CN102642904A - Flocculating agent for treating papermaking waste water and preparation method thereof - Google Patents

Flocculating agent for treating papermaking waste water and preparation method thereof Download PDF

Info

Publication number
CN102642904A
CN102642904A CN2012101222772A CN201210122277A CN102642904A CN 102642904 A CN102642904 A CN 102642904A CN 2012101222772 A CN2012101222772 A CN 2012101222772A CN 201210122277 A CN201210122277 A CN 201210122277A CN 102642904 A CN102642904 A CN 102642904A
Authority
CN
China
Prior art keywords
formula
dispersion agent
agent
preparation
initiator
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.)
Granted
Application number
CN2012101222772A
Other languages
Chinese (zh)
Other versions
CN102642904B (en
Inventor
张文德
徐昆
王明权
李鹏翀
李文波
路璀阁
周光远
王丕新
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hangzhou Kewan New Materials Technology Co Ltd
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CN201210122277.2A priority Critical patent/CN102642904B/en
Publication of CN102642904A publication Critical patent/CN102642904A/en
Application granted granted Critical
Publication of CN102642904B publication Critical patent/CN102642904B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention provides a flocculating agent for treating papermaking waste water. The flocculating agent comprises a dispersing agent and a polymer having a structure shown in a formula (IV), wherein X is polymerization degree, y is polymerization degree, R1 is H or methyl, R2 is amide group, R3 is H and R4 is a substituent group shown in a formula (V); R5 is H or alkyl selecting from carbon numbers of 1-12; n is a positive integer which is more than or equal to 6; and the molecular weight of a polymer having the structure shown in the formula (IV) is 4,000,000-7,000,000. The substituent group shown in the formula (V) is a hydrophobic association group which has good salt tolerance, so that hydrodynamic volume of a polymer molecular chain in a salt water medium is larger, the flocculation capability is strong and the flocculation speed is fast, solid suspended matters in the papermaking waste water with high salt contents can be effectively removed, and a COD (Chemical Oxygen Demand) value can also be remarkably reduced. The invention also provides a preparation method of the flocculating agent for treating papermaking waste water. The method is environment-friendly and is beneficial to popularization.

