CN1096470A - Beta-zeolite-gamma-alumina catalyst and preparation thereof - Google Patents
Beta-zeolite-gamma-alumina catalyst and preparation thereof Download PDFInfo
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- CN1096470A CN1096470A CN 93106946 CN93106946A CN1096470A CN 1096470 A CN1096470 A CN 1096470A CN 93106946 CN93106946 CN 93106946 CN 93106946 A CN93106946 A CN 93106946A CN 1096470 A CN1096470 A CN 1096470A
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Abstract
A kind of beta-zeolite-gamma-alumina catalyst that is used for the benzene liquid phase alkylation reaction, its composition comprises: (1) SiO
2/ Al
2O
3Than H β zeolite 30-70 heavy % that are 20-40; (2) the heavy % of 0.5-10, the preferably fluorine or chlorine of 1-5 heavy %; (3) γ-Al of aequum
2O
3This Preparation of catalysts method is with H β zeolite and γ-Al
2O
3Precursor and ammonium fluoride or ammonium chloride, nitric acid and deionized water kneading and compacting, step such as drying, roasting promptly makes the said catalyst of the present invention then.This catalyst is compared with not halogen-containing β zeolite-aluminium oxide catalyst, can improve ethylbenzene space-time yield 17-20%, ethylbenzene selectivity 1.2-2.4%, characteristics such as it is low to have reaction temperature, and the catalyst runs cycle is long, and the accessory substance xylene content is few.
Description
The present invention relates to a kind of alkylation catalyst, specifically, is a kind of beta-zeolite-gamma-alumina catalyst that is used for benzene and ethene liquid phase alkylation reaction and preparation method thereof.
Ethylbenzene is the raw material of producing polystyrene plastics, industrial mainly is that alkylated reaction by benzene and ethene makes, and its preparation method comprises: alchlor process, with the ZSM-5 zeolite be the vapor-phase alkylation method of catalyst and recently the molecular sieve of report be the liquid-phase alkylation method (United States Patent (USP): 4169111,4185040,4459426 of catalyst; EP402202A1) as U.S. Unocal company exploitation be the liquid-phase alkylation catalyst of acidic components with the macropore ultra-steady Y molecular sieve, be its service cycle 1 year.In United States Patent (USP) 4891458, reported β zeolite-aluminium oxide catalyst with ammonium, rare earth exchanged, this catalyst is mainly used in benzene and propylene liquid-phase alkylation is produced isopropylbenzene or benzene alkylation with ethylene generates the ethylbenzene process.Up to now, do not see the relevant acid and active report that further improves the benzene liquid-phase alkylation catalyst that contains the β zeolite on the document.
Thereby the object of the present invention is to provide a kind of fluorine or chlorine improves its alkylation activity (STY represents with the ethylbenzene space-time yield) and ethylbenzene selectivity with the acidity that increases beta-zeolite-gamma-alumina catalyst Catalysts and its preparation method of in beta-zeolite-gamma-alumina catalyst, introducing.The said catalyst of the present invention, it consists of:
1.SiO
2/ Al
2O
3Than the heavy % of H β zeolite 30-70 for 20-40;
2.0.5-10 heavy %, the preferably fluorine or chlorine of the heavy % of 1-5;
3. γ-the Al of aequum
2O
3
This Preparation of catalysts method is with H β zeolite and γ-Al
2O
3Precursor and ammonium fluoride or ammonium chloride, nitric acid and deionized water kneading and compacting, step such as drying, roasting obtains the said catalyst of the present invention then, and its preparation process comprises:
(1) H β prepare zeolite: with SiO
2/ Al
2O
3Make ammonium type β zeolite (weight ratio of ammonium salt and Na β zeolite be 1.0-2.0) at 80-90 ℃ with the ammonium salt aqueous solution exchange than Na β zeolite, through washing, drying, under air,, make H β zeolite then in 450-550 ℃ of roasting 2-7 hour for 20-40;
(2) H β zeolite and the γ-Al that step (1) is made
2O
3Precursor mix, adding ammonium fluoride or ammonium chloride, nitric acid and deionized water mix pinches, is extruded into the catalyst bar that diameter is the 1.5-2 millimeter, wherein the addition of H β zeolite accounts for the heavy % of 30-70 that catalyst is formed, the addition of ammonium fluoride or ammonium chloride is pressed the heavy % of 0.5-10 in the catalyst, preferably the fluorine or chlorine of the heavy % of 1-5 calculates γ-Al
2O
3The addition of precursor is pressed the γ-Al of aequum in the catalyst
2O
3Calculate, the addition of nitric acid accounts for the heavy % of 0.5-2 of siccative addition, and the addition of deionized water is pinched mixing, extrusion is as the criterion;
(3) strip catalyst that step (2) is made at 450-550 ℃ of roasting 2-7 hour, promptly gets the said catalyst of the present invention after 100-120 ℃ of drying.
The precursor of the said ammonium salt of the present invention is NH
4Cl, (NH
4)
2SO
4, NH
4NO
3; Said γ-Al
2O
3Precursor be boehmite.
