CN110975854B - Catalyst for treating sulfur-containing waste alkali and preparation method and application thereof - Google Patents
Catalyst for treating sulfur-containing waste alkali and preparation method and application thereof Download PDFInfo
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- CN110975854B CN110975854B CN201911315286.1A CN201911315286A CN110975854B CN 110975854 B CN110975854 B CN 110975854B CN 201911315286 A CN201911315286 A CN 201911315286A CN 110975854 B CN110975854 B CN 110975854B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 34
- 239000011593 sulfur Substances 0.000 title claims abstract description 34
- 239000003513 alkali Substances 0.000 title claims abstract description 33
- 239000002699 waste material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 99
- 239000000243 solution Substances 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 239000012876 carrier material Substances 0.000 claims description 34
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 32
- 229910001431 copper ion Inorganic materials 0.000 claims description 32
- 239000012266 salt solution Substances 0.000 claims description 31
- 229910052684 Cerium Inorganic materials 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims description 21
- -1 cerium ions Chemical class 0.000 claims description 21
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 21
- 150000001879 copper Chemical class 0.000 claims description 20
- 239000002048 multi walled nanotube Substances 0.000 claims description 19
- 230000032683 aging Effects 0.000 claims description 17
- 239000012286 potassium permanganate Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 13
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 11
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 11
- KTZTWIUHOOVDLH-UHFFFAOYSA-N copper;ethane-1,2-diol Chemical compound [Cu].OCCO KTZTWIUHOOVDLH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000003518 caustics Substances 0.000 claims 3
- 238000003672 processing method Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000004090 dissolution Methods 0.000 abstract description 8
- 230000009467 reduction Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000003112 inhibitor Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000002815 homogeneous catalyst Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000009279 wet oxidation reaction Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002074 nanoribbon Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/393—
-
- 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
- B01J37/16—Reducing
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- 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
- C02F2101/101—Sulfur compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
Abstract
The invention relates to a catalyst for treating sulfur-containing waste alkali, a preparation method and application thereof. The catalyst shows high-efficiency and stable catalytic effect when used for the oxidation removal of sulfur-containing compounds under alkaline conditions. The Cu-based catalyst prepared by the invention has simple process, can complete the effective reduction of active components such as Cu, Ce, Cd and the like on the carrier without adding additional reducing agent and polymerization inhibitor, and is beneficial to the uniform distribution of the active components on the carrier. When the catalyst is applied to a wet catalytic oxidation reaction system, the alkali resistance of the catalyst is greatly improved, and the element dissolution phenomenon is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of water treatment and material preparation, relates to a catalyst for treating sulfur-containing waste alkali, a preparation method and application thereof, and particularly relates to a multi-active-component homogeneous catalyst for treating high-concentration alkaline sulfur-containing wastewater by wet catalytic oxidation and a preparation method thereof.
Background
In the industrial drainage of petrochemical plants, dye plants and the like, a large amount of sulfide sewage is contained, and especially in the production process of ethylene, acid gas is absorbed by alkali liquor to generate a large amount of waste alkali liquor, wherein sodium sulfide is mainly contained. If the waste water is directly discharged without being treated, the waste water can seriously pollute the environment and can affect the physical health of people.
The method for treating industrial sulfur-containing wastewater mainly comprises air blowing, chemical precipitation, oxidation and other methods. At present, the effective method for treating the waste alkali liquor in China is a Wet Air Oxidation (WAO) method, and most of the method is introduced into the technology of Germany Linde company. The wet air oxidation method can oxidize the sulfide in the sulfur-containing wastewater into pollution-free sulfate, but the reaction temperature in the process is high, and the development of the catalytic wet oxidation method (CWAO) is promoted in order to reduce the reaction temperature. In order to overcome the defects of WAO, wet oxidation reaction in the presence of a catalyst is proposed with the development of a catalytic technology since the 70 th century, the reaction activation energy is reduced by using the catalyst, so that the oxidative decomposition capability is effectively improved, the reaction temperature and pressure are reduced, the reaction rate is accelerated, the reaction time is shortened, the cost is reduced, and good catalytic oxidation performance is generally shown for industrial wastewater. Compared with WAO, the catalyst is added, so that the reaction condition becomes relatively mild, toxic and harmful substances are deeply oxidized, the generation of toxic intermediate substances is reduced, and the application range is expanded. Because of the advantages of CWAO, CWAO is widely applied to the treatment of high-concentration, toxic and harmful industrial wastewater. Therefore, the development and development of more efficient, economical and stable wet oxidation catalysts can improve the oxidative decomposition capability of the catalysts on harmful substances, reduce the temperature and pressure required by the reaction, shorten the reaction time, and have important significance for the practical application of wet oxidation technology.
The research of the wet catalytic oxidation catalyst focuses on a homogeneous catalyst at first, and the reaction of the homogeneous catalysis has lower temperature, stronger selectivity and specific reaction performance. The selectivity and activity of the homogeneous catalyst can be finely designed and formulated by adding promoters, changing the types of solvents, selecting different ligands, and the like. The reaction principle of the homogeneous catalyst is simple and easy to research and grasp. Although the homogeneous catalyst has high activity and strong selectivity and is easy to prepare, the homogeneous catalyst needs to be subjected to subsequent treatment after the reaction is finished, is difficult to recover, has a complex process and is easy to run off, so that secondary pollution is caused. Heterogeneous catalysts exist in a solid form, and have the advantages of high activity, easiness in separation, good stability and the like, so that the research of the heterogeneous catalysts is generally regarded by people. At present, the development and research of wet catalytic oxidation catalysts performed in China are mostly focused on heterogeneous catalysts. At present, the researches on heterogeneous catalysts at home and abroad are mainly divided into the following three categories: noble metals, copper-based, and rare earth.