Description

Flocculation agent of a kind of Processing Paper Wastewater and preparation method thereof
Technical field
The present invention relates to technical field of waste water processing, particularly flocculation agent of a kind of Processing Paper Wastewater and preparation method thereof.
Background technology
Paper industry is the water rich and influential family, as produce per year 100,000 tons of paper the paper mill every day water loss just between 20,005 kilotons to three, 10,005 kilotons.Simultaneously; Paper industry is again a water heavy polluter; The pulping of waste paper, screening, flotation, deinking and copy operation such as paper and can produce a large amount of paper wastes in the production process, its composition mainly comprises tiny suspension fiber, papermaking filler, waste paper impurity and all kinds of inorganic, organic production additives etc., mixes owing to composition; Make the chemical oxygen demand (COD value) and the solid suspension content (SS value) of paper waste all higher, serious pollution of water environment.Therefore, for practicing thrift, protecting China's limited water resource, the technological process of treating papermaking reuse has become the key subjects with realistic meaning and far-reaching significance.
Prior art adopts the flocculation agent Processing Paper Wastewater usually; Reduce its COD value; Like publication number is that the Chinese patent document of CN1101954 discloses a kind of flocculation agent of handling black liquid, and it is made up of 45%～65% (weight) unslaked lime, 10%～25% (weight) Wingdale, 25%～45% (weight) hydrochloric acid (be in concentration 31% hydrochloric acid).Said flocculation agent belongs to inorganic flocculating agent, and molecular weight is low, a little less than the anti-shearing force.When using said flocculation agent Processing Paper Wastewater, the floc sedimentation of formation is easy to scatter under external force, makes low, the overall poor processing effect of clearance such as SS value, colourity, turbidity, salinity and COD value.
Granted publication number discloses a kind of cation type water-soluble polymer dispersion for the Chinese patent document of CN1311004C; Comprise: the water-soluble monomer system of acrylic amide in the inorganic salt solution or USAF RH-1 and monomer composition with formula (I) structure; In formula (I), R 1Be H or methyl, R 2And R 3Be carbon number and be 1～3 alkyl or alkoxyl group, R 4For H or carbon number are 1～3 alkyl, alkoxyl group or benzyl, A is O or NH, and B is that carbon number is 1～3 alkyl or alkoxyl group, X 1Be negative counter ion; The composite dispersing agent that cationic addition polymer dispersion agent and condensation polymer dispersion agent are formed, said cationic addition polymer dispersion agent has formula (II) or formula (III) structure, in formula (II), R 5Be H or methyl, R 6And R 7Be carbon number and be 1～3 alkyl or alkoxyl group, R 8For H or carbon number are 1～3 alkyl, alkoxyl group or benzyl, D is O or NH, and E is that carbon number is 1～3 alkyl or alkoxyl group, X 2Be negative counter ion; In formula (III), R 9And R 10Be H or methyl, R 11And R 12Be H or carbon number and be 1～3 alkyl, X 3Be negative counter ion; Said condensation polymer dispersion agent is the condenses of fatty amine and epoxy chloropropane.
Said cation type water-soluble polymer dispersion can be used as the organic floculant of Processing Paper Wastewater, because composite dispersing agent wherein has good dissemination, makes it can play throwing out preferably, effectively reduces the COD value of paper waste.But; When adopting said cation type water-soluble polymer dispersion to handle the paper waste of saltiness higher (salt concn is more than 0.5M); Because the electron screening effect, the hydrodynamic volume of its macromolecular chain significantly reduces, be difficult to waste water in suspended solid form floc sedimentation closely; Thereby cause flocculating effect relatively poor, be unfavorable for using.
Figure BDA0000156605350000021
Summary of the invention
In order to solve above technical problem, the present invention provides flocculation agent of a kind of Processing Paper Wastewater and preparation method thereof, adopts flocculation agent provided by the invention to handle the higher paper waste of saltiness, and flocculating effect is better, is beneficial to application.
The invention provides a kind of flocculation agent of Processing Paper Wastewater, comprise:
Dispersion agent;
Polymkeric substance with formula (IV) structure:
Figure BDA0000156605350000031
Wherein, x is the polymerization degree; Y is the polymerization degree; R 1Be H or methyl; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V:
Figure BDA0000156605350000032
Wherein, R 5For H or to be selected from carbon number be 1～12 alkyl; N is the positive integer more than or equal to 6;
Said molecular weight with polymkeric substance of formula (IV) structure is 4,000,000～7,000,000.
Preferably, said dispersion agent is for gathering (dimethyl diallyl ammonium chloride), gather (acrylyl oxy-ethyl-trimethyl salmiac) or gathering (methylacryoyloxyethyl trimethyl ammonium chloride); The molecular weight of said dispersion agent is 200,000～1,000,000.
Preferably, the quality of said dispersion agent be said polymkeric substance with formula (IV) structure quality 2%～10%.
The present invention also provides a kind of preparation method of flocculation agent of Processing Paper Wastewater, may further comprise the steps:
In the aqueous solution of inorganic salt; Acrylamido chain alkyl carboxylic acid and acrylic amide or the USAF RH-1 that will have formula (VI) structure carry out copolyreaction in water in the presence of initiator and dispersion agent, obtain comprising the flocculation agent of the said dispersion agent and the Processing Paper Wastewater of the polymkeric substance with formula (IV) structure;
Said acrylamido chain alkyl carboxylic acid has formula (VI) structure:
Figure BDA0000156605350000033
Wherein, R 5For H or to be selected from carbon number be 1～12 alkyl; N is the positive integer more than or equal to 6;
Said polymkeric substance has formula (IV) structure:
Figure BDA0000156605350000041
Wherein, x is the polymerization degree; Y is the polymerization degree; R 1Be H or methyl; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V:
Figure BDA0000156605350000042
Wherein, R 5For H or to be selected from carbon number be 1～12 alkyl; N is the positive integer more than or equal to 6.
Preferably, said have the acrylamido chain alkyl carboxylic acid of formula (VI) structure and the mol ratio of said acrylic amide or USAF RH-1 is 1: 1～10.
Preferably, said dispersion agent is for gathering (dimethyl diallyl ammonium chloride), gather (acrylyl oxy-ethyl-trimethyl salmiac) or gathering (methylacryoyloxyethyl trimethyl ammonium chloride); The molecular weight of said dispersion agent is 200,000～1,000,000; The quality of said dispersion agent be said acrylamido chain alkyl carboxylic acid with formula (VI) structure and said acrylic amide or USAF RH-1 the quality summation 2%～10%.
