CN103301821B - A kind of lignin graft copolymerization compound adsorption resin and preparation method thereof - Google Patents
A kind of lignin graft copolymerization compound adsorption resin and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to technical field of adsorbent resins, be specifically related to a kind of lignin graft copolymerization compound adsorption resin and preparation method thereof.This composite adsorption resin is by acrylamide, maleic anhydride, sodium lignin sulfonate, shitosan, potassium peroxydisulfate and N, N '-methylene-bisacrylamide composition.The method introduces graft copolymerization short chain on lignin molecule chain, and make on lignin structure more regular, molecular weight improves a lot.Described composite adsorption resin has certain water absorbing properties, mainly for improve metal biosorption amount in Diversity metal ion solution system and competitive Adsorption selective.
Description
Technical field
The invention belongs to technical field of adsorbent resins, be specifically related to a kind of high adsorption capacity and high competitive Adsorption optionally lignin graft copolymerization compound adsorption resin and preparation method thereof.
Background technology
At present, it is more common that acrylic monomer modified lignin resin is used as polymeric adsorbent, and modification is mainly realized by the method for low molecule derivatization and vinyl monomer graft copolymerization.Existing lignin, chitosan graft modification by copolymerization be lignin, shitosan grafting vinyl monomer respectively mainly, and by graft copolymerization product for the treatment of single metal ion solution, so far graft copolymerization polymeric adsorbent lignin/chitosan interpenetrating network being prepared by lignin and chitosan blend thing grafting vinyl monomer is seldom had, and will the research report of selective absorption in multiple metal ion mixed solution be applied to, and also rarely found with the research improving its absorption property for the further process of graft copolymerization product.
Summary of the invention
The object of the present invention is to provide and a kind ofly improve lignin graft copolymerization compound adsorption resin of selective absorption performance in multiple metal ion mixed solution and preparation method thereof.This lignin graft copolymerization compound adsorption resin is by lignin, chitosan blend grafting binary vinyl monomer, prepare with inorganic clay compound simultaneously, products therefrom has certain water absorbing properties, mainly for improve metal biosorption amount in Diversity metal ion solution system and competitive Adsorption selective.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of lignin graft copolymerization compound adsorption resin, be that total monomer calculates according to acrylamide and maleic anhydride, formula and content thereof are:
The mass ratio of acrylamide and maleic anhydride is 3-6 ︰ 2,
The mass ratio of sodium lignin sulfonate and total monomer is 0.5-2.0 ︰ 10,
The mass ratio of sodium lignin sulfonate and shitosan is 0.2-2 ︰ 1,
The mass content of potassium peroxydisulfate is the 0.4%-1.0% of total monomer quality,
N, N ' mass content of-methylene-bisacrylamide is the 0.16%-0.28% of total monomer quality,
The mass content of inorganic clay is the 0.1%-10% of total monomer quality.
Preferred formula and content thereof are:
The mass ratio of acrylamide and maleic anhydride is 4-5 ︰ 2,
The mass ratio of sodium lignin sulfonate and total monomer is 0.8-1.5 ︰ 10,
The mass ratio of sodium lignin sulfonate and shitosan is 1-1.5 ︰ 1,
The mass content of potassium peroxydisulfate is the 0.6%-0.8% of total monomer quality,
N, N ' mass content of-methylene-bisacrylamide is the 0.2%-0.25% of total monomer quality,
The mass content of inorganic clay is the 2%-5% of total monomer quality.
Described inorganic clay is preferably selected from bentonite, kaolin, diatomite or imvite.
The preparation method of described lignin graft copolymerization compound adsorption resin, is characterized in that, concrete steps are:
1) quantitative sodium lignin sulfonate is taken by above-mentioned formula and acrylamide is dissolved in distilled water respectively;
2) in acrylamide aqueous solution, maleic anhydride, inorganic clay, N, N is added successively '-methylene-bisacrylamide, stirs, mixes, obtain solution A;
3) then solution A is joined in the aqueous solution of sodium lignin sulfonate, adjustment pH is 2.0-5.0, add potassium peroxydisulfate again, sealing, 1.5h-2.5h is reacted at 60 DEG C-70 DEG C, 1.5h-2.5h is reacted again at 70 DEG C-80 DEG C, then at 80 DEG C-90 DEG C, 1.5h-2.5h is reacted, after having reacted at 80 DEG C-100 DEG C slaking 0.3h-1.2h, cooling, shreds rear methyl alcohol washing by soaking, dry at last 70 DEG C ~ 80 DEG C, pulverize, cross 60 order ~ 100 mesh sieves and obtain lignin graft copolymerization compound adsorption resin.