Among them, the copper catalyst has higher activity than other transition metal oxides, has lower price and higher activity, but has the problem of dissolution and low stability. Therefore, how to effectively improve the tolerance of the catalyst in strong alkali is very important.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problems of low COD conversion rate, unstable catalyst and high dissolution rate of active components in the existing catalyst under an alkaline condition, and provide a catalyst for treating sulfur-containing waste alkali, which can be used for carrying out wet catalytic oxidation on sulfides under the alkaline condition.
The second technical problem to be solved by the invention is to provide a stable preparation method of the catalyst, and specifically, a normal-temperature ethylene glycol reduction method is adopted, a mixed material O-MWCNTs-GONRs-C is adopted as a carrier, no additional reducing agent or polymerization inhibitor is added, the reduction of the active component can be completed under the normal-temperature condition, and the dispersibility and stability of the active component are improved.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
a catalyst for treating sulfur-containing waste alkali comprises the components of a mixed carrier material O-MWCNTs-GONRs-C and a loaded active component; based on the total mass of the catalyst, the loading amount of the active component is 12.1-19.1%, and the carrier is 80.9-87.9%; the active component comprises the following components by taking the total mass of the catalyst as a reference:
(1) main active components: cu in an amount of 9.1 to 10.1%, preferably 9.9 to 10.1%;
(2) auxiliary active components: ce and Cd, wherein the Ce content is 2.0-6.0%, preferably 4.0-6.0%;
the content of Cd is 1.0-3.0%, preferably 2.0-3.0%.
In the catalyst for treating the sulfur-containing waste alkali, Cu, Ce and Cd all exist in the form of metal simple substances.
The catalyst for treating the sulfur-containing waste alkali comprises a mixed carrier material O-MWCNTs-GONRs-C, wherein the mixed carrier material O-MWCNTs (oxidized multi-walled carbon nanotubes) comprises 60-70 wt% of GONRs (oxidized graphene nanoribbons), 3-7 wt% of O-MWCNTs (oxidized multi-walled carbon nanotubes) and 25-45 wt% of C (activated carbon) in terms of the total mass of the mixed carrier material O-MWCNTs-GONRs-C.
The mixed carrier material O-MWCNTs-GONRs-C has the specific surface area of 200-300m 3 /g。
Preferably, the MWCNTs (multi-walled carbon nanotubes) have the length of 50-100nm and the diameter of the inner wall of 20-30 nm.
A process for preparing the catalyst used for treating the waste alkali containing sulfur includes such steps as
1) Preparing a mixed carrier material O-MWCNTs-GONRs-C:
dispersing MWCNTs in concentrated sulfuric acid, adding potassium permanganate, heating at 60-80 deg.C for reaction for 1-3H, and adding the reaction solution into H 2 O 2 Separating the mixture to obtain O-MWCNTS-GONRs;
dispersing O-MWCNTs-GONRs in water, wherein the dispersion concentration range is 5-15g/mL, then adding activated carbon, and uniformly stirring to obtain a solution containing a mixed carrier material O-MWCNTs-GONRs-C;
2) loading active components:
dissolving a copper salt in ethylene glycol, and aging to obtain a copper salt ethylene glycol solution; mixing a copper salt glycol solution, cerium acetate, cadmium acetate and glycol to obtain a composite salt solution, then mixing the salt solution with the solution containing the mixed carrier material O-MWCNTs-GONRs-C in the step 1), uniformly dispersing, simultaneously adjusting the pH to 1-13, preferably 1-2, and separating to obtain the catalyst for treating the sulfur-containing waste alkali.
Further, in the step 1), the dispersion concentration of the MWCNTs in concentrated sulfuric acid is 5-15g/mL, preferably 9.9-10.1 g/mL; the concentration of the concentrated sulfuric acid is not lower than 97%.
Further, in the step 1), the mass ratio of the potassium permanganate to the MWCNTs is 1.0-5.1: 1, preferably 4.9 to 5.1: 1.
the potassium permanganate needs to be slowly added into the MWCNTs concentrated sulfuric acid dispersion liquid within the time range of 0.5-1.5 h; the following addition methods can be used: adding potassium permanganate in a segmented manner, stopping adding when the reaction solution is found to be green, continuing adding after the color is faded, and repeating the operation until the potassium permanganate is added, wherein the reaction solution is stable and metal green; and if the reaction liquid is changed into brown yellow (for example, after the reaction liquid is placed in a water bath kettle and heated at 70 ℃ for 2 hours), the reactor is heated, so that excessive oxidation is avoided.
Further, in the step 1), the reaction solution is added with H with the volume of 10-15 times that of the reaction solution 2 O 2 In a mixture of ice and water of (1), the hydrogen 2 O 2 H in the ice-water mixture of (1) 2 O 2 The concentration is 5-15 wt%; preferably, said H 2 O 2 The ice-water mixed liquid is composed of 30 wt% of H 2 O 2 Mixing water and ice water to prepare the product.
Further, in the step 1), the adding amount of the activated carbon is 20-40 wt% of the mass of the O-MWCNTs-GONRs.
