CN103420758B - Method for preparing propylene from pentene and ethylene - Google Patents
Method for preparing propylene from pentene and ethylene Download PDFInfo
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- CN103420758B CN103420758B CN201210150407.3A CN201210150407A CN103420758B CN 103420758 B CN103420758 B CN 103420758B CN 201210150407 A CN201210150407 A CN 201210150407A CN 103420758 B CN103420758 B CN 103420758B
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- amylene
- ethene
- propylene
- pentene
- catalyzer
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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 a method for preparing propylene from pentene and ethylene, wherein the problem of low pentene conversion rate in the prior art is mainly solved with the present invention. The technical scheme comprises that pentene and ethylene are adopted as raw materials, and pass through a catalyst bed layer at a reaction temperature of 300-400 DEG C under a reaction pressure of 0-3 MPa at a pentene weight space velocity of 1-20 h<-1> to produce propylene, wherein the catalyst comprises, by weight, a) 5-30 parts of at least a metal oxide selected from W, Mo and Re, and b) 70-95 parts of a MSU molecular sieve carrier. With the technical scheme, the problem is well solved, and the method can be used for industrial production of preparation of propylene from pentene and ethylene.
Description
Technical field
The present invention relates to a kind of method of amylene and ethene propylene.
Background technology
Olefin disproportionation is a kind of conversion of olefines process.By under the effect of transition metal compound catalyst, in alkene C=C double bond fracture and again formed, thus obtain new olefin product.As can be represented by the formula olefin disproportionation:
Utilize the disproportionation of amylene, can by relative surplus, C that added value is lower
5olefin feedstock is converted into high added value propylene product, and olefin disproportionation catalyst is the key realizing this technique.
US5898091 and US6166279 reports C
4, C
5olefin treated.Wherein in preparing propylene through olefin disproportionation process, the catalyzer adopted is Re
2o
7/ Al
2o
3, reactor is moving-bed.
US5300718 reports the technique of butene-2 and ethene generation disproportionation reaction propylene, and the catalyzer of use is MgO and WO
3/ SiO
2mixed bed.
CN9721426 reports a kind of preparation method of propylene, and raw materials used is butylene, produces propylene by replacement(metathesis)reaction and isomerization reaction.Wherein 2-amylene and ethene react and generate propylene and 1-butylene under metathesis catalyst exists.
When for amylene and the reaction of ethene propylene, all there is the problem that pentene conversion 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 pentene conversion that exists in prior art is low, provides a kind of method of new amylene and ethene propylene.When the method is used for amylene and the reaction of ethene propylene, there is the advantage that pentene conversion 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 of amylene and ethene propylene, and with amylene and ethene for raw material, be 300 ~ 400 DEG C in temperature of reaction, reaction pressure is 0 ~ 3MPa, and amylene weight space velocity is 1 ~ 20 hour
-1condition under, ethene and amylene generate propylene through beds, and catalyzer used, with weight parts, comprises following component: a) 5 ~ 30 parts are selected from least one metal oxide in W, Mo or Re; B) 70 ~ 95 parts of MSU molecular sieve carriers.
In technique scheme, it is 8 ~ 20 parts with the preferred version of at least one metal oxide consumption in weight parts W, Mo or Re; The preferred version of the specific surface area of catalyzer is 500 ~ 1000 meters
2/ gram, more preferably scheme is 700 ~ 800 meters
2/ gram; The preferred version of amylene weight space velocity is 3 ~ 8 hours
-1; The preferred version of ethene and amylene mol ratio is 5:1 ~ 1, and more preferably scheme is 3:1 ~ 2:1.
