CN1810373A - Catalyst for selective dimerization of isobutene - Google Patents
Catalyst for selective dimerization of isobutene Download PDFInfo
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- CN1810373A CN1810373A CNA2005100236161A CN200510023616A CN1810373A CN 1810373 A CN1810373 A CN 1810373A CN A2005100236161 A CNA2005100236161 A CN A2005100236161A CN 200510023616 A CN200510023616 A CN 200510023616A CN 1810373 A CN1810373 A CN 1810373A
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- catalyst
- isobutene
- phosphoric acid
- selective dimerization
- isooctene
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to one kind of catalyst for selective dimerization of isobutene, and aims at raising both the activity and the oligomer selectivity of catalyst for the selective dimerization so as to raise the isooctane yield. The technological scheme of the present invention is to adopt the catalyst comprising silica carrier with specific surface area of 200-300 sq m/g and pore diameter of 1-100 nm and supported free phosphoric acid accounting for 20-35 wt% in P2O5. The supported catalyst is used in the industrial production of selectively dimereizing mixed C4 olifin to prepare isooctane.
Description
Technical field
The present invention relates to a kind of catalyst that is used for selective dimerization of isobutene.
Background technology
Along with environmental protection requires harsh day by day situation for specification gasoline, the reduction of alkene and arene content in the gasoline, and progressively be limited in interpolation MTBE and other ether compound in the gasoline, world wide faces the problem of octane number deficiency.And alkylate oil is the high-octane rating of the environmental pollution minimum recognized so far, low RVP gasoline component, so the change of specification gasoline has worldwide improved the importance of alkylate oil as the gasoline concoction component.Yet the inherent shortcoming of the alkylation process of liquid acid catalyst has restricted the volume increase significantly of alkylate oil; And the solid acid alkylation processes process studies for a long period of time, though breakthrough has been arranged, commercial Application still has some problems to solve and be perfect.Therefore the nineties later stage, many major companies exploitation or utilize existing oligomerisation and hydrogen addition technology is that raw material obtains with the isooctane by dimerization-hydrogenation with the isobutene is the similar alkylate oil of key component, claims indirect alkylation again.
The industrial catalyst that is used for butene oligomerization mainly contains 3 kinds: cationic ion-exchange resin, solid phosphoric acid catalyst and renewable solid acid catalyst (mainly being silica-alumina and molecular sieve).
C 4 olefin comprises isobutene, butene-1, maleic-2, four kinds of isomers of anti-butene-2, and wherein the isobutene reaction activity is the highest.Selective dimerization of isobutene-the hydrogenation that with the mixed c 4 is raw material can obtain the high-knock rating gasoline component.The oligomerisation reaction activity improves with reaction temperature and catalyst acid intensity, and oligomerization product isooctene selectivity reduces with reaction temperature and the raising of catalyst acid intensity, and the selectivity of isooctene directly influences the octane number of product, and catalyst in the past must be controlled the suitable conversion ratio of isobutene for guaranteeing the isooctene high selectivity.
The EP371938 patent has been introduced a kind of preparation method of phosphoric acid/SiO 2 catalyst, and this catalyst is used for isobutene oligomerisation system gasoline, compares with the conventional solid phosphoric acid catalyst to have intensity and active height, good stability, easily detachable characteristics.Adopting specific area is 52 meters
2/ gram, the aperture is the granular SiO of 60 nanometers
2Be carrier, in phosphoric acid solution, after dipping, the drying,, use phosphoric acid, water or steam moistening again in 350～525 ℃ of roastings.The isobutene oligomerisation result of the catalyst of preparation and industrial traditional catalyst contrasts, and shows and uses SiO
2Be carrier, the yield of oligomerisation gasoline is than the obvious raising of traditional industry catalyst.
Poland's 149574 patents have been introduced a kind of phosphoric acid/SiO
2Catalyst is used for oligomerization of propene and prepares the nonene method, and specific area is 200～300 meters
2/ gram silica-gel carrier is immersed in after preliminary treatment in 60～80% phosphoric acid solutions, and dry back makes catalyst 240 ℃ of roastings.Nonene selectivity 70～75% (weight) when catalyst is used for the propylene trimerization.