Further, in the step 1), the separation method is specifically H 2 O 2 Mixing the mixed solution of ice and water, stirring, standing for layering to remove supernatant, centrifuging, and washing with water; wherein, the stirring time is about 1 to 3 hours, and the standing time is about 10 to 20 hours.
Further, in the step 2), the mass concentration of the copper salt dissolved in the ethylene glycol is 10-30 wt%, preferably 19.9-20.1 wt%. During preparation of the copper salt glycol solution, the copper salt glycol solution is placed under the sunlight or an ultraviolet lamp in the aging process, so that the solution can be irradiated by sufficient ultraviolet light, the light wavelength range is 200-400nm, the intensity range is 4-8, and the ultraviolet light is continuously irradiated; the aging time is more than 90 days; the copper salt is selected from at least one of copper nitrate, copper sulfide and copper chloride, and is preferably copper chloride.
Further, in the step 2), the total metal ion concentration in the composite salt solution is 0.08-0.50mol/L, wherein the molar ratio of cerium ions to copper ions is 0.2-0.6: 1; the molar ratio of cadmium ions to copper ions is 0.1-0.3: 1.
further, in the step 2), after the salt solution is mixed with the solution containing the mixed carrier material O-MWCNTs-GONRs-C, the mass ratio of the O-MWCNTs-GONRs-C to the total metal ions in the mixed salt is 4.23-7.26: 1.
further, in the step 2), a dilute aqueous nitric acid solution is used for adjusting the pH value, and preferably, the concentration of the dilute aqueous nitric acid solution is 0.5-1 wt%.
Further, in the step 2), the separation method specifically comprises standing, separating a solid, washing and drying.
The standing is carried out by sealing and then placing in a cool environment for a sufficient time, such as 10-30h, wherein the environmental temperature is 20-30 ℃.
The washing is carried out by washing with water and ethanol to neutrality, such as washing with deionized water for 2 times, and then washing with ethanol for 2 times.
Drying at the temperature of 70-90 ℃; the time range is 10-15 h; preferably vacuum drying.
Further, in the steps 1) and 2), the adopted dispersing method is ultrasonic and/or stirring, and the preferable method is firstly ultrasonic dispersing and then mechanical stirring; the ultrasonic time is 1-2h, and the intensity is 50-100 rpm; the stirring time is 1-3 h.
The application of the catalyst for treating the sulfur-containing waste alkali is suitable for treating the sulfur-containing waste alkali liquor generated in the processes of ethylene production and catalytic cracking oil refining, wherein the sulfur content range is less than 30000mg/L, and the alkalinity range is 8-14.
Preferably, the type of the waste lye suitable for treatment is the waste lye after acid gas generated by ethylene pyrolysis is removed by alkali washing, wherein sulfur exists in the forms of inorganic ions, organic sulfur ether, mercaptan and the like and is easy to emit foul hydrogen sulfide gas.
The treatment method is used for treating the waste lye and comprises the following steps: under the action of the catalyst for treating the sulfur-containing waste alkali, oxidizing sulfur-containing compounds in the waste alkali liquor into sodium sulfate by using an oxidant, wherein the reaction temperature in the oxidation process is 100-150 ℃, the pressure is gage pressure of 0.2-0.6MPa, and the reaction time is 22-26 h; preferably, the oxidant is air or oxygen or other oxidant.
After the treatment by the method, the CODcr removal rate is as high as 97%; the removal rate of the sulfide content is up to 98 percent, the sulfide content is reduced to be below 420mg/L, and the pH value is reduced to 7; the dissolved copper ion (loss) in the catalyst is less than or equal to 3.15 wt%, the dissolved cerium ion is less than or equal to 0.65 wt%, and the dissolved cadmium ion is less than or equal to 0.10 wt%.
The invention mixes the O-MWCNTs-GONRs material after oxidation opening treatment with active carbon to form a novel mixed carrier O-MWCNTs-GONRs-C with a special interlayer stack structure, then based on the in-situ adsorption and reduction characteristics of a normal-temperature ethylene glycol reduction method, the active component of the catalyst and the carrier material are placed under the same mixed system at the beginning of reduction, the pre-adsorption between the active component and the adsorption sites of the carrier material is firstly carried out before the reduction process, and then the aggregation risk of the active component particles is further reduced by virtue of the mild characteristics of room-temperature reduction reaction, so that the active component Cu nanoparticles can be more uniformly loaded on the surface of the carrier material with smaller particle size, and more active sites are exposed, thereby realizing stable and efficient performance under the wet oxidation condition of high-concentration waste water, and the dissolution problem of the Cu single-system catalyst can be effectively improved by the Cu-Ce system, and the catalyst is further cooperated with Cd element, so that the agglomeration of active components is effectively prevented, the alkali resistance of the catalyst is improved, the catalyst plays a role in protecting strongly alkaline waste liquid, the dissolution phenomenon of each element in the catalyst is integrally reduced, the loss of the active components of the catalyst in the strongly alkaline solution is avoided, and the long-period stability of the catalyst is enhanced.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a novel O-MWCNTs-GONRs-C carrier material, and reduces the risk of dissolution and aggregation of active component particles in the reaction process; the reduction process of the active component can be completed in an environment without additional work by using a normal-temperature ethylene glycol reduction method, so that the particle size of the active component nano particles in the catalyst is smaller, the dispersion is more uniform, and the utilization efficiency of the active component is improved; the Cu-Ce system can effectively improve the dissolution problem of the Cu single-system catalyst. Meanwhile, Cd is added as a protective agent of the catalyst, so that the stability of the catalyst in strongly alkaline wastewater is greatly improved.
