CN102757119B - Preparation method of composite type inorganic polymeric flocculating agent and application thereof - Google Patents

Preparation method of composite type inorganic polymeric flocculating agent and application thereof Download PDF

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CN102757119B
CN102757119B CN201210252716.1A CN201210252716A CN102757119B CN 102757119 B CN102757119 B CN 102757119B CN 201210252716 A CN201210252716 A CN 201210252716A CN 102757119 B CN102757119 B CN 102757119B
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composite type
type inorganic
flocculation agent
inorganic polymer
polymer flocculation
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CN201210252716.1A
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CN102757119A (en
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苏建文
徐家栋
陈建华
王彩冬
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山东新时代药业有限公司
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Abstract

The invention discloses preparation of a composite type inorganic polymeric flocculating agent and an application thereof, and belongs to the field of wastewater treatment. The flocculating agent takes ferrous sulfate septihydrate and sodium silicate as main raw materials; and fewer metal ions including Zn<2+>, Mg<2+>, Ca<2+> and the like are added, and steps of activating, mixing, oxidizing, curing and the like are carried out to prepare the composite type inorganic polymeric flocculating agent. A preparation process of the flocculating agent has the advantages of simple preparation process, low cost and excellent flocculating, de-coloring and dephosphorization effects on sewage; a product is liquid and the product stability is good; and the product can be directly added so that the use is convenient.

Description

A kind of preparation method of composite type inorganic polymer flocculation agent and application thereof

Technical field

The present invention relates to a kind of preparation and application of flocculation agent, relate in particular to a kind of preparation and application of composite type inorganic polymer flocculation agent, belong to field of waste water treatment.

Background technology

Flocculation sedimentation is a kind of not only economy but also simple sewage water treatment method that is generally used at present improving sewage treating efficiency both at home and abroad.According to the chemical constitution of flocculation agent, be divided into inorganic coagulant and organic floculant.

Flocculation agent is in the market mainly aluminium system and iron-based flocculating agent, as Tai-Ace S 150, aluminum chloride, polymerize aluminum chloride (PAC), polyaluminium sulfate (PAS), ferric sulfate, iron(ic) chloride, poly-ferric chloride (PFC) and bodied ferric sulfate (PFS) etc.After aluminium based flocculating agent is disposed of sewage, cause the aluminium content in water outlet to increase, due to the cytogenetic toxicity of aluminium, aluminium causes various diseases after water cycle enters tap water, threatens human health.And iron-based flocculating agent is little to environment and human health risk after using, so iron-based flocculating agent becomes the research heat subject of the scientific domain of flocculating in recent years, and iron-based flocculating agent has the development trend that replaces aluminum salt flocculant at present.Bodied ferric sulfate (PFS) is a kind of well behaved flocculation agent, but after processing, effluent color dilution is higher, and the single bodied ferric sulfate polymerization degree is not high, long-term storage is unstable, easily produce precipitation, therefore in bodied ferric sulfate, introducing organic and inorganic composition carries out the composite modified focus that becomes Recent study to it.

In Chinese patent 200710067347.8, disclose a kind of synthetic method of bodied ferric sulfate, but the synthetic polymeric ferric sulfate flocculant basicity of the method is higher, and basicity is higher, stability is poorer; In Chinese patent 200910042578.2, disclose a kind of iron-based compound water treatment agent FPFS-1 and preparation method, but iron-based composite flocculant prepared by the method is not specifically set forth its decolorizing effect and case history; In Chinese patent 200510049584.2, disclose a kind of composite water purifying agent of use in waste water treatment, but in water purification agent component prepared by the method, aluminum chloride content is high, therefore easily produces secondary pollution.

Summary of the invention

In order to overcome the deficiencies in the prior art, to the invention reside in, provide a kind of composite type inorganic polymer flocculation agent and preparation method thereof.This flocculation agent good stability, good to the flocculation of sewage, decolouring, phosphor-removing effect, product is liquid, easy to use, can be used for the processing of high, medium and low concentration wastewater from chemical industry and municipal effluent; Its preparation method technique is simple, with low cost, without poisonous and harmful ion, can not cause secondary pollution to environment.

