CN108479803A - A kind of stalk load vulcanization bronzing catalyst and preparation method for sewage disposal - Google Patents
A kind of stalk load vulcanization bronzing catalyst and preparation method for sewage disposal Download PDFInfo
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- CN108479803A CN108479803A CN201810200609.1A CN201810200609A CN108479803A CN 108479803 A CN108479803 A CN 108479803A CN 201810200609 A CN201810200609 A CN 201810200609A CN 108479803 A CN108479803 A CN 108479803A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 239000010865 sewage Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000004073 vulcanization Methods 0.000 title claims abstract description 19
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000010902 straw Substances 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 11
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 17
- 230000001007 puffing effect Effects 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 34
- 238000001179 sorption measurement Methods 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 17
- 239000003344 environmental pollutant Substances 0.000 abstract description 11
- 231100000719 pollutant Toxicity 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 3
- 239000011574 phosphorus Substances 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 20
- 238000002798 spectrophotometry method Methods 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 7
- 229940010552 ammonium molybdate Drugs 0.000 description 7
- 235000018660 ammonium molybdate Nutrition 0.000 description 7
- 239000011609 ammonium molybdate Substances 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000005416 organic matter Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 7
- 239000010452 phosphate Substances 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000000017 hydrogel Substances 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical class OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 240000006497 Dianthus caryophyllus Species 0.000 description 1
- 235000009355 Dianthus caryophyllus Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 238000003911 water pollution 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
- 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of stalk load vulcanization bronzing catalyst and preparation method for sewage disposal.Extruder is added in stalk and forms straw bulking object, using puff as carrier, copper acetate and thioacetamide are added in organic solvent, in-situ preparation copper sulfide, centrifugation wash, vulcanize bronzing catalyst for the load of the stalk of sewage disposal to obtain the final product after drying on carrier after hydro-thermal reaction.This method by using straw bulking object microcellular structure, it is strong to the adsorption capacity of the nitrogen and phosphorus pollutants in water, and by the way that copper sulfide is carried on stalk, the efficiency of light energy utilization of gained photochemical catalyst is high, and photocatalytic activity is good, and photocatalytic degradation capability is strong, preparation process is simple simultaneously, raw material is easy to get, and manufacturing cost is low, can be widely used for sewage treatment field.
Description
Technical field
The present invention relates to sewage treatment fields, and in particular to the preparation of photochemical catalyst being used for sewage more particularly to one kind
The stalk load vulcanization bronzing catalyst and preparation method of processing.
Background technology
With the progress of the high speed development and human civilization of science and technology, various environmental pollutions are increasingly severe, wherein water pollution
Particularly cause the extensive attention in global range.In current water process frequently with method be physico-chemical process and biochemical process, there is work
Skill is ripe, is easy to the advantages of heavy industrialization is applied.However, these methods do not make pollutant be destroyed and realize nothing
Evilization inevitably brings waste material and secondary pollution, and restricted application, cost also relatively high.Therefore, energy is developed
Various chemical pollutants, which are degraded to innoxious practical technique, becomes the important research content of various countries' researcher, wherein light
Catalytic oxidation technologies are particularly taken seriously.
Photochemical catalyst is the key that photocatalysis technology, and metal sulfide is a kind of common excellent visible-light photocatalyst,
Its suitable valence band conduction band positions makes metal sulfide have potentially in the fields such as photochemical catalytic oxidation and photodegradation water hydrogen manufacturing
Application prospect.Wherein copper sulfide as a kind of important semi-conducting material, have excellent light, electricity, magnetic and other physics and
Chemical property has been widely used in photocatalysis field.The preparation method of metal sulfide mainly has hydro-thermal method, microemulsion at present
Method, solvent-thermal process method, sol-gel method, template, solid-bed break-up method, liquid phase thermal decomposition method etc..Study better performance
Copper sulfide composite photo-catalyst be its development hot spot.
Chinese invention patent application number 201710406905.2 discloses a kind of system of CdS-CuS nano composite photo-catalysts
Preparation Method, with mercaptobenzothiazoler close cadmium do presoma, through liquid phase thermally decompose be made cadmium sulfide, using cadmium sulfide as core, by from
Son absorption, makes copper sulfide be attached to vulcanization cadmium surfaces, obtains CdS-CuS nano composite photo-catalysts；The invention is easy to operate, ring
Border is friendly, obtains that nano particle pattern is uniform, and the controllable composition metal sulfide of size, atomic ratio, particle is in 10 ~ 20 nm
Between；Ultraviolet light and visible light can be effectively absorbed, to organic pollution object rhodamine B, methylene blue has significant degradation
Effect；It is effective to prevent the compound of light induced electron and hole, improve the efficiency of its photochemical catalyzing.
