CN111804315A - Preparation method of non-mercury catalyst nano material - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 19
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 18
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 14
- 229930006000 Sucrose Natural products 0.000 claims abstract description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 9
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims abstract description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 9
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 9
- 239000011592 zinc chloride Substances 0.000 claims abstract description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000007833 carbon precursor Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 229960004793 sucrose Drugs 0.000 claims abstract 5
- 239000000203 mixture Substances 0.000 claims description 23
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000005720 sucrose Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 6
- 229920002415 Pluronic P-123 Polymers 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000007038 hydrochlorination reaction Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000002791 soaking Methods 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000011943 nanocatalyst Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229920001983 poloxamer Polymers 0.000 abstract 1
- 238000011161 development Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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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
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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
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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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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Abstract
The invention discloses a preparation method of a non-mercury catalyst nano material, belonging to the field of nano catalyst synthesis. The preparation method is divided into three steps, firstly, the silicon dioxide template material is prepared by using the pluronic, and then the mesoporous carbon is obtained by using the silicon dioxide template as a hard template and using the cane sugar as a carbon precursor through a calcining and washing process. And finally, soaking the mesoporous carbon into a prepared solution with copper chloride, tin chloride, zinc chloride and lanthanum chloride as active components, and drying to obtain the catalyst. The obtained catalyst has a mesoporous structure and a larger specific surface area, the dispersion effect of the metal in the carrier is better, the utilization rate of the metal salt is high, and the cost is reasonable. The catalyst is applied to the reaction of preparing chloroethylene by hydrochlorinating acetylene, and has good catalytic activity and selectivity.
Description
Technical Field
The invention belongs to the field of synthesis of nano catalysts, and particularly relates to a preparation method of a non-mercury catalyst for preparing vinyl chloride through acetylene hydrochlorination.
Background
Polyvinyl chloride (PVC) has very wide application in a plurality of fields such as building materials, national defense, industrial production and the like, the synthesized resin is one of five thermoplastic synthetic resins, the synthetic raw material of the PVC can not be separated from the chloroethylene, and the chloroethylene is still prepared by the acetylene method to occupy the leading position based on the current situation that the coal resources in China are rich. The method has simple flow, the conversion rate is as high as 95-99%, but the mercury chloride is used as a catalyst in a large amount, so that the resource shortage of mercury resources is caused, and the mercury serving as a highly toxic substance can greatly damage the environment and threaten the health of human beings. Therefore, the development of non-mercury catalysts is of great significance to the sustainable development of the industry.
Through many years of efforts, more novel non-mercury catalysts with good catalytic properties are continuously researched and developed, and through numerous experiments, researchers find that precious metal catalysts represented by Au and non-metal catalysts represented by materials such as Cu, Sn, Ni and C-N have outstanding catalytic performance and great development potential. In the process of industrial development, the limited loading and adsorption capacity of the used activated carbon carrier on the material limits the catalytic performance of the material to a certain extent. In the last five years, the task groups of Chao S and LiX utilize ZIF-8 as a precursor to obtain the nitrogen-doped carbon material used as a high-performance acetylene hydrochlorination catalyst[1-2]All obtain higher acetylene conversion rate, but a large number of micropores in the material<2nm) are easily blocked after cycling, resulting in a reduction in the specific surface area of the material and hence deactivation. Therefore, through analysis, mesoporous carbon with larger pore diameter (the pore diameter is in a range of 2-50 nm) is a more suitable carrier material, and the ordered mesoporous carbon has higher surface area, larger pore volume and specific mechanical and chemical properties, can effectively adsorb the catalyst, reduce the use of metal salt and increase the uniform dispersion of the catalyst in the carrier.
Reference documents:
[1]Chao S，et al.Sci Rep，2017，7:39 789–39 796.
[2]Li X，et al.Journal of Materials Science，2018，53(7):4913–4926.
disclosure of Invention
The invention aims to provide a preparation method of a non-mercury catalyst for preparing vinyl chloride by hydrochlorination of acetylene, aiming at the defects in the prior art. The preparation process is simple, environment-friendly and low in cost. The problem of low adsorption efficiency of the carrier catalyst in the existing preparation method is solved, and the prepared catalytic material has high catalytic performance and high stability.
