CN103539602B - Method of preparing tetramethyl ethylene by isobutene disproportionation - Google Patents
Method of preparing tetramethyl ethylene by isobutene disproportionation Download PDFInfo
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- CN103539602B CN103539602B CN201210239990.5A CN201210239990A CN103539602B CN 103539602 B CN103539602 B CN 103539602B CN 201210239990 A CN201210239990 A CN 201210239990A CN 103539602 B CN103539602 B CN 103539602B
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Abstract
The invention relates to a method of preparing tetramethyl ethylene by isobutene disproportionation, and is mainly used for solving a problem that target product yield is low in the prior art. By adopting a technical scheme that isobutene is used as a material to contact with a catalyst to react in a fixed bed reactor to generate effluent containing tetramethyl ethylene under conditions of reaction temperature of 350 DEG C-450 DEG C, reaction pressure of 0.2MPa-0.8MPa in terms of absolute pressure and weight space velocity of 2-20 per hour, wherein the used catalyst comprises the following components in parts by weight: (a), 5-50 parts of tungsten oxide; (b), 50-95 parts of magnesium oxide carrier, the problem is solved better. The method can be used for industrial production of preparing tetramethyl ethylene by isobutene disproportionation.
Description
Technical field
The present invention relates to a kind of method for 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 synthesis chrysanthemumic acid.Simultaneously again for the production of spices and other agrochemicals etc., especially replace neohexene production tonalide spices with it, there is the advantages such as cost is low, constant product quality.The synthesis of tetramethyl-ethylene is paid attention to very much.The customary preparation methods of current industrial tetramethyl-ethylene closes reaction by propylene dimerization to generate, and the catalyzer of employing is the catalyzer that all matches.By olefin metathesis technology, C4 conversion of olefines low value-added for relative surplus can be become the tetramethyl-ethylene of high added value.
Olefin metathesis (Olefin metathesis) is a kind of conversion of olefines process.By under the effect of transition-metal catalyst (as W, Mo, Re etc.), in alkene C=C double bond fracture and again formed, thus new olefin product can be obtained.We can represent the dismutation of alkene simply from following reaction formula:
R in reaction formula
1, R
2, R
3, R
4represent different alkyl or hydrogen atom respectively.If wherein the disproportionation reaction (such as formula 1) of same alkene is called self disproportionation (self-metathesis); Disproportionation reaction (formula 2) between different alkene is then called cross disproportionation (cross-metathesis).
It is the technology that tetramethyl-ethylene prepared by raw material that US20030204123 reports with iso-butylene.This technology adopt catalyzer be Tungsten oxide 99.999 load on silicon oxide, temperature of reaction is 343 DEG C, and reaction pressure is 5bar.The selectivity of the evaluating catalyst result display tetramethyl-ethylene prepared by patented method is 42%, and yield is 8%.
When for preparing tetramethylethylene through isobutene metathesis, all there is the problem that target product yield is low in the method in above document.
Summary of the invention
Technical problem to be solved by this invention is the problem that the target product yield that exists in prior art is low, provides a kind of method of new preparing tetramethylethylene through isobutene metathesis.When the method is used for preparing tetramethylethylene through isobutene metathesis reaction, there is the advantage that target product yield is 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 for preparing tetramethylethylene through isobutene metathesis, take iso-butylene as raw material, in fixed-bed reactor, temperature of reaction is 350 ~ 450 DEG C, reaction pressure counts 0.2 ~ 0.8MPa with absolute pressure, and weight space velocity is 2 ~ 20 hours
-1under condition, raw material and catalyst exposure reaction generate the effluent containing tetramethyl-ethylene, and wherein used catalyst is with weight parts, comprises following component: a) Tungsten oxide 99.999 of 5 ~ 50 parts; B) magnesium oxide carrier of 50 ~ 95 parts.
In technique scheme, the preferred version of temperature of reaction is 370 ~ 425 DEG C; Reaction pressure preferred version is 0.4 ~ 0.6MPa; The preferred version of iso-butylene weight space velocity is 4 ~ 10 hours
-1; The consumption preferred version of Tungsten oxide 99.999 is 8 ~ 30% by weight percentage, and more preferably scheme is 10 ~ 20%.
Disproportionation catalyst in the present invention can adopt the method such as dipping, chemisorption, electroless plating, ion-exchange, physical mixed to prepare, preferred version is add magnesium oxide carrier in the aqueous solution containing active ingredient, wherein active ingredient is tungsten source, add field mountain valley with clumps of trees and bamboo powder after stirring for some time, kneading, extrusion obtain finished product.In air atmosphere, roasting obtains catalyzer after drying, and the temperature of roasting is 500 ~ 700 DEG C, and roasting time is 2 ~ 8 hours.
In the present invention during tungsten source, can be the one in wolframic acid, sodium wolframate, ammonium tungstate, ammonium metawolframate, good tungsten source is ammonium metawolframate.
