CN1285549C - Process for producing isopropyl benzene - Google Patents
Process for producing isopropyl benzene Download PDFInfo
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- CN1285549C CN1285549C CN 200410024738 CN200410024738A CN1285549C CN 1285549 C CN1285549 C CN 1285549C CN 200410024738 CN200410024738 CN 200410024738 CN 200410024738 A CN200410024738 A CN 200410024738A CN 1285549 C CN1285549 C CN 1285549C
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- benzene
- isopropyl benzene
- reaction
- organic acid
- catalyzer
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- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims description 32
- 230000008569 process Effects 0.000 title description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 150000007524 organic acids Chemical class 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000002447 crystallographic data Methods 0.000 claims abstract description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 20
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 17
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007791 liquid phase Substances 0.000 claims description 8
- 229940116315 oxalic acid Drugs 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 229960004106 citric acid Drugs 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 21
- -1 silicon aluminate Chemical class 0.000 abstract description 11
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000003756 stirring Methods 0.000 description 11
- 238000005804 alkylation reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization 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
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 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
- 241000219782 Sesbania Species 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001404 mediated effect Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910052726 zirconium Inorganic materials 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 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
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000019353 potassium silicate Nutrition 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
- 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
- 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
- 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
- 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
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 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
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for producing isopropyl benzene, which mainly solves the problems of high reaction temperature, high ratio of benzene to hydrocarbon, and low airspeed of propene of a catalyst used in the prior art. The present invention adopts the technical scheme that the propene and the benzene are adopted as raw materials for a reaction under the conditions of reaction temperature of 100 to 170 DEG C, reaction pressure of 1.5 to 2.8MPa and benzene / olefin molar ratio of 2 to 5, wherein a crystal silicon aluminate with the XRD diffraction data in table 1 is used as the active main body of a catalyst, and the catalyst is firstly treated by high-temperature water vapor of 200 to 1000 DEG C, and then treated by organic acid. Therefore, the problems in the prior art are solved well, and the present invention can be used for the industrial production of the isopropyl benzene.
Description
Technical field
The present invention relates to be used to produce the method for isopropyl benzene.
Background technology
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 isopropyl benzene 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 isopropyl benzene by reverse alkylation.And AlCl
3Though method has than the demulcent reaction conditions, and can improve the productive rate of isopropyl benzene 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 polyisopropylbenzene can change isopropyl benzene into via reverse alkylation; make the isopropyl benzene 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 isopropyl benzene molecular sieve catalyst of heavy industrialization has the Y zeolite of Uop Inc., the beta-molecular sieve of EniChem 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 propylene 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 the conventional art method exists temperature of reaction height, benzene hydrocarbon than the problem high, that the propylene air speed is low, and a kind of new method that is used to produce isopropyl benzene is provided.This method has 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 method that is used to produce isopropyl benzene, with propylene and benzene is reaction raw materials, in temperature of reaction is 100～170 ℃, reaction pressure is 1.5～2.8MPa, benzene/olefin molar ratio is that reaction raw materials contacts the liquid phase synthesizing iso-propylbenzene under 2～5 conditions with catalyzer, and used catalyzer comprises following component by weight percentage:
A) 50～80% crystal aluminosilicate;
B) 20～50% binding agent;
Wherein catalyzer is handled with organic acid after adopting 200～1000 ℃ of high-temperature water vapors to handle again, and crystal aluminosilicate to have an XRD diffraction data as follows:
| 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 |
In the technique scheme, the temperature of reaction preferable range is 120～160 ℃, and the reaction pressure preferable range is 1.5～2.5MPa, and benzene/olefin molar ratio preferable range is 2～4.The binding agent preferable range is selected from aluminum oxide, titanium oxide, zinc oxide, zirconium white or its mixture.The catalyzer preferred version is 400～700 ℃ for the temperature that adopts high-temperature water vapor to handle, and the treatment time is 0.5～20 hour, and the treatment time preferable range is 1～5 hour.The organic acid preferred version is selected from citric acid, tartrate, oxalic acid or Glacial acetic acid, and more preferably scope is selected from oxalic acid; The organic acid concentration preferable range is 0.1～3 mol, and more preferably scope is 0.5～1.5 mol; Organic acid treatment time preferable range is 1～72 hour, and more preferably scope is 24～60 hours.
The preparation method of the crystal aluminosilicate that uses in the inventive method 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 in 140～180 ℃ of following crystallization 50～200 hours.Wherein the feed molar proportioning 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.
The catalyzer that uses in the inventive method can prepare as follows:
A) synthetic crystallization alumino-silicate materials SHY according to the method described above;
B) new synthetic crystal aluminosilicate material SHY is exchanged with ammonium salt, the content that makes alkalimetal ion is wherein dried below 0.05% (weight) then;
C) high-temperature water vapor is handled zeolite;
D) organic acid is handled zeolite.
The ammonium salt that is used for treatment S HY can be ammonium salt commonly used, for example ammonium chloride, ammonium nitrate or ammonium phosphate etc.
In the inventive method by with handling catalyzer with organic acid again behind the steam-treated catalyzer, removed the non-framework aluminum of catalyst surface effectively, increased the aperture of catalyzer, thereby effectively reduce the oligomerisation reaction of alkene at catalyst surface, make reaction product from the catalyzer duct, spread out fast, 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 than 100～170 ℃ of low reaction temperatures, low benzene hydrocarbon has been obtained better technical effect than 2～5 times reactions.
