CN103420758A - Method for preparing propylene from pentene and ethylene - Google Patents
Method for preparing propylene from pentene and ethylene Download PDFInfo
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- CN103420758A CN103420758A CN2012101504073A CN201210150407A CN103420758A CN 103420758 A CN103420758 A CN 103420758A CN 2012101504073 A CN2012101504073 A CN 2012101504073A CN 201210150407 A CN201210150407 A CN 201210150407A CN 103420758 A CN103420758 A CN 103420758A
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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 processed.
Background technology
Olefin disproportionation is a kind of conversion of olefines process.By under the effect of transition metal compound catalyst, the fracture of the two keys of C=C and formation again in alkene, thus obtain new olefin product.As can be represented by the formula olefin disproportionation:
Utilize the disproportionation of amylene, can be by relative surplus, C that added value is lower
5Olefin feedstock is converted into the high added value propylene product, and olefin disproportionation catalyst is the key that realizes this technique.
US5898091 and US6166279 have reported C
4, C
5Olefin treated.Wherein, in the preparing propylene through olefin disproportionation process, the catalyzer adopted is Re
2O
7/ Al
2O
3, reactor is moving-bed.
US5300718 has reported the technique of butene-2 and ethene generation disproportionation reaction propylene processed, and the catalyzer of use is MgO and WO
3/ SiO
2Mixed bed.
CN9721426 has reported a kind of preparation method of propylene, and raw materials used is butylene, by replacement(metathesis)reaction and isomerization reaction, produces propylene.Wherein the 2-amylene reacts and generates propylene and 1-butylene under metathesis catalyst exists with ethene.
, for amylene and ethene propylene reaction processed the time, all there is the problem of amylene low conversion rate in method in above document.
Summary of the invention
Technical problem to be solved by this invention is the problem of the amylene low conversion rate that exists in prior art, and a kind of new amylene and the method for ethene propylene processed are provided.When the method is used for amylene and ethene propylene reaction processed, have advantages of that the amylene transformation efficiency 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 processed, take amylene and ethene as raw material, and in temperature of reaction, be 300～400 ℃, reaction pressure is 0～3MPa, the amylene weight space velocity is 1～20 hour
-1Condition under, ethene and amylene generate propylene through beds, catalyzer used, in parts by weight, 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, the preferred version of at least one metal oxide consumption in parts by weight W, Mo or Re of take is 8～20 parts; 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
-1The 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, with the one-dimensional channels of MCM-41, compares, and it is more conducive to guest molecule at its duct internal diffusion, eliminates diffusional limitation.RO
XThe preparation method of/MSU (R be selected from W, Mo or Re a kind of) molecular sieve catalyst is as follows: take octadecyl polyoxyethylene ether (Brij76), heated and stirred makes it dissolve in deionized water fully, obtain settled solution, regulate pH value with hydrochloric acid, stir 2～5 hours, add tetraethoxy (TEOS), the material proportion of reactant (mol ratio) is: Brij76/H again
2O=0.001～0.002, TEOS/H
2O=0.005～0.01, H
+/ H2O=0.0001～0.01, stir 24～72 hours, and in the reactor of packing into, the crystallization temperature scope in building-up process is 160～190 ℃, and crystallization time is 24～120 hours.Take out, filter, washing, template is removed in roasting, has both obtained MSU; By the MSU the prepared last furnace pot of putting into of pulverizing, the aqueous solution in tungstenic source is poured into wherein equably, then furnace pot is placed under infrared lamp, stir and make tungsten ion be uniformly impregnated within the MSU surface with glass rod; 500～600 ℃ of lower roastings 1～8 hour, obtain pale yellow powder; By pressed powder, fragmentation, be sized to the catalyzer finished product of required order number.
