CN111939885A - Pore diameter adjustable alumina carrier and preparation method thereof - Google Patents
Pore diameter adjustable alumina carrier and preparation method thereof Download PDFInfo
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- CN111939885A CN111939885A CN202010750011.7A CN202010750011A CN111939885A CN 111939885 A CN111939885 A CN 111939885A CN 202010750011 A CN202010750011 A CN 202010750011A CN 111939885 A CN111939885 A CN 111939885A
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- 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
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- 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
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
- B01J35/635—0.5-1.0 ml/g
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- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/04—Preparation of chlorine from hydrogen chloride
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Abstract
The invention discloses an alumina carrier with adjustable pore diameter and a preparation method thereof, wherein the pore diameter of the alumina carrier is gradually increased from the center to the outer surface along the diameter of the particles, the pore diameter is 1-8 nm smaller at the center of the particles than at the position of 50% of the particle diameter, 1-5 nm smaller at the position of 50% of the particle diameter than at the position of 80% of the particle diameter, and 1-5 nm smaller at the position of 80% of the particle diameter than at the outer surface of the particles; the water absorption rate is 65-75%, and the specific surface area is 120-220 m2The pore volume is 0.6-0.8 mL/g, and the diameter of the pore channel is 10-20 nm. The diameter of the pore canal of the invention is gradually increased from the center of the particle to the outer surface along the radial directionCompared with the carrier with the pore channels distributed in a concentrated manner, the trumpet-shaped distribution state which is gradually increased can effectively relieve the problem of low active component loading capacity caused by the blockage of the pore channels on the outer surface, improve the catalytic activity of the catalyst and conveniently and randomly adjust the pore channel size of the carrier.
Description
Technical Field
The invention relates to an alumina carrier used in hydrogen chloride catalytic oxidation process.
Background
As long as over 100 years ago, research on methods for converting hydrogen chloride into chlorine gas has been carried out, and up to now, methods for producing chlorine gas from hydrogen chloride are mainly classified into three methods, namely, an electrolysis method, a direct oxidation method and a catalytic oxidation method, and only a german wood hydrochloric acid electrolysis method and a japanese sumitomo chemical catalytic oxidation method, which have been industrially and stably operated, have been developed. However, the electrolysis method has high operation cost, large investment and high sensitivity to impurities in the hydrochloric acid raw material, and the byproduct hydrogen chloride gas or hydrochloric acid contains more or less other impurities, so the technology for preparing chlorine by electrolyzing hydrochloric acid cannot be popularized and applied in a large area. The catalytic oxidation method has the advantages of strong adaptability of hydrogen chloride raw materials, low energy consumption, stable operation and the like, and becomes the first choice of the technology for preparing chlorine from hydrogen chloride at home and abroad.
In the catalytic oxidation process of hydrogen chloride, a catalyst is an important factor influencing the reaction conversion rate, the reaction efficiency and the like, and is the core of the catalytic oxidation technology, the catalyst mainly comprises active components, auxiliaries and a carrier, and most of the used carrier materials are metal oxides, such as alumina, silicon dioxide, titanium dioxide and the like. The alumina is a porous substance with developed pores, and is characterized by large specific surface area, strong adsorption capacity, wide pore size distribution range, stable high temperature, abundant acid-base sites, and numerous crystal forms, can adapt to crystal phases required by different reaction conditions, and is a catalyst carrier material which is most widely applied in the industries of energy chemical industry, fine chemical industry, environmental chemical industry, automobiles, petroleum and the like.
Patent CN111167468A discloses a copper-based catalyst for catalytic oxidation of hydrogen chloride, the carrier component is a mixture containing silicon and aluminum, and the mechanical strength of the carrier is improved by introducing silicon element, but the pore diameter of the catalyst carrier is centralized distribution, which is easy to cause pore channel blockage, so that the content of the loaded active component is low, and the catalytic efficiency of the catalyst is affected.
