CN102730807A - Technology for preparing hybrid flocculant by gangue base raw material and hybrid flocculant prepared by the same - Google Patents
Technology for preparing hybrid flocculant by gangue base raw material and hybrid flocculant prepared by the same Download PDFInfo
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Abstract
The present invention discloses a technology for preparing hybrid flocculant by gangue base raw material and a hybrid flocculant prepared by the same. The steps of the technology are as follows: preparing the hybrid flocculant by the gangue base waste residue; during the process of synthesis, preparing the gangue base raw material and stirring together the modified gauge base filter residue and acrylamide after alkali and acid extraction; performing vacuum-pumping to pass nitrogen; and adding an initiator to perform polymerization, so as to obtain the gray viscous hybrid flocculant in a gel state. Compare with the prior art, the gangue waste residue of the technology can be fully used, and thus the waste control by waste is realized. The obtained hybrid flocculant has advantages of a strong flocculation ability, high sedimentation speed and high compactness. COD and BOD removal rate of the technology is much higher than that of a single polyacrylamide system and a simple mixture of modified gauge base filter residue and polyacrylamide. The technology also has advantages of less quantity of reagent, relatively higher processing efficiency of waste water of drilling well and coalification, and obviously higher removal efficiency of water turbidity and chroma.
Description
[technical field]
The present invention relates to a kind of preparation technology of material and according to the material of this prepared gained, the process method of preparation hydridization flocculation agent from coal gangue or flyash particularly, and the hydridization flocculation agent that goes out with this prepared.
[background technology]
The flocculation sediment technology is that a kind of processing efficiency is high in sewage treatment process, not only economy but also easy materialization technology.Employed polymeric flocculant is divided into inorganic polymer flocculant and synthetic organic polymer flocculation agent two big classes; Traditional inorganic polymer flocculant is because its dosage is big; Subsidence rate is slow, and certain corrodibility is arranged, and is affected by environment big; And the secondary pollution that causes thus restricts its development.Organic floculant is used for WWT and starts from the end of the fifties; It has compared more advantages with inorganic flocculating agent; Big like: adding less, flocculation ability flco strong, that form, be difficult for few, the non-corrosiveness of waste residue broken, that produce, receive salt, pH value and temperature effect little, but its price is more expensive; And some has certain toxic side effect, and the Use Limitation fruit is limited separately.Therefore; Be to improve processing efficiency, comprehensively inorganic, the organic polymer coargulator advantage of people in recent years is often with the two composite use; But in the water treatment actual mechanical process, need usually to add step by step with organic polymer coargulator with inorganic; Technology is loaded down with trivial details, and facility investment is big, causes use cost corresponding higher.Based on this, composite flocculant arises at the historic moment, and it can overcome many deficiencies of using single flocculation agent; Wide accommodation all has good purifying water effect to lower concentration or high density water quality, colorful wastewater, various industrial sewage, improves organic clearance in the flocculation process; And can reduce the kish ionic concn; Reduce secondary pollution, on the high basis of raising processing efficiency, reduced processing cost, technology simplifies the operation.
