CN111484027A - Kaolin product for catalytic cracking catalyst and preparation method thereof - Google Patents
Kaolin product for catalytic cracking catalyst and preparation method thereof Download PDFInfo
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- CN111484027A CN111484027A CN202010528256.5A CN202010528256A CN111484027A CN 111484027 A CN111484027 A CN 111484027A CN 202010528256 A CN202010528256 A CN 202010528256A CN 111484027 A CN111484027 A CN 111484027A
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- stirring
- kaolin
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- chlorine dioxide
- catalytic cracking
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- 235000012211 aluminium silicate Nutrition 0.000 title claims abstract description 60
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000005995 Aluminium silicate Substances 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000003756 stirring Methods 0.000 claims abstract description 48
- 239000004155 Chlorine dioxide Substances 0.000 claims abstract description 43
- 235000019398 chlorine dioxide Nutrition 0.000 claims abstract description 43
- 239000000047 product Substances 0.000 claims abstract description 41
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 239000003094 microcapsule Substances 0.000 claims abstract description 34
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 26
- 239000012065 filter cake Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 22
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 8
- 238000012216 screening Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 23
- 239000012071 phase Substances 0.000 claims description 21
- 150000007522 mineralic acids Chemical class 0.000 claims description 17
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 17
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 17
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003921 oil Substances 0.000 claims description 15
- 239000004115 Sodium Silicate Substances 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 12
- 239000011162 core material Substances 0.000 claims description 11
- 108010010803 Gelatin Proteins 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000008273 gelatin Substances 0.000 claims description 10
- 229920000159 gelatin Polymers 0.000 claims description 10
- 235000019322 gelatine Nutrition 0.000 claims description 10
- 235000011852 gelatine desserts Nutrition 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229940057995 liquid paraffin Drugs 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 238000001471 micro-filtration Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000011085 pressure filtration Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 239000011449 brick Substances 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 24
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002585 base Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000013068 control sample Substances 0.000 description 8
- 230000009471 action Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 239000004927 clay Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010457 zeolite Substances 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
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kaolin product for a catalytic cracking catalyst and a preparation method thereof, belonging to the technical field of kaolin preparation. The technical key points comprise the following steps: s1, crushing and screening the excavated product containing 90% or more than 90% of halloysite to obtain a kaolin base material; s2, preparing 100-120 parts of kaolin base material into slurry, adding 50-60 parts of chlorine dioxide microcapsules into the slurry, adding 0.5-0.8 part of dispersing agent, blending and uniformly stirring; s3, adjusting the pH value of the slurry to 6-7, then adding 0.65-0.9 part of sodium hydrosulfite into the slurry, and stirring uniformly; s4, concentrating the slurry, and performing filter pressing and dehydration to obtain a filter cake; and S5, drying the filter cake, and crushing to obtain the finished product, wherein the finished product has the advantage of improving the pores and the specific surface of the halloysite.
Description
Technical Field
The invention belongs to the technical field of kaolin preparation, and particularly relates to a kaolin product for a catalytic cracking catalyst and a preparation method thereof
Background
Catalytic cracking is a process of subjecting crude oil to a series of chemical reactions at a certain temperature (460 ℃ -550 ℃) in the presence of a catalyst. The study of catalytic processes and catalytic cracking catalysts (FCC) is a core technology and an important scientific and technological base of the petrochemical industry today. In the history of the development of catalytic cracking catalysts, roughly three major changes have been experienced. The first time, the synthetic aluminum silicate gel is used for replacing activated clay, so that the activity is improved by 2-3 times, and the selectivity is also obviously improved. The second time is to change the molecular sieve, so that the catalytic cracking level is improved by a large step, the gasoline yield is increased by 7-10%, and the coke yield is reduced by about 40%. The evolution of the molecular sieve from X type to Y type makes the quality of the catalyst have a small step. The third time, the carrier route is changed since the middle of the 70 s, the adhesive and kaolin are adopted to replace the synthetic aluminum silicate gel as the carrier, the molecular sieve is used as the active ingredient to prepare the semi-synthetic catalytic cracking catalyst, compared with the molecular sieve catalyst, the catalyst has the advantages that the yield of light oil is improved by more than 3 percent, and the abrasion index is improved by about 3 times.
