CN111569910A - Transition metal zinc-doped molybdenum sulfide composite catalytic powder material and preparation and application thereof - Google Patents
Transition metal zinc-doped molybdenum sulfide composite catalytic powder material and preparation and application thereof Download PDFInfo
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- hexavalent chromium
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 81
- 239000000463 material Substances 0.000 title claims abstract description 63
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000843 powder Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 40
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 72
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006722 reduction reaction Methods 0.000 claims abstract description 29
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000019253 formic acid Nutrition 0.000 claims abstract description 26
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 47
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- 238000004062 sedimentation Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003860 storage Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 18
- 230000009467 reduction Effects 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 7
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 5
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001965 increasing effect Effects 0.000 claims description 5
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- 150000003751 zinc Chemical class 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000036632 reaction speed Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000015556 catabolic process Effects 0.000 claims description 2
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
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- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 239000002028 Biomass Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
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- 239000011790 ferrous sulphate Substances 0.000 description 1
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- 238000005189 flocculation Methods 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses a transition metal zinc-doped molybdenum sulfide composite catalytic powder material, and a preparation method and application thereof. The composite catalytic material has the advantages of excellent performance, large specific surface area, high repeated utilization rate, good dispersibility and the like, and the integrated formic acid coupling reduction reaction device constructed based on the composite catalytic material can efficiently reduce heavy metal hexavalent chromium pollutants; meanwhile, the preparation process is simple in flow, controllable in operation, safe, efficient, green and environment-friendly, and the like, and is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of inorganic catalyst preparation, in particular to a transition metal zinc-doped molybdenum sulfide composite catalytic powder material, and preparation and application thereof.
Background
Heavy metal pollution has been a long-standing environmental concern in countries around the world due to its non-degradable nature. Hexavalent chromium is a common water pollutant and is widely produced in the industrial fields of electroplating, metal processing, tanning, dyes, steel, chemical industry and the like. If the treatment is improper, the ground water is polluted, and the environment and the human health are seriously harmed. In aqueous environments, chromium is present predominantly in the form of hexavalent chromium and trivalent chromium. The two oxidation states of chromium have significantly different chemical properties and different toxicity to the human body. Hexavalent chromium has high mobility and toxicity, and has teratogenic and carcinogenic effects on human bodies. Trivalent chromium is not easy to migrate, has lower toxicity and is an essential trace element related to human health and life. The maximum concentration of hexavalent chromium specified by the domestic drinking water standard of China does not exceed 50 mug/L. Therefore, there is a need to remediate hexavalent chromium contamination in the environment to avoid the severe environmental and health problems caused by hexavalent chromium.
The existing hexavalent chromium treatment methods mainly comprise an electric flocculation method, a membrane separation method, an ion exchange method, an adsorption method and a chemical reduction method. Among them, the chemical reduction method is favored by most researchers because of its advantages such as low cost, high efficiency, and environmental friendliness. The chemical reduction method is to reduce hexavalent chromium into trivalent chromium, and then add alkali to adjust the pH value so as to further precipitate and remove the trivalent chromium. Commonly used reducing agents include ferrous sulfate, sulfur dioxide, sulfites, polyaluminum ferric chloride, and the like. However, the use of these conventional reducing agents introduces other impurity ions, making subsequent separation difficult. Formic acid is a green chemical substance produced by utilizing renewable biomass resources, has the characteristics of low price, strong reducing capability and the like, and is directly mineralized into water and carbon dioxide under the activation of a metal catalyst without generating any toxic intermediate. The formic acid is used as a reducing agent for converting hexavalent chromium into trivalent chromium, and has a great application prospect. It has been found that various noble metal catalysts having high surface energy (e.g., Au, Ag, Pd, and Pt) have been used for the reduction of hexavalent chromium. However, these noble metal-based catalysts have a high investment cost. This limitation has prompted efforts to develop highly efficient non-noble metal catalysts. Molybdenum disulfide is a naturally occurring layered solid that has been used in many areas of catalysis for hydrogen evolution reactions, electrochemical intercalation, hydrogen storage, and coating materials in lithium batteries due to its unique electronic properties. In the chemical reduction method, the theory and experiment that the molybdenum disulfide catalyst is verified is one of the most potential non-noble metal catalysts.
