CN102875312B - Method for preparing tetramethylethylene by olefin metathesis in fluidized bed - Google Patents
Method for preparing tetramethylethylene by olefin metathesis in fluidized bed Download PDFInfo
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- CN102875312B CN102875312B CN201110193446.7A CN201110193446A CN102875312B CN 102875312 B CN102875312 B CN 102875312B CN 201110193446 A CN201110193446 A CN 201110193446A CN 102875312 B CN102875312 B CN 102875312B
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Abstract
The invention relates to a method for preparing tetramethylethylene by olefin metathesis in a fluidized bed, mainly solving the problem of rapid coking and deactivation of catalyst and low yield of tetramethylethylene. The method disclosed herein is characterized by using isobutene as a raw material and contacting the raw material with a fluid catalyst to react to generate a flow containing tetramethylethylene under the reaction conditions comprising a reaction temperature of 360-500 DEG C, a reaction pressure being 0-1MPa based on absolute pressure, and a weight hourly space velocity being 1-20h<-1>, and the fluid catalyst used herein is a tungsten-based catalyst. The method disclosed herein well solves the problems and can be applied for the industrial production of preparing hexene by isobutene metathesis.
Description
Technical field
The present invention relates to a kind of method for fluidized-bed olefin metathesis tetramethyl-ethylene processed.
Background technology
Tetramethyl-ethylene, 2,3-dimethyl-2-butylene, 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 replace neohexene production tonalide spices with it simultaneously, there is the advantages such as cost is low, constant product quality.The synthetic of tetramethyl-ethylene paid attention to very much.The conventional preparation method 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 relative surplus can be become to 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 represent simply from following reaction formula the dismutation of alkene:
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 (formula 2) between different alkene is called cross disproportionation (cross-metathesis).
US20030204123 has reported the technology of preparing tetramethyl-ethylene taking iso-butylene 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 DEG C, and reaction pressure is 5bar.The evaluating catalyst result of preparing by patented method shows that the selectivity of tetramethyl-ethylene is 42%, and yield is 8%.
Method in above document, in the time of the reaction for preparing tetramethylethylene through isobutene metathesis, exists and all exists the quick coking and deactivation of catalyzer to make catalyst life short, and the low problem of tetramethyl-ethylene yield.
Summary of the invention
Technical problem to be solved by this invention is in prior art, to exist the quick coking and deactivation of catalyzer to cause work-ing life short, the problem that tetramethyl-ethylene yield is low, a kind of new method for fluidized-bed olefin metathesis tetramethyl-ethylene processed is provided, the method has catalyzer long service life, the advantage that tetramethyl-ethylene yield is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for fluidized-bed olefin metathesis tetramethyl-ethylene processed, taking iso-butylene as raw material, is 360～500 DEG C in temperature of reaction, reaction pressure is counted 0～1MPa with absolute pressure, and weight space velocity is 1～20 hour
-1condition under, fluid catalyst contact reacts in raw material and fluidized-bed generates the logistics containing tetramethyl-ethylene, wherein fluid catalyst used comprises following component by weight percentage:
A) 0.08～20% Tungsten oxide 99.999;
B) 20～80% be selected from least one of MCM series, SBA series, MSU series mesopore molecular sieve carrier;
C) 10～60% be selected from least one binding agent in aluminium colloidal sol, silicon sol or silicon-aluminum sol.
In technique scheme, the preferable range of temperature of reaction is 380～450 DEG C, and the preferable range of reaction pressure is 0.4～0.6MPa, and the preferable range of weight space velocity is 4～8 hours
-1, the preferable range of Tungsten oxide 99.999 consumption is 2～16%; The preferred version of MCM series mesopore molecular sieve is MCM-48; The preferred version of SBA series mesopore molecular sieve is SBA-15; The preferred version of MSU series mesopore molecular sieve is MSU-x; The preferred version of binding agent is silicon sol.
The preparation technology of catalyzer comprises that slurrying, spraying are shaped, roasting three steps.Conventionally first mesopore molecular sieve carrier is added to appropriate deionized water and soak, add active ingredient tungsten source simultaneously, then stir with high-shear making beating, then add the binding agent of required amount.Intensity for catalyzer and performance, the reinforced order of various raw materials changes the difference there is no greatly, thereby can regulate arbitrarily as required reinforced order.Prepared like this slurry is uniform suspension, generally can place 24 hours and not obvious layering.
Conventionally the solid content of slurry is 25～45%, for reducing evaporation of water amount, reduces energy consumption, and solid content should be tried one's best high.Slurry is under 600 DEG C of inlet temperatures, 350 DEG C of conditions of outlet, and spray drying granulation moulding, must be containing the microsphere particle of a small amount of water, then 550 DEG C of roastings 4 hours in retort furnace.
The microsphere particle catalyzer making is dried to obtain catalyst sample.Sample, by standard test abrasion index, bulk density and granularity, is tested to its physical and chemical indexes.
