CN108201899A - A kind of preparing light olefins from methanol catalyst and preparation method thereof - Google Patents
A kind of preparing light olefins from methanol catalyst and preparation method thereof Download PDFInfo
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- CN108201899A CN108201899A CN201611170325.XA CN201611170325A CN108201899A CN 108201899 A CN108201899 A CN 108201899A CN 201611170325 A CN201611170325 A CN 201611170325A CN 108201899 A CN108201899 A CN 108201899A
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- light olefins
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- preparing light
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- slurries
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 12
- 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 28
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 239000002808 molecular sieve Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000000654 additive Substances 0.000 claims abstract description 16
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000012065 filter cake Substances 0.000 claims abstract description 12
- 238000005360 mashing Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 3
- 241000269350 Anura Species 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 239000011686 zinc sulphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 3
- 229940075614 colloidal silicon dioxide Drugs 0.000 claims description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 239000000470 constituent Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003978 infusion fluid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000271 synthetic detergent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- B01J35/40—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/83—Aluminophosphates (APO 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- 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
- C07C2529/82—Phosphates
- C07C2529/83—Aluminophosphates (APO compounds)
-
- 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)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparing light olefins from methanol catalyst, are calculated as by following each component by dry weight part：20 ~ 50 parts of composite molecular screen, 5 ~ 20 parts of binding agent, 1 ~ 5 part of phosphorus additive, 2 ~ 8 parts of zinc additive, 10 ~ 30 parts of basic anhydride, the method for preparing catalyst are：（1）Molecular sieve is pulverized and sieved, takes fine powder, is ground with being pumped into ball mill after deionized water mashing dispersion；（2）Gained slurries are placed in reaction kettle after heating, sequentially add hydrochloric acid, oxalic acid, then slurries are filtered, wash to obtain composite molecular screen solid filter cake；（3）Molecular sieve filter cake is placed in reaction kettle and is dispersed into slurries with deionized water mashing, adds in the mixed impregnant liquor of binding agent, phosphorus additive, zinc additive, basic anhydride, after dipping, high-temperature calcination obtains catalyst.The catalyst of the present invention has excellent catalytic activity, higher olefine selective and excellent attrition resistance energy, and the industrialization development for coal-to-olefin provides safeguard.
Description
Technical field
The present invention relates to coal chemical technology, especially a kind of preparing light olefins from methanol catalyst and preparation method thereof.
Background technology
Raw material of the alkene as synthetic detergent, plastics, fiber and all kinds of chemical materials, in modern petrochemical industry
It is middle to play very important effect.Traditional light olefin is produced by petroleum cracking, increasingly short with petroleum resources
It lacks, scientists from all over the world are just carrying out the work of search for oil alternate resources in full preparation.Using coal or natural gas as raw material economic cooperation
Into gas methanol, then the work of the low-carbon alkenes such as ethylene is made of methanol and receives the most attention of various countries' researcher.
The methanol-to-olefins technology researched and developed by the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences is taken the lead in 2010 in Baotou coal system
It succeeds in the test run in alkene project, the coal-to-olefin industrialization clean, efficient, good in economic efficiency for extensive realization has been established solid
Basis.The core of methanol-to-olefins technology is its catalyst technology.The activity of catalyst, its selective attrition resistance can be determined
Determine the principal element of methanol-to-olefins Project Economy Benefit.
It is existing zeolite structured（SAPO）Series Molecules sieve has higher work in the synthetic reaction of methanol-to-olefins
Property and selectivity are the preferred catalyst of methanol-to-olefins.But the production preparation process requirement of the catalyst is stringent, and product is received
Rate is not high, expensive, so it is very great to improve product yield meaning；In the existing technological process of production, by grasping meticulously
Make stringent control technic index, be all difficult the product yield for improving catalyst, while there are still volatile for these molecular sieve catalysts
The problems such as work, selectivity of light olefin is relatively low.
Invention content
The purpose of the invention is to overcome the deficiencies of the prior art and provide a kind of preparing light olefins from methanol catalyst and its
Preparation method, the catalyst are used for preparing light olefins from methanol, the active high, Optimalities such as wearability is good, selectivity of product is high
Energy.
