CN104399445A - Preparation method of catalytic cracking catalyst - Google Patents
Preparation method of catalytic cracking catalyst Download PDFInfo
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- CN104399445A CN104399445A CN201410615717.7A CN201410615717A CN104399445A CN 104399445 A CN104399445 A CN 104399445A CN 201410615717 A CN201410615717 A CN 201410615717A CN 104399445 A CN104399445 A CN 104399445A
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- parts
- kaolin
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- catalytic cracking
- cracking catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 29
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 20
- 239000004202 carbamide Substances 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000011549 crystallization solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000002687 intercalation Effects 0.000 claims description 5
- 238000009830 intercalation Methods 0.000 claims description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000295 fuel oil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method of a catalytic cracking catalyst, and belongs to the technical field of catalyst preparation. Raw ores of kaolin are modified to obtain high-quality purified kaolin, and the purified kaolin is used in a catalytic cracking catalyst in order to effectively improve the catalysis efficiency of the prepared catalytic cracking catalyst.
Description
Technical field
The present invention relates to catalyst preparation technical field, particularly relate to a kind of preparation method of catalytic cracking catalyst.
Background technology
In the heavy oil deep process technology of petroleum refining process, catalytic cracking is a kind of most important secondary operations means of oil plant, and it makes more heavy oil obtain lighting.The know-why of catalytic cracking is that macromolecular cleavage becomes micromolecular chemical catalysis process, and be with acid centre be active sites acidic catalyst reaction.The core technology of research catalytic process and catalytic cracking catalyst to be one be now chemical industry and important science and technology basis.Wherein, in current catalytic cracking catalyst, take kaolin as the catalytic cracking catalyst of key component.The catalytic efficiency of this catalytic cracking catalyst is higher than other catalytic cracking catalysts, but due to the poor performance of most feed kaolin, causes the catalytic efficiency of its obtained catalytic cracking catalyst to can not get effective raising always.
Summary of the invention
The invention provides a kind of preparation method of catalytic cracking catalyst, this preparation method effectively can solve the poor performance because of feed kaolin, causes the catalytic efficiency of its obtained catalytic cracking catalyst to can not get the problem effectively improved always.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
It comprises following preparation process:
A, by weight, the abundant mixing and stirring in open container by 80 parts of kaolin and 40 parts ~ 130 parts urea, then proceed in closed container, be heated to 90 DEG C ~ 100 DEG C and carry out insulation reaction, until obtain kaolin-urea intercalated compound that intercalation rate reaches 99%;
B, kaolin-urea intercalated compound obtained for step A to be mixed with 20 parts ~ 40 parts triethanolamines, be heated to 120 DEG C ~ 130 DEG C and carry out insulation reaction 1 hour ~ 2 hours;
C, after step B, 450 parts ~ 1000 parts 0.5mol/L iodomethane ethanolic solutions are added and 1000 parts ~ 2000 parts 0.3mol/L sodium cetanesulfonate aqueous solution are even in the mixture that step B is obtained, first be cooled to 50 DEG C ~ 80 DEG C, insulation reaction 1 hour ~ 2 hours; And then be warming up to 130 DEG C ~ 150 DEG C, insulation reaction 1 hour ~ 2 hours, obtained Modification of kaolin slurry;
D. by the spray-dried one-tenth microballoon of Modification of kaolin slurry that step C is obtained, then at the temperature of 750 DEG C ~ 850 DEG C, roasting 2 hours ~ 4 hours;
E. by microballoon obtained for D step and additional aluminium source, acid solution microballoon in mass ratio: additional aluminium source: the ratio of acid solution=1:0.1 ~ 0.5:0.5 ~ 0.8 stirs, mixes, then under air-proof condition, 90 DEG C ~ 100 DEG C are heated to, isothermal reaction 1 hour ~ 2 hours, filter, drying, obtains refining kaolin;
F. the modified kaolin of E step roasting and alkali crystallization solution to be mixed under the hydrothermal condition being incorporated in 95 DEG C ~ 100 DEG C crystallization 10 hours ~ 15 hours, then filter, wash.
In technique scheme, technical scheme is more specifically: the particle diameter of described microballoon is 0.05 millimeter ~ 0.06 millimeter.
Further, described additional aluminium source is the one in metallic aluminium powder, aluminium chloride.
Further, described acid solution is the one in hydrochloric acid solution, salpeter solution.
Owing to adopting technique scheme, the beneficial effect that the present invention obtains is:
The present invention, by kaolin raw ore is carried out modification, obtains the refining kaolin of high-quality, and is used in catalytic cracking catalyst by this refining kaolin, thus the catalytic efficiency of the catalytic cracking catalyst obtained is effectively improved.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, and protection scope of the present invention is not only confined to following examples.