Detailed Description
The process according to the invention is further illustrated by the following examples, but the invention is not limited to the examples listed, but also encompasses any other known modification within the scope of the claims of the invention.
The main raw materials and reagent sources of the embodiment of the invention are shown in the table 1:
TABLE 1 examples Primary feed sources
Other common raw materials are commercially available unless otherwise specified.
The main test methods and instruments adopted by the embodiment of the invention are shown in table 2:
TABLE 2 Main test methods and instrumentation
The sulfur-containing waste alkali is prepared by self, wherein CODcr is 84360mg/L, sulfide content is 21000mg/L, pH is 10, and the waste alkali is black; the preparation method comprises the following steps: 1.6g of NaOH and 8.4g of NaS are added into 400ml of pure water, and after uniform mixing, ethylene glycol is added dropwise until the COD value in the mixed solution reaches a target value.
The pH value is measured by using broad-spectrum pH test paper, the COD content is measured by using a COD detector, and the metal dissolution condition is measured by using an ion chromatograph.
H 2 O 2 The ice-water mixed solution of (1) adopts 30 wt% of H 2 O 2 Mixing water with ice water.
Example 1
1) Preparing a mixed carrier material O-MWCNTs-GONRs-C:
the method comprises the following steps of ultrasonically dispersing MWCNTs (with the length of 60nm) in concentrated sulfuric acid for 30min, continuously stirring and mixing for 1h, slowly adding potassium permanganate, stopping adding when the reaction liquid is found to be green, continuously adding after the color is desalted, repeating the operation so that the potassium permanganate is added completely, wherein the reaction liquid is stable and metal green, the total time of adding the potassium permanganate is 1h, and the mass ratio of the potassium permanganate to the MWCNTs is 5: 1, heating at 70 ℃ for 2 hours to react, wherein the reaction solution becomes brown yellow, and at the moment, the reactor is heated to avoid excessive oxidation. The reaction solution was then added to 12 volumes of H 2 O 2 In the ice-water mixture (H in the mixture) 2 O 2 The concentration is 10 wt%), stirring is carried out for 2h, then standing is carried out for 15h, after supernatant liquid is separated and removed, centrifugation and pure water washing are carried out to obtain O-MWCNTs-GONRs;
dispersing O-MWCNTs-GONRs in water at a dispersion concentration of 10g/L, adding activated carbon, wherein the addition amount of the activated carbon is 30 wt% of the mass of the O-MWCNTs-GONRs, stirring for 1h until the activated carbon is uniformly dispersed to obtain a solution containing a mixed carrier material O-MWCNTs-GONRs-C, and the specific surface area of the O-MWCNTs-GONRs-C is 250m 2 /g。
2) Loading active components:
dissolving 55g of copper nitrate in 220g (197ml) of ethylene glycol, placing the solution under ultraviolet light to ensure that the solution can obtain enough ultraviolet radiation, wherein the light wavelength range is 200-400nm, the intensity range is 4-8, and the aging light is used for 3 months to obtain a copper salt ethylene glycol solution;
2.75g of copper salt glycol solution (0.55g of copper nitrate), 0.5582g of cerium acetate and 0.2028g of cadmium acetate are dispersed in 50ml of glycol to prepare a uniform mixed salt solution, the total metal ion concentration in the mixed salt solution is 0.1072mol/L, wherein the molar ratio of cerium ions to copper ions is 0.6: 1; the molar ratio of cadmium ions to copper ions is 0.3: 1;
adding the solution containing the mixed carrier material O-MWCNTs-GONRs-C in the step 1) into the mixed salt solution, wherein the sum of the mass of the mixed carrier material O-MWCNTs-GONRs-C and the mass of the active components copper, cerium and cadmium in the mixed salt solution is about 4.4:1 theoretically. Ultrasonically dispersing for 15min at the power of 100rpm, simultaneously dropwise adding 0.1mol/L dilute nitric acid solution to the pH value of 1-1.2, further dispersing by mechanically stirring overnight after ultrasonic homogenization, then sealing and placing in a shade place for standing for 72h, then centrifuging for 5min at 12000rpm to separate, washing collected sediments for 2 times by deionized water, washing for 2 times by ethanol to be neutral, drying for 12h in vacuum at 80 ℃, and obtaining the powdered sulfur-containing waste alkali treated catalyst.
The catalyst comprises the following components: based on the total mass of the catalyst, 9.81 percent of Cu element, 5.78 percent of Ce element, 2.89 percent of Cd element and the balance of carrier;
in the mixed carrier material O-MWCNTs-GONRs-C, GONRs account for 65 wt%, O-MWCNTs account for 5 wt% and C (activated carbon) accounts for 30 wt%, based on the total mass of the mixed carrier material O-MWCNTs-GONRs-C.
The application comprises the following steps:
weighing 1g of the catalyst, putting the catalyst into 400ml of sulfur-containing waste alkali (CODcr is 84360mg/L, sulfide content is 21000mg/L, pH is 10, black), sealing the reactor after feeding, flushing nitrogen to drive air, introducing oxygen to 0.6MPa when the reactor is heated to 120 ℃, starting stirring, and carrying out reaction. During which oxygen is intermittently flushed.