Patent CN102441436A discloses a preparation method of macroporous alumina, in which a physical pore-expanding agent and a chemical pore-expanding agent are added simultaneously during the preparation process, so that the content of macropores is increased, but the pore volume of the carrier is low, the mechanical strength needs to be improved, and the addition of multiple pore-expanding agents also increases the preparation cost of the carrier.
At present, in the research of hydrogen chloride catalytic oxidation catalyst carriers, a preparation technology of a macroporous alumina carrier which can solve pore channel blockage and can maintain certain mechanical strength does not exist.
Disclosure of Invention
The invention aims to provide an alumina carrier with adjustable pore diameter and a preparation method thereof, which overcome the defects in the prior art.
The spherical alumina carrier with the adjustable pore diameter has the particle size of about 3mm, the inner pore diameter of the particles gradually increases from the center to the outer surface along the diameter, the pore diameter is 1-8 nm smaller than the average pore diameter at 50% of the particle diameter at the center of the particles, about 1-5 nm smaller than the average pore diameter at 80% of the particle diameter at 50% of the particle diameter, and 1-5 nm smaller than the average pore diameter at the outer surface of the particles at 80% of the particle diameter;
the water absorption rate is 65-75%, and the specific surface area is 120-220 m2The pore volume is 0.6-0.8 mL/g, and the diameter of the pore channel is mostly distributed between 10nm and 20 nm.
The preparation method of the alumina carrier with adjustable pore diameter comprises the following steps:
(1) mixing an alumina precursor, a silicon-containing substance and an extrusion aid, adding a peptizing agent, kneading, extruding and forming to obtain spherical particles;
(2) then drying for 1-4 h at the temperature of 60-180 ℃;
(3) pre-roasting for 1-8 h at the temperature of 250-450 ℃ to obtain a pre-roasted carrier;
(4) spraying an acidic solution A on the surface of the pre-roasted particles, then spraying an acidic solution B, and standing for 1-3 h at room temperature;
(5) drying at 60-180 ℃ for 1-4 h, and roasting at 500-1000 ℃ for 1-8 h to obtain the alumina carrier with adjustable pore diameter;
in the step (1), the weight parts of the components are as follows:
the alumina precursor is pseudo-boehmite, aluminum hydroxide, aluminum powder or alumina dry glue powder;
the term "pseudoboehmite" is a white powder, also called SB powder, and can be specifically referred to the records of the literature of the new technology of extrusion molding of the trefoil alumina carrier;
the silicon-containing substance is one or more of silica sol, silicon dioxide powder, orthosilicate ester and silicon carbide;
the extrusion aid is one or more of sesbania powder, sweet potato starch, wheat starch, organic polybasic acid and cellulose; such as methyl cellulose, ethyl cellulose, cellulose acetate;
the peptizing agent is one or more of aluminum sol, silica sol, nitric acid, citric acid and water;
the acid solution A is one or more of citric acid, acetic acid and hydrochloric acid with the weight concentration of 2 wt% -15 wt%;
the acid solution B is one or more of citric acid, acetic acid and hydrochloric acid with the weight concentration of 10-25 wt%;
the pre-roasted carrier obtained in the step (3) and the acidic solution A are 1: 0.2-0.5 (weight ratio);
the pre-roasted carrier obtained in the step (3) and the acidic solution B are 1: 0.2-0.5 (weight ratio);
the acid solution A is a low-acid solution with the weight concentration of 2-15 wt%, and the acid solution B is a high-concentration acid solution with the weight concentration of 10-25 wt%;
the pore diameter of the alumina carrier prepared by the invention is gradually increased from the center to the outer surface along the particle diameter, and the increase of the pore diameter is determined by the concentration of the sprayed acid solution. The center of the pore diameter particle of the alumina carrier is 1-8 nm smaller than the average pore diameter of 50% of the particle, the average pore diameter of 50% of the particle is about 1-5 nm smaller than the average pore diameter of 80% of the particle, and the average pore diameter of 80% of the particle is 1-5 nm smaller than the average pore diameter of the outer surface of the particle.
The alumina carrier prepared by the invention has the water absorption rate of 65-75 percent and the specific surface area of 120-220 m2The pore volume is 0.6-0.8 mL/g, the average pore diameter is 10-20 nm, (the pore diameter gradually increases from the center of the spherical particle to the outer surface and is horn-shaped);
the diameter, specific surface area and pore volume of the pore channel can be measured by a nitrogen adsorption and desorption analyzer, and uniform-pore-diameter SiO can be adopted2The preparation of the catalyst carrier is detected by the method reported in the literature;
the water absorption can be detected by adopting a method reported in the patent of a preparation method of a rod-shaped alumina carrier and an alumina carrier;
the alumina carrier with adjustable grain size, which is obtained by the invention, can be used for preparing a catalyst in a hydrogen chloride catalytic oxidation process, has higher mechanical strength, and the pore size of the carrier is gradually increased from the center of the grain to the outer surface in a horn shape, so that the alumina carrier is not easy to block.
The application method is the same as that of the conventional catalyst, such as the method reported in the literature of catalyst for preparing chlorine by catalytic oxidation of hydrogen chloride, preparation method and application.
The invention has the beneficial effects that: the diameter of the pore channel of the catalyst carrier is in a trumpet-shaped distribution state gradually increasing from the center of the particle to the outer surface along the radial direction, compared with the carrier with the pore channel distributed in a concentrated manner, the problem of low active component loading capacity caused by the blockage of the pore channel on the outer surface can be effectively solved, the catalytic activity of the catalyst is improved, and meanwhile, the size of the pore channel of the carrier can be conveniently adjusted at will.
Detailed Description
Example 1
(1) Raw materials for preparation of the carrier: parts by weight
(2) The preparation method of the alumina carrier with adjustable pore diameter comprises the following steps:
uniformly mixing pseudo-boehmite powder, silicon dioxide powder, extrusion aid sesbania powder and extrusion aid methylcellulose, adding peptizing agent water and peptizing agent aluminum sol, kneading for 30min, extruding into strips, forming particles, drying at 100 ℃ for 2h, and roasting at 350 ℃ for 2h to obtain a pre-roasted alumina carrier;
taking 30 parts by weight of the pre-roasted carrier, uniformly spraying 15 parts by weight of citric acid solution with the concentration of 10 wt% on the surface of particles, uniformly spraying 10 parts by weight of citric acid solution with the concentration of 15 wt% on the surface of the particles, standing at room temperature for 2h, drying at 150 ℃ for 2h, and roasting at 800 ℃ for 5h to obtain the alumina carrier with the adjustable pore diameter;
the specific surface area of the alumina carrier is 201m2(g), the average pore diameter at the center-50% of the pore diameter is 11.7nm, the average pore diameter at the 50% -80% of the particle diameter is 14.4nm, the average pore diameter at the 80% -outer surface is 16.1nm, and the strength of the carrier is 103N/cm.
Example 2
(1) Raw materials for preparation of the carrier: parts by weight
(2) The preparation method of the alumina carrier with adjustable pore diameter comprises the steps of kneading, extruding, drying and pre-roasting the carrier as in example 1.
And (3) taking 30 parts by weight of the pre-roasted carrier, uniformly spraying 15 parts by weight of citric acid solution with the concentration of 5 wt% on the surface of the particles, uniformly spraying 10 parts by weight of citric acid solution with the concentration of 15 wt% on the surface of the particles, standing at room temperature for 2 hours, drying at 150 ℃ for 2 hours, and roasting at 800 ℃ for 5 hours. Oxygen obtainedThe specific surface area of the alumina carrier is 217m2(g), the average pore diameter at the center of the pore channel and 50 percent of the particle diameter is 10.6nm, the average pore diameter at the 50 percent to 80 percent of the particle diameter is 13.1nm, the average pore diameter at the 80 percent to the outer surface is 14.9nm, and the strength of the carrier is 99N/cm.
