CN102432090B - Method for preparing flocculation aid for pretreating blue algae biogas slurry - Google Patents
Method for preparing flocculation aid for pretreating blue algae biogas slurry Download PDFInfo
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Abstract
The invention relates to a method for preparing a flocculation aid for pretreating blue algae biogas slurry, and belongs to the technical field of wastewater treatment. The method comprises the following steps of: initiating free radical polymerization of an acrylamide (AM) monomer by using high-valence cerium salt and pentaerythritol as an oxidation reduction system to prepare star polyacrylamide (SPAM), performing chloramination reaction on the SPAM and NaClO, performing Hofmann rearrangement to convert part of amide group into an active isocyanate group, and reacting with .OH in starch to prepare starch-grafted-SPAM (ST-g-SPAM). A rigid and flexible reticular macromolecular structure is formed by grafting the polyacrylamide with a flexible star structure onto a rigid chain serving as aframework of the starch and has a more expanded conformation, so a better flocculation effect can be achieved compared with that of the common linear polymeric flocculant; and the flocculation aid has the characteristics of small using amount, wide adaptable pH range and the like, is convenient to operate and use, and is safe and non-toxic.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to a kind of for the pretreated coagulant aids preparation method of blue alga biogas slurry.
Background technology
The blue-green algae organic content is abundant, and it is carried out producing methane through anaerobic fermentation is that present blue algae resource utilizes a kind of comparatively effectively method of disposal.But the blue-green algae anaerobically fermenting can produce a large amount of blue alga biogas slurries after producing biogas, contains COD, total phosphorus, the NH of higher concentration
3(COD is 350-1000 mg/L to the pollutents such as-N, and TP is 80-350 mg/L, NH
3-N is 15-90 mg/L, turbidity 60-150NTU), and the evil fishy odor is arranged, can discharge after must be treated up to standard, otherwise can cause secondary pollution.At present, processing rarely has report to blue alga biogas slurry both at home and abroad, in view of blue alga biogas slurry turbidity, COD, higher this water quality characteristics of total phosphorous, particularly for the total phosphorus of high density, adopts biological process to process and generally is difficult to obtain satisfied removal effect.Flocculation sedimentation has higher precipitation clearance as a kind of comparatively effectively pretreatment method for wastewater to the suspended solids in waste water and total phosphorus.The present invention intends for the synthetic a kind of high-efficient coagulant aide of blue alga biogas slurry water quality characteristics, blue alga biogas slurry being carried out pre-treatment, thinks that follow-up deep biochemical processing lightens the load.
Inorganic polymer flocculant is strong to the sewage pre-treatment suitability of various complicated ingredients, but has the shortcomings such as the flco of generation is little, dosage is large.Coordinate inorganic polymer flocculant to use coagulant aids, catch interaction energy because of its powerful bridge formation, net and obtain the turbidity removal effect that flocculates preferably, and can greatly reduce the consumption of inorganic polymer flocculant.As the polyacrylamide (PAM) that generally uses at present etc., but the acrylamide monomer that decomposes can have damage neural system, is detrimental to health, and has environmental risk.Therefore, efficient, the nontoxic water treatment coagulant aid of preparation is the focus of present flocculation agent research.As the patent of invention of patent publication No. CN1868909A, a kind of compound diatomite coagulant aids for the garbage leachate sewage disposal is disclosed, by add a certain proportion of r-Al in diatomite
2O
3Molecular material makes compound diatomite flocculation be arranged in the garbage leachate sewage disposal simultaneously and help solidifying dual function, realizes fast neutralization, flocculation, absorption and the sedimentation of sewage.The patent of invention of patent publication No. CN101012080A and CN101012079A, disclose with one of commercially available ammonium acetate, potassium permanganate, water glass, the properties-correcting agent that is mixed with 0.1-1% carries out modification to plant amylum and algae bio molecular substance, a kind of natural biological coagulant aids that develops, itself and aluminum salt flocculant are used in conjunction with, and can increase the effect that net is caught small suspended particle, and the throw out alumen ustum of formation is large, sedimentation is rapid, greatly reduces the characteristics of the usage quantity of aluminium salt.Starch source is extensive, cheap, it is a kind of natural polymer recyclability resource of biodegradable six-membered cyclic, contain multiple hydroxyl, the chemical modifications such as the esterification by hydroxyl, etherificate, oxidation, crosslinked, graft copolymerization, its active group number increases greatly, and polymkeric substance is the cladodification structure, and the flocculation group of dispersion has stronger seizure and short heavy effect to particulate matter in suspension system.One of application of treated starch is exactly as flocculation agent, have nontoxic, be easy to the advantages such as biological degradation.The product of starch and Star-shape Polyacrylamide grafting is harmless, because this product is take the hydrophilic stiff chain of starch as skeleton, is equipped with flexible Star-shape Polyacrylamide and props up the macromole that chain formation is tempered toughness with gentleness.Therefore can be widely used at industrial circles such as water treatment, oil production, papermaking, ore dressings.
