CN101402480A - Method for producing wastewater treatment agent with weathered coal graft organic macromolecule - Google Patents
Method for producing wastewater treatment agent with weathered coal graft organic macromolecule Download PDFInfo
- Publication number
- CN101402480A CN101402480A CNA2008100514283A CN200810051428A CN101402480A CN 101402480 A CN101402480 A CN 101402480A CN A2008100514283 A CNA2008100514283 A CN A2008100514283A CN 200810051428 A CN200810051428 A CN 200810051428A CN 101402480 A CN101402480 A CN 101402480A
- Authority
- CN
- China
- Prior art keywords
- weathered coal
- treatment agent
- wastewater treatment
- organic macromolecule
- azo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a method for preparing a waste water treatment agent by weathered coal grafted organic macro-molecules. The method comprises the following steps: in inorganic salt aqueous solution, a cationoid addition polymer capable of being dissolved in the salt aqueous solution is taken as a dispersant; and cationoid water soluble polymer dispersing liquid with a grain diameter less than 100 microns is prepared by the graft polymerization of weathered coal and methacrylamide or acrylamide and more than one water soluble cationic monomer. The water soluble polymer dispersing liquid can be used for the white water treatment in the paper making industry and the waste water treatment in the food industry, steel smelting factories, the building material industry and the petroleum industry. In particular, the water soluble polymer dispersing liquid has particularly remarkable effects on the sludge dewatering for municipal sewage plants or food factories. Multiple kinds of equipment for sludge dewatering including a caterpillar chain dewatering machine, a filtration type dewatering machine, a centrifugal type dewatering machine, and the like can all use the waste water treatment agent prepared by the weathered coal grafted macro-molecules.
Description
Technical field
The present invention relates to the method for producing wastewater treatment agent with weathered coal graft organic macromolecule.
Background technology
Because have excellent characteristics such as tackifying, flocculence, drag reduction and water-retentivity, water-soluble polymer is widely used in as numerous fields such as wastewater treatment, papermaking.The synthesis material of water-soluble polymer derives from petroleum products.In short supply along with petroleum resources utilizes other raw material to replace petroleum products to become the research and development focus in research and industrial production field.Weathered coal is the low combustion value natural product, wherein contains a large amount of humic acid and can be used for fields such as soil and fertilizer, water conditioner, fluid loss agent.Chinese patent 200410058335.5, CN1244613C, CN1084781C, 97105226 have introduced the processing method of being extracted humic acid by weathered coal.This method can be extracted humic acid effectively with preparation chemical fertilizer, water conditioner, fluid loss agent.But in the process of extracting, need strong acid or highly basic, and need under the pyritous condition, just can reach the ideal yield.Problems such as technology itself exists that power consumption is big, aftertreatment expense height and environmental pollution.
Summary of the invention
For addressing the above problem, the invention provides the method for producing wastewater treatment agent with weathered coal graft organic macromolecule.Relate to by in inorganic salt solution, adding cationic addition polymer dispersion agent, and in this salt brine solution, make the monomer mixture of weathered coal and Methacrylamide or acrylamide and more than one water-soluble cationic monomers formation carry out graft polymerization reaction, prepare the method for producing wastewater treatment agent with weathered coal graft organic macromolecule.
The preparation method's of producing wastewater treatment agent with weathered coal graft organic macromolecule step and condition are:
The water-soluble monomer mixture is by the cationic monomer of the 5-90 mole % of Chemical formula 1 definition, and the Methacrylamide of 10-95 mole % or acrylamide monomer constitute;
Chemical formula 1:
In the formula, R
1Be H or CH
3R
2, R
3Be alkyl or the alkoxyl group of carbon number 1-3; R
4Alkyl or alkoxyl group for H, carbon number 1-3; A is O or NH; B is alkylidene group or the alkylene oxide group of carbon number 1-3; X
1Be halide-ions;
Cationic monomer by the Chemical formula 1 definition is preferred: vinylformic acid dimethylin second fat ester, dimethyl-propyl group acrylamide, the muriate of vinylformic acid methylamino ethyl ester, 3-acrylamido-methyl chlorination propylamine or N, N-two-methyl-N-benzyl vinylformic acid ethamine ester muriate;
