CN100506374C - Olefines double bond isomerizing catalyst and its preparation method - Google Patents
Olefines double bond isomerizing catalyst and its preparation method Download PDFInfo
- Publication number
- CN100506374C CN100506374C CNB2006100299818A CN200610029981A CN100506374C CN 100506374 C CN100506374 C CN 100506374C CN B2006100299818 A CNB2006100299818 A CN B2006100299818A CN 200610029981 A CN200610029981 A CN 200610029981A CN 100506374 C CN100506374 C CN 100506374C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- double bond
- hours
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Abstract
The present invention relates to an olefin isomerization catalyst and a preparation method of the catalyst. The present invention mainly solves the problem that the former similar catalyst has the disadvantages of low specific surface area, little active sites and bad stability. The present invention solves the problem well by adopting a technical proposal that a proper hydroxyl polar solvent is selected; an alkaline earth oxide is hydrated, dried and calcined; the temperature and time are controlled during the course of preparation, and an olefin double-bond isomerization catalyst with larger specific surface area and more active sites is obtained, and which can be used for industrial productions of a dismutation of ethylene and butylene for producing propylene and a butylene double-bond isomerization.
Description
Technical field
The present invention relates to a kind of olefines double bond isomerizing catalyst and preparation method thereof.
Background technology
Double bond isomerization reaction, the transfer of position of double bond in the olefin(e) compound just can be converted into more valuable or less relatively isomers by the alkene that relative worth is lower or superfluous.
At present, market just progressively increases the demand of alhpa olefin, as the 1-butylene, and 1-hexene etc.The production of commercial alhpa olefin is attended by a large amount of isomers usually and produces.With industrial C
4Logistics is an example, and except containing the 1-butylene, the 2-butylene also accounts for significant proportion.By double bond isomerization reaction, the 2-butylene can be converted into the 1-butylene.
On the other hand, in some technology, double bond isomerization reaction will make the boiling point of alkene change, thereby help the separation of product.An example is as C
4In the separation process of hydro carbons,, will make isobutene (boiling point-7 ℃) from C as 1-butylene (boiling point-6 ℃) is converted into 2-butylene (4 ℃ of cis, trans 1 ℃)
4Separation in the logistics becomes simple and easy to do.
In addition, double bond isomerizing catalyst usually makes up to promote disproportionated reaction with disproportionation catalyst.In ethene and preparing propylene by butene disproportionation reaction, the adding of isomerization catalyst can make reactivity be greatly improved simultaneously except the 1-butylene being converted into the required 2-butylene of reaction.
Alkaline earth oxide, magnesia, calcium oxide etc. are reported in the catalytic performance that has excellence in the olefines double bond isomerizing reaction, but under higher reaction temperature, this class catalyst surface can be because reasons such as coking progressively be lost its reactivity.The stability that how to keep this class isomerization catalyst makes it more adapt to industrial application requirements, and the researcher has done a lot of work in this regard.
U.S. Pat 6,875,901B2 points out by adopting the higher magnesia of purity, can make the stability of butylenes double-bond isomerization reaction obtain prolonging.Sulfur content in magnesia is reduced to 74ppm from 2335ppm, and after iron content was reduced to 330ppm from 692ppm, the stability of catalyst extended to 168 hours from 50 hours.
U.S. Pat 4,127,244 have reported a kind of renovation process of magnesia isomerization catalyst.By in regeneration atmosphere, progressively increasing O
2Content, in tail gas, do not have CO
2Produce and feed pure oxygen and continue roasting, the reactivity of catalyst is improved, the catalyst surface carbon distribution reduces simultaneously, and catalyst stability obtains prolonging.
The method of the prolongation double bond isomerizing catalyst stability of above patent report perhaps needs catalyst is further purified, and perhaps needs the pre-treatment program of strict control catalyst, and the alkaline earth oxide specific surface area of catalyst is less simultaneously.