Preferably, said initiator is persulfuric acid salt initiator, hydroperoxide kind initiator or azo-initiator; The quality of said initiator be said acrylamido chain alkyl carboxylic acid with formula (VI) structure and said acrylic amide or USAF RH-1 the quality summation 0.1%～5%.
Preferably, the overall mass concentration in said water of said acrylamido chain alkyl carboxylic acid with formula (VI) structure and said acrylic amide or USAF RH-1 is 10%～40%.
Preferably, said inorganic salt are one or more in Repone K, sodium-chlor, ammonium chloride, vitriolate of tartar, sodium sulfate and the ammonium sulfate; The mass concentration of said inorganic salt in the said aqueous solution is 25%～40%.
Preferably, the temperature of said copolyreaction is 30 ℃～70 ℃; The time of said copolyreaction is 6 hours～10 hours.
Compared with prior art; The present invention is in the aqueous solution of inorganic salt; Acrylamido chain alkyl carboxylic acid and acrylic amide or the USAF RH-1 that will have formula (VI) structure carry out copolyreaction in water in the presence of initiator and dispersion agent, obtain comprising the flocculation agent of the said dispersion agent and the Processing Paper Wastewater of the polymkeric substance with formula (IV) structure.The flocculation agent of said Processing Paper Wastewater is a SEPIGEL 305 water-in-water type dispersion-s, comprises: dispersion agent and as polymkeric substance disperse phase, that have formula (IV) structure.In said polymkeric substance with formula (IV) structure; Substituting group shown in the said formula V is the hydrophobic association group; Have good salt tolerance, make in the brine media hydrodynamic volume of polymer molecular chain bigger, flocculation ability is strong, flocculation rate is fast; The suspended solid in the paper waste of supersalinity can be effectively removed, its COD value can be significantly reduced simultaneously.Experimental result shows that it is the paper waste of 0.5M～2M that the flocculation agent of said Processing Paper Wastewater is handled saltiness, and when the consumption of flocculation agent was 0.15g/L～0.2g/L, the clearance of COD value was more than 73%, and the clearance of suspended solid is more than 83%.
In addition, preparing method's environmental protection of the flocculation agent of Processing Paper Wastewater provided by the invention, and use flocculation agent in flocculation process, not produce secondary pollution, have comparatively significantly environmental benefit.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The invention provides a kind of flocculation agent of Processing Paper Wastewater, comprise:
Dispersion agent;
Polymkeric substance with formula (IV) structure:
Figure BDA0000156605350000051
Wherein, x is the polymerization degree; Y is the polymerization degree; R 1Be H or methyl; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V:
Figure BDA0000156605350000061
Wherein, R 5For H or to be selected from carbon number be 1～12 alkyl; N is the positive integer more than or equal to 6;
Said molecular weight with polymkeric substance of formula (IV) structure is 4,000,000～7,000,000.
In the present invention, the flocculation agent of said Processing Paper Wastewater mainly is made up of polymkeric substance and dispersion agent with formula (IV) structure, is SEPIGEL 305 water-in-water type dispersion-s, and the paper waste of supersalinity is had good throwing out, is beneficial to application.
In the flocculation agent of said Processing Paper Wastewater, as disperse phase, said polymkeric substance with formula (IV) structure is the hydrophobic association type SEPIGEL 305, in formula (IV), and R 1For H or methyl, be preferably H; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V, R 5For H or to be selected from carbon number be 1～12 alkyl, R 5Be preferably H, n is the positive integer more than or equal to 6, and n is preferably the positive integer between 7 to 20, more preferably the positive integer between 8 to 15;
In formula (IV), x is the polymerization degree, and y is the polymerization degree, and the present invention does not have particular restriction to the ratio between x and the y, the ratio of y and x is preferably 1: 1～and 10, more preferably 1: 2～8, most preferably be 1: 3～6; Said molecular weight with polymkeric substance of formula (IV) structure is 4,000,000～7,000,000, is preferably 5,000,000～6,000,000.
In said polymkeric substance with formula (IV) structure; Substituting group shown in the said formula V is the hydrophobic association group; Have good salt tolerance, make in the brine media hydrodynamic volume of polymer molecular chain bigger, flocculation ability is strong, flocculation rate is fast; The suspended solid in the paper waste of supersalinity can be effectively removed, its COD value can be significantly reduced simultaneously.
In the flocculation agent of said Processing Paper Wastewater; Said dispersion agent is this area dispersion agent commonly used; Be preferably cationic polymers, more preferably gather (dimethyl diallyl ammonium chloride), gather (acrylyl oxy-ethyl-trimethyl salmiac) or gather (methylacryoyloxyethyl trimethyl ammonium chloride); The molecular weight of said dispersion agent is preferably 200,000～1,000,000, and more preferably 300,000～800,000, most preferably be 400,000～700,000; The present invention preferably with the lower cationic polymers of molecular weight as dispersion medium, can comparatively stably disperse said polymkeric substance with formula (IV) structure;
The present invention does not have particular restriction to the source of said dispersion agent; The quality optimization of said dispersion agent be said polymkeric substance with formula (IV) structure quality 2%～10%, more preferably 3%～8%, most preferably be 4%～6%.
The present invention also provides a kind of preparation method of flocculation agent of Processing Paper Wastewater, may further comprise the steps:
In the aqueous solution of inorganic salt; Acrylamido chain alkyl carboxylic acid and acrylic amide or the USAF RH-1 that will have formula (VI) structure carry out copolyreaction in water in the presence of initiator and dispersion agent, obtain comprising the flocculation agent of the said dispersion agent and the Processing Paper Wastewater of the polymkeric substance with formula (IV) structure;
Said acrylamido chain alkyl carboxylic acid has formula (VI) structure:
Figure BDA0000156605350000071
Wherein, R 5For H or to be selected from carbon number be 1～12 alkyl; N is the positive integer more than or equal to 6;
Said polymkeric substance has formula (IV) structure:
Wherein, x is the polymerization degree; Y is the polymerization degree; R 1Be H or methyl; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V:
Figure BDA0000156605350000073
Wherein, R 5For H or to be selected from carbon number be 1～12 alkyl; N is the positive integer more than or equal to 6.
The present invention is a main raw material with acrylamido chain alkyl carboxylic acid, acrylic amide or USAF RH-1, initiator and the dispersion agent with formula (VI) structure; Prepare the flocculation agent of Processing Paper Wastewater; Its paper waste to supersalinity has good throwing out, is beneficial to application.
