2000-3000 nm, 400-600nm, 400-1000 nm.
Preferably, the molecular sieve with eight-membered ring crystal pore canal has acid center including but not limited to weak acid, medium strength acid and strong acid, and its corresponding acid amount is not less than 0.6mmol/g, 0.05mmol/g and 0.01mmol/g respectively; it is further preferred that the acidic center comprises, but is not limited to, weak acid and medium strength acid, the corresponding acid amounts of which are not less than 0.8mmol/g and 0.1mmol/g, respectively. The weak acid is an acid center corresponding to a desorption peak with the temperature lower than 250 ℃ on an NH 3 -TPD curve, the medium-strength acid is an acid center corresponding to a desorption peak with the temperature between 250 and 350 ℃ on the NH 3 -TPD curve, and the strong acid is an acid center corresponding to a desorption peak with the temperature higher than 350 ℃ on the NH 3 -TPD curve. More preferably, the weak acid, medium strength acid and strong acid have respective acid amounts of 0.8 to 1.5mmol/g, 0.15 to 0.35mmol/g and 0.01 to 0.25mmol/g, respectively.
According to the invention, the methanol and naphtha and/or heavy oil enter a catalytic cracking (de) device together. The methanol and naphtha and/or heavy oil may be fed through feed nozzles on the same vertical level riser, the methanol and naphtha and/or heavy oil may also be fed through feed nozzles on different vertical levels riser, and further, the methanol may also be fed through the stripper of the catalyst settling zone.
After the catalytic cracking (decomposition) catalyst reacts with small molecular components in naphtha and/or heavy oil or small molecular compounds in macromolecule cracking products to accumulate carbon, the molecular sieve auxiliary agent of the eight-membered ring crystal pore canal in the catalyst further catalyzes the conversion of methanol to prepare low-carbon olefin. Thus, to increase the effective utilization of methanol, it is preferred that the methanol is fed later than the naphtha and/or heavy oil, i.e. the naphtha and/or heavy oil is fed at the bottom of the riser, the methanol feed nozzle is at a higher vertical elevation above the riser than the feed nozzle, or the naphtha and/or heavy oil is fed at the bottom of the riser, the methanol is fed at the stripper of the catalyst settling zone. In order to improve the action time of the methanol and the catalyst and promote the conversion of the methanol to prepare olefin, the feeding of the methanol at the stripper part of the catalyst settling zone is a more preferable feeding mode.
The mass ratio of methanol to the feed of naphtha and/or heavy oil is 1: (1-100), preferably the mass ratio of methanol to the feed of naphtha and/or heavy oil is 1: (2-10).
Preferably, the molecular sieve with eight-membered ring crystal pore canal includes, but is not limited to, one or more of CHA, ERI, LTA, UFI, RTH, RHO, SFW and/or SWY topological structure molecular sieves; further preferably, the molecular sieve with eight-membered ring crystal pore canal includes, but is not limited to, one or more of CHA, LTA, RHO and/or SFW topological structure molecular sieves; still more preferably, the molecular sieve having eight-membered ring crystal channels is a SAPO-34 and/or SSZ-13 molecular sieve having the CHA topology. The mass ratio of the adding amount of the molecular sieve with eight-membered ring crystal pore canal to the adding amount of the catalytic cracking catalyst is 1: (1-100).
In order to obtain better low-carbon olefin yield, most preferably, the mesoporous volume of the molecular sieve of the eight-membered ring crystal pore canal is 0.1-0.25cm 3/g; the grain size is 400-600nm; weak acid, medium strength acid and strong acid and the corresponding acid amount are respectively 0.8-1.5mmol/g, 0.15-0.35mmol/g and 0.01-0.25mmol/g, methanol is fed at the stripper position of the catalyst sedimentation zone, and the ratio of the feeding amount of the methanol to the feeding amount of naphtha and/or heavy oil is 1: (2-10); the mass ratio of the addition amount of the auxiliary agent to the addition amount of the catalytic cracking catalyst is 1: (2-10).
The present invention will be described in detail by way of specific examples. In the following examples and comparative examples, the profile of a Scanning Electron Microscope (SEM) was obtained by measurement with Hitachi 4800, the accelerating voltage was 20KV, and the environment was scanned; the pore distribution map is determined according to the method described in RIPP-90 in petrochemical analysis method written by Yang Cuiding et al; the acidity data were determined using Micrometrics Autochem ii 2920.
