CN1300009C - Physical and chemical dyeing and printing effluent treating process throwing no coagulant and the prepn of supplementary material used - Google Patents
Physical and chemical dyeing and printing effluent treating process throwing no coagulant and the prepn of supplementary material used Download PDFInfo
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- CN1300009C CN1300009C CNB031127959A CN03112795A CN1300009C CN 1300009 C CN1300009 C CN 1300009C CN B031127959 A CNB031127959 A CN B031127959A CN 03112795 A CN03112795 A CN 03112795A CN 1300009 C CN1300009 C CN 1300009C
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Abstract
The present invention relates to a method for treating printing and dyeing waste water in a materialization method without adding flocculating agents and preparation for the used auxiliary materials, particularly to a method for treating printing and dyeing waste water. The present invention prompts a plurality of components in waste water to generate reactions of aggregation, adsorption, complexation, etc. through the catalysis function and the oxidation reduction function of auxiliary materials by purpose-made auxiliary materials which uses SiO2 as a skeleton and contains elements of titanium, nickel, copper, iron, etc., a large amount of floccules are formed under the matching action of coagulant aid which is added subsequently, good conditions for solid-liquid separation are created, and the effect that COD and chromaticity in waste water are removed is reached. With printing and dyeing waste water treated by the method, a COD removal rate is larger than or equal to 60%, and a decolorization ratio is from 70 to 90%. Compared with traditional treating methods that flocculating agents are added, sewage sludge quantity is reduced by more than 50%, and treatment cost is saved by 60% more or less. The present invention treats printing dyeing waste water in a materialization method and a successful invention without adding flocculating agents.
Description
Technical field
The present invention relates to the method for treatment of dyeing and printing, particularly do not relate to and need add flocculation agent, and only use a kind of method of physico-chemical process treatment of dyeing and printing of auxiliary material and the preparation of used auxiliary material.
Background technology
Usually, all add flocculation agent during the physico-chemical process treatment of dyeing and printing, as polymerize aluminum chloride (PAC), bodied ferric sulfate (PFS), through a large amount of flosss of process form such as cohesion, absorption, bridge formation, hydrogen bond associations, through solid-liquid separation, reach the purpose of removing COD and colourity again.The flocculation agent that is added is specialized factory and produces, and is transported to printing and dyeing enterprise then and uses, and the transportation back and forth of article, storage all have inconvenient part.The inefficacy apt to deteriorate that has, the generation mud that has is a lot.Add that these flocculation agent prices all than higher, make cost for wastewater treatment higher, or the like, directly have influence on the processing and the business economic benefit of waste water, also be that China's wastewater processing technology is demanded reason for renewing urgently.
The nineties in last century " nanometer " is pined for, and the processing that a kind of similar nano material is applied to dyeing waste water occurred, and to replace the flocculation agent that adds in the past, the removal of COD and decolorizing effect are all relatively good.But because of this material is very thin, easy loss in service.And this material price is very high, and what have per ton expensively reaches tens thousand of units, directly has influence on cost for wastewater treatment, has influence on the wide popularization and application of this series products.
Also the someone attempts elements such as titanium, nickel are adsorbed on the objects such as silica gel becomes a kind of carrier, and under the help of UV-lamp photograph, the dyeing waste water catalyzed oxidation is substituted the flocculation agent that in the past added, realize that COD removes and the purpose of decolouring, but, do not see the report of large-scale application aborning so far because of reason such as the manufacture difficulty of carrier is bigger.
Summary of the invention
(1) technical problem that will solve
The purpose of this invention is to provide a kind of method of the physico-chemical process treatment of dyeing and printing that does not add flocculation agent and the preparation of used auxiliary material.A kind of new techniques of Dyeing Wastewater Treatment is provided, has fairly obvious environmental benefit and economic benefit.
(2) technical scheme
A kind of method of physico-chemical process treatment of dyeing and printing, present method need not add flocculation agent, adopt a kind of with SiO
2Be skeleton, the special solid matter that contains elements such as titanium, nickel, copper, iron, be called for short auxiliary material, be applied to the processing of dyeing waste water, earlier dyeing waste water is transferred PH to 6-9, drop into auxiliary material, auxiliary material: dyeing waste water is 1: 7-9 (V/V), stirring reaction 5-15 minute, left standstill 5-8 minute, take out supernatant liquid, with the Ca (OH) of 15-20% (W/W) concentration
2Make coagulant aids, transfer PH to 6-9, flocculation sediment, supernatant liquor are handles the back clear liquid.After the processing waste water water yield reaches 50-60 times (V/V) of auxiliary material amount, add fresh auxiliary material to replenish consume so that the amount of original auxiliary material amount 1%-2% is additional, original auxiliary material needn't be regenerated, and can continue repeated use.