Embodiment 1
The preparation method of this catalytic cracking catalyst is as follows:
A, by weight, the abundant mixing and stirring in open container by 80 parts of kaolin and 40 parts of urea, then proceeds in closed container, is heated to 90 DEG C and carries out insulation reaction, until obtain kaolin-urea intercalated compound that intercalation rate reaches 99%;
B, kaolin-urea intercalated compound obtained for step A to be mixed with 40 parts of triethanolamines, be heated to 120 DEG C and carry out insulation reaction 2 hours;
C, after step B, in the mixture that step B is obtained, add 450 parts of 0.5mol/L iodomethane ethanolic solutions and 2000 parts of 0.3mol/L sodium cetanesulfonate aqueous solution are even, be first cooled to 50 DEG C, insulation reaction 2 hours; And then be warming up to 130 DEG C, insulation reaction 2 hours, obtained Modification of kaolin slurry;
D. the spray-dried one-tenth particle diameter of Modification of kaolin slurry step C obtained is the microballoon of 0.05 millimeter, then at the temperature of 750 DEG C, and roasting 4 hours;
E. by microballoon obtained for D step and metallic aluminium powder, hydrochloric acid solution microballoon in mass ratio: metallic aluminium powder: the ratio of hydrochloric acid solution=1:0.1:0.8 stirs, mixes, then under air-proof condition, be heated to 90 DEG C, isothermal reaction 2 hours, filter, drying, obtains refining kaolin;
F. the modified kaolin of E step roasting and alkali crystallization solution to be mixed under the hydrothermal condition being incorporated in 98 DEG C crystallization 14 hours, then filter, wash.
Compared with similar products, the catalytic efficiency of the catalytic cracking catalyst obtained by the present embodiment improves 12%.
Embodiment 2
The preparation method of this catalytic cracking catalyst is as follows:
A, by weight, the abundant mixing and stirring in open container by 80 parts of kaolin and 130 parts of urea, then proceeds in closed container, is heated to 100 DEG C and carries out insulation reaction, until obtain kaolin-urea intercalated compound that intercalation rate reaches 99%;
B, kaolin-urea intercalated compound obtained for step A to be mixed with 20 parts of triethanolamines, be heated to 130 DEG C and carry out insulation reaction 1 hour;
C, after step B, in the mixture that step B is obtained, add 1000 parts of 0.5mol/L iodomethane ethanolic solutions and 1000 parts of 0.3mol/L sodium cetanesulfonate aqueous solution are even, be first cooled to 80 DEG C, insulation reaction 1 hour; And then be warming up to 150 DEG C, insulation reaction 1 hour, obtained Modification of kaolin slurry;
D. the spray-dried one-tenth particle diameter of Modification of kaolin slurry step C obtained is the microballoon of 0.06 millimeter, then at the temperature of 850 DEG C, and roasting 2 hours;
E. by microballoon obtained for D step and aluminium chloride, salpeter solution microballoon in mass ratio: aluminium chloride: the ratio of salpeter solution=1:0.5:0.5 stirs, mixes, then under air-proof condition, be heated to 100 DEG C, isothermal reaction 1 hour, filter, drying, obtains refining kaolin;
F. the modified kaolin of E step roasting and alkali crystallization solution to be mixed under the hydrothermal condition being incorporated in 95 DEG C crystallization 15 hours, then filter, wash.
Compared with similar products, the catalytic efficiency of the catalytic cracking catalyst obtained by the present embodiment improves 14%.
Embodiment 3
The preparation method of this catalytic cracking catalyst is as follows:
A, by weight, the abundant mixing and stirring in open container by 80 parts of kaolin and 80 parts of urea, then proceeds in closed container, is heated to 95 DEG C and carries out insulation reaction, until obtain kaolin-urea intercalated compound that intercalation rate reaches 99%;
B, kaolin-urea intercalated compound obtained for step A to be mixed with 30 parts of triethanolamines, be heated to 125 DEG C and carry out insulation reaction 1.5 hours;
C, after step B, in the mixture that step B is obtained, add 750 parts of 0.5mol/L iodomethane ethanolic solutions and 1500 parts of 0.3mol/L sodium cetanesulfonate aqueous solution are even, be first cooled to 60 DEG C, insulation reaction 1.5 hours; And then be warming up to 140 DEG C, insulation reaction 1.5 hours, obtained Modification of kaolin slurry;
D. the spray-dried one-tenth particle diameter of Modification of kaolin slurry step C obtained is the microballoon of 0.05 millimeter, then at the temperature of 800 DEG C, and roasting 3 hours;
E. by microballoon obtained for D step and metallic aluminium powder, salpeter solution microballoon in mass ratio: metallic aluminium powder: the ratio of salpeter solution=1:0.3:0.7 stirs, mixes, then under air-proof condition, be heated to 95 DEG C, isothermal reaction 1.5 hours, filter, drying, obtains refining kaolin;
F. the modified kaolin of E step roasting and alkali crystallization solution to be mixed under the hydrothermal condition being incorporated in 100 DEG C crystallization 10 hours, then filter, wash.
Compared with similar products, the catalytic efficiency of the catalytic cracking catalyst obtained by the present embodiment improves 13%.
Claims (4)
1. a preparation method for catalytic cracking catalyst, is characterized in that comprising following preparation process:
A, by weight, the abundant mixing and stirring in open container by 80 parts of kaolin and 40 parts ~ 130 parts urea, then proceed in closed container, be heated to 90 DEG C ~ 100 DEG C and carry out insulation reaction, until obtain kaolin-urea intercalated compound that intercalation rate reaches 99%;
B, kaolin-urea intercalated compound obtained for step A to be mixed with 20 parts ~ 40 parts triethanolamines, be heated to 120 DEG C ~ 130 DEG C and carry out insulation reaction 1 hour ~ 2 hours;
C, after step B, 450 parts ~ 1000 parts 0.5mol/L iodomethane ethanolic solutions are added and 1000 parts ~ 2000 parts 0.3mol/L sodium cetanesulfonate aqueous solution are even in the mixture that step B is obtained, first be cooled to 50 DEG C ~ 80 DEG C, insulation reaction 1 hour ~ 2 hours; And then be warming up to 130 DEG C ~ 150 DEG C, insulation reaction 1 hour ~ 2 hours, obtained Modification of kaolin slurry;
D. by the spray-dried one-tenth microballoon of Modification of kaolin slurry that step C is obtained, then at the temperature of 750 DEG C ~ 850 DEG C, roasting 2 hours ~ 4 hours;
E. by microballoon obtained for D step and additional aluminium source, acid solution microballoon in mass ratio: additional aluminium source: the ratio of acid solution=1:0.1 ~ 0.5:0.5 ~ 0.8 stirs, mixes, then under air-proof condition, 90 DEG C ~ 100 DEG C are heated to, isothermal reaction 1 hour ~ 2 hours, filter, drying, obtains refining kaolin;
F. the modified kaolin of E step roasting and alkali crystallization solution to be mixed under the hydrothermal condition being incorporated in 95 DEG C ~ 100 DEG C crystallization 10 hours ~ 15 hours, then filter, wash.
2. catalytic cracking catalyst according to claim 1, is characterized in that: the particle diameter of described microballoon is 0.05 millimeter ~ 0.06 millimeter.
3. catalytic cracking catalyst according to claim 2, is characterized in that: described additional aluminium source is the one in metallic aluminium powder, aluminium chloride.
4. the catalytic cracking catalyst according to claim 1 or 2 or 3, is characterized in that: described acid solution is the one in hydrochloric acid solution, salpeter solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410615717.7A CN104399445B (en) | 2014-11-05 | The preparation method of catalytic cracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410615717.7A CN104399445B (en) | 2014-11-05 | The preparation method of catalytic cracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104399445A true CN104399445A (en) | 2015-03-11 |
| CN104399445B CN104399445B (en) | 2017-01-04 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6613710B2 (en) * | 2001-09-25 | 2003-09-02 | Indian Oil Corporation Limited | Process for preparation of bi-functional fluid catalytic cracking catalyst composition |
| CN102167346A (en) * | 2011-01-30 | 2011-08-31 | 福州大学 | Kaolin nanotube and preparation method thereof |
| CN102188964A (en) * | 2010-03-10 | 2011-09-21 | 中国石油天然气股份有限公司 | Method for preparing modified kaolin with mixed acid |
| CN102583413A (en) * | 2012-02-17 | 2012-07-18 | 中国科学院广州地球化学研究所 | Method for preparing aluminosilicate nanotube by using kaolinite raw material |
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6613710B2 (en) * | 2001-09-25 | 2003-09-02 | Indian Oil Corporation Limited | Process for preparation of bi-functional fluid catalytic cracking catalyst composition |
| CN102188964A (en) * | 2010-03-10 | 2011-09-21 | 中国石油天然气股份有限公司 | Method for preparing modified kaolin with mixed acid |
| CN102167346A (en) * | 2011-01-30 | 2011-08-31 | 福州大学 | Kaolin nanotube and preparation method thereof |
| CN102583413A (en) * | 2012-02-17 | 2012-07-18 | 中国科学院广州地球化学研究所 | Method for preparing aluminosilicate nanotube by using kaolinite raw material |
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Address after: Huanjiang Maonan Autonomous County, Hechi City, the Guangxi Zhuang Autonomous Region 547100 Enzhen North Development Zone Patentee after: Wu Junrong Address before: 545005 the Guangxi Zhuang Autonomous Region Liuzhou Liunan District City Station Road No. 94 District 18 Building 2 unit 401 Patentee before: Wu Junrong |
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Effective date of registration: 20201123 Address after: 535035 5th floor, building 6, light equipment production building, science and Technology Park (business incubation base), No.5 Zhongma street, Qinzhou Industrial Park, Qinzhou City, Guangxi Zhuang Autonomous Region Patentee after: GUANGXI ZHONGMA INDUSTRIAL PARK MANUFACTURED BY YOU TECHNOLOGY Co.,Ltd. Address before: Huanjiang Maonan Autonomous County, Hechi City, the Guangxi Zhuang Autonomous Region 547100 Enzhen North Development Zone Patentee before: Wu Junrong |
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