CN103420468A - Multi-element composite flocculant for treating printing and dying wastewater and textile wastewater and preparing method thereof - Google Patents
Multi-element composite flocculant for treating printing and dying wastewater and textile wastewater and preparing method thereof Download PDFInfo
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Abstract
The invention relates to a multi-element composite flocculant for treating printing and dying wastewater and textile wastewater and a preparing method of the multi-element composite flocculant. The flocculant comprises polymeric aluminium, titanium polysilicic acid aluminium silicate, calcium aluminate powder, aluminium hydroxide gel, konjac glucomannan phosphate, chitosan, sodium silicate and an additive, wherein the deacetylation degree of the chitosan is larger than or equal to 95%. Through appropriate selection of components and proportion, the multi-element composite flocculant has the advantages of being high in flocculation efficiency, small in dosage, wide in temperature application range and pH application range and the like. The multi-element composite flocculant can be used for treatment and purification of the printing and dying wastewater and the textile wastewater and has wide industrialized application prospects and market values.
Description
Technical field
The invention belongs to the dyeing and printing sewage processing technology field, relate more specifically to a kind of polynary composite flocculation agent, preparation method and its usage.
Background technology
Water resources is the necessary resource that the mankind depend on for existence, yet socioeconomic development has but brought the problem demanding prompt solutions such as shortage of water resources, water resource pollution, and the Sustainable development of the mankind's the healthy and earth in its serious threat.Dyeing, as traditional water rich and influential family, is one of important source caused water pollution.Therefore, how effectively to process, purify dyeing waste water and become the key issue that domestic and international environmental protection and Sustainable development mechanism face.
Flocculation technique is one of technology of sewage, purification of waste water processing, and the core of flocculation treatment technology and key point are exactly the choice and operation of flocculation preparation.Flocculation agent is of a great variety, and it mainly is divided into according to inorganic flocculating agent, organic floculant, microbial flocculant and composite flocculation agent.Wherein, inorganic flocculating agent, as Tai-Ace S 150, aluminum chloride, ferric sulfate, iron(ic) chloride etc., it has the advantage that cost is low, but the shortcomings such as flocculation sediment speed is slow, large usage quantity; Organic floculant is generally high molecular polymer, and as polyamine type, quaternary ammonium type, polyacrylamide type etc., it has the advantages such as consumption is few, scum silica frost is few, flocculation ability is strong, but processing costs is high and itself have certain toxicity, and Application Areas is subject to certain restrictions; Microbial flocculant generally by microorganism (as bacterium, actinomycetes.Molds and yeasts etc.) work, but the drawback such as its fermentative production ubiquity raw materials cost is high, fermentation period is long, flocculation activity is low, and flocculating effect is subject to the restriction of microbe species, is difficult to there is universality.
Many reports of existing flocculation agent in prior art, for example:
The Patent Application Publication of CN102897879A a kind of inorganic-organic composite flocculating agent, it comprises a certain proportion of aluminium iron polychloride, polyvinylpyrrolidone, chitosan and red clay, and has the excellent properties such as raw material is easy to get, prepares simply, water treatment effect is good.
The patent of CN101838041B discloses a kind of composite polysaccharide bioflocculant prepared by the complex reaction of polysaccharide bioflocculant, inorganic molysite, and it shows nontoxic, harmless, pollution-free, and the advantage such as flocculation efficiency is high, applied widely.
The Patent Application Publication of CN101717144A a kind of compound coagulant be prepared from by a certain percentage with poly aluminium iron silicate and chitosan, the suitable selection of passing ratio makes composite flocculation agent have stable performance, storage and the advantage such as easy to use, has produced the beneficial effect of synergy.
The Patent Application Publication of CN102674519A a kind ofly take the flocculation agent that polyacrylamide, starch, clorox, Xylo-Mucine, water glass, Potassium Persulphate, S-WAT and water is composited as raw material, its have adding less, flocculation rate fast, produce the plurality of advantages such as mud is few.
Although the flocculation agent of numerous kinds has been developed and has obtained application widely, but how to improve the over-all properties of flocculation agent, need the expense of secondary treatment after reducing flocculation process, and select green, economic flocculation component etc. to remain the major issue of pendulum at sewage treatment area.Thereby, research and develop the focus that efficient polynary composite flocculation agent becomes the research of recent domestic water treatment field.