The starting material that the preparation of used auxiliary material is selected for use
1, water glass (xNa
2OySiO
2) have another name called water glass, be commonly called as bubble flower alkali, technical grade divides two kinds of alkalescence, neutrality, and the present invention adopts neutral water glass, and viscous liquid is creamy white.
2, titanium dioxide (TiO
2) claiming titanium dioxide again, the present invention adopts anatase thpe white powder, TiO
2Content 98%, 45um screenings≤0.1%, the finely powdered that is white in color, proportion 3.84.
3.FeCl
2Solution is handled with hydrochloric acid (HCl) and to be turned over the cylinder tank liquor behind band steel, the wire rod, is grass green or yellow-green liquid, and proportion about 1.1 contains HCl30-40g/L, FeCl
2110-130g/L.
4. solid sulphuric acid copper (CuSO
45H
2O), technical grade, be emerald green particle or powdery, proportion 2.286.
5. nickelous chloride (NiCl
26H
2O), proportion 3.55, green plate crystal body.
The preparation method of auxiliary material divides four processes to finish.
1. at FeCl
2Add the nickelous chloride xln in the waste liquid, nickelous chloride xln: FeCl
2Waste liquid is 0.01-0.015: 1 (V/V), stir stand for standby use after 5-10 minute, and be called for short the first thing.
2. add titanium dioxide in water glass, titanium dioxide: water glass is 0.06-0.08: 1 (V/V) continuously stirring 5-6 minute, the pasty state liquid that is creamy white is called for short the second thing.
3. in proportion the second thing is added in the first thing slowly the second thing: the first thing is 0.45-0.50: 1 (V/V), and constantly stir, obtain canescence or beige xln, take out filter and do, be called for short third thing.
4. third thing and solid sulphuric acid copper are mixed in proportion solid sulphuric acid copper: third thing is 0.01-0.015: 1 (V/V), fire insulation heating in the rot-resistant reactor then becomes reddish-brown or taupe amorphous solid, is required auxiliary material.
Above-mentioned auxiliary material proportion about 0.72, PH3-4 is not dissolved in water, and good dispersiveness is arranged in water.Auxiliary material can be reused, and needn't regenerate, and 100 tons of waste water of every processing only need replenish the amount of consume auxiliary material, get final product and add 1.5-2.0Kg.
Auxiliary material of the present invention is applied to treatment of dyeing and printing, be catalysis and redoxomorphism by auxiliary material, impel reactions such as some compositions in the waste water condense, absorption, complexing, under the mating reaction of the coagulant aids that adds subsequently, form a large amount of flosss, create the good condition of solid-liquid separation, reached the effect of removing COD and colourity in the waste water.Treatment process can be intermittent type or continous way.It is to put into dyeing waste water in a stirred reactor that intermittent type is handled, and transfers PH to 6-9, drops into auxiliary material, stirring reaction 5-15 minute, left standstill 5-8 minute, and take out supernatant liquid, PH is about 4-5, adds the coagulant aids Ca (OH) of 15-20% (W/W) concentration then
2Transfer PH to 6-9, mix slightly and just produce a large amount of throw outs, staticly settle, PH, COD and the colourity of test supernatant liquor.It is that the dyeing waste water Continuous Flow is crossed two treatment troughs that continous way is handled.First mid-auxiliary material of treatment trough advances the groove waste liquid and transfers PH to 6-9.Stir to flow in groove approximate number minute goes out tank liquid PH4-5, advances behind second groove with Ca (OH)
2Regulate PH to 6-9, remove coagulative precipitation, supernatant liquor flows out surveys PH, COD and colourity, is and handles the back clear liquid.
(3) beneficial effect
Adopt the inventive method treatment of dyeing and printing, COD clearance 〉=60% after testing, percent of decolourization 70-90% compares with traditional treatment process that adds flocculation agent, and the sludge quantity of generation reduces more than 50%, saves processing costs about 60%.The present invention is the physico-chemical process treatment of dyeing and printing, need not add the example of a success of flocculation agent.
The used auxiliary material of the present invention can be reused, and needn't regenerate, and cost of supplementary product only is thousands of units/ton, and the part starting material of making auxiliary material are utilization of waste material, meet the requirement of Sustainable development.The main equipment that adopts treatment of dyeing and printing of the present invention only is a reactor that band stirs, and facility investment is few, and floor space is little, and power consumption is few, can not be subjected to weather, and the geographical environment influence can be widely used in all parts of the country.Produce more than 300 ten thousand tons of dyeing waste waters every day by the whole nation, if adopt the inventive method to handle, single-unit is economized and is added one in flocculation agent, several hundred million units that can economize on the use of funds every year, and therefore of the present invention applying has fairly obvious environmental benefit and economic benefit.