Chinese invention patent application number 201611061164.0, which discloses a kind of tool carboxyl and amide groups and loads, nanometer
The composite hydrogel preparation method and application of photochemical catalyst copper sulfide, preparation method are by 2- hydroxy-ethyl acrylates, N- methyl horses
Carrying out sour and distilled water, irradiated polymerization obtains polyalcohol hydrogel after evenly mixing, then using the hydrogel as carrier, passes through original position
Precipitation method precipitating reagent loads nano-photocatalyst nano-copper sulfide；Mole of 2- hydroxy-ethyl acrylates, N- citraconic acid monomers
Than being 1 ~ 9：9 ~ 1, the high-energy ray of the irradiation polymerization is 60Co- gamma-rays or 137Cs- gamma-rays, dose of radiation is 1 ×
104~1×108Gy, polymerization temperature are -95 DEG C ~ -63 DEG C；The irradiation polymerization is 2- hydroxy-ethyl acrylates and N- citraconic acids
Aqueous solution carry out under a shielding gas；The method for loading nano-photocatalyst copper sulfide is the chemical in situ precipitation method.It is applied to
The light degradation removal of organic pollutant has remarkable result in waste water.Composite hydrogel has stronger mechanical performance and heat steady
It is qualitative, it reuses efficient.
Chinese invention patent application number 201410687424.X discloses a kind of copper sulfide/titanium oxide heterojunction photochemical catalyst
Low temperature preparation method.（1）Using the inorganic salts of titanium or organic salt as presoma, it is made using the precipitation method or sol-gel process
Titanium hydroxide（Ti(OH)4）；（2）At a temperature of 400 ~ 650 DEG C, to Ti (OH)4It is roasted, roasts 2 ~ 4 h, obtain TiO2Carrier；
（3）Copper powder and sulphur powder are dispersed in specific solvent, TiO2 carrier impregnations are entered into magnetic agitation in this solvent, 40 ~ 60 DEG C of water-baths
4 ~ 24 h are heated, the CuS generated in the process by copper powder and sulphur powder can load to TiO2On carrier；（4）By above-mentioned CuS/
TiO2Sample is cooled to room temperature, and can be obtained CuS/TiO by being filtered, washed, drying2Heterojunction photocatalyst.
Chinese invention patent application number 201510952421.9 discloses a kind of flower-shaped p-n heterojunction copper sulfide nano of carnation
The preparation of rice material, belongs to technical field of nano material.The invention passes through hydro-thermal process and high temperature first using melamine as raw material
Calcining has synthesized the graphene carbon nitrogen C-g-C3N4 of carbon doping（CCN）, then by anti-with copper chloride dihydrate, the further hydro-thermal of thiocarbamide
CCN-CuS p-n junction hetero-junctions should be synthesized, p-n junction heterojunction structure not only reduces charge transfer resistance, and makes photoinduction
Charge efficiently separates, can effectively light improve catalyst activity.Experiment shows that CCN-CuS p-n junctions prepared by the invention are different
Matter knot nano material shows outstanding visible light catalysis activity and good cyclical stability, can to the degradation rate of rhodamine B
Up to 92.6%, therefore, it can be used for the degradation treatment of organic dye waste water.
According to above-mentioned, the product purity of the solid-bed break-up method that in existing scheme prepared by copper sulfide is high, grain diameter compared with
Greatly, raw material used by sol-gel method is costly and longer etc. the time required to reaction, and copper sulfide photochemical catalyst exists to water
Middle organic pollutant degradation ability is not high, adsorption energy force difference, and wastewater treatment efficiency is undesirable.
Invention content
There is, absorption not high to organic pollutants degradation capability for the wider copper sulfide photochemical catalyst of current application
Can force difference, wastewater treatment efficiency pays no attention to, and that there are product purities is not high for traditional technology of preparing, and grain diameter is larger, process
The problems such as complicated and cost is higher, the present invention proposes that a kind of stalk load for sewage disposal vulcanizes bronzing catalyst and preparation
Method to effectively improve the catalytic degradation ability of photochemical catalyst, while being prepared simply, and cost is relatively low.