The measuring method of index described in the present invention: full weight of iron mark: adopt dichromate titration (GB14591-2006) to measure; Reducing substances is (with Fe 2+meter) massfraction: adopt permanganate titration (GB14591-2006) to measure; Basicity: adopt sodium hydroxide titration (GB14591-2006) to measure; COD-chemical oxygen demand (COD): adopt dichromate titration (GB11914-89) to measure; Colourity: adopt extension rate method (GB11903-1989) to measure; PH value: adopt glass electrode method (GB6920-86) to measure; Total phosphorus: adopt ammonium molybdate spectrophotometry (GB11893-89) to measure.

One of the object of the invention is to disclose a kind of composite type inorganic polymer flocculation agent preparation method, this preparation method be take Producing Titanium Dioxide by product iron vitriol and is made bodied ferric sulfate as main raw material, with widely used water glass, make the poly-silicic acid superpolymer of activation, bodied ferric sulfate carries out complexing with the poly-silicic acid superpolymer of activation, form the polymeric new type water flocculant for treating of multinuclear, add Zn simultaneously 2+, Mg 2+, Ca 2+ion, through the synthetic composite type inorganic polymer flocculation agent of the processes such as overactivation, miscible, oxidation, slaking, composite type inorganic polymer flocculation agent preparation method of the present invention comprises following steps:

1) activation: by after water glass dilute with water, add the vitriol oil, stirring at normal temperature 2.0h carries out activated polymerization, and stirring velocity is 100-120 rev/min, obtains work in-process A;

2) miscible: in work in-process A, to add successively iron vitriol, water, the vitriol oil, Zinc Sulphate Heptahydrate, magnesium sulfate heptahydrate, Calcium Chloride Powder Anhydrous etc., under 40 ℃ of conditions, stir above-mentioned substance is dissolved, stirring velocity is 120-150 rev/min, obtains work in-process B;

3) oxidation: slowly drip sodium chlorate and potassium permanganate in work in-process B, be stirred to sodium chlorate and potassium permanganate dropwises under 55-70 ℃ of condition, stirring velocity is 120-150 rev/min, obtains work in-process C;

4) slaking: work in-process C continuously stirring 3.0h under 55-60 ℃ of condition is carried out to slaking, and stirring velocity is 110-130 rev/min, obtains composite type inorganic polymer flocculation agent.

Wherein the umber of various supplementary material components described above is: iron vitriol is 55～65 parts, be preferably 57-60 part, Zinc Sulphate Heptahydrate is 1.0～1.5 parts, be preferably, 1.2-1.5 part, magnesium sulfate heptahydrate is 1.5～2.0 parts, be preferably 1.8-2.0 part, Calcium Chloride Powder Anhydrous is 1.0～1.5 parts, be preferably 1.2-1.5 part, sodium chlorate is 3.0～3.8 parts, be preferably 3.4-3.7 part, water glass is 0.5～1.0 part, be preferably 0.6-0.8 part, the vitriol oil is 3.6～5.0 parts, be preferably 3.9-4.5 part, potassium permanganate is 0.3～0.5 part, be preferably 0.35-0.45 part.Wherein iron vitriol, water glass are the main supplementary materials that generates high molecular polymer, zinc sulfate, magnesium sulfate, calcium chloride are for improving decolouring, the phosphor-removing effect of product, sodium chlorate is oxygenant, the vitriol oil is used for regulating acidity, catalyzer potassium permanganate is conducive to Reaction time shorten, improves polymerization efficiency.Composite type inorganic polymer flocculation agent preparation flow figure of the present invention can be referring to Figure of description 1.

