CN102604119A - Method for preparing lignosulfonate from papermaking pulping red liquor - Google Patents
Method for preparing lignosulfonate from papermaking pulping red liquor Download PDFInfo
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Abstract
The invention provides a method for preparing lignosulfonate from papermaking pulping red liquor, which comprises the following steps of: carrying out ultrafiltration on the papermaking pulping red liquor to obtain first lignosulfonate and filtrate; adding a pH value regulator into the obtained filtrate to obtain precipitates and supernate; carrying out cation exchange chromatographic separation and anion exchange chromatographic separation on the obtained supernate to obtain monosaccharide and eluent; and carrying out nanofiltration on the obtained eluent to obtain second lignosulfonate. According to the invention, the papermaking pulping red liquor is subjected to repeated ultrafiltration, ionic exchange chromatographic separation and nanofiltration, the lignosulfonate is graded to obtain the lignosulfonate with different molecular weight distributions and the monosaccharide. Products obtained by the method provided by the invention have various types and high added value. The application field of the papermaking pulping red liquor product is widened. Moreover, the products obtained by the method disclosed by the invention have high purity, so that the quality of industrial products made of the products serving as raw materials is improved.
Description
Technical field
The present invention relates to the papermaking wastewater processing technology field, relate in particular to the method that the red liquid of a kind of paper-making pulping prepares sulfonated lignin.
Background technology
In paper industry, mainly adopt sulphite process, sulphate process and three kinds of methods of soda processes to carry out pulping and digesting, wherein the pulp washing waste liquid that obtains of sulphite process is reddish-brown, is commonly called red liquid.Pulping digestion process adopting sulphite process can produce a large amount of red liquid; One ton of wood pulp of every production can produce 11 tons～14 tons red liquid; The solid content that obtains red liquid is about 9.5%～11.5%, and wherein the content of sulfonated lignin is about 5.5%～6.0%, and reducing sugar content is about 2.5%～3.0%; Calcium sulfite and other impurity are about 2.2%～2.5%, with these waste liquids directly the discharging meeting cause serious pollution to environment.
In the red liquid of paper pulp, contain a large amount of sulfonated lignin; This is a kind of important chemical auxiliary agent; It can be used as oilfield additive product, industrial water conditioning agent, process hides auxiliary agent, electroplating additives, dispersion agent, cement water reducing agent, gypsum board manufacture auxiliary agent, inert ingredient, printing and dyeing diffusant, rubber wear-resisting agent etc.; Also can be used as raw material or the midbody of producing dyestuff, vanillin food grade,1000.000000ine mesh, tanning agent, can also replace 50% phenol and formaldehyde condensation to prepare plastics.Sulfonated lignin are linear macromolecule; The sulfonated lignin of different molecular weight have different character, and then can to influence with sulfonated lignin be performance (Pang Yuxia, the Qiu Xueqing of the Chemicals that obtain of raw material; Yang Dongjie; Ou Yangxinping. the performance of different relative molecular mass calcium lignosulfonate water reducers, the journal natural science edition .2002 of South China Science & Engineering University, 30 (1): 53～57.).Therefore, the sulfonated lignin of the different relative molecular masses in the red liquid of paper-making pulping are extracted, solved the discharging of waste liquid problem of environment pollution caused on the one hand, on the other hand, can produce widely used product.
At present, papermaking enterprise generally adds lime putty in the red liquid of paper pulp, carries out the high temperature oxidation hypoglycemic then, makes reducing sugar wherein form saccharic acid and corresponding calcium salt, concentrates and spraying drying through multiple-effect evaporation again, obtains sulfonated lignin.Adopt the content of the sulfonated lignin that this method obtains low, generally be no more than 55%, can only be used to produce low-grade auxiliary agent product; And this method is big at hypoglycemic and evaporating course energy consumption, and production cost is high, and economy is relatively poor.In order to reduce the energy consumption in the production process; Reduce production costs; The method of from red liquid, extracting sulfonated lignin with physical method is disclosed in the prior art; As publication number be the Chinese patent of CN20081004489.0 to disclose a kind of be the method that raw material extracts sulfonated lignin with the sodium sulfite bamboo pulp waste liquor, this method is at first filtered bamboo pulp waste liquor and is sloughed O-fiber with sieve, the filtrating that will obtain is then sloughed heteroproteose cell, solid shape impurity and particulate through filter; The filtrating that will obtain is again carried out separation and purification through ultrafiltration system, after evaporation concentration and drying obtain the lignosulfonic acid salt product.This method can effectively reduce production cost, yet the product that obtains is more single, makes that the Application Areas of product is comparatively narrow.
Summary of the invention
The object of the present invention is to provide the red liquid of a kind of paper-making pulping to prepare the method for sulfonated lignin, the Application Areas of the red liquid product of paper pulp has been widened in the product diversification of method preparation provided by the invention.
The present invention provides the red liquid of a kind of paper-making pulping to prepare the method for sulfonated lignin, may further comprise the steps:
A) the red liquid of paper-making pulping is carried out ultrafiltration, obtain first sulfonated lignin and filtrating;
B) filtrating that said step a) is obtained obtains first nanofiltration liquid concentrator and the waste water through carrying out first nanofiltration;
C) in the first nanofiltration liquid concentrator that said step b) obtains, add pH value regulator, obtain inferior deposition and supernatant;
D) supernatant that said step c) is obtained carries out the cation-exchange chromatography separation to be separated with anion-exchange chromatography, obtains the second lignosulfonic acid salt eluent and mixes the monose elutriant;
E) the second lignosulfonic acid salt eluent that said step d) is obtained is carried out second nanofiltration, obtains second sulfonated lignin;
F) the mixing monose elutriant that said step d) is obtained carries out the 3rd nanofiltration, obtains mixing the monose liquid concentrator.
Preferably, said step a) is specially:
A1) the red liquid of paper-making pulping is carried out first ultrafiltration, obtain the macromole sulfonated lignin and first filtrating;
A2) with said step a1) obtain first filtrating carry out second ultrafiltration, obtain in the molecule sulfonated lignin and second filtrating.
Preferably, said step a1) be specially:
A11) the red liquid of paper-making pulping is carried out one-level ultrafiltration, two-stage ultrafiltering and three grades of ultrafiltration successively, obtain the macromole sulfonated lignin and first filtrating.
Preferably, said step a11) in, the precision of holding back of one-level ultrafiltration is 10000 dalton～25000 dalton, the pressure of one-level ultrafiltration is 0.2MPa～1.0MPa;
The precision of holding back of two-stage ultrafiltering is 10000 dalton～25000 dalton, and the pressure of two-stage ultrafiltering is 0.2MPa～1.0MPa;
The precision of holding back of three grades of ultrafiltration is 10000 dalton～25000 dalton, and the pressure of three grades of ultrafiltration is 0.2MPa～1.0MPa.
