CN1230463A - Solid superstrong acid catalyst for alkylation of isobutane and butene - Google Patents
Solid superstrong acid catalyst for alkylation of isobutane and butene Download PDFInfo
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- CN1230463A CN1230463A CN 98116429 CN98116429A CN1230463A CN 1230463 A CN1230463 A CN 1230463A CN 98116429 CN98116429 CN 98116429 CN 98116429 A CN98116429 A CN 98116429A CN 1230463 A CN1230463 A CN 1230463A
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- catalyst
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- butene
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- alkylate oil
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Abstract
The catalyst consists of the oxide of group IV element e.q. TiO2, ZrO2 and HfO2 as carrier; and the oxide of group VI element, e. q. Cr2O3, MoO3 and WO3 as the first cocatalyst. By adding group VIII element as the second cocatalyst, the strength of the acid and the yield of alkylated product are further raised. The catalyst has one activity 4-5 times higher than that of available solid strong acid SO4(2-)/ZrO2 catalyst. The C8 saturated hydrocarbon content in the product is 75%, greater than that of available similar catalyst.
Description
The invention belongs to iso-butane and butene alkylated a kind of novel solid super-strong acid catalyst.
Along with the development of Modern Traffic cause, unleaded, the no aromatic hydrocarbons of internal combustion engine Fuel Demand and fuel mass, no alkene are required more and more higher, the output of whole world gasoline and additive thereof is the highest in all chemicals.Obtain this gasoline because it has the octane number height so that iso-butane and butene alkylated method are synthetic, the octane susceptibility is low, no aromatic component, olefin(e) centent is very low, the burning back is little to the pollution of environment, the not high series of advantages of Reid vapour pressure (RVP), thereby be a kind of high-quality engine fuel and can be used as the gasoline concoction composition that obtains by petroleum refining.According to external report, the content of alkylate oil reaches 13% in the gasoline that the U.S. uses.
1940's has successively invented sulfuric acid and hydrofluoric acid is the method for catalyst iso-butane and butene alkylated synthetic gasoline, existing more than 70 cover sulfuric acid process devices in the whole world and more than 100 cover hydrofluoric acid subtraction units are produced this gasoline at present, amount to and year to produce an alkylate oil and reach more than 2,000 ten thousand tons, estimates 1998 will be with the speed increase of 10-35%.Sulfuric acid process is a catalyst with 98% sulfuric acid, the hydrofluoric acid method is a catalyst with 96% hydrofluoric acid, these two kinds of acid all have severe corrosive, easily cause severe contamination to environment, harm humans health, particularly the sour treatment of wastes produced in the sulfuric acid process is subjected to the environment aspect and more and more pays close attention to, and the liquid hydrogen fluoric acid is on record for healthy potential harm, along with improving constantly and possible juristic act that environment and secure context are paid close attention to, these two kinds traditional handicrafts of producing gasoline alkylate have been faced with harsh examination.
Recently during the last ten years, the various countries scientist is exploring new solid acid catalyst to replace this two kinds of liquid catalysts.Wherein used various molecular sieves (A.Corma, A.Martinez, C.Martinez, Catal.Lett 28 187-201 1994), super acids (T.Hosei, T.Okada, S.Nojima, T.Imia, JPN, Patent 01,245,853; 01,245,854 1989); Ion exchange resin, the BF3 of appendix, SbF5 (A.Corma, A.Martinez, Catal.Rev-Sa.Eng35 (4) 483-570 1993) solid super acid catalyst such as, these researchs are not success so far, and this is because wherein some catalyst needs higher temperature, the side reaction of alkene oligomerization will take place like this, produce macromolecule product, make catalyst junction charcoal and inactivation, some then in use active constituent be easy to run off.With regard to the present also dissatisfied alkylation catalyst that can replace sulfuric acid, hydrofluoric acid (National Research Coucil ofthe Uniti States, Catalysis ofLooks tothefuture, the catalysis prospect, BJ University Press P144,1993), the catalyst of therefore seeking new synthesizing alkylated gasoline has been regarded as one of problem to be solved of several urgency in a global difficult problem and the catalyticing research field.
The purpose of this invention is to provide a kind of new iso-butane and the alkylating solid super acid catalyst of butene-2.