Summary of the invention
Technical problem to be solved by this invention be in the past in the selective dimerization of isobutene technology catalyst activity and oligomerization product selectivity to be difficult to take into account be the low problem of isooctene yield, a kind of new solid phosphoric acid catalyst that is used for selective dimerization of isobutene is provided.This catalyst has high conversion simultaneously and high selectivity is the high characteristics of isooctene yield.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of solid phosphoric acid catalyst that is used for selective dimerization of isobutene comprises following component by weight percentage:
A) balance carriers silica; With carry thereon
B) 20～35% with P
2O
5The free phosphoric acid of meter;
Wherein the specific area of carrier silica is 200～300 meters
2/ gram, the aperture is 1～100 nanometer.
In the technique scheme, the free phosphoric acid consumption is with P by weight percentage
2O
5The meter preferable range is 25～30%, and the specific area preferable range of carrier silica is 240～280 meters
2/ gram, the aperture preferable range is 5～20 nanometers.
The Preparation of catalysts method that adopts among the present invention is as follows: before Preparation of Catalyst, and carrier S iO
2Drying is 4～12 hours under 120～170 ℃ of conditions, and vacuum impregnation is carried out with 40～80% phosphoric acid solutions in the cooling back, dip time 12～24 hours, and in 100～120 ℃ of dryings, 350～500 ℃ of roastings obtain intermediate; Double-steeping, drying, roasting make catalyst then.
Catalyst activity evaluation of the present invention is carried out in the fixed bed reactors of laboratory, and reactor is a stainless steel tubular type reactor, 18 * 380 millimeters of size Ф, 25 milliliters of interior loading catalysts.Adopt mixed c 4 as reaction raw materials, concentration of olefin 41.45% (weight), isobutylene concentration 22.50% (weight) wherein, all the other are alkane.40～200 ℃ of reaction temperatures, reaction pressure normal pressure～6.0MPa, liquid volume air speed 0.5～3 hour
-1Under the process conditions, raw material olefin is contacted with catalyst of the present invention olefin oligomerization takes place.Reacted material comprises liquid product and gaseous stream, and by gas-liquid separator, liquid product enters liquid trap, and timing sampling analytical reactions product hydrocarbon composition, gaseous stream are that unreacted tail gas regularly enters online gas-chromatography and analyzes.
Among the present invention because adopt silica supports and carry catalyst weight thereon 20～35% with P
2O
5The free phosphoric acid of meter is a catalyst, and mixed c 4 is 40～200 ℃ of reaction temperatures, reaction pressure normal pressure～6.0MPa, liquid volume air speed 0.5～3 hour
-1Oligomerisation reaction technology under the process conditions is applicable to selective dimerization of isobutene production high-knock rating gasoline component fully, makes the isooctene selectivity reach more than 80%, and isobutene conversion has been obtained technical result preferably more than 90%.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Carrier silica descended dry 8 hours at 150 ℃, cooling naturally.Adding 250 gram concentration in 500 milliliters of conical flasks is the phosphoric acid solution of 50% (weight), adds above-mentioned 100 gram silica-gel carriers, 120 ℃ of dryings of 12 hours rear catalysts of vacuum impregnation 16 hours, 350 ℃ of roastings 4 hours; Flooded 12 hours in 50% (weight) phosphoric acid solution, 120 ℃ were descended dry 16 hours again, and 400 ℃ of roastings make catalyst.Wherein free phosphoric acid is with P
2O
5Count 28.65% (weight), the silica supports specific area is 260 meters
2/ gram, the aperture is 11 nanometers.
Test raw material adopts concentration of olefin 41.45% (weight), the wherein mixed c 4 of isobutylene concentration 22.50% (weight).
Carbon four raw material weights are formed (%)
| Propane | Iso-butane | Normal butane | Butene-1 | Isobutene | Anti-butene-2 | Maleic-2 | Butadiene | Total olefin concentration |
| 0.10 | 53.35 | 5.10 | 12.59 | 22.50 | 4.46 | 1.28 | 0.62 | 41.45 |
According to aforesaid evaluating catalyst process, this catalyst is used for the selective dimerization of isobutene reaction, the evaluation process conditions are: 120 ℃ of reaction temperatures, pressure 4.5MPa, liquid volume air speed 2.0 hours
-1The evaluating catalyst result is: catalyst turned round 1008 hours continuously, and isobutene conversion reaches 95.50%, isooctene selectivity 86.00%, isooctene yield 82.13%.Dead catalyst is pulled down the no coking in back, powder phenomenon-tion, still keeps good profile state.