Is dissolving and to make the weight concentration of water-soluble monomer mixture be 1-40% in the inorganic salt solution of 7%-saturation range with the water-soluble monomer mixture in weight concentration, in reaction system, add cationic addition polymer dispersion agent and weathered coal, the regulation system pH value is 2-6, logical nitrogen is with the oxygen in the system of removing under stirring condition, add initiator and carry out polymerization, temperature of reaction is 5-90 ℃, and optimum temps is 15-65 ℃, obtains water-soluble high molecular dispersion liquid in cationoid;
The cation type polymer that described cationic addition polymer dispersion agent is a chemical general formula 2;
Chemical formula 2:
In the formula, R
5Be H or CH
3R
6, R
7Be alkyl or the alkoxyl group of carbon number 1-3; R
8Alkyl or alkoxyl group for H, carbon number 1-3; D is O or NH; E is alkylidene group or the alkylene oxide group of carbon number 1-3; X
2Be halide-ions;
The consumption of described positively charged ion addition polymer dispersion agent is the 1-20% of water-soluble monomer mixture weight, and optimum amount is 2-15%;
Described weathered coal: inorganic salt brinish weight ratio is 5-30: 100; The particle size range of weathered coal is the 20-60 micron, is preferably the 30-50 micron;
Described initiator is an azo-initiator: 2,2-azo two (2-amidine azoles quinoline base propane) two hydrochloric acid (VA-044), 2,2-azo two (2-amidine propane) two hydrochloric acid (V-50), 2,2-Diisopropyl azodicarboxylate (V-60) or 2,2-azo two (2, the 4-methyl pentane nitrile) (V-65); Azo-initiator is preferred: 2, and 2-azo two (2-amidine propane) two hydrochloric acid (V-50) or 2,2-azo two (2-amidine azoles quinoline base propane) two hydrochloric acid (VA-044);
Described inorganic salt are the salt that sodium ion, potassium ion or ammonium ion and halogen ion root, sulfate radical, nitrate radical or phosphate radical form; Preferred inorganic salt are ammonium sulfate, sodium sulfate, sal epsom, sodium phosphate, ammonium phosphate, SODIUM PHOSPHATE, MONOBASIC, sodium chloride or Repone K.
The cationic addition polymer dispersion agent that uses among the present invention is very obvious to the preparation effect of weathered coal graft water-soluble high molecular dispersion liquid in cationoid, but the problem of much still needing in addition and inquire at present in its mechanism aspect.From reacting phenomenon, can do following supposition: salt brine solution, proceed to a certain degree when reacting, during the polymer postcritical that generated, the part polymer is then separated out from salts solution with the form of particle, be that dissolving and the polymer of separating out exist simultaneously in the system, the polymer that is dissolved in this moment in the salt-water liquid increases the overall viscosity of system.After this, along with the increase of separating out amount of polymers, the viscosity of system reduces, and has formed dispersion state.This moment, the smoothing effect between the polymer of precipitation particles and solubilised state made system softer to the conversion of low viscous dispersion state by high viscosity state in the state of two-phase coexistent, and dispersion agent has played special effect in this change procedure.Condensation polymer is compared with the cationic high-molecular of addition polymerization, its molecular weight is lower and ionic equivalent degree is bigger, easily absorption also closely is covered in the surface of particle, the repulsive interaction of sharp useful its electric charge and stablized dispersed particle, between precipitation particles and solubilised state polymer, constitute the microphase-separated state, played the effect of stable dispersion.But owing to the low reason of molecular weight makes that the coating that covers particle surface is thinner relatively, the destruction of the external influence power such as stirring shearing force in being reacted easily.Therefore can increase the intensity of the coating that covers particle surface with the compound use of the addition polymer of higher molecular weight.By the comprehensive action of above each side, the viscosity around the precipitation particles reduces, and makes phase change carry out in stable process.
Beneficial effect: the invention provides the plain boiled water that producing wastewater treatment agent with weathered coal graft organic macromolecule can be used in the papermaking and handle, wastewater treatment in foodstuffs industry, smelting iron and steel factory, building materials industry and the petroleum industry, particularly the sludge dewatering effect for municipal sewage plant or food factory is obvious especially.Be used for the various device of sludge dewatering, as cover equipment such as belt water extracter, filtering type water extracter, centrifugal drier and all can use.Different additions according to the indexs such as turbidity of waste water or mud change to some extent, and scope is solid foreign matter content 0.1-3% in the 0.1-1000ppm of wastewater flow rate or the mud.
Embodiment
Below introduce the synthesis example of dispersion agent.
