CN102372575B - Method for preparing tetramethylethylene through isobutene metathesis - Google Patents
Method for preparing tetramethylethylene through isobutene metathesis Download PDFInfo
- Publication number
- CN102372575B CN102372575B CN2010102618782A CN201010261878A CN102372575B CN 102372575 B CN102372575 B CN 102372575B CN 2010102618782 A CN2010102618782 A CN 2010102618782A CN 201010261878 A CN201010261878 A CN 201010261878A CN 102372575 B CN102372575 B CN 102372575B
- Authority
- CN
- China
- Prior art keywords
- reaction
- tetramethylethylene
- isobutene
- parts
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing tetramethylethylene through isobutene metathesis, and mainly aims to solve the problem of low catalyst activity in previous technologies. The method of the invention adopts isobutene as the raw material, in a fixed bed reactor, at a temperature of 350-450DEG C, under a reaction pressure of 0-1MPa and a weight space velocity of 1-20h<-1>, the raw material is contacted with a catalyst for reaction so as to generate tetramethylethylene, i.e. an effluent of 2, 3-dimethyl-2-butylene. Specifically, the catalyst consists of by weight: 1-30 parts of tungsten oxide and 70-99 parts of an SiO2 vector, and the specific surface area of the catalyst is 250-500m<2>/g. The technical method of the invention well solves the above, and can be used in the industrial tetramethylethylene production through isobutene metathesis.
Description
Technical field
The present invention relates to a kind of method of preparing tetramethylethylene through isobutene metathesis.
Background technology
Tetramethyl-ethylene, as a kind of olefin product of high added value, can be used for the intermediate of agricultural chemicals and spices, is the main raw material of synthetic chrysanthemumic acid.Again for the production of spices and other agrochemicals etc., especially with it, replace neohexene production tonalide spices simultaneously, there is the advantages such as cost is low, constant product quality.The synthetic of tetramethyl-ethylene paid attention to very much.Tetramethyl-ethylene i.e. 2,3-dimethyl-2-butylene, and the conventional preparation method of current industrial hexene closes reaction by propylene dimerization to generate, and the catalyzer of employing is the catalyzer that all matches.By the olefin metathesis technology, C4 conversion of olefines that can relative surplus is low value-added becomes the tetramethyl-ethylene of high added value.
Olefin metathesis (Olefin metathesis) is a kind of conversion of olefines process.Under the effect at transition-metal catalyst (as W, Mo, Re etc.), the fracture of the two keys of C=C and formation again in alkene, thus can obtain new olefin product.We can mean simply from following reaction formula the dismutation of alkene:
R
2-CH＝CH-R
4+R
1-CH＝CH-R
4+R
2-CH＝CH-R
3.........(2)
R in reaction formula
1, R
2, R
3, R
4represent respectively different alkyl or hydrogen atom.If wherein the disproportionation reaction of same alkene (suc as formula 1) is called self disproportionation (self-metathesis); Disproportionation reaction between different alkene (formula 2) is called cross disproportionation (cross-metathesis).
US20030204123 has reported that take iso-butylene prepares the technology of tetramethyl-ethylene as raw material.The catalyzer that this technology adopts is that Tungsten oxide 99.999 loads on silicon oxide, and temperature of reaction is 343 ℃, and reaction pressure is 5bar.
Method in above document is when the reaction for preparing hexane by disproportionating butylene, and specific surface area of catalyst is not high, have that catalyst activity is low simultaneously, reaction velocity is low and product in the low problem of tetramethyl-ethylene yield.
Summary of the invention
Technical problem to be solved by this invention be that the catalyst activity existed in prior art is low, reaction velocity is low and product in the low problem of tetramethyl-ethylene yield, a kind of method of new preparing tetramethylethylene through isobutene metathesis is provided.The method when the iso-butylene disproportionation reaction, have advantages of that catalyst activity is high, reaction velocity is high and product in the tetramethyl-ethylene yield high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing tetramethylethylene through isobutene metathesis, take iso-butylene as raw material, and in temperature of reaction, be 350～450 ℃, reaction pressure is counted 0～1MPa with absolute pressure, and weight space velocity is 1～20 hour
-1under condition, raw material by beds, generates tetramethyl-ethylene, and 2,3-dimethyl-2-butylene, wherein used catalyst, in parts by weight, comprises following component:
A) 1～30 part of Tungsten oxide 99.999;
B) 70～99 parts of SiO
2carrier, wherein the specific surface area of catalyzer is 250～500 meters
2/ gram.
