CN115888786A - Si-modified acetylene hydrochlorination metal-free catalyst, preparation method and application - Google Patents
Si-modified acetylene hydrochlorination metal-free catalyst, preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 38
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000000243 solution Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 238000007598 dipping method Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005416 organic matter Substances 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- 238000007873 sieving Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 4
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract 1
- 239000010931 gold Substances 0.000 abstract 1
- 229910052737 gold Inorganic materials 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 12
- 229910052753 mercury Inorganic materials 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
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- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to the technical field of acetylene hydrochlorination catalysts, and discloses a Si-modified acetylene hydrochlorination metal-free catalyst, a preparation method and application thereof. The invention obtains the specific surface area of 900-1500m by introducing the pore-expanding agent solution for treatment 2 Activated carbon with the average pore diameter of 3-15nm, developed gaps, uniform and stable, and high-quality carrier; the active carbon with 3-5% of Si content is obtained by adopting Si-containing solution for modification treatment, and the metal or non-gold content can be greatly improvedStability of the cargo; the acetylene hydrochlorination metal-free catalyst with the nitrogen content of 5-8% is obtained by adopting the mixed solution of the nitrogen-containing organic matter and the high molecular binder for dipping treatment, and has the advantages of higher catalytic activity, long service life, simple operation process and environmental pollution reduction.
Description
Technical Field
The invention belongs to the field of acetylene hydrochlorination catalysts, and particularly relates to a Si-modified acetylene hydrochlorination metal-free catalyst, a preparation method and application.
Background
The PVC resin is a general resin with large yield and excellent comprehensive performance, and the product of the PVC resin has excellent mechanical property, flame retardance, transparency, chemical resistance and the like, is widely applied to various fields of national economy, is an important component for balancing the chlorine gas as a byproduct in the production of caustic soda serving as an important chemical raw material, and has a great promotion effect on national construction and development. At present, the calcium carbide method is mainly used for producing PVC resin in China.
The calcium carbide method polyvinyl chloride industry is a mercury-consuming household, faces the threat of increasingly exhausted mercury resources, and is also restricted and stressed by international and domestic environmental protection policies. Mercury and its compounds are the global priority pollutants due to their biotoxicity, bioaccumulation, durability, long-distance transport, etc. The mercury pollution can generate great damage to human bodies, environment and the like, the current fields such as industry, agriculture and the like have the figure of mercury element, and along with the continuous development of industrial economy, the phenomenon of mercury pollution is increasingly aggravated, so that people have to pay attention to the prevention and treatment of the mercury pollution, and particularly for the chlor-alkali industry, the mercury pollution discharges a large amount of mercury-containing substances, so that the environment is greatly damaged. In order to protect human health and the environment from the harm of artificial emission of mercury and compounds thereof, the international society puts forward comprehensive control requirements on the supply, trade, use, emission, release and the like of mercury aiming at controlling mercury problems, and supports and encourages the research and development of mercury-free catalysts and processes.
The acetylene hydrochlorination mercury-free catalyst mainly comprises three types of noble metal, non-noble metal and metal-free. From the perspective of catalytic activity and life, noble metal catalysts are the best products for short-term replacement of low-mercury catalysts, but also face large investment once and high running cost, and can be replaced in medium and long term. Patent CN109876864A discloses an ultralow-content noble metal composite catalyst for acetylene hydrochlorination and a preparation method thereof, wherein the method still has the disadvantage of high noble metal recovery pressure although the noble metal content is low, and the catalyst is easily poisoned due to improper use. The non-noble metal catalyst has the advantages of good catalytic activity and low operation cost, but also faces the environmental protection pressure of metal recovery in the waste catalyst and is likely to be replaced for a long time. Although the metal-free catalyst has lower catalytic activity than noble metal and non-noble metal catalysts, the metal-free catalyst has the advantages of low investment and operation cost, easy treatment of waste catalyst and no metal recovery, and is a current research hotspot in the field of acetylene hydrochlorination catalysts. Patent CN109876840A discloses a preparation method and a use method of a metal-free catalyst for preparing vinyl chloride by hydrochlorination of acetylene, and the method is expected to reduce the use amount of a mercury catalyst and reduce environmental pollution.