Synthesis example 1-3: the synthesis example of cationic addition polymer dispersion agent
In the 500mL reaction flask, add the 240g deionized water, add 60g vinylformic acid Trimethylamine ethyl ester (DAC) (seeing Table NO.1 in 1) again, or the mix monomer (seeing Table NO.2 in 1) of 40g vinylformic acid Trimethylamine ethyl ester and 80g acrylamide (AM), or the mix monomer of 20g vinylformic acid Trimethylamine ethyl ester and 100g acrylamide (seeing Table NO.3 in 1), dropping sulfuric acid is 3 with the pH of regulator solution, be warming up to the logical nitrogen in 42 degree backs about 30 minutes, 2% aqueous solution that adds 3g V-50 is with the initiated polymerization system.React stop after 15 hours the heating, obtain dispersion agent synthesis example NO.1, NO.2 and NO.3.(seeing Table 1) records its weight-average molecular weight and cationic degree respectively with static light scattering and colloidal titration analytical method.
Synthesis example 4-6:
In the 500mL reaction flask, add the 240g deionized water, add 60g methacrylic acid Trimethylamine ethyl ester (DMC) (seeing Table NO.4 in 1) again, or the mix monomer (seeing Table NO.5 in 1) of 40g methacrylic acid Trimethylamine ethyl ester and 80g acrylamide (AM), or the mix monomer of 20g methacrylic acid Trimethylamine ethyl ester and 100g acrylamide (seeing Table NO.6 in 1), dropping sulfuric acid is 3 with the PH of regulator solution, be warming up to the logical nitrogen in 42 degree backs about 30 minutes, 2% aqueous solution that adds 3gV-50 is with the initiated polymerization system.React stop after 15 hours the heating, obtain dispersion agent synthesis example NO.4, NO.5 and NO.3.(seeing Table 1) records its weight-average molecular weight and cationic degree respectively with static light scattering and colloidal titration analytical method.
Below introduce the preparation embodiment of producing wastewater treatment agent with weathered coal graft organic macromolecule.
Embodiment 1
In 500 milliliters of 4 mouthfuls of round-bottomed flasks being furnished with prolong, thermometer, nitrogen feeding mouth and agitator, polymeric NO-1 (20%) 25g that adds preparation in the synthesis example 1, weathered coal 15g, 170.4g deionized water, 115g ammonium sulfate, the acrylamide of 67.4g50% concentration, 115g80% vinylformic acid trimethylammonium ethamine ester muriate, heating up and keeping temperature to be 30-33 ℃ makes it to dissolve fully.Logical nitrogen adds the VA-044 aqueous solution initiation reaction of 1.9g1% after 30 minutes.The viscosity of 2.5 hours afterreaction systems of reaction beginning begins to increase, and viscosity reduces and form dispersion liquid after 25 minutes.React and append above-mentioned initiator solution 0.5g after 8 hours and continue reaction 8 hours, obtain producing wastewater treatment agent with weathered coal graft organic macromolecule.The concentration of its dispersion liquid, viscosity and particle diameter are respectively 25%, 185mPa.s and 50 microns.Data see Table 2 embodiment 1.
Embodiment 2-6
Reaction unit and operating method are identical with embodiment 1, prepare producing wastewater treatment agent with weathered coal graft organic macromolecule by dispersant dosage shown in the table 2 and monomer consumption condition.The results are shown in Table 2.
Comparative example 1
In 500 milliliters of 4 mouthfuls of round-bottomed flasks being furnished with prolong, thermometer, nitrogen feeding mouth and agitator, add weathered coal 15g respectively, 178.2g deionized water, 115g ammonium sulfate, the acrylamide of 67.4g50% concentration, 115g80% vinylformic acid trimethylammonium ethamine ester muriate, heating up and keeping temperature to be 30-33 ℃ makes it to dissolve fully.Logical nitrogen adds the VA-044 aqueous solution initiation reaction of 1.9g1% after 30 minutes.The viscosity of 1 hour afterreaction system of reaction beginning begins violent increasing and lasting about 1 hour, and after this viscosity reduces and form dispersion liquid.React and append above-mentioned initiator solution 0.5g after 8 hours and continue reaction 8 hours, obtain the sample of comparative example 1.The results are shown in Table 2 comparative example 1.
Comparative example 2
Reaction unit and operating method are identical with embodiment 1, press the dispersant dosage shown in the table 2 and monomer consumption and condition, and synthetic comparative example 2 the results are shown in Table 2.
Table 1. dispersion agent synthesis example
| NO. | The composition of dispersion agent | Positively charged ion molar weight/meq/g | Molecular weight/ten thousand |
| 1 | The DAC homopolymer | 5.25 | 20 |
| 2 | The DAC/AM multipolymer | 4.52 | 50 |
| 3 | The DAC/AM multipolymer | 5.97 | 70 |
| 4 | The DMC homopolymer | 7.33 | 20 |
| 5 | The DMC/AM multipolymer | 7.01 | 65 |
| 6 | The DMC/AM multipolymer | 6.45 | 90 |
Annotate: DAC: vinylformic acid trimethylammonium ethamine ester muriate;
DMC: methacrylic acid trimethylammonium ethamine ester muriate;
AM: acrylamide.