Comparative example 1
This comparative example is presented to demonstrate the results of an FCC reaction of methanol in an FCC unit without the molecular sieve aid of eight-membered ring crystal channels.
In the FCC unit, heavy oil is fed at the bottom of a riser, the catalyst is a conventional FCC catalyst (CDOS catalyst of China petrochemical catalyst division company Chang Ling catalyst factory), the catalyst-to-oil ratio is 6, the reaction temperature in the riser is 450-500 ℃, and the temperature in a catalyst settling zone is 500-550 ℃. The gas yield of the heavy oil reaction is: ethylene 0.9%, propylene 5.1% and butene 2.4%.
Comparative example 2
This comparative example is presented to demonstrate the performance of a conventional SAPO-34 molecular sieve to catalyze the conversion of methanol under FCC process conditions.
In the FCC unit, heavy oil is fed at the bottom of a riser, methanol is fed at the position of a stripper in a catalytic material sedimentation zone, and the mass ratio of the methanol to the heavy oil is 1:5, the catalyst oil ratio is 6, the main component of the catalyst is still a conventional FCC catalyst, but catalyst auxiliary agents which take conventional SAPO-34 molecular sieves (weak acid, medium strength acid and corresponding acid amount of the strong acid are respectively 0.45mmol/g, 0.71mmol/g and 0.09 mmol/g) as active components are added, the grain size of the SAPO-34 molecular sieve is 400-600 nm, no mesoporous structure exists in the crystal, and the mass ratio of the auxiliary agents to the conventional FCC catalyst is 1:10. the reaction temperature in the riser is 450-500 ℃, and the temperature of the catalyst sedimentation zone is 500-550 ℃.
The methanol conversion was 85.7%, the dimethyl ether selectivity was 2.3%, the ethylene selectivity was 8.9%, the propylene selectivity was 12.3%, and the butene selectivity was 3.9%.
Comparative example 3
This comparative example is presented to demonstrate the performance of a conventional SSZ-13 molecular sieve to catalyze the conversion of methanol under FCC process conditions.
In the FCC unit, heavy oil is fed at the bottom of a riser, methanol is fed at the position of a stripper in a catalytic material sedimentation zone, and the mass ratio of the methanol to the heavy oil is 1:10, the oil ratio is 6. The main component of the catalyst is still a conventional FCC catalyst, but catalyst auxiliary agents which take a conventional SSZ-13 molecular sieve (corresponding acid amounts of weak acid, medium strength acid and strong acid are respectively 0.32mmol/g, 0.63mmol/g and 0.27 mmol/g) as active components are added, the grain size of the SSZ-13 molecular sieve is 400-600 nm, no mesopores exist in the crystal, and the mass ratio of the addition amount of the auxiliary agents to the conventional FCC catalyst is 1:10. the reaction temperature in the riser is 450-500 ℃, and the temperature of the catalyst sedimentation zone is 500-550 ℃.
The conversion of methanol was 89.4%, the selectivity to methyl ether was 3.9%, the selectivity to ethylene was 4.1%, the selectivity to propylene was 6.2%, and the selectivity to butene was 3.6%
Example 1
In the FCC unit, heavy oil is fed at the bottom of a riser, methanol is fed at the position of a stripper in a catalytic material sedimentation zone, and the mass ratio of the methanol to the heavy oil is 1:5, the agent-oil ratio is 6. The main component of the catalyst is still a conventional FCC catalyst, but a catalyst auxiliary agent which takes a hierarchical pore SAPO-34 molecular sieve as an active component is added, the grain size of the hierarchical pore SAPO-34 molecular sieve is 400-600 nm, the volume of intra-crystalline mesopores is 0.18cm 3/g, the corresponding acid amounts of weak acid, medium-strength acid and strong acid are respectively 0.98mmol/g, 0.21mmol/g and 0.03mmol/g, and the mass ratio of the adding amount of the catalyst auxiliary agent to the conventional FCC catalyst is 1:10. the reaction temperature in the riser is 450-500 ℃, and the temperature of the catalyst sedimentation zone is 500-550 ℃.
The gas yields of methanol co-feed with heavy oil are shown in table 1.