Two of the object of the invention is to provide a kind of composite type inorganic polymer flocculation agent, and this composite type inorganic polymer flocculation agent adopts the preparation method of the present invention's flocculation agent described above to make.Wherein the appearance character of this composite type inorganic polymer flocculation agent is reddish-brown thick liquid, its quality index as shown in Table 1:

Table one: the quality index of composite type inorganic polymer flocculation agent

Project Index The massfraction of full iron ??11.5-13％ Reducing substances is (with Fe 2+Meter) massfraction (≤) ??0.005％ Basicity ??13-16％ Density (20 ℃) ??1.48-1.53g/cm 3 PH (1% aqueous solution) value ??2-3

Three of object of the present invention is to provide a kind of application of above-mentioned composite type inorganic polymer flocculation agent, i.e. the application of above-mentioned composite type inorganic polymer flocculation agent in sewage disposal, and wherein said sewage is preferably chemical pharmaceutical waste water and municipal effluent.The embodiment of the present invention 4 and 5 adopts flocculating settling simultaneous test, use respectively inorganic polymer flocculant and commercially available polymerization ferrous sulfate flocculation agent prepared by the present invention to process chemical pharmaceutical waste water and municipal effluent, experimental results show that, inorganic polymer flocculant prepared by the present invention is compared with certain commercially available polymerization ferrous sulfate, adding less, the flco producing is free settling greatly and more, more excellent to chroma in waste water, COD, total phosphorus removal effect.

Composite type inorganic polymer flocculation agent of the present invention and preparation method thereof, compared with prior art, its innovation and the effect reaching are as described below:

1) adopt active silicic acid as coagulant aids, can strengthen the synergistic effect of coagulation, the volume of increase medicament sweeps and net is caught ability, introduces silicate ion simultaneously and improves medicament stability;

2) Zn in reactant 2+, Mg 2+, Ca 2+do not participate in polymerization process, with free state, exist, performance synergy, obviously improves flocculation, decolouring, phosphor-removing effect;

3) iron vitriol, water glass wide material sources, cheap, and various supplementary materials, without poisonous and harmful ion, can not cause secondary pollution to environment;

4) under normal temperature, be liquid, can directly add use, easy to operate;

5) reasonable compatibility of various supplementary materials make product have flocculating effect good, have decolouring dephosphorization function, the advantage such as applied widely concurrently, can be used for COD, to be greater than 5000mg/l, COD be that 1000-5000mg/l and COD are less than the high, medium and low different concns chemical pharmaceutical waste water of 1000mg/l or the processing of municipal effluent.

Accompanying drawing explanation

Fig. 1 is used the inventive method to prepare the schematic flow sheet of composite type inorganic polymer flocculation agent.

Embodiment

Below will further illustrate the present invention by specific embodiment, but it should be appreciated by those skilled in the art that the specific embodiment of the invention and do not limit the present invention in any way.Within taking up an official post and how all fall into protection scope of the present invention with replacement on basis of the present invention.

Embodiment 1:

After 5.52 kilograms of water glass (water glass massfraction is 57%) are diluted by 20 kg of water, add in reactor, add 3.8 kilograms of the vitriol oils, stirring at normal temperature 2h, carries out activated polymerization, and stirring velocity 100-120 rev/min obtains work in-process A; In work in-process A, add successively 116 kilograms of iron vitriols, 34.1 kilograms, water, 3.6 kilograms of the vitriol oils, 3.0 kilograms of Zinc Sulphate Heptahydrates, 4.0 kilograms of magnesium sulfate heptahydrates, 3.0 kilograms of Calcium Chloride Powder Anhydrouss, temperature of reaction kettle is increased to 40 ℃, stirring is dissolved above-mentioned substance, stirring velocity is 120-150 rev/min, obtains work in-process B; In work in-process B, drip 6.2 kilograms of sodium chlorate, 0.6 kilogram, potassium permanganate, temperature of reaction kettle is increased to and under 60 ℃ of conditions, is stirred to sodium chlorate and potassium permanganate dropwises simultaneously slowly, and stirring velocity is 120-150 rev/min, obtains work in-process C; Keep continuously stirring 3.0h under 55-60 ℃ of condition of temperature of reaction kettle to carry out slaking, stirring velocity is 110-130 rev/min, finally obtains composite type inorganic polymer flocculation agent.

