CN108911019A - A kind for the treatment of of dyeing/printing wastewaters and preparation method thereof - Google Patents
A kind for the treatment of of dyeing/printing wastewaters and preparation method thereof Download PDFInfo
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- CN108911019A CN108911019A CN201810861228.8A CN201810861228A CN108911019A CN 108911019 A CN108911019 A CN 108911019A CN 201810861228 A CN201810861228 A CN 201810861228A CN 108911019 A CN108911019 A CN 108911019A
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- dyeing
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- 238000004043 dyeing Methods 0.000 title claims abstract description 66
- 239000002351 wastewater Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052742 iron Inorganic materials 0.000 claims abstract description 33
- 230000004048 modification Effects 0.000 claims abstract description 24
- 238000012986 modification Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 12
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 9
- 235000010413 sodium alginate Nutrition 0.000 claims description 9
- 239000000661 sodium alginate Substances 0.000 claims description 9
- 229940005550 sodium alginate Drugs 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 8
- -1 4- (2- chloroethoxy) Benzene Chloride Chemical compound 0.000 claims description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 229920002620 polyvinyl fluoride Polymers 0.000 claims description 6
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 5
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 229960004756 ethanol Drugs 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- 235000011056 potassium acetate Nutrition 0.000 claims description 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 238000005660 chlorination reaction Methods 0.000 claims 2
- 125000006012 2-chloroethoxy group Chemical group 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- MJEMIOXXNCZZFK-UHFFFAOYSA-N ethylone Chemical compound CCNC(C)C(=O)C1=CC=C2OCOC2=C1 MJEMIOXXNCZZFK-UHFFFAOYSA-N 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 238000005342 ion exchange Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001354 calcination Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- OQUFOZNPBIIJTN-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;sodium Chemical group [Na].OC(=O)CC(O)(C(O)=O)CC(O)=O OQUFOZNPBIIJTN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- 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
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- 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)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of preparation methods for the treatment of of dyeing/printing wastewaters, include the following steps：(1) preparation of porous Ti-La-O-S；(2) porous Ti-La-O-S/ nano zero valence iron surface modification；(3) ion exchange prepares treatment of dyeing/printing wastewaters.The invention also discloses the treatment of dyeing/printing wastewaters being prepared according to the preparation method.Treatment of dyeing/printing wastewaters disclosed by the invention has cheap, good waste water treatment effect, and high-efficient, dosage is few, and dehydrating effect is significant, the small advantage of environmental pollution.
Description
Technical field
The present invention relates to technical field of waste water processing more particularly to a kind for the treatment of of dyeing/printing wastewaters and preparation method thereof.
Background technique
Along with the development and growth of textile industry, the dyeing waste water discharge capacity of textile fabric increases year by year, gives environment and people
Health bring and seriously threaten.As the reinforcement and countries in the world of people's environmental consciousness are to waste water control relevant law
Regulation it is perfect, textile printing and dyeing enterprises are had become to the purified treatment of dyeing waste water and have to face one big important ask
Topic.But dyeing waste water has the characteristics that high chroma, organic principle are complicated low with microbial degradation degree, water supply purification handles band
Many difficulties are carried out.It therefore, is current urgent problem to be solved in the industry to the processing of dyeing waste water.
Currently, the main methods of dyeing waste water have physico-chemical process, biochemical method and chemical method etc..But the prior art
There is also problems for the processing method of dyeing waste water, and if process degradation is poor, decoloration is difficult；Materializing strategy is costly；Processing
Complex process, these problems hinder the fast development of dyeing.In the treatment process of dyeing waste water, essential one
Kind reagent is treatment of dyeing/printing wastewaters, and the quality of performance directly affects the treatment effect of dyeing waste water.It is in the prior art
Waste water treating agent is mainly single molysite, aluminium salt, and dosage is big, and decolorizing effect is poor, and these inorganic agents often have environment
Evil, influences the health of people.
Therefore, a kind of good waste water treatment effect is developed, high-efficient, dosage is few, and dehydrating effect is significant, and environmental pollution is small
Treatment of dyeing/printing wastewaters accords with the demands of the market, and has extensive market value and application prospect.
Summary of the invention
In order to overcome the defects of the prior art, the present invention provides a kind for the treatment of of dyeing/printing wastewaters and preparation method thereof, should
Preparation method simple process, cheap, raw material are easy to get, and are suitable for industrial applications；It is prepared by the preparation method
Treatment of dyeing/printing wastewaters overcomes traditional dyeing and finishing waste water treating agent, and more or less existing dosage is big, and decolorizing effect is poor, environment
It is seriously polluted, it has a single function, the technical problem of water treatment effect difference, there is cheap, good waste water treatment effect, efficiency
Height, dosage is few, and dehydrating effect is significant, the small advantage of environmental pollution.
