CN106800298A - A kind of modified kaolin - Google Patents
A kind of modified kaolin Download PDFInfo
- Publication number
- CN106800298A CN106800298A CN201611244193.0A CN201611244193A CN106800298A CN 106800298 A CN106800298 A CN 106800298A CN 201611244193 A CN201611244193 A CN 201611244193A CN 106800298 A CN106800298 A CN 106800298A
- Authority
- CN
- China
- Prior art keywords
- kaolin
- acid
- roasting
- mixed material
- source
- 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.)
- Pending
Links
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002253 acid Substances 0.000 claims abstract description 29
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 28
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000012467 final product Substances 0.000 claims abstract description 6
- 230000010355 oscillation Effects 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 229910052622 kaolinite Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of modified kaolin, its preparation method is comprised the following steps：S1, mixed material：Cooling obtains roasting kaolin after kaolin is carried out into high-temperature roasting, by roasting kaolin, additional silicon source, outer zincification source and acid addition container, stirs, and mixed material is obtained；Mixed material is processed into 20 30min using the sonic oscillation of the 40kHz of frequency 30；S2, the mixed material filtering that will be prepared from step S1, is washed with deionized product, obtains mix slurry；S3, closed container high temperature heating response is put into by obtained mix slurry in step S2, and the temperature of heating is 120 ~ 165 DEG C, and isothermal reaction is obtained final product for 1 ~ 2 hour.Carried out in confined conditions in the preparation method of modified kaolin of the invention, enable the reaction of silicon source in the materials such as kaolin and zinc source and acid more completely, so that the consumption of inorganic acid reaches minimum, and other performance is also accordingly improved.
Description
Technical field
The present invention relates to technical field of kaolin, and in particular to a kind of modified kaolin.
Background technology
With the growth of World Economics, the demand to the energy increasingly increases.As one of most important energy in the world today
Oil will further be developed, therefore petroleum refining industry will keep its leading in terms of using energy source in 21st century
Status.
In China, current catalytic cracking carries the production task of the gasoline of China 75%, 35% diesel oil and propylene, therefore urges
Change the heart that cracking is also referred to as refinery in China.Therefore catalytic cracking technology also just it is natural become oil it is secondary plus
The dominant technology of work, its core technology is exactly catalyst.
Improving the heavy oil conversion performance of catalyst by improving matrix-active method turns into the direction of research, but related
All it is that the modified kaolin of acid is reused after filtering, washing in technology, because of kaolinic particle very little, causes filtering
Difficulty, it is difficult to carry out large-scale industrial production.
The content of the invention
In order to solve the above problems, the invention provides a kind of modified kaolin.
The present invention is achieved by the following technical programs：A kind of modified kaolin, its preparation method is comprised the following steps：
S1, mixed material：Cooling obtains roasting kaolin after kaolin is carried out into high-temperature roasting, by roasting kaolin, additional aluminium
In source, outer zincification source, acid addition container, stir, mixed material is obtained；By mixed material using the super of frequency 30-40kHz
Sound oscillation processes 20-30min；
S2, the mixed material filtering that will be prepared from step S1, is washed with deionized product, obtains mix slurry；
S3, closed container high temperature heating response is put into by obtained mix slurry in step S2, the temperature of heating for 120 ~
165 DEG C, isothermal reaction is obtained final product for 1 ~ 2 hour.
Preferably, the solid content of mixed material described in step S1 is 10 ~ 20%.
Preferably, acid described in step S1 is monoacid and the mixed acid of binary acid, monoacid and binary acid in mixed acid
Volume ratio be 1 ~ 2:3, acid concentration is 1 ~ 5M, and the consumption of the acid did not had the roasting kaolin, additional silicon source, additional at least
Zinc source surface.
Preferably, the monoacid is hydrochloric acid, perchloric acid or nitric acid, and the binary acid is sulfuric acid.
Preferably, the kaolin source before roasting is in hard kaoline and/or gangue, and crystal kaolinite content >=
95%。
Preferably, kaolinic sintering temperature is 800 ~ 1200 DEG C in step S1, and roasting time is 5 ~ 8 hours.