Summary of the invention
The many defects that exist for prior art, the inventor is through a large amount of further investigations, after having paid sufficient creative work, provides that a kind of flocculation rate is fast, the COD clearance is high, the polynary composite flocculation agent of applied range.
Particularly, the present invention relates generally to three aspects.
First aspect; the present invention relates to a kind of polynary composite flocculation agent, described polynary composite flocculation agent comprises chitosan, water glass and the additive of polymerize aluminum chloride calcium, titanium aluminium silicate polymer magnesium salts, calcium aluminate powder, aluminum hydroxide gel, konjac glucomannan phosphate, degree of deacetylation >=95%.
In described polynary composite flocculation agent, in weight part, its concrete component concentration is as follows:
| Polymerize aluminum chloride calcium | 15-25 |
| Titanium aluminium silicate polymer magnesium salts | 10-20 |
| Calcium aluminate powder | 10-20 |
| Aluminum hydroxide gel | 15-20 |
| Konjac glucomannan phosphate | 5-10 |
| The chitosan of degree of deacetylation>=95% | 6-12 |
| Water glass | 1-5 |
| Additive | 3-12. |
In the present invention, unless otherwise prescribed, the implication of " comprising " be open " comprising " and enclosed " by ... form ".
In described polynary composite flocculation agent of the present invention, the parts by weight of polymerize aluminum chloride calcium are 15-25 part, as are 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts or 25 parts.
In described polynary composite flocculation agent of the present invention, the parts by weight of titanium aluminium silicate polymer magnesium salts are 10-20 part, as are 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts.
In described polynary composite flocculation agent of the present invention, the parts by weight of calcium aluminate powder are 10-20 part, as are 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts.
In described polynary composite flocculation agent of the present invention, the parts by weight of aluminum hydroxide gel are 15-20 part, as are 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts.
In described polynary composite flocculation agent of the present invention, the parts by weight of konjac glucomannan phosphate are 5-10 part, as are 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.
In described polynary composite flocculation agent of the present invention, the parts by weight of the chitosan of degree of deacetylation >=95% are 6-12 part, as are 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts or 12 parts.
In described polynary composite flocculation agent of the present invention, the parts by weight of water glass are 1-5 part, as are 1 part, 2 parts, 3 parts, 4 parts or 5 parts.
In described polynary composite flocculation agent of the present invention, the parts by weight of additive are 3-12 part, as are 3 parts, 6 parts, 9 parts or 12 parts.
In described polynary composite flocculation agent of the present invention, the mixture that additive is pulullan polysaccharide, ZSM-5 molecular sieve, cactus powder, in weight ratio, the ratio of described pulullan polysaccharide, ZSM-5 molecular sieve and cactus powder is 1:1-2:1-2, is preferably 1:1:1.
Second aspect; the present invention relates to the preparation method of above-mentioned polynary composite flocculation agent; specific as follows: that chitosan, water glass and the additive of the polymerize aluminum chloride calcium of above-mentioned weight part, titanium aluminium silicate polymer magnesium salts, calcium aluminate powder, aluminum hydroxide gel, konjac glucomannan phosphate, degree of deacetylation >=95% are added to reaction converter after crushed; be uniformly mixed 3-5 h under 60-70 ℃; product after being uniformly mixed is crossed to 100 mesh sieves, after packing, obtain product.
In described polynary composite flocculation agent of the present invention, polymerize aluminum chloride calcium adopts following step preparation: according to mass ratio, be that 1-1.5:1 takes aluminum oxide and calcium carbonate and mixes, in 800-900 ℃ of lower reacting by heating 6-8 h, then with the cooling rate cool to room temperature of 5-10 ℃/min, obtain intermediate product, it is reaction 1.5-2.5 h in the mass concentration of the 1.5 times of amounts hydrochloric acid that is 50-60% by weight that this intermediate product is dissolved in, and obtains the solid-state polymerization aluminum calcium chloride after evaporate to dryness.