To achieve the above object of the invention, the technical solution adopted by the present invention is that, a kind of preparation side for the treatment of of dyeing/printing wastewaters
Method includes the following steps：
I, the preparation of porous Ti-La-O-S：By titanium source, lanthanum source and ammonium sulfide be added in the container containing alcohol stirring 1~
1.5h is slowly added to acylate later, is vigorously agitated again 2.5~3.5h, transfers the solution into the hydro-thermal of polyvinyl fluoride liner
In reaction kettle, 15~18h is reacted at 180~220 DEG C；It is washed repeatedly after cooling through deionized water and dehydrated alcohol, 75~
It is 20~25 hours dry in 85 DEG C of vacuum oven；Milled 300-400 mesh mesh, later in 450~500 DEG C of nitrogen atmosphere
It encloses lower calcination 6-10 hours, is cooled to room temperature, obtains porous Ti-La-O-S；
II, porous Ti-La-O-S/ nano zero valence iron surface modification：The porous Ti-La-O- that will be prepared by step I
S, nano zero valence iron is scattered in high boiling solvent, then 4 are added thereto, 4'- bis- (9- carbazole) biphenyl, 4- (2- chloroethoxy)
Benzene Chloride is stirred to react 6-8 hours at 60-80 DEG C, after add 9- [3- (triethoxysilicane alkyl) propyl] -9H- carbazole,
Mechanic whirl-nett reaction 1-2 hours, after settle out in water, postposition is dried 12-17 hours at 70-80 DEG C in a vacuum drying oven, is obtained
The porous Ti-La-O-S/ nano zero valence iron of surface modification；
III, the porous Ti-La-O-S/ nano zero valence iron of surface modification being prepared by step II is immersed in 50-60
Mass fraction is to filter, and be washed with water 5 times 15-20 hours in the aqueous solution of the sodium alginate of 5-10%, be placed on vacuum at DEG C
It is dried 15-20 hours at 70-80 DEG C in drying box, then milled 300-400 mesh mesh, obtains treatment of dyeing/printing wastewaters.
Further, titanium source described in step I, lanthanum source, ammonium sulfide, alcohol, acylate mass ratio be 2:0.05:
0.02:(10-15):5。
Further, the alcohol is selected from one or more of ethyl alcohol, propyl alcohol, isopropanol, ethylene glycol, glycerine；It is described
Titanium source is selected from one or more of titanium tetrachloride, butyl titanate；The lanthanum source is in lanthanum chloride, lanthanum nitrate, lanthanum carbonate
One or more.
Further, the acylate is selected from one or more of sodium citrate, sodium acetate, potassium acetate.
Preferably, porous Ti-La-O-S described in step II, nano zero valence iron, high boiling solvent, (the 9- click of 4,4'- bis-
Azoles) biphenyl, 4- (2- chloroethoxy) Benzene Chloride, 9- [3- (triethoxysilicane alkyl) propyl] -9H- carbazole mass ratio be 1:
0.5:(6-10):0.236:0.1:0.05。
Preferably, the high boiling solvent is in dimethyl sulfoxide, n,N-Dimethylformamide, N-Methyl pyrrolidone
It is one or more of.
Preferably, the aqueous solution of the porous Ti-La-O-S/ nano zero valence iron of surface modification described in step III, sodium alginate
Mass ratio be 1:(20-40).
A kind for the treatment of of dyeing/printing wastewaters is prepared according to the preparation method of above-mentioned treatment of dyeing/printing wastewaters.
Generated beneficial effect is by adopting the above technical scheme：
1) treatment of dyeing/printing wastewaters provided by the invention, preparation method simple process, cheap, raw material are easy to get, are suitable for
Industrial applications.
2) treatment of dyeing/printing wastewaters provided by the invention overcomes traditional dyeing and finishing waste water treating agent more or less existing use
Dose is big, and decolorizing effect is poor, and environmental pollution is serious, has a single function, the technical problem of water treatment effect difference, has price low
Honest and clean, good waste water treatment effect is high-efficient, and dosage is few, and dehydrating effect is significant, the small advantage of environmental pollution.