Specific technical solution of the present invention is as follows：
A kind of preparation method of stalk load vulcanization bronzing catalyst for sewage disposal, includes the following steps：
（1）Using extruder, stalk is sent into bulking machine in the way of screw extruding, stalk by it is strong squeeze, stirring,
Shearing, then by puffing, dehydration, cooling, form short texture, porous straw bulking object；
（2）10 ~ 15 parts by weight copper acetates and 12 ~ 18 parts by weight thioacetamides are added in 57 ~ 72 weight parts organic solvents, are mixed
It closes uniformly, and 6 ~ 10 parts by weight steps is added（1）Straw bulking object obtained is as carrier, and heating progress hydro-thermal is anti-after dispersion
It answers, the in-situ preparation copper sulfide on carrier；
（3）To step（2）Product centrifuged, washed, dried, you can be made for sewage disposal stalk load copper sulfide
Photochemical catalyst.
Preferably, step（1）The screw rod number of the extruder is 2 ~ 3, and screw diameter is 20 ~ 30mm, screw rod major diameter
Than being 5:1~8:1, screw pitch be 8 ~ 10mm, helical angle be 30 ~ 40 °, vane tip gap be 15 ~ 20mm, puffing cavity gap be 20 ~
25mm。
Preferably, step（1）The heating temperature in the screw extruding area is 170 ~ 190 DEG C, and revolution speed of screw is 40 ~ 60r/
min。
Preferably, step（1）The initial temperature of the Builking cavity is 200 ~ 240 DEG C, and cooling rate is 25 ~ 30 DEG C/min,
Bulking pressure is 5 ~ 8MPa, and the expanded material residence time is 7 ~ 10min.
Preferably, step（1）The porosity of the straw bulking object is 60 ~ 80%, and popping fold is 5 ~ 8 times.
Preferably, step（2）The organic solvent is in titanium tetrachloride, acetone, chlorine benzene,toluene,xylene, benzene or pyridine
One kind.
Preferably, step（2）The temperature of the hydro-thermal reaction is 140 ~ 160 DEG C, and the time is 4 ~ 5h.
Preferably, step（3）The washing uses acetone, deionized water, absolute ethyl alcohol successively.
Preferably, step（3）The drying is vacuum drying, and temperature is 70 ~ 80 DEG C, and moisture content is no more than after drying
0.5%。
The present invention also provides the stalk load vulcanization bronzings for sewage disposal that a kind of above-mentioned preparation method is prepared
Catalyst.Stalk is sent into bulking machine in the way of screw extruding, material by it is strong squeeze, stirring, shearing, after by it is puffing,
Dehydration, cooling produce short texture, porous puff；Then copper acetate and thioacetamide are added in organic solvent
It is uniformly mixed, above-mentioned straw bulking object is added as carrier, obtains mixed reaction solution；After hydro-thermal reaction, products therefrom is carried out
Centrifugation, washing and drying obtain the photochemical catalyst of copper sulfide load stalk.
The present invention utilize stalk microcellular structure, to the nitrogen and phosphorus pollutants in water have good suction-operated, pass through by
Copper sulfide is carried on stalk, substantially increases copper sulfide photocatalytic degradation capability, and the stalk used is cheap, is prepared
Simple for process, manufacturing cost is low, can be widely used in sewage disposal.
The stalk load vulcanization bronzing catalyst and preparation method that the present invention provides a kind of for sewage disposal, and it is existing
Technology is compared, and the feature and excellent effect protruded is：
1, the method for proposing to prepare the stalk load vulcanization bronzing catalyst for sewage disposal using straw bulking object as carrier.
2, by using the microcellular structure of straw bulking object, there is good suction-operated to the nitrogen and phosphorus pollutants in water.
3, by the way that copper sulfide to be carried on stalk, the efficiency of light energy utilization of copper sulfide is improved, photocatalytic activity is improved,
Substantially increase photocatalytic degradation capability of the photochemical catalyst to dirty water pollutant.