Acrylamido chain alkyl carboxylic acid, acrylic amide or the USAF RH-1 input that the present invention will have formula (IV) structure fills in the reactor drum of the aqueous solution and dispersion agent of inorganic salt; Add entry and initiator and carry out copolyreaction, obtain comprising the flocculation agent of the said dispersion agent and the Processing Paper Wastewater of polymkeric substance with formula (VI) structure.
In the present invention, said hydrophobic association monomer with acrylamido chain alkyl carboxylic acid of formula (IV) structure for the participation copolyreaction, wherein, R 5For H or to be selected from carbon number be 1～12 alkyl, R 5Be preferably H; N is the positive integer more than or equal to 6, and n is preferably the positive integer between 7 to 20, more preferably the positive integer between 8 to 15; Said acrylamido chain alkyl carboxylic acid with formula (IV) structure most preferably is R 5For H, n 6 sad, the R of acrylamido with formula (IV) structure 5For H, n 14 acrylamido palmitic acid, R with formula (IV) structure 5For H, n 10 acrylamido laurostearic acid or R with formula (IV) structure 5It for H, n 9 acrylamido undeeanoic acid with formula (IV) structure.
Said acrylic amide or USAF RH-1 be for participating in another monomer of copolyreaction, can with above-mentioned hydrophobic association monomer generation free radicals copolymerization reaction, generate multipolymer with formula (VI) structure, wherein, R 1Be H or methyl; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V, R 5For H or to be selected from carbon number be 1～12 alkyl, n is the positive integer more than or equal to 6; X, y are the polymerization degree; Said molecular weight with polymkeric substance of formula (IV) structure is 4,000,000～7,000,000, is preferably 5,000,000～6,000,000.
In said polymkeric substance with formula (IV) structure; Substituting group shown in the said formula V is the hydrophobic association group; Have good salt tolerance, make in the brine media hydrodynamic volume of polymer molecular chain bigger, flocculation ability is strong, flocculation rate is fast; The suspended solid in the paper waste of supersalinity can be effectively removed, its COD value can be significantly reduced simultaneously.
The present invention has the acrylamido chain alkyl carboxylic acid of formula (VI) structure and the source of said acrylic amide or USAF RH-1 does not all have particular restriction to said; The mol ratio of said acrylamido chain alkyl carboxylic acid with formula (VI) structure and said acrylic amide or USAF RH-1 is preferably 1: 1～and 10, more preferably 1: 2～8, most preferably be 1: 3～6; The overall mass concentration in said water of said acrylamido chain alkyl carboxylic acid with formula (VI) structure and said acrylic amide or USAF RH-1 is preferably 10%～40%, and more preferably 15%～35%, most preferably be 20%～30%.
The present invention adds the aqueous solution of inorganic salt, make that the monomer dissolution rate is fast, dissolving fully, the reaction system initial viscosity is little; Said inorganic salt are preferably one or more in Repone K, sodium-chlor, ammonium chloride, vitriolate of tartar, sodium sulfate and the ammonium sulfate, more preferably one or both in sodium-chlor, ammonium chloride and the ammonium sulfate; The mass concentration of said inorganic salt in the said aqueous solution is preferably 25%～40%, and more preferably 30%～35%.
In the present invention, said acrylic amide or USAF RH-1 and said two kinds of monomers of acrylamido chain alkyl carboxylic acid with formula (VI) structure carry out copolyreaction under action of evocating.Said initiator is persulfuric acid salt initiator, hydroperoxide kind initiator or azo-initiator; Wherein, Said persulfuric acid salt initiator such as ammonium persulphate, Sodium Persulfate; Said hydroperoxide kind initiator such as hydrogen peroxide, tertbutyl peroxide, said azo-initiator include but not limited to azo-initiator V-50, azo-initiator VA-061 and azo-initiator VA-044; The quality optimization of said initiator be said acrylamido chain alkyl carboxylic acid with formula (VI) structure and said acrylic amide or USAF RH-1 the quality summation 0.1%～5%, more preferably 0.5%～4%, most preferably be 1%～3%;
In the present invention, said copolyreaction is carried out in the presence of dispersion agent, is dispersion polymerization.The quality optimization of said dispersion agent be said acrylamido chain alkyl carboxylic acid with formula (VI) structure and said acrylic amide or USAF RH-1 the quality summation 2%～10%, more preferably 3%～8%, most preferably be 4%～6%;
Said dispersion agent is preferably cationic polymers, more preferably gathers (dimethyl diallyl ammonium chloride), gathers (acrylyl oxy-ethyl-trimethyl salmiac) or gathers (methylacryoyloxyethyl trimethyl ammonium chloride); The molecular weight of said dispersion agent is preferably 200,000～1,000,000, more elects 300,000～800,000 as, most preferably is 400,000～700,000; It is dispersion agent that the present invention preferably adopts the lower cationic polymers of molecular weight, can with the said well behaved SEPIGEL 305 water-in-water type of polymer formation dispersion-s, the i.e. flocculation agent of Processing Paper Wastewater with formula (VI) structure.
In the present invention, the temperature of said copolyreaction is preferably 30 ℃～70 ℃, more preferably 40 ℃～60 ℃; The time of said copolyreaction is preferably 6 hours～and 10 hours, more preferably 7 hours～9 hours; The monomer conversion of said copolyreaction is more than 95%.
After the said copolyreaction, obtain white milky dispersion, i.e. the flocculation agent of Processing Paper Wastewater, it comprises said dispersion agent and said polymkeric substance with formula (VI) structure.
After obtaining the flocculation agent of Processing Paper Wastewater; It is that the paper waste of 0.5M～2M is handled to saltiness that the present invention adopts it; When the consumption of flocculation agent was 0.15g/L～0.2g/L, the clearance of COD value was more than 73%, and the clearance of suspended solid is more than 83%.The flocculation agent that shows Processing Paper Wastewater provided by the invention can effectively be removed the suspended solid in the paper waste of supersalinity, can significantly reduce its COD value simultaneously, and flocculating effect is better, is beneficial to application.
In addition, preparing method's environmental protection of the flocculation agent of Processing Paper Wastewater provided by the invention, and use flocculation agent in flocculation process, not produce secondary pollution, have comparatively significantly environmental benefit.
In order further to understand the present invention, flocculation agent of Processing Paper Wastewater provided by the invention and preparation method thereof is described particularly below in conjunction with embodiment.
Embodiment 1
