CN104607238B - A kind of composite catalyst containing modified montmorillonite used and ZSM-8 and preparation method thereof - Google Patents
A kind of composite catalyst containing modified montmorillonite used and ZSM-8 and preparation method thereof Download PDFInfo
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- CN104607238B CN104607238B CN201510078089.8A CN201510078089A CN104607238B CN 104607238 B CN104607238 B CN 104607238B CN 201510078089 A CN201510078089 A CN 201510078089A CN 104607238 B CN104607238 B CN 104607238B
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- modified montmorillonite
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- montmorillonite used
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 claims description 18
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 229940044658 gallium nitrate Drugs 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010009 beating Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000013467 fragmentation Methods 0.000 claims description 5
- 238000006062 fragmentation reaction Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000012188 paraffin wax Substances 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention provides a kind of composite catalyst containing modified montmorillonite used and ZSM-8 and preparation method thereof, it is modified montmorillonite used as binding agent that this catalyst have employed La, have employed the ZSM-8 of Ga and Zn modification simultaneously, the catalyst obtained thus has higher paraffin conversion and the aromatics yield of Geng Gao than catalyst conventional in prior art, and the deactivation rate of this catalyst reduces greatly, service life is effectively extended.
Description
Technical field
The present invention relates to and a kind ofly comprise ZSM-8 and modified montmorillonite used carbon monoxide-olefin polymeric.
Background technology
Saturated low paraffin conversion become the aromatic hydrocarbons that chemical industry can directly utilize to be the problem of people's extensive concern always.In the several years in past, successively developing utilizes zeolite based catalysts to make the light-hydrocarbon aromatized method preparing aromatic hydrocarbons, but lighter hydrocarbons are converted into aromatic hydrocarbons is on a catalyst a complex process relating to multiple reaction, catalytic activity, optionally control to be the focus paid close attention in this field always.
The lower alkanes that can be used as well known in the prior art is that in the catalyst of aromatic hydrocarbons, normal employing also optionally bonds with suitable binding agent containing rare earth metal.Aluminium oxide and silica are binding agents conventional in this kind of catalyst.In addition, in such catalyst, conventional zeolite is as key component, and modifying element is introduced in molecular sieve mainly through methods such as dipping, ion-exchange and mechanical mixture by the modification for zeolite.
Summary of the invention
The object of this invention is to provide a kind of containing composite catalyst composition that is modified montmorillonite used and ZSM-8, the montmorillonite of La modification is employed as binding agent in this catalyst, and combine the ZSM-8 of Ga and Zn modification, owing to have employed this special component, catalyst is made to have good paraffin conversion and good aromatic hydrocarbons total recovery.
For achieving the above object, the technical solution used in the present invention is:
Containing a method for preparing composite catalyst that is modified montmorillonite used and ZSM-8, it is characterized in that, comprise following steps:
A) preparation that La is modified montmorillonite used: get 0.20g lanthanum nitrate, is dissolved in 140ml deionized water, this solution is heated to 70 DEG C, then adding 15g granularity is 500 object montmorillonites, Keep agitation 30 minutes, after montmorillonite scatter, is warming up to 110 DEG C, stir 10h at such a temperature, filter, spend deionized water 3 times, dried solid product, dried pressed powder is placed in Muffle furnace air atmosphere 550 DEG C of roastings 5 hours, obtains La modified montmorillonite used;
B) preparation of Ga/Zn-ZSM-8: get gallium nitrate and zinc nitrate is dissolved in the deionized water of 250ml, wherein the gross weight of gallium nitrate and zinc nitrate is 0.825g, for subsequent use after stirring and dissolving; ZSM-8 is dispersed in aqueous ammonium nitrate solution, keeps 5 hours at 100 DEG C, dry after filtering; added by dried powder 15g in the solution of above-mentioned gallium nitrate and zinc nitrate, be then warming up to 100 DEG C, constant temperature stirs 20 hours; filter and dry solids, obtain the ZSM-8 of Ga and Zn modification;
C) preparation of catalyst: getting mass ratio is that Ga/Zn-ZSM-8 and La of 3:1 is modified montmorillonite used, adds in agitator, then adds proper amount of silicon colloidal sol and distilled water, dry after making beating, filtration, after 450 DEG C of roasting 0.5h, fragmentation is sieved, and gets 20-100 object particle as finished catalyst.
Stir speed (S.S.) in described step a) is 400 revs/min.
Heating rate in described step b) is 10 DEG C/minute.
Heating rate in described step c) is 10 DEG C/minute.
beneficial effect
The present invention is owing to have employed technique scheme, compared with prior art there is following beneficial effect: it is modified montmorillonite used as binding agent that catalyst of the present invention have employed La, have employed the ZSM-8 of Ga and Zn modification simultaneously, the catalyst obtained thus has higher paraffin conversion and the aromatics yield of Geng Gao than catalyst conventional in prior art, and the deactivation rate of this catalyst reduces greatly, service life is effectively extended.
Detailed description of the invention
Below by embodiment, the invention will be further described.
embodiment 1
The preparation that La is modified montmorillonite used: get 0.20g lanthanum nitrate, be dissolved in 140ml deionized water, this solution is heated to 70 DEG C, then adding 15g granularity is 500 object montmorillonites, Keep agitation 30 minutes, stir speed (S.S.) is 400 revs/min, after montmorillonite scatter, be warming up to 110 DEG C, stir 10h at such a temperature, stir speed (S.S.) is 400 revs/min, filter, spend deionized water 3 times, dried solid product, dried pressed powder is placed in Muffle furnace air atmosphere 550 DEG C of roastings 5 hours, obtains La modified montmorillonite used;
The preparation of Ga/Zn-ZSM-8: get gallium nitrate and zinc nitrate is dissolved in the deionized water of 250ml, wherein the gross weight of gallium nitrate and zinc nitrate is 0.825g, for subsequent use after stirring and dissolving; ZSM-8 is dispersed in aqueous ammonium nitrate solution; heating rate 10 DEG C/minute; keep 5 hours at 100 DEG C; dry after filtering, dried powder 15g is added in the solution of above-mentioned gallium nitrate and zinc nitrate, be then warming up to 100 DEG C; heating rate 10 DEG C/minute; constant temperature stirs 20 hours, filters and dry solids, obtains the ZSM-8 of Ga and Zn modification;
The preparation of catalyst: getting mass ratio is that Ga/Zn-ZSM-8 and La of 3:1 is modified montmorillonite used, add in agitator, then add proper amount of silicon colloidal sol and distilled water, dry after making beating, filtration, heating rate 10 DEG C/minute, after 450 DEG C of roasting 0.5h, fragmentation is sieved, and gets 20-100 object particle as finished catalyst.
comparative example 1
Get Ga/Zn-ZSM-8 and unselected clay that mass ratio is embodiment 1 preparation of 3:1, add in agitator, then add proper amount of silicon colloidal sol and distilled water, dry after making beating, filtration, 450 DEG C are risen to heating rate 10 DEG C/minute, after roasting 0.5h, fragmentation is sieved, and gets 20-100 object particle as finished catalyst.
comparative example 2
Getting mass ratio is that ZSM-8 and La of 3:1 is modified montmorillonite used, adds in agitator, then adds proper amount of silicon colloidal sol and distilled water, dry after making beating, filtration, rise to 450 DEG C, after roasting 0.5h with heating rate 10 DEG C/minute, fragmentation is sieved, and gets 20-100 object particle as finished catalyst.
