CN116459856A - High-stability catalyst for hydrochlorination of acetylene as well as preparation method and application thereof - Google Patents
High-stability catalyst for hydrochlorination of acetylene as well as preparation method and application thereof Download PDFInfo
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- CN116459856A CN116459856A CN202310258183.6A CN202310258183A CN116459856A CN 116459856 A CN116459856 A CN 116459856A CN 202310258183 A CN202310258183 A CN 202310258183A CN 116459856 A CN116459856 A CN 116459856A
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- ruthenium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 39
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 66
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 53
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 39
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 33
- 239000011324 bead Substances 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 238000000498 ball milling Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000002791 soaking Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 36
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- -1 nitrogen-containing heterocyclic compounds Chemical class 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 239000002028 Biomass Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 claims description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 2
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 238000004873 anchoring Methods 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000011068 loading method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000003446 ligand Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000005997 Calcium carbide Substances 0.000 description 2
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- OVMFBUROZSKZPY-UHFFFAOYSA-N acetylene ruthenium Chemical compound [Ru].C#C OVMFBUROZSKZPY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 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
- 239000004408 titanium dioxide Substances 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical class CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- FRKGSNOMLIYPSH-UHFFFAOYSA-N 3-hydroxypyrrolidin-2-one Chemical compound OC1CCNC1=O FRKGSNOMLIYPSH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a high-stability catalyst for acetylene hydrochlorination, and a preparation method and application thereof, and belongs to the technical field of catalyst preparation. The preparation method of the catalyst comprises the following steps: adding a carbon-based carrier, a nitrogen source and a nano inorganic oxide precursor into a zirconium tank according to a certain proportion, adding a plurality of zirconium beads, performing ball milling by adopting a planetary ball mill, roasting at a high temperature under inert gas after ball milling is finished, and cooling to obtain a composite carrier; preparing ruthenium precursor into solution, dripping the solution onto the composite carrier at a certain temperature, keeping the temperature unchanged for soaking after dripping, and finally drying to obtain the high-stability catalyst. The catalyst prepared by anchoring the active components based on auxiliary strategies and inhibiting the agglomeration and loss of the active components has high activity and high stability, reduces the use cost of the catalyst to a certain extent, and is suitable for gradual amplification and even industrialized application.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a high-stability catalyst for acetylene hydrochlorination, and a preparation method and application thereof.
Background
Polyvinyl chloride, abbreviated as PVC, is a high molecular compound generated by polymerization reaction of vinyl chloride, has the advantages of high strength, corrosion resistance and the like, and is widely used in the fields of industry, agriculture, construction, science and technology and the like. More than 80% of vinyl chloride in China is prepared by a calcium carbide method (acetylene hydrochlorination), and mercury-based catalysts are adopted for preparing the vinyl chloride by the industrial calcium carbide method. Mercury is toxic and presents a serious threat to human health and the environment. With the restriction of international water regulations and environmental protection policies, the development of mercury-free catalysts is a necessary premise for sustainable development of the PVC industry.
Mercury-free catalyst systems can be classified into noble metal catalysts, non-noble metal catalysts and metal-free catalysts according to the nature of the active components, wherein noble metal catalysts have been most paid attention to and studied due to their higher activity. The research institutions sequentially conduct pilot test, pilot test and industrial survey line test of the noble-base noble metal catalyst, and a large amount of experimental data show that the gold catalyst has higher activity and higher industrialized application potential. However, gold is expensive, and with the large market fluctuation, a large one-time investment cost is required for industrial application, so that it is important to develop other metal catalysts to reduce the cost. Ruthenium has a lower price than gold and excellent catalytic properties, and has gained increasing attention. In order to further improve the catalytic activity, means such as carrier modification, addition of auxiliary agents, ionic liquid, ligand and the like are used for modifying the ruthenium catalyst, and the activity of the ruthenium-based catalyst is obviously improved through continuous optimization.
Patent (CN 110548499 a) discloses a composite carrier catalyst for hydrochlorination of acetylene and its application, the catalyst is composed of a composite carrier formed by depositing nano-scale inorganic oxide on active carbon, and metal active component deposited on the composite carrier, wherein the metal active component accounts for 0.05% -0.8%, the nano-scale inorganic oxide accounts for 0.5% -8.0%; the active metal component is gold or ruthenium or the combination of gold and ruthenium, cobalt and copper, and the nanoscale inorganic oxide is cerium dioxide, titanium dioxide, zirconium dioxide and lanthanum oxide. The catalyst is prepared by adopting a continuous two-step deposition-precipitation method, has the characteristics of simple and easily-amplified process, environmental protection and no toxicity, is used for preparing vinyl chloride monomer by hydrochlorination of acetylene, has the characteristics of low cost, high activity, good stability and the like, can keep good performance in continuous operation, can keep the acetylene conversion rate to be more than 97 percent, has the vinyl chloride selectivity to be more than 99.5 percent, and can replace the existing mercury chloride catalyst to be used for industrial mass production.
Journal paper ("carbon-supported ruthenium catalyst prepared by coordination stabilization strategy acetylene hydrochlorination reaction performance", wang Xiaolong, etc., catalytic theory report, 10 th period in 2020) regulates and controls the electronic structure of ruthenium catalyst by coordination of ligand (thiourea, phenanthroline and L-lactic acid) and ruthenium, researches the influence of the electronic structure of the active center of the catalyst on the activity and stability of the catalyst, and results show that the specific surface area of the catalyst is not obviously reduced, no pore blocking phenomenon is found, no formation of ruthenium nano particles is detected, and the ruthenium species is highly dispersed. X-ray photoelectron spectrum and ultraviolet-visible absorption spectrum characterization results show that the coordination atoms of the ligand are substituted by RuCl 3 Cl in (a) - Coordination with ruthenium ions, the binding energy of the coordinated ruthenium ions is higher than that of uncomplexed RuCl 3 The AC was shifted to some extent, indicating that the electron structure of ruthenium ion can be controlled by ligand modification of ruthenium catalyst. After further correlation, it was found that the TOF value and apparent activation energy of the ligand-modified ruthenium catalyst in the hydrochlorination of acetylene are in linear relationship with the binding energy position of Ru ions of the ruthenium catalyst, indicating that the structure of the active center of the ruthenium catalyst is related to the structure of the active center ruthenium electron. By adopting HCl-TPD to represent the adsorption of HCl on the ruthenium catalyst, partial ligands such as thiourea and phenanthroline nitrogen species can be found to adsorb and activate HCl, and certain synergistic effect exists between the HCl and ruthenium ions, so that the performance of the catalyst is further improved. The proposed ligand modification method is applicable to high-activity high-stability mercury-free catalystsDesign synthesis provides a new idea and a simple and effective method.
Patent (CN 114146727 a) discloses a ruthenium ethyne hydrochlorination based catalyst and a preparation method thereof, which relates to the field of catalyst preparation, and the ruthenium ethyne hydrochlorination based catalyst: the preparation method comprises the following raw materials: carriers, active ingredients and adjuvants; the carrier is phosphorus doped active carbon; the active component is ruthenium metal salt; the auxiliary agent is one or more of potassium chloride, 1-butyl-3-methylimidazolium salt, PVP and 3-hydroxy-2-pyrrolidone. The active carbon is doped with P, so that the interaction between the carrier and the active component is improved, and the metal salt auxiliary agent and the organic auxiliary agent are matched, so that the activity and stability of the catalyst are further improved.
As an industrial catalyst system, the stability of the catalyst is an important index for evaluating industrial application prospects, especially for noble metal catalyst systems, and poor stability leads to increased catalyst cost. The stability data of the ruthenium-based catalyst still have a large gap from industrial application. The method adopts an auxiliary strategy to anchor the active component and inhibit the agglomeration and loss of the active component, thereby improving the stability of the catalyst, reducing the cost of the catalyst and finally improving the industrial application prospect of the ruthenium-based catalyst.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a high-stability catalyst for acetylene hydrochlorination, and a preparation method and application thereof. The catalyst adopts an auxiliary strategy to anchor the active component, namely, the active component is stabilized by utilizing the synergistic effect of doped nitrogen and nano oxide rich in oxygen vacancies, so that the reaction activity is improved and the stability of the catalyst is improved. The catalyst has the advantages of low load, high activity, good stability and the like, and has better economical efficiency and industrial application prospect.