Above-mentioned preparation method preferably also comprises following saponification step:
The NaOH solution of preparation 0.1mol/L-2.0mol/L as saponification agent, and is heated to 50 DEG C ~ 100 DEG C; Take described lignin graft copolymerization compound adsorption resin, be immersed in the described NaOH solution of 200mL according to every 5g lignin graft copolymerization compound adsorption resin, saponification 0.25h-4.0h at 50 DEG C ~ 100 DEG C, then filters and obtains adsorbent after saponification, cooling, with distilled water flushing, until efflux is in neutral, 70 DEG C ~ 80 DEG C vacuum drying, pulverize, cross 60 order-100 mesh sieves, obtain the lignin graft copolymerization compound adsorption resin after saponification.
Compared with prior art, advantage of the present invention is:
1, lignin graft copolymerization compound adsorption resin introduces graft copolymerization short chain on lignin molecule chain, and make on lignin structure more regular, molecular weight improves a lot, and application performance is better.
2, lignin graft copolymerization compound adsorption resin is better to metal biosorption effect, especially Pb
2+, different disposal method can be taked to be applied according to actual conditions, such as: selective removal Pb from the water body of a certain heavy metal pollution
2+, directly can apply after graft copolymerization synthesis; If do not consider the selective of resin and consider adsorbance, then can be improved the adsorbance of resin further by saponification, saponification resultant can be applied in the water body that many metal ions coexist and remove many kinds of metal ions simultaneously.
3, introduce shitosan in lignin graft copolymerization compound adsorption resin, shitosan and graft copolymer thereof have good absorption property, can improve the adsorbance of lignin graft copolymerization polymeric adsorbent.
4, introduce inorganic clay in lignin graft copolymerization compound adsorption resin, both improve the gel strength of graft copolymerization product, again reduced cost.
5, the preparation method that the present invention relates to is simple, easy to operate, not high to equipment requirement, is easy to suitability for industrialized production.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.Total monomer described in embodiment is acrylamide and maleic anhydride.
embodiment 1:
Take 1.625g sodium lignin sulfonate and 0.82g shitosan is dissolved in 30ml dilute hydrochloric acid solution.Separately getting 19.95g acrylamide is dissolved in distilled water, adds 13.3g maleic anhydride, 1g bentonite, 0.0665g N, N '-methylene-bisacrylamide successively, stirs, mixes (being designated as A liquid) in acrylamide solution.Then A liquid is joined in sodium lignin sulfonate/chitosan blend solution, pH is regulated to be 4.0, add 0.266g potassium peroxydisulfate again, sealing, heat up, after 65 DEG C, 75 DEG C, 85 DEG C each reaction 2 h, 90 DEG C of slaking 0.5h, cooling, shred rear methyl alcohol washing by soaking, dry, pulverize in 70 ~ 80 DEG C of vacuum drying chambers, sieve 60 ~ 100 object bentonite/shitosans/sodium lignin sulfonate-g-acrylamide-maleic acid acid anhydride composite adsorption resin B LAMA(hereinafter referred to as composite adsorption resin B LCAMA).Under room temperature, BLCAMA is at the binary Pb of 100mL, 2mmol/L
2+/ Cu
2+to Pb in solution
2+adsorbance be 0.825mmol/g, Pb
2+to Cu
2+selectivity factor α be 6.01.That is: formulation condition is m (sodium lignin sulfonate): m (total monomer)=0.5:10, m (sodium lignin sulfonate): m (shitosan)=2:1, m (acrylamide): m (maleic anhydride)=3:2, m (potassium peroxydisulfate)=0.8 ﹪, m (N, N '-methylene-bisacrylamide)=0.20 ﹪, m (bentonite)=3%, pH=4 time, gained composite adsorption resin B LCAMA is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 0.925mmol/g, Pb
2+to Cu
2+selectivity factor α be 5.81.
embodiment 2:
Method of operating is with embodiment 1.Formulation condition is m (sodium lignin sulfonate): m (total monomer)=2.0:10, m (sodium lignin sulfonate): m (shitosan)=1:1, m (acrylamide): m (maleic anhydride)=5:2, m (potassium peroxydisulfate)=0.8 ﹪, m (N, N '-methylene-bisacrylamide)=0.20 ﹪, m (kaolin)=1%, pH=4 time, gained composite adsorption resin KLCAMA is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 0.987mmol/g, Pb
2+to Cu
2+selectivity factor α be 5.67.