The technical scheme of the invention is as follows:
a preparation method of a non-mercury catalyst nano material is provided, the obtained particles are ordered porous spheres with the particle size of 200-400 nanometers, and the preparation method comprises the following steps:
a. firstly, preparing a silicon dioxide template material
40g of Pluronic P123 (EO) was added at room temperature20PO70EO20And) dissolved in a mixture of 80ml hydrochloric acid (37%) and 1.4L of distilled water. Then 50ml of 1-butanol were added to the mixture under continuous stirring, and after the end of the dropwise addition, the mixture was stirred for one hour. Finally, 90ml of tetraethyl orthosilicate used as a silicon source is added dropwise and stirring is continued for 24 hours, and hydrothermal treatment is carried out for 24 hours. In a subsequent step, the product was filtered off and dried at ambient temperature for 24 hours, and the template was removed by calcination at 600 ℃.
b. Mesoporous carbon was obtained using the above materials as hard templates and sucrose as carbon precursor. Specifically, 10g of the template material, 14g of sucrose and 1.4g of concentrated sulfuric acid were added to 60ml of distilled water and mixed, and the mixture was heated to 100 ℃ in a muffle furnace and held for 5 hours, and then heated to 150 ℃ and held for 10 hours. The heating process was repeated after adding 8g of sucrose, 1 ml of concentrated sulfuric acid and 50ml of distilled water. Finally, the mixture is put in an argon atmosphere for 5 ℃ min-1The heating rate of (2) is increased to 900 ℃ and kept for 8 hours for carbonization. And finally, removing the silicon dioxide matrix by using hydrofluoric acid with five mass percent at room temperature, filtering, washing and drying to obtain the mesoporous carbon.
c. Preparing a solution of an active component, wherein the active component is a mixture of four components, namely copper chloride, tin chloride, zinc chloride and lanthanum chloride. Soaking mesoporous carbon in the mixed solution at 10 deg.C for 10 min-1The temperature was raised to 100 ℃ and stirred for 5 hours. The weight ratio of copper chloride to the carrier is 0.5-3%, the weight ratio of tin chloride to the carrier is 0.01-1%, the weight ratio of zinc chloride to the carrier is 0.05-1%, and the weight ratio of lanthanum chloride to the carrier is 0.05-0.1%. The sample was finally heated at 400 ℃ for 3 hours under an argon atmosphere.
The prepared catalyst is used for preparing chloroethylene by acetylene hydrochlorination, the catalyst is subjected to packing and tubing, and the airspeed of acetylene is 30/h, HCl/C2H2The reaction was carried out under 1.1 conditions, with the reaction temperature being controlled between 150 ℃ and 200 ℃. The temperature of 10 ℃ between 150 ℃ and 200 ℃ is taken as a section, and 6 sections are taken on average to examine the influence of different temperature sections on the acetylene conversion rate and the vinyl chloride selectivity.
Compared with the prior art, the invention has the beneficial effects that:
1. the mesoporous carbon prepared by the method has higher surface area, larger pore volume and specific mechanical and chemical properties, and can effectively adsorb the catalyst.
2. The prepared catalyst has good effect on selectivity, the conversion rate of acetylene is improved along with temperature, and the conversion rate can reach 95-99%. The active component of the catalyst has high research potential and is worthy of further research.
Drawings
FIG. 1 is an SEM picture of a catalyst prepared by the present invention.
Detailed Description
The preparation of the catalyst material of the present invention is further illustrated by the following specific examples, which are only intended to better understand the content of the present invention and not to limit the scope of the present invention.