In order to achieve the above object, in a first aspect, the present invention provides a highly stable catalyst for hydrochlorination of acetylene, wherein the catalyst is a ruthenium-supported composite carbon-based carrier catalyst, and comprises a nitrogen-doped carbon material, a nano inorganic oxide and a ruthenium species.
In a preferred embodiment, the theoretical mass of nitrogen in the catalyst is 2-15%, preferably 4-10% of the mass of the nitrogen-doped carbon material; the nano inorganic oxide accounts for 0.1-5% of the mass of the nitrogen-doped carbon material, preferably 0.5-2%; the theoretical mass of ruthenium in the catalyst is 0.01-2% of the total catalyst mass, preferably 0.02-1%; the nanometer inorganic oxide is any one or more of cerium dioxide, zirconium dioxide, titanium dioxide and zinc oxide.
In a second aspect, the present invention provides a method for preparing the above-mentioned high-stability catalyst for hydrochlorination of acetylene, comprising the steps of: adding a carbon-based carrier, a nitrogen source and a nano inorganic oxide precursor into a zirconium tank according to a certain proportion, adding a plurality of zirconium beads, performing ball milling by adopting a planetary ball mill, roasting at a high temperature under inert gas after ball milling is finished, and cooling to obtain a composite carrier; preparing ruthenium precursor into solution, dripping the solution onto the composite carrier at a certain temperature, keeping the temperature unchanged for soaking after dripping, and finally drying to obtain the high-stability catalyst.
In a preferred embodiment, the carbon-based carrier is selected from any one or more of activated carbon, carbon nanotubes, graphene, mesoporous carbon, biomass carbon; the nitrogen source is selected from any one or more of urea, dicyandiamide, melamine, aniline and nitrogen-containing heterocyclic compounds; the nitrogen-containing heterocyclic compound is selected from pyridine nitrogen-containing heterocyclic compound and/or pyrrole nitrogen-containing heterocyclic compound; the nanometer inorganic oxide precursor is selected from any one or more of cerium nitrate hexahydrate, zirconium nitrate pentahydrate and titanyl sulfate; the ruthenium precursor is selected from one or more of ruthenium compounds such as ruthenium trichloride, ruthenium tribromide, ammonium hexachlororuthenate, potassium pentachlororuthenate hydrate and the like.
In a preferred embodiment, the ball-milled zirconium pot has a volume of 50-500mL, a zirconium bead diameter of 3-40mm, and a number of 2-10 zirconium beads, preferably 3-8; the ball milling treatment time is 0.1-48h, preferably 0.5-24h, and the rotating speed is 50-500r/min.
In a preferred embodiment, the inert atmosphere for the high temperature calcination is selected from nitrogen, helium and argon, the high temperature calcination temperature being 300-1000 ℃, preferably 400-800 ℃, and the calcination time being 1-10 hours, preferably 2-6 hours.
In a preferred embodiment, the impregnation temperature is 10-70 ℃, preferably 20-40 ℃, and the impregnation time is 1-48 hours, preferably 12-24 hours; the drying temperature is 50-200deg.C, preferably 80-120deg.C, and the drying time is 1-48 hr, preferably 12-24 hr.
In a third aspect, the present invention provides an application of the above-mentioned high-stability catalyst for hydrochlorination of acetylene in hydrochlorination of acetylene, the application method is as follows: filling the catalyst into a fixed bed reaction tube, introducing hydrogen chloride at the reaction temperature for activation treatment, and introducing a mixed gas of acetylene and hydrogen chloride for reaction after the activation treatment is finished.
In a preferred embodiment, the reaction temperature is from 150 to 250℃and preferably from 160 to 190℃and the acetylene space velocity is from 10 to 800h -1 The molar ratio of hydrogen chloride to acetylene is 1:1 to 1.5:1, preferably 1.05:1 to 1.2:1.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method anchors the active component based on an auxiliary strategy, namely, the active component is stabilized by utilizing the synergistic effect of doped nitrogen and the nano oxide rich in oxygen vacancies, the catalyst stability is improved while the reaction activity is improved, and the prepared catalyst has high activity and high stability, reduces the use cost of the catalyst to a certain extent, and is suitable for gradual amplification and even industrialized application.