embodiment 3:
Method of operating is with embodiment 1.Formulation condition is m (sodium lignin sulfonate): m (total monomer)=1.0:10, m (sodium lignin sulfonate): m (shitosan)=2:1, m (acrylamide): m (maleic anhydride)=6:2, m (potassium peroxydisulfate)=1.0 ﹪, m (N, N '-methylene-bisacrylamide)=0.24 ﹪, m (diatomite)=5%, pH=3 time, gained composite adsorption resin GLCAMA is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 0.843mmol/g, Pb
2+to Cu
2+selectivity factor α be 4.91.
embodiment 4:
Method of operating is with embodiment 1.Formulation condition is m (sodium lignin sulfonate): m (total monomer)=1.0:10, m (sodium lignin sulfonate): m (shitosan)=1:2, m (acrylamide): m (maleic anhydride)=4:2, m (potassium peroxydisulfate)=0.4 ﹪, m (N, N '-methylene-bisacrylamide)=0.24 ﹪, m (imvite)=7%, pH=4 time, gained composite adsorption resin M LCAMA is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 0.842mmol/g, Pb
2+to Cu
2+selectivity factor α be 5.43.
embodiment 5:
Method of operating is with embodiment 1.Formulation condition is m (sodium lignin sulfonate): m (total monomer)=1.0:10, m (sodium lignin sulfonate): m (shitosan)=1:5, m (acrylamide): m (maleic anhydride)=4:2, m (potassium peroxydisulfate)=0.4 ﹪, m (N, N '-methylene-bisacrylamide)=0.24 ﹪, m (imvite)=7%, pH=4 time, gained composite adsorption resin M LCAMA is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.342mmol/g, Pb
2+to Cu
2+selectivity factor α be 6.63.
embodiment 6:
Method of operating is with embodiment 1.Formulation condition is m (sodium lignin sulfonate): m (total monomer)=1.0:10, m (sodium lignin sulfonate): m (shitosan)=1:4, m (acrylamide): m (maleic anhydride)=4:2, m (potassium peroxydisulfate)=0.4 ﹪, m (N, N '-methylene-bisacrylamide)=0.24 ﹪, m (bentonite)=7%, pH=4 time, gained composite adsorption resin B LCAMA is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.49mmol/g, Pb
2+to Cu
2+selectivity factor α be 6.39.
embodiment 7:
Select the formula gained resin B LCAMA in embodiment 1, the NaOH solution of preparation 1.0mol/L is as saponification agent.Taking 5g resin B LCAMA is immersed in the above-mentioned alkali lye of 200ml, filter after being heated to 90 DEG C of saponification 2.0h in water bath with thermostatic control and obtain polymeric adsorbent after saponification, cooling, with a large amount of distilled water flushings, until efflux is in neutral, dry, pulverize in 70 ~ 80 DEG C of vacuum drying chambers, sieve, obtain the composite adsorption resin particle of certain particle diameter.Composite adsorption resin after saponification is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.442mmol/g, to Cu
2+adsorbance is 1.29mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.22.That is: Saponification Conditions is C
naOHwhen=1.0mol/L, saponification temperature 90 DEG C, saponification time 2.0h, after saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.442mmol/g, to Cu
2+adsorbance is 1.29mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.22.
embodiment 8:
Adopt the formula gained resin KLCAMA in embodiment 2 to carry out saponification, saponification operation is with embodiment 5.Saponification Conditions is C
naOH=1.6mol/L, saponification temperature 70 DEG C, saponification time 2.0h.After saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.417mmol/g, to Cu
2+adsorbance be 1.1239mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.21.
embodiment 9:
Adopt the formula gained resin GLCAMA in embodiment 3 to carry out saponification, saponification operation is with embodiment 5.Saponification Conditions is C
naOH=2.0mol/L, saponification temperature 60 DEG C, saponification time 2.0h.After saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.314mmol/g, to Cu
2+adsorbance be 1.117mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.85.
embodiment 10:
Adopt the formula gained resin M LCAMA in embodiment 4 to carry out saponification, saponification operation is with embodiment 5.Saponification Conditions is C
naOH=0.1mol/L, saponification temperature 100 DEG C, saponification time 2.0h.After saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.22mmol/g, to Cu
2+adsorbance be 0.79mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.62.
embodiment 11:
Adopt the formula gained resin B LCAMA in embodiment 1 to carry out saponification, saponification operation is with embodiment 5.Saponification Conditions is C
naOH=1.0mol/L, saponification temperature 100 DEG C, saponification time 2.0h.After saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.39mmol/g, to Cu
2+adsorbance be 1.29mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.04.