Preferably, said step a2) be specially:
A21) with said step a1) obtain first filtrating carry out one-level ultrafiltration, two-stage ultrafiltering and three grades of ultrafiltration successively, obtain in the molecule sulfonated lignin and second filtrating.
Preferably, said step a21) in, the precision of holding back of one-level ultrafiltration is 800 dalton～2000 dalton, the pressure of one-level ultrafiltration is 0.5MPa～1.5MPa;
The precision of holding back of two-stage ultrafiltering is 800 dalton～2000 dalton, and the pressure of two-stage ultrafiltering is 0.5MPa～1.4MPa;
The precision of holding back of three grades of ultrafiltration is 800 dalton～2000 dalton, and the pressure of three grades of ultrafiltration is 0.5MPa～1.4MPa.
Preferably, the precision of holding back of nanofiltration is 200 dalton～400 dalton in the said step b), and the pressure of nanofiltration is 2.5-3.0MPa.
Preferably, said step c) is specially:
In the filtrating that said step b) obtains, add the pH regulator agent, said pH value of filtrate is transferred to 4.50～8.00, obtain deposition and supernatant.
Preferably, said pH value regulator is lime slurry, carbonate or ammoniacal liquor.
Preferably, said step e) and f) in the precision of holding back of nanofiltration be 200 dalton～400 dalton independently.
Preferably, also comprise step before the said step a):
The stoste of the red liquid of paper-making pulping is regulated, just filtered and smart filter through the pH value successively, obtain the red liquid of paper-making pulping.
The present invention provides a kind of paper-making pulping method that red liquid is produced sulfonated lignin, may further comprise the steps: a) the red liquid of paper-making pulping is carried out ultrafiltration, obtain first sulfonated lignin and filtrating; B) filtrating that said step a) is obtained is carried out first nanofiltration, obtains first nanofiltration liquid concentrator and the waste water; C) the first nanofiltration liquid concentrator that said step b) is obtained adds pH value regulator, obtains inferior deposition and supernatant; D) supernatant that said step c) is obtained carries out the cation-exchange chromatography separation to be separated with anion-exchange chromatography, obtains the second lignosulfonic acid salt eluent and mixes the monose elutriant; E) the second lignosulfonic acid salt eluent that said step d) is obtained is carried out second nanofiltration, obtains second sulfonated lignin; F) the mixing monose elutriant that said step d) is obtained carries out the 3rd nanofiltration, obtains mixing the monose liquid concentrator.Method provided by the invention is a raw material with the red liquid of paper-making pulping; It is separated and nanofiltration through ultrafiltration, zwitterion exchange chromatography successively, obtain first bigger sulfonated lignin of molecular weight and the second less sulfonated lignin of molecular weight, realized classification sulfonated lignin; The product category that obtains is many; Have diversified advantage, the first sulfonated lignin molecular weight wherein is bigger, can be used to prepare fine chemical products such as high-grade dye dispersant and high-grade cement water reducing agent; The second sulfonated lignin molecular weight is less, can be used as the raw material of preparation vanillin food grade,1000.000000ine mesh etc.; Method provided by the invention is realizing that the sulfonated lignin fractionated has been obtained monose simultaneously; Improved the added value of the red liquid product of paper-making pulping; Said monose comprises pectinose, semi-lactosi, wood sugar, seminose and glucose, and these monose can be used for foodstuffs industry, also can be applied to biological fermentation and produce ethanol, butanols or acetone; Can also conduct produce the raw material of wood sugar, seminose etc., thereby widen the Application Areas of the red liquid product of paper-making pulping.
Experiment shows that the sulfonated lignin that the present invention obtains and the purity of monose are higher, the purity of sulfonated lignin >=80%, and the purity of monose >=95% has improved the quality of spent pulping liquor product.
Further; The further classification of first sulfonated lignin that the present invention will obtain; Obtain the middle middle molecule sulfonated lignin of bigger macromole sulfonated lignin of relative molecular mass and relative molecular mass, make the Application Areas of the sulfonated lignin that obtain obtain more widening.Method provided by the invention adopts repeatedly ultrafiltration, nanofiltration, can also realize the elementary of material concentrated, thereby can effectively reduce the energy consumption in the production process, reduces production costs.
Description of drawings
Fig. 1 provides method preferred process flow diagram for the present invention.
Embodiment
The invention provides the method that the red liquid of a kind of paper-making pulping prepares sulfonated lignin, may further comprise the steps:
A) the red liquid of paper-making pulping is carried out ultrafiltration, obtain first sulfonated lignin and filtrating;
B) filtrating that said step a) is obtained is carried out first nanofiltration, obtains first nanofiltration liquid concentrator and the waste water;
C) in the first nanofiltration liquid concentrator that said step b) obtains, add pH value regulator, obtain inferior deposition and supernatant;
D) supernatant that said step c) is obtained carries out the cation-exchange chromatography separation to be separated with anion-exchange chromatography, obtains the second lignosulfonic acid salt eluent and mixes the monose elutriant;
E) the second lignosulfonic acid salt eluent that said step d) is obtained is carried out second nanofiltration, obtains second sulfonated lignin;
F) the mixing monose elutriant that said step d) is obtained carries out the 3rd nanofiltration, obtains mixing the monose liquid concentrator.
In sulphite process paper-making pulping process; Slurrying washings after the washing boiling is reddish-brown; Be commonly called red liquid; The pH value of red liquid stoste is about 1.80～2.2, wherein contains different sulfonation degree, different sulfonated lignin and the monose of relative molecular mass, also contains Mierocrystalline cellulose, semicellulose and inorganic salt etc.The present invention is the raw material of preparation sulfonated lignin with the red liquid of paper-making pulping; The red liquid of said paper-making pulping can be the red liquid of the slurrying of acid sulfite cooking needlebush; Also can be the red liquid of the herbal slurrying of acid sulfite cooking, the present invention is preferably the red liquid of slurrying of acid sulfite cooking needlebush; The red liquid of said paper-making pulping can be the stoste of the red liquid of paper-making pulping, also can be the red liquid of paper-making pulping after the adjusting pH value.
The pH value of in the present invention, regulating red liquid stoste is preferably carried out according to following method:
The present invention adds pH value regulator in the stoste of the red liquid of paper-making pulping, the pH value of said red liquid is preferably transferred to 4.0～5.1, and more preferably 4.5～5.0.Said in the present invention pH value regulator is preferably carbonate, milk of lime or ammoniacal liquor, and more preferably lime carbonate, magnesiumcarbonate, yellow soda ash, volatile salt, milk of lime or ammoniacal liquor most preferably are milk of lime, yellow soda ash or ammoniacal liquor.The present invention selects according to the kind of the sulphite that adopts in the sulfurous method paper-making process for the selection of pH value regulator; Said pH value regulator is corresponding with said sulphite; If what promptly in paper-making process, adopt is S-WAT, the pH value regulator that then in the red liquid of paper-making pulping, adds is preferably yellow soda ash.