Example 2
In an FCC unit, naphtha is fed at the bottom of a riser, methanol is fed at the stripper position of a catalytic material settling zone, and the mass ratio of methanol to naphtha feed is 1:5, the agent-oil ratio is 6. The main component of the catalyst is still a conventional FCC catalyst, but a catalyst auxiliary agent which takes a hierarchical pore SAPO-34 molecular sieve as an active component is added, the grain size of the hierarchical pore SAPO-34 molecular sieve is 400-600 nm, the volume of intra-crystalline mesopores is 0.16cm 3/g, the corresponding acid amounts of weak acid, medium-strength acid and strong acid are respectively 0.86mmol/g, 0.27mmol/g and 0.08mmol/g, and the mass ratio of the addition amount of the auxiliary agent to the conventional FCC catalyst is 1:10. the reaction temperature in the riser is 450-500 ℃, and the temperature of the catalyst sedimentation zone is 500-550 ℃.
The gas yields of methanol and naphtha co-feeds are shown in table 1.
Example 3
In the FCC unit, heavy oil is fed at the bottom of a riser, methanol is fed at the position of a stripper in a catalytic material sedimentation zone, and the mass ratio of the methanol to the heavy oil is 1:10, the oil ratio is 6. The main component of the catalyst is still a conventional FCC catalyst, but a catalyst auxiliary agent which takes a hierarchical pore SSZ-13 molecular sieve as an active component is added, the grain size of the SSZ-13 molecular sieve is 400-600 nm, the volume of a mesoporous in a crystal is 0.27cm 3/g, the corresponding acid amounts of weak acid, medium-strength acid and strong acid are respectively 1.3mmol/g, 0.32mmol/g and 0.23mmol/g, and the mass ratio of the addition amount of the auxiliary agent to the conventional FCC catalyst is 1:10. the reaction temperature in the riser is 450-500 ℃, and the temperature of the catalyst sedimentation zone is 500-550 ℃.
The gas yields of methanol and naphtha co-feeds are shown in table 1.
Example 4
In the FCC unit, heavy oil is fed at the bottom of a riser, methanol is fed at the position of a stripper in a catalytic material sedimentation zone, and the mass ratio of the methanol to the heavy oil is 1:1 and the oil ratio is 6. The main component of the catalyst is still a conventional FCC catalyst, but a catalyst auxiliary agent which takes a hierarchical pore SAPO-34 molecular sieve as an active component is added, the grain size of the hierarchical pore SAPO-34 molecular sieve is 400-600 nm, the secondary pore volume in a crystal is 0.32cm 3/g, the corresponding acid amounts of weak acid, medium-strength acid and strong acid are respectively 1.3mmol/g, 0.32mmol/g and 0.23mmol/g, and the mass ratio of the addition amount of the auxiliary agent to the conventional FCC catalyst is 1.5:1. the reaction temperature in the riser is 450-500 ℃, and the temperature of the catalyst sedimentation zone is 500-550 ℃.
The gas yields of methanol and naphtha co-feeds are shown in table 1.
Example 5
In the FCC unit, heavy oil is fed at the bottom of a riser, methanol is fed at the position of a stripper in a catalytic material sedimentation zone, and the mass ratio of the methanol to the heavy oil is 1:2, the agent-oil ratio is 6. The main component of the catalyst is still a conventional FCC catalyst, but a catalyst auxiliary agent which takes a hierarchical pore SAPO-34 molecular sieve as an active component is added, the grain size of the hierarchical pore SAPO-34 molecular sieve is 1000-2000 nm, the volume of intra-crystalline mesopores is 0.13cm 3/g, the corresponding acid amounts of weak acid, medium-strength acid and strong acid are respectively 1.46mmol/g, 0.33mmol/g and 0.25mmol/g, and the mass ratio of the addition amount of the auxiliary agent to the conventional FCC catalyst is 1:1. the reaction temperature in the riser is 450-500 ℃, and the temperature of the catalyst sedimentation zone is 500-550 ℃.
The gas yields of methanol and naphtha co-feeds are shown in table 1.
Example 6
In an FCC unit, naphtha is fed at the bottom of a riser, methanol is fed at the stripper position of a catalytic material settling zone, and the mass ratio of methanol to naphtha feed is 1:2, the agent-oil ratio is 6. The main component of the catalyst is still a conventional FCC catalyst, but a catalyst auxiliary agent taking the SAPO-34 molecular sieve as an active component is added, the grain size of the SAPO-34 molecular sieve is 1000-2000 nm, the volume of the intra-crystalline mesopores is 0.05cm 3/g, the corresponding acid amounts of weak acid, medium-strength acid and strong acid are respectively 0.60mmol/g, 0.07mmol/g and 0.03mmol/g, and the mass ratio of the added amount of the catalyst auxiliary agent to the conventional FCC catalyst is 1:4. the reaction temperature in the riser is 450-500 ℃, and the temperature of the catalyst sedimentation zone is 500-550 ℃.