At present, the improvement of the catalytic activity of molybdenum sulfide is mainly realized by means of phase change engineering, defect engineering, impurity element doping and the like. In-plane defect engineering and doping of hetero elements are effective means for activating molybdenum sulfide, increasing the number of active sites and improving catalytic activity. Therefore, finding a cheap means to obtain the molybdenum sulfide material with ultra-small size, element doping and a large amount of in-plane sulfur vacancies has important significance for promoting the progress of the environment. The metal zinc is a typical transition metal, has low price and excellent performance, and shows good compatibility when being combined with molybdenum sulfide, so that zinc ions can easily enter a crystal lattice structure of the molybdenum sulfide after a zinc element is doped into the molybdenum sulfide, the number of surface active sites of the molybdenum sulfide can be effectively increased, the surface activity of the molybdenum sulfide is enhanced, hexavalent chromium is efficiently reduced, and the reaction efficiency is improved. Patent CN109378267A discloses a method for preparing molybdenum sulfide material, which comprises obtaining a photo-etching pattern by a photo-etching method, depositing a molybdenum-based film layer by a film coating process, and finally obtaining a target product by a high-temperature heating method. Patent CN 103641171A discloses Zn2+Regulation and control of synthetic MoS2The material is prepared with Mo source, S source and reductant as material and through adding Zn2+The morphology of the product is regulated and controlled, and MoS is synthesized2Materials, butThe catalyst prepared by the method has the technical defects of easy inactivation, agglomeration, considerable ion leaching, easy secondary pollution of water, difficult recovery and the like. Patent CN110614104A discloses a method for preparing molybdenum sulfide photocatalytic material for treating sewage, which adopts hydrothermal method and in-situ precipitation method to prepare target product for treating sewage, but the conditions for treating sewage require illumination, and sewage cannot be treated simply and rapidly, and the ultraviolet light absorption range is narrow, the light energy utilization rate is low, the energy consumption is large, and the reduction rate of sewage is not high.
In conclusion, the previous reports have the problems of low activity, high cost and the like in the aspects of material preparation process, product performance and a method for reducing hexavalent chromium pollutants. Therefore, the preparation of a catalytic material with low cost, simple operation and excellent performance and a simple, efficient and rapid hexavalent chromium reduction method are in urgent need of discovery.
Disclosure of Invention
The invention aims to provide a transition metal zinc-doped molybdenum sulfide composite catalytic powder material and preparation and application thereof aiming at the defects of the prior art, and the technical problems to be solved are that: the method solves the problems that the material preparation process is complicated, complicated experimental conditions are required, large-scale production cannot be realized, the prepared catalyst is poor in structural stability, low in dispersity and difficult to recover, and secondary pollution is caused to a water body, and the technical problem of how to simply, efficiently and quickly reduce hexavalent chromium pollutants is solved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a transition metal zinc-doped molybdenum sulfide composite catalytic powder material comprises the following steps:
step 1, adding ammonium molybdate tetrahydrate and metal zinc salt into deionized water, stirring for 2-4 hours, adding a sulfur source, and continuously stirring for 1-3 hours to obtain a mixed solution;
and 3, drying and fully grinding the product obtained in the step 2, placing the product in a tubular furnace, heating to 600-700 ℃ under the protection of inert gas, reacting at a constant temperature for 1-3 hours, and cooling to room temperature after the reaction is finished to obtain the transition metal zinc-doped molybdenum sulfide composite catalytic powder material.
Further, in the step 1, the use amount ratio of ammonium molybdate tetrahydrate, transition metal salt and sulfur source is 10-30 mmol: 0.1-0.3 mol: 0.1 to 0.5 mol.
Further, in step 1, the metal zinc salt is one of water-soluble salts of metal zinc, and the sulfur source is at least one of thiourea, sulfur and ammonium tetrathiomolybdate.
Further, in the step 3, the drying is carried out for 10-30 hours at the temperature of 60-80 ℃.
Further, in the step 3, the inert gas is argon or nitrogen, and the flow rate of the inert gas is 0.1-5 mL/min.
Further, in the step 3, the temperature rise rate of the temperature rise is controlled to be 5-10 ℃/min.