Prepared catalyzer is the spheroidal particle of 30～100 microns, and median size is 60 microns, bulk density 0.6～0.8 kg/liter, and abrasion index is 0.5～0.7% hour
-1.
In the present invention, tungsten source can be the one in wolframic acid, sodium wolframate, ammonium tungstate, ammonium metawolframate, and tungsten source is ammonium metawolframate preferably.
Mesoporous material has a kind of type material of nano level homogeneous pore passage structure and bigger serface, is a kind of good support of the catalyst, by load or direct synthesizing active ingredient being introduced to mesoporous carrier, can provide catalyzed reaction needed active sites.Compared with conventional carrier, the active ingredient dispersity on mesoporous material is better, and reactant is more abundant with contacting of active centre, is especially applicable to the reaction system of large flow, high-speed.
Catalyzer prepared by technique scheme is for fluidized-bed olefin dismutation reaction, and the embodiment of the present invention is that iso-butylene disproportionation generates tetramethyl-ethylene.Reaction conditions is as follows: in fluidized bed reactor, temperature of reaction is 360～500 DEG C, and reaction pressure is counted 0～1MPa with absolute pressure, and the mass space velocity of iso-butylene is 1～20 hour
-1.
The present invention is by adopting the molecular sieve carrier of high-ratio surface, and mesopore molecular sieve aperture is 2.7～6.4 nanometers, and specific surface area is 600～1250 meters
2/ gram, improve the dispersity of Tungsten oxide 99.999 at carrier, make the catalyzer of preparation there is higher reactive behavior and tetramethyl-ethylene selectivity, ensure the good physical strength of catalyzer simultaneously.The present invention adopts fluid catalyst as catalysts, in reaction, amount of heat can be withdrawn to reactor, has improved the work-ing life of catalyzer.Adopt method of the present invention, in fluidized-bed reactor, temperature of reaction is 360～500 DEG C, and reaction pressure is counted 0～1MPa with absolute pressure, and the weight space velocity of iso-butylene is 1～20 hour
-1under condition, by catalyzer and reaction raw materials contact reacts, the transformation efficiency of its iso-butylene can reach 27%, the weight yield of tetramethyl-ethylene can reach 17%, higher by 8% than react the yield obtaining with fixed bed catalyst, the life-span of catalyzer can reach 800 hours, and the life-span of fixed bed catalyst is only 400 hours, life nearly one times, obtained technique effect preferably.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Produce MCM-48 mesopore molecular sieve by ordinary method, aperture is 3.4 nanometers, and specific surface area is 1213 meters
2/ gram.
1 kilogram of MCM-48 is added in 2 kilograms of deionized waters and soaked 10 minutes, pull an oar and add containing 200 grams of 63 grams of ammonium metatungstate solutions after 10 minutes, finally add 200 grams of silicon sol (silica content 40%) making beating 15 minutes, obtain the slurry of 40% solid content.This slurry, 600 DEG C of import air temperatures, is gone out to 350 DEG C of conditions of one's intention as revealed in what one says and is spray dried to shape, then catalyzer is made in roasting for 4 hours at 550 DEG C of retort furnaces, the median size of catalyzer is 60 microns, the bulk density of detecting catalyst and abrasion index, the results list 1.
30 grams of catalyzer are arranged in the fluidized-bed reactor of Φ 30mm, taking iso-butylene as raw material at air speed WHSV6 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, the results list 2.
[embodiment 2～6]
With the identical preparation process of embodiment 1, only change different components ratio and mesopore molecular sieve, obtain different catalysts, catalyzer median size is all 60 microns, the bulk density of detecting catalyst and abrasion index, the results list 1.
30 grams of catalyzer are arranged in the fluidized-bed reactor of Φ 30mm, taking iso-butylene as raw material at air speed WHSV6 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, the results list 2.
The physical data of table 1 different catalysts
The evaluation result of table 2 different catalysts
| Example | Molecular sieve title | Isobutene conversion (%) | Tetramethyl-ethylene yield (%) | Life-span (h) |
| 1 | MCM-48 | 27.5 | 17.4 | 830 |
| 2 | MCM-41 | 26.3 | 16.7 | 780 |
| 3 | SBA-15 | 25.3 | 16.1 | 750 |
| 4 | SBA-3 | 26.7 | 17.0 | 860 |
| 5 | MSU-x | 25.9 | 15.6 | 820 |
| 6 | MSU-V | 28.1 | 18.2 | 850 |
[embodiment 7～11]
With embodiment 1 catalyzer, change the appraisal result list 3 of different technology conditions.
Catalyst activity appraisal result under table 3 different technology conditions
Note: pressure is in absolute pressure.
[comparative example 1]
Taking 63 grams of ammonium metawolframates adds in 2 kilograms of deionized waters, after being uniformly dissolved, pour 1 kilogram of MCM-48 into, add 200 grams of silicon sol uniform stirring simultaneously, after stirring for some time, add 1% field mountain valley with clumps of trees and bamboo powder, kneading, extrusion, dry after roasting 4 hours at 550 DEG C, obtain catalyzer finished product.
