CN1704165A - Catalyst for producing alkyl benzene - Google Patents
Catalyst for producing alkyl benzene Download PDFInfo
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- CN1704165A CN1704165A CN 200410024737 CN200410024737A CN1704165A CN 1704165 A CN1704165 A CN 1704165A CN 200410024737 CN200410024737 CN 200410024737 CN 200410024737 A CN200410024737 A CN 200410024737A CN 1704165 A CN1704165 A CN 1704165A
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- catalyzer
- catalyst
- alkylbenzene
- reaction
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- 150000004996 alkyl benzenes Chemical class 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 title abstract description 24
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 29
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 238000002447 crystallographic data Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 29
- 150000001336 alkenes Chemical class 0.000 abstract description 10
- -1 benzene hydrocarbon Chemical class 0.000 abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 33
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 28
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000005804 alkylation reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000018109 developmental process 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
- 238000009826 distribution Methods 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst to produce alkyl benzene which mainly resolves the problem that catalyst exists high reacting temperature, high benzene hydrocarbon rate and low olefin speed. It adopts crystalline alumanosilicate of XRD diffracting data as catalyst active main body which can be used in the industrial production of alkyl benzene.
Description
Technical field
The present invention relates to produce the catalyzer of alkylbenzene.
Background technology
Alkylbenzene is important basic Organic Chemicals, comprises isopropyl benzene, ethylbenzene, butylbenzene and long-chain alkyl benzene etc.Wherein isopropyl benzene is an important intermediate raw material of producing phenol, acetone and alpha-methyl styrene.Phenol more than 90% is to adopt cumene method production in the world at present.The traditional method of industrial production alkylbenzene has the solid phosphoric acid method (SPA method) of UOP (UOP) and the improvement AlCl of Monsanto/Lummus Crest company
3Method.SPA operational condition harshness, impurity is many, can not improve the productive rate of alkylbenzene by reverse alkylation.And AlCl
3Though method has than the demulcent reaction conditions, and can improve the productive rate of alkylbenzene by reverse alkylation, this catalytic erosion is strong, pollute heavy and aftertreatment numerous and diverse.
Molecular sieve liquid phase alkylation methods because reaction conditions mitigations, transformation efficiency height, selectivity is good, impurity is few, pollution-free, do not have to corrode; main by product polyalkylbenzene can change alkylbenzene into via reverse alkylation; make the alkylbenzene productive rate up to more than 99%; be each institute of big industrial group company common concern in recent years, and an advanced technology of competitively development research, to significant " cleaning procedure " technology of environment protection.
The alkylbenzene molecular sieve catalyst of heavy industrialization has the Y zeolite of Uop Inc., the beta-molecular sieve of EniChem company and the MWW type molecular sieve of mobil company at present.
A kind of steam treatment process of zeolite catalyst being carried out the part dealuminzation is provided among the Chinese patent literature CN1113649; CN1125641 provides a kind of method for preparing the isopropyl benzene zeolite catalyst of high reactivity, highly selective, is mainly used in the reaction of bubbling bed, and CN1227770 then adopts mineral acid treatment β zeolite to prepare alkylation catalyst.The common drawback of all above-mentioned catalyzer is temperature of reaction height, high, low, the poor stability of alkene air speed of benzene hydrocarbon ratio, is difficult to industrial application.