The invention also discloses the application of the transition metal zinc-doped molybdenum sulfide composite catalytic powder material prepared by the preparation method in reducing heavy metal hexavalent chromium. The method for reducing the heavy metal hexavalent chromium by using the transition metal zinc-doped molybdenum sulfide composite catalytic powder material comprises the following steps: and constructing a reduction reaction device which comprises a hexavalent chromium sewage storage tank, a formic acid storage tank, a catalytic reactor and a sedimentation tank.
A water inlet is formed in the top of the catalytic reactor; the bottom outlet of the hexavalent chromium sewage storage pool and the bottom outlet of the formic acid storage pool are communicated to the water inlet through a water inlet pump and a throttle valve respectively;
a catalyst bed layer containing a plurality of transition metal zinc-doped molybdenum sulfide composite catalytic powder materials is fixed in the catalytic reactor;
a reacted water outlet is formed in the bottom of the catalytic reactor and communicated to a water inlet in the top of the sedimentation tank through a water outlet pump and a throttle valve; the top of the sedimentation tank is also provided with a sodium hydroxide inlet, the side surface of the sedimentation tank is provided with a water outlet, and the bottom of the sedimentation tank is provided with a chromium hydroxide sludge outlet;
a blower is connected in the catalytic reactor;
the method for reducing the heavy metal hexavalent chromium by using the reduction reaction device comprises the following steps:
loading hexavalent chromium sewage to be treated into a hexavalent chromium sewage storage tank, loading formic acid into a formic acid storage tank, respectively introducing the hexavalent chromium sewage into a catalytic reactor through corresponding water inlet pumps, and regulating the flow through corresponding throttle valves; mixing hexavalent chromium sewage and formic acid, slowly flowing from top to bottom through the composite catalytic powder material, performing catalytic reduction reaction to achieve the degradation effect, and increasing the reaction speed through a blower; introducing the solution after reaction into a sedimentation tank through a water outlet pump, and adding sodium hydroxide into the sedimentation tank for sedimentation treatment; discharging the chromium hydroxide sludge generated after precipitation, leading out the residual solution after treatment from a water outlet, and detecting: if the treated solution reaches the discharge standard, directly discharging; if the treated solution does not meet the discharge standard, the solution is reintroduced into the hexavalent chromium sewage storage pool to form circulation.
Further, in the catalytic reactor, the molar ratio of formic acid to hexavalent chromium is 1.2-4: 1.
further, the optimal pH condition of the reaction of the hexavalent chromium sewage and formic acid is 2-3, and a pH regulator inlet is arranged at the top of the catalytic reactor and used for adding a pH value regulator such as hydrochloric acid or sodium hydroxide to regulate the pH value of the reaction system.
Compared with the prior art, the invention has the beneficial effects that:
(1) the whole preparation process related by the invention is simple and convenient, does not need complex experimental conditions, has good repeatability and is environment-friendly, and the industrial production of the transition metal zinc-doped molybdenum sulfide composite catalytic powder material is realized.
(2) The transition metal zinc used in the invention is cheap and easy to obtain, has good compatibility in the molybdenum sulfide matrix, and can effectively increase the number of active sites on the surface of the molybdenum sulfide, thereby enhancing the surface activity of the molybdenum sulfide and improving the reaction efficiency. According to the invention, the content of sulfur vacancy in the surface of the nanoparticle is effectively regulated and controlled by doping the transition metal zinc and the molybdenum sulfide, so that the catalytic performance of the nanoparticle is regulated and controlled, and a new material is provided for hexavalent chromium reduction.
(3) The composite catalytic powder material prepared by the invention has large reaction contact area and high repeated utilization rate, and is coupled with formic acid for degrading and reducing heavy metal hexavalent chromium pollutants for the first time, the reduction rate reaches 100 percent, and a new method is provided for the field of reducing hexavalent chromium. In addition, the catalyst has high purity, uniform granularity and good dispersibility, and solves the problems of poor dispersibility, easy activation and poisoning, easy aggregation and the like of the traditional powder catalytic material.
(4) Based on the obtained transition metal zinc-doped molybdenum sulfide composite catalytic powder material, the invention also constructs a related reduction reaction device for reducing the heavy metal hexavalent chromium pollutants for the first time. The device can realize large-scale application of reducing hexavalent chromium, and provides a new idea for the field of reducing hexavalent chromium.