After 24 hours of reaction, CODcr is reduced to 2235mg/L, the sulfide content is reduced to 327mg/L, the pH is 7.1, the color is lightened, the content of copper ions dissolved out in the reaction liquid is less than 0.91 percent of the total amount, the content of cerium ions dissolved out in the reaction liquid is less than 0.54 percent of the total amount, and the content of cadmium ions dissolved out in the reaction liquid is less than 0.10 percent of the total amount.
Example 2
The catalyst preparation process differs from example 1 in that step 2) supports the active component:
2.75g of aging copper salt glycol solution (about 0.55g of copper nitrate), 0.1861g of cerium acetate and 0.2028g of cadmium acetate are dispersed in 50ml of glycol to prepare a uniform mixed salt solution, the total metal ion concentration in the mixed salt solution is 0.0846mol/L, wherein the molar ratio of cerium ions to copper ions is 0.2: 1; the molar ratio of cadmium ions to copper ions is 0.3: 1.
the sum of the added mass of the mixed carrier material O-MWCNTs-GONRs-C and the mass of the active components copper, cerium and cadmium in the mixed salt solution is theoretically about 5.9: 1.
The prepared catalyst comprises the following components: based on the total mass of the catalyst, 9.75 percent of Cu element, 1.85 percent of Ce element, 2.85 percent of Cd element and the balance of carrier.
The application comprises the following steps: the procedure of example 1 was followed by replacing the catalyst prepared in this example:
after 24 hours of reaction, the CODcr is reduced to 3197mg/L, the sulfide content is reduced to 817mg/L, the pH is 7.2, the color becomes light, the content of copper ions dissolved out in the reaction liquid is less than 1.21 percent of the total amount, the content of cerium ions dissolved out in the reaction liquid is less than 0.45 percent of the total amount, and the content of cadmium ions dissolved out in the reaction liquid is less than 0.09 percent of the total amount.
Example 3
The catalyst preparation process differs from example 1 in that step 2) supports the active component:
dissolving 47g of copper nitrate in 220g (197ml) of ethylene glycol, placing the solution under ultraviolet light to ensure that the solution can obtain enough ultraviolet radiation, wherein the light wavelength range is 200-400nm, the intensity range is 4-8, and aging light is used for 3 months to obtain a copper salt ethylene glycol solution;
2.67g of aging copper salt glycol solution (about 0.47g of copper sulfate), 0.5582g of cerium acetate and 0.2028g of cadmium acetate are dispersed in 50ml of glycol to prepare a uniform mixed salt solution, the total metal ion concentration in the mixed salt solution is 0.1072mol/L, wherein the molar ratio of cerium ions to copper ions is 0.6: 1; the molar ratio of cadmium ions to copper ions is 0.3: 1;
the prepared catalyst comprises the following components: based on the total mass of the catalyst, the content of Cu element is 9.58 percent, the content of Ce element is 5.85 percent, and the content of Cd element is 2.91 percent.
The application comprises the following steps: the procedure is as in example 1, except that the catalyst prepared in this example is used instead
After 24 hours of reaction, CODcr is reduced to 2531mg/L, sulfide content is reduced to 477mg/L, pH is 7.1, color is lightened, the content of copper ions dissolved out of the reaction liquid is less than 0.89% of the total amount, the content of cerium ions dissolved out of the reaction liquid is less than 0.41% of the total amount, and the content of cadmium ions dissolved out of the reaction liquid is less than 0.09% of the total amount.
Example 4
The catalyst preparation process differs from example 1 in that step 2) supports the active component:
dissolving 47g of copper nitrate in 220g (197ml) of ethylene glycol, placing the solution under ultraviolet light to ensure that the solution can obtain enough ultraviolet radiation, wherein the light wavelength range is 200-400nm, the intensity range is 4-8, and aging light is used for 3 months to obtain a copper salt ethylene glycol solution;
2.67g of aging copper salt glycol solution (about 0.47g of copper sulfate), 0.1861g of cerium acetate and 0.2028g of cadmium acetate are dispersed in 50ml of glycol to prepare a uniform mixed salt solution, the total metal ion concentration in the mixed salt solution is 0.0846mol/L, wherein the molar ratio of cerium ions to copper ions is 0.2: 1; the molar ratio of cadmium ions to copper ions is 0.3: 1;
the prepared catalyst comprises the following components: based on the total mass of the catalyst, the content of Cu element is 9.50%, the content of Ce element is 1.95%, and the content of Cd element is 2.74%.
The application comprises the following steps: the procedure is as in example 1, except that the catalyst prepared in this example is used instead
After 24 hours of reaction, CODcr is reduced to 2758mg/L, the sulfide content is reduced to 477mg/L, the pH is 7.2, the color is lightened, the content of copper ions dissolved out of the reaction liquid is less than 1.30 percent of the total amount, the content of cerium ions dissolved out of the reaction liquid is less than 0.41 percent of the total amount, and the content of cadmium ions dissolved out of the reaction liquid is less than 0.09 percent of the total amount.