But the prior art lacks a metal-free catalyst for acetylene hydrochlorination, which has higher catalytic activity, long service life, simple operation process and capability of reducing environmental pollution.
Disclosure of Invention
Based on the problems in the prior art, the invention aims to provide a Si-modified acetylene hydrochlorination metal-free catalyst, a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a Si-modified acetylene hydrochlorination metal-free catalyst, which has a specific surface area of 900-1500m 2 In g, average pore diameter of3-15nm, 3-5% of Si content and 5-8% of nitrogen content.
The invention also provides a preparation method of the Si modified acetylene hydrochlorination metal-free catalyst, which comprises the following steps:
(1) Crushing and sieving the active carbon raw material to obtain active carbon 1;
(2) Impregnating the activated carbon 1 with a pore-enlarging agent solution, washing with water and drying to obtain activated carbon 2;
(3) Dipping the activated carbon 2 by using a Si-containing solution, and drying to obtain activated carbon 3;
(4) Carbonizing the activated carbon 3 in a nitrogen atmosphere, and then activating by using mixed gas of steam and carbon dioxide to obtain activated carbon 4;
(5) Carrying out acid solution treatment on the activated carbon 4, washing with water and drying to obtain activated carbon 5;
(6) And (3) soaking the activated carbon 5 in a mixed solution of a nitrogenous organic matter and a high-molecular binder, drying, roasting and sieving to obtain the Si-modified acetylene hydrochlorination metal-free catalyst.
Preferably, the activated carbon raw material in the step (1) is at least one of wood chips and coconut shells; the screened specification is 15-25 meshes.
Further preferably, the activated carbon raw material in the step (1) is at least one of wood chips and coconut shells; the screened specification is 20 meshes.
Preferably, the pore-expanding agent solution in the step (2) is at least one of sulfuric acid and hydrogen peroxide.
Preferably, the mass ratio of the pore-expanding agent solution to the activated carbon 1 in the step (2) is (4-6): 1; the mass concentration of the pore-expanding agent solution is 5-10%.
Preferably, the time for the impregnation in the step (2) is 12-16h; the dipping time in the step (3) is 5-10h; the drying temperature is 115-125 ℃.
Preferably, the Si-containing solution in step (3) is a nano-sized silica sol solution.
Preferably, the mass ratio of the Si-containing solution to the activated carbon 2 in the step (3) is (4-6): 1, and the mass concentration of the Si-containing solution is 0.5-5%.
Preferably, the carbonization conditions in step (4) are as follows: the carbonization time is 3-6h, and the carbonization temperature is 500-600 ℃;
the activation conditions are as follows: the activation time is 1-3h, and the activation temperature is 700-800 ℃.
Preferably, the acid solution in step (5) is at least one of hydrochloric acid and sulfamic acid; the mass ratio of the acid solution to the active carbon 4 is (5-10) to 1; the mass concentration of the acid solution is 2-5%.
Preferably, the nitrogen-containing organic matter in the step (6) is at least one of urea and melamine; the macromolecular binder is polyvinylpyrrolidone with molecular weight of 8000-10000.
Preferably, the dipping time in the step (6) is 6-8h, and the drying temperature is 115-125 ℃; the roasting time is 5-8h, and the roasting temperature is 300-400 ℃.
Preferably, the mass ratio of the mixed solution to the activated carbon 5 in the step (6) is (5-10): 1; the mass concentration of the mixed solution is 5-10%; the mass ratio of the nitrogenous organic matter to the high-molecular binder is (5-10): 1.
the invention also provides the application of the Si modified acetylene hydrochlorination metal-free catalyst or the Si modified acetylene hydrochlorination metal-free catalyst prepared by the preparation method in acetylene hydrochlorination reaction.