3) treatment of dyeing/printing wastewaters provided by the invention, ingredient is simple, and the antagonism avoided between multicomponent causes
Water treatment effect is low, saves cost, and porous Ti-La-O-S can have preferable absorption to make due to porous structure to dyestuff
With yttrium and element sulphur adulterate titanyl compound, have light-catalysed characteristic, the knot containing conjugation by doping and surface
The modification of the polymer of structure, expands optical response range, improves photocatalysis efficiency, and Zero-valent Iron is supported on porous Ti-La-O-S
On improve specific surface area, synergistic effect is more efficient so that water treatment effect is more preferable；On the other hand, surface modification polymerize
The corrosion oxidation of nano zero valence iron can be effectively prevented in object, improves the stability for the treatment of of dyeing/printing wastewaters.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, and make features described above of the invention,
Purpose and advantage are more clear understandable, and the present invention will be further explained with reference to the examples below.Embodiment is only used for
It is bright the present invention rather than limit the scope of the invention.
Present invention raw material as used in the following examples is from upper Haiquan sunrise foreign trade Co., Ltd.
Embodiment 1
A kind of preparation method for the treatment of of dyeing/printing wastewaters, includes the following steps：
I, the preparation of porous Ti-La-O-S：By titanium tetrachloride 20g, lanthanum chloride 0.5g and ammonium sulfide 0.2g be added to containing
1h is stirred in the container of ethyl alcohol 100g, sodium citrate 50g is slowly added to later, is vigorously agitated again 2.5h, is transferred the solution into poly-
In the hydrothermal reaction kettle of vinyl fluoride liner, 15h is reacted at 180 DEG C；It is washed repeatedly after cooling through deionized water and dehydrated alcohol,
It is 20 hours dry in 75 DEG C of vacuum oven；Milled 300 mesh mesh, calcination 6 is small under 450 DEG C of nitrogen atmosphere later
When, it is cooled to room temperature, obtains porous Ti-La-O-S；
II, porous Ti-La-O-S/ nano zero valence iron surface modification：The porous Ti-La-O- that will be prepared by step I
S10g, nano zero valence iron 5g are scattered in dimethyl sulfoxide 60g, then 4 are added thereto, 4'- bis- (9- carbazole) biphenyl 2.36g, 4-
(2- chloroethoxy) Benzene Chloride 1g, is stirred to react 6 hours at 60 DEG C, after add 9- [3- (triethoxysilicane alkyl) third
Base] -9H- carbazole 0.5g, mechanic whirl-nett reaction 1 hour, after settle out in water, it is small that postposition dries 12 at 70 DEG C in a vacuum drying oven
When, obtain the porous Ti-La-O-S/ nano zero valence iron of surface modification；
III, the porous Ti-La-O-S/ nano zero valence iron 10g of surface modification being prepared by step II is immersed in 50
It 15 hours in the aqueous solution 200g for the sodium alginate that mass fraction is 5% at DEG C, filters, and be washed with water 5 times, it is dry to be placed on vacuum
It is dried 15 hours at 70 DEG C in dry case, then milled 300 mesh mesh, obtains treatment of dyeing/printing wastewaters.
A kind for the treatment of of dyeing/printing wastewaters is prepared according to the preparation method of above-mentioned treatment of dyeing/printing wastewaters.
Embodiment 2
A kind of preparation method for the treatment of of dyeing/printing wastewaters, includes the following steps：
I, the preparation of porous Ti-La-O-S：Butyl titanate 20g, lanthanum nitrate 0.5g and ammonium sulfide 0.2g are added to and are contained
1.1h is stirred in the container for having propyl alcohol 115g, is slowly added to sodium acetate 50g later, is vigorously agitated again 2.9h, transfers the solution into
In the hydrothermal reaction kettle of polyvinyl fluoride liner, 16h is reacted at 190 DEG C；It is washed repeatedly after cooling through deionized water and dehydrated alcohol
It washs, it is 21 hours dry in 77 DEG C of vacuum oven；Milled 330 mesh mesh, the later calcination under 470 DEG C of nitrogen atmosphere
It 7 hours, is cooled to room temperature, obtains porous Ti-La-O-S；
II, porous Ti-La-O-S/ nano zero valence iron surface modification：The porous Ti-La-O- that will be prepared by step I
S10g, nano zero valence iron 5g are scattered in n,N-Dimethylformamide 75g, then 4 are added thereto, 4'- bis- (9- carbazole) biphenyl
2.36g, 4- (2- chloroethoxy) Benzene Chloride 1g, is stirred to react 7 hours at 65 DEG C, after add 9- [3- (triethoxysilane
Base) propyl] -9H- carbazole 0.5g, mechanic whirl-nett reaction 1.2 hours, after settle out in water, 73 DEG C in a vacuum drying oven of postposition
It is lower to dry 13 hours, obtain the porous Ti-La-O-S/ nano zero valence iron of surface modification；
III, the porous Ti-La-O-S/ nano zero valence iron 10g of surface modification being prepared by step II is immersed in 53
It 17 hours in the aqueous solution 250g for the sodium alginate that mass fraction is 6% at DEG C, filters, and be washed with water 5 times, it is dry to be placed on vacuum
It is dried 17.5 hours at 74 DEG C in dry case, then milled 340 mesh mesh, obtains treatment of dyeing/printing wastewaters.