In above-mentioned preparation method, during Wei Wu source, R source, can be a kind of in wolframic acid, sodium wolframate, ammonium tungstate, ammonium metawolframate, the tungsten source is ammonium metawolframate preferably; During Wei Mu source, R source, can be a kind of in molybdic acid, Sodium orthomolybdate, ammonium dimolybdate, ammonium tetramolybdate, Ammonium Heptamolybdate; Wei Lai source, R source, can be rehenic acid, rehenic acid sodium, rehenic acid ammonium, cross a kind of in rehenic acid, ammonium perrhenate.According to consumption, it is mixed with to rare water and uses.The system crystallization temperature is preferably in 160～180 ℃; The maturing temperature that MSU removes template is 400～600 ℃, is preferably in 550 ℃, and roasting time was at 2～10 hours, be preferably in 6 hours, temperature rise rate is 1 ℃/minute, and calcination atmosphere is air, oxygen, nitrogen or argon gas, is preferably in air or oxygen atmosphere.ROx/MSU (R be selected from W, Mo or Re a kind of) catalyzer calcination atmosphere is air, oxygen, nitrogen or argon gas, be preferably in air or oxygen, maturing temperature is 500～600 ℃, is preferably in 550 ℃, roasting time is preferably in 4 hours, and temperature rise rate is 1 ℃/minute; Catalyzer after roasting can be made the particle of all size on demand, and reasonable size range is 20～40 orders.
The forming method of catalyzer is as follows: by the silicon sol that adds 2%～20% in the good catalyzer of preparation, add 0.5%～5% field mountain valley with clumps of trees and bamboo powder after stirring for some time, kneading, drying, roasting make 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, the mol ratio of ethene and amylene is 1～5, and temperature of reaction is 300～400 ℃, and reaction pressure is 0～3MPa, and the mass space velocity of amylene is 1～20 hour
-1.
In such scheme, the amylene raw material can be 1-amylene, 2-amylene or its mixture.
The present invention, by the carrier using the MSU molecular sieve as catalyzer, makes the specific surface area of catalyzer be doubled than conventional catalyst, thereby has increased the dispersity of active ingredient, has improved the reactive behavior of disproportionation catalyst.Mol ratio at ethene and amylene is 1～5, and temperature of reaction is 300～400 ℃, and reaction pressure is 0～3MPa, and the 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 high energy of the transformation efficiency of (R be selected from W, Mo or Re a kind of) its amylene of catalyzer improves 6%, has obtained technique effect preferably.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
WO
X/ MSU's is synthetic
Take 20 gram octadecyl polyoxyethylene ethers, heated and stirred makes, in its deionized water that is dissolved in 370 milliliters fully, to obtain clear soln.Regulate pH value to 3.7 with hydrochloric acid soln, stir 3 hours, then add the tetraethoxy of 16 milliliters, then stir after 48 hours in the reactor of packing into, the crystallization temperature scope in building-up process is 120 ℃, and crystallization time is 48 hours.After taking-up, through filtration, washing, drying, the temperature rise rate with 1 ℃/minute under air atmosphere is raised to 550 ℃ from room temperature, 550 ℃ of roastings, after 3 hours, obtains product, and recording the gained crystal at X-ray diffractometer is MSU.
Take ammonium metawolframate 0.63 gram and put into beaker, add 20 gram deionized waters, pour equably furnace pot after dissolving into, and it is placed under infrared lamp, with glass rod, stir and make tungsten ion be uniformly impregnated within 10 gram MSU surfaces.By the silicon sol that adds 5% in the good catalyzer of preparation, add 1% field mountain valley with clumps of trees and bamboo powder after stirring for some time, kneading, drying, roasting make finished product later, 550 ℃ of lower roastings 4 hours, obtain pale yellow powder; By pressed powder, fragmentation, be sized to 20～40 purpose catalyzer finished products, be designated as WUS-1.
The evaluation of catalyzer is carried out on the olefin metathesis evaluating apparatus, presses massfraction and calculates, and raw material mainly comprises in weight percentage: 20% 1-amylene and 80% 2-amylene.Reaction is to be 300 ℃ in temperature, and pressure is 3MPa, and the mol ratio of ethene and butylene is 3 and 2.4 hours
-1The air speed condition under estimated, evaluation result is as shown in table 2.