Drawings
FIG. 1 is an XRD diagram of a transition metal zinc-doped molybdenum sulfide composite catalytic powder material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of a transition metal zinc-doped molybdenum sulfide composite catalytic powder material prepared in example 1 of the present invention;
FIG. 3 is a schematic view of a reduction reaction apparatus constructed according to the present invention.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
In the embodiment, the transition metal zinc-doped molybdenum sulfide composite catalytic powder material is prepared by the following steps:
step 1, mixing 12.4mmol ammonium molybdate tetrahydrate and 0.16mol ZnCl2Placing the mixture into a beaker containing 1L of deionized water, stirring the mixture for 2 hours at room temperature, then adding 350mmol of thiourea, and continuing stirring the mixture for 1 hour at room temperature to obtain a mixed solution;
step 3, drying the product obtained in the step 2 at 70 ℃ for 24 hours, fully grinding, placing in a tube furnace, and performing N2Heating to 700 ℃ at a constant speed in the atmosphere at a heating rate of 10 ℃/min, reacting for 2 hours at a constant temperature, and reacting under N2Cooling to room temperature in the atmosphere, fully grinding the obtained black powder, namely the transition metal zinc-doped molybdenum sulfide composite catalytic powder material, and bottling for later use.
Fig. 1 is an XRD chart of the transition metal zinc-doped molybdenum sulfide composite catalytic powder material prepared in this example, from which it can be seen that the transition metal zinc-doped molybdenum sulfide powder material mainly consists of zinc sulfide and molybdenum sulfide.
Fig. 2 is an SEM image of the transition metal zinc-doped molybdenum sulfide composite catalytic powder material prepared in this example, and it can be observed that the transition metal zinc-doped molybdenum sulfide powder material has a petal-shaped layered stacking structure.
In order to verify the catalytic effect of the obtained composite catalytic powder material, a reduction reaction device shown in fig. 3 is firstly constructed: comprises a hexavalent chromium sewage storage tank, a formic acid storage tank, a catalytic reactor and a sedimentation tank;
a water inlet is arranged at the top of the catalytic reactor; the bottom outlet of the hexavalent chromium sewage storage pool and the bottom outlet of the formic acid storage pool are respectively communicated to the water inlet through a water inlet pump and a throttle valve;
a catalyst bed layer containing a plurality of transition metal zinc-doped molybdenum sulfide composite catalytic powder materials prepared by the method is fixed in a catalytic reactor;
a reacted water outlet is arranged at the bottom of the catalytic reactor and communicated to a water inlet at the top of the sedimentation tank through a water outlet pump and a throttle valve; a sodium hydroxide inlet is also arranged at the top of the sedimentation tank, a water outlet is arranged on the side surface of the sedimentation tank, and a chromium hydroxide sludge outlet is arranged at the bottom of the sedimentation tank;
the catalytic reactor is also internally connected with a blower;
specifically, the optimal pH condition of the reaction of the hexavalent chromium sewage and formic acid is 2-3, and a pH regulator inlet is arranged at the top of the catalytic reactor and used for adding a pH value regulator such as hydrochloric acid or sodium hydroxide to regulate the pH value of the reaction system.
Specifically, the method comprises the following steps: the volume of the catalytic reactor is 1L, a catalyst bed layer is fixed in the catalytic reactor, the transition metal zinc-doped molybdenum sulfide composite catalytic powder material prepared by the method is stored in the catalytic reactor, and the thickness of the catalyst bed layer is 50 cm.
Specifically, the method comprises the following steps: a detection instrument is arranged at a water discharge port of the sedimentation tank and used for detecting the concentration of hexavalent chromium in the treated solution: if the treatment reaches the standard, directly discharging the solution; if the treatment does not reach the standard, the solution is reintroduced into the hexavalent chromium sewage storage pool to form circulation.