The catalytic cracking catalyst with kaolin as main component is the main catalyst in petrochemical industry. In more than 40 million tons of catalytic cracking catalysts produced in the world today, almost all catalysts with kaolin as a main component are added. Compared with the synthetic zeolite molecular sieve catalyst, the catalytic cracking catalyst has the advantages of small specific surface area, larger pore volume, good wear resistance, strong alkali and heavy metal pollution resistance and the like, and is more suitable for preparing the catalyst for blending heavy oil or residual oil. The most critical problem of the development of the catalytic cracking catalyst is to have a high-quality natural clay resource. At present, the research on the application products and the production process of kaolin in the fields of paper making, ceramics, rubber and plastics, coatings and the like is quite large.
The Chinese patent with the publication number of CN101798096B discloses a method for preparing kaolin, which comprises the following steps: mining to remove impurities, excavating kaolin mineral aggregate, and primarily separating clay and impurities to obtain a base material; pulping and desanding, namely pulping the base material and desanding to obtain an ore pulp primary material; chemical bleaching, conveying the primary ore pulp material into a high-speed stirring tank for pulp storage, adding a sulfuric acid solution and a sodium dithionite solution, wherein the mass ratio of the sulfuric acid solution to the primary ore pulp material is 0.3: 100-0.8: 100, the mass ratio of the sodium dithionite solution to the primary kaolin ore pulp material is 0.6: 100-1.0: 100, adjusting the pH value of the mixed solution to be 2.0-3.0, and stirring at the speed of 140-180 r/min for 40-45 min to obtain a refined ore pulp material; washing and dehydrating, namely circularly washing and dehydrating the concentrated ore pulp to obtain final ore pulp; drying and pulverizing, namely performing filter pressing and dehydration on the ore pulp final material to obtain a kaolin filter cake, drying the kaolin filter cake, crushing and collecting to obtain a kaolin finished product. In the prior art, the preparation of kaolin is generally carried out by adopting the technical scheme.
However, the kaolin prepared by the above scheme has a small specific surface area and pores, resulting in a small number of active centers, so that its ability to crack petroleum molecules is limited.
Therefore, a new solution is needed to solve the above problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a kaolin product for a catalytic cracking catalyst, which has the advantage of improving the porosity and specific surface of the halloysite.
The second purpose of the invention is to provide a kaolin product for a catalytic cracking catalyst, which has the advantages of large pores and specific surface area and can be suitable for heavy oil catalytic cracking.
In order to achieve the first purpose, the invention provides the following technical scheme:
a preparation method of kaolin product for catalytic cracking catalyst comprises the following steps:
s1, preparing a chlorine dioxide microcapsule;
s11, preparing a stable chlorine dioxide aqueous solution, and performing pressure filtration through a microporous filter membrane to obtain a chlorine dioxide core material;
s12, dissolving gelatin in the chlorine dioxide core material, and dissolving the gelatin in a constant-temperature water bath kettle at 40-50 ℃ for 50-60min to obtain an aqueous phase solution with the gelatin concentration of 1-90 g/L;
s13, dissolving P L A in dichloromethane, and stirring for 120-130min under the condition of mechanical stirring to obtain an oil phase solution with the concentration of P L A of 1-200 g/L;
s14, placing the oil phase solution on a mechanical stirrer for stirring, adding the emulsifier while stirring, adding the water phase solution after uniformly stirring, adding the liquid paraffin under the high-speed stirring of 300-2000r/min for continuous stirring, then stirring at the low speed of 150-200r/min for 120-240min by using a magnetic stirrer, volatilizing dichloromethane, performing vacuum filtration, and performing freeze drying to obtain chlorine dioxide microcapsule powder;
s2, crushing and screening the excavated product containing 90% or more than 90% of halloysite to obtain a kaolin base material;
s3, preparing 100-120 parts of kaolin base material into slurry, adding 50-60 parts of chlorine dioxide microcapsules into the slurry, adding 0.5-0.8 part of dispersing agent, blending and uniformly stirring;
s4, adjusting the pH value of the slurry to 6-7, then adding 0.65-0.9 part of sodium hydrosulfite into the slurry, and stirring uniformly;
s5, concentrating the slurry, and performing filter pressing and dehydration to obtain a filter cake;
and S6, drying the filter cake, and crushing to obtain the finished product.