In technique scheme, the preferable range of temperature of reaction is 370～425 ℃, and more preferably scope is 385～400 ℃; The reaction pressure preferable range is 0.2～0.8MPa, and more preferably scope is 0.4～0.6MPa; Liquid phase air speed preferable range is 2～15 hours
-1, more preferably scope is 4～8 hours
-1; The preferable range of Tungsten oxide 99.999 consumption parts by weight is 2～25 parts, and more preferably scope is 4～20 parts; The preferable range of specific surface area of catalyst is 250～400 meters
2/ gram, more preferably scope is 280～370 meters
2/ gram.
Catalyzer of the present invention can adopt the method preparations such as dipping, chemisorption, electroless plating, ion-exchange, physical mixed, the aqueous solution that preferred version is the tungstenic source is immersed on carrier, concrete scheme is for to put into stirrer by the aqueous solution in tungstenic source and carrier, and adding silicon sol and field mountain valley with clumps of trees and bamboo powder, the stirring kneading makes it Load Balanced and can make catalyzer.
In the present invention during the tungsten source, can be a kind of in wolframic acid, sodium wolframate, ammonium tungstate, ammonium metawolframate, the tungsten source is ammonium metawolframate preferably.
The forming method of catalyzer is as follows: the good catalyzer of preparation is put into to banded extruder, and that extrusion becomes is dry after definite shape, under air atmosphere, roasting makes finished product later, and the temperature of roasting is 500～700 ℃, and roasting time is 2～8 hours.
Catalyzer prepared by technique scheme is for the automatic disproportionation reaction of alkene, and the embodiment of the present invention is that the iso-butylene disproportionation generates tetramethyl-ethylene.Reaction conditions is as follows: in fixed-bed reactor, temperature of reaction is 350～450 ℃, and reaction pressure is counted 0～1MPa with absolute pressure, and the mass space velocity of butylene is 1～20 hour
-1.
The present invention adopts 700～1000 purpose chromatographic silica gels as carrier, has effectively improved the specific surface area of catalyzer, is conducive to being uniformly distributed of catalyst surface Tungsten oxide 99.999, has improved the disproportionation activity of catalyzer.In temperature of reaction, be 400 ℃, reaction pressure is 0.5MPa, butylene air speed be 4 hours
-1under condition, by catalyzer and iso-butylene contact reacts, the transformation efficiency of its iso-butylene can reach 33%, and the weight yield of tetramethyl-ethylene can reach 18%, and yield can improve 8%, has obtained technique effect preferably.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
1 kilogram of 700 purpose chromatographic silica gel and 10 gram sesbania powder are added in stirrer and stir 45 minutes, add 400 gram silicon sol and 63 gram ammonium metawolframates after mediating evenly, the deionized water that simultaneously adds 1 kilogram, kneading, extrusion, drying, later 550 ℃ of lower roastings 4 hours, obtain flaxen catalyzer finished product, the content 5% of Tungsten oxide 99.999.The evaluation of catalyzer is carried out on the olefin metathesis evaluating apparatus, the iso-butylene that raw material is 99.9%.Reaction is to be 385 ℃ in temperature, and pressure is 0.5MPa, and the air speed of butene-1 is 4 hours
-1condition under estimated, evaluation result is as shown in table 2, is designated as SL-1.
[embodiment 2]
Press each step in embodiment 1, only changing ammonium metawolframate is 113 grams, and the charge capacity of the catalyst oxidation tungsten made is 8%, and changing in reaction conditions temperature of reaction and be 350 ℃, reaction pressure is that 0.2MPa and air speed are 1 hour
-1, evaluation result is as shown in table 2, is designated as SL-2.
[embodiment 3]
Press each step in embodiment 1, only changing ammonium metawolframate is 163 grams, and the charge capacity of the catalyst oxidation tungsten made is 12%, and changing in reaction conditions temperature of reaction and be 370 ℃, reaction pressure is that 0.4MPa and air speed are 2 hours
-1, evaluation result is as shown in table 1, is designated as SL-3.
[embodiment 4]
Press each step in embodiment 1, only changing ammonium metawolframate is 212 grams, and the charge capacity of the catalyst oxidation tungsten made is 15%, and changing in reaction conditions temperature of reaction and be 450 ℃, reaction pressure is that 0.6MPa and air speed are 20 hours
-1, evaluation result is as shown in table 2, is designated as SL-4.
[embodiment 5]
Press each step in embodiment 1, only changing ammonium metawolframate is 301 grams, and the charge capacity of the catalyst oxidation tungsten made is 20%, and changing in reaction conditions temperature of reaction and be 425 ℃, reaction pressure is that 0.8MPa and air speed are 15 hours
-1, evaluation result is as shown in table 2, is designated as SL-5.
[embodiment 6]
Press each step in embodiment 1, only changing ammonium metawolframate is 163 grams, and the charge capacity of the catalyst oxidation tungsten made is 12%, and changing in reaction conditions temperature of reaction and be 400 ℃, reaction pressure is that 0.5MPa and air speed are 8 hours
-1, evaluation result is as shown in table 2, is designated as SL-6.
