CN104829782A

CN104829782A - Preparation method of polymeric flocculant

Info

Publication number: CN104829782A
Application number: CN201510237156.6A
Authority: CN
Inventors: 周建; 颜玉荣
Original assignee: Suzhou Xiangyuan Special Fine Chemical Co Ltd
Current assignee: Suzhou Xiangyuan Special Fine Chemical Co Ltd
Priority date: 2015-05-12
Filing date: 2015-05-12
Publication date: 2015-08-12

Abstract

The invention discloses a preparation method of a polymeric flocculant, which is characterized in that the polymeric flocculant is prepared by taking acrylamide (AM), trimethylamine hydrochloride, epoxy chloropropane, tetrachloroethane, methacrylic acid, deionized water, and the like as raw materials and by the following steps: Step 1, a first intermediate (3-chloro-2-hydroxypropyl-trimethyl ammonium chloride) is synthesized; Step 2, a second intermediate (methylacryloy acyloxy-2-hydroxypropyl-trimethyl ammonium chloride) is prepared; and step 3, a cationoid flocculating agent is copolymerized. With the adoption of the method, the prepared polymeric flocculant is high in viscosity average molecular weight, and is particularly applicable to treatment of industrial anion waste water.

Description

A kind of preparation method of polymeric flocculant

Technical field

The invention belongs to field of fine chemical, be specifically related to a kind of preparation method of polymeric flocculant.

Background technology

The treatment process of current trade effluent mainly contains chemical method (oxidation style, Coagulation Method, electrolytic process), physico-chemical processes (absorption method, membrane technique) and biochemical process (throwing bacterium method, anaerobic-aerobic technique).Organic trade effluent is rich in for papermaking, process hides etc., many employing biochemical processs and Coagulation with Treatment.Because the organic substance biological metabolism in these waste water is slow, be difficult to thorough degraded, thus the biochemical treatment time is long, and treatment facility and running expense are very high.Flocculation deposition seperation method is that technology very universal in wastewater treatment, particularly polymeric flocculant cause extensive concern both domestic and external with advantages such as its good flocculating effect, decoloring ability and easy operations.

Publication number be CN103910417A application discloses a kind of composite flocculation agent, this flocculation agent is by inorganic polymer flocculant and Cationic Polyacrylamide Flocculant compound or by inorganic polymer flocculant and anion-polyacrylamide flocculation agent compound, the ratio of the compound use of inorganic polymer flocculant and Cationic Polyacrylamide Flocculant is by weight, 400-500:1-4, the ratio of the compound use of inorganic polymer flocculant and anion-polyacrylamide flocculation agent is by weight, 400-500:1-4.Publication number is the patent application of CN102167431B, disclose a kind of preparation method of the cationic composite flocculating agent for waste drilling fluids disposal, first from discarded collagen, the larger gelatin of relative molecular mass is extracted by alkali process hydrolysis, then different hydrolytic reagent is utilized, extracted gelatin is hydrolyzed into further the moderate collagen protein of relative molecular mass, tanning mechanism in recycling tanning chemistry, choose suitable metal ion load on collagen protein, a kind of cationic composite flocculating agent can be obtained, and the rejected well drilling liquid in anionic property is flocculated.

The flocculation agent mainly carboxyl macromolecular compound of existing industrial application, common are acrylate homopolymer, hydro-polyacrylamide (HPAM), sulfomethylation polyacrylamide etc., but above-mentioned flocculation agent for oil field, process hides, deinking workshop, paper mill produce a large amount of anion-containing waste water and sludge treatment effect poor.Because sewage PH value is lower, flocculation sediment is difficult, and common flocculation agent adds can not negatively charged ion in neutralized wastewater effectively, adds excessively can cause coagulated particles redispersion again, increases the difficulty of aftertreatment, improves processing cost.

Summary of the invention

Goal of the invention: existing treatment technology is not good for the negatively charged ion water treatment effect that pH value is lower, the present invention develops a kind of copolymerization cationic high-molecular polyacrylamide flocculant preparation method.

Technical scheme: it is be raw material with acrylamide (AM), trimethylamine hydrochloride, epoxy chloropropane, tetrachloroethane, methacrylic acid and deionized water etc. that the preparation method of polymeric flocculant of the present invention levies, and prepares as follows:

Step 1 is the synthesis of the first intermediate (3-chloro-2-hydroxypropyl-trimethyl ammonium chloride); Step 2 is the preparation of the second intermediate (methacryloxy-2-hydroxypropyl-trimethyl ammonium chloride); Step 3 is copolymerization cationic flocculant.

