CN1088626C - Solid phosphoric acid catalyst for oligomerization of propene - Google Patents
Solid phosphoric acid catalyst for oligomerization of propene Download PDFInfo
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- CN1088626C CN1088626C CN98110858A CN98110858A CN1088626C CN 1088626 C CN1088626 C CN 1088626C CN 98110858 A CN98110858 A CN 98110858A CN 98110858 A CN98110858 A CN 98110858A CN 1088626 C CN1088626 C CN 1088626C
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- catalyst
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- phosphoric acid
- oligomerization
- propene
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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 solid phosphoric acid catalyst for propene oligomerization, which has a composition general formula: ABaSb(P2O5)c(H2O)d, wherein A is Si, B is at least one of Fe, Ni, Cu, Sb, Bi and Al, S is sulfur, the value of a is from 0.01 to 1.0, the value of b is from 0.01 to 1.0, the value of c is from 1.0 to 1.8, and the value of d is from 0.6 to 1.3. The catalyst used for the propene oligomerization reaction has the characteristics of high catalytic activity and high selectivity for dodecylene. The catalyst can be used for industrial production.
Description
The present invention relates to a kind of propene oligomerization solid phosphoric acid catalyst.
As everyone knows, prepare tripolymer and tetrameric exemplary, produce nonene and laurylene by the acidic catalyst oligomerisation by propylene for olefin(e) oligomerization.Be characterized in that technical process is comparatively simple, technology maturation, the difference of synthetic method are to use different catalyst.According to relevant documents and materials, up to now, people produce tripolymer and tetrameric industrial catalyst from propylene, mostly still, continue to use the catalyst of phosphoric acid series, the liquid phosphoric acid catalyst that comprises California Research company, the pyrophosphate copper catalyst of Kellogg company, the phosphoric acid-quartzy catalyst of Standard Oil company etc.In the report most typical catalyst be American UOP company in nineteen thirty-five initiative by the coincide solid phosphoric acid diatomite catalyst of gasoline of oligomerization of propene production.So far oligomerization of propene prepares the technology of the tripolymer (nonene) and the tetramer (laurylene), uses this catalyst mostly, and is described as patents such as USP3112350, BP1181728, Ger offen 2134154, USP3132109.
Now, adopt traditional oligomerization of propene to produce in the technology of nonene, laurylene, it is essential and select long catalyst of high activity, high selectivity, high strength and life-span for use.As previously mentioned, prepare in tripolymer and the tetrameric technology in olefin(e) oligomerization, oligomerization of propene is prepared nonene, laurylene, and employed catalyst also exists shortcomings such as selectivity is low, intensity difference, easily argillization, easily coking, the life-span is short, the product carbon number distribution is wide.In order to improve activity of such catalysts and selectivity, a kind of solid phosphate catalyst that is used for olefin(e) oligomerization is disclosed among the Chinese patent ZL92103504.7 (CN1032121C).It mainly is to be catalyst component with the Si-P-Fe-B system.When this catalyst was used for oligomerization of propene technology, the liquid product of producing was based on nonene.It is about about 56% that its selectivity reaches, and the selectivity of dodecylene reports about about 22% according to the document.Find through experimental verification that above-mentioned reaction result is 200 ℃ of reaction temperatures, keep obtaining under the reactor feed gas water content 1750PPm condition.Because the main active constituent of solid phosphoric acid catalyst is a free phosphorus and in conjunction with attitude phosphorus.Free phosphorus mainly is made up of orthophosphoric acid, pyrophosphoric acid and a small amount of polyphosphoric acids; Mainly form in conjunction with attitude phosphorus by orthophosphoric acid silicon and pyrophosphoric acid silicon.Orthophosphoric acid silicon and pyrophosphoric acid silicon can react under the effect of reaction raw materials steam, cause free phosphorus rising in the catalyst, make catalyst activity higher; The investigation result who obtains is higher; Can make the easy argillization of catalyst simultaneously, shorten the service life of catalyst.The above-mentioned data of announcing in the document are investigated the higher result of result just, and empirical tests allows in unstripped gas under the water content 200PPm condition, and the nonene selectivity is about 54% among the above-mentioned document ZL92103504.7, and the selectivity of dodecylene is lower, is about about 16%.Because laurylene and derivative thereof are the raw materials of producing plasticizer, washing agent and lube oil additive, the selectivity that therefore how to improve dodecylene has become the target of people's pursuits.
To the objective of the invention is the low defective of dodecylene selectivity that exists in the above-mentioned document in order overcoming, a kind of new propene oligomerization solid phosphoric acid catalyst to be provided, this catalyst has high activity, and the dodecylene in the liquid product also has high selectivity simultaneously.
The objective of the invention is to realize by following technical scheme: a kind of propene oligomerization solid phosphoric acid catalyst, its composition contains following general formula:
AB
aS
b(P
2O
5)
c·(H
2O)
d
A is Si in the formula;
B is selected from least a among Fe, Ni, Cu, Sb, Bi or the Al;
S is a sulphur;
Wherein the value of a is 0.01～1.0;
The value of b is 0.01～1.0;
The value of c is 1.0～1.8;
The value of d is 0.6～1.3.