The more composite flocculation agent of current research has inorganic-inorganic composite type, inorganic-synthetic organic polymer compound; And the research of inorganic-natural organic high-molecular composite flocculant report is less relatively, and rare especially for the research report of inorganic-organic hybridization thing.Announced on June 2nd, 2010 like State Intellectual Property Office; Publication No. is that the application for a patent for invention " a kind of organic-inorganic in-situ composite flocculant and preparation method thereof " of CN 101717141A discloses a kind of synthesis technique; With the inorganic powder is disperse phase; Add acrylic amide, initiator and solvent composition mixed solution system, carried out home position polymerization reaction 10～24 hours at 40～70 ℃; Wherein, the mass percent that inorganic powder accounts for solution system is 1～60%, and the mass percent that acrylic amide accounts for solution system is 1～50%, and the mass ratio of initiator and acrylic amide is 0.5～2: 100.Said initiator is Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, ABVN, BPO or hydrogen peroxide.In this patented claim embodiment 6 for flyash as inorganic powder, acrylic amide and vinylformic acid prepare inorganic composite floculant as the comonomer in-situ polymerization.Concrete operations are: 0.2g flyash are dissolved in the 50ml zero(ppm) water, add 3g acrylic amide, 2g vinylformic acid, and 60 ℃ of reactions of 60mg Diisopropyl azodicarboxylate 12 hours, logical nitrogen reflux obtains gel-like material after the reaction, broken after the vacuum-drying.But there is following weak point in this kind inorganic-organic hybridization flocculation agent preparation method: 1. raw material selection, and selecting untreated flyash for use is starting material, the prepared using degree is poor; 2. the selection of initiator, selecting Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, ABVN, BPO or hydrogen peroxide for use is initiator, the polymerization efficiency of initiation is low; 3. because the product stability factor, products obtained therefrom needs vacuum-drying, but the product hardness that obtains after the vacuum-drying is very big, pulverizes difficulty, and the product after pulverizing is difficult to disperse in sewage, influences flocculating effect.The efficient and rational research that makes full use of synthetic its hydridization flocculation agent of solid waste is rarely reported.
Solid waste turns waste into wealth, and the treatment of wastes with processes of wastes against one another is environmental improvement and the most promising developing direction of refuse renewable resources.The spoil based raw material mainly comprises coal gangue and flyash.China is the maximum coal mining state in the whole world, is brought to the coal gangue on ground with the exploitation of coal, become maximum solid waste source, so the comprehensive treating process of coal gangue has become, and people pays special attention to and problem demanding prompt solution.Contain elements such as a large amount of iron, silicon, aluminium in the coal gangue, utilize its synthesizing inorganic flocculation agent to cause people's research enthusiasm greatly in recent years.And flyash is through the product behind the power plant high temperature sintering, and wherein silicon, aluminium, ferro element can strippings, and therefore utilizing the various flocculation agents of fly-ash Preparation also is a research focus in flocculation agent field in recent years.The inventor applied for to China national Department of Intellectual Property on 06 10th, 2010; Application number is that disclosing a kind of in 201010197036.5 by name " technology that the preparation of spoil based raw material gathers ferrosilicoaluminum and this prepared go out gather ferrosilicoaluminum flocculation agent " is that main raw material prepares inorganic polymer flocculant with spoil base material---gather the technology of ferrosilicoaluminum; In building-up process, active spoil based raw material is got the raw materials ready, alkali is carried under the heating and pressurizing, acid is carried under the heating and pressurizing, heating state slowly concentrates polymerization down becomes and gathers the ferrosilicoaluminum flocculation agent.This technology is prepared to go out to gather the ferrosilicoaluminum flocculation agent, it is characterized in that being the tawny semi-solid material.To carry the back filter residue often discarded but alkali is carried in the acid of this kind technology, utilizes and insufficient.
[summary of the invention]
Technical assignment of the present invention is the deficiency to above prior art; Provide a kind of spoil based raw material that utilizes to prepare the hydridization flocculation agent that hydridization flocculation agent technology and this prepared go out; The coal gangue waste residue that this kind technology utilization has extracted the ferrosilicoaluminum element is a base material, passes through the spoil base-hydridization flocculation agent that obtains Cheap highly effective with acrylic amide polymerization under action of evocating.
The technical scheme that the present invention solves its technical problem is: a kind of spoil based raw material prepares hydridization flocculation agent technology; It is characterized in that: with spoil base material is main raw material, and preparation hydridization flocculation agent is in building-up process; Pulverize activation spoil based raw material through alkali carry, acid is carried, be washed till in the neutral filter residue and add acrylic amide; Under nitrogen protection, add the initiator initiated polymerization, its concrete process step is following:
(1) get the raw materials ready: activation spoil based raw material is pulverized;
(2) alkali is carried: in the activated feedstock of step 1, add 10～30%NaOH solution, with coal gangue fine powder solvent and solute weight ratio be 2: 1 to 8: 1; Reaction times 2～3h, solid-liquid separation, the filtrating of collection is the alkali extract;
(3) acid is carried: in the filter residue of step 2, add the inorganic acid solution of 10%～30% concentration, solvent and solute weight ratio is 2: 1 to 8: 1; Reaction times 2～3h, solid-liquid separation, the filtrating of collection is sour extract, and the filter residue of collecting is a modification spoil base filter residue;
(4) react: to neutral, adding concentration is 5%～20% acrylic amide with the flushing of step 3 gained modification spoil base filter residue, and modification spoil base filter residue and acrylic amide weight ratio are 0.2: 1 to 1: 1, and churning time 0.5～2h gets head product;
(5) deoxidation: vacuumize logical nitrogen;
(6) polymerization: adding concentration is 0.5%～3% initiator; Head product and initiator weight ratio are 50: 1 to 120: 1; 43～80 ℃ of polymerization temperatures, polymerization time 5～10h gets thick gel state hydridization flocculation agent.