Further we find, add stopper in step 1; Add emulsifying agent in step 3, initiator has better effect.The preferred hydroquinone monomethyl ether of described stopper, emulsifying agent are class 80 of department; The preferred Diisopropyl azodicarboxylate of described initiator.

Further, carry out according to the following steps: (following concentration is all weight percentage, and described number is by weight):

The synthesis of step 1:3-chloro-2-hydroxypropyl-trimethyl ammonium chloride

60 ~ 90 parts of trimethylamine hydrochlorides are dissolved in 300 ~ 800 parts of chloroforms, adjust ph is 5 ~ 8, be warming up to 20 ~ 60 DEG C constant, (pH value is 1 ~ 5 to add epoxy chloropropane solution, add-on is 30 ~ 100 parts), add in 0.5 ~ 5 hour, leave standstill and add tetrachloroethane 5 ~ 40 parts after 1 ~ 6 hour, fuming hydrochloric acid 2 ~ 12 parts of l are added after 5 ~ 20 hours, adjust ph is 3 ~ 8, reaction proceeds to obtain mixed solution in 10 ~ 30 hours, the underpressure distillation when bath temperature 30 ~ 90 DEG C, solid content cools after purification when reaching 90% ~ 95%, with washed with isopropyl alcohol half dryed product, again with ether washing and filtering at twice after filtration, filtrate decompression Distillation recovery, vacuum-drying purification at 20 ~ 90 DEG C, obtain high-purity 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride.

Step 2: the preparation of methacryloxy-2-hydroxypropyl-trimethyl ammonium chloride

40 ~ 100 parts of methacrylic acids are joined in NaOH ethanol solution, formed pH value 4 ~ 9 methacrylic acid sodium ethoxide solution, add the alcohol immersion of 100 ~ 500 parts, get 50 ~ 200 parts, the intermediate obtained in step one, add dehydrated alcohol 100 ~ 400 parts, add hydroquinone of polymerization retarder monomethyl ether 100 ~ 500 parts, the methacrylic acid sodium ethoxide solution adding immersion is again heated with stirring to 30 ~ 100 DEG C, constant temperature 2 ~ 8 hours, add hydrochloric acid 1 ~ 7 part, adjust ph is 3 ~ 8, in-10 ~ 10 DEG C of freezing and crystallizings after mixed solution filters, suction filtration, recrystallization, by the crystal ether cleaning and dipping collected 0.5 ~ 4 hour, suction filtration obtains the vacuum-drying at 20 ~ 80 DEG C of pale yellow powder crystal.

Step 3: the preparation of copolymerization cationic flocculant

50 ~ 300 parts, intermediate step 2 obtained and ionized water dissolve and are ground into 20 ~ 60% cation mono liquid solutions, acrylamide 30 ~ 200 parts adds dehydrated alcohol 50 ~ 200 parts dissolving, be positioned over-10 ~ 10 DEG C of frozen recrystallizations, the aqueous solution of 10 ~ 80% is made into after suction filtration, add 1 ~ 8% ethanol 1 ~ 7 part again, distill 0.5 ~ 5 hour, cleaned acrylamide 20 ~ 80% aqueous solution 10 ~ 60 parts is joined in the cationic monomer aqueous solution of 10 ~ 60%, add EDTA0.1 ~ 0.5 part, adjust ph is 5 ~ 9, add 5 ~ 12 parts of classes of emulsifying agent department 80, 2 ~ 8 parts of Zerols, add normal hexane 40 ~ 140 parts again, hexanaphthene 40 ~ 140 parts is configured to mixed solution, logical nitrogen, vacuumize 0.5 ~ 4 hour, be warming up to 20 ~ 60 DEG C, add Diisopropyl azodicarboxylate 0.1 ~ 0.5 part and sodium bisulfite, when emulsion temperature reaches 10 ~ 50 DEG C, ammonium persulfate solution is dripped in 0.5 ~ 4 hour, be warming up to 10-60 DEG C constant 1 ~ 6 hour, add inferior sodium phosphate 0.5 ~ 1 part, be warming up to 20 ~ 90 DEG C constant 1 ~ 6 hour, obtain reactant, cure 5 ~ 20 hours, cure material and grind rear use 20 ~ 80 parts of ethyl acetate immersions 5 ~ 10 hours again, filtering drying, obtain finished product.

Beneficial effect: the product viscosity-average molecular weight that the method for the invention obtains is high, is specially adapted to the process of industrial negatively charged ion waste water.