In mass concentration is 25% sodium chloride aqueous solution; According to mol ratio is 1: 1, will have that the acrylamido of formula (VI) structure is sad to be dropped in the reaction flask with two kinds of monomers of acrylic amide, is that 200,000 gather (dimethyl diallyl ammonium chloride) is dispersion agent with the molecular weight that accounts for above-mentioned two kinds of monomer total masses 5%; Add entry; Regulating the overall mass concentration of above-mentioned two kinds of monomers is 20%, adds 0.1% ammonium persulphate of above-mentioned two kinds of monomer mass summations then, in temperature is to carry out free radicals copolymerization reaction under 70 ℃ the condition; The time of copolyreaction is 10 hours; Obtain white milky dispersion, promptly comprise the flocculation agent of the above-mentioned dispersion agent and the Processing Paper Wastewater of the polymkeric substance with formula (IV) structure, monomer conversion is 99.2%.
In formula (IV), R 1Be H; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V, R 5Be H, n is 6; X is the polymerization degree; Y is the polymerization degree; Said molecular weight with polymkeric substance of formula (IV) structure is 4,100,000.
The flocculation agent that adopts said Processing Paper Wastewater is that the paper waste of 0.5M is handled to saltiness; When the consumption of the flocculation agent of said Processing Paper Wastewater is 0.2g/L; The COD value is reduced to 195.3mg/L by 1248.6mg/L; The clearance of COD value is 84.4%, and the clearance of suspended solid is 91.4%.
Embodiment 2
In mass concentration is 40% aqueous ammonium chloride solution; According to mol ratio is 1: 10, and two kinds of monomers of acrylamido palmitic acid and acrylic amide that will have formula (VI) structure drop in the reaction flask, is that 1,000,000 gather (acrylyl oxy-ethyl-trimethyl salmiac) is dispersion agent with the molecular weight that accounts for above-mentioned two kinds of monomer total masses 2%; Add entry; Regulating the overall mass concentration of above-mentioned two kinds of monomers is 10%, adds 5% hydrogen peroxide of above-mentioned two kinds of monomer mass summations then, in temperature is to carry out free radicals copolymerization reaction under 70 ℃ the condition; The time of copolyreaction is 6 hours; Obtain white milky dispersion, promptly comprise the flocculation agent of the above-mentioned dispersion agent and the Processing Paper Wastewater of the polymkeric substance with formula (IV) structure, monomer conversion is 97.5%.
In formula (IV), R 1Be H; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V, R 5Be H, n is 14; X is the polymerization degree; Y is the polymerization degree; Said molecular weight with polymkeric substance of formula (IV) structure is 6,900,000.
The flocculation agent that adopts said Processing Paper Wastewater is that the paper waste of 1M is handled to saltiness; When the consumption of the flocculation agent of said Processing Paper Wastewater is 0.15g/L; The COD value is reduced to 218.7mg/L by 1029.8mg/L; The clearance of COD value is 78.8%, and the clearance of suspended solid is 87.4%.
Embodiment 3
In mass concentration is 30% ammonium sulfate solution; According to mol ratio is 1: 5, and two kinds of monomers of acrylamido laurostearic acid and acrylic amide that will have formula (VI) structure drop in the reaction flask, is that 600,000 gather (methylacryoyloxyethyl trimethyl ammonium chloride) is dispersion agent with the molecular weight that accounts for above-mentioned two kinds of monomer total masses 10%; Add entry; Regulating the overall mass concentration of above-mentioned two kinds of monomers is 40%, adds 5% azo-initiator VA-044 of above-mentioned two kinds of monomer mass summations then, in temperature is to carry out free radicals copolymerization reaction under 30 ℃ the condition; The time of copolyreaction is 8 hours; Obtain white milky dispersion, promptly comprise the flocculation agent of the above-mentioned dispersion agent and the Processing Paper Wastewater of the polymkeric substance with formula (IV) structure, monomer conversion is 98.1%.
In formula (IV), R 1Be H; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V, R 5Be H, n is 10; X is the polymerization degree; Y is the polymerization degree; Said molecular weight with polymkeric substance of formula (IV) structure is 5,800,000.
The flocculation agent that adopts said Processing Paper Wastewater is that the paper waste of 2M is handled to saltiness; When the consumption of the flocculation agent of said Processing Paper Wastewater is 0.15g/L; The COD value is reduced to 367.4mg/L by 1408.3mg/L; The clearance of COD value is 73.9%, and the clearance of suspended solid is 93.4%.
Embodiment 4
In the aqueous solution that contains sodium-chlor and ammonium sulfate, the mass concentration of sodium-chlor and ammonium sulfate is respectively 8% and 20%, is 1: 7 according to mol ratio; Acrylamido undeeanoic acid and two kinds of monomers of acrylic amide that will have formula (VI) structure drop in the reaction flask; With the molecular weight that accounts for above-mentioned two kinds of monomer total masses 7% is that 700,000 gather (acrylyl oxy-ethyl-trimethyl salmiac) is dispersion agent, adds entry, and regulating the overall mass concentration of above-mentioned two kinds of monomers is 30%; 1% the ammonium persulphate that adds above-mentioned two kinds of monomer mass summations then; Be to carry out free radicals copolymerization reaction under 35 ℃ the condition in temperature, the time of copolyreaction is 8 hours, obtains white milky dispersion; Promptly comprise the flocculation agent of the above-mentioned dispersion agent and the Processing Paper Wastewater of the polymkeric substance with formula (IV) structure, monomer conversion is 96.9%.
In formula (IV), R 1Be H; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V, R 5Be H, n is 9; X is the polymerization degree; Y is the polymerization degree; Said molecular weight with polymkeric substance of formula (IV) structure is 5,500,000.
The flocculation agent that adopts said Processing Paper Wastewater is that the paper waste of 1M is handled to saltiness; When the consumption of the flocculation agent of said Processing Paper Wastewater is 0.2g/L; The COD value is reduced to 243.2mg/L by 1372.6mg/L; The clearance of COD value is 82.3%, and the clearance of suspended solid is 83.8%.
Can know by above embodiment; It is the paper waste of 0.5M～2M that the flocculation agent of said Processing Paper Wastewater is handled saltiness; When the consumption of flocculation agent was 0.15g/L～0.2g/L, the clearance of COD value was more than 73%, and the clearance of suspended solid is more than 83%.Show that flocculation agent provided by the invention is strong to the flocculation ability of the higher paper waste of saltiness, flocculation rate is fast, can effectively remove suspended solid wherein, can significantly reduce its COD value simultaneously, flocculating effect is better, is beneficial to application.
In addition, preparing method's environmental protection of the flocculation agent of Processing Paper Wastewater provided by the invention, and use flocculation agent in flocculation process, not produce secondary pollution, have comparatively significantly environmental benefit.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.