The gas yields of methanol and naphtha co-feeds are shown in table 1.
Example 7
In the FCC unit, heavy oil is fed at the bottom of a riser, methanol is fed at the position of a stripper in a catalytic material sedimentation zone, and the mass ratio of the methanol to the heavy oil is 1:2, the agent-oil ratio is 6. The main component of the catalyst is still a conventional FCC catalyst, but a catalyst auxiliary agent which takes a hierarchical pore SAPO-34 molecular sieve as an active component is added, the grain size of the hierarchical pore SAPO-34 molecular sieve is 2000-3000 nm, the volume of intra-crystalline mesopores is 0.36cm 3/g, the corresponding acid amounts of weak acid, medium-strength acid and strong acid are respectively 1.57mmol/g, 0.37mmol/g and 0.29mmol/g, and the mass ratio of the addition amount of the auxiliary agent to the conventional FCC catalyst is 1:3. the reaction temperature in the riser is 450-500 ℃, and the temperature of the catalyst sedimentation zone is 500-550 ℃.
The gas yields of methanol and naphtha co-feeds are shown in table 1.
Example 8
In an FCC unit, naphtha is fed at the bottom of a riser, methanol is fed at the middle of the riser, and the mass ratio of methanol to naphtha feed is 1:5, the agent-oil ratio is 6. The main component of the catalyst is still a conventional FCC catalyst, but a catalyst auxiliary agent which takes a hierarchical pore SAPO-34 molecular sieve as an active component is added, the grain size of the hierarchical pore SAPO-34 molecular sieve is 400-600 nm, the volume of intra-crystalline mesopores is 0.16cm 3/g, the corresponding acid amounts of weak acid, medium-strength acid and strong acid are respectively 0.86mmol/g, 0.27mmol/g and 0.08mmol/g, and the mass ratio of the addition amount of the catalyst auxiliary agent to the conventional FCC catalyst is 1:10. the reaction temperature in the riser is 450-500 ℃, and the temperature of the catalyst sedimentation zone is 500-550 ℃.
The gas yields of methanol and naphtha co-feeds are shown in table 1.
Example 9
In the FCC unit, heavy oil and methanol are fed at the bottom of the riser, and the mass ratio of the methanol to the heavy oil is 1:5, the agent-oil ratio is 6. The main component of the catalyst is still a conventional FCC catalyst, but a catalyst auxiliary agent which takes a hierarchical pore SAPO-34 molecular sieve as an active component is added, the grain size of the hierarchical pore SAPO-34 molecular sieve is 400-600 nm, the volume of intra-crystalline mesopores is 0.24cm 3/g, the corresponding acid amounts of weak acid, medium-strength acid and strong acid are respectively 1.16mmol/g, 0.19mmol/g and 0.01mmol/g, and the mass ratio of the addition amount of the catalyst auxiliary agent to the conventional FCC catalyst is 1:5. the reaction temperature in the riser is 450-500 ℃, and the temperature of the catalyst sedimentation zone is 500-550 ℃. The gas yields of methanol and naphtha co-feeds are shown in table 1.
