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:
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:
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:
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:
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:
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:
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:
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:
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.