By adopting the technical scheme, the chlorine dioxide microcapsules are added into the halloysite, so that the chlorine dioxide microcapsules can be embedded into pores of the halloysite under the action of the dispersing agent in the pulping process, and the P L A is corroded under the action of moisture along with the preparation of the halloysite, so that the chlorine dioxide and water react to generate hydrochloric acid, and the hydrochloric acid can corrode the inner walls of the pores of the halloysite, thereby expanding the pores of the halloysite and improving the specific surface area of the halloysite.
More preferably, the filtration precision of the microfiltration membrane is 0.5 to 1 μm.
By adopting the technical scheme, the filtering precision of the microporous filter membrane is 0.5-1 μm, so that the size of the chlorine dioxide microcapsule is less than 1 μm, and the chlorine dioxide can enter pores of the halloysite, thereby having a corrosion effect on the inner walls of the pores; the size of the chlorine dioxide microcapsule is larger than 0.5 μm, so that the chlorine dioxide microcapsule can be conveniently collected, and the problem that the chlorine dioxide microcapsule is difficult to collect due to the undersize of the chlorine dioxide microcapsule is avoided.
More preferably, the emulsifier in S13 is spn 80.
By adopting the technical scheme.
More preferably, the dispersing agent is a mixed solution of a sodium hexametaphosphate solution and sodium silicate, and the weight part ratio of the sodium hexametaphosphate solution to the sodium silicate is 1: 2.5-4.
By adopting the technical scheme, the dispersing agent is added into the slurry to be adsorbed on the surfaces of the particles, and the properties of the surfaces of the particles are changed, so that the interaction force between the particles and water and between the particles is changed, the particles have stronger repulsive force, and the flocculation time of the slurry is prolonged; in the actual production process, because the sodium hexametaphosphate solution is high in price, the amount of the sodium hexametaphosphate solution can be reduced by blending the weight part ratio of the sodium hexametaphosphate solution to the sodium silicate under the condition of not influencing the effect of the dispersing agent, and the aim of reducing the production cost is fulfilled.
More preferably, 1.2-2.5 parts of inorganic acid is further added into the S4, and the inorganic acid is one or more of sulfuric acid, hydrochloric acid and nitric acid.
By adopting the technical scheme, the inorganic acid is added, so that the inner wall of the pores of the halloysite can be corroded, and the effect of further enlarging the pores is achieved; meanwhile, under the action of inorganic acid, the speed of converting chlorine dioxide into hydrochloric acid is increased, so that the hydrochloric acid in the gaps corrodes the inner walls of the gaps, and the problem that the gaps are too small due to the fact that the inorganic acid solution cannot permeate into the aluminum atoms in the kaolin structure and cannot be contacted for treatment due to the influence of capillary effect is avoided.
More preferably, the inorganic acid is sulfuric acid.
By adopting the technical scheme, the inorganic acid adopts sulfuric acid, so that the bleaching effect on the pulp can be realized before the corrosion effect on the kaolin pores is realized, and the whiteness of the halloysite is improved.
More preferably, the filter cake in S5 is made into a brick.
By adopting the technical scheme, when the yield of the kaolin is high, the filter cakes are piled together for air drying, and the filter cake in the central part needs longer air drying time; after making the filter cake into the brick body, can be convenient for the staff to carry, stack the filter cake, can avoid the filter cake to pile up together and influence the air-dry speed of filter cake simultaneously.
In order to achieve the second purpose, the invention provides the following technical scheme:
a kaolin product for a catalytic cracking catalyst, which is prepared by the method for preparing a kaolin product for a catalytic cracking catalyst according to any one of claims 1 to 7.
By adopting the technical scheme, the kaolin product for the catalytic cracking catalyst prepared by adopting the scheme has larger pores and specific surface area, and can be suitable for catalytic cracking of heavy oil.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) adding chlorine dioxide microcapsules into the halloysite, so that the chlorine dioxide microcapsules can be embedded into pores of the halloysite under the action of a dispersing agent in the pulping process, and along with the preparation of the halloysite, P L A is corroded under the action of moisture, so that chlorine dioxide and water react to generate hydrochloric acid, and the hydrochloric acid can corrode the inner walls of the pores of the halloysite, thereby expanding the pores of the halloysite and improving the specific surface area of the halloysite;
(2) the filtering precision of the microporous filter membrane is 0.5-1 μm, so that the size of the chlorine dioxide microcapsule is less than 1 μm, and the chlorine dioxide can enter pores of the halloysite, thereby having a corrosion effect on the inner walls of the pores; the size of the chlorine dioxide microcapsule is larger than 0.5 mu m, so that the chlorine dioxide microcapsule can be conveniently collected, and the problem that the chlorine dioxide microcapsule is difficult to collect due to the undersize of the chlorine dioxide microcapsule is avoided;
(3) under the action of inorganic acid, the speed of converting chlorine dioxide into hydrochloric acid is increased, so that the hydrochloric acid corrodes the inside of the pore, and the inside of the pore is further corroded compared with the corrosion of the inorganic acid, thereby achieving the effect of improving the pore.