After obtaining preparing the raw material of sulfonated lignin, the present invention prepares sulfonated lignin and monose preferably according to technical process shown in Figure 1.Fig. 1 provides method preferred process flow diagram for the present invention.F1 just filters journey among the figure; F2 is the smart journey that filters; V1, P1 and UF1 form the one-level ultrafiltration in first ultrafiltration; V2, P2 and UF2 form the two-stage ultrafiltering in first ultrafiltration; V3, P3 and UF3 form three grades of ultrafiltration in first ultrafiltration, and wherein V1, V2 and V3 are that container for storing liquid, P1, P2 and P3 are that centrifugal fresh feed pump, UF1, UF2 and UF3 are hyperfiltration membrane assembly; V4, P4 and UF4 form the one-level ultrafiltration in second ultrafiltration; V5, P5 and UF5 form the two-stage ultrafiltering in second ultrafiltration; V6, P6 and UF6 form three grades of ultrafiltration in second ultrafiltration, and wherein V4, V5 and V6 are that container for storing liquid, P4, P5 and P6 are that centrifugal fresh feed pump, UF4, UF5 and UF6 are hyperfiltration membrane assembly; V7, P7 and N1 form the nanofiltration that second filtrating is carried out, and wherein V7 is that container for storing liquid, P7 are that centrifugal fresh feed pump, N1 are nanofiltration membrane component; T1 is a cation-exchange chromatography; T2 is an anion-exchange chromatography; V8, P8 and N2 form the nanofiltration that liquid glucose is carried out, and V9, P9 and N3 form the nanofiltration that elutriant is carried out, and wherein V8 and V9 are that container for storing liquid, P8 and P9 are that centrifugal fresh feed pump, N2 and N3 are nanofiltration membrane component.Concrete technological process is following:
After obtaining preparing the raw material of sulfonated lignin; Mechanical impurity in the red liquid of paper-making pulping; Mainly be of the influence of fiber fines such as Walocel MT 20.000PV to preparation sulfonated lignin process; The present invention preferably removes mechanical impurity wherein before red liquid carries out ultrafiltration to paper-making pulping, be specially:
The red liquid of paper-making pulping successively through filter just and smart filter, is obtained the filtrating that the red liquid of paper-making pulping is removed mechanical impurity, and as the raw material of preparation sulfonated lignin, said filter just is referring to the F1 process among Fig. 1, and the F2 process among Fig. 1 is participated in said smart filter.The sulfonated lignin, monose and the inorganic salt that comprise different relative molecular masses in the filtrating of the process that obtains filter just and smart filter.The present invention does not have special limitation to said filter just and smart filter, adopts the technical scheme of filter just well known to those skilled in the art and smart filter to get final product.In the present invention, the preferred flame filter press that adopts of said filter just, the said filtering accuracy of filter just is preferably 20 μ m～300 μ m, and more preferably 35 μ m～140 μ m most preferably are 50 μ m～105 μ m; Said smart filter is preferably fine filting machine, and the filtering accuracy of said smart filter is preferably 0.5 μ m～8 μ m, and more preferably 1.0 μ m～5.0 μ m most preferably are 2.0 μ m～4.0 μ m.
After removing the mechanical impurity in the red liquid stoste of paper-making pulping, the filtrating that the present invention will obtain is carried out ultrafiltration, obtains first sulfonated lignin and filtrating.Kind variation more for the lignosulfonic acid product salt that makes preparation; The present invention preferably carries out first ultrafiltration and second ultrafiltration to the filtrating that the red liquid of paper-making pulping is removed mechanical impurity successively; Make the sulfonated lignin of winning obtain further classification; Obtain the middle middle molecule sulfonated lignin of bigger macromole sulfonated lignin of molecular weight and molecular weight; The process of said first ultrafiltration is preferably the process shown in first ultrafiltration among Fig. 1, and the process of said second ultrafiltration is preferably the process shown in second ultrafiltration among Fig. 1, is specially:
The filtrating of a1) the red liquid of paper-making pulping being removed mechanical impurity is carried out first ultrafiltration, obtains the macromole sulfonated lignin and first filtrating;
A2) with said step a1) obtain first filtrating carry out second ultrafiltration, obtain in the molecule sulfonated lignin and second filtrating.
Obtain product gas purity in order to improve, the filtrating that the present invention preferably adopts the mode of classification ultrafiltration that the red liquid of said paper-making pulping is removed mechanical impurity is carried out first ultrafiltration, is specially:
The red liquid of paper-making pulping is removed the filtrating of mechanical impurity and is carried out one-level ultrafiltration, two-stage ultrafiltering and three grades of ultrafiltration successively, obtain the macromole sulfonated lignin and first filtrating, be specially:
After removing the mechanical impurity in the red liquid of paper-making pulping, the present invention preferably under the condition of pressurization and heating, carries out the one-level ultrafiltration with the filtrating of removing mechanical impurity that obtains, and obtains first liquid concentrator and the 3rd filtrating.As shown in Figure 1, in said one-level ultrafiltration, the filtrating of removing mechanical impurity that preferably will obtain is stored among the container for storing liquid V1, through centrifugal fresh feed pump P1 said filtrating is squeezed among the hyperfiltration membrane assembly UF1.The present invention is after obtaining first liquid concentrator; Preferably 70%～95% first liquid concentrator circulation is returned among the container for storing liquid V1; More preferably 75%～90%, preferably with remaining 5%～30% first liquid concentrator raw material as next step, more preferably 10%～25%.In the present invention, the precision of holding back of said one-level ultrafiltration is preferably 10000 dalton～25000 dalton, more preferably 15000 dalton～20000 dalton; The membrane flux of ultra-filtration membrane is preferably 10L/m in the said one-level ultrafiltration
2H～30L/m
2H, more preferably 12L/m
2H～28L/m
2H; The pressure of said pressurization is preferably 0.1MPa～1.5MPa, and more preferably 0.2MPa～1.0MPa most preferably is 0.4MPa～0.8MPa; The temperature of said heating is preferably 25 ℃～55 ℃, more preferably 30 ℃～50 ℃, most preferably is 35 ℃～45 ℃.
The solid content of first liquid concentrator according to the invention is preferably 15wt%～50wt%, more preferably 19wt%～40wt%; Wherein the ratio of macromole sulfonated lignin preferred >=80.0%, more preferably >=85.0%; The molecular weight of said macromole sulfonated lignin is preferably 14000～100000.