Claims (10)

1. the flocculation agent of a Processing Paper Wastewater comprises:
Dispersion agent;
Polymkeric substance with formula (IV) structure:
Figure FDA0000156605340000011
Wherein, x is the polymerization degree; Y is the polymerization degree; R 1Be H or methyl; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V:
Figure FDA0000156605340000012
Wherein, R 5For H or to be selected from carbon number be 1～12 alkyl; N is the positive integer more than or equal to 6;
Said molecular weight with polymkeric substance of formula (IV) structure is 4,000,000～7,000,000.
2. the flocculation agent of Processing Paper Wastewater according to claim 1 is characterized in that, said dispersion agent is for gathering (dimethyl diallyl ammonium chloride), gather (acrylyl oxy-ethyl-trimethyl salmiac) or gathering (methylacryoyloxyethyl trimethyl ammonium chloride); The molecular weight of said dispersion agent is 200,000～1,000,000.
3. the flocculation agent of Processing Paper Wastewater according to claim 1 and 2 is characterized in that, the quality of said dispersion agent be said polymkeric substance with formula (IV) structure quality 2%～10%.
4. the preparation method of the flocculation agent of a Processing Paper Wastewater may further comprise the steps:
In the aqueous solution of inorganic salt; Acrylamido chain alkyl carboxylic acid and acrylic amide or the USAF RH-1 that will have formula (VI) structure carry out copolyreaction in water in the presence of initiator and dispersion agent, obtain comprising the flocculation agent of the said dispersion agent and the Processing Paper Wastewater of the polymkeric substance with formula (IV) structure;
Said acrylamido chain alkyl carboxylic acid has formula (VI) structure:
Figure FDA0000156605340000021
Wherein, R 5For H or to be selected from carbon number be 1～12 alkyl; N is the positive integer more than or equal to 6;
Said polymkeric substance has formula (IV) structure:
Figure FDA0000156605340000022
Wherein, x is the polymerization degree; Y is the polymerization degree; R 1Be H or methyl; R 2Be carboxamido-group; R 3Be H; R 4Be the substituting group shown in the formula V:
Figure FDA0000156605340000023
Wherein, R 5For H or to be selected from carbon number be 1～12 alkyl; N is the positive integer more than or equal to 6.
5. preparation method according to claim 4 is characterized in that, said have the acrylamido chain alkyl carboxylic acid of formula (VI) structure and the mol ratio of said acrylic amide or USAF RH-1 is 1: 1～10.
6. preparation method according to claim 4 is characterized in that, said dispersion agent is for gathering (dimethyl diallyl ammonium chloride), gather (acrylyl oxy-ethyl-trimethyl salmiac) or gathering (methylacryoyloxyethyl trimethyl ammonium chloride); The molecular weight of said dispersion agent is 200,000～1,000,000; The quality of said dispersion agent be said acrylamido chain alkyl carboxylic acid with formula (VI) structure and said acrylic amide or USAF RH-1 the quality summation 2%～10%.
7. preparation method according to claim 4 is characterized in that, said initiator is persulfuric acid salt initiator, hydroperoxide kind initiator or azo-initiator; The quality of said initiator be said acrylamido chain alkyl carboxylic acid with formula (VI) structure and said acrylic amide or USAF RH-1 the quality summation 0.1%～5%.
8. preparation method according to claim 4 is characterized in that, the overall mass concentration in said water of said acrylamido chain alkyl carboxylic acid with formula (VI) structure and said acrylic amide or USAF RH-1 is 10%～40%.
9. preparation method according to claim 4 is characterized in that, said inorganic salt are one or more in Repone K, sodium-chlor, ammonium chloride, vitriolate of tartar, sodium sulfate and the ammonium sulfate; The mass concentration of said inorganic salt in the said aqueous solution is 25%～40%.
10. preparation method according to claim 4 is characterized in that, the temperature of said copolyreaction is 30 ℃～70 ℃; The time of said copolyreaction is 6 hours～10 hours.
CN201210122277.2A 2012-04-24 2012-04-24 Flocculating agent for treating papermaking waste water and preparation method thereof Active CN102642904B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210122277.2A CN102642904B (en) 2012-04-24 2012-04-24 Flocculating agent for treating papermaking waste water and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210122277.2A CN102642904B (en) 2012-04-24 2012-04-24 Flocculating agent for treating papermaking waste water and preparation method thereof