In described polynary composite flocculation agent of the present invention, titanium aluminium silicate polymer magnesium salts adopts following step preparation: the sodium silicate aqueous solution that the preparation mass concentration is 3.5-4.5%, add the sulfuric acid that mass concentration is 30-40% to regulate pH=3-4, stirring at normal temperature reaction 20-30min, then add aluminum chloride in solution, sal epsom and titanium chloride, make aluminium salt, magnesium salts, each metallic element in titanium salt and the mol ratio of silicon are 0.6-0.7:1, heat-up rate with 2-5 ℃/min after stirring is warmed up to 60-80 ℃, slaking 1-2 days at this temperature, obtain titanium aluminium silicate polymer magnesium salts after dry solidification.
In described polynary composite flocculation agent of the present invention, aluminum hydroxide gel adopts following step preparation: take a certain amount of crystalline aluminium hydroxide, add wherein is the mass concentration of the 6 times of amounts hydrochloric acid that is 50-60% and the water of 8 times of amounts by weight, under 100-110 ℃, the condition of 0.2-0.35 Mpa, dissolve, reaction 8-10 h, cooling, precipitation obtains aluminum hydroxide gel.
In described polynary composite flocculation agent of the present invention, konjac glucomannan phosphate adopts following step preparation: in 60-80 ml water, add urea 2-3 g, NaH
2PO
4And Na
2HPO
4Each 3-5 g, add 90-110 g Rhizoma amorphophalli powder wherein after stirring and dissolving, stir, and bakes 0.5-1 h under 155-160 ℃.After cooling, drying konjac glucomannan phosphate.
In described polynary composite flocculation agent of the present invention, cactus powder adopts the preparation of following step: take Root and stem of Cholla through drying, pulverize, cross 80 mesh sieves, drying obtains cactus powder.
The 3rd aspect, the present invention relates to the purposes that above-mentioned polynary composite flocculation agent is processed for printing and dyeing, textile sewage.
The plurality of advantages such as polynary composite flocculation agent of the present invention shows by the synergy between each component that flocculation efficiency is high, adding less, the COD clearance is high and temperature, pH be applied widely, have industrial prospect and marketable value widely.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and purpose only are used for exemplifying the present invention; not real protection scope of the present invention is formed to any type of any restriction, more non-protection scope of the present invention is confined to this.
Preparation example 1: the preparation of polymerize aluminum chloride calcium
Take respectively 150 g aluminum oxide and 150 g calcium carbonate and mix, in 850 ℃ of lower reacting by heating 8 h, then with the cooling rate cool to room temperature of 8 ℃/min, obtain intermediate product, this intermediate product is dissolved in to reaction 2 h in the hydrochloric acid that the mass concentration of 450 g is 50-60%, obtain the solid-state polymerization aluminum calcium chloride after evaporate to dryness, standby.
Preparation example 2: the preparation of titanium aluminium silicate polymer magnesium salts
The sodium silicate aqueous solution that the preparation mass concentration is 4%, add the sulphur acid for adjusting pH that mass concentration is 40%=4, stirring at normal temperature is reacted 30 min, then add aluminum chloride, sal epsom and titanium chloride in solution, making each metal ion in aluminium salt, magnesium salts, titanium salt and the mol ratio of silicon is 0.6:1, heat-up rate with 4 ℃/min after stirring is warmed up to 70 ℃, and at this temperature, slaking is 2 days, obtains titanium aluminium silicate polymer magnesium salts after dry solidification.
Preparation example 3: the preparation of aluminum hydroxide gel
Take 50 g crystalline aluminium hydroxide, adding wherein is the mass concentration of the 300 g hydrochloric acid that is 50% and the water of 400 g by weight, under 105 ℃, the condition of 0.2 Mpa, dissolve, and reaction 8h, cooling, precipitation obtains aluminum hydroxide gel.
Preparation example 4: the preparation of konjac glucomannan phosphate
Add urea 3 g, NaH in 80 ml water
2PO
4And Na
2HPO
4Each 4g, add 100 g Rhizoma amorphophalli powders wherein after stirring and dissolving, stir, and bakes 1 h under 160 ℃.After cooling, drying konjac glucomannan phosphate.
Preparation example 5: the preparation of cactus powder
Take 500 g Root and stem of Cholla through drying, pulverize, cross 80 mesh sieves, drying obtains cactus powder.