Compared with the prior art, the invention has the following technical effects:
the invention provides a Si-modified acetylene hydrochlorination metal-free catalyst, a preparation method and application thereof, wherein the specific surface area of the catalyst is 900-1500m by treatment of a pore-enlarging agent solution 2 The active carbon with the average pore diameter of 3-15nm has developed gaps, is uniform and stable, and is a high-quality carrier; the active carbon with 3 to 5 percent of Si content is obtained by modification treatment of the Si-containing solution, and the stability of metal or nonmetal carriers can be greatly improved; the acetylene hydrochlorination metal-free catalyst with the nitrogen content of 5-8% is obtained by dipping the mixed solution of the nitrogen-containing organic matter and the macromolecular binder, and has high catalytic activity and long service life.
Detailed Description
To better illustrate the patent, the following examples are now set forth. The following examples are intended to provide those skilled in the art with a more detailed understanding of the present invention, or to provide further insubstantial modifications and adaptations of the invention in light of the above teachings. However, the scope of the present invention is not limited by these examples.
It should be noted that the raw materials used in the present invention are all common commercial products, and thus the sources thereof are not particularly limited. Example 1:
(1) Crushing 500g of sawdust and sieving the sawdust with a 20-mesh sieve to obtain activated carbon 1;
(2) Soaking activated carbon 1 in a sulfuric acid solution for 12 hours, washing with water and drying, wherein the mass ratio of the sulfuric acid solution to the activated carbon 1 is 4;
(3) Dipping the activated carbon 2 in a nano-scale silica sol solution for 5h, and drying at 120 ℃, wherein the mass ratio of the nano-scale silica sol solution to the activated carbon 2 is 4;
(4) Carbonizing the activated carbon 3 at 500 ℃ for 6h in the nitrogen atmosphere, then switching to a mixed gas of water vapor and carbon dioxide, and activating at 700 ℃ for 3h to obtain activated carbon 4;
(5) Treating the activated carbon 4 with a hydrochloric acid solution, washing with water and drying, wherein the mass ratio of the hydrochloric acid solution to the activated carbon 4 is 5;
(6) Soaking activated carbon 5 in a mixed solution of urea and polyvinylpyrrolidone for 6h, drying at 120 ℃, and roasting at 300 ℃ for 8h, wherein the mass ratio of the mixed solution to the activated carbon 5 is 5:1, the mass concentration of the mixed solution is 10%, and the mass ratio of urea to polyvinylpyrrolidone is 5: and 1, sieving to obtain the Si modified acetylene hydrochlorination metal-free catalyst.
Example 2:
(1) Crushing 500g of sawdust and sieving the sawdust with a 20-mesh sieve to obtain activated carbon 1;
(2) Soaking the activated carbon 1 in a hydrogen peroxide solution for 16 hours, washing and drying, wherein the mass ratio of the hydrogen peroxide solution to the activated carbon 1 is 6;
(3) Dipping activated carbon 2 in a nano-scale silica sol solution for 10h, and drying at 120 ℃, wherein the mass ratio of the nano-scale silica sol solution to the activated carbon 2 is 6;
(4) Carbonizing the activated carbon 3 at 600 ℃ for 3h in the nitrogen atmosphere, then switching to a mixed gas of water vapor and carbon dioxide, and activating at 800 ℃ for 1h to obtain activated carbon 4;
(5) Treating the activated carbon 4 with sulfamic acid solution, washing with water and drying, wherein the mass ratio of the sulfamic acid solution to the activated carbon 4 is 10;
(6) Dipping activated carbon 5 in a mixed solution of melamine and polyvinylpyrrolidone for 8h, drying at 120 ℃, and roasting at 400 ℃ for 5h, wherein the mass ratio of the mixed solution to the activated carbon 5 is 10:1, the mass concentration of the mixed solution is 5%, and the mass ratio of melamine to polyvinylpyrrolidone is 10: and 1, sieving to obtain the Si modified acetylene hydrochlorination metal-free catalyst.
Example 3:
(1) Crushing 500g of sawdust and sieving the sawdust with a 20-mesh sieve to obtain activated carbon 1;
(2) Soaking the activated carbon 1 in a hydrogen peroxide solution for 15 hours, washing and drying, wherein the mass ratio of the hydrogen peroxide solution to the activated carbon 1 is 5;
(3) Dipping the activated carbon 2 in a nano-silica sol solution for 8h, and drying at 120 ℃, wherein the mass ratio of the nano-silica sol solution to the activated carbon 2 is (5);
(4) Carbonizing the activated carbon 3 at 500 ℃ for 5h in a nitrogen atmosphere, then switching to a mixed gas of water vapor and carbon dioxide, and activating at 700 ℃ for 2h to obtain activated carbon 4;
(5) Treating the activated carbon 4 with a hydrochloric acid solution, washing with water and drying, wherein the mass ratio of the hydrochloric acid solution to the activated carbon 4 is 7;
(6) Soaking activated carbon 5 in a mixed solution of urea and polyvinylpyrrolidone for 7h, drying at 120 ℃, and roasting at 300 ℃ for 6h, wherein the mass ratio of the mixed solution to the activated carbon 5 is 7.5:1, the mass concentration of the mixed solution is 7.5%, and the mass ratio of urea to polyvinylpyrrolidone is 7.5: and 1, sieving to obtain the Si modified acetylene hydrochlorination metal-free catalyst.
Comparative example 1:
this comparative example relates to a Si-modified acetylene hydrochlorination metal-free catalyst, differing from example 3 only in that step (2) is omitted.
Comparative example 2:
this comparative example relates to a Si-modified acetylene hydrochlorination metal-free catalyst, differing from example 3 only in that step (3) is omitted.
Comparative example 3:
the present comparative example relates to a Si-modified acetylene hydrochlorination metal-free catalyst, which is different from example 3 only in that the mixed solution in the step (6) is changed into a urea solution, no polyvinylpyrrolidone is added, and the mass ratio of the urea solution to the activated carbon 5 is 7.5:1, the mass concentration of the urea solution is 7.5 percent.
Test experiments:
the acetylene hydrochlorination metal-free catalysts obtained in the above examples 1 to 3 and comparative examples 1 to 3 were tested for specific surface area, average pore diameter, si content, and nitrogen content, respectively, and measured at T =180 ℃ under normal pressure and C 2 H 2 Volume space velocity of 30h -1 、n(HCl)：n(C 2 H 2 ) The initial conversion and the lifetime of more than 70% conversion are tested under the condition of 1.05, the BET method and the pore size method are commonly used for testing the specific surface area and the pore size, and the ICP-OES method is commonly used for testing the content of Si and the content of nitrogen, and the specific comparison results are shown in Table 1.
TABLE 1 comparison of test indexes of examples 1-3 and comparative examples 1-3
The following conclusions can be drawn by comparing examples 1 to 3 with comparative examples 1 to 3:
comparison of examples 1-3 yields: the specific surface area obtained by the method is 900-1500m 2 The catalyst has the advantages that the initial catalytic activity is more than 90%, the service life of more than 70% of conversion rate reaches more than 1500h, and the performance is excellent;
comparison of comparative example 1 with example 3 yields: the acetylene hydrochlorination metal-free catalyst does not adopt a pore-expanding agent to treat active carbon in the preparation process, so that the obtained catalyst is low in specific surface area, large in average pore size and low in Si and nitrogen loading capacity, and further the initial conversion rate and the service life of more than 70% of the conversion rate are greatly reduced;
comparison of comparative example 2 with example 3 gives: the acetylene hydrochlorination metal-free catalyst is not modified by adopting nano-grade silica sol in the preparation process, so that the service life of the catalyst is reduced by more than 70 percent of conversion rate, and the silica sol can reduce the loss of nitrogen in the operation process of the catalyst and stabilize a carrier framework;
comparison of comparative example 3 with example 3 gives: the acetylene hydrochlorination metal-free catalyst is not treated by polyvinylpyrrolidone in the preparation process, so that the service life of the catalyst is reduced by more than 70 percent of conversion rate, and the loss of nitrogen in the operation process of the catalyst can be reduced due to the polyvinylpyrrolidone.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and do not limit the protection scope of the present invention, and those skilled in the art can make simple modifications or equivalent substitutions on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The Si-modified acetylene hydrochlorination metal-free catalyst is characterized in that the specific surface area of the Si-modified acetylene hydrochlorination metal-free catalyst is 900-1500m 2 Per g, the average pore diameter is 3-15nm, the Si content is 3% -5% and the nitrogen content is 5% -8%.
2. A method for preparing the Si-modified acetylene hydrochlorination metal-free catalyst according to claim 1, characterized in that: the method comprises the following steps:
(1) Crushing and sieving an active carbon raw material to obtain active carbon 1;
(2) Impregnating the activated carbon 1 with a pore-enlarging agent solution, washing with water and drying to obtain activated carbon 2;
(3) Dipping the activated carbon 2 by using a Si-containing solution, and drying to obtain activated carbon 3;
(4) Carbonizing the activated carbon 3 in a nitrogen atmosphere, and then activating by using mixed gas of steam and carbon dioxide to obtain activated carbon 4;
(5) Carrying out acid solution treatment on the activated carbon 4, washing with water and drying to obtain activated carbon 5;
(6) And (3) soaking the activated carbon 5 in a mixed solution of a nitrogenous organic matter and a high-molecular binder, drying, roasting and sieving to obtain the Si-modified acetylene hydrochlorination metal-free catalyst.
3. The production method according to claim 2, characterized in that: in the step (1), the active carbon raw material is at least one of sawdust and coconut shells.
4. The method of claim 2, wherein: in the step (2), the pore-expanding agent solution is at least one of sulfuric acid and hydrogen peroxide; the mass ratio of the pore-expanding agent solution to the activated carbon 1 is (4-6) to 1; the mass concentration of the pore-expanding agent solution is 5-10%; the time for the impregnation is 12-16h.
5. The method of claim 2, wherein: the Si-containing solution in the step (3) is a nano-scale silica sol solution; the dipping time is 5-10h; the drying temperature is 120 ℃; the mass ratio of the Si-containing solution to the active carbon 2 is (4-6) to 1; the mass concentration of the Si-containing solution is 0.5-5%.
6. The production method according to claim 2, characterized in that: the carbonization conditions in the step (4) are as follows: the carbonization time is 3-6h, and the carbonization temperature is 500-600 ℃; the activation conditions are as follows: the activation time is 1-3h, and the activation temperature is 700-800 ℃.
7. The method of claim 2, wherein: the acid solution in the step (5) is at least one of hydrochloric acid and sulfamic acid; the mass ratio of the acid solution to the active carbon 4 is (5-10) to 1; the mass concentration of the acid solution is 2-5%.
8. The method of claim 2, wherein: the nitrogen-containing organic matter in the step (6) is at least one of urea and melamine; the macromolecular binder is polyvinylpyrrolidone, and the molecular weight is 8000-10000.
9. The method of claim 2, wherein: the dipping time in the step (6) is 6-8h, and the drying temperature is 115-125 ℃; the roasting time is 5-8h, and the roasting temperature is 300-400 ℃; the mass ratio of the mixed solution to the activated carbon 5 is (5-10): 1; the mass concentration of the mixed solution is 5-10%; the mass ratio of the nitrogen-containing organic matter to the high-molecular binder is (5-10): 1.
10. use of the Si-modified acetylene hydrochlorination metal-free catalyst according to claim 1 or the Si-modified acetylene hydrochlorination metal-free catalyst prepared by the preparation method according to any one of claims 2 to 9 in acetylene hydrochlorination reactions.
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| CN202211319665.XA CN115888786A (en) | 2022-10-26 | 2022-10-26 | Si-modified acetylene hydrochlorination metal-free catalyst, preparation method and application |
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| CN202211319665.XA CN115888786A (en) | 2022-10-26 | 2022-10-26 | Si-modified acetylene hydrochlorination metal-free catalyst, preparation method and application |
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| CN115888679A (en) * | 2022-10-26 | 2023-04-04 | 鄂尔多斯市瀚博科技有限公司 | Si-modified activated carbon carrier, catalyst, preparation method and application |
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Inventor after: Zhao Changsen Inventor after: Niu Qiang Inventor after: Zhu Ruibo Inventor after: Wang Xinlong Inventor before: Zhao Changsen Inventor before: Niu Qiang Inventor before: Zhu Ruibo Inventor before: Wang Xinlong Inventor before: Dai Guoqiang |