Example 1
a. Firstly, preparing a silicon dioxide template material
40g of Pluronic P123 (EO) was added at room temperature20PO70EO20And) dissolved in a mixture of 80ml hydrochloric acid (37%) and 1.4L of distilled water. Then 50ml of 1-butanol were added to the mixture under continuous stirring, and after the end of the dropwise addition, the mixture was stirred for one hour. Finally, 90ml of tetraethyl orthosilicate used as a silicon source is added dropwise and stirring is continued for 24 hours, and hydrothermal treatment is carried out for 24 hours. In a subsequent step, the product was filtered off and dried at ambient temperature for 24 hours, and the template was removed by calcination at 600 ℃.
b. Mesoporous carbon was obtained using the above materials as hard templates and sucrose as carbon precursor. The specific process is as follows10g of the template material, 14g of sucrose and 1.4g of concentrated sulfuric acid were added to 60ml of distilled water and mixed, and the mixture was heated to 100 ℃ in a muffle furnace for 5 hours and then heated to 150 ℃ for 10 hours. The heating process was repeated after adding 8g of sucrose, 1 ml of concentrated sulfuric acid and 50ml of distilled water. Finally, the mixture is put in an argon atmosphere for 5 ℃ min-1The heating rate of (2) is increased to 900 ℃ and kept for 8 hours for carbonization. And finally, removing the silicon dioxide matrix by using hydrofluoric acid with five mass percent at room temperature, filtering, washing and drying to obtain the mesoporous carbon.
c. Preparing a solution of an active component, wherein the active component is a mixture of four components, namely copper chloride, tin chloride, zinc chloride and lanthanum chloride. Soaking mesoporous carbon in the mixed solution at 10 deg.C for 10 min-1The temperature was raised to 100 ℃ and stirred for 5 hours. The weight ratio of copper chloride to the carrier is 1-2%, the weight ratio of tin chloride to the carrier is 0.5-1%, the weight ratio of zinc chloride to the carrier is 0.5-1%, and the weight ratio of lanthanum chloride to the carrier is 0.08-0.1%. The sample was finally heated at 400 ℃ for 3 hours under an argon atmosphere.
d. The prepared catalyst shows good effect in the aspect of selectivity, and the conversion rate of acetylene reaches 95.3%.
Example 2
a. Firstly, preparing a silicon dioxide template material
40g of Pluronic P123 (EO) was added at room temperature20PO70EO20And) dissolved in a mixture of 80ml hydrochloric acid (37%) and 1.4L of distilled water. Then 50ml of 1-butanol were added to the mixture under continuous stirring, and after the end of the dropwise addition, the mixture was stirred for one hour. Finally, 90ml of tetraethyl orthosilicate used as a silicon source is added dropwise and stirring is continued for 24 hours, and hydrothermal treatment is carried out for 24 hours. In a subsequent step, the product was filtered off and dried at ambient temperature for 24 hours, and the template was removed by calcination at 600 ℃.
b. Mesoporous carbon was obtained using the above materials as hard templates and sucrose as carbon precursor. The specific procedure is as follows, 10g of template material, 14g of sucrose and 1.4g of concentrated sulfuric acid are added into 60ml of distilled water to be mixed, the mixture is heated to 100 ℃ in a muffle furnace and kept for 5 hours, and then the temperature is raisedTo 150 ℃ for 10 hours. The heating process was repeated after adding 8g of sucrose, 1 ml of concentrated sulfuric acid and 50ml of distilled water. Finally, the mixture is put in an argon atmosphere for 5 ℃ min-1The heating rate of (2) is increased to 900 ℃ and kept for 8 hours for carbonization. And finally, removing the silicon dioxide matrix by using hydrofluoric acid with five mass percent at room temperature, filtering, washing and drying to obtain the mesoporous carbon.
c. Preparing a solution of an active component, wherein the active component is a mixture of four components, namely copper chloride, tin chloride, zinc chloride and lanthanum chloride. Soaking mesoporous carbon in the mixed solution at 10 deg.C for 10 min-1The temperature was raised to 100 ℃ and stirred for 5 hours. The weight ratio of copper chloride to the carrier is 1-1.5%, the weight ratio of tin chloride to the carrier is 0.5-0.7%, the weight ratio of zinc chloride to the carrier is 0.5-0.6%, and the weight ratio of lanthanum chloride to the carrier is 0.08-0.1%. The sample was finally heated at 400 ℃ for 3 hours under an argon atmosphere.
d. The prepared catalyst shows good effect in the aspect of selectivity, and the conversion rate of acetylene reaches 98.1%.
