CN103041848B - Catalyst used for heterogeneously producing isoalkene by utilizing direct-chain olefin skeleton and preparation method thereof - Google Patents
Catalyst used for heterogeneously producing isoalkene by utilizing direct-chain olefin skeleton and preparation method thereof Download PDFInfo
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- CN103041848B CN103041848B CN201110313279.5A CN201110313279A CN103041848B CN 103041848 B CN103041848 B CN 103041848B CN 201110313279 A CN201110313279 A CN 201110313279A CN 103041848 B CN103041848 B CN 103041848B
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- zeolite
- isoalkene
- sodium potassium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 150000001336 alkenes Chemical group 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims description 11
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 61
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000010457 zeolite Substances 0.000 claims abstract description 61
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000011734 sodium Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001657 ferrierite group Inorganic materials 0.000 claims abstract description 6
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 244000275012 Sesbania cannabina Species 0.000 claims abstract 2
- 238000007493 shaping process Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 229910052570 clay Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011591 potassium Substances 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 26
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 11
- 238000006317 isomerization reaction Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 235000004213 low-fat Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst used for heterogeneously producing isoalkene by utilizing a direct-chain olefin skeleton. The catalyst comprises an FER zeolite and a binder, wherein the FER zeolite is a sodium potassium hydrogen type FER zeolite, and based on the percentage by weight of zeolite, Na2O content is 0.02-0.1%, K2O content is 1.0-5.0%, and mole ratio of SiO2 to Al2O3 is 8-50. The catalyst provided by the invention is obtained by fully mixing the FER zeolite powder, the binder, sesbania powder, inorganic acid and water, moulding the obtained mixture and then drying and roasting. The ferrierite adopted by the invention is of a sodium potassium hydrogen type, and the catalyst prepared by the method provided by the invention has isoalkene selectivity compared with the hydrogen type FER zeolite containing no sodium or/and potassium.
Description
Technical field
The present invention relates to a kind of linear chain olefin skeleton isomerism and produce isoalkene Catalysts and its preparation method, specifically, the n-butene skeletal isomerization that the present invention relates to a kind of high selectivity produces isobutene catalyst and method for preparing catalyst.
Background technology
Along with market is to the continuous growth of high-knock rating gasoline demand, the demand of the low fat race alkyl ether as octane enhancers mixed also is increased thereupon.These alkyl ethers are methyl tertiary butyl ether(MTBE) (MTBE), ethyl tert-butyl ether (ETBE) and tert amyl methyl ether(TAME) mainly.Such as the aggregate demand of China's isoalkyl ether additive in 2010 is more than 3,000,000 tons.The high market demand of isoalkyl ether will certainly pull the demand to raw material isoalkene, and the isoalkene adopting traditional catalytic cracking and cracking of ethylene route to produce is difficult to meet the need of market.
In order to obtain more isoalkene, linear alkene can be produced the isoalkene of band methyl branch by skeletal isomerization approach, as n-butene skeletal isomerization production isobutene or positive amylene skeletal isomerization produce iso-amylene.The key of linear chain olefin skeleton isomerism technology is to develop high performance catalyst.Catalyst for this reaction can be divided into two kinds: one is open surface type catalyst, as fluoridized or chloride alumina catalyst; Another kind is zeolite catalyst, as ferrierite, TON type zeolite and AEL type sial phosphorus molecular sieve.
Ferrierite or title FER zeolite, be a kind of central hole structure zeolite, its basic structural unit is five-membered ring, and these five-membered rings are organically connected by ten-ring, octatomic ring and hexatomic ring again and form FER zeolitic frameworks.FER zeolite has one dimension ten-ring straight hole road (0.42 × 0.54 nm) along [001] direction, along [010] direction, there is one dimension octatomic ring straight hole road (0.35 × 0.48 nm), two kinds of ducts intersect vertically, its cross section ovalize, the class basket structure space diameter that two intersections, duct are formed is about 0.6 to 0.7 nm.Discovered in recent years FER zeolite in n-butene skeletal isomerization preparing isobutene process, have good catalytic activity, selective and stability (Hou vi ka J. and Ponec V., Catal. Rev.-Sci. Eng.,
1997,
39 (4), 319).