After obtaining remaining 5%～30% first liquid concentrator, the present invention preferably under pressurization and heating condition, preferably carries out two-stage ultrafiltering with said first liquid concentrator after dilution, obtain second liquid concentrator and the 4th filtrating.As shown in Figure 1, in said two-stage ultrafiltering, first liquid concentrator that preferably will obtain is stored among the container for storing liquid V2, through centrifugal fresh feed pump P2 said first liquid concentrator is squeezed among the hyperfiltration membrane assembly UF2.The present invention preferably returns the circulation of 75%～95% second liquid concentrator among the container for storing liquid V2 after obtaining second liquid concentrator, and more preferably 80%～90%, preferably with remaining 5%～25% raw material as next step, more preferably 10%～20%.In the present invention, the precision of holding back of said two-stage ultrafiltering is preferably 10000 dalton～25000 dalton, more preferably 15000 dalton～20000 dalton; The membrane flux of ultra-filtration membrane is preferably 5L/m in the said two-stage ultrafiltering
2H～30L/m
2H, more preferably 8L/m
2H～25L/m
2H; The pressure of said pressurization is preferably 0.1MPa～1.5MPa, and more preferably 0.2MPa～1.0MPa most preferably is 0.4MPa～0.8MPa; The temperature of said heating is preferably 25 ℃～55 ℃, more preferably 30 ℃～50 ℃, most preferably is 35 ℃～45 ℃; The multiple of said dilution is preferably 1.1 times～8 times, more preferably 1.5 times～5 times.
The solid content of second liquid concentrator according to the invention is preferably 15wt%～50wt%, more preferably 18wt%～40wt%; Wherein the ratio of macromole sulfonated lignin preferred >=87.0%, more preferably >=92%; The molecular weight of said macromole sulfonated lignin is preferably 19000～100000.
After obtaining remaining 5%～25% second liquid concentrator; The present invention is preferably under pressurization and heating condition; Said second liquid concentrator is preferably carried out three grades of ultrafiltration after dilution, obtain the 3rd liquid concentrator and the 5th filtrating, comprise the macromole sulfonated lignin in said the 3rd liquid concentrator.As shown in Figure 1, in said three grades of ultrafiltration, second liquid concentrator that preferably will obtain is stored among the container for storing liquid V3, through centrifugal fresh feed pump P3 said second liquid concentrator is squeezed among the hyperfiltration membrane assembly UF3.The present invention is after obtaining the 3rd liquid concentrator; Preferably the circulation of 75%～95% the 3rd liquid concentrator is returned among the container for storing liquid V3, more preferably 80%～90%, preferred remaining 5%～25% is the product of first ultrafiltration; Be the macromole sulfonated lignin, more preferably 10%～20%.In the present invention, the precision of holding back of said three grades of ultrafiltration is preferably 10000 dalton～25000 dalton, more preferably 15000～20000 dalton; The membrane flux of ultra-filtration membrane is preferably 5L/m in said three grades of ultrafiltration
2H～35L/m
2H, more preferably 10L/m
2H～28L/m
2H; The pressure of said pressurization is preferably 0.1MPa～1.5MPa, and more preferably 0.2MPa～1.0MPa most preferably is 0.4MPa～0.8MPa; The temperature of said heating is preferably 25 ℃～55 ℃, more preferably 30 ℃～50 ℃, most preferably is 35 ℃～45 ℃; Said extension rate is preferably 2 times～6 times, more preferably 3 times～5 times.
The solid content of the 3rd liquid concentrator according to the invention is preferably 15wt%～50wt%, more preferably 18wt%～40wt%; In the said solid content ratio of macromole sulfonated lignin preferred >=93.0%, more preferably >=98%, the molecular weight of said macromole sulfonated lignin is preferably 19000～97000.
After obtaining 5%～25% the 3rd liquid concentrator, the present invention preferably carries out evaporation concentration and drying with said the 3rd liquid concentrator, obtains macromole lignosulfonic acid product salt, and said macromole sulfonated lignin molecular weight is preferably 12000～100000; More preferably 15000～97000; The content of said macromole sulfonated lignin>=80%, more preferably>=90%, the content of reducing sugar≤3%, moisture content is 1%～17%.The macromole sulfonated lignin that obtain can be used for preparing fine chemical products such as high-grade dye dispersant.The present invention does not have particular restriction to said evaporation concentration and exsiccant condition, adopts evaporation concentration well known to those skilled in the art and exsiccant technical scheme to get final product.
When obtaining the macromole sulfonated lignin, the present invention also obtains first filtrating, and said first filtrating comprises the 3rd filtrating, the 3rd filtrating and the 5th filtrating that technique scheme obtains.
After obtaining first filtrating, the present invention preferably adopts the mode of classification ultrafiltration that said first filtrating is carried out second ultrafiltration, and the molecule xylogen and second filtrating in obtaining are specially:
First filtrating that technique scheme obtains is carried out one-level ultrafiltration, two-stage ultrafiltering and three grades of ultrafiltration successively, and the molecule sulfonated lignin and second filtrating in obtaining are specially:
After obtaining first filtrating, the present invention preferably under the condition of pressurization and heating, carries out the one-level ultrafiltration with said first filtrating, obtains the 4th liquid concentrator and the 6th filtrating.As shown in Figure 1, in said one-level ultrafiltration, first filtrating that preferably will obtain is stored among the container for storing liquid V4, through centrifugal fresh feed pump P4 said first filtrating is squeezed among the hyperfiltration membrane assembly UF4.The present invention is after obtaining the 4th liquid concentrator; Preferably 85%～98% the 4th liquid concentrator circulation is returned among the container for storing liquid V4; More preferably 90%～96%, preferably with remaining 2%～15% the 4th liquid concentrator raw material as next step, more preferably 4%～10%.In the present invention, the precision of holding back of said one-level ultrafiltration is preferably 800 dalton～2000 dalton, more preferably 1000 dalton～1500 dalton; The membrane flux of the ultra-filtration membrane of said one-level ultrafiltration is preferably 10L/m
2H～40L/m
2H, more preferably 15L/m
2H～35L/m
2H most preferably is 18L/m
2H～30L/m
2H; The pressure of said pressurization is preferably 0.5MPa～1.5MPa, more preferably 0.9MPa～1.3MPa; The temperature of said heating is preferably 25 ℃～55 ℃, more preferably 30 ℃～50 ℃, most preferably is 35 ℃～45 ℃.
