CN1073124A - Propene oligomer catalyst and preparation method thereof - Google Patents
Propene oligomer catalyst and preparation method thereof Download PDFInfo
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- CN1073124A CN1073124A CN91111341A CN91111341A CN1073124A CN 1073124 A CN1073124 A CN 1073124A CN 91111341 A CN91111341 A CN 91111341A CN 91111341 A CN91111341 A CN 91111341A CN 1073124 A CN1073124 A CN 1073124A
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- alumina silicate
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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
A kind of alumina silicate catalyst that is applicable to propylene oligomerization and preparation method thereof.Contain 100-300 gram Na with every liter
2The waterglass of O and every liter contain 100-200 gram Al
2O
3Acidifying aluminum sulfate mix in proportion, and add certain density Fe
2(SO
4)
3, transfer pH to 4-5, be mixed into colloid at 0 ℃, can use through aging, suction filtration, washing, oven dry, roasting, moulding and after with the nitrogen purging.80-110 ℃ of reaction temperatures, reaction pressure 2.0MPa, liquid air speed 1.5h
-1Catalyst life 900kg product oil under the condition/more than the kg catalyst, olefin conversion 85%, three, tetramer selectivity are more than 62%.Catalyst provided by the invention has overcome the easy argillization of phosphoric acid/kieselguhr catalyst, caking stops up the shortcoming of reactor, owing to do not support other composition, prepares simple, cheap.
Description
The present invention relates to a kind of alumina silicate catalyst that comprises silica and aluminium oxide and preparation method thereof.
Propylene oligomerization not only can be produced high quality engine fuel, also can produce to be used for high-performance plasticizer.Surfactant, lube oil additive, the C of field of fine chemical such as polyesters agricultural chemicals
7～C
12Higher alkene.This promotes that for comprehensive utilization petroleum chemical enterprise gas resource the development of fine chemistry industry is significant.
It is at present, industrial that what be widely used in propylene oligomerization is the phosphoric acid/kieselguhr catalyst.This catalyst is phosphoric acid and acid carrier effect generation silicophosphate etc. under reaction condition, makes catalyst argillization, caking stop up reactor, needs often shut-down mediation reactor.According to Industrial and Engineering Chemistry(1933) Vo1.25 No10 report U.S. General Motors research laboratory once studied with alumina silicate and was used for propylene oligomerization as catalyst, obtained C
5～C
23Alkene, but olefin conversion fails to surpass 30%.Also the someone did similar work later on, but all can't be used for industrial production because of olefin conversion is too low.Hydrocarbon Processing60(3) 1981 report french petroleum research institute at the beginning of the eighties are the propylene dimerization catalyst of carrier with the alumina silicate, but three, the selection of tetramer is lower, and price is also more expensive simultaneously.
The phosphoric acid/kieselguhr catalyst that the purpose of this invention is to provide indexs such as a kind of olefin conversion, catalyst life, three, tetramer selectivity and American UOP company is suitable, reaction temperature is low, reaction pressure is little, and does not in use have the propene oligomer catalyst of argillization, agglomeration problems.This Preparation of catalysts method also is provided simultaneously.
Catalyst composition provided by the present invention is: Al
2O
38-30%(wt%), S
iO
270-92%, Fe
2O
30.5-2.5%, Na
2This catalyst of O～0.15%. is at reaction temperature 80-110 ℃, reaction pressure 2.2MPa, liquid air speed 1.5h
-1Can reach following technical indicator under the condition:
Olefin conversion (wt%): 85%
Three, tetramer selectivity (wt%):＞62%
Catalyst life (Kg product oil/kg catalyst):＞900
The preparation method:
Get every liter and contain 100-300gNa
2The waterglass of O and every liter contain 100-200gAl
2O
3Acidifying Al
2(SO
4)
3Solution mixes by a certain percentage, adds 0.5～2.5%(Fe
2O
3Content) Fe
2(SO
4)
3Solution, mixed liquor is in PH=4～5, fully be mixed into colloid under 0 ℃ of condition, and kept 2-3 hour, be warming up to 40-45 ℃ and wore out 12 hours, suction filtration, the back 100 ℃ of oven dry of washing 24 hours, cooling, 800 ℃ ± 20 ℃ roastings 12 hours after the moulding, be heated to 200～400 ℃ before the use gradually, heating begins promptly to feed drying nitrogen and purges, under this temperature, purged 8-10 hour.Nitrogen flow rate is 150-200M
3/ M
3Catalyst hour (normal pressure).Purge used nitrogen, should be earlier with 500 ℃ of baked 5A molecular sieve dryings.