US 5,510,560 discloses a kind of Hydrogen FER zeolite catalyst for linear chain olefin skeleton isomerism, and with adopting, silica, clay or binder free are shaping to be compared, and the isobutene productive rate of the catalyst adopting aluminium oxide to obtain as binding agent is higher.US 5,523,510 discloses a kind of linear chain olefin skeleton isomerism catalyst, and this catalyst for active component, by steam and pickling processes, can improve catalyst isobutene productive rate with Hydrogen FER zeolite.It is the preparation method of the zeolite catalyst of isoalkene that CN1142787A discloses a kind of isomerizating straight-chain that makes, with Hydrogen FER zeolite for catalyst group main component, the wherein Na of FER zeolite
2o weight content is lower than 0.05%.CN1860320A discloses the catalyst that a kind of linear alkene isomery becomes isoalkene, this catalyst with Hydrogen FER zeolite for main component, the wherein Na of FER zeolite
2o weight content is lower than 0.1%.In above-mentioned patent, all adopt Hydrogen FER zeolite as catalyst, on these catalyst, initial isoalkene is selective and productive rate is usually lower, and is attended by more side reaction.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of linear chain olefin skeleton isomerism and produce isoalkene catalyst and preparation method, catalyst of the present invention is used for linear chain olefin skeleton isomerism production isoalkene and has more superior reactivity worth.
Linear chain olefin skeleton isomerism of the present invention is produced isoalkene catalyst and is mainly comprised FER zeolite and binding agent, and wherein FER zeolite is sodium potassium Hydrogen FER zeolite, by weight zeolite percentages, and its Na
2o content is 0.02%-0.1%, is preferably 0.06%-0.1%, K
2o content is 1.0%-5.0%, is preferably 3.0%-5.0%, SiO
2/ Al
2o
3mol ratio is 8-50, is preferably 15-20.
In catalyst of the present invention, binding agent is one or more in aluminium oxide, silica or clay.
In catalyst of the present invention, sodium potassium Hydrogen FER zeolite is sodium potassium type FER zeolite after ammonium ion part exchanges, and then roasting obtains sodium potassium Hydrogen FER zeolite.Sodium potassium type FER zeolite can be commercial goods or prepare by existing scheme.FER zeolite is concrete as ZSM-35, ferrierite, ZSM-23, ZSM-38 etc.In sodium potassium type FER zeolite, sodium is with Na
2the content of O quality meter is generally 0.5%-2%, and potassium is with K
2the content of O quality meter is generally 5%-6%.The method of operating that ammonium ion part exchanges generally comprises following steps: being pulled an oar with ammonium salt solution by sodium potassium type FER zeolite mixes, under temperature is 20 ~ 95 DEG C of conditions preferably under 20 ~ 60 DEG C of conditions, exchange 1 ~ 2 hour, exchange disposed slurry after filtration, filter cake deionized water cleaning down, oven dry, roasting obtain sodium potassium Hydrogen ferrierite.
In catalyst of the present invention, the weight content of sodium potassium Hydrogen FER zeolite is generally 60%-95%.
Catalyst of the present invention is produced in isoalkene at linear chain olefin skeleton isomerism and is applied, and linear alkene is generally C
4-C
5linear alkene.The reaction condition suitable for n-butene skeletal isomerization comprises: reaction temperature is 300 ~ 650 DEG C, preferably 300 ~ 450 DEG C; N-butene dividing potential drop is 0.01 ~ 0.5 MPa, preferably 0.01 ~ 0.15 MPa; Weight (hourly) space velocity (WHSV) is 0.1 ~ 50 h
-1, preferably 0.5 ~ 15 h
-1.The reaction condition suitable for positive amylene skeletal isomerization comprises: reaction temperature is 200 ~ 600 DEG C, preferably 200 ~ 400 DEG C; Positive amylene dividing potential drop is 0.01 ~ 0.5 MPa, preferably 0.01 ~ 0.15 MPa; Weight (hourly) space velocity (WHSV) is 0.1 ~ 50 h
-1, preferably 1 ~ 20 h
-1.Above-mentioned C
4-C
5linear alkene feed stream in can contain inactive diluent, as N
2, H
2or alkane etc.