[embodiment 2]
WO
X/ MSU's is synthetic
Press each step in embodiment 1, only changing ammonium metawolframate is 1.13 grams, and the catalyzer made is designated as WUS-2, and its appreciation condition and result are as shown in table 2.
[embodiment 3]
WO
X/ MSU's is synthetic
Press each step in embodiment 1, only changing ammonium metawolframate is 3.01 grams, and the catalyzer made is designated as WUS-3, and its appreciation condition and result are as shown in table 2.
[embodiment 4]
WO
X/ MSU's is synthetic
Press each step in embodiment 1, only changing ammonium metawolframate is 1.63 grams, and the catalyzer made is designated as WUS-4, and its appreciation condition and result are as shown in table 2.
[embodiment 5]
WO
X/ MSU's is synthetic
Press each step in embodiment 1, only changing ammonium metawolframate is 5.16 grams, and the catalyzer made is designated as WUS-5, and its appreciation condition and result are as shown in table 2.
[embodiment 6]
MoO
X/ MSU's is synthetic
Press each step in embodiment 1, only changing ammonium dimolybdate is 1.48 grams, and the catalyzer made is designated as WUS-6, and its appreciation condition and result are as shown in table 2.
[embodiment 7]
ReO
X/ MSU's is synthetic
Press each step in embodiment 1, only changing the rehenic acid ammonium is 0.85 gram, and the catalyzer oxygen made is designated as WUS-7, and its appreciation condition and result are as shown in table 2.
[embodiment 8]
Press each step in embodiment 1, the active ingredient added is 0.63 gram ammonium metawolframate and 0.1 gram 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
Get the sample WUS-1 of above-mentioned drying～8 and be placed in tube furnace, with gas space velocity 1000 hours
-1Pass into air, with the temperature rise rate of 1 ℃/minute, by room temperature, rise to 550 ℃, and passing under the condition of nitrogen, 550 ℃ keep 4 hours.
Sample after roasting carries out low temperature N
2The absorption 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 gram 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 30 milliliters of deionized waters, under agitation is added drop-wise to respectively in the silica gel sample, and standing drying, dry 4 hours at 120 ℃, is placed in 550 ℃ of lower roastings of retort furnace 6 hours, obtains 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 (umber) | Temperature of reaction (℃) | Ethene and amylene mol ratio | Reaction pressure (MPa) | Reaction velocity (h -1) | Amylene transformation efficiency (%) | 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 |
Annotate: reaction pressure is in absolute pressure.
Claims (7)
1. the method for an amylene and ethene propylene processed, take amylene and ethene as raw material, in temperature of reaction, is 300～400 ℃, and reaction pressure is 0～3MPa, and the amylene weight space velocity is 1～20 hour
-1Condition under, ethene and amylene generate propylene through beds, catalyzer used, in parts by weight, 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.
2. the method for amylene according to claim 1 and ethene propylene processed, is characterized in that take that the consumption that parts by weight are selected from least one metal oxide in W, Mo or Re is 8～20 parts.
3. the method for amylene according to claim 1 and ethene propylene processed, the specific surface area that it is characterized in that catalyzer is 500～1000 meters
2/ gram.
4. the method for amylene according to claim 3 and ethene propylene processed, the specific surface area that it is characterized in that catalyzer is 700～800 meters
2/ gram.
5. the method for amylene according to claim 1 and ethene propylene processed, is characterized in that the amylene weight space velocity is 3～8 hours
-1.
6. the method for amylene according to claim 1 and ethene propylene processed, the mol ratio that it is characterized in that ethene and amylene is 1～5.
7. the method for ethene and butylene propylene processed according to claim 8, the mol ratio that it is characterized in that 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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|---|---|---|---|
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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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