Embodiment 2:

After 3.46 kilograms of water glass (water glass massfraction is 57%) are diluted by 15 kg of water, add in reactor, add 3.5 kilograms of the vitriol oils, stirring at normal temperature 2h, carries out activated polymerization, and stirring velocity 100-120 rev/min obtains work in-process A; In work in-process A, add successively 130 kilograms of iron vitriols, 26.1 kilograms, water, 6.3 kilograms of the vitriol oils, 2.0 kilograms of Zinc Sulphate Heptahydrates, 3.0 kilograms of magnesium sulfate heptahydrates, 2.0 kilograms of Calcium Chloride Powder Anhydrouss, temperature of reaction kettle is increased to 40 ℃, stirring is dissolved above-mentioned substance, stirring velocity is 120-150 rev/min, obtains work in-process B; In work in-process B, drip 7.6 kilograms of sodium chlorate, 0.84 kilogram, potassium permanganate, temperature of reaction kettle is increased to stir under 65 ℃ of conditions and is oxidizing to sodium chlorate and potassium permanganate dropwises simultaneously slowly, and stirring velocity is 120-150 rev/min, obtains work in-process C; Keep continuously stirring 3.0h under 60-70 ℃ of condition of temperature of reaction kettle to carry out slaking, stirring velocity is 110-130 rev/min, finally obtains composite type inorganic polymer flocculation agent.

Embodiment 3:

After 4.62 kilograms of water glass (water glass massfraction is 57%) are diluted by 20 kg of water, add in reactor, add 4.0 jin of the vitriol oils, stirring at normal temperature 2h, carries out activated polymerization, and stirring velocity 100-120 rev/min obtains work in-process A; In work in-process A, add successively 122 kilograms of iron vitriols, 48 kilograms, water, 5.0 kilograms of the vitriol oils, 2.6 kilograms of Zinc Sulphate Heptahydrates, 3.4 kilograms of magnesium sulfate heptahydrates, 2.4 kilograms of Calcium Chloride Powder Anhydrouss, temperature of reaction kettle is increased to 40 ℃, stirring is dissolved above-mentioned substance, stirring velocity is 120-150 rev/min, obtains work in-process B; In work in-process B, drip 7.1 kilograms of sodium chlorate, 0.77 kilogram, potassium permanganate, temperature of reaction kettle is increased to stir under 55 ℃ of conditions and is oxidizing to sodium chlorate and potassium permanganate dropwises simultaneously slowly, and stirring velocity is 120-150 rev/min, obtains work in-process C; Keep continuously stirring 3.0h under 55-60 ℃ of condition of temperature of reaction kettle to carry out slaking, stirring velocity is 110-130 rev/min, finally obtains composite type inorganic polymer flocculation agent.

Embodiment 4:

Get two parts of the chemical industry pharmacy waste water 1000mL of Shandong a certain chemical pharmaceutical enterprise and be placed in respectively two 1000mL beakers, the composite type inorganic polymer flocculation agent that portion adds present method to prepare, portion adds certain commercially available polymeric ferric sulfate flocculant (Linyi Jin Yuan green technology company limited), two parts are all stirred after 5 minutes and form flco, get respectively supernatant liquor and measure after standing sedimentation 30min.Result is as follows:

Table two: the treatment effect simultaneous test to chemical pharmaceutical waste water

Embodiment 5:

Get two parts of a certain municipal sewage plant, Shandong municipal effluent 1000mL and be placed in respectively two 1000mL beakers, the composite type inorganic polymer flocculation agent that portion adds present method to prepare, portion adds certain commercially available polymeric ferric sulfate flocculant (Linyi Jin Yuan green technology company limited), two parts are all stirred after 5 minutes and form flco, get respectively supernatant liquor and measure after standing sedimentation 30min.Result is as follows:

Table three: the treatment effect simultaneous test to municipal effluent

Claims (8)