Embodiment:

Below by way of specific embodiment, described in detail the inventive method, in embodiment, per-cent is weight.The optimum implementation that we find is:

The synthesis of step 1:3-chloro-2-hydroxypropyl-trimethyl ammonium chloride

Take trimethylamine hydrochloride 780.8g, add chloroform 6400ml stirring and dissolving and be placed on logical nitrogen in reactor, by 5mol/LNaOH (add-on 80 ~ 90ml) solution adjust ph 6.4 ~ 6.7, be warming up to 34 ~ 35 DEG C constant, slow dropping pH value 2 ~ 3 epoxy chloropropane (add-on 786g) solution, complete in 3 hours, tetrachloroethane 212ml is added after 4 hours, fuming hydrochloric acid 80ml is added after 12 hours, adjust ph is 6.4, reaction proceeds to close nitrogen in 22 hours, be cooled to room temperature and obtain mixed solution, the underpressure distillation when bath temperature 70 DEG C, solid content cools after purification when reaching 90% ~ 95%, with washed with isopropyl alcohol half dryed product of 1000ml, 600ml ether washing and filtering is at twice used again after filtration, filtrate decompression Distillation recovery, vacuum-drying purification at 50 DEG C, obtain high-purity 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride for subsequent use.

Getting methacrylic acid 688.7g slowly joins in NaOH ethanol solution, stirring and dissolving formed pH value 6.4 ~ 7.0 methacrylic acid sodium ethoxide solution, the industrial alcohol adding 2400ml after cooling soaks, get the first intermediate 1504g, put into reactor, add dehydrated alcohol 2600ml again, heating for dissolving, add hydroquinone of polymerization retarder monomethyl ether 3450mg, the methacrylic acid sodium ethoxide solution of immersion is joined in reactor and is heated with stirring to 78 DEG C, constant temperature 5 hours, add fuming hydrochloric acid 40ml, adjust ph is 6.0, be cooled to room temperature and obtain mixed solution, in-5 DEG C of freezing and crystallizings after mixed solution filters, suction filtration, filtrate recrystallization three times, by the crystal ether cleaning and dipping collected 2 hours, suction filtration obtains the vacuum-drying at 50 DEG C of pale yellow powder crystal, save backup at collecting 10 DEG C, sample.

Step 3: the preparation of copolymerization cationic flocculant

Get the second intermediate 1580g, add ionized water 2150ml dissolving colloidal mill and be ground into 40% cationic monomer solution for standby, industry acrylamide 1170g adds dehydrated alcohol 400ml and dissolves the water-bath of 50 DEG C, be positioned over-5 DEG C of frozen recrystallizations, the deionized water adding 1000ml after suction filtration purification is made into the aqueous solution of 50%, add 5% ethanol 50ml again, water-bath underpressure distillation deoxidation in 2 hours, cleaned acrylamide 50% aqueous solution 400ml is joined in the cationic monomer aqueous solution of 35%, add EDTA3.6g, adjust ph is 7.0, add class of emulsifying agent department 80-92g, Zerol-46g, add normal hexane 1000ml again, hexanaphthene 1000ml is configured to mixed solution, be placed in reactor and pass into nitrogen, vacuumize deoxygenation 2 hours, be warming up to 30 DEG C, add Diisopropyl azodicarboxylate 2.42g and sodium bisulfite (claiming sodium bisulfite 7.26g to be dissolved in 20ml deionized water), when emulsion temperature reaches 35 DEG C, ammonium persulfate solution (claiming ammonium persulphate 4.84g to be dissolved in 200ml deionized water) is dripped in 2 hours, be warming up to 35 DEG C constant 4 hours, add inferior sodium phosphate 7.26g, be warming up to 60 DEG C constant 3 hours, be cooled to room temperature and obtain reactant, be placed in 95 DEG C and cure 12 hours, cure material and grind rear 500ml ethyl acetate immersion a few hours filtering drying again, obtain finished product.

Can obtain copolymerization cationic high-molecular polyacrylamide flocculant by above-mentioned three-step reaction, product becomes dry powder to exist, and calculate polymer yield from charging capacity and be greater than 96.9%, monomer conversion is more than 90%, and viscosity-average molecular weight is 2 ~ 5 × 10 ⁶.