The overall microstructure of the catalyst obtained according to the invention is shown in the attached FIG. 1, in which: the obtained catalyst has the advantages of uniform particle distribution, large specific surface area, high utilization rate of metal salt and contribution to improvement of catalytic conversion.
Claims (9)
1. A preparation method of a non-mercury catalyst nano material is characterized by comprising the following steps:
comprises the steps of preparing a silica template material;
comprises the steps of using the obtained material as a hard template and using sucrose as a carbon precursor to obtain mesoporous carbon;
comprises the steps of preparing a solution of an active component, immersing the obtained mesoporous carbon into the obtained solution, and heating under an argon atmosphere.
2. The method for preparing non-mercury catalyst nano-material according to claim 1, which is characterized in that: the preparation method of the silicon dioxide template material comprises the steps of dissolving Pluronic P123 in a mixture of hydrochloric acid and distilled water at normal temperature, adding 1-butanol into the mixture under continuous stirring, continuing stirring the mixture for one hour after dropwise adding, finally, dropwise adding tetraethyl orthosilicate serving as a silicon source, continuing stirring for 24 hours, carrying out hydrothermal treatment for 24 hours, filtering a product out in the subsequent step, drying for 24 hours at normal temperature, and removing the template through calcination at 600 ℃.
3. The method for preparing non-mercury catalyst nano-material according to claim 1, which is characterized in that: the preparation method of the mesoporous carbon comprises the steps of adding the template material, cane sugar and concentrated sulfuric acid into distilled water for mixing, heating the mixture in a muffle furnace to 100 ℃ for 5 hours, heating to 150 ℃ for 10 hours; adding sucrose, concentrated sulfuric acid and distilled water, and repeating the heating process; then it was put under argon atmosphere at 5 ℃ for min-1Heating to 900 ℃ at the heating rate, and keeping for 8 hours for carbonization; and finally, removing the silicon dioxide matrix by using hydrofluoric acid with five mass percent at room temperature, filtering, washing and drying to obtain the mesoporous carbon.
4. The method for preparing non-mercury catalyst nano-material according to claim 1, which is characterized in that: the active component is a mixture of copper chloride, tin chloride, zinc chloride and lanthanum chloride, and the mesoporous carbon carrier is immersed in the mixed solution for 10 ℃ min-1Heating to 100 deg.c and stirring for 5 hr; the sample was finally heated at 400 ℃ for 3 hours under an argon atmosphere.
5. The method for preparing non-mercury catalyst nano-material according to claim 2, which is characterized in that: the dosage is that the pluronic P123 is 40-100 g, the hydrochloric acid is a 37% hydrochloric acid solution of 80-100 ml, the distilled water is 1.4-2L, the 1-butanol is 50-100 ml, and the tetraethyl orthosilicate is 90-150 ml.
6. The method for preparing non-mercury catalyst nano-material according to claim 3, which is characterized in that: the template material is 10-40 g, the cane sugar is 10-40 g, the concentrated sulfuric acid is 1-4 g, and the distilled water is 60-100 ml.
7. The method for preparing non-mercury catalyst nano-material according to claim 4, which is characterized in that: the weight ratio of the copper chloride to the carrier is 0.5-5%, the weight ratio of the tin chloride to the carrier is 0.05-5%, the weight ratio of the zinc chloride to the carrier is 0.01-10%, and the weight ratio of the lanthanum chloride to the carrier is 0.05-5%.
8. Use of the non-mercury catalyst nanomaterial obtained by the preparation method according to any one of claims 1 to 7, characterized in that: the method is used for preparing vinyl chloride by hydrochlorination of acetylene.
9. Use of the non-mercury catalyst nanomaterial according to claim 8, characterized in that: at an acetylene space velocity of 30/h, HCl/C2H2The reaction was carried out under 1.1 conditions, with the reaction temperature being controlled between 150 ℃ and 200 ℃.
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