Summary of the invention
The objective of the invention is for solving in blue alga biogas slurry solids content highlyer, be difficult to sedimentation, and general flocculation agent produces the little problem of flco.Be coagulant aids by the starch-grafted Star-shape Polyacrylamide (ST-g-SPAM) that makes, be used in conjunction with the processing blue alga biogas slurry with the inorganic flocculating agent polysilicate aluminum ferric chloride, form the flco alumen ustum large, sedimentation fast and greatly reduce the inorganic flocculating agent usage quantity.
The present invention seeks to be achieved by the following measures: a kind of for the pretreated coagulant aids of blue alga biogas slurry, synthetic take Zulkovsky starch as material modification.
A kind of preparation method for blue alga biogas slurry pre-treatment coagulant aids, carry out according to following step:
One, Star-shape Polyacrylamide (SPAM) colloid is synthetic:
Monomer acrylamide (AM), reductive agent tetramethylolmethane and oxygenant ceric ammonium nitrate are mixed with the aqueous solution that mass concentration is 5-10% respectively, add AM solution and reductant solution in reaction flask, reaction flask vacuumizes rear inflated with nitrogen and repeatedly seals after 3 abundant deoxygenations, add a certain amount of oxygenant, it is mixed, then reaction flask is inserted in 47.5 ℃ of waters bath with thermostatic control, reaction 16h namely gets the SPAM colloid;
Two, the preparation of ST-g-SPAM:
(1) in the SPAM colloid that the NaClO of 10 ℃ and NaOH mixed solution is added to 10 ℃ under stirring action, temperature control namely gets Huffman (Hofmann) rearrangement product of SPAM at 35 ℃ of reaction 20min;
(3) get Zulkovsky starch and distilled water according to 1/20(g/mL) ratio puts into container, and in logical nitrogen situation, 80 ℃ of lower gelatinization 90min, then be cooled to 48 ℃ of temperature of reaction in thermostat water bath;
(4) the hofmann rearrangement product with SPAM is added in gelatinization of starch solution, reacts 40min under 48 ℃, with the 4mol/L sulphuric acid soln, reaction medium is used by alkalescence subsequently to transfer to subacidity pH=6-7, and reaction 20min uses anhydrous Na
2SO
3Termination reaction.Use the 6mol/L hcl acidifying, pH=3-4 pours acidizing fluid in the ethanol of 10 times of its volumes, separates out white depositions, uses washing with acetone, and 60 ℃ of vacuum-dryings get thick product; Be that the ethylene glycol of 6:4, the mixed liquid dipping of glacial acetic acid wash 3 times with volume ratio, be drying to obtain coagulant aids ST-g-SPAM power-product under 60 ℃.
Tetramethylolmethane in aforesaid method: the mol ratio of ceric ammonium nitrate and acrylamide: n (OH): n (Ce
4+): n (AM)=1:1:117-3:1:105.
N in aforesaid method (AM): n (NaOH): n (NaClO)=1:1:2.
In aforesaid method, starch and AM mass ratio are 1:1.5.
ST-g-SPAM coagulant aids of the present invention help solidifying principle: in blue alga biogas slurry, solids content is higher, be difficult to sedimentation, coagulant aids ST-g-SPAM has the reticulated structure of coupling hardness with softness, the flco adsorpting aggregation that inorganic flocculating agent can be produced together, multi-faceted seizure suspended particles play the effect of " net is caught ", form than big flocculating body, accelerate floc settling velocity, better bring into play inorganic flocculating agent charge neutrality ST-g-SPAM adsorption bridging synergy.