The MSU molecular sieve used in the present invention is the mesopore molecular sieve with three-dimensional vermiform pore passage structure, and compared with the one-dimensional channels of MCM-41, it is more conducive to guest molecule at its duct internal diffusion, eliminates diffusional limitation.RO
xthe preparation method of/MSU (R is selected from the one in W, Mo or Re) molecular sieve catalyst is as follows: take octadecyl polyoxyethylene ether (Brij76), heated and stirred makes it dissolve completely in deionized water, obtain settled solution, pH value is regulated with hydrochloric acid, stir 2 ~ 5 hours, add tetraethoxy (TEOS) again, the material proportion (mol ratio) of reactant is: Brij76/H
2o=0.001 ~ 0.002, TEOS/H
2o=0.005 ~ 0.01, H
+/ H2O=0.0001 ~ 0.01, stirs 24 ~ 72 hours, and load in reactor, the crystallization temperature scope in building-up process is 160 ~ 190 DEG C, and crystallization time is 24 ~ 120 hours.Take out, filter, washing, template is removed in roasting, both obtains MSU; The MSU prepared is pulverized and lastly puts into furnace pot, the aqueous solution in tungstenic source is poured into wherein equably, under then furnace pot being placed in infrared lamp, stirring with glass rod and make tungsten ion be uniformly impregnated within MSU surface; At 500 ~ 600 DEG C, roasting 1 ~ 8 hour, obtains pale yellow powder; By pressed powder, fragmentation, be sized to the finished catalyst of required order number.
In above-mentioned preparation method, when R source is tungsten source, can be the one in wolframic acid, sodium wolframate, ammonium tungstate, ammonium metawolframate, good tungsten source is ammonium metawolframate; When R source is molybdenum source, can be the one in molybdic acid, Sodium orthomolybdate, ammonium dimolybdate, ammonium tetramolybdate, Ammonium Heptamolybdate; R source is rhenium source, can be rehenic acid, rehenic acid sodium, rehenic acid ammonium, the one crossed in rehenic acid, ammonium perrhenate.According to consumption, be mixed with rare water and used.System crystallization temperature is preferably at 160 ~ 180 DEG C; The maturing temperature that MSU removes template is 400 ~ 600 DEG C, and preferably at 550 DEG C, roasting time was at 2 ~ 10 hours, preferably at 6 hours, temperature rise rate is 1 DEG C/min, and calcination atmosphere is air, oxygen, nitrogen or argon gas, preferably in air or oxygen atmosphere.ROx/MSU (R is selected from the one in W, Mo or Re) catalyzer calcination atmosphere is air, oxygen, nitrogen or argon gas, preferably in air or oxygen, maturing temperature is 500 ~ 600 DEG C, preferably at 550 DEG C, roasting time is preferably at 4 hours, and temperature rise rate is 1 DEG C/min; Catalyzer after roasting can make the particle of all size on demand, and reasonable size range is 20 ~ 40 orders.
The forming method of catalyzer is as follows: by adding the silicon sol of 2% ~ 20% in the good catalyzer of preparation, add the field mountain valley with clumps of trees and bamboo powder of 0.5% ~ 5% after stirring for some time, kneading, dry, roasting obtained finished product later.
Catalyzer prepared by technique scheme is for olefin dismutation reaction, and the embodiment of the present invention is that amylene and ethene disproportionation reaction generate propylene.Reaction conditions is as follows: in fixed-bed reactor, and the mol ratio of ethene and amylene is 1 ~ 5, and temperature of reaction is 300 ~ 400 DEG C, and reaction pressure is 0 ~ 3MPa, and the mass space velocity of amylene is 1 ~ 20 hour
-1.
In such scheme, amylene raw material can be 1-amylene, 2-amylene or its mixture.
The present invention, by using the carrier of MSU molecular sieve as catalyzer, makes the specific surface area of catalyzer be doubled than conventional catalyst, thus adds the dispersity of active ingredient, improve the reactive behavior of disproportionation catalyst.Be 1 ~ 5 in the mol ratio of ethene and amylene, temperature of reaction is 300 ~ 400 DEG C, and reaction pressure is 0 ~ 3MPa, and amylene mass space velocity is 1 ~ 20 hour
-1under condition, by catalyzer and ethene, amylene contact reacts, the transformation efficiency of its amylene can reach 66%, contrast RO
x/ SiO
2the most high energy of the transformation efficiency of (R is selected from the one in W, Mo or Re) its amylene of catalyzer improves 6%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
WO
xthe synthesis of/MSU
Take 20 grams of octadecyl polyoxyethylene ethers, heated and stirred makes it be dissolved in completely in the deionized water of 370 milliliters, obtains clear soln.Regulate pH value to 3.7 with hydrochloric acid soln, stir 3 hours, then add the tetraethoxy of 16 milliliters, then load in reactor after stirring 48 hours, the crystallization temperature scope in building-up process is 120 DEG C, and crystallization time is 48 hours.Through filtration, washing, drying after taking-up, under air atmosphere, be raised to 550 DEG C with the temperature rise rate of 1 DEG C/min from room temperature, obtain product 550 DEG C of roastings after 3 hours, recording gained crystal at X-ray diffractometer is MSU.