The solid content of the 4th liquid concentrator according to the invention is preferably 15wt%～30wt%, more preferably 18wt%～26wt%; The ratio of wherein middle molecule sulfonated lignin is preferred >=and 84.0%, more preferably >=90%; The molecular weight of molecule sulfonated lignin is preferably 800～20000 in said, and more preferably 1000～8000.
After obtaining remaining 2%～15% the 4th liquid concentrator, the present invention preferably under pressurization and heating condition, preferably carries out two-stage ultrafiltering with said the 4th liquid concentrator after dilution, obtain the 5th liquid concentrator and the 7th filtrating.Of Fig. 1, in said two-stage ultrafiltering, the present invention preferably is stored in said the 4th liquid concentrator among the container for storing liquid V5, through centrifugal fresh feed pump P5 said the 4th liquid concentrator is squeezed among the hyperfiltration membrane assembly UF5.The present invention is after obtaining the 4th liquid concentrator; Preferably 75%～95% the 4th liquid concentrator circulation is returned among the container for storing liquid V5; More preferably 80%～90%, preferably with remaining 5%～25% the 4th liquid concentrator raw material as next step, more preferably 10%～20%.In the present invention, the precision of holding back of said two-stage ultrafiltering is preferably 800 dalton～2000 dalton, more preferably 1000 dalton～1500 dalton; The membrane flux of the ultra-filtration membrane of said two-stage ultrafiltering is preferably 5L/m
2H～30L/m
2H, more preferably 8L/m
2H～25L/m
2H; The pressure of said pressurization is preferably 0.5MPa～1.5MPa, more preferably 0.9MPa～1.2MPa; The temperature of said heating is preferably 25 ℃～55 ℃, more preferably 30 ℃～50 ℃, most preferably is 35 ℃～45 ℃; The solid content of said the 5th liquid concentrator is preferably 10wt%～30wt%, more preferably 15wt%～25wt%; The multiple of said dilution is preferably 1.1 times～8 times, more preferably 1.5 times～5 times.
The solid content of the 5th liquid concentrator according to the invention is preferably 10wt%～30wt%, and more preferably 15wt%～25wt% most preferably is 18wt%～22wt%; The ratio of wherein middle molecule sulfonated lignin is preferred >=and 90.0%, more preferably >=95%; The molecular weight of molecule sulfonated lignin is preferably 800～20000 in said, and more preferably 1200～8000.
After obtaining remaining 5%～25% the 5th liquid concentrator; The present invention is preferably under the condition of pressurization and heating; Said the 5th liquid concentrator is preferably carried out three grades of ultrafiltration after dilution, obtain the 6th liquid concentrator and the 8th filtrating, said the 6th liquid concentrator comprises middle molecule sulfonated lignin.As shown in Figure 1, in said three grades of ultrafiltration, the 5th liquid concentrator that preferably will obtain is stored among the container for storing liquid V6, through centrifugal fresh feed pump P6 said the 5th liquid concentrator is squeezed among the hyperfiltration membrane assembly UF6.The present invention is after obtaining the 6th liquid concentrator; Preferably 75%～95% the 6th liquid concentrator circulation is returned among the container for storing liquid V6; More preferably 80%～90%; Preferred remaining 5%～25% the 6th liquid concentrator is the product of second ultrafiltration, promptly in the molecule sulfonated lignin, more preferably 10%～20%.In the present invention, the precision of holding back of said three grades of ultrafiltration is preferably 800 dalton～2000 dalton, more preferably 1000 dalton～1500 dalton; The membrane flux of the ultra-filtration membrane of said three grades of ultrafiltration is preferably 10L/m
2H～40L/m
2H, more preferably 15L/m
2H～35L/m
2H most preferably is 20L/m
2H～30L/m
2H; The pressure of said pressurization is preferably 0.5MPa～1.5MPa, more preferably 0.9MPa～1.2MPa; The temperature of said heating is preferably 25 ℃～55 ℃, more preferably 30 ℃～50 ℃, most preferably is 35 ℃～45 ℃; The multiple of said dilution is preferably 2 times～8 times, more preferably 3 times～5 times.
The solid content of the 6th liquid concentrator according to the invention is preferably 10wt%～30wt%, and more preferably 15wt%～25wt% most preferably is 18wt%～22wt%; The ratio of wherein middle molecule sulfonated lignin is preferred >=90.0%, more preferably >=95%, said in the molecular weight of molecule sulfonated lignin be preferably 800～20000, more preferably 1200～8000.
After obtaining 5%～25% the 6th liquid concentrator; The present invention preferably carries out evaporation concentration and drying with said the 6th liquid concentrator; Molecule lignosulfonic acid product salt in obtaining, said in the molecular weight of molecule sulfonated lignin be preferably 800～20000, more preferably 1000～8000; Content>=80% of molecule sulfonated lignin in said; More preferably>=85%, most preferably be>=90%, the content of reducing sugar≤3%; The content of moisture is 1%～17%, and the middle molecule sulfonated lignin that obtain can be used for preparing fine chemical products such as high-grade cement water reducing agent.The present invention does not have particular restriction to said evaporation concentration and exsiccant condition, adopts evaporation concentration well known to those skilled in the art and exsiccant technical scheme to get final product.
In the molecule sulfonated lignin, the present invention also obtains second filtrating in obtaining, and said second filtrating comprises the 6th filtrating, the 7th filtrating and the 8th filtrating that technique scheme obtains.
After obtaining second filtrating; The present invention adds pH value regulator in said second filtrating; Carry out sedimentation, obtain deposition and supernatant, the said sulphite deposition that is precipitated as; Said supernatant comprises the monose and second sulfonated lignin, and said second sulfonated lignin are the small molecules sulfonated lignin.
In the present invention, in order to reduce the energy consumption in settling process, the present invention preferably under the condition of pressurization and heating, carries out nanofiltration with said second filtrating before carrying out sedimentation, obtain the liquid concentrator of nanofiltration.As shown in Figure 1, in said nanofiltration, the present invention preferably is stored in said second filtrating among the container for storing liquid V7, through centrifugal fresh feed pump P7 said second filtrating is squeezed among the nanofiltration membrane component N1.The present invention preferably returns the circulation of 80%～95% nanofiltration liquid concentrator among the container for storing liquid V7 after obtaining the liquid concentrator of nanofiltration, preferably with remaining 5%～15% the nanofiltration liquid concentrator raw material as next step.In the present invention, the precision of holding back of said nanofiltration is preferably 100 dalton～500 dalton, more preferably 200 dalton～400 dalton; The membrane flux of the nf membrane of said nanofiltration is preferably 15L/m
2H～30L/m
2H, more preferably 20L/m
2H～26L/m
2H; The pressure of said pressurization is preferably 2.0MPa～5.0MPa, and more preferably 2.5MPa～4.0MPa most preferably is 2.8MPa～3.0MPa; The temperature of said heating is preferably 25 ℃～55 ℃, more preferably 30 ℃～50 ℃, most preferably is 35 ℃～45 ℃.