(2) The catalyst of the invention has simple preparation process and low cost, and is easy for industrial batch preparation.
Detailed Description
For a better illustration of this patent, the following examples are presented. The following examples are presented to enable one of ordinary skill in the art to more fully understand the invention or to make various insubstantial modifications and adaptations in light of the disclosure herein. However, the scope of the present invention is not limited by these examples. The protection scope of the invention is set forth in the appended claims. It is to be noted that the raw materials used in the present invention are all common commercial products, and the sources thereof are not particularly limited.
Example 1
20g of active carbon, 10g of urea and 5g of cerium nitrate hexahydrate are weighed and placed in a 100mL zirconium pot, 2 zirconium beads with the diameter of 20mm, 3 zirconium beads with the diameter of 5mm and 2 zirconium beads with the diameter of 3mm are added, the zirconium pot is placed in a planetary ball mill, and ball milling is carried out for 1h at the rotating speed of 200 r/min. After ball milling, the materials are collected in a crucible, and are placed in a tube furnace, nitrogen is introduced into the tube furnace, and roasting is carried out for 3 hours at 600 ℃ to obtain the composite carrier. Ruthenium trichloride was formulated as a solution at a ruthenium loading of 0.5%, and added dropwise to the resulting composite support at room temperature. And (3) immersing for 12 hours at room temperature after the dripping is finished, and then placing in a 120 ℃ oven for drying for 12 hours to obtain the catalyst A. Loading 10mL of catalyst A into a fixed bed reactor, introducing nitrogen, heating to 180 ℃, drying for 1h, introducing hydrogen chloride for activation for 1h, and introducing a mixed gas of hydrogen chloride and acetylene at 180 ℃ for 180h -1 And HCl/C 2 H 2 The volume ratio is 1.05.
Example 2
20g of active carbon, 10g of melamine/dicyandiamide (mass ratio 1:1) and 5g of cerium nitrate hexahydrate are weighed and placed into a 100mL zirconium pot, 2 zirconium beads with the diameter of 20mm, 3 zirconium beads with the diameter of 5mm and 2 zirconium beads with the diameter of 3mm are added, the zirconium pot is placed into a planetary ball mill, and ball milling is carried out for 1h at the rotating speed of 200 r/min. After ball milling, the materials are collected in a crucible, and are placed in a tube furnace, nitrogen is introduced into the tube furnace, and roasting is carried out for 3 hours at 600 ℃ to obtain the composite carrier. Ruthenium trichloride was formulated as a solution at a ruthenium loading of 0.5%, and added dropwise to the resulting composite support at room temperature. And (3) immersing for 12 hours at room temperature after the dripping is finished, and then placing in a 120 ℃ oven for drying for 12 hours to obtain the catalyst B. Loading 10mL of catalyst B into a fixed bed reactor, introducing nitrogen, heating to 180 ℃, drying for 1h, introducing hydrogen chloride for activation for 1h, and introducing a mixed gas of hydrogen chloride and acetylene at 180 ℃ for 180h -1 And HCl/C 2 H 2 The volume ratio is 1.05.
Example 3
20g of activated carbon, 10g of melamine/dicyandiamide (mass ratio 1:1) and 7g of zirconium nitrate pentahydrate are weighedPlacing the mixture into a 100mL zirconium pot, adding 2 zirconium beads with the diameter of 20mm, 3 zirconium beads with the diameter of 5mm and 2 zirconium beads with the diameter of 3mm, placing the zirconium pot into a planetary ball mill, and ball milling for 1h at the rotating speed of 200 r/min. After ball milling, the materials are collected in a crucible, and are placed in a tube furnace, nitrogen is introduced into the tube furnace, and roasting is carried out for 3 hours at 600 ℃ to obtain the composite carrier. Ruthenium trichloride was formulated as a solution at a ruthenium loading of 0.5%, and added dropwise to the resulting composite support at room temperature. And (3) immersing for 12 hours at room temperature after the dripping is finished, and then placing in a 120 ℃ oven for drying for 12 hours to obtain the catalyst C. Loading 10mL of catalyst C into a fixed bed reactor, introducing nitrogen, heating to 180 ℃, drying for 1h, introducing hydrogen chloride for activation for 1h, and introducing a mixed gas of hydrogen chloride and acetylene at 180 ℃ for 180h -1 And HCl/C 2 H 2 The volume ratio is 1.05.