The value preferable range of a is 0.02～0.06 in the technique scheme, and the value optimum range of a is 0.02～0.04; The value preferable range of b is 0.02～0.05; The value preferable range of c is 1.2～1.5; The value preferable range of d is 0.72～1.0.
A introduces with the diatomite form in the technical program, and B introduces with corresponding oxide or corresponding salt form, S can sulfur oxide or the compound mode introduce.
Preparation of catalysts method of the present invention adopts the blending method preparation.Earlier that the solution blending of A component and S component, B component is even, and then with the polyphosphoric acids blend of 80～85% weight percent concentration, the atomic ratio between above-mentioned a, b, c, d is met the requirements.Behind the extruded moulding, earlier 100～250 ℃ of dry down processing 1～10 hour, roasting 1～15 hour under 450～650 ℃ of conditions then adopts the gaseous mixture activation of air-steam to make above-mentioned catalyst again.Air wherein: the mol ratio of water vapour is 0.5～1.5: 1, and the temperature of catalyst activation is 200～400 ℃, and soak time is 3～5 hours.
The solid phosphate catalyst that makes in this way can be used for olefin(e) oligomerization fully and prepares the tripolymer and the tetramer, is specially adapted to oligomerization of propene and prepares nonene, laurylene, can obtain gratifying effect.
For the technology of propylene oligomerization, normally in fixed bed reactors, carry out.Required oligomerisation reaction condition and described in the prior art quite similar, the process conditions that it is general: reaction temperature is that 150～230 ℃, reaction pressure are that 2.0～5.0MPa, liquid volume air speed are 1～3hr
-1, reaction raw materials concentration of olefin be 40～55%, all the other are alkane.Raw material to preparation nonene, laurylene is to use the mixture of propylene and propane.Except these necessary conditions, the researcher generates tripolymer as much as possible for making reaction, suppressing side reaction effectively produces, often adopt catalyst suitably to be diluted with reactor top, or adopt and improve linear speed, reduction reactor inlet temperatures, or reduce all kinds of method such as coolant temperature, also be effectively.
When catalyst of the present invention is used for propylene oligomerization, for obtaining more correct data and prolonging catalyst life, test shows, moisture content in the raw material must be controlled, keep the water content of raw material when entering conversion zone less than 300PPm, at this moment, can correctly demonstrate the high activity and the high selectivity of catalyst of the present invention.The product of reaction gained can directly obtain nonene and laurylene and other fraction through common isolation technics.
The evaluation of catalyst of the present invention is to carry out interior loading catalyst 100ml in internal diameter is the stainless steel tubular type reactor of 25mm.Reaction raw materials consists of propylene 47.6% (wt) and propane 52.4% (wt), liquid volume air speed are 2.0hr
-1, wherein the water content in the raw material is that 200PPm, reaction temperature are that 200 ℃, reaction pressure are that 4.0MPa, reactor product adopt gc analysis, calculates the Carbon balance before and after the reaction simultaneously.
Below in conjunction with embodiment catalyst of the present invention is done further narration, wherein single receipts, the conversion ratio of each product, optionally be defined as follows:
The present invention by add oxide or the salt that is selected from Fe, Ni, Cu, Sb, Bi or Al element in P, Si system, makes catalyst have higher activity based on solid phosphoric acid; In P, Si system, introduce the oxide or the salt of S component, make H
3PO
4/ SiO
2Introduced SO in the structure
4 2-/ SiO
2Structure makes catalyst can improve the selectivity of dodecylene especially effectively, makes whole catalyst not only have high reaction activity and high, and can deepen the degree of depth of propylene oligomerization, improves the selectivity of dodecylene.To the mechanism inventor of this reaction also still be difficult to resolve release clear.