embodiment 12:
Adopt the formula gained resin KLCAMA in embodiment 2 to carry out saponification, saponification operation is with embodiment 5.Saponification Conditions is C
naOH=1.0mol/L, saponification temperature 80 DEG C, saponification time 2.0h.After saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.29mmol/g, to Cu
2+adsorbance be 1.197mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.14.
embodiment 13:
Adopt the formula gained resin GLCAMA in embodiment 3 to carry out saponification, saponification operation is with embodiment 5.Saponification Conditions is C
naOH=2.0mol/L, saponification temperature 60 DEG C, saponification time 2.5h.After saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.38mmol/g, to Cu
2+adsorbance be 1.251mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.08.
embodiment 14:
Adopt the formula gained resin M LCAMA in embodiment 4 to carry out saponification, saponification operation is with embodiment 5.Saponification Conditions is C
naOH=1.0mol/L, saponification temperature 50 DEG C, saponification time 2.0h.After saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.158mmol/g, to Cu
2+adsorbance be 1.08mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.21.
embodiment 15
Adopt the formula gained resin B LCAMA in embodiment 1 to carry out saponification, saponification operation is with embodiment 5.Saponification Conditions is C
naOH=1.0mol/L, saponification temperature 90 DEG C, saponification time 1.5h.After saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.484mmol/g, to Cu
2+adsorbance be 1.388mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.36.
embodiment 16:
Adopt the formula gained resin KLCAMA in embodiment 2 to carry out saponification, saponification operation is with embodiment 5.Saponification Conditions is C
naOH=1.0mol/L, saponification temperature 90 DEG C, saponification time 3.0h.After saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.361mmol/g, to Cu
2+adsorbance be 1.259mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.12.
embodiment 17:
Adopt the formula gained resin GLCAMA in embodiment 3 to carry out saponification, saponification operation is with embodiment 5.Saponification Conditions is C
naOH=1.0mol/L, saponification temperature 90 DEG C, saponification time 4.0h.After saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.437mmol/g, to Cu
2+adsorbance be 1.295mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.09.
embodiment 18:
Adopt the formula gained resin M LCAMA in embodiment 4 to carry out saponification, saponification operation is with embodiment 5.Saponification Conditions is C
naOH=0.5mol/L, saponification temperature 90 DEG C, saponification time 0.25h.After saponification, composite adsorption resin is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.193mmol/g, to Cu
2+adsorbance be 0.858mmol/g, Pb
2+to Cu
2+selectivity factor α be 1.43.
embodiment 19:
Method of operating is with embodiment 1.Formulation condition is m (sodium lignin sulfonate): m (total monomer)=1.5:10, m (sodium lignin sulfonate): m (shitosan)=1:3, m (acrylamide): m (maleic anhydride)=6:2, m (potassium peroxydisulfate)=0.8 ﹪, m (N, N '-methylene-bisacrylamide)=0.20 ﹪, m (kaolin)=1%, pH=4 time, gained composite adsorption resin KLCAMA is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 1.387mmol/g, Pb
2+to Cu
2+selectivity factor α be 6.27.
embodiment 20:
Method of operating is with embodiment 1.Formulation condition is m (sodium lignin sulfonate): m (total monomer)=2.0:10, m (sodium lignin sulfonate): m (shitosan)=1:1, m (acrylamide): m (maleic anhydride)=5:2, m (potassium peroxydisulfate)=0.8 ﹪, m (N, N '-methylene-bisacrylamide)=0.20 ﹪, m (kaolin)=3%, pH=2 time, gained composite adsorption resin KLCAMA is at binary Pb
2+/ Cu
2+to Pb in solution
2+adsorbance be 0.587mmol/g, Pb
2+to Cu
2+selectivity factor α be 4.67.