Example 3
(1) Raw materials for preparation of the carrier: parts by weight
(2) The preparation method of the alumina carrier with adjustable pore diameter comprises the following steps:
the carrier was kneaded, extruded, dried and pre-baked as in example 1.
And (2) uniformly spraying 15 parts by weight of 10 wt% acetic acid solution on the surface of the particle from 30 parts by weight of the pre-roasted carrier, uniformly spraying 10 parts by weight of 15 wt% acetic acid solution on the surface of the particle, standing at room temperature for 1h, drying at 150 ℃ for 2h, and roasting at 750 ℃ for 4 h. The specific surface area of the obtained alumina carrier is 197m2The average pore diameter of the center of the pore channel at 50 percent of the particle size is 12.9nm, the average pore diameter of the particle size of 50 percent to 80 percent is 15.4nm, the average pore diameter of the particle size of 80 percent to the outer surface is 16.8nm, and the strength of the carrier is 108N/cm.
Comparative example 1
The carrier raw material, kneading, extruding, drying and pre-baking conditions were the same as in example 1.
And (3) taking 30 parts by weight of the pre-roasted carrier, uniformly spraying 25 parts by weight of 15 wt% acetic acid solution on the surface of the particles, standing at room temperature for 2h, drying at 150 ℃ for 2h, and roasting at 800 ℃ for 4 h. The specific surface area of the obtained alumina carrier is 191m2(g) the average pore diameter at the center of the pore channel and 50% of the particle diameter is 12.4nm, the average pore diameter at the particle diameter of 50% -80% of the pore channel is 12.4nm, the average pore diameter at the particle diameter of 80% -outer surface is 12.4nm, and the strength of the carrier is102N/cm。
Comparative example 2
Weighing 50 parts by weight of pseudo-boehmite powder, 6 parts by weight of sesbania powder and 3 parts by weight of cellulose, uniformly mixing, adding 60 parts by weight of water and 50 parts by weight of aluminum sol, and comparing with example 1, only adding no SiO2The powder, kneaded, extruded, dried, and pre-baked were the same as in example 1.
And (2) taking 30 parts by weight of the pre-roasted particles, uniformly spraying 15 parts by weight of citric acid solution with the concentration of 10 wt% on the surfaces of the particles, uniformly spraying 10 parts by weight of citric acid solution with the concentration of 15 wt% on the surfaces of the particles, standing at room temperature for 2 hours, drying at 150 ℃ for 2 hours, and roasting at 800 ℃ for 5 hours. The specific surface area of the obtained alumina carrier was 203m2(g), the average pore diameter at the center of the pore channel and 50% of the particle diameter is 12.3nm, the average pore diameter at the 50% -80% of the particle diameter is 14.7nm, the average pore diameter at the 80% -outer surface is 16.2nm, and the strength of the carrier is 83N/cm.
As can be seen from the test data of examples 1 to 3 and comparative examples 1 and 2:
by spraying the acidic solution A and the acidic solution B, the diameter of the pore canal from the center of the alumina carrier particle to the outer surface is gradually increased.
The addition of the siliceous material can improve the strength of the alumina carrier.
Claims (9)
1. The pore diameter of the alumina carrier is gradually increased from the center to the outer surface along the diameter of the alumina carrier, the diameter of the pore channel is 1-8 nm smaller than the average pore diameter of 50% of the particle diameter at the center of the particle, about 1-5 nm smaller than the average pore diameter of 80% of the particle diameter at the 50% of the particle diameter, and 1-5 nm smaller than the average pore diameter of the outer surface of the particle at the 80% of the particle diameter;
the water absorption rate is 65-75%, and the specific surface area is 120-220 m2The pore volume is 0.6-0.8 mL/g, and the diameter of the pore channel is 10-20 nm.