principal feature of the present invention: the Polyacrylamide Grafted of flexible star structure is formed the net macromolecular structure of tempering toughness with gentleness to the skeleton of starch stiff chain, has the conformation that more stretches, thereby can obtain than the better flocculating effect of common linear polymeric flocculant, be applied to ST-g-SPAM in the pre-treatment of blue alga biogas slurry as coagulant aids, after adding, inorganic flocculating agent adds coagulant aids, the electrical neutralizing effect of inorganic flocculating agent and the bridge formation throwing out of organic polymer coargulator are combined, utilize the reticulated structure of coupling hardness with softness of coagulant aids ST-g-SPAM, the flco adsorpting aggregation that inorganic flocculating agent can be produced together, multi-faceted seizure suspended particles, has the flco of formation large, the advantage that settling velocity is fast, and water quality treatment is limpid, the waste residue water ratio is low, sludge volume is little, flocculating effect is better than the treatment effect that uses separately inorganic flocculating agent under the same terms, its effect of flocculant is remarkable.It is few that this flocculation agent has a consumption, adapts to the pH scope wide, easy for operation, the characteristics such as safety non-toxic.
Description of drawings
Fig. 1 is the infrared spectrogram of the starch-grafted Star-shape Polyacrylamide of coagulant aids (ST-g-SPAM) in the present invention.
Embodiment
The composition principle of ST-g-SPAM coagulant aids of the present invention is: take high price cerium salt and tetramethylolmethane as redox system, cause the radical polymerization of AM monomer, make SPAM, SPAM and NaClO carry out the chloramination reaction, reset the rear section amide group through Hofmann and change active isocyanate groups into, make ST-g-SPAM with OH reaction in starch.The ST-g-SPAM infrared spectrogram shows: at 3435cm
-1The strong broad peak at place is the stretching vibration absorption peak of acid amides N-H key, and this is overlapped generation of absorption peak due to the stretching vibration of-OH and N-H key; At 2925cm
-1Neighbouring is methylene radical-CH
2-the stretching vibration absorption peak, 1667cm
-1Neighbouring is the stretching vibration absorption peak of carbonyl C=O in amide group; At 1417cm
-1Near the forearm peak that occurs be C-C bond bending vibration absorption peak; 1000-1225cm
-1Between absorption peak obvious especially, with the C-O group, and 936cm
-1And 763cm
-1The place is the glucose ring vibration absorption peak, and this explanation product is starch-grafted Star-shape Polyacrylamide multipolymer.
The ST-g-SPAM coagulant aids preparation that the present invention makes below is provided and is applied to 5 embodiment of blue alga biogas slurry:
Embodiment 1
Monomer A M, reductive agent tetramethylolmethane and oxygenant ceric ammonium nitrate are mixed with respectively the aqueous solution of 5% mass concentration in advance, add the AM solution of 30mL and contain reductive agent 1.8 * 10 in reaction flask
-4The aqueous solution of mol, reaction flask vacuumize (inflated with nitrogen) 3 times repeatedly, fully seal after deoxygenation, add to contain oxygenant 1.8 * 10
-4The aqueous solution of mol shakes reaction flask it is mixed, and then reaction flask is inserted in 47.5 ℃ of waters bath with thermostatic control, and reaction 16h namely gets the SPAM colloid.With the NaClO of the 0.02mol of 10 ℃ and 0.04mol NaOH mixed solution be added under stirring action in the SPAM solution of 10 ℃,, temperature control namely gets the Hofmann rearrangement product of SPAM at 35 ℃ of reaction 20min.
Be 1:1.5 according to starch and AM mass ratio, the 1g Zulkovsky starch is put into reactor, add the distilled water of 20mL, in logical nitrogen situation, 80 ℃ of lower gelatinization 90min, then be cooled to 48 ℃ of temperature of reaction in thermostat water bath.
Rearrangement product is added in gelatinization of starch solution, reacts 40min under 48 ℃, with the 4mol/L sulphuric acid soln, reaction medium solution is transferred to subacidity pH=6-7 by alkalescence subsequently, reaction 20min uses the 0.84g anhydrous Na
2SO
3Termination reaction.Use the 6mol/L hcl acidifying, pH=3-4 pours acidizing fluid in the ethanol of 10 times of its volumes, separates out white depositions, uses washing with acetone, and 60 ℃ of vacuum-dryings get thick product.Wash 3 times with the ethylene glycol of 6:4, the mixed liquid dipping of glacial acetic acid, be drying to obtain the flocculation agent power-product under 60 ℃.Gained ST-g-SPAM dry powder is made into the 1g/L solution for later use.
Blue alga biogas slurry is carried out flocculation treatment, use polysilicate aluminum ferric chloride to make flocculation agent, the definite former water flocculation of chamber beaker test uses separately the optimum quantum of utilization of polysilicate aluminum ferric chloride to be the 4mL/250mL blue alga biogas slurry at first by experiment.During compound use, raw water turbidity is 120NTU, polysilicate aluminum ferric chloride dosage 1mL, and when coagulant aids solution dosage was 4mL, delivery turbidity was 1.6NTU, clearance reaches 98.66%.
Embodiment 2-5
Embodiment 2-5 is to have adopted in the coagulant aids building-up process different monomer concentrations, oxygenant consumption, reductive agent consumption, NaClO consumption, NaOH consumption and starch consumption from the difference of embodiment 1, and other raw material consumption is all identical with operational condition.The proportioning raw materials of embodiment 1-5 sees Table 1, and corresponding blue alga biogas slurry treatment effect sees Table 2.
Table 1
Table 2
Claims (1)
1. preparation method who is used for blue alga biogas slurry pre-treatment coagulant aids is characterized in that carrying out according to following step:
One, the Star-shape Polyacrylamide colloid is synthetic:
It is the 5-10% aqueous solution that monomer acrylamide, reductive agent tetramethylolmethane and oxygenant ceric ammonium nitrate are mixed with mass concentration respectively, add AM solution and reductant solution in reaction flask, reaction flask vacuumizes rear inflated with nitrogen and repeatedly seals after 3 abundant deoxygenations, add a certain amount of oxygenant, it is mixed, then reaction flask is inserted in 47.5 ℃ of waters bath with thermostatic control, reaction 16h namely gets the SPAM colloid; The mol ratio of tetramethylolmethane, ceric ammonium nitrate and acrylamide: 1:1:117-3:1:105 wherein;
Two, the preparation of ST-g-SPAM:
(1) in the SPAM colloid that the NaClO of 10 ℃ and NaOH mixed solution is added to 10 ℃ under stirring action, temperature control namely gets the hofmann rearrangement product of SPAM at 35 ℃ of reaction 20min; The mol ratio of acrylamide, NaOH and NaClO: 1:1:2 wherein;
(2) get Zulkovsky starch and put into container according to the 1g Zulkovsky starch than the ratio of 20 mL distilled water with distilled water, in logical nitrogen situation, 80 ℃ of lower gelatinization 90min, then be cooled to 48 ℃ of temperature of reaction in thermostat water bath, wherein starch and AM mass ratio: 1:1.5;
(3) the hofmann rearrangement product with SPAM is added in gelatinization of starch solution, reacts 40min under 48 ℃, with the 4mol/L sulphuric acid soln, reaction medium is used by alkalescence subsequently to transfer to subacidity pH=6-7, and reaction 20min uses anhydrous Na
2SO
3Termination reaction;
Use the 6mol/L hcl acidifying, pH=3-4 pours acidizing fluid in the ethanol of 10 times of its volumes, separates out white depositions, uses washing with acetone, and 60 ℃ of vacuum-dryings get thick product; Be that the ethylene glycol of 6:4, the mixed liquid dipping of glacial acetic acid wash 3 times with volume ratio, be drying to obtain coagulant aids ST-g-SPAM power-product under 60 ℃.
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| CN103484371B (en) * | 2013-09-30 | 2016-01-06 | 福州大学 | A kind of environment-friendly type collects the method for micro-algae |
| FR3016363B1 (en) * | 2014-01-15 | 2017-05-26 | Snf Sas | AQUEOUS SOLUTION OF ACRYLAMIDE-DERIVED CATIONIC COPOLYMERS, PROCESS FOR PREPARATION AND USE |
| CN103936119B (en) * | 2014-04-18 | 2015-04-08 | 芜湖凯奥尔环保科技有限公司 | Polysilicate ferric aluminum chloride/fluorescent brightener composite cyanobacteria treatment agent and manufacturing method thereof |
| CN103936123B (en) * | 2014-04-18 | 2015-04-08 | 芜湖凯奥尔环保科技有限公司 | Oxidation-reduction powdery blue algae treating agent and production method thereof |
| CN106699964B (en) * | 2016-11-15 | 2019-04-09 | 湖北兴发化工集团股份有限公司 | A kind of anion-polyacrylamide flocculant, preparation method and applications |
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