Catalyzer prepared by technique scheme is for olefin dismutation reaction, and the embodiment of the present invention is that isobutene disproportionation reaction generates tetramethyl-ethylene.Reaction conditions is as follows: in fixed-bed reactor, and temperature of reaction is 350 ~ 450 DEG C, and reaction pressure counts 0.2 ~ 0.8MPa with absolute pressure, and weight space velocity is 2 ~ 20 hours
-1.
The present invention adopts alkaline-earth metal oxide magnesium as the carrier of catalyzer, active centre due to polymerization is strong acid center, therefore by effectively can suppress the polymerization in isobutene disproportionation reaction to the control of alkaline earth metal content, improve selectivity and the yield of target product tetramethyl-ethylene.Be 350 ~ 450 DEG C in temperature of reaction, reaction pressure counts 0.2 ~ 0.8MPa with absolute pressure, and weight space velocity is 2 ~ 20 hours
-1condition under, by catalyzer and iso-butylene contact reacts, its target product tetramethyl-ethylene weight yield can reach 16%, contrast WO
3/ SiO
2the most high energy of its tetramethyl-ethylene yield of catalyzer improves 6%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Take 500 grams of commodity MgO, add 2.5 liters of deionized waters, the white opacity solution obtained is in 80 DEG C of heated and stirred after 5 hours, and moisture in suction filtration solution, product dries 6 hours to obtain magnesium oxide carrier at 120 DEG C.
The carrier magnesium oxide of 200 grams and the sesbania powder of 1% are mixed evenly and put into stirrer, stir and add 19 grams of ammonium metawolframates after 12 minutes, then add 250 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be designated as SL-1.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and calculate by massfraction, raw material is the iso-butylene of 99.7%.Reaction is 350 DEG C in temperature, and pressure counts 0.6MPa with absolute pressure, and the weight space velocity of iso-butylene is 4.8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 2]
Take 500 grams of commodity MgO, add 2 liters of deionized waters, the white opacity solution obtained leaves standstill 2 hours in 60 DEG C of heated and stirred after 4 hours, moisture in suction filtration solution, and product dries 4 hours to obtain magnesium oxide carrier at 120 DEG C.
The carrier magnesium oxide of 200 grams and the sesbania powder of 1% are mixed evenly and put into stirrer, stir and add 24 grams of ammonium metawolframates after 30 minutes, then add 150 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be designated as SL-2.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and reaction is 400 DEG C in temperature, and pressure counts 0.2MPa with absolute pressure, and the weight space velocity of iso-butylene is 10 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 3]
Take 500 grams of commodity MgO, add 1.5 liters of deionized waters, the white opacity solution obtained leaves standstill 2 hours in 100 DEG C of heated and stirred after 2 hours, moisture in suction filtration solution, and product dries 8 hours to obtain magnesium oxide carrier at 100 DEG C.
The carrier magnesium oxide of 200 grams and the sesbania powder of 1% are mixed evenly and put into stirrer, stir and add 48 grams of ammonium metawolframates after 20 minutes, then add 180 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be designated as SL-3.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and reaction is 370 DEG C in temperature, and pressure counts 0.8MPa with absolute pressure, and the weight space velocity of iso-butylene is 2 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 4]
By each step in embodiment 1, the content changing active ingredient ammonium metawolframate is 72 grams.Catalyzer is designated as SL-4.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and reaction is 450 DEG C in temperature, and pressure counts 0.4MPa with absolute pressure, and the weight space velocity of iso-butylene is 15 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 5]
By each step in embodiment 1, the content changing active ingredient ammonium metawolframate is 12 grams.Catalyzer is designated as SL-5.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and reaction is 425 DEG C in temperature, and pressure counts 0.5MPa with absolute pressure, and the weight space velocity of iso-butylene is 20 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 6]
By each step in embodiment 1, the content changing active ingredient ammonium metawolframate is 120 grams.Catalyzer is designated as SL-6.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and reaction is 400 DEG C in temperature, and pressure is 0.5MPa, and the weight space velocity of iso-butylene is 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 7]
By each step in embodiment 1, the active ingredient added is 19 grams of ammonium metawolframates and 5 grams of ammonium molybdates, and catalyzer is designated as SL-7.
Appreciation condition is identical with embodiment 1, and evaluation result is as shown in table 1.
[comparative example 1]
The sesbania powder of the Support Silica of 200 grams and 1% is mixed evenly and puts into stirrer, stirs and add 19 grams of ammonium metawolframates after 12 minutes, then add 250 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be designated as BJL-1.
Appreciation condition is with example 1, and evaluation result is as shown in table 2.
[comparative example 2]
The sesbania powder of the Support Silica of 200 grams and 1% is mixed evenly and puts into stirrer, stirs and add 24 grams of ammonium metawolframates after 30 minutes, then add 150 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be denoted as BJL-2.
Appreciation condition is with example 2, and evaluation result is as shown in table 2.
[comparative example 3]
The sesbania powder of the Support Silica of 200 grams and 1% is mixed evenly and puts into stirrer, stirs and add 48 grams of ammonium metawolframates after 20 minutes, then add 180 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be designated as BJL-3.
