CN1055876C - Alkylated catalyst for preparation of alkylbenzene - Google Patents
Alkylated catalyst for preparation of alkylbenzene Download PDFInfo
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- CN1055876C CN1055876C CN96116227A CN96116227A CN1055876C CN 1055876 C CN1055876 C CN 1055876C CN 96116227 A CN96116227 A CN 96116227A CN 96116227 A CN96116227 A CN 96116227A CN 1055876 C CN1055876 C CN 1055876C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to an alkylation catalyst for zeolites, which is composed of zeolites whose silica-alumina ratio (molar ratio) is from 2 to 20, wherein platinum is added on the zeolites, and at least one metal out of gallium, nickel, cobalt, silver and iridium is added without coerciveness. When used for preparing cumene and ethylenzene, the catalyst has the advantages of long service life, high production capacity of devices, etc., and can be widely used for producing alkylbenzene.
Description
The present invention relates to a kind of alkylation catalyst of zeolite, particularly about preparing the zeolite catalyst of isopropylbenzene.
Isopropylbenzene is a kind of important Organic Chemicals, belongs to the substituted arene compound.It is a main intermediate compound of producing phenol, acetone and AMS, also is simultaneously the auxiliary element as aviation gasoline, increases the octane number of gasoline.The catalyst of propylene and benzene synthesizing iso-propylbenzene has multiple, traditional catalyst that crystallization and noncrystalline silica, boron fluoride, aluminium oxide and phosphoric acid, alchlor and solid phosphoric acid catalyst are arranged.All there are shortcomings such as seriously corroded, equipment investment is big, the three wastes are many in these conventional catalyst technologies.In recent years, along with people to the going deep into of molecular sieve research, some companies are devoted to utilize the isopropylbenzene new technology development of zeolites as catalysts.Reported the new technology of utilizing the y-type zeolite molecular sieve to produce isopropylbenzene among the patent documentation EP0272830.This patented technology has overcome the deficiency of using traditional catalyst to exist, but also there is the poor stability of catalyst in it, and the regeneration period is short, just needed in 700 hours to drive regeneration; Reaction velocity is low, in propylene air speed 0.10hr only
-1, shortcoming such as plant capacity is low.For overcoming the shortcoming that above-mentioned catalyst exists, provide a kind of catalyst can make plant capacity raising and regeneration period grow, stablize.We have invented a kind of new zeolite alkylated catalyst.
The objective of the invention is to realize by following technical scheme: the present invention adopts zeolite to make alkylation catalyst, this zeolite has the silica alumina ratio (mol ratio of silica/alundum (Al) of 2-20, on zeolite also load at least a metal that is selected from gallium, nickel, cobalt, silver, iridium of Metal Palladium and non-imposed adding.
In the above-mentioned zeolite alkylated catalyst, the type of zeolite can be y-type zeolite, zeolite beta, modenite, ZSM-5 type zeolite, and the preferable range of the silica alumina ratio of used zeolite (mol ratio) is 2～8.The Metal Palladium content of load in catalyst is 0.003～3.0% (weight), and preferable range is 1～1.5% (weight); At least a tenor that is selected from gallium, nickel, cobalt, silver, iridium of non-imposed adding is 0～3.0% (weight), and preferable range is 0.5～2.0% (weight).This zeolite alkylated catalyst can be used for preparing the alkylation process of isopropylbenzene, ethylbenzene.
The zeolite of Shi Yonging is that the zeolite that forms commodity forms through modification in the present invention, the zeolite that at first will have 2～20 silica alumina ratios is after acid exchange, ammonia exchange, sodium metal ion and the total content of metallic potassium ion in zeolitic frameworks are controlled within 1 ‰, then after the drying, impregnating metal palladium and non-imposed adding is selected from metals such as gallium, nickel, cobalt, silver, iridium on zeolite.Advantages such as after handling like this, zeolite has just possessed good activity, is used for alkylation and prepares isopropylbenzene, ethylbenzene process, has reaction liquid phase air speed height, and plant capacity is big, and catalyst life is long have obtained good effect.
[embodiment 1]
Get 100 gram NaY type zeolite powders, its silica alumina ratio (mol ratio) is 2.0, and this NaY type zeolite powder is carried out the acid exchange with acid earlier, carries out the ammonium exchange with ammonium salt then, makes the Na in the zeolite
+Ion concentration is less than 1 ‰.To hand over through peracid, the zeolite of ammonium after handing over, dipping PdCl
2Solution makes that Metal Palladium content is 0.09% (weight) in the catalyst, after the oven dry, grinds evenly, kneads with aluminium oxide, pressure forming, promptly gets preformed catalyst.