Detailed Description
The present invention will be described in further detail with reference to examples.
In the following examples and comparative examples:
chlorine dioxide is produced by Lin \26384A;
the gelatin is prepared from Henan Boyang Biotechnology limited company;
p L A was polylactic acid sold by Dongguan Juduo trade company, Inc.;
the span 80 is span 80 produced by Guangdong Runhua chemical Co., Ltd;
the liquid paraffin is sold by Fushun Shengwei petrochemical product sale limited company;
the sodium hexametaphosphate is sodium hexametaphosphate produced by eastern Bai chemical Co., Ltd, Suzhou;
the sodium silicate is produced by Shijiazhuang Hengruid science and technology limited;
the sodium hydrosulfite is produced by Hunan province silver bridge science and technology limited company;
the sulfuric acid, hydrochloric acid and nitric acid are commercially available sulfuric acid, hydrochloric acid and nitric acid.
Preparation example 1:
the preparation of the chlorine dioxide microcapsule comprises the following steps:
s1, preparing 100ml of stable chlorine dioxide aqueous solution with the concentration of 37000 mg/L, and obtaining a chlorine dioxide core material after pressure filtration through a microporous filter membrane with the filtration precision of 0.5 mu m;
s2, dissolving 0.1g of gelatin in the chlorine dioxide core material, and dissolving in a constant-temperature water bath kettle at 40 ℃ for 60min to obtain a water phase solution for later use;
s3, dissolving 0.1g of P L A in 100ml of dichloromethane, and stirring for 120min under the condition of mechanical stirring to completely dissolve the solution to obtain an oil phase solution;
s4, measuring 30ml of oil phase solution, placing the oil phase solution on a mechanical stirrer for stirring, adding 0.3ml of span 80 emulsifier while stirring, adding 30ml of water phase solution after uniformly stirring, adding 20ml of liquid paraffin after stirring for 5min at 300r/min, continuing stirring for 1min, transferring and stirring for 180min at low speed of 200r/min by using a magnetic stirrer, volatilizing dichloromethane, carrying out vacuum filtration, and carrying out freeze drying to obtain microcapsule powder.
Preparation example 2:
the preparation of the chlorine dioxide microcapsule comprises the following steps:
s1, preparing 100ml of stable chlorine dioxide aqueous solution with the concentration of 37000 mg/L, and obtaining a chlorine dioxide core material after pressure filtration through a microporous filter membrane with the filtration precision of 0.5 mu m;
s2, dissolving 5g of gelatin in the chlorine dioxide core material, and dissolving for 60min in a constant-temperature water bath kettle at 40 ℃ to obtain a water phase solution for later use;
s3, dissolving 10g of P L A in 100ml of dichloromethane, and stirring for 120min under the condition of mechanical stirring to completely dissolve the solution to obtain an oil phase solution;
s4, measuring 30ml of oil phase solution, placing the oil phase solution on a mechanical stirrer for stirring, adding 3ml of span 80 emulsifier while stirring, adding 3ml of water phase solution after uniformly stirring, adding 20ml of liquid paraffin after stirring for 2min at 1200r/min, continuing stirring for 1min, transferring and stirring for 180min at a low speed of 200r/min by using a magnetic stirrer, volatilizing dichloromethane, carrying out vacuum filtration, and carrying out freeze drying to obtain microcapsule powder.