The present invention can be achieved through the following technical solutions：
A kind of preparing light olefins from methanol catalyst, the catalyst are calculated as by following each component by dry weight part：Compound molecule
20 ~ 50 parts of sieve, 5 ~ 20 parts of binding agent, 1 ~ 5 part of phosphorus additive, 2 ~ 8 parts of zinc additive, 10 ~ 30 parts of basic anhydride, the catalysis
Agent has well-regulated three-dimensional eight annulus pore passage structure, and pore size is 0.36 × 0.36nm；
Further, the composite molecular screen be ZSM-5 molecular sieve, it is SAPO molecular sieve, at least two compound in A1PO molecular sieves
It forms；
Further, the composite molecular screen contains tri- kinds of molecular sieve structures of MFI, AEI and AFI；
Further, the binding agent is aluminium polychloride, colloidal silicon dioxide, colloidal alumina, alumina silicate colloid, aluminium oxide
One kind in powder and boehmite powder；
Further, the basic anhydride are one kind in MgO, CaO, LaO and CeO；
Further, the phosphorus additive is H3PO4、(NH4) H2PO4、(NH4) 2HPO4、(NH4) 3PO4In one kind；
Further, the zinc additive is Zn (NO3)2、ZnCl2、ZnSO4In one kind；
Further, the preparation method of the preparing light olefins from methanol catalyst, includes the following steps：
（1）Molecular sieve is pulverized and sieved, takes the following fine powder of 150 mesh, it is 40 ~ 45 %'s to be dispersed into solid content with deionized water mashing
Slurries are then pumped into ball mill and are ground；
（2）Step（1）Gained slurries, which are placed in reaction kettle, to heat up, then sequentially add hydrochloric acid, oxalic acid removing institute association Ca,
After the dirts such as Mg, Al, Fe, slurries are filtered, are washed, obtain composite molecular screen solid filter cake；
（3）By composite molecular screen solid filter cake be placed in reaction kettle with deionized water mashing be dispersed into slurries, add binding agent,
Phosphorus additive, zinc additive, basic anhydride mixed impregnant liquor dipping after, high-temperature calcination obtains catalyst；
Further, the step（2）Slurries, which are placed in reaction kettle, is warming up to 70 ~ 90 DEG C；
Further, the step（3）Dip time is 6 ~ 12 hours, and calcination temperature is 400 ~ 700 DEG C, and calcination time 2 ~ 6 is small
When.
A kind of preparing light olefins from methanol catalyst of the present invention and preparation method thereof, has following advantageous effect：
1st, a kind of main component of preparing light olefins from methanol catalyst of the present invention is composite molecular screen, and composite molecular screen has three-dimensional
Eight annulus pore passage structures, pore size are 0.36 × 0.36nm；The heap density for the catalyst prepared is 0. 7 ~ 0.9g/ml,
Granularity is 20 ~ 300 μm, and specific surface area is not less than 230m2/ g, abrasion index is no more than 0. 5%/h, based on above-mentioned excellent property
Can parameter, this catalyst has the catalytic activity of excellent methanol-to-olefins, higher olefine selective and excellent wear-resistant
Consumption energy.
2nd, it overcomes and is deposited using traditional one-component catalyst in methanol to olefins reaction using the catalyst of the present invention
Product in C2 =~C4 =Total selectivity of light olefin is low and C5The problem of more than high-carbon constituent content is higher, than being used alone
There is better catalytic activity, C when ZSM-5, SAPO catalyst2 =~C4 =Total selectivity of light olefin improves 21.4% ~ 27.5%, C5
More than high-carbon component reduces by 17.7% ~ 43%, C in product5More than high-carbon constituent content is less than 13%, this shows using the present invention's
Catalyst can obtain good technique effect in methanol to olefins reaction.
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, with reference to embodiment to this hair
Bright technical solution is described in further detail.
Embodiment 1
A kind of preparing light olefins from methanol catalyst, the catalyst are made of following each component based on dry weight part： ZSM-5
Molecular sieve, 20 parts of SAPO molecular sieve composite molecular screen, 10 parts of colloidal silicon dioxide, (NH4)2HPO43 parts, ZnCl25 parts,
MgO15 parts, the catalyst has well-regulated three-dimensional eight annulus pore passage structure, and pore size is 0.36 × 0.36nm；
（1）ZSM-5 molecular sieve, SAPO molecular sieve are pulverized and sieved, take the following fine powder of 150 mesh, is dispersed into deionized water mashing
Solid content is the slurries of 45 %, is then pumped into ball mill and is ground；
（2）Ground slurries are put into reaction kettle and are warming up to 70 DEG C, then sequentially add hydrochloric acid, oxalic acid, the association of removing institute
Ca, Mg, Al, slurries filter, washed, obtain composite molecular screen solid filter cake by the dirts such as Fe；
（3）The composite molecular screen solid filter cake that dry weight is 20 parts is put into reaction kettle slurry with deionized water mashing dispersion
Liquid adds dry weight as 10 parts of colloidal silicon dioxides, 3 parts (NH4)2HPO4, 5 parts of ZnCl2, 15 parts of MgO hybrid infusion
Liquid is sufficiently impregnated 8 hours, is calcined 4 hours at 600 DEG C and is obtained catalyst, the composite molecular screen contains MFI, AEI and AFI tri-
Kind molecular sieve structure.Performance parameter of the gained catalyst in methanol to olefins reaction is shown in Table 1.