A kind for the treatment of of dyeing/printing wastewaters is prepared according to the preparation method of above-mentioned treatment of dyeing/printing wastewaters.
Embodiment 3
A kind of preparation method for the treatment of of dyeing/printing wastewaters, includes the following steps：
I, the preparation of porous Ti-La-O-S：By titanium tetrachloride 20g, lanthanum carbonate 0.5g and ammonium sulfide 0.2g be added to containing
1.3h is stirred in the container of isopropanol 130g, is slowly added to potassium acetate 50g later, is vigorously agitated again 2.9h, transfers the solution into
In the hydrothermal reaction kettle of polyvinyl fluoride liner, 16.5h is reacted at 200 DEG C；After cooling repeatedly through deionized water and dehydrated alcohol
Washing, it is 23.5 hours dry in 79 DEG C of vacuum oven；Milled 350 mesh mesh, later under 470 DEG C of nitrogen atmosphere
It calcination 8 hours, is cooled to room temperature, obtains porous Ti-La-O-S；
II, porous Ti-La-O-S/ nano zero valence iron surface modification：The porous Ti-La-O- that will be prepared by step I
S10g, nano zero valence iron 5g are scattered in N-Methyl pyrrolidone 80g, then 4 are added thereto, 4'- bis- (9- carbazole) biphenyl
2.36g, 4- (2- chloroethoxy) Benzene Chloride 1g, is stirred to react 7.2 hours at 70 DEG C, after add 9- [3- (triethoxysilicane
Alkyl) propyl] -9H- carbazole 0.5g, mechanic whirl-nett reaction 1.5 hours, after settle out in water, postposition in a vacuum drying oven 75
It is dried 15 hours at DEG C, obtains the porous Ti-La-O-S/ nano zero valence iron of surface modification；
III, the porous Ti-La-O-S/ nano zero valence iron 10g of surface modification being prepared by step II is immersed in 56
It 18 hours in the aqueous solution 320g for the sodium alginate that mass fraction is 8% at DEG C, filters, and be washed with water 5 times, it is dry to be placed on vacuum
It is dried 18 hours at 77 DEG C in dry case, then milled 360 mesh mesh, obtains treatment of dyeing/printing wastewaters.
A kind for the treatment of of dyeing/printing wastewaters is prepared according to the preparation method of above-mentioned treatment of dyeing/printing wastewaters.
Embodiment 4
A kind of preparation method for the treatment of of dyeing/printing wastewaters, includes the following steps：
I, the preparation of porous Ti-La-O-S：Titanium source 20g, lanthanum source 0.5g and ammonium sulfide 0.2g are added to containing alcohol 135g
Container in stir 1.4h, be slowly added to acylate 50g later, be vigorously agitated again 3.4h, transfer the solution into polyvinyl fluoride
In the hydrothermal reaction kettle of liner, 17h is reacted at 215 DEG C；It is washed repeatedly after cooling through deionized water and dehydrated alcohol, at 84 DEG C
Vacuum oven in dry 24.5 hours；Milled 390 mesh mesh, calcination 9.5 is small under 490 DEG C of nitrogen atmosphere later
When, it is cooled to room temperature, obtains porous Ti-La-O-S；The alcohol is ethyl alcohol, propyl alcohol, ethylene glycol, glycerine in mass ratio 1:2:3:
1 mixture mixed.The titanium source is titanium tetrachloride, butyl titanate in mass ratio 2:3 mixtures mixed；Institute
Stating lanthanum source is lanthanum chloride, lanthanum nitrate, lanthanum carbonate in mass ratio 1:2:5 mix mixture；The acylate is citric acid
Sodium, sodium acetate, potassium acetate in mass ratio 1:3:2 mixtures mixed；
II, porous Ti-La-O-S/ nano zero valence iron surface modification：The porous Ti-La-O- that will be prepared by step I
S10g, nano zero valence iron 5g are scattered in high boiling solvent 95g, then 4 are added thereto, 4'- bis- (9- carbazole) biphenyl 2.36g,
4- (2- chloroethoxy) Benzene Chloride 1g, is stirred to react 7.8 hours at 78 DEG C, after add 9- [3- (triethoxysilicane alkyl)
Propyl] -9H- carbazole 0.5g, mechanic whirl-nett reaction 1.9 hours, after settle out in water, postposition is dried at 79 DEG C in a vacuum drying oven
16 hours, obtain the porous Ti-La-O-S/ nano zero valence iron of surface modification；The high boiling solvent is dimethyl sulfoxide, N, N- diformazan
Base formamide, N-Methyl pyrrolidone in mass ratio 1:2:4 mixtures mixed；
III, the porous Ti-La-O-S/ nano zero valence iron 10g of surface modification being prepared by step II is immersed in 59
It 19 hours in the aqueous solution 380g for the sodium alginate that mass fraction is 9% at DEG C, filters, and be washed with water 5 times, it is dry to be placed on vacuum
It is dried 19 hours at 79 DEG C in dry case, then milled 390 mesh mesh, obtains treatment of dyeing/printing wastewaters.