Preparation example 3:
the preparation of the chlorine dioxide microcapsule comprises the following steps:
s1, preparing 100ml of stable chlorine dioxide aqueous solution with the concentration of 37000 mg/L, and obtaining a chlorine dioxide core material after pressure filtration through a microporous filter membrane with the filtration precision of 0.5 mu m;
s2, dissolving 10g of gelatin in the chlorine dioxide core material, and dissolving for 60min in a constant-temperature water bath kettle at 40 ℃ to obtain a water phase solution for later use;
s3, dissolving 20g of P L A in 100ml of dichloromethane, and stirring for 120min under the condition of mechanical stirring to completely dissolve the solution to obtain an oil phase solution;
s4, measuring 30ml of oil phase solution, placing the oil phase solution on a mechanical stirrer for stirring, adding 6ml of span 80 emulsifier while stirring, adding 1.5ml of water phase solution after uniformly stirring, adding 20ml of liquid paraffin after stirring for 3min at 2000r/min, continuing stirring for 1min, transferring and stirring for 180min at low speed of 200r/min by using a magnetic stirrer, volatilizing dichloromethane, carrying out vacuum filtration, and carrying out freeze drying to obtain microcapsule powder.
Preparation example 4:
the preparation of chlorine dioxide microcapsules differs from preparation example 3 in that:
the filtration precision of the microfiltration membrane in S1 was 0.7. mu.m.
Preparation example 5:
the preparation of chlorine dioxide microcapsules differs from preparation example 3 in that:
the filtration precision of the microfiltration membrane in S1 was 0.9. mu.m.
Preparation example 6:
the preparation of chlorine dioxide microcapsules differs from preparation example 3 in that:
the filtration precision of the microfiltration membrane in S1 was 1.0. mu.m.
Example 1: a method for preparing a kaolin product for a catalytic cracking catalyst, comprising the steps of:
s1, grinding a product containing more than 90% of halloysite in the mass by a ball mill, and screening by a vibrating screen to obtain a kaolin base material;
s2, preparing 100 parts of kaolin base material into slurry, adding 50 parts of chlorine dioxide microcapsules into the slurry, adding 0.5 part of mixed solution of sodium hexametaphosphate solution and sodium silicate, blending and uniformly stirring, wherein the weight part ratio of the sodium hexametaphosphate solution to the sodium silicate is 1: 2.5;
s3, adjusting the pH value of the slurry to 6, then adding 0.65 part of sodium hydrosulfite into the slurry, and stirring uniformly;
s4, concentrating the slurry, and performing filter pressing and dehydration to obtain a filter cake;
and S5, drying the filter cake, and crushing to obtain the finished product.
Example 2: a method for preparing a kaolin product for a catalytic cracking catalyst, comprising the steps of:
s1, grinding a product containing more than 90% of halloysite in the mass by a ball mill, and screening by a vibrating screen to obtain a kaolin base material;
s2, preparing 110 parts of kaolin base material into slurry, adding 55 parts of chlorine dioxide microcapsules into the slurry, adding 0.65 part of mixed solution of sodium hexametaphosphate solution and sodium silicate, blending and uniformly stirring, wherein the weight part ratio of the sodium hexametaphosphate solution to the sodium silicate is 1: 3.3;
s3, adjusting the pH value of the slurry to 6, then adding 0.75 part of sodium hydrosulfite into the slurry, and stirring uniformly;
s4, concentrating the slurry, and performing filter pressing and dehydration to obtain a filter cake;
and S5, drying the filter cake, and crushing to obtain the finished product.
Example 3: a method for preparing a kaolin product for a catalytic cracking catalyst, comprising the steps of:
s1, grinding a product containing more than 90% of halloysite in the mass by a ball mill, and screening by a vibrating screen to obtain a kaolin base material;
s2, preparing 120 parts of kaolin base material into slurry, adding 60 parts of chlorine dioxide microcapsules into the slurry, adding 0.8 part of mixed solution of sodium hexametaphosphate solution and sodium silicate, blending and uniformly stirring, wherein the weight part ratio of the sodium hexametaphosphate solution to the sodium silicate is 1: 4;
s3, adjusting the pH value of the slurry to 7, then adding 0.9 part of sodium hydrosulfite into the slurry, and stirring uniformly;
s4, concentrating the slurry, and performing filter pressing and dehydration to obtain a filter cake;
and S5, drying the filter cake, and crushing to obtain the finished product.
Example 4: a method for preparing a kaolin product for a catalytic cracking catalyst, which is different from example 3 in that: and 1.2 parts of inorganic acid is also added into the S4, wherein the inorganic acid is concentrated sulfuric acid.
Example 5: a method for preparing a kaolin product for a catalytic cracking catalyst, which is different from example 4 in that: the inorganic acid is concentrated hydrochloric acid.