Embodiment 2
A kind of preparing light olefins from methanol catalyst, the catalyst are made of following each component based on dry weight part：SAPO points
Sub- sieve, 40 parts of A1PO molecular sieves composite molecular screen, 15 parts of alumina silicate colloid, (NH4)3PO43 parts, ZnSO46 parts, CaO25 parts,
The catalyst has well-regulated three-dimensional eight annulus pore passage structure, and pore size is 0.36 × 0.36nm；
（1）SAPO molecular sieve, A1PO molecular sieves are pulverized and sieved, take the following fine powder of 150 mesh, is dispersed into deionized water mashing solid
Content is the slurries of 42 %, is then pumped into ball mill and is ground；
（2）Ground slurries are put into reaction kettle and are warming up to 85 DEG C, then sequentially add hydrochloric acid, oxalic acid, the association of removing institute
Ca, Mg, Al, slurries filter, washed, obtain composite molecular screen solid filter cake by the dirts such as Fe；
（3）The composite molecular screen solid filter cake that dry weight is 40 parts is put into reaction kettle slurry with deionized water mashing dispersion
Liquid adds dry weight as 15 parts of alumina silicate colloids, 3 parts (NH4)3PO4, 6 parts of ZnSO4, 25 parts of CaO mixed impregnant liquor fill
Sub-dip stain 12 hours calcines at 550 DEG C and obtains within 3 hours catalyst, and the composite molecular screen contains tri- kinds of MFI, AEI and AFI
Molecular sieve structure.Performance parameter of the gained catalyst in methanol to olefins reaction is shown in Table 1.
Embodiment 3
A kind of preparing light olefins from methanol catalyst, the catalyst are made of following each component based on dry weight part：SAPO points
Sub- sieve, 45 parts of ZSM-5 molecular sieve, 12 parts of aluminium polychloride, H3PO42 parts, Zn (NO3)26 parts, LaO15 parts, the catalyst tool
Well-regulated three-dimensional eight annulus pore passage structure, pore size are 0.36 × 0.36nm；
（1）SAPO molecular sieve, ZSM-5 molecular sieve are pulverized and sieved, take the following fine powder of 150 mesh, is dispersed into deionized water mashing
Solid content is the slurries of 40 %, is then pumped into ball mill and is ground；
（2）Ground slurries are put into reaction kettle and are warming up to 85 DEG C, then sequentially add hydrochloric acid, oxalic acid, the association of removing institute
Ca, Mg, Al, slurries filter, washed, obtain composite molecular screen solid filter cake by the dirts such as Fe；
（3）The composite molecular screen solid filter cake that dry weight is 45 parts is put into reaction kettle slurry with deionized water mashing dispersion
Liquid adds dry weight as 12 parts of aluminium polychlorides, 2 parts of H3PO4, 6 parts of Zn (NO3)2, the mixed impregnant liquor of 15 parts of LaO it is abundant
Dipping 9 hours, calcines at 650 DEG C and obtains within 2 hours catalyst, the composite molecular screen contains tri- kinds of molecules of MFI, AEI and AFI
Sieve structure.Performance parameter of the gained catalyst in methanol to olefins reaction is shown in Table 1.
Meanwhile for the particular technique effect for assessing a kind of preparing light olefins from methanol catalyst of the present invention, respectively from
C2 =~C4 =Selectivity, C5More than high-carbon constituent content, three aspect performance of abrasion index, catalyst, ZSM-5 to Examples 1 to 3
Molecular sieve, SAPO molecular sieve catalytic effect tested.Specific test data is as shown in table 1：
1 embodiment of table, 1 ~ 3 gained catalyst performance test data
As can be seen from Table 1, with more when composite molecular sieve catalyst of the invention is than being used alone ZSM-5, SAPO catalyst
Good catalytic activity, C2 =~C4 =Total selectivity of light olefin improves 21.4% ~ 27.5%, C5More than high-carbon component reduction by 17.7% ~
43%, C in product5More than high-carbon constituent content is less than 13%, while abrasion index is below 0. 5%/h, this shows the catalyst
With excellent catalytic activity, higher olefine selective and excellent attrition resistance energy, and the preparation side of the composition
Method is simple and easy to get, of low cost.