Summary of the invention
Technical problem to be solved by this invention is that catalyzer of the prior art exists temperature of reaction height, benzene hydrocarbon than the problem high, that the alkene air speed is low, and a kind of catalyzer of new production alkylbenzene is provided.This catalyzer has when being used to produce alkylbenzene that temperature of reaction is low, benzene hydrocarbon is than characteristics low, that the catalyst regeneration cycle is long.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyzer of producing alkylbenzene comprises following component by weight percentage:
A) 30～80% crystal aluminosilicate;
B) 20～70% binding agent;
Wherein crystal aluminosilicate has following XRD diffraction data:
| 2 θ diffraction angle | Diffraction peak intensity (I/I 0×100) |
| ????6.5° | ????28.8±0.1 |
| ????7.2° | ????17.3±0.1 |
| ????8.8° | ????15.4±0.1 |
| ????9.7° | ????53.8±0.1 |
| ????13.5° | ????39.4±0.1 |
| ????14° | ????28.8±0.1 |
| ????14.3° | ????19.2±0.1 |
| ????15.4° | ????23.1±0.1 |
| ????19.5° | ????34.6±0.1 |
| ????22.2° | ????69.2±0.1 |
| ????23.8° | ????23.1±0.1 |
| ????25.5° | ????100±0.1 |
| ????26.2° | ????65.4±0.1 |
| ????27.5° | ????46.7±0.1 |
| ????31° | ????27.9±0.1 |
| ????35.8° | ????15.4±0.1 |
。
In the technique scheme, the specific surface area preferred version of crystal aluminosilicate is 500～600 meters
2/ gram, pore volume preferred version are 0.45～0.7 milliliter/gram.The binding agent preferred version is selected from aluminum oxide, titanium oxide, zinc oxide, zirconium white or its mixture, and more preferably scheme is selected from aluminum oxide, zinc oxide or its mixture.The consumption preferable range of crystal aluminosilicate is 50～70% by weight percentage, and the consumption preferable range of binding agent is 30～50%.
The preparation method of the crystal aluminosilicate that uses among the present invention is as follows:
With silicon source (silicon sol, water glass etc.), aluminium source (sodium aluminate, Tai-Ace S 150 etc.) and organic ammonium (hexanediamine, hexa-methylene imonium), caustic soda, water according to following mixed evenly after, under the effect of directed agents organic ammonium,, filter, washing, oven dry obtain finished product SHY crystal aluminosilicate in 140～180 ℃ of following crystallization 50～200 hours.Wherein material molar ratio is as follows: (molecular ratio, M refers to organic ammonium)
SiO
2∶Al
2O
3＝20～200
SiO
2∶Na
2O??＝100～200
SiO
2∶H
2O???＝0.01～0.1
SiO
2∶M＝2～8
The charging capacity of directed agents is 0.1%～10% of a silicon source weight.
Preparation of catalysts method of the present invention is as follows:
A) the crystal aluminosilicate material SHY with above-mentioned preparation exchanges with ammonium salt, and the content that makes alkalimetal ion is wherein dried below 0.05% (weight) then;
B) will exchange qualified crystalline aluminosilicate salt material SHY and inorganic oxide binder and mix, add shaping assistant, kneading, extrusion, oven dry roasting, pelletizing gets finished catalyst again.
The ammonium salt that is used to handle crystal aluminosilicate material SHY can be ammonium salt commonly used, for example ammonium chloride, ammonium nitrate or ammonium phosphate etc.
In the catalyzer of the present invention, owing to adopt and have the crystal aluminosilicate of table 1 XRD diffraction data as the activity of such catalysts main body, be used for propylene and benzene and produce the isopropyl benzene process, the inventor is surprised to find that: effectively reduce the oligomerisation reaction of alkene at catalyst surface, make reaction product from the catalyzer duct, to spread out apace, suppressed the carbon distribution that reaction mass generates at the catalyst surface dehydrocyclization effectively, thereby improved the reaction stability of catalyzer, make that catalyzer can be at lower temperature of reaction (100～170 ℃), the reaction down of low benzene/olefin molar ratio (2～5) has obtained better technical effect.
Description of drawings
Fig. 1 is the XRD diffractogram of crystal aluminosilicate material SHY.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
1500 gram water glass (modulus=2.8) are evenly mixed with 500 gram hexamethylene imines, 50 gram sodium aluminates and 25 gram sodium hydroxide are evenly mixed in 500 gram water, above-mentioned two kinds of solution are evenly mixed under violent stirring, continue to stir 2 hours, adding 500 gram water stirred 1 hour, above-mentioned mixed good solution is formed jelly at 10 ℃ after aging 100 hours, standby.