Example 6: a method for preparing a kaolin product for a catalytic cracking catalyst, which is different from example 4 in that: the inorganic acid is concentrated nitric acid.
Example 7: a method for preparing a kaolin product for a catalytic cracking catalyst, which is different from example 4 in that: the inorganic acid adopts a mixture of concentrated sulfuric acid and concentrated hydrochloric acid, wherein the weight ratio of the concentrated sulfuric acid to the concentrated hydrochloric acid is 1: 1.
Example 8: a method for preparing a kaolin product for a catalytic cracking catalyst, which is different from example 4 in that: the inorganic acid is a mixture of concentrated sulfuric acid and concentrated nitric acid, wherein the weight ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 1.
Example 9: a method for preparing a kaolin product for a catalytic cracking catalyst, which is different from example 4 in that: and (5) preparing the filter cake in the S4 into a brick body.
Example 10: a kaolin product for a catalytic cracking catalyst, prepared by the method of preparation of a kaolin product for a catalytic cracking catalyst of examples 1-9.
Comparative example 1: kaolin was prepared according to example 1 disclosed in the chinese patent publication No. CN 101798096B.
Comparative example 2: a kaolin clay comprising the steps of:
s1, grinding a product containing more than 90% of halloysite in the mass by a ball mill, and screening by a vibrating screen to obtain a kaolin base material;
s2, preparing 120 parts of kaolin base material into slurry, adding 0.8 part of mixed solution of sodium hexametaphosphate solution and sodium silicate, blending and uniformly stirring, wherein the weight part ratio of the sodium hexametaphosphate solution to the sodium silicate is 1: 4;
s3, adjusting the pH value of the slurry to 7, then adding 0.9 part of sodium hydrosulfite into the slurry, and stirring uniformly;
s4, concentrating the slurry, and performing filter pressing and dehydration to obtain a filter cake;
and S5, drying the filter cake, and crushing to obtain the finished product.
And (3) performance testing:
experimental samples: the kaolin obtained in examples 1 to 9 was used as test samples 1 to 9, and the kaolin in comparative example 1 was used as control sample 1.
Experiment 1: specific surface area test
The experimental method comprises the following steps: the test samples 1 to 9 and the control sample 1 were tested with reference to GB/T19587-2004 "determination of specific surface area of solid substance by BET method by gas adsorption".
The experimental results are as follows: the test results of the test samples 1 to 9 and the control sample 1 are shown in Table 1.
Experiment 2: pore size testing
The experimental method comprises the following steps: the test samples 1-9 and the control sample 1 were tested according to the Hg porosity test method.
The experimental results are as follows: the test results of the test samples 1 to 9 and the control sample 1 are shown in Table 1 as cumulative intrusion volumes of 100. mu.m, 200. mu.m and 300. mu.m, respectively.
TABLE 1
And (3) analyzing experimental data: as can be seen from the comparison of the experimental samples 1-9 and the control sample 1, the specific surface areas of the experimental samples 1-9 are all larger than 452m2In contrast to control sample 1, which has a specific surface area of only 25m2The specific surface area of the experimental samples 1-9 is obviously larger than that of the control sample 1, which shows that the specific surface area of the kaolin prepared according to the method is obviously improved; meanwhile, it can be seen that the pore diameters of the kaolins prepared according to the method are between 200 μm and 300 μm as in the cumulative press-in volumes of the experimental samples 1 to 9 and the comparative example 1 at the pores of 50 μm, 100 μm and 200 μm; the chlorine dioxide microcapsules can be seen to have the effect of improving the gaps of the halloysite through experimental samples 1-9 and comparative example 2.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (8)
1. A preparation method of kaolin products for catalytic cracking catalysts is characterized by comprising the following steps:
s1, preparing a chlorine dioxide microcapsule;
s11, preparing a stable chlorine dioxide aqueous solution, and performing pressure filtration through a microporous filter membrane to obtain a chlorine dioxide core material;
s12, dissolving gelatin in the chlorine dioxide core material, and dissolving the gelatin in a constant-temperature water bath kettle at 40-50 ℃ for 50-60min to obtain an aqueous phase solution with the gelatin concentration of 1-90 g/L;
s13, dissolving P L A in dichloromethane, and stirring for 120-130min under the condition of mechanical stirring to obtain an oil phase solution with the concentration of P L A of 1-200 g/L;
s14, placing the oil phase solution on a mechanical stirrer for stirring, adding the emulsifier while stirring, adding the water phase solution after uniformly stirring, adding the liquid paraffin under the high-speed stirring of 300-2000r/min for continuous stirring, then stirring at the low speed of 150-200r/min for 120-240min by using a magnetic stirrer, volatilizing dichloromethane, performing vacuum filtration, and performing freeze drying to obtain chlorine dioxide microcapsule powder;
s2, crushing and screening the excavated product containing 90% or more than 90% of halloysite to obtain a kaolin base material;
s3, preparing 100-120 parts of kaolin base material into slurry, adding 50-60 parts of chlorine dioxide microcapsules into the slurry, adding 0.5-0.8 part of dispersing agent, blending and uniformly stirring;
s4, adjusting the pH value of the slurry to 6-7, then adding 0.65-0.9 part of sodium hydrosulfite into the slurry, and stirring uniformly;
s5, concentrating the slurry, and performing filter pressing and dehydration to obtain a filter cake;
and S6, drying the filter cake, and crushing to obtain the finished product.