30 grams of catalyzer are arranged in the fixed-bed reactor of Φ 30mm, taking iso-butylene as raw material at air speed WHSV6 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, evaluation result is as shown in table 4.
[comparative example 2]
With the identical preparation process of comparative example 1, change carrier and different components ratio and obtain different catalysts.
30 grams of catalyzer are arranged in the fixed-bed reactor of Φ 30mm, taking iso-butylene as raw material at air speed WHSV6 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, the results list 4.
[comparative example 3]
1 kilogram of conventional silicon oxide is added in 2 kilograms of deionized waters and soaked 10 minutes, pull an oar and add containing 200 grams of 63 grams of ammonium metatungstate solutions after 10 minutes, finally add 200 grams of silicon sol (silica content 40%) making beating 15 minutes, obtain the slurry of 40% solid content.This slurry, 600 DEG C of import air temperatures, is gone out to 350 DEG C of conditions of one's intention as revealed in what one says and is spray dried to shape, then catalyzer is made in roasting for 4 hours at 550 DEG C of retort furnaces, the median size of catalyzer is 60 microns.
30 grams of catalyzer are arranged in the fluidized-bed reactor of Φ 30mm, taking iso-butylene as raw material at air speed WHSV6 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, the results list 4.
[comparative example 4]
With the identical preparation process of comparative example 3, only change different components ratio and obtain different catalysts.
30 grams of catalyzer are arranged in the fluidized-bed reactor of Φ 30mm, taking iso-butylene as raw material at air speed WHSV6 hour
-1, under 400 DEG C and 0.5MPa condition, check and rate catalyst performance, the results list 4.
Table 4 activity rating of catalyst result
Claims (7)
1. for a method for fluidized-bed olefin metathesis tetramethyl-ethylene processed, taking iso-butylene as raw material, be 380～450 DEG C in temperature of reaction, reaction pressure is counted 0.4～0.6MPa with absolute pressure, and weight space velocity is 1～20 hour
-1condition under, fluid catalyst contact reacts in raw material and fluidized-bed generates the logistics containing tetramethyl-ethylene, wherein fluid catalyst used comprises following component by weight percentage:
A) 0.08～20% Tungsten oxide 99.999;
B) 20～80% be selected from least one of MCM series, SBA series, MSU series mesopore molecular sieve carrier;
C) 10～60% be selected from least one binding agent in aluminium colloidal sol, silicon sol or silicon-aluminum sol.
2. the method for fluidized-bed olefin metathesis tetramethyl-ethylene processed according to claim 1, is characterized in that weight space velocity is 4～8 hours
-1
3. the method for fluidized-bed olefin metathesis tetramethyl-ethylene processed according to claim 1, is characterized in that the consumption of Tungsten oxide 99.999 is 2～16% by weight percentage.
4. the method for fluidized-bed olefin metathesis tetramethyl-ethylene processed according to claim 1, it is characterized in that being selected from MCM series mesopore molecular sieve is MCM-48.
5. the method for fluidized-bed olefin metathesis tetramethyl-ethylene processed according to claim 1, it is characterized in that being selected from SBA series mesopore molecular sieve is SBA-15.
6. the method for fluidized-bed olefin metathesis tetramethyl-ethylene processed according to claim 1, it is characterized in that being selected from MSU series mesopore molecular sieve is MSU-x.
7. the method for fluidized-bed olefin metathesis tetramethyl-ethylene processed according to claim 1, is characterized in that binding agent is selected from silicon sol.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660517A (en) * | 1969-11-06 | 1972-05-02 | Phillips Petroleum Co | Conversion of olefins |
| US3729524A (en) * | 1969-11-06 | 1973-04-24 | Phillips Petroleum Co | Conversion of olefins |
| US4542249A (en) * | 1984-05-04 | 1985-09-17 | Phillips Petroleum Company | Olefin conversions and catalysts |
| CN1590354A (en) * | 2003-09-03 | 2005-03-09 | 中国石油化工股份有限公司 | Method of raising butene disproportionation reaction activity |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6583329B1 (en) * | 1998-03-04 | 2003-06-24 | Catalytic Distillation Technologies | Olefin metathesis in a distillation column reactor |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660517A (en) * | 1969-11-06 | 1972-05-02 | Phillips Petroleum Co | Conversion of olefins |
| US3729524A (en) * | 1969-11-06 | 1973-04-24 | Phillips Petroleum Co | Conversion of olefins |
| US4542249A (en) * | 1984-05-04 | 1985-09-17 | Phillips Petroleum Company | Olefin conversions and catalysts |
| CN1590354A (en) * | 2003-09-03 | 2005-03-09 | 中国石油化工股份有限公司 | Method of raising butene disproportionation reaction activity |
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