Claims

1. the preparation method of a polymeric flocculant, it is characterized in that with acrylamide, trimethylamine hydrochloride, epoxy chloropropane, tetrachloroethane, methacrylic acid and deionized water etc. for raw material, prepare as follows: step 1, the synthesis of the first intermediate 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride; Step 2, the preparation of the second intermediate methacryloxy-2-hydroxypropyl-trimethyl ammonium chloride; Step 3, copolymerization cationic flocculant.

2. the preparation method of polymeric flocculant as claimed in claim 1, it is characterized in that described step 1 is: be dissolved in by 60 ~ 90 parts of trimethylamine hydrochlorides in 300 ~ 800 parts of chloroforms, adjust ph is 5 ~ 8, be warming up to 20 ~ 60 DEG C constant, add epoxy chloropropane solution, add in 0.5 ~ 5 hour, leave standstill and add tetrachloroethane 5 ~ 40 parts after 1 ~ 6 hour, fuming hydrochloric acid 2 ~ 12 parts is added after 5 ~ 20 hours, adjust ph is 3 ~ 8, reaction proceeds to obtain mixed solution in 10 ~ 30 hours, the underpressure distillation when bath temperature 30 ~ 90 DEG C, solid content cools after purification when reaching 90% ~ 95% and obtains intermediate one.

3. the preparation method of polymeric flocculant as claimed in claim 1, it is characterized in that described step 2 is: join in NaOH ethanol solution by 40 ~ 100 parts of methacrylic acids, formed pH value 4 ~ 9 methacrylic acid sodium ethoxide solution, add the alcohol immersion of 100 ~ 500 parts, get one 50 ~ 200 parts, the intermediate obtained in step 1, add dehydrated alcohol 100 ~ 400 parts, add hydroquinone of polymerization retarder monomethyl ether 100 ~ 500 parts, the methacrylic acid sodium ethoxide solution adding immersion is again heated with stirring to 30 ~ 100 DEG C, constant temperature 2 ~ 8 hours, add hydrochloric acid 1 ~ 7 part, adjust ph is 3 ~ 8, in-10 ~ 10 DEG C of freezing and crystallizings after mixed solution filters, suction filtration, recrystallization, obtain intermediate two.

4. the preparation method of polymeric flocculant as claimed in claim 1, it is characterized in that described step 3 is: 2 50 ~ 300 parts, intermediate and ionized water are dissolved and are ground into 20 ~ 60% cation mono liquid solutions, acrylamide 30 ~ 200 parts adds dehydrated alcohol 50 ~ 200 parts dissolving, be positioned over-10 ~ 10 DEG C of frozen recrystallizations, the aqueous solution of 10 ~ 80% is made into after suction filtration, add 1 ~ 8% ethanol 1 ~ 7 part again, distill 0.5 ~ 5 hour, cleaned acrylamide 20 ~ 80% aqueous solution 10 ~ 60 parts is joined in the cationic monomer aqueous solution of 10 ~ 60%, add EDTA0.1 ~ 0.5 part, adjust ph is 5 ~ 9, add 5 ~ 12 parts of classes of emulsifying agent department 80, 2 ~ 8 parts of Zerols, add normal hexane 40 ~ 140 parts again, hexanaphthene 40 ~ 140 parts is configured to mixed solution, logical nitrogen, vacuumize 0.5 ~ 4 hour, be warming up to 20 ~ 60 DEG C, add Diisopropyl azodicarboxylate 0.1 ~ 0.5 part and sodium bisulfite, when emulsion temperature reaches 10 ~ 50 DEG C, ammonium persulfate solution is dripped in 0.5 ~ 4 hour, be warming up to 10-60 DEG C constant 1 ~ 6 hour, add inferior sodium phosphate 0.5 ~ 1 part, be warming up to 20 ~ 90 DEG C constant 1 ~ 6 hour, reaction terminates, finished product is obtained through aftertreatment.

5. the preparation method of polymeric flocculant as claimed in claim 1, it is characterized in that the epoxy chloropropane solution ph described in step 1 is 1 ~ 5, add-on is 30 ~ 100 parts.

6. the preparation method of polymeric flocculant as claimed in claim 1, it is characterized in that the purification described in step 3, concrete grammar is: with washed with isopropyl alcohol half dryed product, again with ether washing and filtering at twice after filtration, filtrate decompression Distillation recovery, vacuum-drying purification at 20 ~ 90 DEG C.

7. the preparation method of polymeric flocculant as claimed in claim 1, it is characterized in that the aftertreatment described in step 3, concrete grammar is: cure 5 ~ 20 hours, cures material and grinds rear use 20 ~ 80 parts of ethyl acetate immersions 5 ~ 10 hours again, filter, dry.