4, preparation process of the invention is simple, and raw material is easy to get, and manufacturing cost is low, can be widely used for sewage treatment field.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Preparation process is：
（1）Using extruder, stalk is sent into bulking machine in the way of screw extruding, stalk by it is strong squeeze, stirring,
Shearing, then by puffing, dehydration, cooling, form short texture, porous straw bulking object；The screw rod number of extruder is 2,
Screw diameter is 25m, screw slenderness ratio 6:1, screw pitch 9mm, helical angle are 35 °, and vane tip gap is 18mm, Builking cavity
Gap is 23m；The heating temperature in screw extruding area is 180 DEG C, revolution speed of screw 50r/min；The initial temperature of Builking cavity is 220
DEG C, cooling rate is 28 DEG C/min, and bulking pressure 6MPa, the expanded material residence time is 8min；The hole of straw bulking object
Rate is 70%, and popping fold is 5 times；
（2）13 parts by weight copper acetates and 15 parts by weight thioacetamides are added in 64 weight parts organic solvents, are uniformly mixed, and
8 parts by weight steps are added（1）Straw bulking object obtained is as carrier, and heating progress hydro-thermal reaction, former on carrier after dispersion
Position generates copper sulfide；Organic solvent is titanium tetrachloride；The temperature of hydro-thermal reaction is 150 DEG C, time 4.5h；
（3）To step（2）Product centrifuged, washed, dried, you can be made for sewage disposal stalk load copper sulfide
Photochemical catalyst；Washing uses acetone, deionized water, absolute ethyl alcohol successively；Dry is vacuum drying, and temperature is 75 DEG C, after dry
Moisture content is 0.4%.
Test method：
Photochemical catalyst made from 10g embodiments 1 is taken, puts into the simulated wastewater that 100mL contains phosphate and ammonia nitrogen, is placed in respectively
In light protected environment, it is stirred to react 8h at 25 DEG C, is repeated 3 times experiment, ammonia-nitrogen content is measured using Berthelot spectrophotometry
Changing value total nitrogen adsorption rate and total nitrogen are calculated separately using the phosphatic changes of contents value of Ammonium Molybdate Spectrophotometric Method for Determination
Adsorption rate, to characterize its adsorption capacity；
It takes 10g embodiments 1 that photochemical catalyst is made, puts into 100mL organic matter sewage, be placed under sunlight irradiation, at 25 DEG C
8h is reacted, is fully tested three times, the changing value of BOD in sewage is measured using BOD analyzers, BOD removal rates are calculated, to table
Levy photocatalytic degradation capability.
The ammonia nitrogen pollutant adsorption capacity of the copper sulfide photochemical catalyst of the embodiment 1 measured by the above method, BOD are removed
Rate and manufacturing cost are as shown in table 1.
Embodiment 2
Preparation process is：
（1）Using extruder, stalk is sent into bulking machine in the way of screw extruding, stalk by it is strong squeeze, stirring,
Shearing, then by puffing, dehydration, cooling, form short texture, porous straw bulking object；The screw rod number of extruder is 2,
Screw diameter is 20mm, screw slenderness ratio 5:1, screw pitch 8mm, helical angle are 30 °, and vane tip gap is 15mm, puffing
Cavity gap is 20mm；The heating temperature in screw extruding area is 170 DEG C, revolution speed of screw 40r/min；The initial temperature of Builking cavity is
200 DEG C, cooling rate is 25 DEG C/min, and bulking pressure 5MPa, the expanded material residence time is 7min；The hole of straw bulking object
Gap rate is 60%, and popping fold is 5 times；
（2）10 parts by weight copper acetates and 12 parts by weight thioacetamides are added in 72 weight parts organic solvents, are uniformly mixed, and
6 parts by weight steps are added（1）Straw bulking object obtained is as carrier, and heating progress hydro-thermal reaction, former on carrier after dispersion
Position generates copper sulfide；Organic solvent is acetone；The temperature of hydro-thermal reaction is 140 DEG C, time 5h；
（3）To step（2）Product centrifuged, washed, dried, you can be made for sewage disposal stalk load copper sulfide
Photochemical catalyst；Washing uses acetone, deionized water, absolute ethyl alcohol successively；Dry is vacuum drying, and temperature is 70 DEG C, after dry
Moisture content is 0.5%.
Test method：
Photochemical catalyst made from 10g embodiments 2 is taken, puts into the simulated wastewater that 100mL contains phosphate and ammonia nitrogen, is placed in respectively
In light protected environment, it is stirred to react 8h at 25 DEG C, is repeated 3 times experiment, ammonia-nitrogen content is measured using Berthelot spectrophotometry
Changing value total nitrogen adsorption rate and total nitrogen are calculated separately using the phosphatic changes of contents value of Ammonium Molybdate Spectrophotometric Method for Determination
Adsorption rate, to characterize its adsorption capacity；
It takes 10g embodiments 2 that photochemical catalyst is made, puts into 100mL organic matter sewage, be placed under sunlight irradiation, at 25 DEG C
8h is reacted, is fully tested three times, the changing value of BOD in sewage is measured using BOD analyzers, BOD removal rates are calculated, to table
Levy photocatalytic degradation capability.