The preparation method of catalyst of the present invention comprises following process: sodium potassium Hydrogen FER zeolite powder, binding agent, extrusion aid, inorganic acid and water fully mix, and by shaping for gained mixture, drier, roasting obtains final catalyst.
In method provided by the invention, described binding agent can be binding agent conventional in the catalyst preparing of this area, as one or more mixtures in aluminium oxide, silica or clay.Preferred binding agent is aluminium oxide, as boehmite.Extrusion aid is generally sesbania powder.Inorganic acid is nitric acid, hydrochloric acid or sulfuric acid, shaping for making molecular sieve and binding agent be convenient to, the preferred nitric acid of wherein said inorganic acid.
In method provided by the invention, by weight percentage, the weight ratio of sodium potassium Hydrogen FER zeolite and binding agent is 19:1 to 1.5:1 to material used, preferred 9:1 to 1.5:1.
In method provided by the invention, catalyst can adopt extrusion, pressed disc method, a ball or spin comminution granulation shaping, and wherein preferably extrusion is shaping.Catalyst is dried 5 ~ 20 hours in 80 ~ 150 DEG C after shaping, roasting 2 ~ 15 hours at being 400-600 DEG C, the preferred 450-550 DEG C of sintering temperature.
Adopt method provided by the invention, obtained catalyst can be used for C
4-C
5linear chain olefin skeleton isomerism produces isoalkene process, is particularly suitable for use in n-butene skeletal isomerization and produces isobutene process.Term used herein " linear alkene ", may also be referred to as " positive alkene ", as described in n-butene, comprising any one or more mixture in 1-butylene, trans-2-butene and cis-2-butene.Term " isoalkene " is often referred to the alkene of band methyl branch, as isobutene.
Effect of the present invention and benefit are the sodium potassium Hydrogen FER zeolite catalyst adopting the method for the invention provides obtained, under the same reaction conditions, have higher selective isobutene than Hydrogen FER zeolite catalyst.Employing the invention provides method and obtains catalyst, effectively can suppress side reaction, has higher application prospect.
Detailed description of the invention
In order to set forth the present invention further, provide following illustrative embodiment.
the preparation of sodium potassium Hydrogen FER zeolite and Hydrogen FER zeolite
HSZ-720KOA type NaK-FER zeolite used in the following example, is provided by eastern Cao Da (Shanghai) trade Co., Ltd, wherein by weight percentage, and Na
2o content is 0.9%, K
2o content is 6.32%.Na in each embodiment
2o and K
2o content is by x-ray fluorescence spectrometry.The chemical reagent used, as indicated without special, is AR.
By the NaK-FER zeolite of 20 g and 400 g deionized waters respectively with certain mass NH
4cl mixes making beating, NH used
4cl quality refers to table 1, and through gained slurries, under room temperature, (25 DEG C) stir 2 hours, then filter, and filter cake 30 times of deionized water cleaning downs to zeolite butt weight, dry and 550 DEG C of roastings through 110 DEG C, obtain corresponding sodium potassium Hydrogen FER zeolite.
By the NaK-FER zeolite of 200 g, the NH of 214 g
4cl and 4000 g deionized waters mix making beating, under room temperature, (25 DEG C) stir 2 hours, filter, under room temperature, (25 DEG C) repeat above-mentioned exchange process again, through filtering after exchange, and gained filter cake 30 times of deionized water cleaning downs to NaK-FER zeolite butt weight, dry and 550 DEG C of roastings through 110 DEG C, obtain Hydrogen FER zeolite, be numbered A-6, refer to table 1.