Inorganic acid solution in the above-mentioned steps 3 is meant the mixing acid of hydrochloric acid, sulfuric acid any one or arbitrary proportion.
Spoil base activated feedstock in the above-mentioned steps 1 is a flyash.
Or the spoil base activated feedstock preparation technology in the above-mentioned steps 1 is: the colliery powder comminution is thin, adds CaCO
3Perhaps Na
2CO
3, perhaps CaCO
3Mixture with NaOH mixes, and 600 ℃～800 ℃ add thermal bake-out, is incubated 1 hour and gets spoil base activated feedstock.
Concrete operations in the above-mentioned steps 5 are at first container to be vacuumized under the magnetic agitation, and logical then nitrogen repeats 1～3 time.
Initiator described in the above-mentioned steps 6 is a ceric ammonium nitrate, or the persulfuric acid salt, or ceric ammonium nitrate and 1: 1 mixture of persulphate weight ratio.
Persulfuric acid salt described in the above-mentioned steps 6 comprises ammonium persulphate, Sodium Persulfate, Potassium Persulphate.
Above-mentioned steps 2 is 1～6 MPa with step 3 reaction pressure, and temperature of reaction is 100～120 ℃.
The thick gel state hydridization flocculation agent adding weight ratio that above-mentioned steps 6 is produced is 1: 1 a water, has carried out the stirring homogenize with dispersing emulsification machine, obtains stable suspension at last.
Above-mentioned spoil based raw material prepares the prepared hydridization flocculation agent that goes out of hydridization flocculation agent technology, it is characterized in that being the thick gel state material of grey.
Compared with prior art, the present invention has the following advantages:
1, the starting material utilization is abundant: the acid of spoil based raw material is carried alkali and is carried sour extract and the alkali extract of back gained and can be used for preparing and gather the ferrosilicoaluminum flocculation agent; The sex change filter residue is used for preparing the hydridization flocculation agent; Reduce production cost and end product price, reached the second stage employ of waste resource;
2, gained hydridization flocculation agent flocculation ability is high: in the active spoil based raw material a large amount of active silicas and aluminum oxide are arranged, in alkali lye, activated alumina and silicon oxide and alkali react, and its structure is further changed; Its specific surface area is significantly increased, increased its adsorptive power, and its interlamellar spacing is increased, reduced the intercalation potential barrier; Intercalation polymeric is taken place more easily, and the polymerization degree increases, and polymerization time shortens, and therefore can obviously improve the flocculation ability of flocculation agent; Flocculating effect is good, and is adding less, and the flco of formation is thick; COD, BOD and oleaginousness clearance are high, so lowered cost for wastewater treatment, economic benefit is high;
3, polymerization is abundant: select ceric ammonium nitrate for use, or the persulfuric acid salt, or ceric ammonium nitrate and persulphate mixture, acrylamide triggered radical polymerization and copolymerization effect are superior to other initiators;
4, proterties is stable: hydridization flocculation agent of the present invention has good ageing resistance, can have room temperature environment and does not degrade with gel state, has both save Drying of gels and shattering process, has also save dry powder flocculating agent swelling process before use; Improved flocculating property; Reduced the environmental pollution in product energy consumption and the production process, the suspension that gel state perhaps dilutes homogenize formation can use, and flocculation rate is fast; After adding in the sewage; Flocculation rate is very fast, and flocculation very soon is easy to use after the adding.