Example 4
20g of active carbon, 10g of melamine/dicyandiamide (mass ratio 1:1) and 6.7g of titanyl sulfate are weighed and placed into a 100mL zirconium pot, 2 zirconium beads with the diameter of 20mm, 3 zirconium beads with the diameter of 5mm and 2 zirconium beads with the diameter of 3mm are added, the zirconium pot is placed into a planetary ball mill, and ball milling is carried out for 1h at the rotating speed of 200 r/min. After ball milling, the materials are collected in a crucible, and are placed in a tube furnace, nitrogen is introduced into the tube furnace, and roasting is carried out for 3 hours at 600 ℃ to obtain the composite carrier. Ruthenium trichloride was formulated as a solution at a ruthenium loading of 0.5%, and added dropwise to the resulting composite support at room temperature. And (3) immersing for 12 hours at room temperature after the dripping is finished, and then placing in a 120 ℃ oven for drying for 12 hours to obtain the catalyst D. Loading 10mL of catalyst D into a fixed bed reactor, introducing nitrogen, heating to 180 ℃, drying for 1h, introducing hydrogen chloride for activation for 1h, and introducing a mixed gas of hydrogen chloride and acetylene at 180 ℃ for 180h -1 And HCl/C 2 H 2 The volume ratio is 1.05.
Example 5
20g of active carbon, 5g of melamine/dicyandiamide (mass ratio 1:1) and 7g of zirconium nitrate pentahydrate are weighed and placed into a 100mL zirconium pot, 2 zirconium beads with the diameter of 20mm, 3 zirconium beads with the diameter of 5mm and 2 zirconium beads with the diameter of 3mm are added, the zirconium pot is placed into a planetary ball mill, and ball milling is carried out at the rotating speed of 200r/minAnd 1h. After ball milling, the materials are collected in a crucible, and are placed in a tube furnace, nitrogen is introduced into the tube furnace, and roasting is carried out for 3 hours at 600 ℃ to obtain the composite carrier. Ruthenium trichloride was formulated as a solution at a ruthenium loading of 0.5%, and added dropwise to the resulting composite support at room temperature. And (3) immersing for 12 hours at room temperature after the dripping is finished, and then placing in a 120 ℃ oven for drying for 12 hours to obtain the catalyst E. Loading 10mL of catalyst E into a fixed bed reactor, introducing nitrogen, heating to 180 ℃, drying for 1h, introducing hydrogen chloride for activation for 1h, and introducing a mixed gas of hydrogen chloride and acetylene at 180 ℃ for 180h -1 And HCl/C 2 H 2 The volume ratio is 1.05.
Example 6
20g of active carbon, 10g of melamine/dicyandiamide (mass ratio 1:1) and 7g of zirconium nitrate pentahydrate are weighed and placed into a 100mL zirconium pot, 2 zirconium beads with the diameter of 20mm, 3 zirconium beads with the diameter of 5mm and 2 zirconium beads with the diameter of 3mm are added, the zirconium pot is placed into a planetary ball mill, and ball milling is carried out for 1h at the rotating speed of 200 r/min. After ball milling, the materials are collected in a crucible, and are placed in a tube furnace, nitrogen is introduced into the tube furnace, and roasting is carried out for 3 hours at 600 ℃ to obtain the composite carrier. Ruthenium trichloride was formulated as a solution at a ruthenium loading of 0.1%, and added dropwise to the resulting composite support at room temperature. And (3) immersing for 12 hours at room temperature after the dripping is finished, and then placing in a 120 ℃ oven for drying for 12 hours to obtain the catalyst F. Loading 10mL of catalyst F into a fixed bed reactor, introducing nitrogen, heating to 180 ℃, drying for 1h, introducing hydrogen chloride for activation for 1h, and introducing a mixed gas of hydrogen chloride and acetylene at 180 ℃ for 180h -1 And HCl/C 2 H 2 The volume ratio is 1.05.