By the research to alkylated reaction mechanism, course of reaction is as follows on the basis of having summed up lot of documents and experimental studies results:
Can assert that catalyst should exist B-acid and L-acid simultaneously in reaction, composition has proton H
+With negative hydrogen ion H
-The dual-use function that shifts.Thereby abandoned the usual system SO that uses in the document
4 2-/ MO
2(M=Fe, Ti, Zr, K.Arata, Appl, Catal, A.General 146 3-32 (1996)) use the oxide of six family's elements instead, mainly are the oxides for carrier and column IV element such as Ti, Zr, Hf, mainly are Cr
2O
3, MoO
3, WO
3Be combined into the super acids of a new generation.And on this super acids, add eight family's metal and processing, to strengthen the transfer velocity of negative hydrogen ion in the reaction, improve the yield of alkylate.
Catalyst provided by the invention is with four family's metal Ti, Zr, the salt of Hf, ZrOCl
2By dripping NH
4OH, hydroxide is made as carrier in pH=9～10, adds 12-21% six family metal oxide MoO with infusion process
3Or WO
3Make solid super-strong acid as first auxiliary agent, introduce 0.25～2.0% transition metal Pt then with infusion process, Co, Fe, Mn, Ni, after the 873K-1073K roasting make.Catalyst in reaction temperature is＜373K, pressure 2.0～3.0MP, and alkane/alkene is than 10～20 and air speed 2-4h
-1Condition under the catalyst activity represented with the alkylate oil yield be 0.18-0.45g, C
4 =Conversion ratio reaches 60-80%, C in the alkylate oil
8Saturated hydrocarbon content＞65%.Ratio is by SO
4 2-/ ZrO
2The activity of the usual solid super-strong acid of forming is high approximately 4～5 times, and the activity after adding different eight family's elements between＜2.0% is significantly improved, and following bioactive sequence: Pt＞Co＞Fe＞Mn＞Ni is arranged.
The catalyst that makes by the present invention is compared the alkylate yield under the same conditions and generally can be improved 4～5 times, C in the product with catalyst of the same type
8Saturated hydrocarbon content accounts for 75%, greater than the literature value of catalyst of the same type.
Embodiment 1:
With ZrOCl
28H
2O is in the aqueous solution (0.4mol/l) made of raw material, splashes into 28%NH
4OH solution, control pH value 9～10 is made the zirconium hydroxide colloid.Products therefrom 1mol/l H behind the dry 3h of 393K
2SO
4Flooded the H that elimination is unnecessary 1 hour
2SO
4, product is made super acids SO in 923K roasting 6h
4 2-/ ZrO
2With the product internal diameter of packing into is in the stainless steel reactor of 6m/m, behind 573K bubbling air activation 4h, cools the temperature to 343K.At pressure 0.8MP, alkane/alkene ratio～10, air speed 4h
-1Condition under react, behind the 4h alkylate oil 0.18g, C
4 =Conversion ratio 7.7%, C in the product
5-7Content is 12.1%, C
8～74.1%,＞C
9Content is 13.9%.Embodiment 2:
The SO that makes by embodiment 1
4 2-/ ZrO
2Super acids is 2.0% H with Pt content
2PtCl
6XH
2The O solution impregnation in the reactor of packing into, flows reduction 3h with the hydrogen (He balance) that contains 10% under the constant temperature of 623K after the 393K drying.Cool the temperature to behind the 343K under the condition identical and react with embodiment 1.After the 4h reaction, get alkylate oil 0.42g, butene conversion 17.8%, C
5～7Content is 6.0%, C
8～68.2%,＞C
9Content 25.2%.Embodiment 3:
The zirconium hydroxide that is made by embodiment 1 is 15% (NH with W content
4)
3H
5(H
2(WO
4)
6) H
2O solution impregnation product makes super acids WO after the 1073K roasting
3/ ZrO
2Under the condition identical, react with embodiment 1.In the identical time, obtain gasoline alkylate 0.43g, C
4 =Conversion ratio is 18.3%, C in the product
5～7Content 11.6%, C
8～74.9%,＞C
9Content 13.5%.Embodiment 4:
The WO that will make by embodiment 3
3/ ZrO
2Super acidic catalyst is 2% H with Pt content
2PtCl
6XH