[embodiment]
Embodiment 1, utilizes fly-ash Preparation hydridization flocculation agent, and concrete steps are following:
(1) get the raw materials ready: flyash is crossed 80 mesh sieves;
(2) alkali is carried: in the activated feedstock of step 1, add 10%NaOH solution, with flyash fine powder solvent and solute weight ratio be 2: 1; Reaction times 2h, solid-liquid separation, the filtrating of collection is the alkali extract;
(3) acid is carried: in the filter residue of step 2, add the hydrochloric acid soln of 10% concentration, solvent and solute weight ratio is 2: 1; Reaction times 2h, solid-liquid separation, the filtrating of collection is sour extract, and the filter residue of collecting is the modified coal ash filter residue;
(4) react: to neutral, adding concentration is 5% acrylic amide with the flushing of step 3 gained modified coal ash filter residue, and filter residue and acrylic amide weight ratio are 0.2: 1, and churning time 0.5h gets head product;
(5) deoxidation: vacuumize logical nitrogen 1 time;
(6) polymerization: add ammonium persulphate, concentration is 0.5%; Head product and ammonium persulphate weight ratio are 50: 1; 43～45 ℃ of polymerization temperatures, polymerization time 5h gets the thick gel state material of grey, is the hydridization flocculation agent.
Embodiment 2, utilize fly-ash Preparation hydridization flocculation agent, and concrete steps are following:
(1) get the raw materials ready: flyash is crossed 80 mesh sieves;
(2) alkali is carried: in the activated feedstock of step 1, add 15%NaOH solution, with flyash fine powder solvent and solute weight ratio be 5: 1; Reaction times 2h, solid-liquid separation, the filtrating of collection is the alkali extract, temperature of reaction: 100 ℃, reaction pressure is 5 MPas;
(3) acid is carried: in the filter residue of step 2, add the sulphuric acid soln of 15% concentration, solvent and solute weight ratio is 5: 1; Reaction times 2h, solid-liquid separation, the filtrating of collection is sour extract, and the filter residue of collecting is the modified coal ash filter residue, temperature of reaction: 100 ℃, reaction pressure is 5 MPas;
(4) reaction: to neutral, adding concentration is 10% acrylic amide with the flushing of step 3 gained modified coal ash filter residue, and modified coal ash and acrylic amide mass ratio are 0.3: 1, churning time 1h;
(5) deoxidation: vacuumize logical nitrogen 2 times;
(6) polymerization: add ceric ammonium nitrate, concentration is 1.7%; Head product and ceric ammonium nitrate weight ratio are 80: 1; 75 ℃ of polymerization temperatures, polymerization time 6h gets the thick gel state material of grey, is the hydridization flocculation agent.
Embodiment 3, utilize fly-ash Preparation hydridization flocculation agent, and concrete steps are following:
(1) get the raw materials ready: flyash is crossed 100 mesh sieves;
(2) alkali is carried: in the activated feedstock of step 1, add 30%NaOH solution, with flyash fine powder solvent and solute weight ratio be 5: 1; Reaction times 3h, solid-liquid separation, the filtrating of collection is the alkali extract, temperature of reaction: 120 ℃, reaction pressure is 1 MPa;
(3) acid is carried: in the filter residue of step 2, add the salpeter solution of 30% concentration, solvent and solute weight ratio is 5: 1; Reaction times 3h, solid-liquid separation, the filtrating of collection is sour extract, and the filter residue of collecting is the modified coal ash filter residue, temperature of reaction: 120 ℃, reaction pressure is 1 MPa;
(4) reaction: to neutral, adding concentration is 20% acrylic amide with the flushing of step 3 gained modified coal ash filter residue, and modified coal ash and acrylic amide weight ratio are 1: 1, churning time 2h;
(5) deoxidation: earlier container is vacuumized under stirring, logical then nitrogen repeats 3 times;
(6) polymerization: add ceric ammonium nitrate and 1: 1 complex concentration of ammonium persulphate weight ratio 2%; The weight ratio of head product and ceric ammonium nitrate and ammonium persulphate mixture is 100: 1; 50～55 ℃ of polymerization temperatures, polymerization time 10h gets thick gel state hydridization flocculation agent.