The ammonia nitrogen pollutant adsorption capacity of the copper sulfide photochemical catalyst of the embodiment 2 measured by the above method, BOD are removed
Rate and manufacturing cost are as shown in table 1.
Embodiment 3
Preparation process is：
（1）Using extruder, stalk is sent into bulking machine in the way of screw extruding, stalk by it is strong squeeze, stirring,
Shearing, then by puffing, dehydration, cooling, form short texture, porous straw bulking object；The screw rod number of extruder is 3,
Screw diameter is 30mm, screw slenderness ratio 8:1, screw pitch 10mm, helical angle are 40 °, and vane tip gap is 20mm, puffing
Cavity gap is 25mm；The heating temperature in screw extruding area is 190 DEG C, revolution speed of screw 60r/min；The initial temperature of Builking cavity is
240 DEG C, cooling rate is 30 DEG C/min, and bulking pressure 8MPa, the expanded material residence time is 10min；Straw bulking object
Porosity is 80%, and popping fold is 8 times；
（2）15 parts by weight copper acetates and 18 parts by weight thioacetamides are added in 57 weight parts organic solvents, are uniformly mixed, and
10 parts by weight steps are added（1）Straw bulking object obtained is as carrier, and heating progress hydro-thermal reaction, former on carrier after dispersion
Position generates copper sulfide；Organic solvent is chlorobenzene；The temperature of hydro-thermal reaction is 160 DEG C, time 4h；
（3）To step（2）Product centrifuged, washed, dried, you can be made for sewage disposal stalk load copper sulfide
Photochemical catalyst；Washing uses acetone, deionized water, absolute ethyl alcohol successively；Dry is vacuum drying, and temperature is 80 DEG C, after dry
Moisture content is 0.3%.
Test method：
Photochemical catalyst made from 10g embodiments 3 is taken, puts into the simulated wastewater that 100mL contains phosphate and ammonia nitrogen, is placed in respectively
In light protected environment, it is stirred to react 8h at 25 DEG C, is repeated 3 times experiment, ammonia-nitrogen content is measured using Berthelot spectrophotometry
Changing value total nitrogen adsorption rate and total nitrogen are calculated separately using the phosphatic changes of contents value of Ammonium Molybdate Spectrophotometric Method for Determination
Adsorption rate, to characterize its adsorption capacity；
It takes 10g embodiments 3 that photochemical catalyst is made, puts into 100mL organic matter sewage, be placed under sunlight irradiation, at 25 DEG C
8h is reacted, is fully tested three times, the changing value of BOD in sewage is measured using BOD analyzers, BOD removal rates are calculated, to table
Levy photocatalytic degradation capability.
The ammonia nitrogen pollutant adsorption capacity of the copper sulfide photochemical catalyst of the embodiment 3 measured by the above method, BOD are removed
Rate and manufacturing cost are as shown in table 1.
Embodiment 4
Preparation process is：
（1）Using extruder, stalk is sent into bulking machine in the way of screw extruding, stalk by it is strong squeeze, stirring,
Shearing, then by puffing, dehydration, cooling, form short texture, porous straw bulking object；The screw rod number of extruder is 2,
Screw diameter is 23mm, screw slenderness ratio 6:1, screw pitch 8mm, helical angle are 32 °, and vane tip gap is 16mm, puffing
Cavity gap is 22mm；The heating temperature in screw extruding area is 175 DEG C, revolution speed of screw 45r/min；The initial temperature of Builking cavity is
210 DEG C, cooling rate is 26 DEG C/min, and bulking pressure 6MPa, the expanded material residence time is 8min；The hole of straw bulking object
Gap rate is 65%, and popping fold is 6 times；
（2）11 parts by weight copper acetates and 14 parts by weight thioacetamides are added in 68 weight parts organic solvents, are uniformly mixed, and
7 parts by weight steps are added（1）Straw bulking object obtained is as carrier, and heating progress hydro-thermal reaction, former on carrier after dispersion
Position generates copper sulfide；Organic solvent is toluene；The temperature of hydro-thermal reaction is 145 DEG C, time 5h；
（3）To step（2）Product centrifuged, washed, dried, you can be made for sewage disposal stalk load copper sulfide
Photochemical catalyst；Washing uses acetone, deionized water, absolute ethyl alcohol successively；Dry is vacuum drying, and temperature is 72 DEG C, after dry
Moisture content is 0.4%.