1. a preparation method for composite type inorganic polymer flocculation agent, is characterized in that described preparation method comprises the following steps:
1) activation: by after water glass dilute with water, add the vitriol oil, stirring at normal temperature 2.0h carries out activated polymerization and obtains work in-process A;
2) miscible: in work in-process A, to add successively iron vitriol, water, the vitriol oil, Zinc Sulphate Heptahydrate, magnesium sulfate heptahydrate, Calcium Chloride Powder Anhydrous, under 40 ℃ of conditions, stir and make above-mentioned substance dissolve to obtain work in-process B;
3) oxidation: slowly drip sodium chlorate and potassium permanganate under 55-70 ℃ of condition in work in-process B, stirring and dissolving obtains work in-process C;
4) slaking: work in-process C continuously stirring 3.0h under 55-60 ℃ of condition is obtained to composite type inorganic polymer flocculation agent;
In wherein said preparation method, the umber of each component is: iron vitriol is 55～65 parts, Zinc Sulphate Heptahydrate is 1.0～1.5 parts, magnesium sulfate heptahydrate is 1.5～2.0 parts, Calcium Chloride Powder Anhydrous is 1.0～1.5 parts, sodium chlorate is 3.0～3.8 parts, water glass is 0.5～1.0 part, and the vitriol oil is 3.6～5.0 parts, and potassium permanganate is 0.3～0.5 part.
2. the preparation method of composite type inorganic polymer flocculation agent as claimed in claim 1, is characterized in that the umber of each component in described preparation method is:
Iron vitriol is 57-60 part, and Zinc Sulphate Heptahydrate is 1.2-1.5 part, and magnesium sulfate heptahydrate is 1.8-2.0 part, Calcium Chloride Powder Anhydrous is 1.2-1.5 part, and sodium chlorate is 3.4-3.7 part, and water glass is 0.6-0.8 part, the vitriol oil is 3.9-4.5 part, and potassium permanganate is 0.3～0.4 part.
3. the composite type inorganic polymer flocculation agent that described in claim 1 or 2, the preparation method of composite type inorganic polymer flocculation agent prepares.
4. composite type inorganic polymer flocculation agent as claimed in claim 3, is characterized in that its quality index is: the massfraction of full iron is 11.5-13%; Reducing substances is with Fe 2+meter, in described composite type inorganic polymer flocculation agent, the massfraction of reducing substances is≤0.005%; Basicity is 13-16%; In the time of 20 ℃, density is 1.48-1.53g/cm3; The pH value of described composite type inorganic polymer flocculation agent 1% aqueous solution is 2-3.
5. composite type inorganic polymer flocculation agent as claimed in claim 3, is characterized in that its appearance character is reddish-brown thick liquid.
6. the application of composite type inorganic polymer flocculation agent claimed in claim 3 in sewage disposal.
7. application as claimed in claim 6, is characterized in that described sewage is chemical pharmaceutical waste water or municipal effluent.
8. the application of composite type inorganic polymer flocculation agent as claimed in claim 6, is characterized in that described composite type inorganic polymer flocculation agent has decolouring dephosphorization function.
CN201210252716.1A 2012-07-15 2012-07-15 Preparation method of composite type inorganic polymeric flocculating agent and application thereof CN102757119B (en)

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CN103964555A (en) * 2014-04-19 2014-08-06 青岛食之礼中草药研究所 Compound type water treatment flocculating agent and preparation method thereof
CN103922453B (en) * 2014-05-14 2016-03-16 山东盛阳集团有限公司 A kind of coking chemical waste water flocculation agent and preparation method thereof and application
CN104495997A (en) * 2015-01-09 2015-04-08 刘树芹 Printing and dyeing wastewater cleaning agent, as well as preparation method and application thereof
CN105502610A (en) * 2016-01-28 2016-04-20 叶君芝 Efficient sewage dephosphorizing flocculating agent and preparation method thereof
CN106865714A (en) * 2017-03-20 2017-06-20 天津中瑞水处理剂有限公司 A kind of composite type polymeric flocculant and preparation method thereof
CN107445276A (en) * 2017-09-11 2017-12-08 杨帅 Composite environment-friendly type flocculant and its preparation method and application
CN108773891A (en) * 2018-06-05 2018-11-09 任丘市佳孚化工有限公司 A kind of dephosphorization agent and preparation method thereof

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CN101439897A (en) * 2008-07-03 2009-05-27 中国环境科学研究院 Preparation of composite flocculant for recovering phosphor in sewerage and phosphor recovering process

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