Comparative example 1
20g of activated carbon was weighed and placed in a beaker, ruthenium trichloride was prepared into a solution according to a ruthenium loading of 0.5%, and the solution was added dropwise to the obtained activated carbon support at room temperature. And (3) immersing for 12 hours at room temperature after the dripping is finished, and then placing in a 120 ℃ oven for drying for 12 hours to obtain the catalyst C1. Loading 10mL of catalyst C1 into a fixed bed reactor, introducing nitrogen, heating to 180 ℃, drying for 1h, introducing hydrogen chloride for activation for 1h, and introducing a mixed gas of hydrogen chloride and acetylene at 180℃,180h -1 And HCl/C 2 H 2 The volume ratio is 1.05.
Comparative example 2
20g of active carbon and 10g of melamine/dicyandiamide (mass ratio of 1:1) are weighed and placed into a 100mL zirconium pot, 2 zirconium beads with the diameter of 20mm, 3 zirconium beads with the diameter of 5mm and 2 zirconium beads with the diameter of 3mm are added, the zirconium pot is placed into a planetary ball mill, and ball milling is carried out for 1h at the rotating speed of 200 r/min. After ball milling, the materials are collected in a crucible, and are placed in a tube furnace, nitrogen is introduced into the tube furnace, and roasting is carried out for 3 hours at 600 ℃ to obtain the composite carrier. Ruthenium trichloride was formulated as a solution at a ruthenium loading of 0.5%, and added dropwise to the resulting composite support at room temperature. And (3) immersing for 12 hours at room temperature after the dripping is finished, and then placing in a 120 ℃ oven for drying for 12 hours to obtain the catalyst C2. Loading 10mL of catalyst C2 into a fixed bed reactor, introducing nitrogen, heating to 180 ℃, drying for 1h, introducing hydrogen chloride for activation for 1h, and introducing a mixed gas of hydrogen chloride and acetylene at 180 ℃ for 180h -1 And HCl/C 2 H 2 The volume ratio is 1.05.
Comparative example 3
20g of active carbon and 7g of zirconium nitrate pentahydrate are weighed and placed in a 100mL zirconium tank, 2 zirconium beads with the diameter of 20mm, 3 zirconium beads with the diameter of 5mm and 2 zirconium beads with the diameter of 3mm are added, the zirconium tank is placed in a planetary ball mill, and ball milling is carried out for 1h at the rotating speed of 200 r/min. After ball milling, the materials are collected in a crucible, and are placed in a tube furnace, nitrogen is introduced into the tube furnace, and roasting is carried out for 3 hours at 600 ℃ to obtain the composite carrier. Ruthenium trichloride was formulated as a solution at a ruthenium loading of 0.5%, and added dropwise to the resulting composite support at room temperature. And (3) immersing for 12 hours at room temperature after the dripping is finished, and then placing in a 120 ℃ oven for drying for 12 hours to obtain the catalyst C3. Loading 10mL of catalyst C3 into a fixed bed reactor, introducing nitrogen, heating to 180 ℃, drying for 1h, introducing hydrogen chloride for activation for 1h, and introducing a mixed gas of hydrogen chloride and acetylene at 180 ℃ for 180h -1 And HCl/C 2 H 2 The volume ratio is 1.05.
The catalyst evaluation is shown in Table 1.
TABLE 1
Based on the comparison of the data in Table 1, it can be seen that the high stability catalyst prepared in the examples of the present application has a higher acetylene conversion and a better stability in the hydrochlorination of acetylene for 180 hours -1 Under the condition of acetylene airspeed, the deactivation rate of the first 24 hours is less than 0.1%/h. In addition, compared with comparative example 1, comparative example 2 has more nitrogen doping treatment, the conversion rate of acetylene is improved by 11.5%, and the selectivity of vinyl chloride is improved by 0.4%; compared with comparative example 1, comparative example 3 has more nano oxide, the conversion rate of acetylene is improved by 10.7%, and the selectivity of chloroethylene is improved by 0.4%; example 3 has more nitrogen doping treatment and nano-oxide compared with comparative example 1, the conversion rate of acetylene is increased by 28.2%, the selectivity of vinyl chloride is increased by more than 1%, the improvement degree is larger than the sum of the nitrogen doping alone and the nano-oxide modification alone, namely, as can be seen from example 3 and comparative examples 1-3, the synergistic effect is achieved between the nitrogen doping treatment and the nano-oxide modification of the carrier.