The foregoing is only a preferred embodiment of the present invention, not makees limitation in any form to the present invention；It is all
The those of ordinary skill of the industry can be shown in by specification and described above and swimmingly implement the present invention；It is but all familiar
Professional and technical personnel without departing from the scope of the present invention, makes using disclosed above technology contents
A little variation, modification and evolution equivalent variations, be the present invention equivalent embodiment；Meanwhile all realities according to the present invention
Variation, modification and evolution of any equivalent variations that matter technology makees above example etc. still fall within the technology of the present invention
Within the protection domain of scheme.
Claims (10)
1. a kind of preparing light olefins from methanol catalyst, which is characterized in that the catalyst presses dry weight part by following each component
It is calculated as：20 ~ 50 parts of composite molecular screen, 5 ~ 20 parts of binding agent, 1 ~ 5 part of phosphorus additive, 2 ~ 8 parts of zinc additive, basic anhydride 10 ~
30 parts, the catalyst has well-regulated three-dimensional eight annulus pore passage structure, and pore size is 0.36 × 0.36nm.
2. preparing light olefins from methanol catalyst according to claim 1, which is characterized in that the composite molecular screen is ZSM-
At least two are combined in 5 molecular sieves, SAPO molecular sieve, A1PO molecular sieves.
3. preparing light olefins from methanol catalyst according to claim 2, which is characterized in that the composite molecular screen contains
Tri- kinds of molecular sieve structures of MFI, AEI and AFI.
4. preparing light olefins from methanol catalyst according to claim 3, which is characterized in that the binding agent is polyaluminium
One kind in aluminium, colloidal silicon dioxide, colloidal alumina, alumina silicate colloid, alumina powder and boehmite powder.
5. preparing light olefins from methanol catalyst according to claim 4, which is characterized in that the basic anhydride for MgO,
One kind in CaO, LaO and CeO.
6. preparing light olefins from methanol catalyst according to claim 5, which is characterized in that the phosphorus additive is H3PO4、
(NH4) H2PO4、(NH4) 2HPO4、(NH4) 3PO4In one kind.
7. preparing light olefins from methanol catalyst according to claim 6, which is characterized in that the zinc additive is Zn
(NO3)2、ZnCl2、ZnSO4In one kind.
8. the preparation method of the preparing light olefins from methanol catalyst according to claim 1 ~ 7 any one, which is characterized in that
Include the following steps：
（1）Molecular sieve is pulverized and sieved, takes the following fine powder of 150 mesh, it is 40 ~ 45 %'s to be dispersed into solid content with deionized water mashing
Slurries are then pumped into ball mill and are ground；
（2）Step（1）Gained slurries, which are placed in reaction kettle, to heat up, and then sequentially adds hydrochloric acid, oxalic acid, the Ca of removing institute association,
Slurries are filtered, washed by the dirts such as Mg, Al, Fe, obtain composite molecular screen solid filter cake；
（3）By composite molecular screen solid filter cake be placed in reaction kettle with deionized water mashing be dispersed into slurries, add binding agent,
Phosphorus additive, zinc additive, basic anhydride mixed impregnant liquor dipping after, high-temperature calcination obtains catalyst.
9. the preparation method of preparing light olefins from methanol catalyst according to claim 8, the step（2）Slurries are placed in instead
It answers and 70 ~ 90 DEG C is warming up in kettle.
10. the preparation method of preparing light olefins from methanol catalyst according to claim 8, the step（3）Dip time
It it is 6 ~ 12 hours, calcination temperature is 400 ~ 700 DEG C, and calcination time is 2 ~ 6 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110721739A (en) * | 2019-10-24 | 2020-01-24 | 杜成荣 | Preparation method of olefin catalyst prepared from methanol |
| CN111097503A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | AEI/MFI composite structure molecular sieve catalyst, preparation method and application thereof |
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2016
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111097503A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | AEI/MFI composite structure molecular sieve catalyst, preparation method and application thereof |
| CN110721739A (en) * | 2019-10-24 | 2020-01-24 | 杜成荣 | Preparation method of olefin catalyst prepared from methanol |
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