Summary of the invention
Technical problem to be solved by this invention one of is to be little at the alkaline earth oxide specific surface area of catalyst that exists in the prior art, is used for the relatively poor problem of olefines double bond isomerizing reaction stability, and a kind of new olefines double bond isomerizing catalyst is provided; Two of technical problem to be solved by this invention is the preparation methods that do not relate to the bigger serface double bond isomerizing catalyst in the existing machine technology, and a kind of preparation method of new olefines double bond isomerizing catalyst is provided.Have with the olefines double bond isomerizing catalyst of this method preparation that specific area is big, the activated centre is many, be used for olefines double bond isomerizing reaction and butylene, the good characteristics of ethene disproportionation preparation of propene catalytic stability.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of olefines double bond isomerizing catalyst may further comprise the steps successively:
(a) with the alkaline earth oxide being raw material, is the hydration solvent with the polar solvent of hydroxyl, and the weight ratio of raw material and hydration solvent is 1: 1～10, and the mixture of raw material and hydration solvent product of 0.5～24 hour of hydrolysis under 20～100 ℃ of temperature is A;
(b) product A through washing, behind the suction filtration under 60～140 ℃ of temperature dry 4～24 hours catalyst precarsor be B;
(c) catalyst precarsor B is under 300～900 ℃ in temperature, and roasting got required catalyst in 1～10 hour;
Wherein the key component of gained catalyst is an alkaline earth oxide, and its specific area is 100～500 meters
2/ gram.
In the technique scheme, the preferred version of alkaline earth oxide is selected from least a in magnesia, calcium oxide, strontium oxide strontia, barium monoxide or the radium oxide, and its weight content preferable range is greater than 97%; Hydration solvent preferred version is selected from water or contains the lower aliphatic alcohols of 1～4 carbon atom; The weight ratio preferable range of raw material and hydration solvent is 1: 1～6; The hydrolysis temperature preferable range is 50～90 ℃, and the hydrolysis time preferable range is 2～10 hours; The baking temperature preferable range is 60～120 ℃, and drying time, preferable range was 6～15 hours; The sintering temperature preferable range is 400～650 ℃, and the roasting time preferable range is 2～8 hours; Catalyst precarsor B calcination atmosphere preferred version is air or catalyst is inert gasses.
Alkaline earth oxide can with hydroxyl-bearing solvent generation aquation, generate hydroxide.High temperature sintering can make hydroxide again dehydration obtain oxide.In the said process, the oxygen atom of dehydration may be from the oxygen atom in the solvent, also may be the oxygen atom from former alkaline earth oxide plane of crystal.Therefore, dehydration will cause the blemish of alkaline earth oxide, make the cation that the surface go up to exist exposes and the negative oxygen ion center of different ligancies, and cationic omission can form more negative oxygen ion group on limit, the angle, alkalescence is improved, and specific area also can increase simultaneously.
The isomerization catalyst for preparing in the technique scheme can be selected spin, extruding slivering, method moulding such as compressing tablet for use.
Adopt the olefines double bond isomerizing catalyst of technique scheme preparation to can be used in olefines double bond isomerizing and ethene, the preparing propylene by butene disproportionation reaction.
Butylenes double-bond isomerization reaction of the present invention.Reaction condition is: in the fixed bed reactors, reaction temperature is 0～550 ℃, reaction pressure is 0～3.5MPa, and the liquid phase air speed is 0.1～10 hour
-1Under the condition, 1-butylene generation double-bond isomerization generates the 2-butylene.
Ethene of the present invention and preparing propylene by butene disproportionation reaction.The disproportionation catalyst that uses in the reaction is 15 weight %WO
3/ SiO
2Disproportionation catalyst, the weight ratio of isomerization catalyst and disproportionation catalyst are 5: 1.Reaction condition is: in the fixed bed reactors, reaction temperature is 0～550 ℃, is 0～3.5MPa in the gauge pressure reaction pressure, the liquid phase air speed is 0.1～10 hour
-Under 1 condition, butylene and ethene generation disproportionated reaction generate propylene.
The present invention passes through the hydration again of commercial alkaline metal oxide and dehydration once more, and it is big to have obtained specific area, the olefines double bond isomerizing catalyst that alkali number is big.Use the stability of such catalyst butylenes double-bond isomerization reaction to extend to 330 hours from 200 hours, the stability of preparing propylene by butene disproportionation extended to 360 hours from 250 hours, had obtained better technical effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
The hydrolysis of MgO and drying
Take by weighing 50 gram commodity MgO, add 200 ml methanol, the white opacity solution that obtains adds thermal agitation after 5 hours in 50 ℃ of water-baths, moisture in the suction filtration solution, and product is designated as A 120 ℃ of oven dry 6 hours.
[embodiment 2]
The hydrolysis of MgO and drying
Take by weighing 50 gram commodity MgO, add 300 ml deionized water, the white opacity solution that obtains adds thermal agitation in 60 ℃ of water-baths and left standstill after 2 hours 3 hours again, moisture in the suction filtration solution, and product is designated as B 80 ℃ of oven dry 12 hours.
[embodiment 3]
The hydrolysis of CaO and drying
Take by weighing 50 gram commodity CaO, add 400 milliliters of ethanol, the white opacity solution that obtains adds thermal agitation in 90 ℃ of water-baths and left standstill after 1 hour 3 hours again, moisture in the suction filtration solution, and product is designated as C 80 ℃ of oven dry 12 hours.
[embodiment 4]
The hydrolysis of BaO and drying
Take by weighing 50 gram commodity BaO, add 200 milliliters and remove methyl alcohol, the white opacity solution that obtains adds thermal agitation after 10 hours in 40 ℃ of water-baths, moisture in the suction filtration solution, and product is designated as D 60 ℃ of oven dry 15 hours.
[embodiment 5]
The roasting of hydrolysis prods
Sample A, B, C, D remove hydration moisture by roasting after the hydrolysis.Get above-mentioned drying sample respectively at roasting in the Muffle furnace, wherein sintering temperature is followed successively by 400 ℃, and 500 ℃, 550 ℃ and 650 ℃; Roasting time was followed successively by 8 hours, and 6.5 hours, 5 hours and 2 hours; Calcination atmosphere respectively is air, nitrogen, air, air; Obtain the sample after the roasting.
[embodiment 6]
The pore structure of hydrolysis MgO and modification MgO does not characterize
The pore structure analysis of table 1 MgO
[embodiment 7]
The moulding of sample and disproportionation preparation of propene
Pressed disc method is adopted in the moulding of sample, behind the 2.0MPa compressing tablet, grinds with mortar, and screening 20～40 order samples are stand-by.
In length is 110 centimetres, and internal diameter is that 2.5 centimetres reactor lower curtate adding volume is 110 centimetres
3, granularity is 10～20 order glass marble fillers; The disproportionation catalyst and the 20 gram double bond isomerizing catalysts of 4 gram formings are added reactor, and the weight ratio of disproportionation catalyst and isomerization catalyst is 1: 5, and the catalyst upper end adds 60 centimetres again
3, granularity is 10～20 order glass marble fillers.Reactor is warming up to 550 ℃ under the air conditions that feeds 100 ml/min, and after keeping 4 hours under this temperature, uses N then
2Purged 8 hours, and reduced to 300 ℃ of reaction temperatures.
Reactor stops to feed nitrogen, and feeds the ethylene raw of 99.5%1-butene feedstock and 99.9% from the reactor upper end, and butylene: ethylene molar ratio is 1:2, and the liquid quality air speed is 0.12 hour
-1, reaction system pressure is by the control valve control of reactor outlet, and pressure is controlled at 3.0MPa.Product after release by the gas-chromatography on-line analysis.
Table 2 different catalysts disproportionation preparation of propene data
[embodiment 8]
The reaction of 1-isomerization of butene
In length is 110 centimetres, and internal diameter is that 2.5 centimetres reactor lower curtate adding volume is 110 centimetres
3, granularity is 10～20 order glass marble fillers; 20 gram forming double bond isomerizing catalysts are added reactor, and the catalyst upper end adds 60 centimetres again
3, granularity is 10～20 order glass marble fillers.Reactor is warming up to 550 ℃ under the air conditions of 10 liters/hour of feedings, and after keeping 2 hours under this temperature, uses N then
2Purged 1 hour, and reduced to 300 ℃ of reaction temperatures.
Reactor stops to feed nitrogen, and feeds the 99.5%1-butene feedstock from the reactor upper end, and the liquid quality air speed is 0.12 hour
-1, reaction system pressure is by the control valve control of reactor outlet, and pressure is controlled at 3.0MPa.Product after release by the gas-chromatography on-line analysis.
The reaction of table 3 1-isomerization of butene
[embodiment 9]
1-hexene double bond isomerization reaction
Catalyst filling and pretreatment condition are as described in [embodiment 7].Reaction raw materials is a 1-hexene (〉 99%), 200 ℃ of reaction temperatures, reaction pressure is controlled at 3.0MPa, and the charging air speed is 0.5 hour
-1
The isomerization reaction of table 4 1-hexene
Claims (4)
1, a kind of preparation method of olefines double bond isomerizing catalyst may further comprise the steps successively:
(a) with the alkaline earth oxide being raw material, is the hydration solvent with the polar solvent of hydroxyl, and the weight ratio of raw material and hydration solvent is 1: 1～10, and the mixture of raw material and hydration solvent product of 0.5～24 hour of hydrolysis under 20～100 ℃ of temperature is A;
(b) product A through washing, behind the suction filtration under 60～140 ℃ of temperature dry 4～24 hours catalyst precarsor be B;
(c) catalyst precarsor B is under 300～900 ℃ in temperature, and roasting got required catalyst in 1～10 hour;
Wherein the key component of gained catalyst is an alkaline earth oxide, and its specific area is 100～500 meters
2/ gram.
2, the preparation method of olefines double bond isomerizing catalyst according to claim 1 is characterized in that alkaline earth oxide is selected from least a in magnesia, calcium oxide, strontium oxide strontia, barium monoxide or the radium oxide.
3, the preparation method of olefines double bond isomerizing catalyst according to claim 1 is characterized in that the hydration solvent is selected from water or contains the lower aliphatic alcohols of 1～4 carbon atom; The weight ratio of raw material and hydration solvent is 1: 3～6; Hydrolysis temperature is 50～90 ℃, and hydrolysis time is 2～10 hours; Baking temperature is 60～120 ℃, and be 6～15 hours drying time; Sintering temperature is 400～650 ℃, and roasting time is 2～8 hours.
4, the preparation method of olefines double bond isomerizing catalyst according to claim 1 is characterized in that catalyst precarsor B calcination atmosphere is air or catalyst is inert gasses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100299818A CN100506374C (en) | 2006-08-11 | 2006-08-11 | Olefines double bond isomerizing catalyst and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100299818A CN100506374C (en) | 2006-08-11 | 2006-08-11 | Olefines double bond isomerizing catalyst and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101121121A CN101121121A (en) | 2008-02-13 |
| CN100506374C true CN100506374C (en) | 2009-07-01 |
Family
ID=39083742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100299818A Active CN100506374C (en) | 2006-08-11 | 2006-08-11 | Olefines double bond isomerizing catalyst and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100506374C (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102143929B (en) | 2008-09-04 | 2014-12-03 | 鲁姆斯科技公司 | Olefin isomerization and metathesis catalyst |
| CN101597199B (en) * | 2009-07-22 | 2013-01-02 | 中国石油化工集团公司 | Method for producing propylene |
| CN102188965A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Method for preparing catalyst for olefin double bond isomerization |
| CN102875310B (en) * | 2011-07-12 | 2015-04-08 | 中国石油化工股份有限公司 | Method of butene double bound isomerization |
| CN103030495B (en) * | 2011-09-29 | 2014-10-15 | 中国石油化工股份有限公司 | Method for manufacturing propylene by butene and ethylene disproportionation |
| CN103030498B (en) * | 2011-09-30 | 2015-02-11 | 中国石油化工股份有限公司 | Method for producing propylene by virtue of disproportionating of amylene |
| CN103420766B (en) * | 2012-05-16 | 2015-02-11 | 中国石油化工股份有限公司 | Method for preparing 2-butene through 1-butene double bond isomerization |
| CN103418362B (en) * | 2012-05-16 | 2016-08-03 | 中国石油化工股份有限公司 | Olefines double bond isomerizing catalyst and preparation method thereof |
| CN103539618B (en) * | 2012-07-12 | 2015-07-08 | 中国石油化工股份有限公司 | Hexene double-bond isomerization method |
| CN103772107B (en) * | 2012-10-25 | 2015-09-09 | 中国石油化工股份有限公司 | The method of preparing propylene by butene disproportionation |
| EP2862629A1 (en) * | 2013-10-15 | 2015-04-22 | Borealis AG | Catalyst and process for olefin metathesis reaction |
| CN109464335A (en) * | 2018-12-11 | 2019-03-15 | 深圳市逸高生物技术有限公司 | A kind of method of solanum red pigment production times maintenance hair essence |
-
2006
- 2006-08-11 CN CNB2006100299818A patent/CN100506374C/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 高分子保护沉淀法制备超细纳米氧化镁. 王海霞等.无机化学学报，第22卷第2期. 2006 |
| 高分子保护沉淀法制备超细纳米氧化镁. 王海霞等.无机化学学报，第22卷第2期. 2006 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101121121A (en) | 2008-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100506374C (en) | Olefines double bond isomerizing catalyst and its preparation method | |
| CN105289743B (en) | It is a kind of to be used to produce vanadium-phosphor oxide catalyst of maleic anhydride and preparation method thereof | |
| CN101462044B (en) | Catalyst for producing crotonaldehyde | |
| CN109701627B (en) | Composite catalyst containing spinel structure and application thereof in one-step preparation of olefin from synthesis gas | |
| CN102773106A (en) | Catalyst for preparing low carbon olefin by synthetic gas as well as preparation method and application of catalyst | |
| CN102188965A (en) | Method for preparing catalyst for olefin double bond isomerization | |
| CN104549295B (en) | Olefin isomerization catalyst | |
| CN101768040B (en) | Method for preparing propylene from butylene and ethylene | |
| CN103420766B (en) | Method for preparing 2-butene through 1-butene double bond isomerization | |
| CN100413828C (en) | Method for producing ethene and hexene through dismutation of butylene | |
| CN105582933A (en) | Catalyst used for double-bond isomerization | |
| CN100467124C (en) | Catalyst for producing isobutene by cracking methyl tert-butyl ether | |
| CN113856743B (en) | Catalyst for propylene production and environment-friendly process for propylene production | |
| CN104549351B (en) | Isomerization catalyst | |
| CN112441866B (en) | Method for producing n-butene from isobutene | |
| CN1490081A (en) | Fixed bed catalyst for producing propene from butylene by disproportion | |
| CN104447163B (en) | The method producing propylene | |
| CN102875310B (en) | Method of butene double bound isomerization | |
| CN106944059A (en) | A kind of preparation method of synthesis gas full methanation catalyst | |
| CN112441865B (en) | Method for preparing butene-2 from isobutene | |
| US20160030929A1 (en) | Method for preparing catalyst for glycerin dehydration, and method for preparing acrolein | |
| CN105080535A (en) | Butene disproportionation catalyst | |
| CN104549212A (en) | Double-bond isomerization catalyst | |
| CN115368200B (en) | Method for preparing paraxylene by biomass conversion | |
| CN112844355B (en) | Catalyst for preparing ethylene and propylene by catalyzing bioethanol, and process and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |