CN114100659A - Nitrogen-boron co-doped metal-free catalyst and preparation method and application thereof - Google Patents
Nitrogen-boron co-doped metal-free catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- -1 saccharide compounds Chemical class 0.000 claims abstract description 19
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- 239000004005 microsphere Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000007038 hydrochlorination reaction Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 22
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 14
- 239000008103 glucose Substances 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 10
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 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 description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 229960002523 mercuric chloride Drugs 0.000 abstract description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 238000005303 weighing Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000967 suction filtration Methods 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a nitrogen-boron co-doped metal-free catalyst, a preparation method and application thereof, and relates to the technical field of catalytic materials. The metal-free catalyst of the invention is prepared by the following steps: mixing saccharide compounds with water, carrying out hydrothermal reaction, washing, filtering and drying to obtain micro carbon spheres; and mixing the obtained carbon microspheres with a nitrogen precursor, a boron precursor and deionized water, and roasting after water bath to obtain the metal-free catalyst. The method utilizes a hydrothermal method to prepare a microspherical carbon sphere precursor, and then nitrogen and boron are doped to obtain the metal-free catalyst. The preparation method of the metal-free catalyst is green and environment-friendly, the preparation process is simple, and the metal-free catalyst can replace a toxic mercuric chloride catalyst. The obtained nitrogen-boron co-doped metal-free catalyst is applied to the fixed bed acetylene hydrochlorination reaction and has good catalytic activity and stability.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a nitrogen and boron co-doped metal-free catalyst, a preparation method and application thereof, and further relates to a nitrogen and boron co-doped metal-free catalyst for acetylene hydrochlorination, a preparation method and application thereof.
Background
Polyvinyl chloride (PVC) is one of five general-purpose plastics in the world, and has wide application in building materials, industrial products, daily necessities, floor leathers, floor tiles, artificial leather, pipes, electric wires and cables, packaging films, foaming materials, sealing materials, fibers and the like. PVC is obtained by polymerization of Vinyl Chloride (VCM) monomer, and VCM is generally produced by methods including acetylene, ethylene oxychlorination and ethane oxychlorination, and around 90% of the current VCM production is produced by the acetylene process. At present, the industrial catalyst for preparing vinyl chloride by the acetylene method adopts a mercury catalyst system, however, the use of the mercury catalyst is limited due to the increasing exhaustion of mercury resources and the threat of mercury to the environment and human bodies. On the other hand, national and international regulations and policies have been successively issued to further restrict the use of mercury, and therefore, the development of mercury-free catalysts is imperative.
According to the active components, the mercury-free catalyst can be divided into a noble metal catalyst, a non-noble metal catalyst and a metal-free catalyst, wherein the activity of the noble metal catalyst in the acetylene hydrochlorination reaction is generally higher than that of the non-noble metal catalyst, and the activity of the non-noble metal catalyst is higher than that of the non-metal catalyst. At present, most universities, scientific research institutions and enterprises are focused on developing metal catalysts including precious metal catalysts and non-precious metal catalysts, so that the activity and stability of the metal catalysts are greatly improved, however, the metal catalysts have the problems of high cost and complex recovery, and the development of the non-metal mercury-free catalysts is very important for acetylene hydrochlorination.
The carbon-nitrogen material has the advantages of higher specific surface area, adjustable structure, abundant surface functional groups, high stability and the like, and is used in a plurality of catalytic reactions, and the carbon-nitrogen material also gets more and more attention in acetylene hydrochlorination. Li Xingyun et al (Nature Communication,2014,5,3688) report a catalyst SiC @ N-C for silicon carbide surface deposition of a nitrogen-doped carbon layer, which catalyst is at 150 ℃ and 36h-1The conversion rate of acetylene is stabilized at about 80 percent within 160 hours of reaction under the condition. Dong Xiaoobin et al (Journal of Catalysis,2018,359,161-170) reported that SBA-15 was used as a hard template to synthesize nitrogen-sulfur double-doped mesoporous carbon, and the catalyst was used at 220 ℃ for 36h-1The conversion rate of acetylene reaches more than 80 percent within 100 hours of reaction under the condition. Zhao Jia et al (Journal of Catalysis,2019,373,240-249) reported a nitrogen and phosphorus double-doped carbon-based catalyst at 280 ℃ and 30h-1Under the condition, the acetylene conversion rate reaches 98.1 percent. The reports in the above documents show that the activity of the metal-free catalyst is generally low, and the stability is poor, so how to further improve the activity and the stability of the metal-free catalyst is a key technical difficulty for improving the industrial application of the metal-free catalyst in the hydrochlorination of acetylene.
In view of the above, the invention utilizes the synergistic effect among various heteroatoms to promote the adsorption of the reaction gas hydrogen chloride in the acetylene hydrochlorination reaction, thereby realizing the significant improvement of the activity and stability of the catalyst.
Disclosure of Invention
The invention aims to provide a nitrogen-boron co-doped metal-free catalyst, and a preparation method and application thereof. The preparation method of the metal-free catalyst is green and environment-friendly, the preparation process is simple, and the metal-free catalyst can replace a toxic mercuric chloride catalyst. The obtained nitrogen-boron co-doped metal-free catalyst is applied to the fixed bed acetylene hydrochlorination reaction and has good catalytic activity and stability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
firstly, the invention provides a preparation method of a nitrogen-boron co-doped metal-free catalyst for acetylene hydrochlorination, which comprises the following steps:
(1) mixing saccharide compounds with water, carrying out hydrothermal reaction, washing, filtering and drying to obtain micro carbon spheres;
(2) and mixing the obtained carbon microspheres with a nitrogen precursor, a boron precursor and deionized water, and roasting after water bath to obtain the metal-free catalyst.
The term "carbohydrate" refers to an organic substance consisting of three elements of carbon, hydrogen and oxygen, and from the chemical structure, the carbohydrate is polyhydroxy aldehyde ketone and polymers thereof.
Preferably, in the step (1), the saccharide compound is at least one selected from glucose, fructose, sucrose and starch; further preferably glucose.
Preferably, in the step (1), the water is at least one of deionized water, distilled water, ultrapure water and purified water.
Preferably, in the step (1), the mass ratio of the saccharide compound to the deionized water is 1: 30-50, and more preferably 1: 40.
preferably, in step (1), the hydrothermal reaction is performed in an autoclave lined with polytetrafluoroethylene.
Preferably, in the step (1), the temperature of the hydrothermal reaction is 160-240 ℃, and the time of the hydrothermal reaction is 4-12 h; further preferably, the temperature of the hydrothermal reaction is 180 ℃ and the time of the hydrothermal reaction is 6 hours.
Preferably, in the step (1), the washing is performed by washing with deionized water and ethanol for multiple times.
Preferably, in the step (1), the filtration mode is suction filtration.
Preferably, in the step (1), the drying temperature is 50-120 ℃, and the drying time is 2-12 h; further preferably, the drying temperature is 80 ℃, and the drying time is 6 h.
Preferably, in the step (2), the nitrogen precursor is at least one of dicyandiamide, urea, polyvinylpyrrolidone, and melamine, and is more preferably polyvinylpyrrolidone.
Preferably, in the step (2), the boron precursor is at least one of boric acid, sodium tetraborate, and sodium borohydride, and more preferably boric acid.
Preferably, in the step (2), the mass ratio of the micro carbon spheres, the nitrogen precursor and the boron precursor is 5: 0.46 to 1.18: 0.84 to 1.3.
Preferably, in the step (2), the temperature of the water bath is 30-60 ℃, and the time of the water bath is 1-5 hours.
Preferably, in the step (2), the roasting atmosphere is one or more of nitrogen, helium and argon, the roasting temperature is 450-750 ℃, and the roasting time is 2-6 hours; further preferably, the roasting is carried out at 700 ℃ for 3h under a nitrogen atmosphere.
Furthermore, the invention provides the nitrogen-boron co-doped metal-free catalyst prepared by the preparation method, which consists of carbon element, nitrogen element, boron element and oxygen element.
Preferably, the nitrogen-boron co-doped metal-free catalyst consists of 5-15% of nitrogen element and boron element, 3-10% of oxygen element and the balance of carbon element according to mass fraction.
Preferably, the nitrogen-boron co-doped metal-free catalyst is solid microspheres with a mesoporous structure, the particle size is 100-500 nm, and the specific surface area is 500-1500 m2The pore diameter is 2-10 nm.
Finally, the invention provides the application of the nitrogen-boron co-doped metal-free catalyst in preparing vinyl chloride by catalyzing acetylene hydrochlorination.
Preferably, the application comprises the following steps: the catalyst is filled into a fixed bed reactor, and mixed gas of acetylene and hydrogen chloride is introduced for reaction after drying and hydrogen chloride activation.
Further preferably, the reaction temperature is 160-240 ℃, and the space velocity of acetylene is 10-100 h-1The molar ratio of the hydrogen chloride to the acetylene is 1.05-1.2: 1.
The invention has the beneficial effects that:
the metal-free catalyst prepared by the invention has regular appearance, only contains carbon, nitrogen, boron and oxygen elements, has high purity and does not contain other impurities; the catalyst has simple preparation method and low cost, and is easy to be prepared in industrial batch; the catalyst is applied to acetylene hydrochlorination and has good activity and stability.
Detailed Description
The present invention will be further explained with reference to specific examples in order to make the technical means, the technical features, the technical objectives and the effects of the present invention easier to understand, but the following examples are only preferred embodiments of the present invention, and not all embodiments of the present invention. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention. In the following examples, unless otherwise specified, all the operations were performed by conventional methods, all the equipments were performed by conventional methods, and the materials of the equipments used in the respective examples were the same.
Example 1
Weighing 10g of glucose, adding 400mL of deionized water, stirring uniformly, transferring into a 500mL high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing up, sealing and putting into an oven. And (3) carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, circularly washing with deionized water and ethanol until the suction filtration liquid is colorless, and then placing the obtained solid in a vacuum drying oven at 80 ℃ for drying for 6h to obtain the carbon microspheres.
Weighing 5g of micro carbon spheres, 0.64g of urea and 0.84g of boric acid, dissolving in 20mL of deionized water, uniformly mixing, carrying out water bath at 60 ℃ for 5h, and then roasting at 700 ℃ for 3h under a nitrogen atmosphere to obtain the metal-free catalyst A.
Example 2
Weighing 10g of glucose, adding 400mL of deionized water, stirring uniformly, transferring into a 500mL high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing up, sealing and putting into an oven. And (3) carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, circularly washing with deionized water and ethanol until the suction filtration liquid is colorless, and then placing the obtained solid in a vacuum drying oven at 80 ℃ for drying for 6h to obtain the carbon microspheres.
Weighing 5g of micro carbon spheres, 0.46g of melamine and 0.84g of boric acid, dissolving in 20mL of deionized water, uniformly mixing, carrying out water bath at 60 ℃ for 5h, and then roasting at 700 ℃ for 3h under a nitrogen atmosphere to obtain the metal-free catalyst B.
Example 3
Weighing 10g of glucose, adding 400mL of deionized water, stirring uniformly, transferring into a 500mL high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing up, sealing and putting into an oven. And (3) carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, circularly washing with deionized water and ethanol until the suction filtration liquid is colorless, and then placing the obtained solid in a vacuum drying oven at 80 ℃ for drying for 6h to obtain the carbon microspheres.
Weighing 5g of micro carbon spheres, 1.18g of polyvinylpyrrolidone and 0.84g of boric acid, dissolving in 20mL of deionized water, uniformly mixing, carrying out water bath at 60 ℃ for 5h, and then roasting at 700 ℃ for 3h under a nitrogen atmosphere to obtain the metal-free catalyst C.
Example 4
Weighing 10g of glucose, adding 400mL of deionized water, stirring uniformly, transferring into a 500mL high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing up, sealing and putting into an oven. And (3) carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, circularly washing with deionized water and ethanol until the suction filtration liquid is colorless, and then placing the obtained solid in a vacuum drying oven at 80 ℃ for drying for 6h to obtain the carbon microspheres.
Weighing 5g of micro carbon spheres, 0.64g of urea and 1.3g of sodium tetraborate, dissolving in 20mL of deionized water, uniformly mixing, carrying out water bath at 60 ℃ for 5h, and then roasting at 700 ℃ for 3h under a nitrogen atmosphere to obtain the metal-free catalyst D.
Example 5
Weighing 10g of glucose, adding 400mL of deionized water, stirring uniformly, transferring into a 500mL high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing up, sealing and putting into an oven. And (3) carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, circularly washing with deionized water and ethanol until the suction filtration liquid is colorless, and then placing the obtained solid in a vacuum drying oven at 80 ℃ for drying for 6h to obtain the carbon microspheres.
Weighing 5g of micro carbon spheres, 0.46g of dicyandiamide and 0.84g of boric acid, dissolving the mixture in 20mL of deionized water, uniformly mixing, carrying out water bath at 60 ℃ for 5h, and roasting at 700 ℃ for 3h under a nitrogen atmosphere to obtain the metal-free catalyst E.
Example 6
Weighing 10g of glucose, adding 400mL of deionized water, stirring uniformly, transferring into a 500mL high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing up, sealing and putting into an oven. And (3) carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, circularly washing with deionized water and ethanol until the suction filtration liquid is colorless, and then placing the obtained solid in a vacuum drying oven at 80 ℃ for drying for 6h to obtain the carbon microspheres.
Weighing 5g of micro carbon spheres, 1.18g of polyvinylpyrrolidone and 0.84g of boric acid, dissolving in 20mL of deionized water, uniformly mixing, carrying out water bath at 60 ℃ for 5h, and then roasting at 600 ℃ for 3h under a nitrogen atmosphere to obtain the metal-free catalyst F.
Comparative example 1
Weighing 10g of glucose, adding 400mL of deionized water, stirring uniformly, transferring into a 500mL high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing up, sealing and putting into an oven. And (3) carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, circularly washing with deionized water and ethanol until the suction filtration liquid is colorless, and then placing the obtained solid in a vacuum drying oven at 80 ℃ for drying for 6h to obtain the carbon microspheres.
5g of carbon microspheres were weighed and calcined at 700 ℃ for 3 hours under nitrogen atmosphere to obtain the metal-free catalyst comparative example C1.
Comparative example 2
Weighing 10g of glucose, adding 400mL of deionized water, stirring uniformly, transferring into a 500mL high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing up, sealing and putting into an oven. And (3) carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, circularly washing with deionized water and ethanol until the suction filtration liquid is colorless, and then placing the obtained solid in a vacuum drying oven at 80 ℃ for drying for 6h to obtain the carbon microspheres.
Weighing 5g of micro carbon spheres and 1.18g of polyvinylpyrrolidone into 20mL of deionized water, uniformly mixing, then carrying out water bath at 60 ℃ for 5h, and then roasting at 600 ℃ for 3h under a nitrogen atmosphere to obtain the metal-free catalyst comparative example C2.
Comparative example 3
Weighing 10g of glucose, adding 400mL of deionized water, stirring uniformly, transferring into a 500mL high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing up, sealing and putting into an oven. And (3) carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, circularly washing with deionized water and ethanol until the suction filtration liquid is colorless, and then placing the obtained solid in a vacuum drying oven at 80 ℃ for drying for 6h to obtain the carbon microspheres.
Weighing 5g of micro carbon spheres and 0.84g of boric acid in 20mL of deionized water, uniformly mixing, then carrying out water bath at 60 ℃ for 5h, and then roasting at 600 ℃ for 3h under a nitrogen atmosphere to obtain the metal-free catalyst comparative example C3.
Comparative example 4
Weighing 20g of glucose, 0.64g of urea and 0.84g of boric acid, dissolving in 400mL of deionized water, uniformly stirring, transferring into a 500mL high-pressure reaction kettle with a polytetrafluoroethylene lining, screwing up, sealing and putting into an oven. After carrying out hydrothermal reaction at 180 ℃ for 6h, naturally cooling to room temperature, circularly washing with deionized water and ethanol until the suction filtration liquid is colorless, then placing the obtained solid in a vacuum drying oven at 80 ℃ for drying for 6h, and then roasting at 600 ℃ for 3h under nitrogen atmosphere to obtain the metal-free catalyst comparative example C4.
Detection of catalytic Performance
Respectively taking 10ml of catalyst A-C4 for catalytic performance detection, loading the catalyst into a fixed bed reactor, introducing nitrogen, heating to 200 ℃, drying for 1h, introducing hydrogen chloride for activation for 1h, introducing a mixed gas of hydrogen chloride and acetylene at 200 ℃ for 30h-1And HCl/C2H2The volume ratio is 1.08. The results are shown in table 1:
table 1.
| Catalyst and process for preparing same | Acetylene conversion (%) | Vinyl chloride selectivity (%) |
| A | 82.9 | >99 |
| B | 81.3 | >99 |
| C | 91.2 | >99 |
| D | 86.5 | >99 |
| E | 85.1 | >99 |
| F | 87.6 | >99 |
| Comparative example C1 | 51.3 | 98.2 |
| Comparative example C2 | 67.8 | 99.1 |
| Comparative example C3 | 64.3 | 98.8 |
| Comparative example C4 | 73.6 | 98.5 |
From the data comparison in table 1, one can obtain: the nitrogen-boron co-doped metal-free catalyst prepared in the embodiment of the application has higher acetylene conversion rate in acetylene hydrochlorination reaction for 30h-1Space velocity condition of acetyleneUnder the condition of high stability, the acetylene conversion rate is above 81.3-91.2%, and the chloroethylene selectivity is greater than 99%.
The present invention is not limited to the above-described preferred embodiments, but rather, the present invention is to be construed broadly and cover all modifications, equivalents, and improvements falling within the spirit and scope of the present invention.
Claims (10)
1. A preparation method of a nitrogen-boron co-doped metal-free catalyst for acetylene hydrochlorination is characterized by comprising the following steps:
(1) mixing saccharide compounds with water, carrying out hydrothermal reaction, washing, filtering and drying to obtain micro carbon spheres;
(2) and mixing the obtained carbon microspheres with a nitrogen precursor, a boron precursor and deionized water, and roasting after water bath to obtain the metal-free catalyst.
2. The production method according to claim 1, wherein in the step (1), the sugar compound is at least one selected from the group consisting of glucose, fructose, sucrose and starch, preferably glucose; the mass ratio of the saccharide compound to the deionized water is 1: 30-50, preferably 1: 40.
3. the preparation method according to claim 1, wherein in the step (1), the hydrothermal reaction is carried out in an autoclave lined with polytetrafluoroethylene; the temperature of the hydrothermal reaction is 160-240 ℃, the time of the hydrothermal reaction is 4-12 h, preferably, the temperature of the hydrothermal reaction is 180 ℃, and the time of the hydrothermal reaction is 6 h.
4. The preparation method according to claim 1, wherein in the step (1), the drying temperature is 50-120 ℃ and the drying time is 2-12h, preferably, the drying temperature is 80 ℃ and the drying time is 6 h.
5. The method according to claim 1, wherein in step (2), the nitrogen precursor is at least one of dicyandiamide, urea, polyvinylpyrrolidone and melamine, preferably polyvinylpyrrolidone; the boron precursor is at least one of boric acid, sodium tetraborate and sodium borohydride, preferably boric acid; the mass ratio of the micro carbon spheres to the nitrogen precursor to the boron precursor is 5: 0.46 to 1.18: 0.84 to 1.3.
6. The preparation method according to claim 1, wherein in the step (2), the temperature of the water bath is 30-60 ℃, and the time of the water bath is 1-5 hours.
7. The preparation method according to claim 1, wherein in the step (2), the roasting atmosphere is one or more of nitrogen, helium and argon, the roasting temperature is 450-750 ℃, the roasting time is 2-6 h, and preferably, the roasting is carried out at 700 ℃ for 3h in a nitrogen atmosphere.
8. The nitrogen-boron co-doped metal-free catalyst prepared by the preparation method according to any one of claims 1 to 7, which is characterized by consisting of carbon, nitrogen, boron and oxygen; preferably, the nitrogen-boron co-doped metal-free catalyst consists of 5-15% of nitrogen element and boron element, 3-10% of oxygen element and the balance of carbon element according to mass fraction.
9. The nitrogen-boron co-doped metal-free catalyst of claim 8, wherein the nitrogen-boron co-doped metal-free catalyst is a solid microsphere with a mesoporous structure, the particle size is 100-500 nm, the specific surface area is 500-1500 m2/g, and the pore size is 2-10 nm.
10. Use of a nitrogen-boron co-doped metal-free catalyst prepared by the preparation method according to any one of claims 1 to 7 or according to claim 8 or 9 for catalyzing hydrochlorination of acetylene to produce vinyl chloride;
preferably, the application comprises the following steps: filling a catalyst into a fixed bed reactor, drying and activating by hydrogen chloride, and introducing mixed gas of acetylene and hydrogen chloride for reaction; further preferably, the reaction temperature is 160-240 ℃, the space velocity of acetylene is 10-100 h < -1 >, and the molar ratio of hydrogen chloride to acetylene is 1.05-1.2: 1.
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