Embodiment 1
Take polymerize aluminum chloride calcium 15 g, titanium aluminium silicate polymer magnesium salts 15 g, calcium aluminate powder 20 g, aluminum hydroxide gel 15 g, konjac glucomannan phosphate 6 g, chitosan 8 g, water glass 2 g of degree of deacetylation >=95%, pulullan polysaccharide 2 g, ZSM-5 molecular sieve 2 g, cactus powder 2 g and add after crushed reaction converter; be uniformly mixed 3 h under 65 ℃; product after being uniformly mixed is crossed to 100 mesh sieves; obtain product after packing, obtain polynary composite flocculation agent DF-1.
Embodiment 2
Take polymerize aluminum chloride calcium 20 g, titanium aluminium silicate polymer magnesium salts 10 g, calcium aluminate powder 15 g, aluminum hydroxide gel 20 g, konjac glucomannan phosphate 8 g, chitosan 6 g, water glass 5 g of degree of deacetylation >=95%, pulullan polysaccharide 4 g, ZSM-5 molecular sieve 4 g, cactus powder 4 g and add after crushed reaction converter; be uniformly mixed 5 h under 60 ℃; product after being uniformly mixed is crossed to 100 mesh sieves; obtain product after packing, obtain polynary composite flocculation agent DF-2.
Embodiment 3
Take polymerize aluminum chloride calcium 25 g, titanium aluminium silicate polymer magnesium salts 15 g, calcium aluminate powder 10 g, aluminum hydroxide gel 16 g, konjac glucomannan phosphate 10 g, chitosan 12 g, water glass 1 g of degree of deacetylation >=95%, pulullan polysaccharide 1 g, ZSM-5 molecular sieve 1 g, cactus powder 1 g and add after crushed reaction converter; be uniformly mixed 4 h under 70 ℃; product after being uniformly mixed is crossed to 100 mesh sieves; obtain product after packing, obtain polynary composite flocculation agent DF-3.
Embodiment 4
Take polymerize aluminum chloride calcium 16 g, titanium aluminium silicate polymer magnesium salts 20 g, calcium aluminate powder 12 g, aluminum hydroxide gel 18 g, konjac glucomannan phosphate 5 g, chitosan 10 g, water glass 4 g of degree of deacetylation >=95%, pulullan polysaccharide 3 g, ZSM-5 molecular sieve 3 g, cactus powder 3 g and add after crushed reaction converter; be uniformly mixed 4.5 h under 65 ℃; product after being uniformly mixed is crossed to 100 mesh sieves; obtain product after packing, obtain polynary composite flocculation agent DF-4.
Comparative Examples 1-2
Except not adding polymerize aluminum chloride calcium, implemented Comparative Examples 1 and 2 with the same way as with embodiment 1,3 respectively, obtain composite flocculation agent D1 and D2.
Comparative Examples 3-4
Except not adding titanium aluminium silicate polymer magnesium salts, implemented Comparative Examples 3 and 4 with the same way as with embodiment 1,3 respectively, obtain composite flocculation agent D3 and D4.
Comparative Examples 5-6
Except not adding calcium aluminate powder, implemented Comparative Examples 5 and 6 with the same way as with embodiment 1,3 respectively, obtain composite flocculation agent D5 and D6.
Comparative Examples 7-8
Except not adding aluminum hydroxide gel, implemented Comparative Examples 7 and 8 with the same way as with embodiment 1,3 respectively, obtain composite flocculation agent D7 and D8.
Comparative Examples 9-10
Except not adding konjac glucomannan phosphate, implemented Comparative Examples 9,10 with the same way as with embodiment 1,3 respectively, obtain composite flocculation agent D9 and D10.
Comparative Examples 11-12
Except the chitosan that does not add degree of deacetylation >=95%, implemented Comparative Examples 11,12 with the same way as with embodiment 1,3 respectively, obtain composite flocculation agent D11 and D12.
Comparative Examples 13-14
Except not adding additive, implemented Comparative Examples 13,14 with the same way as with embodiment 1,3 respectively, obtain composite flocculation agent D13 and D14.
Comparative Examples 15-17
Except not adding respectively pulullan polysaccharide, ZSM-5 molecular sieve and cactus powder, implemented Comparative Examples 15-17 with the same way as with embodiment 1, obtain composite flocculation agent D15, D16 and D17.
Comparative Examples 18
Except not adding water glass, implemented Comparative Examples 18 with the same way as with embodiment 1 and obtained composite flocculation agent D18.