Catalyst provided by the invention, advantage such as it is simple to have a preparation, and raw material is easy to get, and is cheap, and in reaction, do not have the argillization agglomeration problems, the key technical indexes is suitable with American UOP company phosphoric acid/kieselguhr catalyst, price but less than its 1/6.So this catalyst is expected to replace the phosphoric acid/kieselguhr catalyst and is widely used in propylene oligomerization.
Catalyst of the present invention is as follows with used several catalyst technology economic indicator contrast both at home and abroad:
Several catalyst technology economic indicators
Three, the four poly-catalysts selective life-spans of reaction temperature olefin conversion
The catalyst title
(℃) (wt%) (wt%) (kg product oil/kg catalyst)
Uop Inc.
170－220 85 60 900
H
3PO
4/ diatomite
Oil six factories
180－230 76 60 230
H
3PO
4/ diatomite
France's alumina silicate
－ 80 46 880
The carrier catalyst
Catalyst of the present invention
80－110 85 62 ＞900
CLL-3
The catalyst price only is equivalent to the sixth of Uop Inc.'s product.
Example 1
Get 300 milliliters every liter and contain 250 gram Na
2The waterglass of O and 100 milliliters every liter contain 160 gram Al
2O
3Acidified aluminum sulfate solution, add the Fe of 70 milliliters of 0.2M
2(SO
4)
3Solution is transferred PH=4～5, fully is mixed into colloid at 0 ℃, and keeps 2 hours, be warming up to then 40-45 ℃ aging 12 hours, suction filtration, washing, 100 ℃ of oven dry hour, 800 ℃ of calcination activations are 12 hours after the moulding.Purged 8 hours with drying nitrogen at 200-400 ℃ before using.At reaction temperature 80-110 ℃, reaction pressure 2.2MPa air speed 1.5h
-1Under the condition, be raw material reaction with 66% propylene, olefin conversion 73%, three tetramer selectivity 62%.With 99% propylene is raw material reaction, olefin conversion 85%, three, tetramer selectivity 64%.
Example 2
Get 500 milliliters every liter and contain 250 gram Na
2The waterglass of O and 200 milliliters every liter contain 160 gram Al
2O
3Acidified aluminum sulfate solution, add 50 milliliters of 0.2MFe
2(SO
4)
3Solution, at PH=4-5,0 ℃ is mixed into glue, 40-45 ℃ aging 12 hours, suction filtration, washing, 100 ℃ of oven dry 24 hours, 800 ℃ of roastings are 12 hours after the moulding.Purged 8-10 hour with drying nitrogen at 200-400 ℃ before using, at reaction temperature 80-110 ℃, reaction pressure 2.2MPa, air speed 1.5h
-1Under the condition, 99% propylene is a raw material reaction, olefin conversion 86%, three, tetramer selectivity 63%.
Example 3
Get 250 milliliters every liter and contain 250 gram Na
2The waterglass of O and 100 milliliters every liter contain 160 gram Al
2O
3Acidified aluminum sulfate solution, add 20 milliliters of 0.2MFe
2(SO
4)
3Solution, at PH=4-5,0 ℃ is mixed into glue, and 40-45 ℃ was worn out 12 hours.Purged 9 hours with drying nitrogen at 250 ℃ before using.At 100 ℃ of reaction temperatures, reaction pressure 2.2MPa, air speed 1.5h
-1Under the condition, be raw material reaction with 99% propylene, olefin conversion 84%, three, tetramer selectivity 66%.
Claims (4)
1, a kind of preparation method of alumina silicate catalyst gets every liter and contains 100～300gNa
2The waterglass of O and every liter contain 100～200gAl
2O
3Acidifying Al
2(SO
4)
3Solution is in 2.5～3: 1 ratio is mixed, mixed liquor is at PH=4-5, after fully being mixed into colloid under 0 ℃ of condition and keeping 2-3 hour, being warming up to 40-45 ℃ wore out 12 hours, after washing, suction filtration dried 24 hours for 100 ℃, place under 800 ℃ ± 20 ℃ conditions roasting cooling forming after 12 hours, it is characterized in that alumina silicate after the moulding is heated to 200-400 ℃ and feed drying nitrogen and purge gradually.
2, the method for claim 1 is characterized in that: waterglass and Al
2(SO
4)
3Need in the mixed liquor to add to contain Fe
2O
30.5～2.5% Fe
2(SO
4)
3Solution.
3, method as claimed in claim 1 or 2 is characterized in that: the flow velocity that purges nitrogen is 150-200M
3/ M
3Catalyst hour (normal pressure).Purge time is 8-12 hour.
4, a kind of alumina silicate catalyst that is used for propylene oligomerization, composition is:
Al
2O
38-30%（wt%），S
iO
270-92%，Fe
2O
30.5-2.5%，Na
2O0～0.15%。At reaction temperature 80-110 ℃, reaction pressure 2.2MPa, liquid air speed 1.5h
-1Can reach as follows under the condition
Technical indicator: olefin conversion (wt%): 85%
Three, four poly-selectivity (wt%):＞62%
Catalyst life (Kg product oil/kg catalyst):＞900
It is characterized in that: catalyst is by claim 1 or 2 or 3 described method preparations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91111341A CN1037161C (en) | 1991-12-08 | 1991-12-08 | Propene oligomer catalyst and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91111341A CN1037161C (en) | 1991-12-08 | 1991-12-08 | Propene oligomer catalyst and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1073124A true CN1073124A (en) | 1993-06-16 |
| CN1037161C CN1037161C (en) | 1998-01-28 |
Family
ID=4910579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91111341A Expired - Fee Related CN1037161C (en) | 1991-12-08 | 1991-12-08 | Propene oligomer catalyst and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1037161C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067918C (en) * | 1998-04-13 | 2001-07-04 | 中国石油化工总公司 | Solid ziegler catalyst for olefins and preparation thereof |
| CN104324734A (en) * | 2014-09-26 | 2015-02-04 | 沈阳化工大学 | Preparation method of catalyst suitable for synthesizing C8 and C12 through oligomerization of 1-butene |
| CN108246342A (en) * | 2018-01-16 | 2018-07-06 | 西南化工研究设计院有限公司 | A kind of in-situ synthetic method of Ni-based oligomerization of propene molecular sieve catalyst |
-
1991
- 1991-12-08 CN CN91111341A patent/CN1037161C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067918C (en) * | 1998-04-13 | 2001-07-04 | 中国石油化工总公司 | Solid ziegler catalyst for olefins and preparation thereof |
| CN104324734A (en) * | 2014-09-26 | 2015-02-04 | 沈阳化工大学 | Preparation method of catalyst suitable for synthesizing C8 and C12 through oligomerization of 1-butene |
| CN108246342A (en) * | 2018-01-16 | 2018-07-06 | 西南化工研究设计院有限公司 | A kind of in-situ synthetic method of Ni-based oligomerization of propene molecular sieve catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1037161C (en) | 1998-01-28 |
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