The solid content of nanofiltration liquid concentrator according to the invention is preferably 5.0wt%～20.0wt%; 8.0wt%～14.0wt% more preferably, wherein the ratio of small molecules sulfonated lignin is preferably 27.0%～31.0%, and more preferably 28.5%～30.0%; The ratio of monose is preferably 48.0%～52.0%; More preferably 49.5%～51.0%, the ratio of sulphite is preferably 18.0%～24.0%, and more preferably 19.5%～22%.
After obtaining 5%～15% nanofiltration liquid concentrator, the present invention adds pH value regulator in said nanofiltration liquid concentrator, and the pH value of said liquid concentrator is preferably transferred to 4.50～8.00, and more preferably 5.00～6.50, obtain deposition and supernatant after leaving standstill.Said pH value regulator is preferably lime slurry or carbonate; Lime slurry more preferably; Be preferably 5h～30h, more preferably 8h～24h said rest time.The deposition that obtains is the deposition of sulfite ion, and said deposition can be used in the papermaking digesting process again, has realized the recycling of resource.The solid content of supernatant according to the invention is preferably 5.0wt%～15wt%; 6.0wt%～11wt% more preferably, wherein the ratio of sulfonated lignin is preferably 35%～38%, and more preferably 36.0%～37.0%; The ratio of monose is preferably 60.0%～65.0%; More preferably 61.5%～63.5%, the ratio of inorganic salt is preferably 0.3%～0.5%, and more preferably 0.35%～0.45%.
After obtaining supernatant, the present invention carries out the cation-exchange chromatography separation with said supernatant and separates with anion-exchange chromatography, obtains liquid glucose and elutriant, and said liquid glucose comprises monose.The present invention can carry out cation-exchange chromatography with said supernatant earlier and separate, and then carries out anion-exchange chromatography and separate; Also can earlier said supernatant be carried out anion-exchange chromatography and separate, and then carry out cation-exchange chromatography and separate, obtain liquid glucose and elutriant.As shown in Figure 1, the present invention preferably carries out cation-exchange chromatography earlier and separates, and shown in T1 among Fig. 1, carries out anion-exchange chromatography again and separates, shown in T2 among Fig. 1.In order to adapt to the continuous production in the industrial production; The present invention is preferably switched after ion exchange resin absorption is saturated, and with cationic resin column eluent and resin anion(R.A) eluent the chromatographic column of said cation-exchange chromatography and the chromatographic column of anion-exchange chromatography is carried out wash-out and resin regeneration respectively.The present invention is to the condition in said cation-exchange chromatography separation and the anion-exchange chromatography sepn process; Kind like eluent; Concentration, elution time etc. do not have special limitation, adopt cation-exchange chromatography separation well known to those skilled in the art and the isolating technical scheme of anion-exchange chromatography to get final product.
The solid content of liquid glucose according to the invention is preferably 3.5wt%～6.5wt%, wherein the ratio of sulfonated lignin preferred≤0.1%, more preferably≤0.08%; The ratio of monose preferably>=99.1%; More preferably>=99.5%, the ratio of inorganic salt is preferred≤and 0.1%, more preferably≤0.08%; The solid content of said elutriant is preferably 7.0wt%～8.5wt%, wherein the ratio of sulfonated lignin preferred>=98%, more preferably>=99%; The ratio of monose preferably≤0.1%; More preferably≤0.05%, the ratio of inorganic salt is preferred≤and 0.5%, more preferably≤0.03%.
In order to improve the content of monose in the liquid glucose, the present invention preferably under the condition of pressurization and heating, carries out nanofiltration with said liquid glucose and concentrates, and obtains the liquid glucose liquid concentrator.As shown in Figure 1, the present invention preferably is stored in said liquid glucose among the container for storing liquid V8, through centrifugal fresh feed pump P8 said liquid glucose is squeezed among the nanofiltration membrane component N2.After obtaining the liquid glucose liquid concentrator, the present invention preferably returns 85%～95% circulation of said liquid concentrator among the container for storing liquid V8, and preferred 5%～15% liquid glucose liquid concentrator is the monose product.In the present invention, the precision of holding back of said nanofiltration is preferably 200 dalton～400 dalton; The membrane flux of the nf membrane of said nanofiltration is preferably 10L/m
2H～35L/m
2H, more preferably 15L/m
2H～31L/m
2H; The pressure of said pressurization is preferably 2.0MPa～4.0MPa, and more preferably 2.5MPa～3.5MPa most preferably is 2.8MPa～3.0MPa; The temperature of said heating is preferably 25 ℃～55 ℃, more preferably 30 ℃～50 ℃, most preferably is 35 ℃～45 ℃.The solid content of liquid glucose liquid concentrator according to the invention is preferably 5wt%～20wt%; 8wt%～16wt% more preferably, wherein the ratio of monose preferred>=99.0%, more preferably>=99.8%; The ratio of sulfonated lignin≤0.1%; More preferably≤0.05%, the ratio of inorganic salt is preferred≤and 0.1%, more preferably≤0.05%.
After obtaining the liquid glucose liquid concentrator, the present invention preferably carries out two with said liquid glucose liquid concentrator imitates evaporation, obtains secondary and concentrates liquid glucose; Said secondary is concentrated liquid glucose carry out spraying drying, obtain monose, the present invention imitates evaporation to said two and spraying drying does not have special limitation, adopts two effect evaporations well known to those skilled in the art and spray-dired technical scheme to get final product.The mass concentration that secondary according to the invention concentrates liquid glucose is preferably 40%～55%, and more preferably 45%～50%; With total reducing sugar amount in the red liquid stoste is benchmark, the yield that calculates monose is preferred >=and 80%, more preferably >=85%.Said monose comprises pectinose, semi-lactosi, wood sugar, seminose and glucose, and the monose that obtains can be used to prepare the raw material of pectinose, semi-lactosi, wood sugar, seminose or glucose or be used for food or other industry as mixing molasses.