Get the above-mentioned catalyst that makes 21 grams, be positioned in the fixed bed reactors, catalyst shape is φ 1.6mm, contains 90%Y type zeolite in the catalyst, 10% aluminium oxide.Under 195 ℃ of temperature, pressure 2.6MPa condition, benzene and propylene react by beds, and wherein the inlet amount of benzene is that 468 Grams Per Hours, propylene feed amount are 42 Grams Per Hours, calculate with propylene, and weight liquid air speed is 2.0.This reaction was investigated through 1000 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Its isopropylbenzene selectivity is 98.0% (calculating with propyl group)." comparative example 1 "
Get 100 gram NaY type zeolite powders, its silica alumina ratio (mol ratio) is 2.0, and this NaY type zeolite powder is carried out the acid exchange with acid earlier, carries out the ammonium exchange with ammonium salt then, makes the Na in the zeolite
+Ion concentration is less than 1 ‰.After the oven dry of above-mentioned zeolite, grind evenly, knead, pressure forming with aluminium oxide, promptly make preformed catalyst.
Get the above-mentioned catalyst that makes 21 grams, be positioned in the fixed bed reactors, catalyst shape is φ 1.6mm, contains 90%Y type zeolite in the catalyst, 10% aluminium oxide.195 ℃ of temperature, under the pressure 2.6MPa condition, benzene and propylene react by beds, and wherein the inlet amount of benzene is that 468 Grams Per Hours, propylene feed amount are 42 Grams Per Hours, calculate with propylene, and weight liquid air speed is 2.0.This reaction was investigated through 100 hours, and by analysis, the isopropylbenzene selectivity is 97.8%, and the selectivity computational methods of isopropylbenzene are with example 1.Investigate through 140 hours to reaction, begin to have detected propylene in the product, catalyst inactivation substantially be described at this moment.[embodiment 2]
Get 100 gram NaY type zeolite powders, its silica alumina ratio (mol ratio) is 5.0, and this NaY type zeolite powder is carried out the acid exchange with acid earlier, carries out the ammonium exchange with ammonium salt then, makes the Na in the zeolite
+Ion concentration is less than 1 ‰.To hand over through peracid, the zeolite of ammonium after handing over, dipping PdCl
2Solution, Ni (NO
3)
2Solution C o (No
3)
2Solution makes that Metal Palladium content is that 0.003% (weight), metallic nickel content are that 0.5% (weight), metallic cobalt content are 0.2% (weight) in the catalyst, after the oven dry, grinds evenly, kneads with aluminium oxide, pressure forming, promptly gets preformed catalyst.
Get the above-mentioned catalyst that makes 21 grams, be positioned in the fixed bed reactors, catalyst shape is φ 1.6mm, contains 90%Y type zeolite in the catalyst, 10% aluminium oxide.Under 182 ℃ of temperature, pressure 2.0MPa condition, benzene and propylene react by beds, and wherein the inlet amount of benzene is that 702 Grams Per Hours, propylene feed amount are 42 Grams Per Hours, calculate with propylene, and weight liquid air speed is 2.0.This reaction was investigated through 1000 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Its isopropylbenzene selectivity is 98.7%, and isopropylbenzene selectivity computational methods are with embodiment 1.[embodiment 3]
Get 100 gram NaY type zeolite powders, its silica alumina ratio (mol ratio) is 3.0, and this NaY type zeolite powder is carried out the acid exchange with acid earlier, carries out the ammonium exchange with ammonium salt then, makes the Na in the zeolite
+Ion concentration is less than 1 ‰.To hand over through peracid, the zeolite of ammonium after handing over, dipping PdCl
2Solution, Ga (NO
3)
3Solution, Ni (No
3)
2Solution, AgNO
3Solution, Ir (NO
3)
2Solution makes that Metal Palladium content is that 0.8% (weight), gallium content are that 0.1% (weight), metallic nickel content are that 0.3% (weight), argent content are that 0.1% (weight), metal iridium content are 0.2% in the catalyst.After the oven dry, grind evenly, knead with aluminium oxide, compression molding, promptly get preformed catalyst.