Embodiment 4, utilize fly-ash Preparation hydridization flocculation agent, and concrete steps are following:
(1) get the raw materials ready: flyash is crossed 100 mesh sieves;
(2) alkali is carried: in the activated feedstock of step 1, add 20%NaOH solution, with flyash fine powder solvent and solute weight ratio be 8: 1; Reaction times 3h, solid-liquid separation, the filtrating of collection is the alkali extract; Temperature of reaction: 1 ℃, reaction pressure is 6 MPas;
(3) acid is carried: in the filter residue of step 2, add the hydrochloric acid soln of 20% concentration, solvent and solute weight ratio is 8: 1; Reaction times 3h, solid-liquid separation, the filtrating of collection is sour extract, and the filter residue of collecting is the modified coal ash filter residue, temperature of reaction: 150 ℃, reaction pressure is 6 MPas;
(4) reaction: to neutral, adding concentration is 15% acrylic amide with the flushing of step 3 gained modified coal ash filter residue, and filter residue and acrylic amide weight ratio are 0.8: 1, churning time 2h;
(5) deoxidation: earlier container is vacuumized under the magnetic agitation, logical then nitrogen repeats 2 times;
(6) polymerization: add ceric ammonium nitrate and 1: 1 complex concentration of Sodium Persulfate weight ratio 3%; The weight ratio of head product and ceric ammonium nitrate, Sodium Persulfate mixture is 120: 1; 75～80 ℃ of polymerization temperatures, polymerization time 10h gets thick gel state hydridization flocculation agent;
(7) the thick gel state hydridization flocculation agent adding weight ratio that is produced is 1: 1 a water, has carried out the stirring homogenize with dispersing emulsification machine, homogenize time 1min, and rotating speed 8000r/min obtains stable suspension at last.
Embodiment 5, utilize fly-ash Preparation hydridization flocculation agent, and concrete steps are following:
(1) get the raw materials ready: flyash is crossed 100 mesh sieves;
(2) alkali is carried: in the activated feedstock of step 1, add 15%NaOH solution, with flyash fine powder solvent and solute weight ratio be 5: 1; Reaction times 2.5h, solid-liquid separation, the filtrating of collection is the alkali extract;
(3) acid is carried: in the filter residue of step 2, add the sulphuric acid soln of 15% concentration, solvent and solute weight ratio is 5: 1; Reaction times 2.5h, solid-liquid separation, the filtrating of collection is sour extract, and the filter residue of collecting is the modified coal ash filter residue;
(4) reaction: to neutral, adding concentration is 5% acrylic amide with the flushing of step 3 gained modified coal ash filter residue, and filter residue and acrylic amide weight ratio are 0.2: 1, churning time 0.5h;
(5) deoxidation: vacuumize logical nitrogen;
(6) polymerization: add ceric ammonium nitrate and 1: 1 complex concentration of Potassium Persulphate weight ratio 2%; The weight ratio of head product and ceric ammonium nitrate, Potassium Persulphate mixture is 50: 1; 43～45 ℃ of polymerization temperatures, polymerization time 8h gets thick gel state hydridization flocculation agent;
(7) the thick gel state hydridization flocculation agent adding weight ratio that is produced is 1: 1 a water, has carried out the stirring homogenize with dispersing emulsification machine, obtains stable suspension at last.
Among the embodiment 1～5, it is auxiliary that flyash need not acvator, and omitted the step of high-temperature roasting, and the cost and the energy save material.
Embodiment 6, utilize coal gangue to prepare the hydridization flocculation agent, and the batching in the step 1 is a coal gangue, pulverize levigately, add and the CaCO of volume of material than 3: 4
3Mix, 600 ℃ add thermal bake-out, are incubated 1 hour and get spoil base activated feedstock.All the other processing parameter steps are identical with technology among the embodiment 1.Use CaCO in this kind process program
3Activation, cost value is cheap, and sedimentation is fast.