Take ammonium metawolframate 0.63 gram and put into beaker, add 20 grams of deionized waters, after dissolving, pour furnace pot into equably, and under it is placed in infrared lamp, stirs with glass rod and make tungsten ion be uniformly impregnated within 10 grams of MSU surfaces.By adding the silicon sol of 5% in the good catalyzer of preparation, add the field mountain valley with clumps of trees and bamboo powder of 1% after stirring for some time, kneading, dry, roasting obtained finished product later, at 550 DEG C, roasting 4 hours, obtains pale yellow powder; By pressed powder, fragmentation, be sized to 20 ~ 40 object finished catalyst, be designated as WUS-1.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and calculate by massfraction, raw material mainly comprises with weight: the 1-amylene of 20% and the 2-amylene of 80%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, and the mol ratio of ethene and butylene is 3 and 2.4 hours
-1space velocities under evaluate, evaluation result is as shown in table 2.
[embodiment 2]
WO
xthe synthesis of/MSU
By each step in embodiment 1, only changing an ammonium metawolframate is 1.13 grams, and obtained catalyzer is designated as WUS-2, its appreciation condition and result as shown in table 2.
[embodiment 3]
WO
xthe synthesis of/MSU
By each step in embodiment 1, only changing an ammonium metawolframate is 3.01 grams, and obtained catalyzer is designated as WUS-3, its appreciation condition and result as shown in table 2.
[embodiment 4]
WO
xthe synthesis of/MSU
By each step in embodiment 1, only changing an ammonium metawolframate is 1.63 grams, and obtained catalyzer is designated as WUS-4, its appreciation condition and result as shown in table 2.
[embodiment 5]
WO
xthe synthesis of/MSU
By each step in embodiment 1, only changing an ammonium metawolframate is 5.16 grams, and obtained catalyzer is designated as WUS-5, its appreciation condition and result as shown in table 2.
[embodiment 6]
MoO
xthe synthesis of/MSU
By each step in embodiment 1, only changing an ammonium dimolybdate is 1.48 grams, and obtained catalyzer is designated as WUS-6, its appreciation condition and result as shown in table 2.
[embodiment 7]
ReO
xthe synthesis of/MSU
By each step in embodiment 1, only changing a rehenic acid ammonium is 0.85 gram, and obtained catalyzer oxygen is designated as WUS-7, its appreciation condition and result as shown in table 2.
[embodiment 8]
By each step in embodiment 1, the active ingredient added is 0.63 gram of ammonium metawolframate and 0.1 gram of Lithium Oxide 98min.Catalyzer is designated as WUS-8.Appreciation condition is identical with embodiment 1, and evaluation result is as shown in table 2.
[embodiment 9]
The roasting of synthetic sample
Sample WUS-1 ~ 8 of getting above-mentioned drying were placed in tube furnace, with gas space velocity 1000 hours
-1pass into air, rise to 550 DEG C with the temperature rise rate of 1 DEG C/min by room temperature, and under the condition passing into nitrogen, 550 DEG C keep 4 hours.
Sample after roasting carries out low temperature N
2absorption test, measurement result is as follows:
Table 1 RO
xthe BET analytical results of/MSU sample
| Sample | WUS-1 | WUS-2 | WUS-3 | WUS-4 | WUS-5 | WUS-6 | WUS-7 | WUS-8 |
| S BET(rice 2/ gram) | 1050 | 984 | 857 | 744 | 880 | 760 | 820 | 1020 |
[comparative example 1]
Pickling process prepares WO
x/ SiO
2sample
Take 20 grams of silica gel samples (15 order), its specific surface is 350 meters
2/ gram, SiO
2content is 99.9%, separately takes ammonium metawolframate 2.72 grams, adds deionized water 30 milliliters, is under agitation added drop-wise in silica gel sample respectively, leaves standstill and dries, and dries 4 hours at 120 DEG C, to be placed at retort furnace 550 DEG C roasting 6 hours, to obtain sample 12%WO
x/ SiO
2be designated as BJS, its evaluation result is as shown in table 2.
