CN1155531A - Process for preparation of alkyl benzene - Google Patents
Process for preparation of alkyl benzene Download PDFInfo
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- CN1155531A CN1155531A CN 96116225 CN96116225A CN1155531A CN 1155531 A CN1155531 A CN 1155531A CN 96116225 CN96116225 CN 96116225 CN 96116225 A CN96116225 A CN 96116225A CN 1155531 A CN1155531 A CN 1155531A
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- zeolite
- isopropyl benzene
- benzene
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Abstract
A process for preparing alkylbenzene features using zeolite whose Si/Al ratio is 2-20 as catalyst which carries metal Pd and at least one of Ga, Ni, Co, Ag and Ir. The reaction takes place at 150-250 deg.C, 0.7-4.0nMPa, and 4-20 of benzene to -ene ratio in liquid phase. Its advantages include long service life of catalyst and high production capacity of apparatus.
Description
The present invention relates to a kind of benzene process, particularly prepare the technology of alkylbenzene about zeolites as catalysts with loaded metal palladium and promoter metal thereof.
Ethylbenzene, isopropyl benzene are a kind of important Organic Chemicals, belong to the substituted arene compound.Wherein isopropyl benzene is a main intermediate compound of producing phenol, acetone and alpha-methyl styrene, also is simultaneously the ancillary component as aviation spirit, increases the octane value of gasoline.The catalyzer of propylene and benzene synthesizing iso-propylbenzene has multiple, traditional catalyzer that crystallization and noncrystalline silicon-dioxide, boron fluoride, aluminum oxide and phosphoric acid, aluminum chloride and solid phosphoric acid catalyst are arranged.All there are shortcomings such as seriously corroded, facility 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 isopropyl benzene new technology development of zeolites as catalysts.Reported the new technology of utilizing the y-type zeolite molecular sieve to produce isopropyl benzene 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 catalyzer 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 catalyzer and technology thereof exist, provide a kind of catalyzer can make plant capacity raising and regeneration period grow, stablize.We have invented a kind of new preparation benzene process.
The objective of the invention is to realize by following technical scheme: ethene, propylene and composition thereof are at 150～250 ℃ of temperature of reaction, reaction pressure 0.7～4.0MPa, benzene: alkene (mol ratio) is 4～20, under the liquid-phase condition, with benzene prepared in reaction ethylbenzene, isopropyl benzene and composition thereof, having the zeolites as catalysts of 2-20 silica alumina ratio (mol ratio of silicon-dioxide/aluminium sesquioxide), on zeolite also load at least a metal that is selected from gallium, nickel, cobalt, silver, iridium of palladium metal and non-imposed adding.
Among the abovementioned alkyl benzene preparation technology, the preferable range of temperature of reaction is 180～210 ℃, and the reaction pressure preferable range is 1.0～2.0Mpa.The type of zeolite can be y-type zeolite, zeolite beta, mordenite, ZSM-5 type zeolite, and the preferable range of the silica alumina ratio of used zeolite (mol ratio) is 2～8.The palladium metal content of load in catalyzer is 0.003～3.0% (weight), and preferable range is 1～1.5% (weight); At least a metal content 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).
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 99.5 ion and the total content of potassium metal ion in zeolite framework 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 isopropyl benzene, 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 content is less than 1 ‰.To hand over through peracid, the zeolite of ammonium after handing over, dipping PdCl
2Solution makes that palladium metal content is 0.09% (weight) in the catalyzer, after the oven dry, grinds evenly, kneads with aluminum oxide, pressure forming, promptly gets preformed catalyst.
Get the above-mentioned catalyzer that makes 21 grams, be positioned in the fixed-bed reactor, catalyst shape is φ 1.6mm, contains 90%Y type zeolite in the catalyzer, 10% aluminum 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 reaction product, and activity of such catalysts, selectivity do not descend.Its isopropyl benzene 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 acid exchange with acid earlier, carries out ammonium with ammonium salt then and exchanges, and makes Na+ ion content in the zeolite less than 1 ‰.After the oven dry of above-mentioned zeolite, grind evenly, knead, pressure forming with aluminum oxide, promptly make preformed catalyst.
Get the above-mentioned catalyzer that makes 21 grams, be positioned in the fixed-bed reactor, catalyst shape is φ 1.6mm, contains 90%Y type zeolite in the catalyzer, 10% aluminum 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 isopropyl benzene selectivity is 97.8%, and the selectivity method of calculation of isopropyl benzene are with example 1.Investigate through 140 hours to reaction, begin to have detected propylene in the reaction product, catalyzer 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 content 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 palladium metal content is that 0.003% (weight), metallic nickel content are that 0.5% (weight), cobalt metal content are 0.2% (weight) in the catalyzer, after the oven dry, grinds evenly, kneads with aluminum oxide, pressure forming, promptly gets preformed catalyst.
Get the above-mentioned catalyzer that makes 21 grams, be positioned in the fixed-bed reactor, catalyst shape is φ 1.6mm, contains 90%Y type zeolite in the catalyzer, 10% aluminum 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 reaction product, and activity of such catalysts, selectivity do not descend.Its isopropyl benzene selectivity is 98.7%, and isopropyl benzene selectivity method of calculation 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 content 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 palladium metal 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 catalyzer.After the oven dry, grind evenly, knead with aluminum oxide, compression molding, promptly get preformed catalyst.