A kind for the treatment of of dyeing/printing wastewaters is prepared according to the preparation method of above-mentioned treatment of dyeing/printing wastewaters.
Embodiment 5
A kind of preparation method for the treatment of of dyeing/printing wastewaters, includes the following steps：
I, the preparation of porous Ti-La-O-S：Butyl titanate 20g, lanthanum carbonate 0.5g and ammonium sulfide 0.2g are added to and are contained
1.5h is stirred in the container for having glycerine 150g, sodium citrate 50g is slowly added to later, is vigorously agitated again 3.5h, and solution is turned
It moves on in the hydrothermal reaction kettle of polyvinyl fluoride liner, reacts 18h at 220 DEG C；It is anti-through deionized water and dehydrated alcohol after cooling
After backwashing is washed, 25 hours dry in 85 DEG C of vacuum oven；Milled 400 mesh mesh, later under 500 DEG C of nitrogen atmosphere
It calcination 10 hours, is cooled to room temperature, obtains porous Ti-La-O-S；
II, porous Ti-La-O-S/ nano zero valence iron surface modification：The porous Ti-La-O- that will be prepared by step I
S10g, nano zero valence iron 5g are scattered in n,N-Dimethylformamide 100g, then 4 are added thereto, 4'- bis- (9- carbazole) biphenyl
2.36g, 4- (2- chloroethoxy) Benzene Chloride 1g, is stirred to react 8 hours at 80 DEG C, after add 9- [3- (triethoxysilane
Base) propyl] -9H- carbazole 0.5g, mechanic whirl-nett reaction 2 hours, after settle out in water, postposition is in a vacuum drying oven at 80 DEG C
It dries 17 hours, obtains the porous Ti-La-O-S/ nano zero valence iron of surface modification；
III, the porous Ti-La-O-S/ nano zero valence iron 10g of surface modification being prepared by step II is immersed in 60
20 hours in the aqueous solution 400g for the sodium alginate that mass fraction is 10% at DEG C, filters, and be washed with water 5 times, be placed on vacuum
It is dried 20 hours at 80 DEG C in drying box, then milled 400 mesh mesh, obtains treatment of dyeing/printing wastewaters.
A kind for the treatment of of dyeing/printing wastewaters is prepared according to the preparation method of above-mentioned treatment of dyeing/printing wastewaters.
Comparative example
This example provides a kind for the treatment of of dyeing/printing wastewaters, and preparation method and formula are real with Chinese invention patent CN105084441B
Apply example 3.