Test method：
Photochemical catalyst made from 10g embodiments 4 is taken, puts into the simulated wastewater that 100mL contains phosphate and ammonia nitrogen, is placed in respectively
In light protected environment, it is stirred to react 8h at 25 DEG C, is repeated 3 times experiment, ammonia-nitrogen content is measured using Berthelot spectrophotometry
Changing value total nitrogen adsorption rate and total nitrogen are calculated separately using the phosphatic changes of contents value of Ammonium Molybdate Spectrophotometric Method for Determination
Adsorption rate, to characterize its adsorption capacity；
It takes 10g embodiments 4 that photochemical catalyst is made, puts into 100mL organic matter sewage, be placed under sunlight irradiation, at 25 DEG C
8h is reacted, is fully tested three times, the changing value of BOD in sewage is measured using BOD analyzers, BOD removal rates are calculated, to table
Levy photocatalytic degradation capability.
The ammonia nitrogen pollutant adsorption capacity of the copper sulfide photochemical catalyst of the embodiment 4 measured by the above method, BOD are removed
Rate and manufacturing cost are as shown in table 1.
Embodiment 5
Preparation process is：
（1）Using extruder, stalk is sent into bulking machine in the way of screw extruding, stalk by it is strong squeeze, stirring,
Shearing, then by puffing, dehydration, cooling, form short texture, porous straw bulking object；The screw rod number of extruder is 3,
Screw diameter is 28mm, screw slenderness ratio 7:1, screw pitch 10mm, helical angle are 38 °, and vane tip gap is 18mm, puffing
Cavity gap is 24mm；The heating temperature in screw extruding area is 185 DEG C, revolution speed of screw 55r/min；The initial temperature of Builking cavity is
235 DEG C, cooling rate is 28 DEG C/min, and bulking pressure 7MPa, the expanded material residence time is 9min；The hole of straw bulking object
Gap rate is 75%, and popping fold is 7 times；
（2）14 parts by weight copper acetates and 16 parts by weight thioacetamides are added in 61 weight parts organic solvents, are uniformly mixed, and
9 parts by weight steps are added（1）Straw bulking object obtained is as carrier, and heating progress hydro-thermal reaction, former on carrier after dispersion
Position generates copper sulfide；Organic solvent is dimethylbenzene；The temperature of hydro-thermal reaction is 155 DEG C, time 4h；
（3）To step（2）Product centrifuged, washed, dried, you can be made for sewage disposal stalk load copper sulfide
Photochemical catalyst；Washing uses acetone, deionized water, absolute ethyl alcohol successively；Dry is vacuum drying, and temperature is 78 DEG C, after dry
Moisture content is 0.5%.
Test method：
Photochemical catalyst made from 10g embodiments 5 is taken, puts into the simulated wastewater that 100mL contains phosphate and ammonia nitrogen, is placed in respectively
In light protected environment, it is stirred to react 8h at 25 DEG C, is repeated 3 times experiment, ammonia-nitrogen content is measured using Berthelot spectrophotometry
Changing value total nitrogen adsorption rate and total nitrogen are calculated separately using the phosphatic changes of contents value of Ammonium Molybdate Spectrophotometric Method for Determination
Adsorption rate, to characterize its adsorption capacity；
It takes 10g embodiments 5 that photochemical catalyst is made, puts into 100mL organic matter sewage, be placed under sunlight irradiation, at 25 DEG C
8h is reacted, is fully tested three times, the changing value of BOD in sewage is measured using BOD analyzers, BOD removal rates are calculated, to table
Levy photocatalytic degradation capability.
The ammonia nitrogen pollutant adsorption capacity of the copper sulfide photochemical catalyst of the embodiment 5 measured by the above method, BOD are removed
Rate and manufacturing cost are as shown in table 1.