After obtaining elutriant, the present invention preferably under the condition of pressurization and heating, carries out nanofiltration with said elutriant, obtains the nanofiltration liquid concentrator, comprises the small molecules xylogen in the said nanofiltration liquid concentrator.As shown in Figure 1, the present invention preferably is stored in said elutriant among the container for storing liquid V9, through centrifugal fresh feed pump P9 said elutriant is squeezed among the nanofiltration membrane component N3.After the present invention obtains the nanofiltration liquid concentrator, preferably 80%～95% nanofiltration liquid concentrator circulation is returned among the container for storing liquid V9, preferred remaining 5%～20% nanofiltration liquid concentrator is a small molecules lignosulfonic acid product salt of the present invention.In the present invention, the precision of holding back of said nanofiltration is preferably 200 dalton～400 dalton; The membrane flux of the nf membrane of said nanofiltration is preferably 10L/m
2H～30L/m
2H, more preferably 15L/m
2H～30L/m
2H most preferably is 16L/m
2H～18L/m
2H; The pressure of said pressurization is preferably 2.0MPa～4.0MPa, more preferably 2.6MPa～3.0MPa; The temperature of said heating is preferably 25 ℃～55 ℃, more preferably 30 ℃～50 ℃, most preferably is 35 ℃～45 ℃.
The solid content of nanofiltration liquid concentrator according to the invention is preferably 10wt%～30wt%; 14wt%～22wt% more preferably; The ratio of small molecules sulfonated lignin>=98.0% wherein, more preferably>=99.0%, the molecular weight of said small molecules sulfonated lignin is preferred≤and 1200; More preferably≤1000, the small molecules sulfonated lignin that obtain can be used as the raw material for preparing vanillin food grade,1000.000000ine mesh.
The present invention is a benchmark with sulfonated lignin total amount in the red liquid stoste, the preferred yield of yield that calculates macromole lignosulfonic acid product salt is preferred >=and 35%, more preferably >=40%, most preferably be >=45%; Middle molecule lignosulfonic acid product salt >=9%, more preferably >=15%, most preferably be >=20%; The yield of small molecules lignosulfonic acid product salt is preferred >=and 20%, more preferably >=25%, most preferably be >=30%, hence one can see that, and method provided by the invention is higher to the yield of sulfonated lignin.
As shown in Figure 1, in the present invention, obtain filtrating and the elutriant except that product in the process of preparation monose and small molecules sulfonated lignin, preferably said filtrating and elutriant are squeezed into waste water and go not have water treatment system, carry out further abatement processes.
The present invention is a raw material with the red liquid of paper-making pulping; It is carried out repeatedly ultrafiltration, ion-exchange chromatography separation and nanofiltration successively; Obtained bigger first sulfonated lignin and the second less xylogen flavine salt of relative molecular mass of relative molecular mass, realized the classification to sulfonated lignin, the product category that obtains is more; The first sulfonated lignin relative molecular mass wherein is bigger; Can be used to prepare fine chemical products such as high-grade dye dispersant and high-grade cement water reducing agent, the second sulfonated lignin relative molecular mass is less, can be used for the preparation of vanillin food grade,1000.000000ine mesh etc.; Method provided by the invention has improved value-added content of product at the higher monose of purity that the sulfonated lignin fractionated is also obtained simultaneously, has widened the Application Areas of the red liquid product of paper-making pulping.
In order to further specify the present invention, below in conjunction with embodiment the method that the red liquid of paper-making pulping provided by the invention prepares sulfonated lignin is described in detail, but can not they be interpreted as the qualification to protection domain of the present invention.
Embodiment 1
The red liquid of slurrying that with 2634.8L, pH value is 1.85 acid sulphite process boiling needlebush is raw material; Prepare calcium lignin sulphonate and monose according to technical process shown in Figure 1; Preparation process correlation parameter is referring to table 1, table 2 and table 3, and table 1 prepares the experiment condition and the result of macromole sulfonated lignin for the embodiment of the invention; Table 2 is the experiment condition and the result of molecule sulfonated lignin in the embodiment of the invention preparation; Table 3 prepares the experiment condition and the result of monose and small molecules sulfonated lignin for the embodiment of the invention.
Total amount with sulfonated lignin in the red liquid stoste is a benchmark, and the productive rate that calculates the macromole calcium lignin sulphonate is 19.86%, and the yield of middle molecule calcium lignin sulphonate is 37.2%, and the yield of small molecules sulfonated lignin is 29.0%.
Embodiment 2
, 2260L, pH value add milk of lime in being the red liquid of slurrying of 2.01 acid sulphite process boiling needlebush; Its pH value is transferred to 4.86; Prepare calcium lignin sulphonate and monose according to technical process shown in Figure 1; Preparation process correlation parameter is referring to table 1, table 2 and table 3, and table 1 prepares the experiment condition and the result of macromole sulfonated lignin for the embodiment of the invention; Table 2 is the experiment condition and the result of molecule sulfonated lignin in the embodiment of the invention preparation; Table 3 prepares the experiment condition and the result of monose and small molecules sulfonated lignin for the embodiment of the invention.
Total amount with sulfonated lignin in the red liquid stoste is a benchmark, and the yield that calculates the macromole calcium lignin sulphonate is 22.1%, and the yield of middle molecule calcium lignin sulphonate is 46.0%, and the yield of small molecules calcium lignin sulphonate is 31.0%.
Embodiment 3
, 2400L, pH value add milk of lime in being the red liquid of slurrying of 1.93 acid sulphite process boiling needlebush; Its pH value is transferred to 5.01; Prepare calcium lignin sulphonate and monose according to technical process shown in Figure 1; Preparation process correlation parameter is referring to table 1, table 2 and table 3, and table 1 prepares the experiment condition and the result of macromole sulfonated lignin for the embodiment of the invention; Table 2 is the experiment condition and the result of molecule sulfonated lignin in the embodiment of the invention preparation; Table 3 prepares the experiment condition and the result of monose and small molecules sulfonated lignin for the embodiment of the invention.
Total amount with sulfonated lignin in the red liquid stoste is a benchmark, and the yield that calculates the macromole sodium lignosulfonate is 9.47%, and the yield of middle molecule sodium lignosulfonate is 48.85%, and the yield of small molecules sodium lignosulfonate is 32.26%.
Embodiment 4
, 2800L, pH value add yellow soda ash in being the red liquid of slurrying of 1.94 acid sulphite process boiling needlebush; Its pH value is transferred to 4.79; Prepare sodium lignosulfonate and monose according to technical process shown in Figure 1; Preparation process correlation parameter is referring to table 1, table 2 and table 3, and table 1 prepares the experiment condition and the result of macromole sulfonated lignin for the embodiment of the invention; Table 2 is the experiment condition and the result of molecule sulfonated lignin in the embodiment of the invention preparation; Table 3 prepares the experiment condition and the result of monose and small molecules sulfonated lignin for the embodiment of the invention.
Total amount with sulfonated lignin in the red liquid stoste is a benchmark, and the yield that calculates the macromole sodium lignosulfonate is 22.1%, and the yield of middle molecule sodium lignosulfonate is 40.53%, and the yield of small molecules sodium lignosulfonate is 26.55%.