[embodiment 7]
Press each step in embodiment 1, only changing ammonium metawolframate is 163 grams, and the charge capacity of the catalyst oxidation tungsten made is 12%, and the change reaction pressure is 1MPa, and evaluation result, as shown in table 2 and table 3, is designated as SL-7.
[embodiment 8]
Press each step in embodiment 1, only changing ammonium metawolframate is 163 grams, and the charge capacity of the catalyst oxidation tungsten made is 12%, and the air speed that the change reaction pressure is 0.1MPa and iso-butylene is 8 hours
-1, evaluation result, as shown in table 2 and table 3, is designated as SL-8.
[embodiment 9]
Press each step in embodiment 1, only changing ammonium metawolframate is 163 grams, and the charge capacity of the catalyst oxidation tungsten made is 12%, and the air speed that changes iso-butylene is 15 hours
-1, evaluation result, as shown in table 2 and table 3, is designated as SL-9.
[embodiment 10]
BET analyzes
Sample SL-1～the SL-9 that gets above-mentioned drying carries out low temperature N
2the absorption test, measurement result is as follows:
The BET analytical results of table 1 sample
[comparative example 1]
1 kilogram of 200 purpose chromatographic silica gel and 10 gram sesbania powder are added in stirrer and stir 45 minutes, add 400 gram silicon sol and 163 gram ammonium metawolframates after mediating evenly, the deionized water that simultaneously adds 1 kilogram, kneading, extrusion, drying, later 550 ℃ of lower roastings 4 hours, obtain flaxen catalyzer finished product, the content 12% of Tungsten oxide 99.999, be designated as BJL-1, and its specific surface area is 210 meters
2/ gram.The evaluation of catalyzer is carried out on the olefin metathesis evaluating apparatus, the iso-butylene that raw material is 99.9%.Reaction is to be 400 ℃ in temperature, and pressure is 1MPa, and the air speed of iso-butylene is 4 hours
-1condition under estimated, evaluation result is as shown in table 3.
[comparative example 2]
Press each step Kaolinite Preparation of Catalyst in comparative example 1, be designated as BJL-2, its specific surface area is 205 meters
2/ gram.The air speed that to change temperature of reaction in reaction conditions and be 400 ℃, pressure be 0.1MPa and iso-butylene is 8 hours
-1, evaluation result is as shown in table 3.
[comparative example 3]
Press each step Kaolinite Preparation of Catalyst in comparative example 1, be designated as BJL-4, its specific surface area is 215 meters
2/ gram.The air speed that to change temperature of reaction and be 400 ℃, pressure be 0.5MPa and iso-butylene is 15 hours
-1, evaluation result is as shown in table 3.
Table 2 different loads amount WO
3/ SiO
2the evaluation result of sample under the differential responses condition
Table 312%WO
3/ SiO
2the evaluation result of sample under the differential responses condition
Example and comparative example in his-and-hers watches 3 compare, under identical temperature of reaction, pressure and air speed, because SL-7～9 are different with the specific surface area of BJL-1～3, can find out, the yield of the SL-7 that specific surface area is large～target product tetramethyl-ethylene that 9 reactions obtain is higher, illustrate and adopt high order to count the catalyzer that chromatographic silica gel is done carrier, the high-specific surface area of catalyzer is conducive to being uniformly distributed of catalyst surface Tungsten oxide 99.999, improves the disproportionation activity of catalyzer.
Claims (7)
1. the method for a preparing tetramethylethylene through isobutene metathesis, take iso-butylene as raw material, in temperature of reaction, is 350～450 ℃, and reaction pressure is counted 0～1MPa with absolute pressure, and weight space velocity is 1～20 hour
-1under condition, raw material by beds, generates tetramethyl-ethylene, and 2,3-dimethyl-2-butylene, wherein used catalyst, in parts by weight, comprises following component:
A) 1～30 part of Tungsten oxide 99.999;
B) 70～99 parts of SiO
2carrier, wherein the specific surface area of catalyzer is 250～500 meters
2/ gram;
Described carrier is 700～1000 purpose chromatographic silica gels.
2. the method for preparing tetramethylethylene through isobutene metathesis according to claim 1, is characterized in that temperature of reaction is 370～425 ℃, and reaction pressure is counted 0.2～0.8MPa with absolute pressure, and weight space velocity is 2～15 hours
-1.
3. the method for preparing tetramethylethylene through isobutene metathesis according to claim 2, is characterized in that temperature of reaction is 385～400 ℃, and reaction pressure is 0.4～0.6MPa, and weight space velocity is 4～8 hours
-1.