[embodiment 2]
25 gram sodium aluminates and the dissolving in 500 gram water of 20 gram sodium hydroxide are evenly mixed, adding 500 gram (40% weight) silicon sol stirs, adding 800 gram pure water again stirs evenly mixed, colloidal sol 50 grams that add preparation among the embodiment 1, continue to stir after 2 hours and change in the crystallizing kettle, stirred crystallization 100 hours at 165 ℃, filtration washing is to PH=8,150 ℃ of oven dry.The specific surface area of gained sample is 550 meters
2/ gram, pore volume are 0.5 milliliter/gram, and the XRD diffraction data is as shown in table 1, and the XRD diffractogram as shown in Figure 1.
Table 1 XRD diffraction data
| 2 θ diffraction angle | Diffraction peak intensity (I/I 0×100) |
| ????6.5° | ????28.8 |
| ????7.3° | ????17.2 |
| ????8.8° | ????15.5 |
| ????9.7° | ????53.6 |
| ????13.5° | ????39.5 |
| ????14° | ????28.8 |
| ????14.3° | ????19.1 |
| ????15.4° | ????23.2 |
| ????19.5° | ????34.6 |
| ????22.2° | ????69.2 |
| ????23.8° | ????23.1 |
| ????25.5° | ????100 |
| ????26.2° | ????65.3 |
| ????27.5° | ????46.7 |
| ????31° | ????27.8 |
| ????35.8° | ????15.4 |
Get above-mentioned synthetic crystal aluminosilicate material 100 grams, add 0.5 mol ammonium nitrate solution, be warming up to 95 ℃ of exchanges 2 hours, exchange repeatedly 6 times, make alkali metal ion content measured in the crystal aluminosilicate less than 100ppm, crystal aluminosilicate 90 grams that above-mentioned exchange is good mix evenly with 25 gram aluminum oxide, 10 gram zinc oxide, add 200 milliliter of 5% weight nitric acid solution, 5 gram sesbania powder are mediated extruded moulding after 1 hour, the catalyzer of forming 150 ℃ of oven dry, is warming up to 580 ℃ of roastings then and obtained finished catalyst in 4 hours under air atmosphere.
[embodiment 3]
The catalyst powder of preparation among the embodiment 2 is broken into 20～60 purpose particles, gets 1.0 gram catalyzer and carry out propylene liquid-phase alkylation reaction in fixed-bed reactor, reaction conditions is, propylene air speed=1.5 hour
-1, temperature of reaction=140 ℃, reaction pressure=2.5MPa, reaction product is an isopropyl benzene, propylene conversion=100%, selectivity of product 99.2%, total benzene/olefin molar ratio is 2.1, reacts and does not observe the catalyst activity loss in 2000 hours, and outlet isopropyl benzene concentration reaches 44%.
[embodiment 4]
25 gram sodium aluminates and the dissolving in 500 gram water of 20 gram sodium hydroxide are evenly mixed, adding 800 gram (40% weight) silicon sol stirs, adding 800 gram pure water again stirs evenly mixed, colloidal sol 30 grams that add preparation among the embodiment 1, continue stirring and change in the crystallizing kettle after 2 hours, stirred crystallization 130 hours at 165 ℃, filtration washing is to PH=7,150 ℃ of oven dry, the specific surface area of gained sample is 520 meters
2/ gram, pore volume are 0.48 milliliter/gram.Get above-mentioned synthetic crystal aluminosilicate 100 grams, add 1 mol ammonium chloride solution, be warming up to 95 ℃ of exchanges 2 hours, exchange repeatedly 6 times, alkali metal ion content measured in the gained crystal aluminosilicate is less than 150ppm, crystal aluminosilicate 90 grams that above-mentioned exchange is good mix evenly with 25 gram aluminum oxide, 10 gram zinc oxide, add 200 milliliter of 5% weight nitric acid solution, 5 gram sesbania powder are mediated extruded moulding after 1 hour, and the catalyzer of forming was obtained finished catalyst in 4 hours being warming up to 580 ℃ of roastings after 150 ℃ of oven dry under air atmosphere.