Table 2. dispersion synthesis example prescription and result
| Real | Monomer is dense | Disperse | Addition | Weathered coal | DAC | DMA | ABC | AAm | Dispersion is sticking |
| Execute example | Degree (WT%) | Agent | (WT％) | Concentration (WT%) | Degree/mPa.s | ||||
| 1 | 25.0 | No.1 | 4.0 | 5 | 50 | 50 | 180 | ||
| 2 | 25.0 | No.2 | 5.0 | 10 | 50 | 20 | 30 | 150 | |
| 3 | 25.0 | No.3 | 5.0 | 30 | 40 | 20 | 40 | 250 | |
| 4 | 23.0 | No.4 | 4.0 | 5 | 10 | 50 | 40 | 200 | |
| 5 | 22.3 | No.5 | 4.0 | 10 | 40 | 60 | 190 | ||
| 6 | 25.0 | No.6 | 5.0 | 30 | 40 | 20 | 40 | 220 | |
| Comparative example | |||||||||
| 1 | 25.0 | - | 0 | 5 | 50 | 50 | 1350 | ||
| 2 | 21.0 | - | 0 | 10 | 50 | 20 | 30 | 2530 |
Annotate: DAC: vinylformic acid trimethylammonium ethamine ester muriate;
AAM: acrylamide;
DMC: methacrylic acid trimethylammonium ethamine ester muriate;
ABC: ethyl propenoate-N, N-dimethyl-N-benzyl ammonia chloride.
Claims (7)
1, the method for producing wastewater treatment agent with weathered coal graft organic macromolecule is characterized in that, step and condition are:
The water-soluble monomer mixture is by the cationic monomer of the 5-90 mole % of Chemical formula 1 definition, and the Methacrylamide of 10-95 mole % or acrylamide monomer constitute;
Chemical formula 1:
In the formula, R
1Be H or CH
3R
2, R
3Be alkyl or the alkoxyl group of carbon number 1-3; R
4Alkyl or alkoxyl group for H, carbon number 1-3; A is O or NH; B is alkylidene group or the alkylene oxide group of carbon number 1-3; X
1Be halide-ions;
Is dissolving and to make the weight concentration of water-soluble monomer mixture be 1-40% in the inorganic salt solution of 7%-saturation range with the water-soluble monomer mixture in weight concentration, in reaction system, add cationic addition polymer dispersion agent and weathered coal, the regulation system pH value is 2-6, logical nitrogen is with the oxygen in the system of removing under stirring condition, add initiator and carry out polymerization, temperature of reaction is 5-90 ℃, obtains producing wastewater treatment agent with weathered coal graft organic macromolecule;
The cation type polymer that described cationic addition polymer dispersion agent is a chemical general formula 2;
Chemical formula 2:
In the formula, R
5Be H or CH
3R
6, R
7Be alkyl or the alkoxyl group of carbon number 1-3; R
8Alkyl or alkoxyl group for H, carbon number 1-3; D is O or NH; E is alkylidene group or the alkylene oxide group of carbon number 1-3; X
2Be halide-ions;
The consumption of described positively charged ion addition polymer dispersion agent is the 1-20% of water-soluble monomer mixture weight;
Described weathered coal: inorganic salt brinish weight ratio is 5-30: 100; The particle size range of weathered coal is the 20-60 micron;
Described initiator is an azo-initiator: 2, and 2-azo two (2-amidine azoles quinoline base propane) two hydrochloric acid, 2,2-azo two (2-amidine propane) two hydrochloric acid, 2,2-Diisopropyl azodicarboxylate or 2,2-azo two (2, the 4-methyl pentane nitrile);
Described inorganic salt are the salt that sodium ion, potassium ion or ammonium ion and halogen ion root, sulfate radical, nitrate radical or phosphate radical form.
2, the method for producing wastewater treatment agent with weathered coal graft organic macromolecule as claimed in claim 1, it is characterized in that described cationic monomer by the Chemical formula 1 definition is: vinylformic acid dimethylin second fat ester, dimethyl-propyl group acrylamide, the muriate of vinylformic acid methylamino ethyl ester, 3-acrylamido-methyl chlorination propylamine or N, N-two-methyl-N-benzyl vinylformic acid ethamine ester muriate.
3, the method for producing wastewater treatment agent with weathered coal graft organic macromolecule as claimed in claim 1, the consumption that it is characterized in that described positively charged ion addition polymer dispersion agent is the 2-15% of water-soluble monomer mixture weight.