Table 2 evaluating catalyst result
| Example | Active ingredient (number) | Temperature of reaction (DEG C) | Ethene and amylene mol ratio | Reaction pressure (MPa) | Reaction velocity (h -1) | Pentene conversion (%) | Propylene Selectivity (%) |
| WUS-1 | 5 | 300 | 3 | 3 | 2.4 | 66.3 | 57.2 |
| WUS-2 | 8 | 325 | 4 | 1.5 | 8 | 64.7 | 54.7 |
| WUS-3 | 20 | 380 | 5 | 1 | 10 | 64.4 | 55.8 |
| WUS-4 | 12 | 350 | 2 | 2 | 4 | 66.4 | 56.8 |
| WUS-5 | 30 | 400 | 1 | 0.5 | 20 | 63.0 | 54.2 |
| WUS-6 | 12 | 350 | 2 | 2 | 4 | 65.9 | 55.0 |
| WUS-7 | 12 | 350 | 2 | 2 | 4 | 65.5 | 55.3 |
| WUS-8 | 5 | 300 | 3 | 3 | 2.4 | 66.1 | 56.8 |
| BJS | 12 | 350 | 2 | 2 | 4 | 60.5 | 50.4 |
Note: reaction pressure is in absolute pressure.
Claims (6)
1. a method for amylene and ethene propylene, with amylene and ethene for raw material, be 300 ~ 400 DEG C in temperature of reaction, reaction pressure is 0 ~ 3MPa, and amylene weight space velocity is 1 ~ 20 hour
-1condition under, ethene and amylene generate propylene through beds, and catalyzer used, with weight parts, comprises following component: a) 5 ~ 30 parts are selected from least one metal oxide in W, Mo or Re; B) 70 ~ 95 parts of MSU molecular sieve carriers; The specific surface area of catalyzer is 500 ~ 1000 meters
2/ gram.
2. the method for amylene according to claim 1 and ethene propylene, is characterized in that the consumption being selected from least one metal oxide in W, Mo or Re with weight parts is 8 ~ 20 parts.
3. the method for amylene according to claim 1 and ethene propylene, is characterized in that the specific surface area of catalyzer is 700 ~ 800 meters
2/ gram.
4. the method for amylene according to claim 1 and ethene propylene, is characterized in that amylene weight space velocity is 3 ~ 8 hours
-1.
5. the method for amylene according to claim 1 and ethene propylene, is characterized in that the mol ratio of ethene and amylene is 1 ~ 5.
6. the method for ethene and butylene propylene according to claim 5, is characterized in that the mol ratio of ethene and amylene is 2 ~ 3.
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|---|---|---|---|
| CN201210150407.3A CN103420758B (en) | 2012-05-16 | 2012-05-16 | Method for preparing propylene from pentene and ethylene |
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| CN103420758B true CN103420758B (en) | 2015-06-10 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182069A (en) * | 1996-09-27 | 1998-05-20 | 巴斯福股份公司 | Preparation of propene |
| EP1487768B1 (en) * | 2002-03-15 | 2007-09-19 | Institut Francais Du Petrole | Multi-step method of converting a charge containing olefins with four, five or more carbon atoms in order to produce propylene |
| CN101768040A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Method for preparing propylene from butylene and ethylene |
-
2012
- 2012-05-16 CN CN201210150407.3A patent/CN103420758B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182069A (en) * | 1996-09-27 | 1998-05-20 | 巴斯福股份公司 | Preparation of propene |
| EP1487768B1 (en) * | 2002-03-15 | 2007-09-19 | Institut Francais Du Petrole | Multi-step method of converting a charge containing olefins with four, five or more carbon atoms in order to produce propylene |
| CN101768040A (en) * | 2009-01-07 | 2010-07-07 | 中国石油化工股份有限公司 | Method for preparing propylene from butylene and ethylene |
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| CN103420758A (en) | 2013-12-04 |
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