Performance test
Flocculation agent is tested disposal effect of dyeing wastewater
Experimental procedure:
1, (pH is 7.6, and turbidity is 280 NTU, and COD is 415.4 mg/L, and colourity is 357 times, and specific conductivity is 0.85 * 10 to get respectively 150 ml printing and dyeing mill waste water
3μ Scm
-1) be placed in respectively 250 ml Erlenmeyer flasks, drop into wherein a certain amount of various flocculation agent under 25 ℃, shake or rock after 20 min sedimentation and flocculate after 30 min and take sample.
2, turbidity adopts the GB13200-91 spectrophotometric determination; Colourity adopts platinum cobalt State Standard Colorimetry to measure, fixed by YS-2000 liquid colourity instrumentation; COD adopts potassium dichromate process to measure;
Its calculation formula is as follows:
Turbidity removal/look/COD leads (%)=(1-
A 1 /
A 0 ) * 100%.
In formula:
A 0 For water sample is processed front value;
A 1 For the value after the water sample processing.
The flocculating effect test result is as shown in table 1.
Table 1. flocculating effect experimental data
3, adopt temperature regulating device that waste water stoste is adjusted to different temperature, and then adopt aforesaid method to carry out flocculation agent treatment of dyeing wastewater experiment under condition of different temperatures, result is as shown in table 2.
Flocculating effect experimental data under table 2. differing temps
4, regulate waste water stoste to different pH with mineral acid or alkali, and then adopt aforesaid method to carry out the experiment of flocculation agent treatment of dyeing and printing under condition of different pH, result is as shown in table 3.
Flocculating effect experimental data under the different pH of table 3.
5, the flocculation rate for the treatment of of dyeing wastewater experiment, the turbidity test result under different flocculation times is as shown in table 4.
The experimental data of table 4. flocculation time on the flocculating effect impact
6, flocculation agent flocculant for treating waste water dosage experiment, add the turbidity results of various dose flocculation agent under flocculation 30 min as shown in table 5.
Table 5. flocculation agent consumption experimental data
Interpretation of result:
As shown in Table 1, polynary composite flocculation agent of the present invention reveals good flocculating effect by the suitable option table of component, and, when using separately the prepared active principle of the application or conventional bodied ferric sulfate as flocculation agent, flocculating effect all significantly descends.
From the result of table 2 and table 3, temperature range and pH scope that polynary composite flocculation agent of the present invention is applicable are all wider, therefore applied widely, are conducive to industrialized application.
As shown in Table 4, polynary composite flocculation agent of the present invention has the short excellent effect of flocculation time, can reach in the short period of time good sewage disposal and decontamination effect improving; And can find out from the result of table 5, polynary composite flocculation agent of the present invention has adding less characteristics, with other flocculation agents, compare, can adopt a small amount of flocculation agent of the present invention to process isodose sewage and can reach good wastewater treatment efficiency, thereby greatly saved the cost of sewage disposal or purification, there are wide market outlook.
In sum, the suitable option table of polynary composite flocculation agent of the present invention by component and ratio reveals that flocculation efficiency is high, adding less, temperature and many excellent properties such as the pH scope of application is wide, and while changing any a kind of component wherein, corresponding effect all reduces the first mate, this has proved apparently the selection of specific components and ratio and has made between each component to show excellent synergy, has obtained beyond thought technique effect.
The purposes that should be appreciated that these embodiment only limits the scope of the invention for the present invention being described but not being intended to.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various changes, modification and/or modification to the present invention, within these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. a polynary composite flocculation agent, it comprises chitosan, water glass and the additive of polymerize aluminum chloride calcium, titanium aluminium silicate polymer magnesium salts, calcium aluminate powder, aluminum hydroxide gel, konjac glucomannan phosphate, degree of deacetylation >=95%.
2. polynary composite flocculation agent as claimed in claim 1, it is characterized in that: in described polynary composite flocculation agent, in weight part, its concrete component concentration is as follows:
。
3. polynary composite flocculation agent as claimed in claim 2, it is characterized in that: the mixture that described additives is pulullan polysaccharide, ZSM-5 molecular sieve, cactus powder, the weight ratio of described pulullan polysaccharide, ZSM-5 molecular sieve and cactus powder is 1:1-2:1-2.