Example 5
The catalyst preparation process differs from example 1 in that step 2) supports the active component:
dissolving 39g of copper nitrate in 220g (197ml) of ethylene glycol, placing the solution under ultraviolet light to ensure that the solution can obtain enough ultraviolet irradiation, wherein the light wavelength range is 200-400nm, the intensity range is 4-8, and the aging light is irradiated for 3 months to obtain a copper salt ethylene glycol solution;
2.59g of aging copper salt ethylene glycol solution (about 0.39g of copper chloride), 0.5582g of cerium acetate and 0.2028g of cadmium acetate are dispersed in 50ml of ethylene glycol to prepare a uniform mixed salt solution, the total metal ion concentration in the mixed salt solution is 0.1072mol/L, wherein the molar ratio of cerium ions to copper ions is 0.6: 1; the molar ratio of cadmium ions to copper ions is 0.3: 1;
the prepared catalyst comprises the following components: based on the total mass of the catalyst, the content of Cu element is 9.79%, the content of Ce element is 5.95%, and the content of Cd element is 2.96%.
The application comprises the following steps: the procedure is as in example 1, except that the catalyst prepared in this example is used instead
After 24 hours of reaction, CODcr is reduced to 2337mg/L, the sulfide content is reduced to 464mg/L, the pH is 7.1, the color is lightened, the content of copper ions dissolved out of the reaction solution is less than 0.75 percent of the total amount, the content of cerium ions dissolved out of the reaction solution is less than 0.38 percent of the total amount, and the content of cadmium ions dissolved out of the reaction solution is less than 0.08 percent of the total amount.
Example 6
The preparation process of the catalyst is different from that of the example 1 in that the active component is loaded in the step 2)
Dissolving 39g of copper nitrate in 220g (197ml) of ethylene glycol, placing the solution under ultraviolet light to ensure that the solution can obtain enough ultraviolet radiation, wherein the light wavelength range is 200-400nm, the intensity range is 4-8, and aging light is used for 3 months to obtain a copper salt ethylene glycol solution;
2.59g of aging copper salt ethylene glycol solution (about 0.39g of copper chloride), 0.1861g of cerium acetate and 0.2028g of cadmium acetate are dispersed in 50ml of ethylene glycol to prepare a uniform mixed salt solution, the total metal ion concentration in the mixed salt solution is 0.0846mol/L, wherein the molar ratio of cerium ions to copper ions is 0.2: 1; the molar ratio of cadmium ions to copper ions is 0.3: 1;
the prepared catalyst comprises the following components: based on the total mass of the catalyst, the content of Cu element is 9.73 percent, the content of Ce element is 1.84 percent, and the content of Cd element is 2.83 percent.
The application comprises the following steps: the procedure is as in example 1, except that the catalyst prepared in this example is used instead
After 24 hours of reaction, CODcr is reduced to 2421mg/L, the sulfide content is reduced to 514mg/L, the pH is 7.2, the color is lightened, the content of copper ions dissolved out in the reaction solution is less than 1.11 percent of the total amount, the content of cerium ions dissolved out in the reaction solution is less than 0.39 percent of the total amount, and the content of cadmium ions dissolved out in the reaction solution is less than 0.08 percent of the total amount.
Comparative example 1
The difference between the preparation process of the catalyst and the example 1 is that, in the step 2), 2.75g of aged copper salt glycol solution (about 0.55g of copper nitrate) and 0.2028g of cadmium acetate are taken as the loaded active component and dispersed in 50ml of glycol to prepare a uniform mixed salt solution, the total metal ion concentration in the mixed salt solution is 0.0734mol/L, wherein the molar ratio of cadmium ions to copper ions is 0.3: 1;
the prepared catalyst comprises the following components: based on the total mass of the catalyst, the content of Cu element is 9.67 percent, and the content of Cd element is 2.95 percent.
The application comprises the following steps: the procedure is as in example 1, replacing the catalyst prepared in this comparative example
After 24 hours of reaction, CODcr is reduced to 6065mg/L, the sulfide content is reduced to 1445mg/L, the pH is 8.1, the color is lightened, the percentage of copper ions dissolved out in the reaction liquid is about 4.44%, and the percentage of cadmium ions dissolved out in the reaction liquid is about 0.08%.
Comparative example 2
The difference between the preparation process of the catalyst and the example 1 is that, in the step 2), 2.75g of aged copper salt glycol solution (about 0.55g of copper nitrate) and 0.5582g of cerium acetate are taken as the loaded active component to be dispersed in 50ml of glycol to prepare a uniform mixed salt solution, the total metal ion concentration in the mixed salt solution is 0.0903mol/L, wherein the molar ratio of cerium ions to copper ions is 0.6: 1;
the prepared catalyst comprises the following components: based on the total mass of the catalyst, the content of Cu element is 9.77 percent, the content of Ce element is 5.84 percent, and the content of Cd element is 0 percent; the mixed carrier material O-MWCNTs-GONRs-C, wherein the GONRs account for 65 wt%, the O-MWCNTs account for 5 wt%, and the C (activated carbon) accounts for 30 wt%.
The application comprises the following steps: the procedure is as in example 1, replacing the catalyst prepared in this comparative example
After 24 hours of reaction, CODcr was reduced to 4716mg/L, the sulfide content was reduced to 1018mg/L, the pH was 7.8, the color was light, the percentage of copper ions dissolved out of the reaction solution was about 4.51%, and the percentage of cerium ions dissolved out of the reaction solution was about 0.61%.
Comparative example 3
The difference between the preparation process of the catalyst and the example 1 is that the mixed carrier material is replaced by O-MWCNTs-GONRs, and the GONRs account for 93 wt%The O-MWCNTs account for about 7 wt%, and the specific surface area of the O-MWCNTs-GONRs-C is 250m based on the total mass of the mixed carrier material O-MWCNTs-GONRs 2 /g。
The prepared catalyst comprises the following components: based on the total mass of the catalyst, the content of Cu element is 9.05 percent, the content of Ce element is 5.41 percent, and the content of Cd element is 2.50 percent.