4. the method for preparing tetramethylethylene through isobutene metathesis according to claim 1, is characterized in that take that parts by weight Tungsten oxide 99.999 consumption is as 2～25 parts.
5. the method for preparing tetramethylethylene through isobutene metathesis according to claim 4, is characterized in that take that parts by weight Tungsten oxide 99.999 consumption is as 4～20 parts.
6. the method for preparing tetramethylethylene through isobutene metathesis according to claim 1, the specific surface area that it is characterized in that catalyzer is 250～400 meters
2/ gram.
7. the method for preparing tetramethylethylene through isobutene metathesis according to claim 1, the specific surface area that it is characterized in that catalyzer is 280～370 meters
2/ gram.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102618782A CN102372575B (en) | 2010-08-23 | 2010-08-23 | Method for preparing tetramethylethylene through isobutene metathesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102618782A CN102372575B (en) | 2010-08-23 | 2010-08-23 | Method for preparing tetramethylethylene through isobutene metathesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102372575A CN102372575A (en) | 2012-03-14 |
| CN102372575B true CN102372575B (en) | 2013-12-18 |
Family
ID=45791865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102618782A Active CN102372575B (en) | 2010-08-23 | 2010-08-23 | Method for preparing tetramethylethylene through isobutene metathesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102372575B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739433B (en) * | 2012-10-17 | 2015-07-08 | 中国石油化工股份有限公司 | Method of preparing tetramethylethylene by olefin metathesis in fluidized bed |
| CN104549225B (en) * | 2013-10-28 | 2017-06-20 | 中国石油化工股份有限公司 | Olefin disproportionation catalyst |
| CN106824169B (en) * | 2015-12-03 | 2019-09-06 | 中国石油化工股份有限公司 | Olefin metathesis catalyst and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030204123A1 (en) * | 1998-03-04 | 2003-10-30 | Catalytic Distillation Technologies | Olefin metathesis |
| CN1516617A (en) * | 2001-06-13 | 2004-07-28 | Abb路慕斯全球股份有限公司 | Catalyst consisting of transition metal supported on high purity silica for metathesis of olefin(s) |
-
2010
- 2010-08-23 CN CN2010102618782A patent/CN102372575B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030204123A1 (en) * | 1998-03-04 | 2003-10-30 | Catalytic Distillation Technologies | Olefin metathesis |
| CN1516617A (en) * | 2001-06-13 | 2004-07-28 | Abb路慕斯全球股份有限公司 | Catalyst consisting of transition metal supported on high purity silica for metathesis of olefin(s) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102372575A (en) | 2012-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102040454B (en) | Method for preparing hexane by disproportionating butylene | |
| CN102372575B (en) | Method for preparing tetramethylethylene through isobutene metathesis | |
| CN102372572B (en) | Method for preparing propylene through C4 disproportionation | |
| CN103772115B (en) | Iso-butylene produces the method for tetramethyl-ethylene | |
| CN102464552B (en) | Method for preparing 2,3-dimethyl-2-butylene through isobutylene disproportionation | |
| CN105582933B (en) | Catalyst for double-bond isomerization | |
| CN103030514B (en) | Method for preparing 2,3-dimethyl-2-butene through isobutene disproportionation | |
| CN102464551B (en) | Method for preparing tetramethyl-ethylene through disproportionated reaction of isobutene | |
| CN105080535B (en) | Catalyst for butylene disproportionation | |
| CN103030513B (en) | Method for preparing hexene by butylene disproportionation reaction | |
| CN104275193B (en) | metathesis catalyst | |
| CN103420774B (en) | For the method for preparing hexane by disproportionating butylene | |
| CN103030507B (en) | Method for producing propylene by virtue of disproportionating of amylene and ethylene | |
| CN104549225B (en) | Olefin disproportionation catalyst | |
| CN103739431B (en) | For the method for ethene and butylene propylene | |
| CN103030506B (en) | Method for producing propylene by virtue of disproportionating of amylene | |
| CN104549351A (en) | Isomerization catalyst | |
| CN105214643B (en) | Catalyst for metathesis reaction | |
| CN104549226B (en) | Catalyst used for olefin disproportionation | |
| CN103772116B (en) | For the method for preparing hexane by disproportionating butylene | |
| CN103739433B (en) | Method of preparing tetramethylethylene by olefin metathesis in fluidized bed | |
| CN103539602B (en) | Method of preparing tetramethyl ethylene by isobutene disproportionation | |
| CN103420772B (en) | For the method for butylene hexene | |
| CN105251529B (en) | A kind of loaded catalyst and preparation method thereof and the synthetic method for being catalyzed long chain alkylphenol | |
| CN103420755B (en) | Method for propylene preparation through butane disproportionation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |