CN103894225A - Aluminum trichloride immobilized type catalyst as well as preparation method and application thereof - Google Patents
Aluminum trichloride immobilized type catalyst as well as preparation method and application thereof Download PDFInfo
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- CN103894225A CN103894225A CN201410109374.7A CN201410109374A CN103894225A CN 103894225 A CN103894225 A CN 103894225A CN 201410109374 A CN201410109374 A CN 201410109374A CN 103894225 A CN103894225 A CN 103894225A
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- molecular sieve
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Abstract
The invention relates to an aluminum trichloride immobilized type catalyst as well as a preparation method and an application thereof and belongs to the field of synthesis of a molecular sieve catalyst. According to the aluminum trichloride immobilized type catalyst, the catalyst is obtained by immobilizing aluminum trichloride on a molecular sieve carrier; the molecular sieve carrier is prepared from the following components in percentage by mass: 40-60% of a molecular sieve, 20-40% of water, 1-20% of Al2O3 and 1-10% of sesbania powder; the sum of the mass percents of all the components is 100%; and the molecular sieve is a beta molecular sieve or a ZSM-5 molecular sieve. According to the aluminum trichloride immobilized type catalyst, the pore diameter has the selectivity and the catalyst is applicable to overlapping C4 olefins to produce high-carbon olefins. The catalyst provided by the invention has a shape selection effect so that an olefin oligomerization reaction is carried out in a pore channel of the catalyst; the product takes a product with few mono-substituted methyl branch olefins as a main part; and compared with other molecular sieves, the service life of the catalyst is easy to prolong.
Description
Technical field
The present invention relates to a kind of alchlor solid-carrying type Catalysts and its preparation method and application, belong to the synthetic field of molecular sieve catalyst.
Background technology
The catalyst that at present coincidence process uses is SSPA, but the easy argillization of solid phosphoric acid catalyst SSPA, life-span are short, and high boiling component is low, is particularly not suitable for producing higher olefins industrial chemicals.Document CN1398832A discloses a kind of method of low-carbon alkene oligomerisation or superimposed production carbon six above alkene, and superimposed product mostly is dimer, and product side chain is many, and liquid is received low.The method of the existing superimposed production higher olefins of C 4 olefin is to utilize solid phosphoric acid catalyst.Solid phosphoric acid catalyst easy problem such as the short and higher olefins poor selectivity of argillization, life-span in the superimposed production higher olefins of C 4 olefin process.
Summary of the invention
The object of this invention is to provide a kind of alchlor solid-carrying type catalyst.
A kind of alchlor solid-carrying type catalyst, described catalyst is by obtaining on molecular sieve carrier immobilized alchlor,
Described molecular sieve carrier by mass percentage, is made by following component: molecular sieve: 40～60%, and water: 20～40%, Al
2o
3: 1～20%, sesbania powder: 1～10%, above-mentioned each constituent mass percentage sum is 100%,
Wherein, described molecular sieve is beta-molecular sieve or ZSM-5 molecular sieve.
Especially, above-mentioned molecular sieve carrier is by making as follows: raw material is mixed to rear compressing tablet or extruded moulding, and in 180～200 DEG C of oven dry, fragmentation,
Wherein, described raw material by mass percentage, is made up of following component: molecular sieve: 40～60%, and water: 20～40%, Al
2o
3: 1～20%, sesbania powder: 1～10%,
Wherein, described molecular sieve is beta-molecular sieve or ZSM-5 molecular sieve.
Beta-molecular sieve of the present invention and ZSM-5 molecular sieve can business be buied or make according to the disclosed method of prior art, and preferably its silica alumina ratio is 100/0.
Compression molding of the present invention and extruded moulding technique are the state of the art, those skilled in the art can in business can buy or the disclosed moulding of prior art or extrusion device in carry out.
It is 3～5mm spheric granules that fragmentation described in technique scheme is preferably crushed to average grain diameter by gained material after compressing tablet or extruded moulding.
Alchlor solid-carrying type catalyst of the present invention, described alchlor is immobilized on molecular sieve carrier as follows: make gaseous state AlCl
3contact with molecular sieve carrier.
Especially, described alchlor is immobilized on molecular sieve carrier as follows: molecular sieve carrier is placed in to fixed bed reactors, is warming up to 200 ± 10 DEG C; Heat solid AlCl
3make its distillation, in fixed bed reactors, pass into nitrogen, utilize nitrogen by gaseous state AlCl
3bring reactor into, detect fixed bed reactors outlet AlCl simultaneously
3gas content, detects that fixed bed reactors outlet has AlCl
3when gas, close gas phase and import and export.
Alchlor solid-carrying type catalyst of the present invention, described molecular sieve carries out calcination process as follows: will with gaseous state AlCl
3after contact, the molecular sieve carrier of gained load alchlor carries out roasting in 230～250 DEG C.
Molecular sieve of the present invention preferably carries out pretreatment as follows: molecular sieve is dried at 180～200 DEG C.
Another object of the present invention is to provide the preparation method of above-mentioned alchlor solid-carrying type catalyst.
A preparation method for alchlor solid-carrying type catalyst, comprises following processing step:
1. molecular sieve is dried at 180～200 DEG C, described molecular sieve is beta-molecular sieve or ZSM-5 molecular sieve;
2. raw material is mixed to rear compressing tablet or extruded moulding, in 180～200 DEG C of oven dry, fragmentation, wherein, described raw material by mass percentage, is made up of following component: molecular sieve: 40～60%, and water: 20～40%, Al
2o
3: 1～20%, sesbania powder: 1～10%, obtain molecular sieve carrier;
3. by gaseous state AlCl
3contact and adsorb with molecular sieve carrier;
4. absorption after, by step 3. the molecular sieve carrier of gained load alchlor carry out roasting in 230～250 DEG C.
In technique scheme, described step 2. in, it is 3～5mm spheric granules that described fragmentation is preferably crushed to average grain diameter by gained material after compressing tablet or extruded moulding; Described step 3. in, described alchlor is immobilized on molecular sieve carrier as follows: molecular sieve carrier is placed in to fixed bed reactors, is warming up to 200 ± 10 DEG C; Heat solid AlCl
3make its distillation, in fixed bed reactors, pass into nitrogen, utilize nitrogen by gaseous state AlCl
3bring reactor into, detect fixed bed reactors outlet AlCl simultaneously
3gas content, detects that fixed bed reactors outlet has AlCl
3when gas, close gas phase and import and export.
Another object of the present invention is to provide above-mentioned alchlor solid-carrying type catalyst and produces in higher olefins and apply at catalysis C4 alkene oligomerization.
C4 alkene oligomerization is produced the method for higher olefins, and described method is taking C4 alkene as raw material, and taking alchlor solid-carrying type catalyst as catalyst, described catalyst is by obtaining on molecular sieve carrier immobilized alchlor,
Described molecular sieve carrier by mass percentage, is made by following component: molecular sieve: 40～60%, and water: 20～40%, Al
2o
3: 1～20%, sesbania powder: 1～10%, above-mentioned each constituent mass percentage sum is 100%, wherein, described molecular sieve is beta-molecular sieve or ZSM-5 molecular sieve.
Especially, the method that above-mentioned C4 alkene oligomerization is produced higher olefins is preferable in fixed bed reactors, is 0～50 DEG C in reaction temperature, and reaction pressure is 1～3MPa, and liquid hourly space velocity (LHSV) is 0.5～2h
-1, C4 alkene is contacted with described alchlor solid-carrying type catalyst.
C4 alkene of the present invention is preferably selected from refinery's hybrid C 4, cracking of ethylene C4, at least one in 1-butylene, isobutene, cis-2-butene and Trans-2-butene.
Beneficial effect of the present invention is: the aperture of alchlor solid-carrying type of the present invention has shape selectivity, is applicable to C4 alkene oligomerization produces higher olefins by it.Due to the shape effect of selecting of catalyst of the present invention, olefin oligomerization carries out in catalyst duct, makes product to be with a small amount of monosubstituted methyl branch olefin product as main, is conducive to the prolongation of catalyst life compared with other molecular sieves.Selecting suitable reaction condition and having specific silicon aluminum ratio is that 100/0 catalyst can effectively suppress cracking, cross the generation of the side reactions such as cracking, cyclisation, aromatisation, hydrogen migration, and product is taking superimposed product as main.The method C8 that alkene oligomerization of the present invention is produced higher olefins selectively can reach 83.8%; Be not less than 70% at conversion ratio, higher olefins is selectively not less than in 60% situation, and catalyst single pass life reaches 480h, can obtain good technique effect.
Detailed description of the invention
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Test method described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
In following embodiment, described alchlor solid-carrying type catalyst is prepared as follows:
1. beta-molecular sieve is dried at 190 DEG C;
2. raw material is mixed to rear extruded moulding, in 190 DEG C of oven dry, be crushed to 3～5mm spheric granules, wherein, described raw material by mass percentage, is made up of following component: beta-molecular sieve 60%, water: 25%, Al
2o
3: 10%, sesbania powder: 5%, wherein, the silica alumina ratio of beta-molecular sieve is 100/0;
3. molecular sieve carrier is placed in to fixed bed reactors, is warming up to 200 ± 10 DEG C; Heat solid AlCl
3make its distillation, in fixed bed reactors, pass into nitrogen, utilize nitrogen by gaseous state AlCl
3bring reactor into, detect fixed bed reactors outlet AlCl simultaneously
3gas content, detects that fixed bed reactors outlet has AlCl
3when gas, close gas phase and import and export;
4. absorption after, by step 3. the molecular sieve carrier of gained load alchlor carry out roasting in 240 ± 5 DEG C.
In following embodiment, raw material: cis-2-butene (from second branch factory of oil MEK workshop, Fushun), directly do not use through purified treatment, wherein, sulphur: 14ppm, alkynes: 500ppm, diene: 100～300ppm.
Embodiment 1
The present embodiment explanation is applicable to the invention provides the reaction temperature of technique.
C4 alkene oligomerization is produced a method for higher olefins, alchlor solid-carrying type catalyst 3g and cis-2-butene, and reaction pressure 2MPa, liquid hourly space velocity (LHSV) is 1h
-1, 10,30 or 50 DEG C of reaction temperatures, gained butylene building-up reactions the results are shown in table 1.
At table 1 differential responses temperature, the reactant liquor of butylene building-up reactions is received and liquid phase composition
In embodiment, described " liquid receipts " refer to that the weight of product liquid in products therefrom accounts for the percentage of whole product gross weights.
Embodiment 2
This implementation is applicable to invention provides the reaction pressure of technique.
C4 alkene oligomerization is produced a method for higher olefins, alchlor solid-carrying type catalyst 3g and cis-2-butene, and 30 DEG C of reaction temperatures, liquid hourly space velocity (LHSV) is 1h
-1, reaction pressure 1,2 or 3MPa, gained butylene building-up reactions the results are shown in table 2.
Under table 2 differential responses pressure, the reactant liquor of butylene building-up reactions is received and liquid phase composition
Embodiment 3
The present embodiment explanation is applicable to invention provides the liquid hourly space velocity (LHSV) of technique
C4 alkene oligomerization is produced the method for higher olefins, alchlor solid-carrying type catalyst 3g and cis-2-butene, and 30 DEG C of reaction temperatures, liquid hourly space velocity (LHSV) is 1 or 2h
-1, reaction pressure 3MPa, gained butylene building-up reactions the results are shown in table 3.
Under the different liquid hourly space velocity (LHSV)s of table 3, the reactant liquor of butylene building-up reactions is received and liquid phase composition
Embodiment 4
The present embodiment explanation has the catalytic reaction effect of the catalyst of Different Silicon aluminum ratio.The difference of the present embodiment three kinds of solid-carried catalysts used is the silica alumina ratio difference of the raw materials used molecular sieve of Kaolinite Preparation of Catalyst, is respectively 25/1,100/0,100/1.
C4 alkene oligomerization is produced a method for higher olefins, alchlor solid-carrying type catalyst 3g and cis-2-butene, and 30 DEG C of reaction temperatures, liquid hourly space velocity (LHSV) is 2h
-1, reaction pressure 3MPa, gained butylene building-up reactions the results are shown in table 4.
Table 4 Different Silicon aluminum ratio molecular sieve raw material makes catalyst and receives and liquid phase composition for the reactant liquor of butylene building-up reactions
Embodiment 5
The single pass life of the present embodiment explanation catalyst.
C4 alkene oligomerization is produced a method for higher olefins, alchlor solid-carrying type catalyst 3g and cis-2-butene, and 30 DEG C of reaction temperatures, liquid hourly space velocity (LHSV) is 2h
-1, reaction pressure 3MPa, silica alumina ratio 100/0.Gained butylene building-up reactions the results are shown in table 5.
The reactant liquor of table 5 different time butylene building-up reactions is received and liquid phase composition
In upper table, " sample time " is all in the 10:00 on described date sampling.
Claims (9)
1. an alchlor solid-carrying type catalyst, described catalyst is by obtaining on molecular sieve carrier immobilized alchlor,
Described molecular sieve carrier by mass percentage, is made by following component: molecular sieve: 40～60%, and water: 20～40%, Al
2o
3: 1～20%, sesbania powder: 1～10%,
Wherein, described molecular sieve is beta-molecular sieve or ZSM-5 molecular sieve.
2. catalyst according to claim 1, is characterized in that: described molecular sieve carrier makes as follows: raw material is mixed to rear compressing tablet or extruded moulding, and in 180～200 DEG C of oven dry, fragmentation,
Wherein, described raw material by mass percentage, is made up of following component: molecular sieve: 40～60%, and water: 20～40%, Al
2o
3: 1～20%, sesbania powder: 1～10%,
Wherein, described molecular sieve is beta-molecular sieve or ZSM-5 molecular sieve.
3. catalyst according to claim 1 and 2, is characterized in that: described alchlor is immobilized on molecular sieve carrier as follows: make gaseous state AlCl
3contact with molecular sieve carrier.
4. catalyst according to claim 1, is characterized in that: described molecular sieve carries out calcination process as follows: will with gaseous state AlCl
3molecular sieve carrier after contact carries out roasting in 230～250 DEG C.
5. catalyst according to claim 1, is characterized in that: described molecular sieve carries out pretreatment as follows: molecular sieve is dried at 180～200 DEG C.
6. a preparation method for alchlor solid-carrying type catalyst, is characterized in that: comprise following processing step:
1. molecular sieve is dried at 180～200 DEG C, described molecular sieve is beta-molecular sieve or ZSM-5 molecular sieve;
2. raw material is mixed to rear compressing tablet or extruded moulding, in 180～200 DEG C of oven dry, fragmentation, wherein, described raw material by mass percentage, is made up of following component: molecular sieve: 40～60%, and water: 20～40%, Al
2o
3: 1～20%, sesbania powder: 1～10%, obtain molecular sieve carrier;
3. by gaseous state AlCl
3contact and adsorb with molecular sieve carrier;
4. absorption after, by step 3. the molecular sieve carrier of gained load alchlor carry out roasting in 230～250 DEG C.
7. C4 alkene oligomerization is produced a method for higher olefins, it is characterized in that: described method is taking C4 alkene as raw material, taking alchlor solid-carrying type catalyst described in claim 1 as catalyst.
8. method according to claim 7, is characterized in that: in fixed bed reactors, be 0～50 DEG C in reaction temperature, reaction pressure is 1～3MPa, and liquid hourly space velocity (LHSV) is 0.5～2h
-1, C4 alkene is contacted with described alchlor solid-carrying type catalyst.
9. method according to claim 7, is characterized in that: described C4 alkene is selected from refinery's hybrid C 4, cracking of ethylene C4, at least one in 1-butylene, isobutene, cis-2-butene and Trans-2-butene.
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| CN201410109374.7A CN103894225B (en) | 2014-03-21 | 2014-03-21 | A kind of alchlor immobilized AlCl_3 catalyst and preparation method thereof and application |
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|---|---|---|---|
| CN201410109374.7A CN103894225B (en) | 2014-03-21 | 2014-03-21 | A kind of alchlor immobilized AlCl_3 catalyst and preparation method thereof and application |
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| CN103894225B CN103894225B (en) | 2016-03-09 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947759A (en) * | 2018-07-20 | 2018-12-07 | 山西潞安纳克碳化工有限公司 | A method of alkylnaphthalene is prepared using coal-to-olefin |
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|---|---|---|---|---|
| CN102247885A (en) * | 2011-05-20 | 2011-11-23 | 大连理工大学 | Method for preparing AlCl3/zeolite molecular sieve solid acid catalyst |
| US20130225397A1 (en) * | 2010-08-23 | 2013-08-29 | Shanghai Research Institute Of Petrochemical Technology, Sinopec | Binderless Molecular Sieve Catalyst and a Preparation Method Thereof |
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2014
- 2014-03-21 CN CN201410109374.7A patent/CN103894225B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130225397A1 (en) * | 2010-08-23 | 2013-08-29 | Shanghai Research Institute Of Petrochemical Technology, Sinopec | Binderless Molecular Sieve Catalyst and a Preparation Method Thereof |
| CN102247885A (en) * | 2011-05-20 | 2011-11-23 | 大连理工大学 | Method for preparing AlCl3/zeolite molecular sieve solid acid catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 石先哲: "AlCl3固载化催化剂的研制及其在异丁烯低度聚合中的应用", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947759A (en) * | 2018-07-20 | 2018-12-07 | 山西潞安纳克碳化工有限公司 | A method of alkylnaphthalene is prepared using coal-to-olefin |
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Effective date of registration: 20180417 Address after: 116318 western Changxing Island Industrial Park, Changxing Island Economic Zone, Dalian, Liaoning Patentee after: Dalian Longyuan Chemical Co., Ltd Address before: 116000, room 15, building 439, hi tech building, 03 Huangpu Road, Ganjingzi District, Liaoning, Dalian Patentee before: Dalian Longtai Technology Development Co., Ltd. |
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