2The O solution impregnation, after the 393K drying, pack in the reactor, under the constant temperature of 623K with containing 10% hydrogen stream (He balance) reduction 3h, temperature is dropped to 343K reacts under the condition identical with embodiment 1, after the 4h reaction, get alkylate oil 1.4g, butene conversion 60.0%, C in the alkylate oil
5～7Account for 12.1%, C
8～74.3%,＞C
9Account for 13.6%.Embodiment 5:
The Pt-WO that will make by embodiment 4
3/ ZrO
2Super acidic catalyst after the processing identical with embodiment 4, in reaction temperature 373K, pressure 20 atmospheric pressure, iso-butane/butylene=26.3, air speed 4h
-1Condition under react 4h and obtain alkylate oil 2.67g, butene conversion 80.0%, C in the alkylate oil
5～7Account for 10.7%, C
8～66.8%,＞C
9Account for 20.0%.Embodiment 6:
Pt-WO among the embodiment 4
3/ ZrO
2It is that the metal ion aqueous solution such as 2.0% cobalt nitrate, ferric nitrate, manganese nitrate, nickel nitrate replace H that super acidic catalyst is used metal ion content instead
2PtCl
6XH
2O dipping, with embodiment 4 identical conditions under carry out activity test.Get following bioactive sequence: Pt＞Co＞Fe＞Mn＞Ni, product distributes basic identical in the alkylate oil.
Claims (3)
1. an iso-butane and butene alkylated solid super acid catalyst is characterized in that catalyst system is with four family's metal Ti, Zr, the salt of Hf, ZrOCl
2By dripping NH
4OH, hydroxide is made as carrier in pH=9～10, adds 12-21% six family metal oxide MoO with infusion process
3Or WO
3Make solid super-strong acid as first auxiliary agent, introduce 0.25～2.0% transition metal Pt then with infusion process, Co, Fe, Mn, Ni, after the 873K-1073K roasting make.
2. catalyst as claimed in claim 1 is characterized in that being＜373K in reaction temperature, pressure 2.0～3.0MP, and alkane/alkene is than 10～20 and air speed 2-4h
-1Condition under the catalyst activity represented with the alkylate oil yield be 0.18-0.45g, C
4 =Conversion ratio reaches 60-80%, C in the alkylate oil
8Saturated hydrocarbon content＞65%.
3. catalyst as claimed in claim 1, the activity that it is characterized in that adding behind difference eight family's elements of＜2.0% (weight %) is significantly improved, and following bioactive sequence: Pt＞Co＞Fe＞Mn＞Ni is arranged.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98116429 CN1230463A (en) | 1998-07-27 | 1998-07-27 | Solid superstrong acid catalyst for alkylation of isobutane and butene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98116429 CN1230463A (en) | 1998-07-27 | 1998-07-27 | Solid superstrong acid catalyst for alkylation of isobutane and butene |
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| Publication Number | Publication Date |
|---|---|
| CN1230463A true CN1230463A (en) | 1999-10-06 |
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ID=5225063
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98116429 Pending CN1230463A (en) | 1998-07-27 | 1998-07-27 | Solid superstrong acid catalyst for alkylation of isobutane and butene |
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|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101543786B (en) * | 2008-03-27 | 2012-05-30 | 中国石油化工股份有限公司 | Magnetic solid acid catalyst and preparation method and application thereof |
| CN111686793A (en) * | 2020-05-28 | 2020-09-22 | 宁夏大学 | Composite catalyst and preparation and application thereof |
| CN112007652A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Solid acid catalyst and application thereof |
-
1998
- 1998-07-27 CN CN 98116429 patent/CN1230463A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101543786B (en) * | 2008-03-27 | 2012-05-30 | 中国石油化工股份有限公司 | Magnetic solid acid catalyst and preparation method and application thereof |
| CN112007652A (en) * | 2019-05-31 | 2020-12-01 | 中国石油化工股份有限公司 | Solid acid catalyst and application thereof |
| CN111686793A (en) * | 2020-05-28 | 2020-09-22 | 宁夏大学 | Composite catalyst and preparation and application thereof |
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