The application comprises the following steps: the procedure is as in example 1, replacing the catalyst prepared in this comparative example
After 24 hours of reaction, CODcr was reduced to 4117mg/L, sulfide content was reduced to 1040mg/L, pH was 7.5, color became light, the content of copper ions dissolved out of the reaction solution was about 0.89% of the total amount, the content of cerium ions dissolved out of the reaction solution was about 0.50% of the total amount, and the content of cadmium ions dissolved out of the reaction solution was about 0.08% of the total amount.
Comparative example 4
The preparation process of the catalyst is different from that of the example 1 in that the carrier material uses active carbon as a carrier, the dispersion concentration in the aqueous solution is 10g/mL, and the specific surface area of C is 250m 2 /g。
The prepared catalyst comprises the following components: based on the total mass of the catalyst, the content of Cu element is 7.65 percent, the content of Ce element is 4.21 percent, and the content of Cd element is 1.98 percent; the carrier material is 100% C.
The application comprises the following steps: the procedure is as in example 1, replacing the catalyst prepared in this comparative example
After 24 hours of reaction, CODcr was reduced to 12611mg/L, sulfide content was reduced to 3295mg/L, pH was 9.0, color was lightened, the content of copper ions eluted from the reaction solution was about 0.70% of the total amount, the content of cerium ions eluted from the reaction solution was about 0.31% of the total amount, and the content of cadmium ions eluted from the reaction solution was about 0.05% of the total amount.
Comparative example 5
The preparation process of the catalyst is different from that of the example 1 in that, in the step 2), the loaded active component dissolves copper nitrate in ethylene glycol, 20 wt% of the loaded active component is taken, 2.75g of unaged copper salt ethylene glycol solution (about 0.55g of copper nitrate), 0.5582g of cerium acetate and 0.2028g of cadmium acetate are dispersed in 50ml of ethylene glycol to prepare a uniform mixed salt solution, the total metal ion concentration in the mixed salt solution is 0.09236mol/L, and the molar ratio of cerium ions to copper ions is 0.6: 1; the molar ratio of cadmium ions to copper ions is 0.3: 1;
the prepared catalyst comprises the following components: based on the total mass of the catalyst, the content of Cu element is 1.51 percent, the content of Ce element is 0.60 percent, and the content of Cd element is 0.21 percent.
The application comprises the following steps: the procedure is as in example 1, replacing the catalyst prepared in this comparative example
After 24 hours of reaction, CODcr was reduced to 40383mg/L, sulfide content was reduced to 10500mg/L, pH was 9.5, color was lightened, the content of copper ions eluted from the reaction solution was about 0.50% of the total amount, the content of cerium ions eluted from the reaction solution was about 0.25% of the total amount, and the content of cadmium ions eluted from the reaction solution was about 0.04% of the total amount.
The results of inventive examples 1-6 and comparative examples 1-5 are shown in Table 1:
TABLE 1
Claims (17)
1. A catalyst for treating sulfur-containing waste alkali is characterized in that the components of the catalyst comprise a mixed carrier material O-MWCNTs-GONRs-C and a loaded active component; based on the total mass of the catalyst, the loading amount of the active component is 12.1-19.1%, and the carrier is 80.9-87.9%; the active component comprises the following components by taking the total mass of the catalyst as a reference:
(1) main active components: cu, the content of which is 9.1-10.1%;
(2) auxiliary active components: ce and Cd, wherein the content of Ce is 2.0-6.0%, and the content of Cd is 1.0-3.0%;
the preparation method of the catalyst for treating the sulfur-containing waste alkali comprises the following steps:
1) preparing a mixed carrier material O-MWCNTs-GONRs-C:
dispersing MWCNTs in concentrated sulfuric acid, adding potassium permanganate, heating at 60-80 deg.C for reaction for 1-3H, and adding the reaction solution into H 2 O 2 Separating the mixture to obtain O-MWCNTS-GONRs; dispersing O-MWCNTs-GONRs in water, and concentratingThe degree ranges from 5g/mL to 15g/mL, then active carbon is added and stirred uniformly to obtain a solution containing a mixed carrier material O-MWCNTs-GONRs-C;
2) loading active components:
dissolving a copper salt in ethylene glycol, and aging to obtain a copper salt ethylene glycol solution; mixing a copper salt glycol solution, cerium acetate, cadmium acetate and glycol to obtain a composite salt solution, mixing the salt solution with the solution containing the mixed carrier material O-MWCNTs-GONRs-C in the step 1), uniformly dispersing, adjusting the pH to 1-13, and separating to obtain the catalyst for treating the sulfur-containing waste alkali.
2. The catalyst of claim 1, wherein the active component comprises, based on the total mass of the catalyst:
(1) main active components: cu, the content of which is 9.9-10.1%;
(2) auxiliary active components: ce and Cd, wherein the content of Ce is 4.0-6.0%, and the content of Cd is 2.0-3.0%.