[embodiment 5]
The catalyst powder of preparation among the embodiment 4 is broken into 20～60 purpose particles, gets 1.0 gram catalyzer and carry out propylene liquid-phase alkylation reaction in fixed-bed reactor, reaction conditions is, propylene air speed=2.0 hour
-1, temperature of reaction=150 ℃, reaction pressure=2.8MPa, reaction product is an isopropyl benzene, propylene conversion=100%, selectivity of product 99.4%, total benzene/olefin molar ratio is 2.5, reacts and does not observe the catalyst activity loss in 2500 hours, and outlet isopropyl benzene concentration is 38%.
[comparative example 1]
To be broken into 20～60 purpose particles with the Y zeolite catalyst powder of same procedure preparation, and get 1.0 gram catalyzer and carry out the propylene liquid-phase alkylation reaction in fixed-bed reactor, reaction conditions is, propylene air speed=0.3 hour
-1, temperature of reaction=190 ℃, reaction pressure=3.0MPa, reaction product is an isopropyl benzene, initial propylene conversion=100%, selectivity of product 99.2%, total benzene/olefin molar ratio is 5.0, react after 1500 hours propylene conversion and reduces to 95%, and exporting isopropyl benzene concentration is 25%.
[comparative example 2]
To be ground into 20～60 purpose particles with the beta-zeolite catalyst of same procedure preparation, and get 1.0 gram catalyzer and carry out the propylene liquid-phase alkylation reaction in fixed-bed reactor, reaction conditions is, propylene air speed=0.75 hour
-1, temperature of reaction=160 ℃, reaction pressure=2.8Mpa, reaction product is an isopropyl benzene, initial propylene conversion=100%, selectivity of product 99.3%, total benzene/olefin molar ratio is 3.0, react after 2000 hours propylene conversion and reduces to 98%, and exporting isopropyl benzene concentration is 31.8%.
[embodiment 6]
In 200 ml waters, dissolve 80 gram sodium aluminates and 14 gram sodium hydroxide evenly mixed, adding 600 gram (40% weight) silicon sol stirs, adding 600 gram pure water again stirs evenly mixed, add 200 gram hexamethylene imines, add colloidal sol 50 grams of preparation among the embodiment 1, continue stirring and change in the crystallizing kettle after 2 hours, stirred crystallization 120 hours at 155 ℃, filtration washing is to PH=9,150 ℃ of oven dry.Get above-mentioned synthetic crystal aluminosilicate 100 grams, add 1 mol ammonium nitrate solution, be warming up to 95 ℃ of exchanges 2 hours, exchange repeatedly 6 times, alkali metal ion content measured in the gained crystal aluminosilicate is less than 100ppm, crystal aluminosilicate 90 grams that above-mentioned exchange is good mix evenly with 25 gram aluminum oxide, 10 gram zinc oxide, add 200 milliliter of 5% weight nitric acid solution, 5 gram sesbania powder are mediated extruded moulding after 1 hour, and the catalyzer of forming was obtained finished catalyst in 4 hours being warming up to 580 ℃ of roastings after 150 ℃ of oven dry under air atmosphere.
[embodiment 7]
The catalyst powder of preparation among the embodiment 6 is broken into 20～60 purpose particles, gets 1.0 gram catalyzer and carry out the ethene liquid phase alkylation reaction in fixed-bed reactor, reaction conditions is, ethene air speed=1.0 hour
-1, temperature of reaction=255 ℃, reaction pressure=4.0MPa, reaction product is an ethylbenzene, conversion of ethylbenzene=100%, selectivity of product 99.5%, total benzene/olefin molar ratio is 2.5, reacts not detect propylene in the product in 2500 hours, reactor outlet isopropyl benzene concentration 37.8%.