Description of drawings
Accompanying drawing is the process flow sheet of treatment of dyeing and printing.
Embodiment
Embodiment 1
The preparation of auxiliary material
1. get 1000mlFeCL
2Waste liquid is put in the 2000ml beaker, adds 40g nickelous chloride tabular crystal, is stirred to whole dissolvings, and is standby, is called for short the first thing.
2. get 300ml water glass and be put in the 500ml beaker, add the 20ml titanium dioxide, stirred 5-6 minute, the material pasty state liquid that is creamy white, abbreviation second thing.
3. get 600ml first thing and be put in the 1000ml beaker, add the second thing while stirring slowly, the second thing adds soon, just occurs the canescence crystallisate in the beaker.After the second thing adds, continue again slowly to stir, at this moment in beaker, occur crystallisate in a large number, left standstill in restir 2-3 minute, altogether about 560ml canescence crystallisate, leach green liquid, crystallisate is standby, is called for short third thing.
With filter about 450ml green liquid, add 150ml first thing again, continue to make the second thing then and add test, the 580ml grey black crystallisate of getting back of test for the second time also is third thing.
4. above-mentioned 1140ml third thing is put into the 2000ml enamelled cup, adds 25g solid sulphuric acid copper again, heats on gas range after mixing.Constantly stir the stirring material during heating.Heated 15-20 minute, material is the brown particle shape, stop heating after, leave standstill cooling, after 40 minutes, material is the reddish-brown amorphous granular, is required auxiliary material, altogether auxiliary material 985ml, granularity is 0.1-4 centimetre and does not wait that proportion is 0.72, PH3.5.
Waste water is from chemical fibre factory, Henan county, and velveteen waste water is chocolate, frowziness, pH value 10.5, COD
Cr3590mg/l, 800 times of colourities.Use H earlier
2SO
4Transfer waste water pH value to 8.5.Get 300ml waste water in the 500ml beaker, drop into above auxiliary material 35ml, stirring reaction 10 minutes left standstill 5-6 minute.It is 4.5 that upper strata light brown liquid is surveyed pH value.Add 18% concentration C a (OH) then
2Liquid is transferred pH value to 6.5, mixes slightly and just produces a large amount of throw outs, staticly settles, and occurs the supernatant liquor of beige rapidly, the pH value of test supernatant liquor, COD and colourity.
Get 300ml waste water again, add in the beaker of the wet shape reddish-brown auxiliary material of left 36ml, continue above test, test amounts to 3 times, and the test result of 3 supernatant liquors is as follows.
Embodiment 3
Waste water is contained printing and dyeing company limited from Jiangyin City's letter, chemical fibre, grey cloth coating dyeing composite waste, and PH9.0 is purple blue, COD
Cr890mg/l, 380 times of colourities.The wet shape reddish-brown auxiliary material of the 35ml that the foregoing description 2 is left is earlier with clear water washing 1 time, later in the 500ml beaker, mix with the 300ml dyeing waste water, continuously stirring 10 minutes left standstill 1-2 minute again, getting canescence upper strata liquid test pH value is 5.0, adds 18% concentration C a (OH) again
2Transfer PH to 8.5, after the coagulative precipitation, the pH value of test supernatant liquor, COD and colourity repeat above test 2 times, and 3 times the supernatant liquor test result is as follows.
Embodiment 4
Waste water is from Wuxi Samsung printing and dyeing company limited, the cotton dyeing waste-water, and PH6.5 is puce, COD
Cr1067mg/l, 680 times of colourities.The foregoing description 3 remaining 35ml shape reddish-brown auxiliary material that wets with clear water washing 1 time, adds the new auxiliary material of 0.5g earlier then, get the 300ml dyeing waste water in beaker, continuously stirring 10 minutes left standstill 1-2 minute, testing light grey upper strata liquid pH value is 5.0, adds 18% concentration C a (OH) again
2Transfer PH to 8.5, other is identical with embodiment 2,3, and 3 times the supernatant liquor test result is as follows.Being left wet shape reddish-brown auxiliary material in the beaker is 37ml.
Claims (3)
1. the method for a physico-chemical process treatment of dyeing and printing is characterized in that adopting a kind of with SiO
2Be skeleton, the special solid matter that contains titanium, nickel, copper, ferro element, be called for short auxiliary material, be applied to the processing of dyeing waste water, earlier dyeing waste water is transferred PH to 6-9, drop into auxiliary material, auxiliary material: dyeing waste water is 1: 7-9 (V/V), stirring reaction 5-15 minute, left standstill 5-8 minute, take out supernatant liquid, with the Ca (OH) of 15-20% (W/W) concentration
2Make coagulant aids, transfer PH to 6-9, flocculation sediment, supernatant liquor are handles the back clear liquid.