The sewage for taking certain printing and dyeing mill to be discharged, is equally divided into 6 parts, is handled respectively with above-mentioned waste water treating agent, and testing result is shown in
Table 1
Table 1
| Chroma removal rate (%) | Turbidity removal rate (%) | COD removal rate (%) | |
| Detection method | GB11903-1989 | GB/T13200-1991 | GB11914-89 |
| Embodiment 1 | 94.4 | 95.1 | 94.8 |
| Embodiment 2 | 96.1 | 96.2 | 96.1 |
| Embodiment 3 | 97.2 | 96.9 | 97.2 |
| Embodiment 4 | 98.0 | 97.4 | 97.9 |
| Embodiment 5 | 99.2 | 98.9 | 98.7 |
| Comparative example | 89.5 | 85.6 | 80.6 |
As can be seen from the above table, treatment of dyeing/printing wastewaters disclosed by the embodiments of the present invention has more excellent wastewater treatment
Effect.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection scope by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of preparation method for the treatment of of dyeing/printing wastewaters, which is characterized in that include the following steps：
I, the preparation of porous Ti-La-O-S：Titanium source, lanthanum source and ammonium sulfide are added to 1~1.5h of stirring in the container containing alcohol,
It is slowly added to acylate later, is vigorously agitated again 2.5~3.5h, transfers the solution into the hydrothermal reaction kettle of polyvinyl fluoride liner
In, 15~18h is reacted at 180~220 DEG C；It is washed repeatedly after cooling through deionized water and dehydrated alcohol, at 75~85 DEG C
It is 20~25 hours dry in vacuum oven；Milled 300-400 mesh mesh is burnt under 450~500 DEG C of nitrogen atmosphere later
It burns 6-10 hours, is cooled to room temperature, obtains porous Ti-La-O-S；
II, porous Ti-La-O-S/ nano zero valence iron surface modification：By the porous Ti-La-O-S being prepared by step I, receive
Rice Zero-valent Iron is scattered in high boiling solvent, then 4 are added thereto, 4'- bis- (9- carbazole) biphenyl, 4- (2- chloroethoxy) chlorination
Benzene is stirred to react 6-8 hours at 60-80 DEG C, after add 9- [3- (triethoxysilicane alkyl) propyl] -9H- carbazole, it is mechanical
Be stirred to react 1-2 hours, after settle out in water, postposition is dried 12-17 hours at 70-80 DEG C in a vacuum drying oven, obtains surface
Modify porous Ti-La-O-S/ nano zero valence iron；
III, the porous Ti-La-O-S/ nano zero valence iron of surface modification being prepared by step II is immersed at 50-60 DEG C
Mass fraction is to filter, and be washed with water 5 times 15-20 hours in the aqueous solution of the sodium alginate of 5-10%, be placed on vacuum drying
It is dried 15-20 hours at 70-80 DEG C in case, then milled 300-400 mesh mesh, obtains treatment of dyeing/printing wastewaters.
2. the preparation method for the treatment of of dyeing/printing wastewaters according to claim 1, which is characterized in that titanium source described in step I,
Lanthanum source, ammonium sulfide, alcohol, acylate mass ratio be 2:0.05:0.02:(10-15):5.
3. the preparation method for the treatment of of dyeing/printing wastewaters according to claim 1, which is characterized in that the alcohol be selected from ethyl alcohol,
One or more of propyl alcohol, isopropanol, ethylene glycol, glycerine.
4. the preparation method for the treatment of of dyeing/printing wastewaters according to claim 1, which is characterized in that the titanium source is selected from tetrachloro
Change one or more of titanium, butyl titanate.
5. the preparation method for the treatment of of dyeing/printing wastewaters according to claim 1, which is characterized in that the lanthanum source is selected from chlorination
One or more of lanthanum, lanthanum nitrate, lanthanum carbonate.
6. the preparation method for the treatment of of dyeing/printing wastewaters according to claim 1, which is characterized in that the acylate is selected from
One or more of sodium citrate, sodium acetate, potassium acetate.
7. the preparation method for the treatment of of dyeing/printing wastewaters according to claim 1, which is characterized in that porous described in step II
Ti-La-O-S, nano zero valence iron, high boiling solvent, 4,4'- bis- (9- carbazole) biphenyl, 4- (2- chloroethoxy) Benzene Chloride, 9-
The mass ratio of [3- (triethoxysilicane alkyl) propyl] -9H- carbazole is 1:0.5:(6-10):0.236:0.1:0.05.
8. the preparation method for the treatment of of dyeing/printing wastewaters according to claim 1, which is characterized in that the high boiling solvent choosing
From one or more of dimethyl sulfoxide, N,N-dimethylformamide, N-Methyl pyrrolidone.
9. the preparation method for the treatment of of dyeing/printing wastewaters according to claim 1, which is characterized in that surface described in step III
Modify porous Ti-La-O-S/ nano zero valence iron, sodium alginate aqueous solution mass ratio be 1:(20-40).
10. a kind of printing and dyeing that the preparation method of any one of -9 treatment of dyeing/printing wastewaters according to claim 1 is prepared are useless
Water treatment agent.
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