The method for degrading the heavy metal hexavalent chromium by using the reduction reaction device comprises the following steps:
the sewage of hexavalent chromium (the initial chromium concentration is 100mg/L) to be treated is filled into a hexavalent chromium sewage storage pool, formic acid is filled into a formic acid storage pool, the formic acid and the formic acid are respectively led into a catalytic reactor through corresponding water inlet pumps, and the flow is adjusted through corresponding throttle valves; the hexavalent chromium sewage and formic acid are mixed and slowly flow from top to bottom to pass through the composite catalytic powder material, the catalytic reduction reaction is carried out to achieve the reduction effect, the reaction speed is increased through a blower, and the molar ratio of formic acid to hexavalent chromium in the catalytic reactor is 2: 1; introducing the solution after reaction into a sedimentation tank through a water outlet pump, and adding sodium hydroxide into the sedimentation tank for sedimentation treatment; discharging the chromium hydroxide sludge generated after precipitation, leading out the residual solution after treatment from a water outlet, and detecting: if the treated solution reaches the discharge standard, directly discharging; if the treated solution does not meet the discharge standard, the solution is reintroduced into the hexavalent chromium sewage storage pool to form circulation.
The final hexavalent chromium reduction rate was tested to be 100% according to the method of this example.
Example 2
In this embodiment, a transition metal zinc-doped molybdenum sulfide composite catalytic powder material is prepared by the same method as in embodiment 1, except that: ZnCl2The amount of (B) is 0.01 mol.
The composite catalytic powder material obtained in the embodiment is used for reducing the heavy metal hexavalent chromium according to the same structure and method in the embodiment 1, and the final reduction rate of the hexavalent chromium is 84%.
Example 3
In this embodiment, a transition metal zinc-doped molybdenum sulfide composite catalytic powder material is prepared by the same method as in embodiment 1, except that: ZnCl2The amount of (B) is 0.09 mol.
The composite catalytic powder material obtained in the embodiment is used for reducing the heavy metal hexavalent chromium according to the same structure and method in the embodiment 1, and the final reduction rate of the hexavalent chromium is 88%.
Example 4
In this embodiment, a transition metal zinc-doped molybdenum sulfide composite catalytic powder material is prepared by the same method as in embodiment 1, except that: ZnCl2The amount of (B) is 0.24 mol.
The composite catalytic powder material obtained in the embodiment is used for reducing the heavy metal hexavalent chromium according to the same structure and method in the embodiment 1, and the final reduction rate of the hexavalent chromium is 83%.
Example 5
In this embodiment, a transition metal zinc-doped molybdenum sulfide composite catalytic powder material is prepared by the same method as in embodiment 1, except that: ZnSO is selected as the zinc salt4。
The composite catalytic powder material obtained in the embodiment is used for reducing the heavy metal hexavalent chromium according to the same structure and method in the embodiment 1, and the final reduction rate of the hexavalent chromium is 95%.
Example 6
In this embodiment, a transition metal zinc-doped molybdenum sulfide composite catalytic powder material is prepared by the same method as in embodiment 1, except that: zn (NO) is selected as zinc salt3)2。
The composite catalytic powder material obtained in the embodiment is used for reducing the heavy metal hexavalent chromium according to the same structure and method in the embodiment 1, and the final reduction rate of the hexavalent chromium is 90%.
Example 7
In this embodiment, a transition metal zinc-doped molybdenum sulfide composite catalytic powder material is prepared by the same method as in embodiment 1, except that:zn (CH) is selected as zinc salt3COO)2。
The composite catalytic powder material obtained in the embodiment is used for reducing the heavy metal hexavalent chromium according to the same structure and method in the embodiment 1, and the final reduction rate of the hexavalent chromium is 93%.
Example 8
In this embodiment, a transition metal zinc-doped molybdenum sulfide composite catalytic powder material is prepared by the same method as in embodiment 1, except that: the sulfur source is sulfur.
The composite catalytic powder material obtained in the embodiment is used for reducing the heavy metal hexavalent chromium according to the same structure and method in the embodiment 1, and the final reduction rate of the hexavalent chromium is 89%.
Example 9
In this embodiment, a transition metal zinc-doped molybdenum sulfide composite catalytic powder material is prepared by the same method as in embodiment 1, except that: the sulfur source is ammonium tetrathiomolybdate.