2. A preparation method of an alumina carrier with adjustable pore diameter is characterized by comprising the following steps:
(1) mixing an alumina precursor, a silicon-containing substance and an extrusion aid, adding a peptizing agent, kneading, extruding into strips and forming into particles;
(2) then drying for 1-4 h at the temperature of 60-180 ℃;
(3) pre-roasting for 1-8 h at the temperature of 250-450 ℃ to obtain a pre-roasted carrier;
(4) spraying an acidic solution A on the surface of the pre-roasted particles, then spraying an acidic solution B, and standing for 1-3 h at room temperature;
(5) drying for 1-4 h at 60-180 ℃, and roasting for 1-8 h at 500-1000 ℃ to obtain the alumina carrier with adjustable pore diameter.
3. The method according to claim 2, wherein in the step (1), the weight parts of the components are as follows:
4. the method according to claim 2, wherein the silicon-containing substance is one or more of silica sol, silica powder, orthosilicate ester and silicon carbide;
5. the method as claimed in claim 2, wherein the extrusion aid is one or more of sesbania powder, sweet potato starch, wheat starch, organic polybasic acid and cellulose; such as methyl cellulose, ethyl cellulose, cellulose acetate.
6. The method according to claim 2, wherein the peptizing agent is one or more of aluminum sol, silica sol, nitric acid, citric acid and water.
7. The method according to claim 2, wherein the acidic solution A is one or more of citric acid, acetic acid and hydrochloric acid with a weight concentration of 2-15 wt%;
the acid solution B is one or more of citric acid, acetic acid and hydrochloric acid with the weight concentration of 10-25 wt%.
8. The method according to claim 2, wherein the pre-calcined carrier and acidic solution A obtained in step (3) is 1: 0.2-0.5 (weight ratio);
the pre-roasted carrier obtained in the step (3) and the acidic solution B are 1: 0.2-0.5 (weight ratio);
the acid solution A is a low-acid solution with the weight concentration of 2-15 wt%, and the acid solution B is a high-concentration acid solution with the weight concentration of 10-25 wt%.
9. An alumina support prepared according to the method of any one of claims 2 to 8.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115957740A (en) * | 2023-01-03 | 2023-04-14 | 中化泉州石化有限公司 | Heavy oil hydrotreating catalyst and preparation method thereof |
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|---|---|---|---|---|
| US5925592A (en) * | 1995-10-04 | 1999-07-20 | Katoh; Akira | Process for preparing alumina carrier |
| CN102441436A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of alumina carrier |
| CN105983444A (en) * | 2015-01-27 | 2016-10-05 | 中国石油天然气股份有限公司 | A kind of preparation method of alumina carrier |
| CN106914279A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Alumina carrier and its preparation method |
| CN110075855A (en) * | 2019-05-16 | 2019-08-02 | 西安凯立新材料股份有限公司 | A kind of dehydrogenation and its preparation method and application |
| CN111167468A (en) * | 2020-01-03 | 2020-05-19 | 万华化学集团股份有限公司 | A kind of catalyst for producing chlorine by oxychlorination and its preparation method and application |
-
2020
- 2020-07-30 CN CN202010750011.7A patent/CN111939885A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5925592A (en) * | 1995-10-04 | 1999-07-20 | Katoh; Akira | Process for preparing alumina carrier |
| CN102441436A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method of alumina carrier |
| CN105983444A (en) * | 2015-01-27 | 2016-10-05 | 中国石油天然气股份有限公司 | A kind of preparation method of alumina carrier |
| CN106914279A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Alumina carrier and its preparation method |
| CN110075855A (en) * | 2019-05-16 | 2019-08-02 | 西安凯立新材料股份有限公司 | A kind of dehydrogenation and its preparation method and application |
| CN111167468A (en) * | 2020-01-03 | 2020-05-19 | 万华化学集团股份有限公司 | A kind of catalyst for producing chlorine by oxychlorination and its preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115957740A (en) * | 2023-01-03 | 2023-04-14 | 中化泉州石化有限公司 | Heavy oil hydrotreating catalyst and preparation method thereof |
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