4, the method for producing wastewater treatment agent with weathered coal graft organic macromolecule as claimed in claim 1, the particle size range that it is characterized in that described weathered coal is the 30-50 micron.
5, the method for producing wastewater treatment agent with weathered coal graft organic macromolecule as claimed in claim 1 is characterized in that described azo-initiator is: 2, and 2-azo two (2-amidine propane) two hydrochloric acid or 2,2-azo two (2-amidine azoles quinoline base propane) two hydrochloric acid.
6, the method for producing wastewater treatment agent with weathered coal graft organic macromolecule as claimed in claim 1 is characterized in that described inorganic salt are ammonium sulfate, sodium sulfate, sal epsom, sodium phosphate, ammonium phosphate, SODIUM PHOSPHATE, MONOBASIC, sodium chloride or Repone K.
7, the method for producing wastewater treatment agent with weathered coal graft organic macromolecule as claimed in claim 1 is characterized in that described adding initiator carries out polymerization, and temperature of reaction is 15-65 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100514283A CN101402480A (en) | 2008-11-17 | 2008-11-17 | Method for producing wastewater treatment agent with weathered coal graft organic macromolecule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100514283A CN101402480A (en) | 2008-11-17 | 2008-11-17 | Method for producing wastewater treatment agent with weathered coal graft organic macromolecule |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101402480A true CN101402480A (en) | 2009-04-08 |
Family
ID=40536666
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100514283A Pending CN101402480A (en) | 2008-11-17 | 2008-11-17 | Method for producing wastewater treatment agent with weathered coal graft organic macromolecule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101402480A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753118A (en) * | 2016-03-07 | 2016-07-13 | 华北理工大学 | Novel seawater purifying agent and preparation method thereof |
-
2008
- 2008-11-17 CN CNA2008100514283A patent/CN101402480A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753118A (en) * | 2016-03-07 | 2016-07-13 | 华北理工大学 | Novel seawater purifying agent and preparation method thereof |
| CN105753118B (en) * | 2016-03-07 | 2018-05-25 | 华北理工大学 | A kind of new seawater cleaning agent and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20190153300A1 (en) | Method for preparing an aqueous polyacrylamide solution | |
| US20190144574A1 (en) | Method for preparing an aqueous polyacrylamide solution | |
| Guan et al. | Effect of template on structure and properties of cationic polyacrylamide: characterization and mechanism | |
| CN104556331B (en) | PAC (polyaluminium chloride)-modified sodium alginate inorganic-organic composite flocculant and preparation method thereof | |
| WO2017186685A1 (en) | Method for preparing an aqueous polyacrylamide solution | |
| CN1257512A (en) | Preparation of water soluble polymer dispersions from vinylamide monomers | |
| CN102250291A (en) | Ampholytic modified grafted starch flocculant | |
| CN108349762B (en) | Method for treating aqueous effluents | |
| BG63635B1 (en) | Pulverization dried polymer compositions and methods for their preparation | |
| EP3445723A1 (en) | Amphoteric polymer, process for production thereof, and use thereof, to treat aqueous dispersions | |
| Xu et al. | Preparation of cationic polyacrylamide by aqueous two-phase polymerization | |
| CN101786647B (en) | Accelerating sedimentation type flocculating agent for removing insoluble substances in polyaluminum chloride and preparation method thereof | |
| CN102356048A (en) | Compositions for conditioning of mud | |
| JP2006291024A (en) | Sludge dehydrating agent composition and method for dehydrating sludge | |
| CN101402480A (en) | Method for producing wastewater treatment agent with weathered coal graft organic macromolecule | |
| WO2017040795A1 (en) | Polymeric microparticles as filtration and/or clarifying aids in phosphoric acid production | |
| CN101003601A (en) | Method for preparing water-soluble high molecular dispersion liquid in cationoid | |
| CN103694394B (en) | A kind of synthetic method of zwitter-ion polyacrylamide copolymer and obtained multipolymer are as the application of flocculation agent | |
| KR20000016793A (en) | Spray-drying oil recovery process | |
| WO2012125918A1 (en) | Process for improving the flow rate of an aqueous dispersion | |
| CN105273131A (en) | Preparation method of cationic polyacrylamide emulsion | |
| CN101786646B (en) | Methods for preparing and applying sedimentation acceleration agent used for removing insoluble substances from polyaluminium chloride | |
| JP6729641B2 (en) | Method for treating organic wastewater and composition for treating organic wastewater | |
| CN109265593B (en) | Dimethyl diallyl ammonium chloride solid polymer | |
| JP7216967B2 (en) | Organic wastewater treatment method and its use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090408 |