2, the preparation method of the used auxiliary material of method according to claim 1 is characterized in that the preparation of auxiliary material divides 4 processes to finish;
(1) at FeCl
2Add the nickelous chloride xln in the waste liquid, nickelous chloride xln: FeCl
2Waste liquid is 0.01-0.015: 1 (V/V), stir stand for standby use after 5-10 minute, and be called for short the first thing;
(2) add titanium dioxide in water glass, titanium dioxide: water glass is 0.06-0.08: 1 (V/V), and continuously stirring 5-6 minute, the pasty state liquid that is creamy white was called for short the second thing;
(3) in proportion the second thing is added in the first thing slowly the second thing: the first thing is 0.45-0.50: 1 (V/V), and constantly stir, obtain canescence or beige xln, take out filter and do, be called for short third thing;
(4) third thing and solid sulphuric acid copper are mixed in proportion solid sulphuric acid copper: third thing is 0.01-0.015: 1 (V/V), fire insulation heating in the rot-resistant reactor then becomes reddish-brown or taupe amorphous solid, is required auxiliary material.
3, method according to claim 1, it is characterized in that special auxiliary material proportion 0.72, PH3-4 is not dissolved in water, and good dispersiveness is arranged in water, when being applied to treatment of dyeing and printing, can reuse, needn't regenerate, when handling 50-60 that wastewater flow rate reaches the auxiliary material amount doubly after (v/v), replenish with the amount of original auxiliary material amount 1%-2% and to add fresh auxiliary material, to replenish consume.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031127959A CN1300009C (en) | 2003-01-27 | 2003-01-27 | Physical and chemical dyeing and printing effluent treating process throwing no coagulant and the prepn of supplementary material used |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031127959A CN1300009C (en) | 2003-01-27 | 2003-01-27 | Physical and chemical dyeing and printing effluent treating process throwing no coagulant and the prepn of supplementary material used |
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| Publication Number | Publication Date |
|---|---|
| CN1440937A CN1440937A (en) | 2003-09-10 |
| CN1300009C true CN1300009C (en) | 2007-02-14 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105645617B (en) * | 2015-12-30 | 2017-06-30 | 中信环境技术（广州）有限公司 | A kind of dye wastewater treatment device and method |
| CN108285233A (en) * | 2017-01-09 | 2018-07-17 | 北京水木方科技有限公司 | A kind of method of Recovery Purifying titanium white waste liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19618074A1 (en) * | 1996-03-04 | 1997-09-11 | Ind Tech Res Inst | Waste liquor treatment to reduce chemical oxygen demand |
| US6123854A (en) * | 1996-11-08 | 2000-09-26 | Hinomaru Kogyo Corporation | Flocculant compositions and water treatment method using the same |
| CN1296920A (en) * | 2000-12-21 | 2001-05-30 | 费兴祖 | Process for high-quality treatment of waste dyeing water with waste solution of ferrous sulfate or ferrous chloride |
-
2003
- 2003-01-27 CN CNB031127959A patent/CN1300009C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19618074A1 (en) * | 1996-03-04 | 1997-09-11 | Ind Tech Res Inst | Waste liquor treatment to reduce chemical oxygen demand |
| US6123854A (en) * | 1996-11-08 | 2000-09-26 | Hinomaru Kogyo Corporation | Flocculant compositions and water treatment method using the same |
| CN1296920A (en) * | 2000-12-21 | 2001-05-30 | 费兴祖 | Process for high-quality treatment of waste dyeing water with waste solution of ferrous sulfate or ferrous chloride |
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|---|---|
| CN1440937A (en) | 2003-09-10 |
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Assignee: Wuxi Xingyi Coating Environmental Protection Equipment Co., Ltd. Assignor: Fei Xingzu Contract fulfillment period: 2007.2.12 to 2023.1.26 contract change Contract record no.: 2008320000097 Denomination of invention: Physical and chemical dyeing and printing effluent treating process throwing no coagulant and the prepn of supplementary material used Granted publication date: 20070214 License type: Exclusive license Record date: 2008.8.19 |
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Free format text: EXCLUSIVE LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.2.12 TO 2023.1.26 Name of requester: NONE WUXI XINGYI PAINTING ENVIRONMENTAL PROTECTION Effective date: 20080819 |
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Granted publication date: 20070214 Termination date: 20130127 |
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