Get the above-mentioned catalyzer that makes 21 grams, be positioned in the fixed-bed reactor, catalyst shape is φ 1.6mm, contains 90%Y type zeolite in the catalyzer, 10% aluminum 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 reaction product, and activity of such catalysts, selectivity do not descend.Its isopropyl benzene selectivity is 97.1%, and isopropyl benzene selectivity method of calculation 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 reaction product, and activity of such catalysts, selectivity do not descend.Its isopropyl benzene selectivity is 96.4%, and isopropyl benzene selectivity method of calculation are pressed embodiment 1.[embodiment 5]
According to each step of embodiment 3, the zeolite type of adding is a mordenite, 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 reaction product, and activity of such catalysts, selectivity do not descend.Its isopropyl benzene selectivity is 95.2%, and isopropyl benzene selectivity method of calculation 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 catalyzer is 168 grams, and reaction was investigated through 20 hours, did not detect propylene in the reaction product, and activity of such catalysts, selectivity do not descend.Its isopropyl benzene selectivity is 96.9%, and isopropyl benzene selectivity method of calculation 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 content 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 palladium metal content is 0.95% in the catalyzer, and metallic nickel content is that 0.5% (weight), cobalt metal content are 0.75% (weight), after the oven dry, grinds evenly, kneads with aluminum oxide, pressure forming, promptly gets formed catalyst.
Get the above-mentioned catalyzer that makes 21 grams, be positioned in the fixed-bed reactor, catalyst shape is φ 1.6mm, contains 90%Y type zeolite in the catalyzer, 10% aluminum 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 reaction product, and activity of such catalysts, selectivity do not descend.Its ethylbenzene selectivity is 90%.The ethylbenzene selectivity method of calculation are with embodiment 1.
Claims (9)
1. one kind prepares ethylbenzene, isopropyl benzene and miscellany technology thereof, by ethene, propylene and composition thereof at 150～250 ℃ of temperature of reaction, reaction pressure 0.7～4.0MPa, benzene: alkene (mol ratio): 4～20, under the liquid-phase condition with the benzene reaction, with silica alumina ratio (mol ratio) is that 2～20 zeolite is a catalyzer, on zeolite also load at least a metal that is selected from gallium, nickel, cobalt, silver, iridium of palladium metal and non-imposed adding.
2. be used to prepare ethylbenzene, isopropyl benzene and composition thereof technology according to claim 1 is described, it is characterized in that temperature of reaction is 180～210 ℃.
3. be used to prepare ethylbenzene, isopropyl benzene and composition thereof technology according to claim 1 is described, it is characterized in that reaction pressure is 1.0～2.0MPa.
4. be used to prepare ethylbenzene, isopropyl benzene and composition thereof technology according to claim 1 is described, it is characterized in that used zeolite is Y type, β type, mordenite, ZSM-5 type zeolite.
5. be used to prepare ethylbenzene, isopropyl benzene and composition thereof technology according to claim 1 is described, it is characterized in that the silica alumina ratio (mol ratio) of used zeolite is 2～8.
6. be used to prepare ethylbenzene, isopropyl benzene and composition thereof technology according to claim 1 is described, it is characterized in that loaded metal palladium content is 0.003～3% (weight) on the zeolite.
7. be used to prepare ethylbenzene, isopropyl benzene and composition thereof technology according to claim 1 is described, it is characterized in that loaded metal palladium content is 1～1.5% (weight) on the zeolite.
8. be used to prepare ethylbenzene, isopropyl benzene and composition thereof technology according to claim 1 is described, at least a metal content that is selected from gallium, nickel, cobalt, silver, iridium that it is characterized in that non-imposed adding is 0～3.0% (must measure).
9. be used to prepare ethylbenzene, isopropyl benzene and composition thereof technology according to claim 1 is described, it is characterized in that at least a metal content 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 |
|---|---|---|---|
| CN96116225A CN1053175C (en) | 1996-01-25 | 1996-01-25 | Process for preparation of alkyl benzene |
| 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 |
|---|---|---|---|
| CN96116225A CN1053175C (en) | 1996-01-25 | 1996-01-25 | Process for preparation of alkyl benzene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1155531A true CN1155531A (en) | 1997-07-30 |
| CN1053175C CN1053175C (en) | 2000-06-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96116225A Expired - Lifetime CN1053175C (en) | 1996-01-25 | 1996-01-25 | Process for preparation of alkyl benzene |
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| Country | Link |
|---|---|
| CN (1) | CN1053175C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114493C (en) * | 1999-06-24 | 2003-07-16 | 中国石油化工集团公司 | Catalyst and process for prodn. of alkyl benzene |
| CN106278794A (en) * | 2015-06-04 | 2017-01-04 | 常州瑞华化工工程技术有限公司 | The common liquid-phase alkylation of ethylene, propylene produces ethylbenzene and the method and apparatus of isopropylbenzene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4399059A (en) * | 1980-12-02 | 1983-08-16 | Mobil Oil Corporation | Zeolite catalysts modified with group IIIA metal |
| US4798816A (en) * | 1986-12-19 | 1989-01-17 | Union Oil Company Of California | Process for increasing the selectivity of an alkylation catalyst for monoalkylation |
-
1996
- 1996-01-25 CN CN96116225A patent/CN1053175C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114493C (en) * | 1999-06-24 | 2003-07-16 | 中国石油化工集团公司 | Catalyst and process for prodn. of alkyl benzene |
| CN106278794A (en) * | 2015-06-04 | 2017-01-04 | 常州瑞华化工工程技术有限公司 | The common liquid-phase alkylation of ethylene, propylene produces ethylbenzene and the method and apparatus of isopropylbenzene |
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| Publication number | Publication date |
|---|---|
| CN1053175C (en) | 2000-06-07 |
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