Publications (2)

Publication Number Publication Date
CN102642904A true CN102642904A (en) 2012-08-22
CN102642904B CN102642904B (en) 2014-04-09

Family

ID=46656030

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210122277.2A Active CN102642904B (en) 2012-04-24 2012-04-24 Flocculating agent for treating papermaking waste water and preparation method thereof

Country Status (1)

Country Link
CN (1) CN102642904B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104163887A (en) * 2014-07-10 2014-11-26 中昊(大连)化工研究设计院有限公司 Hydrophobically associating dimethyl diallyl ammonium chloride cation flocculating agent and preparation method thereof
CN105600894A (en) * 2015-12-23 2016-05-25 佛山市中科院环境与安全检测认证中心有限公司 Flocculant for sewage treatment
CN106279554A (en) * 2016-08-11 2017-01-04 中国科学院长春应用化学研究所 A kind of hyper-branched polymer flocculating demulsifier processing oil-containing high salt industrial wastewater and preparation method thereof and using method
CN110655156A (en) * 2019-10-18 2020-01-07 上海霖动环保科技有限公司 Catalytic flue gas desulfurization wastewater flocculant and preparation method thereof
CN110724535A (en) * 2019-11-01 2020-01-24 河南城建学院 Novel ecological garden greening soil remediation treatment agent and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6531531B1 (en) * 1998-08-24 2003-03-11 Green Technology Inc. Method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant to be used for the treatment of waste water
CN1880353A (en) * 2006-01-25 2006-12-20 四川师范大学 Water-soluble organic amphiprotic polymeric flocculant and preparation method
US7250462B2 (en) * 2001-06-11 2007-07-31 Hymo Corporation Amphoteric water-soluble polymer dispersion and use thereof
CN101249996A (en) * 2007-12-11 2008-08-27 四川师范大学 Organic high polymer coagulant and preparation method thereof
CN101613435A (en) * 2009-07-30 2009-12-30 江苏江达生态科技有限公司 A kind of cationic terpolymer that contains hydrophobic grouping and preparation method thereof and application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6531531B1 (en) * 1998-08-24 2003-03-11 Green Technology Inc. Method and composition of a hydrophilic polymer dispersion containing an inorganic flocculant to be used for the treatment of waste water
US7250462B2 (en) * 2001-06-11 2007-07-31 Hymo Corporation Amphoteric water-soluble polymer dispersion and use thereof
CN1880353A (en) * 2006-01-25 2006-12-20 四川师范大学 Water-soluble organic amphiprotic polymeric flocculant and preparation method
CN101249996A (en) * 2007-12-11 2008-08-27 四川师范大学 Organic high polymer coagulant and preparation method thereof
CN101613435A (en) * 2009-07-30 2009-12-30 江苏江达生态科技有限公司 A kind of cationic terpolymer that contains hydrophobic grouping and preparation method thereof and application