Appreciation condition is with example 3, and evaluation result is as shown in table 2.
Table 1
| Example | WO 3Content (number) | Temperature of reaction (DEG C) | Reaction pressure (MPa) | Reaction velocity (h -1) | The transformation efficiency (%) of iso-butylene | Tetramethyl-ethylene weight yield (%) |
| SL-1 | 8 | 350 | 0.6 | 4.8 | 61.0 | 16.0 |
| SL-2 | 10 | 400 | 0.2 | 10 | 63.1 | 15.3 |
| SL-3 | 20 | 370 | 0.8 | 2 | 64.7 | 15.8 |
| SL-4 | 30 | 450 | 0.4 | 15 | 60.8 | 15.5 |
| SL-5 | 5 | 425 | 0.5 | 20 | 58.4 | 14.1 |
| SL-6 | 50 | 400 | 0.5 | 8 | 60.1 | 14.5 |
| SL-7 | 8 | 350 | 0.6 | 4.8 | 61.0 | 15.8 |
Table 2
| Example | WO 3Content (number) | Temperature of reaction (DEG C) | Reaction pressure (MPa) | Reaction velocity (h -1) | The transformation efficiency (%) of iso-butylene | Tetramethyl-ethylene weight yield (%) |
| SL-1 | 8 | 350 | 0.6 | 4.8 | 61.0 | 16.0 |
| SL-2 | 10 | 400 | 0.2 | 10 | 63.1 | 15.3 |
| SL-3 | 20 | 370 | 0.8 | 2 | 64.7 | 15.8 |
| BJL-1 | 8 | 350 | 0.6 | 4.8 | 52.2 | 9.1 |
| BJL-2 | 10 | 400 | 0.2 | 10 | 53.5 | 8.4 |
| BJL-3 | 20 | 370 | 0.8 | 2 | 54.0 | 8.8 |
Claims (4)
1. for a method for preparing tetramethylethylene through isobutene metathesis, be raw material with iso-butylene, in fixed-bed reactor, temperature of reaction is 350 ~ 450 DEG C, and reaction pressure counts 0.2 ~ 0.8MPa with absolute pressure, and weight space velocity is 2 ~ 20 hours
-1under condition, raw material and catalyst exposure reaction generate the effluent containing tetramethyl-ethylene, and wherein used catalyst is with weight parts, comprises following component: a) Tungsten oxide 99.999 of 5 ~ 50 parts; B) magnesium oxide carrier of 50 ~ 95 parts.
2. the method for preparing tetramethylethylene through isobutene metathesis according to claim 1, it is characterized in that temperature of reaction is 370 ~ 425 DEG C, reaction pressure counts 0.4 ~ 0.6MPa with absolute pressure, and weight space velocity is 4 ~ 10 hours
-1.
3. the method for preparing tetramethylethylene through isobutene metathesis according to claim 1, is characterized in that catalyzer is 8 ~ 30 parts with the consumption of weight parts Tungsten oxide 99.999.
4. the method for preparing tetramethylethylene through isobutene metathesis according to claim 3, is characterized in that catalyzer is 10 ~ 20 parts with the consumption of weight parts Tungsten oxide 99.999.
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Citations (6)
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| US6130181A (en) * | 1998-08-17 | 2000-10-10 | Basf Aktiengesellschaft | Metathesis catalyst, and its preparation and use |
| CN101428228A (en) * | 2008-09-11 | 2009-05-13 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and method of producing the same |
| CN101687182A (en) * | 2007-07-26 | 2010-03-31 | 三井化学株式会社 | Process for reactivation of metathesis catalysts and process for production of olefins comprising the reactivation |
| CN101992086A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Catalyst for producing alpha, alpha-dimethyl benzyl alcohol by hydrogenation of cumene hydroperoxide and preparation method thereof |
| CN102464551A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing tetramethyl-ethylene through disproportionated reaction of isobutene |
| CN102464552A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing 2,3-dimethyl-2-butylene through isobutylene disproportionation |
-
2012
- 2012-07-12 CN CN201210239990.5A patent/CN103539602B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6130181A (en) * | 1998-08-17 | 2000-10-10 | Basf Aktiengesellschaft | Metathesis catalyst, and its preparation and use |
| CN101687182A (en) * | 2007-07-26 | 2010-03-31 | 三井化学株式会社 | Process for reactivation of metathesis catalysts and process for production of olefins comprising the reactivation |
| CN101428228A (en) * | 2008-09-11 | 2009-05-13 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and method of producing the same |
| CN101992086A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Catalyst for producing alpha, alpha-dimethyl benzyl alcohol by hydrogenation of cumene hydroperoxide and preparation method thereof |
| CN102464551A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing tetramethyl-ethylene through disproportionated reaction of isobutene |
| CN102464552A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for preparing 2,3-dimethyl-2-butylene through isobutylene disproportionation |
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