Key of the present invention is in the preparation process of β zeolite aluminium oxide catalyst, introduces the acidity of nonmetal halogen compounds with acidity, the particularly Bronsted acid of raising catalyst.Said nonmetal halogen compounds can be fluoride, chloride or bromide, and is better with fluoride, as BF
3, NH
4BF
4, HF, NH
4F, (NH
4)
2SiF
6, CF
3COOH, CF
3CH
2OH etc.The introducing method of nonmetal halogen compounds can adopt kneading method, also can adopt methods such as solution impregnation and steam treated.
The said catalyst of the present invention can be used for benzene liquid-phase alkylation process, ethylbenzene space-time yield 17-20% is compared, can be improved to this catalyst with not halogen-containing β zeolite-aluminium oxide catalyst, improve ethylbenzene selectivity 1.2-2.4%, this catalyst also has characteristics such as reaction temperature is low, the catalyst runs cycle long, the accessory substance xylene content is few.
Following example will the invention will be further described.
Example 1
With 60 gram Na β zeolite (oil three factories, Si
2O/Al
2O
3Ratio=20, Na
2The heavy % of O 0.8) is added to (NH of 1N
4)
2SO
4(79.2 gram (NH in the solution
4)
2SO
4(chemical pure, 57601 chemical plant, Beijing) are dissolved in the 1.2 liter deionized waters), 90 ℃ of exchanges 2 hours, be the deionized water washing of 2.4 liters then with total amount, 120 ℃ of dryings, 550 ℃ of following roastings 6 hours make H β zeolite 54 and restrain.
Get 15 gram H β zeolites and 18 gram S β powder (a kind of boehmite, West Germany's import, α Al
2O
3H
2After 91.6%, 540 ℃ of roasting of O, Al
2O
383.1 heavy % intends thin H
2O degree of crystallinity about 80%, 241 meters of specific surfaces
2/ gram, 0.45 milliliter/gram of pore volume) mixes, add 1.75 gram ammonium fluorides (chemical pure, Beijing chemical reagent two factories) and appropriate amount of deionized water (addition of deionized water is pinched mixing, extrusion is as the criterion) and mix on banded extruder that to pinch back extruded moulding, make diameter be 1.5 millimeters catalyst bar, then 120 ℃ of dryings 12 hours, again in muffle furnace in 550 ℃ of roastings 6 hours, be chilled to room temperature and make the catalyst A that fluorine content is 3 heavy %.
Example 2-3
Make catalyst B, the C that fluorine content is respectively 1 heavy % and 5 heavy % by example 1 described method.
Comparative Examples 1
Do not add during except moulding the fluoride, other preparation process and feeding quantity make catalyst D with example 1.
Example 4
On the pressurization static bed reaction unit of U.S.'s CDS-900 continuous-flow, be raw material with benzene and ethene, evaluate catalysts A-D carries out liquid phase alkylation reaction activity and selectivity.Catalyst grain size is the 16-20 order, 8 milliliters of loading amounts, and with the dilution of 16-20 order quartz sand, thinner ratio is 3: 1,200 ℃ of reaction temperatures, reaction pressure 2.94MPa, benzene/ethylene molecule is than=8: 1, and reaction result sees Table 1.
As can be seen from Table 1: when the catalyst that adopts the present invention to make carried out the liquid phase alkylation reaction of benzene and ethene, the selectivity of activity of such catalysts and ethylbenzene all was better than not adding the β zeolite-aluminium oxide catalyst of halogen.As catalyst A-C that the present invention makes, the catalyst D that makes with comparative example 1 under above-mentioned reaction condition compares, and the ethylbenzene space-time yield improves 17-20%, and ethylbenzene selectivity improves 1.2-2.4%.
Table 1
Annotate: (1) STY is ethylbenzene space-time yield (Space time yield);
(2) ethylbenzene selectivity=(EB)/(A) * 100%
(3) phenethyl selectivity=(EB+PEB)/(A) * 100%
Wherein A, EB, PEB represent respectively in the alkylation liquid, the concentration m% of benzene, ethylbenzene, many ethylbenzene.
(4) Cat represents catalyst (Catalyst).
Claims (5)
1, a kind of beta-zeolite-gamma-alumina catalyst that is used for the benzene liquid phase alkylation reaction is characterized in that the composition of this catalyst comprises:
(1) SiO
2/ Al
2O
3Than the heavy % of H β zeolite 30-70 for 20-40;
(2) fluorine or chlorine of the heavy % of 0.5-10;
(3) γ-Al of aequum
2O
3
2, according to the said catalyst of claim 1, the content that it is characterized in that fluorine or chlorine in (2) is the heavy % of 1-5.