Embodiment 5
The red liquid of slurrying that with 3000L, pH value is 1.81 acid sulphite process boiling needlebush is raw material; Prepare magnesium lignosulfonate and monose according to technical process shown in Figure 1; Preparation process correlation parameter is referring to table 1, table 2 and table 3, and table 1 prepares the experiment condition and the result of macromole sulfonated lignin for the embodiment of the invention; Table 2 is the experiment condition and the result of molecule sulfonated lignin in the embodiment of the invention preparation; Table 3 prepares the experiment condition and the result of monose and small molecules sulfonated lignin for the embodiment of the invention.
Total amount with sulfonated lignin in the red liquid stoste is a benchmark, and the yield that calculates the macromole magnesium lignosulfonate is 20.25%, and the yield of middle molecule magnesium lignosulfonate is 41.82%, and the yield of small molecules magnesium lignosulfonate is 27.02%.
Embodiment 6
, 3000L, pH value add ammoniacal liquor in being the red liquid of slurrying of 1.64 acid sulphite process boiling needlebush; Its pH value is transferred to 4.66; Prepare ammonium lignosulphonate and monose according to technical process shown in Figure 1; Preparation process correlation parameter is referring to table 1, table 2 and table 3, and table 1 prepares the experiment condition and the result of macromole sulfonated lignin for the embodiment of the invention; Table 2 is the experiment condition and the result of molecule sulfonated lignin in the embodiment of the invention preparation; Table 3 prepares the experiment condition and the result of monose and small molecules sulfonated lignin for the embodiment of the invention.
Total amount with sulfonated lignin in the red liquid stoste is a benchmark, and the yield that calculates macromole ammonium lignosulphonate is 21.79%, and the yield of middle molecule ammonium lignosulphonate is 41.06%, and the yield of small molecules ammonium lignosulphonate is 28.84%.
Table 1 embodiment of the invention prepares the experiment condition and the result of macromole sulfonated lignin
The experiment condition and the result of molecule sulfonated lignin in the preparation of table 2 embodiment of the invention
Table 3 embodiment of the invention prepares the experiment condition and the result of monose and small molecules sulfonated lignin
* be benchmark with total reducing sugar amount in the red liquid stoste
Can know by above embodiment; Method provided by the invention; The red liquid of paper-making pulping after the adjusting pH value or the stoste of the red liquid of paper-making pulping are directly carried out multi-ultrafiltration, chromatographic separation and repeatedly nanofiltration, realized the classification of sulfonated lignin, but also the higher monose of the purity that obtains.The product that method provided by the invention obtains is various, and added value is high, has increased the Application Areas of the red liquid product of paper-making pulping.In addition, method provided by the invention adopts ultrafiltration and nanofiltration, has also realized the concentrating of product reduced the energy consumption in the production process, has reduced production cost.
The above only is a preferred implementation of the present invention; 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 make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (11)
1. the red liquid of paper-making pulping prepares the method for sulfonated lignin, may further comprise the steps:
A) the red liquid of paper-making pulping is carried out ultrafiltration, obtain first sulfonated lignin and filtrating;
B) filtrating that said step a) is obtained is carried out first nanofiltration, obtains first nanofiltration liquid concentrator and the waste water;
C) in the first nanofiltration liquid concentrator that said step b) obtains, add pH value regulator, obtain inferior deposition and supernatant;
D) supernatant that said step c) is obtained carries out the cation-exchange chromatography separation to be separated with anion-exchange chromatography, obtains the second lignosulfonic acid salt eluent and mixes the monose elutriant;
E) the second lignosulfonic acid salt eluent that said step d) is obtained is carried out second nanofiltration, obtains second sulfonated lignin;
F) the mixing monose elutriant that said step d) is obtained carries out the 3rd nanofiltration, obtains mixing the monose liquid concentrator.
2. method according to claim 1 is characterized in that, said step a) is specially:
A1) the red liquid of paper-making pulping is carried out first ultrafiltration, obtain the macromole sulfonated lignin and first filtrating;
A2) with said step a1) obtain first filtrating carry out second ultrafiltration, obtain in the molecule sulfonated lignin and second filtrating.
3. method according to claim 2 is characterized in that, said step a1) be specially:
A11) the red liquid of paper-making pulping is carried out one-level ultrafiltration, two-stage ultrafiltering and three grades of ultrafiltration successively, obtain the macromole sulfonated lignin and first filtrating.
4. method according to claim 3 is characterized in that, said step a11) in, the precision of holding back of one-level ultrafiltration is 10000 dalton～25000 dalton, the pressure of one-level ultrafiltration is 0.2MPa～1.0MPa;
The precision of holding back of two-stage ultrafiltering is 10000 dalton～25000 dalton, and the pressure of two-stage ultrafiltering is 0.2MPa～1.0MPa;
The precision of holding back of three grades of ultrafiltration is 10000 dalton～25000 dalton, and the pressure of three grades of ultrafiltration is 0.2MPa～1.0MPa.
5. method according to claim 2 is characterized in that, said step a2) be specially:
A21) with said step a1) obtain first filtrating carry out one-level ultrafiltration, two-stage ultrafiltering and three grades of ultrafiltration successively, obtain in the molecule sulfonated lignin and second filtrating.
6. preparation method according to claim 5 is characterized in that, said step a21) in, the precision of holding back of one-level ultrafiltration is 800 dalton～2000 dalton, the pressure of one-level ultrafiltration is 0.5MPa～1.5MPa;
The precision of holding back of two-stage ultrafiltering is 800 dalton～2000 dalton, and the pressure of two-stage ultrafiltering is 0.5MPa～1.4MPa;
The precision of holding back of three grades of ultrafiltration is 800 dalton～2000 dalton, and the pressure of three grades of ultrafiltration is 0.5MPa～1.4MPa.
7. preparation method according to claim 1 is characterized in that, in the said step b), the precision of holding back of first nanofiltration is 200 dalton～400 dalton, and the pressure of nanofiltration is 2.5-3.0MPa.
8. preparation method according to claim 1 is characterized in that, said step c) is specially:
In the first nanofiltration liquid concentrator that said step b) obtains, add the pH regulator agent, said pH value of filtrate is transferred to 4.50～8.00, obtain inferior deposition and supernatant.
9. preparation method according to claim 8 is characterized in that, said pH value regulator is lime slurry, carbonate or ammoniacal liquor.
10. method according to claim 1 is characterized in that, second nanofiltration and f in the said step e)) in the precision of holding back of the 3rd nanofiltration be 200 dalton～400 dalton independently.
11. method according to claim 1 is characterized in that, also comprises step before the said step a):
The stoste of the red liquid of paper-making pulping is regulated, just filtered and smart filter through the pH value successively, obtain the red liquid of paper-making pulping.
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Application publication date: 20120725 |