[embodiment 2]
Method for preparing catalyst and test raw material adopt 65% (weight) phosphorus concentration acid solution with embodiment 1, make the catalyst free phosphoric acid with P
2O
5Count 31.20% (weight), the silica supports specific area is 245 meters
2/ gram, the aperture is 5 nanometers.140 ℃ of reaction temperatures, pressure 5.0MPa, liquid volume air speed 2.5 hours
-1The initial activity evaluation result: isobutene conversion 100%, isooctene average selectivity 80.25%, the isooctene yield reaches 80.25%.
[embodiment 3]
Method for preparing catalyst and test raw material adopt 40% phosphorus concentration acid solution with embodiment 1, make the catalyst free phosphoric acid with P
2O
5Count 25.80% (weight), the silica supports specific area is 280 meters
2/ gram, the aperture is 18 nanometers.100 ℃ of reaction temperatures, pressure 3.5MPa, liquid volume air speed 1.5 hours
-1Initial activity evaluation result: isobutene conversion 100%, isooctene selectivity 82.00%, isooctene yield 82.00%.
[comparative example 1]
Use the Amberlyst-15 resin catalyst, the evaluating apparatus of use embodiment 1 and condition, step are carried out the selective dimerization of isobutene test.
65 ℃ of reaction temperatures, isobutene conversion 100%, isooctene selectivity 52.14%, isooctene yield 52.14%; 45 ℃ of reaction temperatures, isobutene conversion 42.10%, isooctene selectivity 79.28%, isooctene yield 33.38%.
Claims (3)
1, a kind of solid phosphoric acid catalyst that is used for selective dimerization of isobutene comprises following component by weight percentage:
A) balance carriers silica; With carry thereon
B) 20～35% with P
2O
5The free phosphoric acid of meter;
Wherein the specific area of carrier silica is 200～300 meters
2/ gram, the aperture is 1～100 nanometer.
2, the solid phosphoric acid catalyst that is used for selective dimerization of isobutene according to claim 1, the consumption that it is characterized in that free phosphoric acid by weight percentage is with P
2O
5Count 25～30%.
3, the solid phosphoric acid catalyst that is used for selective dimerization of isobutene according to claim 1, the specific area that it is characterized in that carrier silica is 240～280 meters
2/ gram, the aperture is 5～20 nanometers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005100236161A CN1810373A (en) | 2005-01-26 | 2005-01-26 | Catalyst for selective dimerization of isobutene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005100236161A CN1810373A (en) | 2005-01-26 | 2005-01-26 | Catalyst for selective dimerization of isobutene |
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| Publication Number | Publication Date |
|---|---|
| CN1810373A true CN1810373A (en) | 2006-08-02 |
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ID=36843571
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|---|---|---|---|
| CNA2005100236161A Pending CN1810373A (en) | 2005-01-26 | 2005-01-26 | Catalyst for selective dimerization of isobutene |
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|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402540B (en) * | 2008-07-16 | 2012-10-31 | 岳阳桦科化工有限责任公司 | Method for producing isooctene with coproduction of sec-butyl carboxylate with selective superposition of butylene |
| CN107652152A (en) * | 2017-10-24 | 2018-02-02 | 丹东明珠特种树脂有限公司 | Isobutene building-up reactions process of preparing |
| CN107754852A (en) * | 2017-10-24 | 2018-03-06 | 丹东明珠特种树脂有限公司 | The cationic ion-exchange resin modified catalyst and its method of modifying of isobutene building-up reactions |
-
2005
- 2005-01-26 CN CNA2005100236161A patent/CN1810373A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402540B (en) * | 2008-07-16 | 2012-10-31 | 岳阳桦科化工有限责任公司 | Method for producing isooctene with coproduction of sec-butyl carboxylate with selective superposition of butylene |
| CN107652152A (en) * | 2017-10-24 | 2018-02-02 | 丹东明珠特种树脂有限公司 | Isobutene building-up reactions process of preparing |
| CN107754852A (en) * | 2017-10-24 | 2018-03-06 | 丹东明珠特种树脂有限公司 | The cationic ion-exchange resin modified catalyst and its method of modifying of isobutene building-up reactions |
| CN107652152B (en) * | 2017-10-24 | 2020-07-03 | 丹东明珠特种树脂有限公司 | Isobutylene polymerization preparation process |
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