3, claim 1 or 2 said Preparation of catalysts methods is characterized in that:
(1) with SiO
2/ Al
2O
3Than being exchanged into ammonium type β zeolite at 80-90 ℃ with ammonium salt aqueous solution for the Na β zeolite of 20-40, wherein the weight ratio of ammonium salt and Na β zeolite is 1.0-2.0, through washing, drying, in 450-550 ℃ of roasting 2-7 hour, makes H β zeolite under air then;
(2) H β zeolite and the γ-Al that (1) is made
2O
3Precursor mix, adding ammonium fluoride or ammonium chloride, nitric acid and proper amount of deionized water are mixed and are pinched, be extruded into the catalyst bar of 1.5-2.0 millimeter, wherein the addition of H β zeolite accounts for the heavy % of 30-70 that catalyst is formed, the fluorine or chlorine that the addition of ammonium fluoride or ammonium chloride is pressed the heavy % of 0.5-10 in the catalyst calculates γ-Al
2O
3The addition of precursor is pressed the γ-Al of aequum in the catalyst
2O
3Calculate, the addition of nitric acid accounts for the heavy % of 0.5-2.0 of siccative addition, and the addition of deionized water is pinched mixing, extrusion is as the criterion:
(3) strip catalyst that (2) are made, through 100-120 ℃ dry after at 450-550 ℃ of roasting 2-7 hour.
4,, it is characterized in that the precursor of ammonium salt in (1) is NH according to the said preparation method of claim 3
4Cl, (NH
4)
2SO
4, NH
4NO
3
5, according to the said preparation method of claim 3, it is characterized in that γ-Al
2O
3Precursor be boehmite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93106946A CN1041387C (en) | 1993-06-15 | 1993-06-15 | Beta-zeolite-gamma-alumina catalyst and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93106946A CN1041387C (en) | 1993-06-15 | 1993-06-15 | Beta-zeolite-gamma-alumina catalyst and its preparation |
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| Publication Number | Publication Date |
|---|---|
| CN1096470A true CN1096470A (en) | 1994-12-21 |
| CN1041387C CN1041387C (en) | 1998-12-30 |
Family
ID=4986501
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93106946A Expired - Lifetime CN1041387C (en) | 1993-06-15 | 1993-06-15 | Beta-zeolite-gamma-alumina catalyst and its preparation |
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| Country | Link |
|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073887C (en) * | 1997-08-08 | 2001-10-31 | 北京燕化石油化工股份有限公司化工二厂 | Catalyst for alkylation to prepare ethylbenzene, its preparation process, and new technology for preparing ethylbenzene by alkylation |
| US6504071B2 (en) | 1999-12-10 | 2003-01-07 | Beijing Institute Of Clothing Technology | Process and apparatus for preparation of ethylbenzene by alkylation of benzene with dilute ethylene contained in dry gas by catalytic distillation |
| CN1296133C (en) * | 2004-01-19 | 2007-01-24 | 中国石油化工股份有限公司 | Catalyst containing MCM-22 zeolite |
| CN101992117A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Reformate non-hydroisomerization olefin-reducing catalyst |
| CN101433859B (en) * | 2007-11-15 | 2011-06-15 | 中国石油化工股份有限公司 | Catalyst for alkylation reaction and preparation method thereof |
| CN102616804A (en) * | 2011-01-27 | 2012-08-01 | 中国石油化工股份有限公司 | Copper-containing beta molecular sieve and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5116794A (en) * | 1988-03-30 | 1992-05-26 | Uop | Method for enhancing the activity of zeolite beta |
| US4859822A (en) * | 1988-05-19 | 1989-08-22 | Mobil Oil Corporation | Microwaveable container |
| US4906601A (en) * | 1988-12-16 | 1990-03-06 | Exxon Research And Engineering Company | Small particle low fluoride content catalyst |
-
1993
- 1993-06-15 CN CN93106946A patent/CN1041387C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073887C (en) * | 1997-08-08 | 2001-10-31 | 北京燕化石油化工股份有限公司化工二厂 | Catalyst for alkylation to prepare ethylbenzene, its preparation process, and new technology for preparing ethylbenzene by alkylation |
| US6504071B2 (en) | 1999-12-10 | 2003-01-07 | Beijing Institute Of Clothing Technology | Process and apparatus for preparation of ethylbenzene by alkylation of benzene with dilute ethylene contained in dry gas by catalytic distillation |
| CN1296133C (en) * | 2004-01-19 | 2007-01-24 | 中国石油化工股份有限公司 | Catalyst containing MCM-22 zeolite |
| CN101433859B (en) * | 2007-11-15 | 2011-06-15 | 中国石油化工股份有限公司 | Catalyst for alkylation reaction and preparation method thereof |
| CN101992117A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Reformate non-hydroisomerization olefin-reducing catalyst |
| CN101992117B (en) * | 2009-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | Reformate non-hydroisomerization olefin-reducing catalyst |
| CN102616804A (en) * | 2011-01-27 | 2012-08-01 | 中国石油化工股份有限公司 | Copper-containing beta molecular sieve and preparation method thereof |
| CN102616804B (en) * | 2011-01-27 | 2013-12-25 | 中国石油化工股份有限公司 | Copper-containing beta molecular sieve and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1041387C (en) | 1998-12-30 |
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Expiration termination date: 20130615 Granted publication date: 19981230 |