The main preparation condition of table 1 FER zeolite and product composition
| Numbering | NaK-FER（g）* | NH 4Cl（g）* | H 2O（g）* | Na 2O（wt%）** | K 2O（wt%）** | SiO 2/Al 2O 3Mol ratio * * |
| A-1 | 20 | 0.43 | 400 | 0.26 | 5.80 | 17 |
| A-2 | 20 | 1.07 | 400 | 0.08 | 4.51 | 17 |
| A-3 | 20 | 2.14 | 400 | 0.06 | 3.37 | 17 |
| A-4 | 20 | 4.28 | 400 | 0.06 | 2.21 | 17 |
| A-5 | 20 | 10.7 | 400 | 0.04 | 1.12 | 17 |
| A-6 | 200 | 214 | 4000 | 0 | 0 | 17 |
* NH
4 +exchange slurry forms;
FER zeolite composition after * process.
catalyst preparing
The preparation method of catalyst is described by following illustrative embodiment.Catalyst preparing binding agent used is SW-17 type aluminium hydrate powder, and pore volume is 0.47-0.53 ml/g, is greater than 250 m than table
2/ g, average pore size is 7.5-8.5 nm, and by Zibo, safe photoinitiator chemical Co., Ltd provides.
prepared by sodium potassium Hydrogen FER zeolite catalyst
Respectively by sodium potassium Hydrogen FER Wessalith CS-1, A-2, A-3, A-4, A-5, mediate the dense thick paste body of formation with SW-17 aluminium hydrate powder, sesbania powder, nitric acid and deionized water (mass ratio is 45:5:1.5:1:50) at CD4X1TS type multifunction catalyst forming machine, adopt the stainless steel moulded board in 1.0 mm holes extruded.Gained extrudate prior to drying under room temperature 24 hours, then is dried 24 hours in 110 DEG C, and finally in 520 DEG C of roastings 12 hours, obtain final catalyst, respective markers is B-1, B-2, B-3, B-4, B-5, and its composition lists in table 2.
hydrogen FER zeolite catalyst B-6
The catalyst B-6 of preparation, as a comparative example.By Hydrogen FER Wessalith CS-6, mediate the dense thick paste body of formation with SW-17 aluminium hydrate powder, sesbania powder, nitric acid and deionized water (mass ratio is 45:5:1.5:1:50) at CD4X1TS type multifunction catalyst forming machine, adopt the stainless steel moulded board in 1.0 mm holes extruded.Gained extrudate prior to drying under room temperature 24 hours, then dries 24 h hour in 110 DEG C, and finally in 520 DEG C of roastings 12 hours, obtain final catalyst, be labeled as B-6, its composition lists in table 2.
Table 2 catalyst mainly forms (mass percent)
| Catalyst forms | Na 2O | K 2O | SiO 2 | Al 2O 3 |
| B-1 | 0.23 | 5.22 | 76.65 | 17.90 |
| B-2 | 0.07 | 4.06 | 77.94 | 17.93 |
| B-3 | 0.05 | 3.03 | 78.90 | 18.02 |
| B-4 | 0.05 | 1.99 | 79.87 | 18.09 |
| B-5 | 0.04 | 1.01 | 80.80 | 18.15 |
| B-6 | 0 | 0 | 81.62 | 18.38 |
evaluating catalyst
Adopt the performance of n-butene skeletal isomerization reaction evaluating catalyst.Reaction is being carried out close on the micro-trans-chromatogram arrangement of continuous-flow fixed bed of normal pressure, 1 g is crushed to the stainless steel reaction pipe flat-temperature zone that 20-40 object catalyst loads internal diameter 10 mm, fill 20-40 object quartz sand up and down, in order to support catalyst bed, and make flow of feed gas radial distribution even.Before each evaluating catalyst, by catalyst first pretreatment 10 hours in the High Purity Nitrogen atmosphere of 500 DEG C, then reaction temperature need be cooled to.Unstripped gas be containing 1-butylene volume fraction be 10% 1-butylene and the gaseous mixture that forms of high pure nitrogen.Product adopts the on-line analysis of Agilent 7890 type gas-chromatography.N-butene skeletal isomerization reaction condition: temperature is 350 DEG C, stagnation pressure 0.12 MPa, weight (hourly) space velocity (WHSV) is 4 h
-1.