Claims (2)
1. a lignin graft copolymerization compound adsorption resin, is characterized in that, be that total monomer calculates according to acrylamide and maleic anhydride, formula and content thereof are:
The mass ratio of acrylamide and maleic anhydride is 3-6 ︰ 2,
The mass ratio of sodium lignin sulfonate and total monomer is 0.5-2.0 ︰ 10,
The mass ratio of sodium lignin sulfonate and shitosan is 0.2-2 ︰ 1,
The mass content of potassium peroxydisulfate is the 0.4%-1.0% of total monomer quality,
N, N ' mass content of-methylene-bisacrylamide is the 0.16%-0.28% of total monomer quality,
The mass content of inorganic clay is the 0.1%-10% of total monomer quality; Described inorganic clay is selected from bentonite, diatomite or imvite;
Preparation method is:
1) take quantitative sodium lignin sulfonate by above-mentioned formula and shitosan is dissolved in dilute hydrochloric acid solution, obtain sodium lignin sulfonate/chitosan blend solution; And acrylamide is dissolved in distilled water, obtain acrylamide aqueous solution;
2) in acrylamide aqueous solution, maleic anhydride, inorganic clay, N, N is added successively '-methylene-bisacrylamide, stirs, mixes, obtain solution A;
3) then solution A is joined in sodium lignin sulfonate/chitosan blend solution, adjustment pH is 2.0-5.0, add potassium peroxydisulfate again, sealing, 1.5h-2.5h is reacted at 60 DEG C-70 DEG C, 1.5h-2.5h is reacted again at 70 DEG C-80 DEG C, then at 80 DEG C-90 DEG C, 1.5h-2.5h is reacted, after having reacted at 80 DEG C-100 DEG C slaking 0.3h-1.2h, cooling, shred rear methyl alcohol washing by soaking, last dry at 70 DEG C ~ 80 DEG C, pulverize, cross 60 order ~ 100 mesh sieves, obtain lignin graft copolymerization compound adsorption resin;
4) saponification process further: the NaOH solution of preparation 0.1mol/L-2.0mol/L as saponification agent, and is heated to 50 DEG C ~ 100 DEG C; Take described lignin graft copolymerization compound adsorption resin, be immersed in the described NaOH solution of 200mL according to every 5g lignin graft copolymerization compound adsorption resin, saponification 0.25h-4.0h at 50 DEG C ~ 100 DEG C, then filters and obtains adsorbent after saponification, cooling, with distilled water flushing, until efflux is in neutral, vacuum drying at 70 DEG C ~ 80 DEG C, pulverizes, cross 60 order-100 mesh sieves, obtain the lignin graft copolymerization compound adsorption resin after saponification.
2. lignin graft copolymerization compound adsorption resin according to claim 1, it is characterized in that according to acrylamide and maleic anhydride being that total monomer calculates, formula and content thereof are:
The mass ratio of acrylamide and maleic anhydride is 4-5 ︰ 2,
The mass ratio of sodium lignin sulfonate and total monomer is 0.8-1.5 ︰ 10,
The mass ratio of sodium lignin sulfonate and shitosan is 1-1.5 ︰ 1,
The mass content of potassium peroxydisulfate is the 0.6%-0.8% of total monomer quality,
N, N ' mass content of-methylene-bisacrylamide is the 0.2%-0.25% of total monomer quality,
The mass content of inorganic clay is the 2%-5% of total monomer quality.
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| CN105944699B (en) * | 2016-07-11 | 2019-03-22 | 中南林业科技大学 | A kind of composite adsorption resin |
| CN105944689B (en) * | 2016-07-11 | 2019-03-22 | 中南林业科技大学 | A kind of compound adsorbent |
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| CN106540665A (en) * | 2016-11-03 | 2017-03-29 | 江苏百博木业有限公司 | A kind of formaldehyde adsorbent |
| CN109647358B (en) * | 2018-12-29 | 2021-09-14 | 湘潭大学 | Preparation method of maleic anhydride modified lignosulfonate-based adsorption material and application of adsorption material in wastewater treatment |
| CN111410752B (en) * | 2019-01-04 | 2021-11-26 | 华南农业大学 | Hydrogel nanocomposite and preparation method and application thereof |
| CN110564381B (en) * | 2019-09-28 | 2021-07-20 | 重庆威能钻井助剂有限公司 | Composite filtrate reducer for drilling fluid and preparation method thereof |
| CN110668582A (en) * | 2019-10-29 | 2020-01-10 | 盘林(厦门)生物科技有限责任公司 | Biological compound water treatment agent and preparation method and application thereof |
| CN113893822B (en) | 2021-10-22 | 2022-08-09 | 华南理工大学 | Lignin grading porous carbon with high specific surface area and preparation method and application thereof |
| CN115999520A (en) * | 2023-02-16 | 2023-04-25 | 内蒙古农业大学 | Method for preparing pH response lignin-based adsorbent |
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| CN102294199A (en) * | 2011-05-16 | 2011-12-28 | 福州大学 | Lignosulfonate grafted copolymer dispersant, preparation technology thereof, and application thereof |
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