Claims (6)
1, a kind of catalyzer of producing alkylbenzene comprises following component by weight percentage:
A) 30～80% crystal aluminosilicate;
B) 20～70% binding agent;
Wherein crystal aluminosilicate has following XRD diffraction data:
2 θ diffraction angle Diffraction peak intensity (I/I
0×100)
??6.5° ??28.8±0.1
??7.2° ??17.3±0.1
??8.8° ??15.4±0.1
??9.7° ??53.8±0.1
??13.5° ??39.4±0.1
??14° ??28.8±0.1
??14.3° ??19.2±0.1
??15.4° ??23.1±0.1
??19.5° ??34.6±0.1
??22.2° ??69.2±0.1
??23.8° ??23.1±0.1
??25.5° ??100±0.1
??26.2° ??65.4±0.1
??27.5° ??46.7±0.1
??31° ??27.9±0.1
??35.8° ??15.4±0.1
。
2, according to the catalyzer of the described production alkylbenzene of claim 1, the specific surface area that it is characterized in that crystal aluminosilicate is 500～600 meters
2/ gram, pore volume are 0.45～0.7 milliliter/gram.
3,, it is characterized in that binding agent is selected from aluminum oxide, titanium oxide, zinc oxide, zirconium white or its mixture according to the catalyzer of the described production alkylbenzene of claim 1.
4,, it is characterized in that binding agent is selected from aluminum oxide, zinc oxide or its mixture according to the catalyzer of the described production alkylbenzene of claim 3.
5,, it is characterized in that the consumption of crystal aluminosilicate is 50～70% by weight percentage according to the catalyzer of the described production alkylbenzene of claim 1.
6,, it is characterized in that the consumption of binding agent is 30～50% by weight percentage according to the catalyzer of the described production alkylbenzene of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100247373A CN100391607C (en) | 2004-05-28 | 2004-05-28 | Catalysts for the production of alkylbenzenes |
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| CNB2004100247373A CN100391607C (en) | 2004-05-28 | 2004-05-28 | Catalysts for the production of alkylbenzenes |
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| CN1704165A true CN1704165A (en) | 2005-12-07 |
| CN100391607C CN100391607C (en) | 2008-06-04 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7754921B2 (en) | 2005-09-29 | 2010-07-13 | Basf Se | Shaped body comprising an aluminosilicate and aluminium oxide and process for the continuous preparation of methylamines |
| CN104447174A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Production method of sec-butylbenzene |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1057451A (en) * | 1986-07-29 | 1992-01-01 | 美孚石油公司 | A kind of preparation method of ether |
| CN1074392A (en) * | 1992-01-13 | 1993-07-21 | 中国科学院大连化学物理研究所 | The zeolite catalyst of preparing ethyl benzene from alkylated styrene |
| US5827491A (en) * | 1993-04-26 | 1998-10-27 | Mobil Oil Corporation | Process for preparing the synthetic porous crystalline material MCM-56 |
| US5362697A (en) * | 1993-04-26 | 1994-11-08 | Mobil Oil Corp. | Synthetic layered MCM-56, its synthesis and use |
| DE60332834D1 (en) * | 2002-05-23 | 2010-07-15 | Consejo Superior Investigacion | MICROPOROUS CRYSTALLINE ZEOLITE MATERIAL (ZEOLITH ITQ-22), SYNTHESIS METHOD THEREFOR AND USE THEREOF AS A CATALYST |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7754921B2 (en) | 2005-09-29 | 2010-07-13 | Basf Se | Shaped body comprising an aluminosilicate and aluminium oxide and process for the continuous preparation of methylamines |
| CN101300069B (en) * | 2005-09-29 | 2012-01-18 | 巴斯夫欧洲公司 | Moulding containing an aluminosilicate and aluminium oxide and method of continuously producing methylamines |
| CN104447174A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Production method of sec-butylbenzene |
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| CN100391607C (en) | 2008-06-04 |
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