Embodiment 7, utilize coal gangue to prepare the hydridization flocculation agent, and the batching in the step 1 is a coal gangue, pulverize levigately, are incorporated as and the Na of volume of material than 3: 4
2CO
3, the heating maturing temperature is 800 ℃, is incubated 1 hour and gets spoil base activated feedstock.All the other processing parameter steps are identical with technology among the embodiment 2.
Embodiment 8, utilize coal gangue to prepare the hydridization flocculation agent, and the batching of step 1 is a coal gangue, pulverize levigately, add acvator and be the CaCO with 1: 1 mixed of volume of material than 3: 4
3With NaOH; The heating maturing temperature is 700 ℃, is incubated 1 hour and gets spoil base activated feedstock.All the other processing parameter steps are identical with technology among the embodiment 3.
Embodiment 9, utilize coal gangue to prepare the hydridization flocculation agent, and wherein, the batching in the step 1 is a coal gangue, pulverize levigately, add and the CaCO of volume of material than 3: 4
3Mix, 700 ℃ add thermal bake-out, are incubated 1 hour and get spoil base activated feedstock.All the other processing parameter steps are identical with technology among the embodiment 4.
Embodiment 10, utilize coal gangue to prepare the hydridization flocculation agent, and wherein, the batching in the step 1 is a coal gangue, pulverize levigately, are incorporated as and the Na of volume of material than 3: 4
2CO
3, the heating maturing temperature is 600 ℃, is incubated 1 hour and gets spoil base activated feedstock.All the other processing parameter steps are identical with technology among the embodiment 5.
In above-mentioned each technology, the sour extract that alkali extract that step 3 draws and step 4 draw can be used for producing and gather the ferrosilicoaluminum flocculation agent, and its operation can be 1: 1 to 2: 1 for the volume ratio of sour extract and alkali extract; 70 ℃～100 ℃ of temperature of reaction dropwise add sour extract in the alkali extract, and the mixed solution of soda acid extracting solution is carried out slowly concentrating polymerization, and resultant tawny semi-solid gathers the ferrosilicoaluminum flocculation agent.The present invention's conception is to make full use of the residue that the preparation of spoil based raw material gathers the ferrosilicoaluminum flocculation agent; In the active spoil based raw material a large amount of active silicas and aluminum oxide are arranged; In alkali lye, activated alumina and silicon oxide and alkali react, and its structure is further changed; Its specific surface area is significantly increased, and is 172.4m like its specific surface area of sex change coal gangue behind the acid-alkali treatment among the embodiment 7
2/ g (handles surface area 28.3m far above the active coal spoil without acid-alkali treatment
2/ g).Removing specific surface area significantly increases, and has increased outside its adsorptive power, and acid-alkali treatment also makes its interlamellar spacing increase, and has reduced the intercalation potential barrier, and intercalation polymeric is taken place more easily, and the polymerization degree increases, and therefore can obviously improve the flocculation ability of flocculation agent.
The suspension that hydridization flocculation agent dilution homogenize forms adds and is prone in the sewage disperse, and system is even, and adds dose and control more easily, and is easy to use.
It is as shown in table 1 to use this technology gained hydridization flocculation agent to handle Shengli Oil Field well-drilling waste water treatment effect.Wherein, the CODcr analytical procedure is GB/T11914-1989, and the BOD analytical procedure is HJ/T86-2002, and the oil-contg analytical procedure is GB/T16488-1996.Each embodiment gained hydridization flocculation agent of this technology is an experimental group, and control group I is single SEPIGEL 305, and control Group II is the simple mixtures of SEPIGEL 305 and modified gangue filter residue, and each is organized dosage and is 0.2mg/ml.
This technology of table 1 gained hydridization flocculation agent is to the treatment effect of Shengli Oil Field well-drilling waste water
Drop into behind the well-drilling waste water with the control group I of dosage and control group II and not see obvious flocculation phenomenon in 2 hours.