TABLE 1
| Methanol conversion/% | Dimethyl ether/% | Ethylene/% | Propylene/% | Butene/% | |
| Comparative example 1 | 0.9 | 5.1 | 2.4 | ||
| Comparative example 2 | 85.7 | 2.3 | 8.9 | 12.3 | 3.9 |
| Comparative example 3 | 89.4 | 3.9 | 4.1 | 6.2 | 3.6 |
| Example 1 | 100 | 0 | 15.5 | 13.1 | 5.6 |
| Example 2 | 100 | 0 | 16.3 | 13.8 | 5.9 |
| Example 3 | 100 | 0 | 8.7 | 11.2 | 4.2 |
| Example 4 | 100 | 0 | 35.1 | 14.2 | 8.0 |
| Example 5 | 100 | 0 | 19.3 | 11.1 | 6.2 |
| Example 6 | 92.4 | 6.2 | 17.2 | 11.5 | 3.9 |
| Example 7 | 100 | 0.1 | 15.4 | 16.2 | 7.6 |
| Example 8 | 100 | 1.9 | 8.7 | 11.3 | 4.4 |
| Example 9 | 100 | 0.2 | 6.9 | 13.2 | 5.1 |
Claims (11)
1. A method for increasing yield of low-carbon olefin is characterized in that methanol and naphtha and/or heavy oil enter a catalytic cracking reaction device together, a molecular sieve with eight-membered ring crystal pore canal is used as an auxiliary agent of a catalytic cracking catalyst, the molecular sieve with eight-membered ring crystal pore canal comprises weak acid, medium-strength acid and strong acid, and the corresponding acid amount is not lower than 0.6mmol/g, 0.05mmol/g and 0.01mmol/g respectively, the weak acid is an acid center corresponding to a desorption peak with the temperature lower than 250 ℃ on an NH 3 -TPD curve, the medium-strength acid is an acid center corresponding to a desorption peak with the temperature between 250 and 350 ℃ on an NH 3 -TPD curve, and the strong acid is an acid center corresponding to a desorption peak with the temperature higher than 350 ℃ on an NH 3 -TPD curve; the molecular sieve with eight-membered ring crystal pore canal at least contains 1-2 nm of intragranular ultra-micropores and 2-50 nm of mesopores, the volume of the mesopores is 0.01-0.36 cm 3/g, and the grain size is 50-10000 nm; the mass ratio of methanol to the feed of naphtha and/or heavy oil is 1: (1-100); the mass ratio of the addition amount of the molecular sieve with eight-membered ring crystal pore canal to the addition amount of the catalytic cracking catalyst is 1: (1-100).
2. The method of claim 1, wherein the molecular sieve with eight-membered ring crystal channels has a mesoporous volume of 0.05-0.36 cm 3/g.
3. The method of claim 1, wherein the molecular sieve having eight-membered ring crystal channels has a grain size of 200-3000 nm.
4. The method of claim 1, wherein the weak and medium strength acids have respective acid amounts of not less than 0.8mmol/g and 0.1mmol/g, respectively.
5. The process according to claim 1, wherein the weak, medium strength and strong acids have respective acid amounts of 0.8-1.5mmol/g, 0.15-0.35mmol/g and 0.01-0.25mmol/g, respectively.
6. The process of claim 1 wherein naphtha and/or heavy oil is fed at the bottom of the riser and methanol is fed at any location in the riser.
7. The process of claim 1 wherein naphtha and/or heavy oil is fed at the bottom of the riser and methanol is fed at the stripper section of the catalyst settling zone of the catalytic cracker.
8. The method according to claim 1, wherein the mass ratio of methanol to the feed amount of naphtha and/or heavy oil is 1: (2-10).
9. The method of claim 1, wherein the molecular sieve having eight membered ring crystal channels is selected from one or more of CHA, ERI, LTA, UFI, RTH, RHO, SFW, SWY topology molecular sieves.
10. The method of claim 9, wherein the molecular sieve having eight-membered ring crystal channels is a silica-alumina molecular sieve, a phosphoalumina molecular sieve, or a heteroatom molecular sieve.
11. The method of claim 1, wherein the molecular sieve having eight membered ring crystal pore channels is a SAPO-34 or SSZ-13 molecular sieve.
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| CN102040227A (en) * | 2009-10-20 | 2011-05-04 | 中国石油化工股份有限公司 | Ultrafine grain molecular sieve for preparation of low-carbon alkene by petroleum hydrocarbon cracking as well as catalyst and application thereof |
| CN102816590A (en) * | 2011-06-09 | 2012-12-12 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin through petroleum hydrocarbon oil catalytic cracking |
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| US7459596B1 (en) * | 2005-07-26 | 2008-12-02 | Uop Llc | Nanocrystalline silicalite for catalytic naphtha cracking |
| CN102040227A (en) * | 2009-10-20 | 2011-05-04 | 中国石油化工股份有限公司 | Ultrafine grain molecular sieve for preparation of low-carbon alkene by petroleum hydrocarbon cracking as well as catalyst and application thereof |
| CN102816590A (en) * | 2011-06-09 | 2012-12-12 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin through petroleum hydrocarbon oil catalytic cracking |
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