Table 3 evaluating catalyst result (mole percent)
| Catalyst | N-butene conversion (%) | Selective isobutene (%) | Isobutene productive rate (%) |
| B-1 | 37.8 | 84.2 | 31.8 |
| B-2 | 59.2 | 75.4 | 44.6 |
| B-3 | 64.5 | 64.8 | 41.8 |
| B-4 | 65.5 | 60.5 | 39.6 |
| B-5 | 67.1 | 58.2 | 39.0 |
| B-6 | 66.7 | 56.6 | 37.8 |
Table 3 compares catalyst provided by the invention and Hydrogen FER zeolite catalyst to n-butene skeletal isomerization reactivity worth.Visible, compare with Hydrogen FER zeolite catalyst B-6, the selective isobutene of sodium potassium Hydrogen FER zeolite catalyst B-2, B-3, B-4 and B-5 provided by the invention is higher.This shows to adopt the obtained catalyst of the inventive method effectively can suppress side reaction, improves catalyst isoalkene selective.Under guarantee isobutene productive rate is greater than the condition of 40%, the selective isobutene of optimization catalyst B-2 of the present invention is significantly higher than Hydrogen FER zeolite catalyst B-6, is that a kind of desirable linear chain olefin skeleton isomerism produces isoalkene catalyst.
Claims (9)
1. linear chain olefin skeleton isomerism produces an isoalkene catalyst, it is characterized in that: linear chain olefin skeleton isomerism is produced isoalkene catalyst and comprised FER zeolite and binding agent, and wherein FER zeolite is sodium potassium Hydrogen FER zeolite, by weight zeolite percentages, and Na
2o content is 0.06%-0.1%, K
2o content is 3.0%-5.0%, SiO
2/ Al
2o
3mol ratio is 8-50.
2. according to catalyst according to claim 1, it is characterized in that: the SiO of sodium potassium Hydrogen FER zeolite
2/ Al
2o
3mol ratio is 15-20.
3. according to catalyst according to claim 1, it is characterized in that: binding agent is one or more in aluminium oxide, silica or clay.
4. according to catalyst according to claim 1, it is characterized in that: FER zeolite is ZSM-35, ferrierite, ZSM-23 or ZSM-38.
5. according to catalyst according to claim 1, it is characterized in that: in catalyst, the weight content of sodium potassium Hydrogen FER zeolite is 60%-95%.
6. according to catalyst according to claim 1, it is characterized in that: linear alkene is C
4-C
5linear alkene.
7. linear chain olefin skeleton isomerism described in a claim 1 produces the preparation method of isoalkene catalyst, comprise: sodium potassium Hydrogen FER zeolite powder, binding agent, extrusion aid, inorganic acid and water fully mix, by shaping for gained mixture, drier, roasting obtains final catalyst.
8. in accordance with the method for claim 7, it is characterized in that: binding agent is one or more in aluminium oxide, silica or clay, extrusion aid is sesbania powder, and inorganic acid is nitric acid, hydrochloric acid or sulfuric acid.
9. in accordance with the method for claim 7, it is characterized in that: the drying of catalyst after shaping for drying 5 ~ 20 hours at 80 ~ 150 DEG C, and roasting is roasting 2 ~ 15 hours at 400 ~ 600 DEG C.
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| CN105478160B (en) * | 2014-09-19 | 2017-11-17 | 北京安耐吉能源工程技术有限公司 | A kind of method of modifying of ferrierite and a kind of ferrierite and its application |
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| US5510560A (en) * | 1993-08-30 | 1996-04-23 | Texaco Inc. | Skeletal isomerization of n-olefins to iso-olefins on binded ferrierite zeolites |
| CN1142787A (en) * | 1993-12-29 | 1997-02-12 | 壳牌石油公司 | Process for preparing a zeolite catalyst for the isomerizing of linear olefins to issolefins |
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| CN1068320A (en) * | 1991-06-05 | 1993-01-27 | 莱昂德尔石油化学公司 | The normal olefine isomery is become the method for isoolefine |
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