Above result shows: this technology gained hydridization flocculation agent processing Shengli Oil Field well-drilling waste water flocculation ability is strong, and settling velocity is fast, and the flco degree of compactness of formation is higher, even under the speed of 50r/min, stirred 1 minute, flco does not peel off yet.Well-drilling waste water and coalification waste water treatment efficiency are higher, and its COD and BOD clearance are far above single polyacrylamide amine system, and the simple mixtures of SEPIGEL 305 and coal gangue waste residue, and dosage is few.The turbidity of water and color removal efficient are obviously high.Experimental result shows; The hydridization flocculation agent that obtains is handled triumph well-drilling waste water COD clearance and is reached 85.5～96.2%; BOD clearance 83.5～94.5%; And still darker with the simple mixtures processed waste water color of the single SEPIGEL 305 of dosage and SEPIGEL 305 and modified gangue filter residue, drop into and do not see obvious flocculation phenomenon in 2 hours behind the well-drilling waste water, and simple mechanical mixture does not have significant difference than its single polyacrylamide amine system yet.
In addition; Hydridization flocculation agent of the present invention has good ageing resistance; Can there be room temperature environment and do not degrade with gel state; Both save Drying of gels and shattering process, also save dry powder flocculating agent swelling process before use, improved flocculating property, reduced the environmental pollution in product energy consumption and the production process.Embodiment 1,2,3,6,7,8 products are gel state, can directly use, and embodiment 4,5,9,10 dilutions become stable suspension also can be used, easy to use.
Claims (10)
1. a spoil based raw material prepares hydridization flocculation agent technology; It is characterized in that: with spoil base material is main raw material, and preparation hydridization flocculation agent is in building-up process; Pulverize activation spoil based raw material through alkali carry, acid is carried, be washed till in the neutral filter residue and add acrylic amide; Under nitrogen protection, add the initiator initiated polymerization, its concrete process step is following:
(1) get the raw materials ready: activation spoil based raw material is pulverized;
(2) alkali is carried: in the activated feedstock of step (1), add 10～30%NaOH solution, with activation spoil base fine powder solvent and solute weight ratio be 2: 1 to 8: 1; Reaction times 2～3h, solid-liquid separation, the filtrating of collection is the alkali extract;
(3) acid is carried: in the filter residue of step (2), add the inorganic acid solution of 10%～30% concentration, solvent and solute weight ratio is 2: 1 to 8: 1; Reaction times 2～3h, solid-liquid separation, the filtrating of collection is sour extract, and the filter residue of collecting is a modification spoil base filter residue;
(4) react: to neutral, adding concentration is 5%～20% acrylic amide with the flushing of step (3) gained modification spoil base filter residue, and modification spoil base filter residue and acrylic amide weight ratio are 0.2: 1 to 1: 1, and churning time 0.5～2h gets head product;
(5) deoxidation: vacuumize logical nitrogen;
(6) polymerization: adding concentration is 0.5%～3% initiator; Head product and initiator weight ratio are 50: 1 to 120: 1; 43～80 ℃ of polymerization temperatures, polymerization time 5～10h gets thick gel state hydridization flocculation agent.
2. spoil based raw material according to claim 1 prepares hydridization flocculation agent technology, it is characterized in that inorganic acid solution in the said step (3) is meant the mixing acid of hydrochloric acid, sulfuric acid any one or arbitrary proportion.
3. spoil based raw material according to claim 1 prepares hydridization flocculation agent technology, it is characterized in that the spoil base activated feedstock in the said step (1) is a flyash.
4. spoil based raw material according to claim 1 prepares hydridization flocculation agent technology, and it is characterized in that the spoil base activated feedstock preparation technology in the said step (1) is: the colliery powder comminution is thin, adds CaCO
3Perhaps Na
2CO
3, perhaps CaCO
3Mixture with NaOH mixes, and 600 ℃～800 ℃ add thermal bake-out, is incubated 1 hour and gets spoil base activated feedstock.
5. spoil based raw material according to claim 1 prepares hydridization flocculation agent technology, it is characterized in that the concrete operations in the said step (5) at first vacuumize container for stirring down, and logical then nitrogen repeats 1～3 time.
6. spoil based raw material according to claim 1 prepares hydridization flocculation agent technology, it is characterized in that the initiator described in the said step (6) is a ceric ammonium nitrate, or the persulfuric acid salt, or ceric ammonium nitrate and 1: 1 mixture of persulphate weight ratio.
7. spoil based raw material according to claim 6 prepares hydridization flocculation agent technology, it is characterized in that the persulfuric acid salt described in the said step (6) comprises ammonium persulphate, Sodium Persulfate, Potassium Persulphate.
8. spoil based raw material according to claim 1 prepares hydridization flocculation agent technology, it is characterized in that said step (2) and step (3) reaction pressure are 1～6 MPa, and temperature of reaction is 100～120 ℃.
9. prepare hydridization flocculation agent technology according to arbitrary described spoil based raw material in the claim 1 to 8; It is characterized in that it is 1: 1 water that thick gel state hydridization flocculation agent that said step (6) produced adds weight ratio; Carry out the stirring homogenize with dispersing emulsification machine, obtained stable suspension at last.
10. the spoil based raw material of claim 1 prepares the prepared hydridization flocculation agent that goes out of hydridization flocculation agent technology, it is characterized in that being the thick gel state material of grey.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410208672.1A CN103991940B (en) | 2011-03-29 | 2011-03-29 | A kind of coal ash for manufacturing is for hybrid flocculant technique |
| CN201110088436.7A CN102730807B (en) | 2011-03-29 | 2011-03-29 | Technology for preparing hybrid flocculant by gangue base raw material and hybrid flocculant prepared by the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110088436.7A CN102730807B (en) | 2011-03-29 | 2011-03-29 | Technology for preparing hybrid flocculant by gangue base raw material and hybrid flocculant prepared by the same |
Related Child Applications (1)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106630242A (en) * | 2015-10-29 | 2017-05-10 | 宝山钢铁股份有限公司 | Process and device for rapidly removing total organic carbon and chroma in coking reverse osmosis concentrated water |
| CN108079937A (en) * | 2018-01-26 | 2018-05-29 | 辽宁大学 | A kind of adsorbent based on discarded gangue and its preparation method and application |
| CN114315024A (en) * | 2021-12-25 | 2022-04-12 | 广东台泉环保科技有限公司 | Emergency treatment process for garbage penetrating fluid |
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| CN106219710A (en) * | 2016-09-27 | 2016-12-14 | 合肥天翔环境工程有限公司 | Water treatment composite flocculant |
| CN107857332A (en) * | 2017-11-28 | 2018-03-30 | 安徽比伦生活用纸有限公司 | A kind of method applied flyash in papermaking black purified treatment |
| CN107935143A (en) * | 2017-12-04 | 2018-04-20 | 包头钢铁（集团）有限责任公司 | Inorganic coagulant and preparation method thereof |
| CN111389346B (en) * | 2020-03-24 | 2022-09-09 | 陕西煤化选煤技术有限公司 | Preparation of composite magnetic material modified fly ash and method for treating slime water |
| CN111704194B (en) * | 2020-06-30 | 2022-09-13 | 广西夏阳环保科技有限公司 | Composite sewage treatment agent based on inorganic non-metallic mineral material and application |
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| CN101830477A (en) * | 2010-06-10 | 2010-09-15 | 济宁医学院 | Technology for preparing PSAF (Polymer Silica Aluminum Ferrum) by waste rock base raw material and PSAF flocculant prepared by same |
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| CN106630242A (en) * | 2015-10-29 | 2017-05-10 | 宝山钢铁股份有限公司 | Process and device for rapidly removing total organic carbon and chroma in coking reverse osmosis concentrated water |
| CN108079937A (en) * | 2018-01-26 | 2018-05-29 | 辽宁大学 | A kind of adsorbent based on discarded gangue and its preparation method and application |
| CN108079937B (en) * | 2018-01-26 | 2020-07-14 | 辽宁大学 | Adsorbent based on waste coal gangue and preparation method and application thereof |
| CN114315024A (en) * | 2021-12-25 | 2022-04-12 | 广东台泉环保科技有限公司 | Emergency treatment process for garbage penetrating fluid |
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| CN103991940A (en) | 2014-08-20 |
| CN103991940B (en) | 2016-02-03 |
| CN102730807B (en) | 2014-07-23 |
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