Preferably, the additional silicon source is metallic aluminium powder.
Preferably, the outer zincification source is metal zinc.
Modified kaolin of the invention is to carry out in confined conditions, and reaction can more completely, so that the use of inorganic acid
Amount reaches minimum, improves kaolinic performance；）Modified kaolin of the invention obtained have flourishing middle macropore pore volume and
Activity, stronger preventing from heavy metal ability is shown using the catalyst prepared containing this modified kaolin slurries.
Specific embodiment
The invention will be further described with the following Examples.
A kind of modified kaolin of embodiment 1, is prepared by following steps：
S1, mixed material：By the kaolin of crystal kaolinite content >=95% after 800 ~ 1200 DEG C of 5 ~ 8h of high-temperature roasting, cooling,
Roasting kaolin is obtained, by roasting kaolin, additional silicon source（Metallic aluminium powder）, outer zincification source（Metal zinc）And acid（Concentration 3M's
Mixed acid）Add in container, stir, prepared solid content is 15% mixed material；Mixed material is used into frequency 30-
The sonic oscillation treatment 25min of 40kHz；
Wherein, sour consumption is do not had the roasting kaolin, additional silicon source, outer zincification source surface；Mixed acid is by perchloric acid
With sulfuric acid according to volume ratio be 1.5:3 prepare；
S2, the mixed material filtering that will be prepared from step S1, is washed with deionized product, obtains mix slurry；
S3, closed container high temperature heating response is put into by obtained mix slurry in step S2, the temperature of heating for 140 ~
155 DEG C, isothermal reaction is obtained final product for 2 hours.
A kind of modified kaolin of embodiment 2, is prepared by following steps：
S1, mixed material：By the kaolin of crystal kaolinite content >=95% after 800 ~ 1200 DEG C of 5 ~ 8h of high-temperature roasting, cooling,
Roasting kaolin is obtained, by roasting kaolin, additional silicon source（Metallic aluminium powder）, outer zincification source（Metal zinc）And acid（Concentration 1M's
Mixed acid）Add in container, stir, prepared solid content is 10% mixed material；Mixed material is used into frequency 30-
The sonic oscillation treatment 20min of 40kHz；
Wherein, sour consumption is do not had the roasting kaolin, additional silicon source, outer zincification source surface；Mixed acid be by nitric acid and
Sulfuric acid is 1 according to volume ratio:3 prepare；
S2, the mixed material filtering that will be prepared from step S1, is washed with deionized product, obtains mix slurry；
S3, closed container high temperature heating response is put into by obtained mix slurry in step S2, the temperature of heating for 150 ~
165 DEG C, isothermal reaction is obtained final product for 1 hour.
A kind of modified kaolin of embodiment 3, is prepared by following steps：
S1, mixed material：By the kaolin of crystal kaolinite content >=95% after 800 ~ 1200 DEG C of 5 ~ 8h of high-temperature roasting, cooling,
Roasting kaolin is obtained, by roasting kaolin, additional silicon source（Metallic aluminium powder）, outer zincification source（Metal zinc）And acid（Concentration 5M's
Mixed acid）Add in container, stir, prepared solid content is 20% mixed material；Mixed material is used into frequency 30-
The sonic oscillation treatment 30min of 40kHz；
Wherein, sour consumption is do not had the roasting kaolin, additional silicon source, outer zincification source surface；Mixed acid be by hydrochloric acid and
Sulfuric acid is 1 according to volume ratio：3 prepare；
S2, the mixed material filtering that will be prepared from step S1, is washed with deionized product, obtains mix slurry；
S3, closed container high temperature heating response is put into by obtained mix slurry in step S2, the temperature of heating for 120 ~