4. polynary composite flocculation agent as described as claim 1-3 any one, it is characterized in that: described polymerize aluminum chloride calcium adopts following step preparation: according to mass ratio, be that 1-1.5:1 takes aluminum oxide and calcium carbonate and mixes, in 800-900 ℃ of lower reacting by heating 6-8 h, then with the cooling rate cool to room temperature of 5-10 ℃/min, obtain intermediate product, it is to react 1.5-2.5h in the mass concentration of the 1.5 times of amounts hydrochloric acid that is 50-60% by weight that this intermediate product is dissolved in, and obtains the solid-state polymerization aluminum calcium chloride after evaporate to dryness.
5. polynary composite flocculation agent as described as claim 1-4 any one, it is characterized in that: described titanium aluminium silicate polymer magnesium salts adopts following step preparation: the sodium silicate aqueous solution that the preparation mass concentration is 3.5-4.5%, add sulphur acid for adjusting pH=3-4 that mass concentration is 30-40%, stirring at normal temperature reaction 20-30 min, then add aluminum chloride in solution, sal epsom and titanium chloride, make aluminium salt, magnesium salts, each metallic element in titanium salt and the mol ratio of silicon are 0.6-0.7:1, heat-up rate with 2-5 ℃/min after stirring is warmed up to 60-80 ℃, slaking 1-2 days at this temperature, obtain titanium aluminium silicate polymer magnesium salts after dry solidification.
6. polynary composite flocculation agent as described as claim 1-5 any one, it is characterized in that: described aluminum hydroxide gel adopts following step preparation: take a certain amount of crystalline aluminium hydroxide, add wherein is the mass concentration of the 6 times of amounts hydrochloric acid that is 50-60% and the water of 8 times of amounts by weight, under 100-110 ℃, the condition of 0.2-0.35 Mpa, dissolve, reaction 8-10 h, cooling, precipitation obtains aluminum hydroxide gel.
7. polynary composite flocculation agent as described as claim 1-6 any one is characterized in that: described konjac glucomannan phosphate adopts following step preparation: in 60-80 ml water, add urea 2-3 g, NaH
2PO
4And Na
2HPO
4Each 3-5 g, add 90-110 g Rhizoma amorphophalli powder wherein after stirring and dissolving, stir, and bakes 0.5-1 h under 155-160 ℃, after cooling, drying konjac glucomannan phosphate.
8. polynary composite flocculation agent as described as claim 1-7 any one is characterized in that: described cactus powder adopts following step preparation: take Root and stem of Cholla through drying, pulverize, cross 80 mesh sieves, drying obtains cactus powder.
9. as the preparation method of the described polynary composite flocculation agent of claim 1-8 any one; it is characterized in that: chitosan, water glass and the additive of the polymerize aluminum chloride calcium of above-mentioned weight part, titanium aluminium silicate polymer magnesium salts, calcium aluminate powder, aluminum hydroxide gel, konjac glucomannan phosphate, degree of deacetylation >=95% are added to reaction converter after crushed; be uniformly mixed 3-5 h under 60-70 ℃; product after being uniformly mixed is crossed to 100 mesh sieves, after packing, obtain product.
10. the purposes that polynary composite flocculation agent as described as claim 1-8 any one is processed for printing and dyeing, textile sewage.
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| CN106477695A (en) * | 2015-08-27 | 2017-03-08 | 中国石油天然气股份有限公司 | Composite flocculation agent, its preparation method and process for treating oil field sewage |
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| CN105668744A (en) * | 2016-04-06 | 2016-06-15 | 太仓市锦达印染有限公司 | Textile dyeing wastewater flocculant |
| CN107758826A (en) * | 2017-12-20 | 2018-03-06 | 葛延瑱 | A kind of preparation method of sewage treatment flocculating agent |
| CN107758826B (en) * | 2017-12-20 | 2018-08-31 | 北京荣士都生物科技有限公司 | A kind of preparation method of sewage treatment flocculating agent |
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| CN109574294A (en) * | 2018-11-12 | 2019-04-05 | 武汉华喻燃能工程技术有限公司 | A method of heavy metal ion is removed using pulullan polysaccharide and aluminium chloride |
| CN114380375A (en) * | 2022-01-19 | 2022-04-22 | 海南绿峰资源开发有限公司 | Preparation method of composite flocculant for treating tailings |
| CN114380375B (en) * | 2022-01-19 | 2023-11-21 | 海南绿峰资源开发有限公司 | Preparation method of composite flocculant for treating tailings |
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