Get the above-mentioned catalyst that makes 21 grams, be positioned in the fixed bed reactors, catalyst shape is φ 1.6mm, contains 90%Y type zeolite in the catalyst, 10% aluminium oxide.Under 210 ℃ of temperature, pressure 2.6MPa condition, benzene and propylene react by beds, and wherein the inlet amount of benzene is that 702 Grams Per Hours, propylene feed amount are 42 Grams Per Hours.This reaction was investigated through 1000 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Its isopropylbenzene selectivity is 97.1%, and isopropylbenzene selectivity computational methods are with embodiment 1.[embodiment 4]
According to each step of embodiment 3, the zeolite type of adding is the β type, and silica alumina ratio (mol ratio) is 14.0.The metal of dipping is palladium 1.2% (weight), gallium 0.1% (weight), nickel 0.3% (weight), cobalt 0.7% (weight), silver 0.2% (weight), makes preformed catalyst.
According to the investigation method of embodiment 3, reaction was investigated through 1000 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Its isopropylbenzene selectivity is 96.4%, and isopropylbenzene selectivity computational methods are pressed embodiment 1.[embodiment 5]
According to each step of embodiment 3, the zeolite type of adding is a modenite, and silica alumina ratio (mol ratio) is 15.The metal of dipping is palladium 1.5% (weight), gallium 0.1% (weight), nickel 0.8% (weight), cobalt 0.2% (weight), iridium 0.1% (weight), makes preformed catalyst.
According to the investigation method of embodiment 3, the catalytic amount of adding is 84 grams, and reaction was investigated through 45 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Its isopropylbenzene selectivity is 95.2%, and isopropylbenzene selectivity computational methods are pressed embodiment 1.[embodiment 6]
According to each step of embodiment 3, the zeolite type of adding is the ZSM-5 type, and silica alumina ratio (mol ratio) is 20.The metal of dipping is palladium 2.0% (weight), nickel 0.4% (weight), cobalt 0.2% (weight), silver 0.1% (weight), iridium 0.1% (weight), makes preformed catalyst.
According to the investigation method of embodiment 3, the amount that adds catalyst is 168 grams, and reaction was investigated through 20 hours, did not detect propylene in the product, and activity of such catalysts, selectivity do not descend.Its isopropylbenzene selectivity is 96.9%, and isopropylbenzene selectivity computational methods are pressed embodiment 1.[embodiment 7]
Get 100 gram NaY type zeolite powders, its silica alumina ratio (mol ratio) is 5.0, and this NaY type zeolite powder is carried out the acid exchange with acid earlier, carries out the ammonium exchange with ammonium salt then, makes the Na in the zeolite
+Ion concentration is less than 1 ‰.To hand over through peracid, the zeolite of ammonium after handing over, dipping PdCl
2Solution, Ni (NO
3)
2Solution, Co (NO
3)
2Solution makes that Metal Palladium content is 0.95% in the catalyst, and metallic nickel content is that 0.5% (weight), metallic cobalt content are 0.75% (weight), after the oven dry, grinds evenly, kneads with aluminium oxide, pressure forming, promptly gets formed catalyst.
Get the above-mentioned catalyst that makes 21 grams, be positioned in the fixed bed reactors, catalyst shape is φ 1.6mm, contains 90%Y type zeolite in the catalyst, 10% aluminium oxide.Under 250 ℃ of temperature, pressure 4.0MPa condition, benzene and ethene react by beds, and wherein the inlet amount of benzene is that 400 Grams Per Hours, ethylene feed amount are 10.5 Grams Per Hours, calculate with ethene, and weight liquid air speed is 0.5hr
-1This reaction was investigated through 1000 hours, did not detect ethene in the product, and activity of such catalysts, selectivity do not descend.Its ethylbenzene selectivity is 90%.The ethylbenzene selectivity computational methods are with embodiment 1.
Claims (7)
1. alkylation catalyst that is used to prepare alkylbenzene, by silica alumina ratio (mol ratio) is that 2～20 zeolite is formed, it is characterized in that by weight percentage, on the zeolite also load 0.003～3.0% Metal Palladium and at least a metal that is selected from gallium, nickel, cobalt, silver, iridium of non-imposed adding.
2. according to the described alkylation catalyst that is used to prepare alkylbenzene of claim 1, it is characterized in that used zeolite is a y-type zeolite.