135 DEG C, isothermal reaction is obtained final product for 2 hours.
Claims (8)
1. a kind of modified kaolin, it is characterised in that：Its preparation method is comprised the following steps：
S1, mixed material：Cooling obtains roasting kaolin after kaolin is carried out into high-temperature roasting, by roasting kaolin, additional aluminium
In source, outer zincification source, acid addition container, stir, mixed material is obtained；By mixed material using the super of frequency 30-40kHz
Sound oscillation processes 20-30min；
S2, the mixed material filtering that will be prepared from step S1, is washed with deionized product, obtains mix slurry；
S3, closed container high temperature heating response is put into by obtained mix slurry in step S2, the temperature of heating for 120 ~
165 DEG C, isothermal reaction is obtained final product for 1 ~ 2 hour.
2. a kind of modified kaolin according to claim 1, it is characterised in that the solid of mixed material described in step S1 contains
Measure is 10 ~ 20%.
3. a kind of modified kaolin according to claim 1, it is characterised in that the acid is mixed for monoacid and binary acid
Acid is closed, the volume ratio of monoacid and binary acid is 1 ~ 2 in mixed acid:3, acid concentration is 1 ~ 5M, and the sour consumption did not had described
Roasting kaolin, additional silicon source, outer zincification source.
4. a kind of modified kaolin according to claim 3, it is characterised in that the monoacid be hydrochloric acid, perchloric acid or
Nitric acid, the binary acid is sulfuric acid.
5. a kind of modified kaolin according to claim 1, it is characterised in that the kaolin source before roasting is in hard
Kaolin and/or gangue, and crystal kaolinite content >=95%.
6. a kind of modified kaolin according to claim 1, it is characterised in that kaolinic sintering temperature is in step S1
800 ~ 1200 DEG C, roasting time is 5 ~ 8 hours.
7. a kind of modified kaolin according to claim 1, it is characterised in that the additional silicon source is metallic aluminium powder.
8. a kind of modified kaolin according to claim 1, it is characterised in that the outer zincification source is metal zinc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611244193.0A CN106800298A (en) | 2016-12-29 | 2016-12-29 | A kind of modified kaolin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611244193.0A CN106800298A (en) | 2016-12-29 | 2016-12-29 | A kind of modified kaolin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106800298A true CN106800298A (en) | 2017-06-06 |
Family
ID=58985194
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611244193.0A Pending CN106800298A (en) | 2016-12-29 | 2016-12-29 | A kind of modified kaolin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106800298A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2120571A (en) * | 1982-05-21 | 1983-12-07 | Grace W R & Co | Cracking catalyst and catalyst support compositions |
| US4843052A (en) * | 1982-05-21 | 1989-06-27 | W. R. Grace & Co.-Conn. | Acid-reacted metakaolin catalyst and catalyst support compositions |
| CN1195014A (en) * | 1997-03-31 | 1998-10-07 | 中国石油化工总公司 | Process for modifying kaolin |
| CN1449866A (en) * | 2003-04-25 | 2003-10-22 | 中山大学 | Inorganic intercalation nano catalyst and preparation process 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 |
| CN102188963A (en) * | 2010-03-10 | 2011-09-21 | 中国石油天然气股份有限公司 | Method for modifying kaolin |
-
2016
- 2016-12-29 CN CN201611244193.0A patent/CN106800298A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2120571A (en) * | 1982-05-21 | 1983-12-07 | Grace W R & Co | Cracking catalyst and catalyst support compositions |
| US4843052A (en) * | 1982-05-21 | 1989-06-27 | W. R. Grace & Co.-Conn. | Acid-reacted metakaolin catalyst and catalyst support compositions |
| CN1195014A (en) * | 1997-03-31 | 1998-10-07 | 中国石油化工总公司 | Process for modifying kaolin |
| CN1449866A (en) * | 2003-04-25 | 2003-10-22 | 中山大学 | Inorganic intercalation nano catalyst and preparation process 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 |
| CN102188963A (en) * | 2010-03-10 | 2011-09-21 | 中国石油天然气股份有限公司 | Method for modifying kaolin |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170606 |
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| RJ01 | Rejection of invention patent application after publication |