3. The catalyst of claim 1, wherein the composition of the mixed support material O-MWCNTs-godrs-C comprises godrs, O-MWCNTs, C, 60-70 wt% of godrs, 3-7 wt% of O-MWCNTs, 25-45 wt% of C, based on the total mass of the mixed support material O-MWCNTs-godrs-C;
the specific surface area of the mixed carrier material O-MWCNTs-GONRs-C is 200-300m 3 /g。
4. The catalyst of claim 3, wherein the MWCNTs have a length of 50-100nm and an inner wall diameter of 20-30 nm.
5. A method for preparing the catalyst for the sulfur-containing waste alkali treatment according to any one of claims 1 to 4, characterized by comprising the steps of:
1) preparing a mixed carrier material O-MWCNTs-GONRs-C:
dispersing MWCNTs in concentrated sulfuric acid, adding potassium permanganate, heating at 60-80 deg.C for reaction for 1-3 hr, and reactingAddition of reaction solution to H 2 O 2 Separating the mixture to obtain O-MWCNTS-GONRs; dispersing O-MWCNTs-GONRs in water, wherein the dispersion concentration range is 5-15g/mL, then adding activated carbon, and uniformly stirring to obtain a solution containing a mixed carrier material O-MWCNTs-GONRs-C;
2) loading active components:
dissolving a copper salt in ethylene glycol, and aging to obtain a copper salt ethylene glycol solution; mixing a copper salt glycol solution, cerium acetate, cadmium acetate and glycol to obtain a composite salt solution, mixing the salt solution with the solution containing the mixed carrier material O-MWCNTs-GONRs-C in the step 1), uniformly dispersing, adjusting the pH to 1-13, and separating to obtain the catalyst for treating the sulfur-containing waste alkali.
6. The preparation method according to claim 5, wherein in step 1), the MWCNTs are dispersed in concentrated sulfuric acid at a concentration ranging from 5 to 15 g/L; the concentration of the concentrated sulfuric acid is not lower than 97%;
the mass ratio of the potassium permanganate to the MWCNTs is 1.0-5.1: 1; the potassium permanganate feeding time is 0.5-1.5 h;
adding the reaction solution into H with the volume of 10-15 times that of the reaction solution 2 O 2 In a mixture of ice and water of (1), the hydrogen 2 O 2 H in the ice-water mixture of (1) 2 O 2 The concentration is 5-15 wt%;
the adding amount of the activated carbon is 20-40 wt% of the mass of the O-MWCNTs-GONRs.
7. The method according to claim 6, wherein the MWCNTs are dispersed in concentrated sulfuric acid at a concentration ranging from 9.9 to 10.1 g/L.
8. The preparation method according to claim 6, wherein the mass ratio of the potassium permanganate to the MWCNTs is 4.9-5.1: 1.
9. the preparation method according to claim 5, wherein in the step 1), the potassium permanganate is added in a staged manner, the addition is stopped when the reaction solution is found to be green, the addition is continued after the color is faded, and the operation is repeated until the addition of the potassium permanganate is finished, and then the reaction solution is in a stable metal green color.
10. The method according to claim 5, wherein in step 1), the separation method is specifically with H 2 O 2 Mixing the mixed solution of ice and water, stirring, standing for layering to remove supernatant, centrifuging, and washing with water; wherein the stirring time is 1-3h, and the standing time is 10-20 h.
11. The preparation method according to claim 5, wherein in the step 2), the mass concentration of the copper salt dissolved in the ethylene glycol is 10-30 wt%;
during preparation, the copper salt glycol solution is placed under sunlight or an ultraviolet lamp in the aging process, the light wavelength range is 200-400nm, and the intensity range is 4-8; the aging time is more than 90 days;
the copper salt is selected from at least one of copper nitrate, copper sulfide and copper chloride.
12. The method according to claim 11, wherein the copper salt is dissolved in ethylene glycol at a concentration of 19.9 to 20.1 wt%.
13. The method according to claim 5, wherein in the step 2), the total metal ion concentration in the composite salt solution is 0.08-0.50mol/L, and the molar ratio of cerium ions to copper ions is 0.2-0.6: 1; the molar ratio of cadmium ions to copper ions is 0.1-0.3: 1;
after the salt solution is mixed with a solution containing a mixed carrier material O-MWCNTs-GONRs-C, the mass ratio of the O-MWCNTs-GONRs-C to the total metal ions in the composite salt is 4.23-7.26: 1.
14. the method according to claim 5, wherein in the step 2), the pH value is adjusted by dilute aqueous nitric acid;
the separation method specifically comprises the steps of standing, separating solids, washing and drying; wherein the washing method comprises washing with water and ethanol to neutral, drying at 70-90 deg.C for 10-15 hr.
15. The method of claim 14, wherein the dilute aqueous nitric acid solution has a concentration of 0.5 to 1 wt%.
16. Use of a catalyst for the treatment of sulfur-containing spent caustic as defined in any one of claims 1 to 4 or a catalyst for the treatment of sulfur-containing spent caustic prepared by a process as defined in any one of claims 5 to 15 for the treatment of spent caustic produced in ethylene production and catalytic cracking oil refining processes, wherein the sulfur content is in the range of less than 30000mg/L and the alkalinity is in the range of 8 to 14;
the processing method comprises the following steps: under the action of the catalyst for treating sulfur-containing waste alkali as described in any one of claims 1 to 4 or the catalyst for treating sulfur-containing waste alkali prepared by the method as described in any one of claims 5 to 15, oxidizing sulfur-containing compounds in the waste alkali solution into sodium sulfate by using an oxidizing agent, wherein the reaction temperature in the oxidation process is 100-150 ℃, the gauge pressure is 0.2-0.6MPa, and the reaction time is 22-26 h.
17. Use according to claim 16, wherein the oxidant is air or oxygen.
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