Claims (4)
1., containing a modified montmorillonite used preparation method with the composite catalyst of ZSM-8, it is characterized in that, comprise following steps:
A) preparation that La is modified montmorillonite used: get 0.20g lanthanum nitrate, is dissolved in 140ml deionized water, this solution is heated to 70 DEG C, then adding 15g granularity is 500 object montmorillonites, Keep agitation 30 minutes, after montmorillonite scatter, is warming up to 110 DEG C, stir 10h at such a temperature, filter, spend deionized water 3 times, dried solid product, dried pressed powder is placed in Muffle furnace air atmosphere 550 DEG C of roastings 5 hours, obtains La modified montmorillonite used;
B) preparation of Ga/Zn-ZSM-8: get gallium nitrate and zinc nitrate is dissolved in the deionized water of 250ml, wherein the gross weight of gallium nitrate and zinc nitrate is 0.825g, for subsequent use after stirring and dissolving; ZSM-8 is dispersed in aqueous ammonium nitrate solution, keeps 5 hours at 100 DEG C, dry after filtering; added by dried powder 15g in the solution of above-mentioned gallium nitrate and zinc nitrate, be then warming up to 100 DEG C, constant temperature stirs 20 hours; filter and dry solids, obtain the ZSM-8 of Ga and Zn modification;
C) preparation of catalyst: getting mass ratio is that Ga/Zn-ZSM-8 and La of 3:1 is modified montmorillonite used, adds in agitator, then adds proper amount of silicon colloidal sol and distilled water, dry after making beating, filtration, after 450 DEG C of roasting 0.5h, fragmentation is sieved, and gets 20-100 object particle as finished catalyst.
2. preparation method according to claim 1, is characterized in that: the stir speed (S.S.) in step a) is all about 400-500 rev/min.
3. preparation method according to claim 1, is characterized in that: the heating rate in step b) is 10 DEG C/minute.
4. preparation method according to claim 1, is characterized in that: the heating rate in step c) is 10 DEG C/minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510078089.8A CN104607238B (en) | 2015-02-15 | 2015-02-15 | A kind of composite catalyst containing modified montmorillonite used and ZSM-8 and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510078089.8A CN104607238B (en) | 2015-02-15 | 2015-02-15 | A kind of composite catalyst containing modified montmorillonite used and ZSM-8 and preparation method thereof |
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| CN104607238A CN104607238A (en) | 2015-05-13 |
| CN104607238B true CN104607238B (en) | 2015-11-25 |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111090C (en) * | 1999-11-19 | 2003-06-11 | 中国科学院山西煤炭化学研究所 | Dual-component modified zeolite catalyst for aromatizing reaction of hydrocarbons |
| US9388092B2 (en) * | 2011-12-20 | 2016-07-12 | Saudi Basic Industries Corporation | Performance of Ga- and Zn-exchanged ZSM-5 zeolite catalyst for conversion of oxygenates to aromatics |
| CN103372456A (en) * | 2012-04-13 | 2013-10-30 | 上海中科高等研究院 | Molecular sieve based catalyst and preparation and application thereof |
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Inventor after: Xing Zhiyong Inventor after: Kang Lei Inventor after: Liu Yatong Inventor after: Li Nana Inventor before: Li Yuhua |
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Effective date of registration: 20151104 Address after: 150030 Xiangfang City, Harbin Province Wood Street, No. 59, No. Applicant after: Northeast Agricultural University Address before: Zhao Shi Shi Xin Cun Jiyang street 311899 Zhejiang city in Shaoxing Province, Zhuji City, No. 580 Applicant before: Li Yuhua |
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Inventor after: Li Yuhua Inventor before: Xing Zhiyong Inventor before: Kang Lei Inventor before: Liu Yatong Inventor before: Li Nana |
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Effective date of registration: 20160905 Address after: Zhao Shi Shi Xin Cun Jiyang street 311899 Zhejiang city in Shaoxing Province, Zhuji City, No. 580 Patentee after: Li Yuhua Address before: 150030 Xiangfang City, Harbin Province Wood Street, No. 59, No. Patentee before: Northeast Agricultural University |
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Effective date of registration: 20170515 Address after: 061000 chemical Avenue South, Cangzhou Lingang Development Zone, Cangzhou, Hebei Patentee after: Hebei Huamao Weiye Technology Co., Ltd. Address before: Zhao Shi Shi Xin Cun Jiyang street 311899 Zhejiang city in Shaoxing Province, Zhuji City, No. 580 Patentee before: Li Yuhua |
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Address after: 061000 South Chemical Avenue, Lingang Development Zone, Cangzhou City, Hebei Province Patentee after: Huamao Weiye Green Technology Co.,Ltd. Address before: 061000 South Chemical Avenue, Cangzhou Lingang Development Zone, Cangzhou City, Hebei Province Patentee before: Hebei Huamao Weiye Technology Co.,Ltd. |