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104163887A (en) * 2014-07-10 2014-11-26 中昊(大连)化工研究设计院有限公司 Hydrophobically associating dimethyl diallyl ammonium chloride cation flocculating agent and preparation method thereof
CN105600894A (en) * 2015-12-23 2016-05-25 佛山市中科院环境与安全检测认证中心有限公司 Flocculant for sewage treatment
CN106279554A (en) * 2016-08-11 2017-01-04 中国科学院长春应用化学研究所 A kind of hyper-branched polymer flocculating demulsifier processing oil-containing high salt industrial wastewater and preparation method thereof and using method
CN106279554B (en) * 2016-08-11 2018-11-27 中国科学院长春应用化学研究所 A kind of hyper-branched polymer flocculating demulsifier and preparation method thereof handling oil-containing industrial wastewater with high salt and application method
CN110655156A (en) * 2019-10-18 2020-01-07 上海霖动环保科技有限公司 Catalytic flue gas desulfurization wastewater flocculant and preparation method thereof
CN110724535A (en) * 2019-11-01 2020-01-24 河南城建学院 Novel ecological garden greening soil remediation treatment agent and preparation method thereof

Also Published As

Publication number Publication date
CN102642904B (en) 2014-04-09

Similar Documents

Publication Publication Date Title
CN102642904B (en) Flocculating agent for treating papermaking waste water and preparation method thereof
CN100551941C (en) Dispersion polymeric acrylamide emulsion and the application in oil field mining liquid is handled thereof
CN101249996B (en) Organic high polymer coagulant preparation method
CN104085971B (en) Compound cationic flocculant and preparation method thereof
KR100777638B1 (en) Method of clarifying water using low molecular weight cationic dispersion polymers
CN103964557B (en) A kind of method utilizing paper mill sludge to prepare positively charged ion organic floculant
KR101846041B1 (en) Methods of preparing novel halide anion free quaternary ammonium salt monomers, polymerization methods therefor, and methods of use of the resulting polymers
CN102583684B (en) Method for preparing flocculating agent from paper mill sludge
CN104556331A (en) PAC (polyaluminium chloride)-modified sodium alginate inorganic-organic composite flocculant and preparation method thereof
CN103254443B (en) Preparation method of textile waste cellulose based sewage flocculant
CN114262412B (en) Anti-shearing modified polyacrylamide and application thereof
CN100402564C (en) Water soluble organic amphoteric high molecule copolymer and its preparation method
CN102617793A (en) Flocculating agent and preparation method thereof
US6258279B1 (en) Hydrophilic cationic dispersion polymer for paper mill color removal
CN103539891A (en) Amphoteric flocculant preparation method
JP6134940B2 (en) Coagulation treatment method for oil-containing cleaning wastewater
CN105001381A (en) Preparation method for papermaking sludge based amphoteric polymer flocculent
CN105776465B (en) A kind of compound coagulant for treatment of dyeing wastewater and preparation method thereof
CN100453573C (en) Positive ion organic high polymer coagulant and preparation method thereof
CN105273131A (en) Preparation method of cationic polyacrylamide emulsion
CN115894807A (en) Super-concentrated coagulant and preparation method thereof
EP4367256A2 (en) Biological method for obtaining monomers comprising an ethylenic unsaturation by bioconversion of a bio-sourced compound comprising at least one nitrile function
CN104017429A (en) High molecular deinking agent and preparation method thereof
US20220169545A1 (en) Methods and compositions for treating produced water
CN100368452C (en) Water-soluble organic amphiprotic polymeric flocculant and preparation method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20160603

Address after: 130022 Changchun people's street, Jilin, No. 5625

Patentee after: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences

Patentee after: Zhejiang Zhongke Chemical Technology Co., Ltd.

Address before: 130022 Changchun people's street, Jilin, No. 5625

Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences

Patentee before: Changchun Institute of Applied Chemistry Chinese Academy of Sciences Hangzhou Branch

TR01 Transfer of patent right

Effective date of registration: 20190709

Address after: 310014 Lime Dam No. 7, Gongshu District, Hangzhou City, Zhejiang Province

Patentee after: Hangzhou Research Institute of Chemical Technology Co., Ltd.

Address before: 130022 No. 5625 Renmin Street, Jilin, Changchun

Co-patentee before: Zhejiang Zhongke Chemical Technology Co., Ltd.

Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20190718

Address after: 311305 No. 168 Qianwu Road, Qingshan Lake Street, Linan District, Hangzhou City, Zhejiang Province

Patentee after: Hangzhou Kewan New Materials Technology Co., Ltd.

Address before: 310014 lime dam No. 7, Hangzhou, Zhejiang, Gongshu District

Patentee before: Hangzhou Research Institute of Chemical Technology Co., Ltd.

TR01 Transfer of patent right