The invention will be further elaborated below by embodiment.[embodiment 1]
The aluminum sulfate solution blend of the diatomite of 210g drying and a certain amount of 13.4% (weight) is even, again the polyphosphoric acid (weight concentration 83.5%) of this material and 140 ℃ was mediated several minutes in kneader, the powder ball material of gained is dry 2hr under 180 ℃, extruded moulding is that diameter is the cylindrical particle of 4 * 6mm, insert that the heating rate with 300 ℃/hr rises to 560 ℃ in the muffle furnace, constant temperature calcining 1.5hr stops heating afterwards, treat that it cools off naturally, take out after 15 hours.The catalyst that roasting is good is packed in the stainless steel tubular type activation tower of φ 45 * 3 * 800mm, and with certain air speed, make bubbling air: the mol ratio of water vapour is 1.2: 1.0, and in 250 ℃ of activation 4hr down, catalyst consists of:
SiS
0.038Al
0.025(P
2O
5)
1.3·(H
2O)
0.8
Adopt aforementioned evaluating catalyst process conditions to investigate, the investigation result is: the propylene conversion per pass is 79%, C
9The alkene selectivity is 59.5%, C
12Alkene selectivity 20.8%, C
9Alkene+C
12Alkene overall selectivity 80.3%.[embodiment 2]
Press the preparation method of embodiment 1, make catalyst and consist of: SiS
0.045Al
0.030(P
2O
5)
1.3(H
2O)
0.8Use is with embodiment 1 investigation condition examination catalyst, and appraisal result is: propylene conversion per pass 79.6%, C
9Alkene selectivity 60.2%, C
12Alkene selectivity 20.5%, C
9Alkene+C
12Alkene overall selectivity 80.7%.[embodiment 3]
Press the preparation method of embodiment 1, replace the aluminum sulfate solution of 13.4% (weight) with the copperas solution of 16% (weight), catalyst consists of: SiS
0.034Fe
0.034(P
2O
5)
1.3(H
2O)
0.8Use is with embodiment 1 investigation condition examination catalyst, and appraisal result is: propylene conversion per pass 79.3%, C
9Alkene selectivity 60.7%, C
12Alkene selectivity 19.3%, C
9Alkene+C
12Alkene overall selectivity 80.0%.[comparative example 1]
Press the catalyst of embodiment 1 in the Chinese patent 92103504.7 (CN1032121C), it consists of Si
1Cu
0.247B
0.8(P
2O
5)
1.45(H
2O)
0.8Employing is with the embodiment of the invention 1 investigation condition examination catalyst, and its result is: propylene conversion per pass 77.2%, C
9Alkene selectivity 54.4%, C
12Alkene selectivity 16.3%, C
9Alkene+C
12Alkene overall selectivity 70.7%.
Claims (5)
1, a kind of propene oligomerization solid phosphoric acid catalyst, its composition contains following general formula:
AB
aS
b(P
2O
5)
c·(H
2O)
d
A is Si in the formula;
B is selected from least a among Fe, Ni, Cu, Sb, Bi or the Al;
S is a sulphur;
Wherein the value of a is 0.01～1.0;
The value of b is 0.01～1.0;
The value of c is 1.0～1.8;
The value of d is 0.6～1.3.
2, according to the described propene oligomerization solid phosphoric acid catalyst of claim 1, the value that it is characterized in that a is 0.02～0.06.
3, according to the described propene oligomerization solid phosphoric acid catalyst of claim 2, the value that it is characterized in that a is 0.02～0.04.
4, according to the described propene oligomerization solid phosphoric acid catalyst of claim 1, the value that it is characterized in that b is 0.02～0.05.
5, according to the described propene oligomerization solid phosphoric acid catalyst of claim 1, the value that it is characterized in that c is 1.2～1.5; The value of d is 0.72～1.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110858A CN1088626C (en) | 1998-05-20 | 1998-05-20 | Solid phosphoric acid catalyst for oligomerization of propene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110858A CN1088626C (en) | 1998-05-20 | 1998-05-20 | Solid phosphoric acid catalyst for oligomerization of propene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1235874A CN1235874A (en) | 1999-11-24 |
| CN1088626C true CN1088626C (en) | 2002-08-07 |
Family
ID=5220874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110858A Expired - Lifetime CN1088626C (en) | 1998-05-20 | 1998-05-20 | Solid phosphoric acid catalyst for oligomerization of propene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1088626C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110935434A (en) * | 2019-12-09 | 2020-03-31 | 北京石油化工学院 | Catalyst for preparing nonene and dodecene by propylene oligomerization and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4334118A (en) * | 1981-06-01 | 1982-06-08 | Chevron Research | Solid phosphoric acid catalyzed olefin polymerization process |
| US4946815A (en) * | 1988-12-23 | 1990-08-07 | Uop | Solid phosphoric acid catalyst |
| CN1056828A (en) * | 1988-12-29 | 1991-12-11 | 美国环球油品公司 | Porosu solid phosphoric acid catalyst system and application thereof |
| CN1078663A (en) * | 1992-05-15 | 1993-11-24 | 中国石油化工总公司 | The solid phosphate catalyst that is used for olefin(e) oligomerization |
-
1998
- 1998-05-20 CN CN98110858A patent/CN1088626C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4334118A (en) * | 1981-06-01 | 1982-06-08 | Chevron Research | Solid phosphoric acid catalyzed olefin polymerization process |
| US4946815A (en) * | 1988-12-23 | 1990-08-07 | Uop | Solid phosphoric acid catalyst |
| CN1056828A (en) * | 1988-12-29 | 1991-12-11 | 美国环球油品公司 | Porosu solid phosphoric acid catalyst system and application thereof |
| CN1078663A (en) * | 1992-05-15 | 1993-11-24 | 中国石油化工总公司 | The solid phosphate catalyst that is used for olefin(e) oligomerization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1235874A (en) | 1999-11-24 |
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Granted publication date: 20020807 |