2. The method of claim 1, wherein the microfiltration membrane has a filtration accuracy of 0.5 to 1 μm.
3. The method of claim 1, wherein the emulsifier in S13 is spn 80.
4. The method of claim 1, wherein the dispersant is a mixed solution of sodium hexametaphosphate solution and sodium silicate, and the weight ratio of the sodium hexametaphosphate solution to the sodium silicate is 1: 2.5-4.
5. The method of claim 1, wherein 1.2-2.5 parts of an inorganic acid is further added to the S4, and the inorganic acid is one or more of sulfuric acid, hydrochloric acid and nitric acid.
6. The method of claim 5, wherein the mineral acid is sulfuric acid.
7. The method of claim 1, wherein the filter cake of S5 is made into brick.
8. A kaolin product for a catalytic cracking catalyst, which is prepared by the method for preparing the kaolin product for the catalytic cracking catalyst according to any one of claims 1 to 7.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040237845A1 (en) * | 2002-11-15 | 2004-12-02 | Alan Hunton | Stabilized chlorine dioxide as oxidizing agent for use in pulp |
| CN101380595A (en) * | 2008-10-21 | 2009-03-11 | 天津大学 | Preparation method of catalyst of oxidation sweetening of oil product |
| CN102669176A (en) * | 2012-05-30 | 2012-09-19 | 吕永生 | Slow-release chlorine dioxide solid disinfectant |
| CN104030307A (en) * | 2014-05-16 | 2014-09-10 | 茂名市茂群高岭土有限公司 | Kaolin for preparing heavy-oil catalytic cracking catalyst |
| CN104030306A (en) * | 2014-05-16 | 2014-09-10 | 茂名市茂群高岭土有限公司 | Kaolin for kaolinic catalytic cracking catalyst |
| CN107353611A (en) * | 2017-06-30 | 2017-11-17 | 广西大学 | The preparation technology of slow released ClO 2 microcapsule antibacterial film |
-
2020
- 2020-06-11 CN CN202010528256.5A patent/CN111484027B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040237845A1 (en) * | 2002-11-15 | 2004-12-02 | Alan Hunton | Stabilized chlorine dioxide as oxidizing agent for use in pulp |
| CN101380595A (en) * | 2008-10-21 | 2009-03-11 | 天津大学 | Preparation method of catalyst of oxidation sweetening of oil product |
| CN102669176A (en) * | 2012-05-30 | 2012-09-19 | 吕永生 | Slow-release chlorine dioxide solid disinfectant |
| CN104030307A (en) * | 2014-05-16 | 2014-09-10 | 茂名市茂群高岭土有限公司 | Kaolin for preparing heavy-oil catalytic cracking catalyst |
| CN104030306A (en) * | 2014-05-16 | 2014-09-10 | 茂名市茂群高岭土有限公司 | Kaolin for kaolinic catalytic cracking catalyst |
| CN107353611A (en) * | 2017-06-30 | 2017-11-17 | 广西大学 | The preparation technology of slow released ClO 2 microcapsule antibacterial film |
Non-Patent Citations (1)
| Title |
|---|
| 李建颖等: "《食品添加剂速查手册》", 30 November 2017, 天津：南开大学出版社 * |
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