Embodiment 6
Preparation process is：
（1）Using extruder, stalk is sent into bulking machine in the way of screw extruding, stalk by it is strong squeeze, stirring,
Shearing, then by puffing, dehydration, cooling, form short texture, porous straw bulking object；The screw rod number of extruder is 3,
Screw diameter is 26mm, screw slenderness ratio 6:1, screw pitch 9mm, helical angle are 36 °, and vane tip gap is 18mm, puffing
Cavity gap is 23mm；The heating temperature in screw extruding area is 175 DEG C, revolution speed of screw 60r/min；The initial temperature of Builking cavity is
225 DEG C, cooling rate is 28 DEG C/min, and bulking pressure 6MPa, the expanded material residence time is 8min；The hole of straw bulking object
Gap rate is 75%, and popping fold is 7 times；
（2）13 parts by weight copper acetates and 16 parts by weight thioacetamides are added in 63 weight parts organic solvents, are uniformly mixed, and
8 parts by weight steps are added（1）Straw bulking object obtained is as carrier, and heating progress hydro-thermal reaction, former on carrier after dispersion
Position generates copper sulfide；Organic solvent is pyridine；The temperature of hydro-thermal reaction is 155 DEG C, time 5h；
（3）To step（2）Product centrifuged, washed, dried, you can be made for sewage disposal stalk load copper sulfide
Photochemical catalyst；Washing uses acetone, deionized water, absolute ethyl alcohol successively；Dry is vacuum drying, and temperature is 76 DEG C, after dry
Moisture content is 0.4%.
Test method：
Photochemical catalyst made from 10g embodiments 6 is taken, puts into the simulated wastewater that 100mL contains phosphate and ammonia nitrogen, is placed in respectively
In light protected environment, it is stirred to react 8h at 25 DEG C, is repeated 3 times experiment, ammonia-nitrogen content is measured using Berthelot spectrophotometry
Changing value total nitrogen adsorption rate and total nitrogen are calculated separately using the phosphatic changes of contents value of Ammonium Molybdate Spectrophotometric Method for Determination
Adsorption rate, to characterize its adsorption capacity；
It takes 10g embodiments 6 that photochemical catalyst is made, puts into 100mL organic matter sewage, be placed under sunlight irradiation, at 25 DEG C
8h is reacted, is fully tested three times, the changing value of BOD in sewage is measured using BOD analyzers, BOD removal rates are calculated, to table
Levy photocatalytic degradation capability.
The ammonia nitrogen pollutant adsorption capacity of the copper sulfide photochemical catalyst of the embodiment 6 measured by the above method, BOD are removed
Rate and manufacturing cost are as shown in table 1.
Comparative example 1
Preparation process is：
（1）13 parts by weight copper acetates and 16 parts by weight thioacetamides are added in 63 weight parts organic solvents, are uniformly mixed, and
The stalk of 8 parts by weight is added and heats progress hydro-thermal reaction, the in-situ preparation copper sulfide on carrier as carrier, after dispersion；It is organic
Solvent is pyridine；The temperature of hydro-thermal reaction is 155 DEG C, time 5h；
（2）To step（1）Product centrifuged, washed, dried, you can the copper sulfide photocatalysis for sewage disposal is made
Agent；Washing uses acetone, deionized water, absolute ethyl alcohol successively；Dry is vacuum drying, and temperature is 76 DEG C, moisture content after drying
It is 0.4%.
Test method：
Photochemical catalyst made from 10g comparative examples 1 is taken, puts into the simulated wastewater that 100mL contains phosphate and ammonia nitrogen, is placed in respectively
In light protected environment, it is stirred to react 8h at 25 DEG C, is repeated 3 times experiment, ammonia-nitrogen content is measured using Berthelot spectrophotometry
Changing value total nitrogen adsorption rate and total nitrogen are calculated separately using the phosphatic changes of contents value of Ammonium Molybdate Spectrophotometric Method for Determination
Adsorption rate, to characterize its adsorption capacity；
It takes 10g comparative examples 1 that photochemical catalyst is made, puts into 100mL organic matter sewage, be placed under sunlight irradiation, at 25 DEG C
8h is reacted, is fully tested three times, the changing value of BOD in sewage is measured using BOD analyzers, BOD removal rates are calculated, to table
Levy photocatalytic degradation capability.As shown in table 1.
Table 1：
Claims (10)
1. a kind of preparation method of stalk load vulcanization bronzing catalyst for sewage disposal, which is characterized in that including following
Step：
（1）Using extruder, stalk is sent into bulking machine in the way of screw extruding, stalk by it is strong squeeze, stirring,
Shearing, then by puffing, dehydration, cooling, form short texture, porous straw bulking object；
（2）10 ~ 15 parts by weight copper acetates and 12 ~ 18 parts by weight thioacetamides are added in 57 ~ 72 weight parts organic solvents, are mixed
It closes uniformly, and 6 ~ 10 parts by weight steps is added（1）Straw bulking object obtained is as carrier, and heating progress hydro-thermal is anti-after dispersion
It answers, the in-situ preparation copper sulfide on carrier；
（3）To step（2）Product centrifuged, washed, dried, you can be made for sewage disposal stalk load copper sulfide
Photochemical catalyst.