The invention will be further elaborated below by embodiment.
Description of drawings
Accompanying drawing 1 is the XRD diffractogram of crystal aluminosilicate SHY.
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 and 25 gram aluminum oxide, 10 gram zinc oxide, 15 gram zirconium whites, 5 gram titanium oxide are evenly mixed, add 200 milliliter of 5% weight nitric acid solution, 5 gram sesbania powder are mediated extruded moulding after 1 hour, with the catalyzer of forming 150 ℃ of oven dry, under air atmosphere, be warming up to 580 ℃ of roastings 4 hours then, with above-mentioned product of roasting with 550 ℃ of water vapors with 0.5 hour
-1Handled 2 hours, cooling is placed in the oxalic acid solution of 1 normal concentration 50 ℃ and soaked 48 hours, and distilled water cleans to neutral, and oven dry obtains finished catalyst.
[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=1.7 hour
-1, temperature of reaction=150 ℃, reaction pressure=2.6MPa, reaction product is an isopropyl benzene, propylene conversion=100%, selectivity of product 99.3%, 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 and 25 gram aluminum oxide, 10 gram zinc oxide, 15 gram zirconium whites, 5 gram titanium oxide are evenly mixed, add 200 milliliter of 5% weight nitric acid solution, 5 gram sesbania powder are mediated extruded moulding after 3 hours, the catalyzer of forming is being warming up to 580 ℃ of roastings 4 hours under air atmosphere after 150 ℃ of oven dry, with above-mentioned product of roasting with 450 ℃ of water vapors with 1.0 hours
-1Handled 5 hours, cooling is placed in the oxalic acid solution of 1 normal concentration 50 ℃ and soaked 48 hours, and distilled water cleans to neutral, and oven dry obtains finished catalyst.
[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=155 ℃, 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 37.3%.
[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=170 ℃, reaction pressure=2.8MPa, reaction product is an isopropyl benzene, initial propylene conversion=100%, selectivity of product is greater than 99.3%, total benzene/olefin molar ratio is 3.0, react after 1500 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 and 25 gram aluminum oxide, 10 gram zinc oxide, 15 gram zirconium whites, 5 gram titanium oxide are evenly mixed, add 200 milliliter of 5% salpeter solution, 5 gram sesbania powder are mediated extruded moulding after 3 hours, the catalyzer of forming is being warming up to 580 ℃ of roastings 4 hours under air atmosphere after 150 ℃ of oven dry, with above-mentioned product of roasting with 600 ℃ of water vapors with 0.2 hour
-1Handled 2 hours, cooling was placed in the oxalic acid solution of 1.0 normal concentrations soak at room temperature 48 hours, and distilled water cleans to neutral, and oven dry obtains finished catalyst.
[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=2.5 hour
-1, temperature of reaction=155 ℃, reaction pressure=2.7MPa, reaction product is an isopropyl benzene, propylene conversion=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 (9)
1, a kind of method that is used to produce isopropyl benzene, with propylene and benzene is reaction raw materials, in temperature of reaction is 100～170 ℃, reaction pressure is 1.5～2.8MPa, benzene/olefin molar ratio is that reaction raw materials contacts the liquid phase synthesizing iso-propylbenzene under 2～5 conditions with catalyzer, and used catalyzer comprises following component by weight percentage:
A) 50～80% crystal aluminosilicate;
B) 20～50% binding agent;
Wherein catalyzer is handled with organic acid after adopting 200～1000 ℃ of high-temperature water vapors to handle again, and crystal aluminosilicate to have an XRD diffraction data as follows:
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
2,, it is characterized in that binding agent is selected from aluminum oxide, titanium oxide, zinc oxide, zirconium white or its mixture according to the described method that is used to produce isopropyl benzene of claim 1.
3,, it is characterized in that temperature of reaction is 120～160 ℃ according to the described method that is used to produce isopropyl benzene of claim 1.
4,, it is characterized in that reaction pressure is 1.5～2.5MPa according to the described method that is used to produce isopropyl benzene of claim 1.
5,, it is characterized in that benzene/olefin molar ratio is 2～4 according to the described method that is used to produce isopropyl benzene of claim 1.
6, according to the described method that is used to produce isopropyl benzene of claim 1, it is characterized in that the temperature that catalyzer adopts high-temperature water vapor to handle is 400～700 ℃, the treatment time is 0.5～20 hour.
7,, it is characterized in that the time that catalyzer is handled with high-temperature water vapor is 1～5 hour according to the described method that is used to produce isopropyl benzene of claim 6.
8, according to the described method that is used to produce isopropyl benzene of claim 1, it is characterized in that organic acid is selected from citric acid, tartrate, oxalic acid or Glacial acetic acid, organic acid concentration is 0.1～3 mol, the organic acid treatment time is 1～72 hour.
9, the described according to Claim 8 method that is used to produce isopropyl benzene is characterized in that organic acid is an oxalic acid, and organic acid concentration is 0.5～1.5 mol, and the organic acid treatment time is 24～60 hours.
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|---|---|---|---|
| CN 200410024738 CN1285549C (en) | 2004-05-28 | 2004-05-28 | Process for producing isopropyl benzene |
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|---|---|---|---|
| CN 200410024738 CN1285549C (en) | 2004-05-28 | 2004-05-28 | Process for producing isopropyl benzene |
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| CN1285549C true CN1285549C (en) | 2006-11-22 |
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| CN103664493A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for synthesizing isopropyl benzene |
| 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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