The composite catalytic powder material obtained in the embodiment is used for reducing the heavy metal hexavalent chromium according to the same structure and method in the embodiment 1, and the final reduction rate of the hexavalent chromium is 100%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a transition metal zinc-doped molybdenum sulfide composite catalytic powder material is characterized by comprising the following steps:
step 1, adding ammonium molybdate tetrahydrate and metal zinc salt into deionized water, stirring for 2-4 hours, adding a sulfur source, and continuously stirring for 1-3 hours to obtain a mixed solution;
step 2, carrying out hydrothermal reaction on the mixed solution obtained in the step 1 at the temperature of 100-200 ℃ for 10-20 h;
and 3, drying and fully grinding the product obtained in the step 2, placing the product in a tubular furnace, heating to 600-700 ℃ under the protection of inert gas, reacting at a constant temperature for 1-3 hours, and cooling to room temperature after the reaction is finished to obtain the transition metal zinc-doped molybdenum sulfide composite catalytic powder material.
2. The method of claim 1, wherein: in the step 1, the using amount ratio of ammonium molybdate tetrahydrate, the metal zinc salt and the sulfur source is 10-30 mmol: 0.1-0.3 mol: 0.1 to 0.5 mol.
3. The production method according to claim 1 or 2, characterized in that: in the step 1, the metal zinc salt is one of water-soluble salts of metal zinc; the sulfur source is at least one of thiourea, sulfur and ammonium tetrathiomolybdate.
4. The production method according to claim 1 or 2, characterized in that: in the step 3, the drying is carried out for 10-30 h at the temperature of 60-80 ℃.
5. The production method according to claim 1 or 2, characterized in that: in the step 3, the inert gas is argon or nitrogen, and the flow rate of the inert gas is 0.1-5 mL/min.
6. The production method according to claim 1 or 2, characterized in that: in the step 3, the temperature rise rate of the temperature rise is controlled to be 5-10 ℃/min.
7. A transition metal zinc-doped molybdenum sulfide composite catalytic powder material prepared by the preparation method of any one of claims 1 to 6.
8. The use of the transition metal zinc-doped molybdenum sulfide composite catalytic powder material of claim 7 in the reduction of hexavalent chromium as a heavy metal.
9. A method for reducing heavy metal hexavalent chromium by using the transition metal zinc-doped molybdenum sulfide composite catalytic powder material of claim 7, which is characterized by comprising the following steps: constructing a reduction reaction device which comprises a hexavalent chromium sewage storage tank, a formic acid storage tank, a catalytic reactor and a sedimentation tank;
a water inlet is formed in the top of the catalytic reactor; the bottom outlet of the hexavalent chromium sewage storage pool and the bottom outlet of the formic acid storage pool are communicated to the water inlet through a water inlet pump and a throttle valve respectively;
a catalyst bed layer containing a plurality of transition metal zinc-doped molybdenum sulfide composite catalytic powder materials is fixed in the catalytic reactor;
a reacted water outlet is formed in the bottom of the catalytic reactor and communicated to a water inlet in the top of the sedimentation tank through a water outlet pump and a throttle valve; the top of the sedimentation tank is also provided with a sodium hydroxide inlet, the side surface of the sedimentation tank is provided with a water outlet, and the bottom of the sedimentation tank is provided with a chromium hydroxide sludge outlet;
a blower is connected in the catalytic reactor;
the method for reducing the heavy metal hexavalent chromium by using the reduction reaction device comprises the following steps:
loading hexavalent chromium sewage to be treated into a hexavalent chromium sewage storage tank, loading formic acid into a formic acid storage tank, respectively introducing the hexavalent chromium sewage into a catalytic reactor through corresponding water inlet pumps, and regulating the flow through corresponding throttle valves; mixing hexavalent chromium sewage and formic acid, slowly flowing from top to bottom through the composite catalytic powder material, performing catalytic reduction reaction to achieve the degradation effect, and increasing the reaction speed through a blower; introducing the solution after reaction into a sedimentation tank through a water outlet pump, and adding sodium hydroxide into the sedimentation tank for sedimentation treatment; discharging the chromium hydroxide sludge generated after precipitation, leading out the residual solution after treatment from a water outlet, and detecting: if the treated solution reaches the discharge standard, directly discharging; if the treated solution does not meet the discharge standard, the solution is reintroduced into the hexavalent chromium sewage storage pool to form circulation.
10. The method of claim 9, wherein: in the catalytic reactor, the molar ratio of formic acid to hexavalent chromium is 1.2-4: 1.
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