2. the preparation method of a kind of stalk load vulcanization bronzing catalyst for sewage disposal according to claim 1,
It is characterized in that：Step（1）The screw rod number of the extruder is 2 ~ 3, and screw diameter is 20 ~ 30mm, screw slenderness ratio 5:1
~8:1, screw pitch is 8 ~ 10mm, and helical angle is 30 ~ 40 °, and vane tip gap is 15 ~ 20mm, and puffing cavity gap is 20 ~ 25mm.
3. the preparation method of a kind of stalk load vulcanization bronzing catalyst for sewage disposal according to claim 1,
It is characterized in that：Step（1）The heating temperature in the screw extruding area is 170 ~ 190 DEG C, and revolution speed of screw is 40 ~ 60r/min.
4. the preparation method of a kind of stalk load vulcanization bronzing catalyst for sewage disposal according to claim 1,
It is characterized in that：Step（1）The initial temperature of the Builking cavity is 200 ~ 240 DEG C, and cooling rate is 25 ~ 30 DEG C/min, puffing pressure
Power is 5 ~ 8MPa, and the expanded material residence time is 7 ~ 10min.
5. the preparation method of a kind of stalk load vulcanization bronzing catalyst for sewage disposal according to claim 1,
It is characterized in that：Step（1）The porosity of the straw bulking object is 60 ~ 80%, and popping fold is 5 ~ 8 times.
6. the preparation method of a kind of stalk load vulcanization bronzing catalyst for sewage disposal according to claim 1,
It is characterized in that：Step（2）The organic solvent is one in titanium tetrachloride, acetone, chlorine benzene,toluene,xylene, benzene or pyridine
Kind.
7. the preparation method of a kind of stalk load vulcanization bronzing catalyst for sewage disposal according to claim 1,
It is characterized in that：Step（2）The temperature of the hydro-thermal reaction is 140 ~ 160 DEG C, and the time is 4 ~ 5h.
8. the preparation method of a kind of stalk load vulcanization bronzing catalyst for sewage disposal according to claim 1,
It is characterized in that：Step（3）The washing uses acetone, deionized water, absolute ethyl alcohol to be washed successively.
9. the preparation method of a kind of stalk load vulcanization bronzing catalyst for sewage disposal according to claim 1,
It is characterized in that：Step（3）The drying is vacuum drying, and temperature is 70 ~ 80 DEG C, and moisture content is no more than 0.5% after drying.
10. a kind of stalk for sewage disposal that any one of claim 1 ~ 9 preparation method is prepared loads vulcanization
Bronzing catalyst.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110201700A (en) * | 2019-06-11 | 2019-09-06 | 武汉纺织大学 | A kind of CuS-CuO-CN peroxide composite catalyst and its preparation method and application for high-level oxidation technology |
| CN110813249A (en) * | 2019-11-19 | 2020-02-21 | 淮阴师范学院 | Straw-puffed biological matrix material with sandwich type frame and preparation method and application thereof |
| CN112169379A (en) * | 2020-10-22 | 2021-01-05 | 陕西师范大学 | Biomass airbag/TiO with floating oil absorption2Composite material |
-
2018
- 2018-03-12 CN CN201810200609.1A patent/CN108479803A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110201700A (en) * | 2019-06-11 | 2019-09-06 | 武汉纺织大学 | A kind of CuS-CuO-CN peroxide composite catalyst and its preparation method and application for high-level oxidation technology |
| CN110201700B (en) * | 2019-06-11 | 2022-04-08 | 武汉纺织大学 | CuS-CuO-CN peroxide composite catalyst for advanced oxidation technology and preparation method and application thereof |
| CN110813249A (en) * | 2019-11-19 | 2020-02-21 | 淮阴师范学院 | Straw-puffed biological matrix material with sandwich type frame and preparation method and application thereof |
| CN112169379A (en) * | 2020-10-22 | 2021-01-05 | 陕西师范大学 | Biomass airbag/TiO with floating oil absorption2Composite material |
| CN112169379B (en) * | 2020-10-22 | 2022-04-12 | 陕西师范大学 | Biomass airbag/TiO with floating oil absorption2Composite material |
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