3. according to the described alkylation catalyst that is used to prepare alkylbenzene of claim 1, it is characterized in that used zeolite is zeolite beta, modenite, ZSM-5 type zeolite.
4. according to the described alkylation catalyst that is used to prepare alkylbenzene of claim 1, it is characterized in that the silica alumina ratio (mol ratio) of used zeolite is 2～8.
5. according to the described alkylation catalyst that is used to prepare alkylbenzene of claim 1, the content that it is characterized in that carried metal palladium on the used zeolite is 1～1.5% (weight).
6. according to the described alkylation catalyst that is used to prepare alkylbenzene of claim 1, it is characterized in that at least a tenor that is selected from gallium, nickel, cobalt, silver, iridium of non-imposed adding is 0～3.0% (weight).
7. according to the described alkylation catalyst that is used to prepare alkylbenzene of claim 6, it is characterized in that at least a tenor that is selected from gallium, nickel, cobalt, silver, iridium of non-imposed adding is 0.5～2% (weight).
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116227A CN1055876C (en) | 1996-01-25 | 1996-01-25 | Alkylated catalyst for preparation of alkylbenzene |
| PCT/CN1997/000002 WO1997026990A1 (en) | 1996-01-25 | 1997-01-08 | A catalyst for producing alkyl-benzene and method of producing alkyl-benzene using the catalyst |
| EP97900192A EP0818238A4 (en) | 1996-01-25 | 1997-01-08 | A catalyst for producing alkyl-benzene and method of producing alkyl-benzene using the catalyst |
| TW086100494A TW362992B (en) | 1996-01-25 | 1997-01-17 | A catalyst for preparing alkylbenzene and a process for preparing alkylbenzene with said catalyst which achieves a long catalyst service life and a high production rate of alkylbenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96116227A CN1055876C (en) | 1996-01-25 | 1996-01-25 | Alkylated catalyst for preparation of alkylbenzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1155450A CN1155450A (en) | 1997-07-30 |
| CN1055876C true CN1055876C (en) | 2000-08-30 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96116227A Expired - Fee Related CN1055876C (en) | 1996-01-25 | 1996-01-25 | Alkylated catalyst for preparation of alkylbenzene |
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| Country | Link |
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| CN (1) | CN1055876C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308273C (en) * | 2004-09-27 | 2007-04-04 | 华东理工大学 | Process for preparing isopropyl benzene by catalytically hydrogenolysis alpha, alpha dimethyl benzyl alcohol |
| CN101045208B (en) * | 2006-03-27 | 2010-05-12 | 中国石油化工股份有限公司 | Dealkylation and alkyl-transfering catalyst for C9 or more heavy aromatic hydrocarbons |
| CN110653003B (en) * | 2018-06-28 | 2022-08-09 | 中国石油化工股份有限公司 | Solid acid catalyst, preparation method and alkylation reaction method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3738977A (en) * | 1971-04-22 | 1973-06-12 | Union Oil Co | Polymerization of ethylene with a supported palladium catalyst |
| JPS62246532A (en) * | 1986-04-16 | 1987-10-27 | Maruzen Petrochem Co Ltd | Alkylation of phenol |
| CN1052655A (en) * | 1989-12-22 | 1991-07-03 | 陶氏化学公司 | The alkylation of benzene or substituted benzene or the transalkylation method of alkylated benzenes and catalyzer |
| CN1072353A (en) * | 1991-11-20 | 1993-05-26 | 中国石油化工总公司金陵石油化工公司 | Alkene and benzene alkylation solid acid catalyst |
-
1996
- 1996-01-25 CN CN96116227A patent/CN1055876C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3738977A (en) * | 1971-04-22 | 1973-06-12 | Union Oil Co | Polymerization of ethylene with a supported palladium catalyst |
| JPS62246532A (en) * | 1986-04-16 | 1987-10-27 | Maruzen Petrochem Co Ltd | Alkylation of phenol |
| CN1052655A (en) * | 1989-12-22 | 1991-07-03 | 陶氏化学公司 | The alkylation of benzene or substituted benzene or the transalkylation method of alkylated benzenes and catalyzer |
| CN1072353A (en) * | 1991-11-20 | 1993-05-26 | 中国石油化工总公司金陵石油化工公司 | Alkene and benzene alkylation solid acid catalyst |
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|---|---|
| CN1155450A (en) | 1997-07-30 |
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