Finally, it should be noted that the above description is only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and that the simple modification and equivalent substitution of the technical solution of the present invention can be made by those skilled in the art without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The high-stability catalyst for the hydrochlorination of acetylene is characterized by being a composite carbon-based carrier supported ruthenium catalyst and comprising a nitrogen-doped carbon-based carrier, a nano inorganic oxide and a ruthenium species.
2. The highly stable catalyst according to claim 1, wherein the theoretical mass of nitrogen in the catalyst is 2-15%, preferably 4-10% of the mass of the nitrogen-doped carbon material; the nano inorganic oxide accounts for 0.1-5% of the mass of the nitrogen-doped carbon material, preferably 0.5-2%; the theoretical mass of ruthenium in the catalyst is 0.01-2%, preferably 0.02-1% of the total catalyst mass.
3. The high stability catalyst of claim 1, wherein the nano inorganic oxide is any one or more of ceria, zirconia, titania and zinc oxide.
4. A process for preparing a highly stable catalyst according to any one of claims 1 to 3, comprising the steps of: adding a carbon-based carrier, a nitrogen source and a nano inorganic oxide precursor into a zirconium tank according to a certain proportion, adding a plurality of zirconium beads, performing ball milling by adopting a planetary ball mill, roasting at a high temperature under inert gas after ball milling is finished, and cooling to obtain a composite carrier; preparing ruthenium precursor into solution, dripping the solution onto the composite carrier at a certain temperature, keeping the temperature unchanged for soaking after dripping, and finally drying to obtain the high-stability catalyst.
5. The method of claim 4, wherein the carbon-based carrier is selected from any one or more of activated carbon, carbon nanotubes, graphene, mesoporous carbon, biomass carbon; the nitrogen source is selected from any one or more of urea, dicyandiamide, melamine, aniline and nitrogen-containing heterocyclic compounds; the nitrogen-containing heterocyclic compound is selected from pyridine nitrogen-containing heterocyclic compound and/or pyrrole nitrogen-containing heterocyclic compound; the nanometer inorganic oxide precursor is selected from any one or more of cerium nitrate hexahydrate, zirconium nitrate pentahydrate and titanyl sulfate; the ruthenium precursor is selected from one or more of ruthenium compounds such as ruthenium trichloride, ruthenium tribromide, ammonium hexachlororuthenate, potassium pentachlororuthenate hydrate and the like.
6. The preparation method according to claim 4, wherein the ball-milling zirconium tank has a volume of 50-500mL, a zirconium bead diameter of 3-40mm, and a number of 2-10 zirconium beads, preferably 3-8 zirconium beads; the ball milling treatment time is 0.1-48h, preferably 0.5-24h, and the rotating speed is 50-500r/min.
7. The process according to claim 4, wherein the inert atmosphere for the high temperature calcination is selected from nitrogen, helium and argon, and the high temperature calcination temperature is 300 to 1000 ℃, preferably 400 to 800 ℃, and the calcination time is 1 to 10 hours, preferably 2 to 6 hours.
8. The process according to claim 4, wherein the impregnation temperature is 10-70 ℃, preferably 20-40 ℃, and the impregnation time is 1-48 hours, preferably 12-24 hours; the drying temperature is 50-200deg.C, preferably 80-120deg.C, and the drying time is 1-48 hr, preferably 12-24 hr.
9. Use of the high stability catalyst for hydrochlorination of acetylene according to any of claims 1 to 3 or prepared by the preparation method according to any of claims 4 to 8 in hydrochlorination of acetylene, characterized in that the method of application is as follows: filling the catalyst into a fixed bed reaction tube, introducing hydrogen chloride at the reaction temperature for activation treatment, and introducing a mixed gas of acetylene and hydrogen chloride for reaction after the activation treatment is finished.
10. Use according to claim 9, wherein the reaction temperature is 150-250 ℃, preferably 160-190 ℃, and the acetylene space velocity is 10-800h -1 The molar ratio of hydrogen chloride to acetylene is 1:1 to 1.5:1, preferably 1.05:1 to 1.2:1.
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