CN105386364A - Method for reducing and removing organic pollutant deposition and ink during pulping papermaking production - Google Patents
Method for reducing and removing organic pollutant deposition and ink during pulping papermaking production Download PDFInfo
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- CN105386364A CN105386364A CN201410449235.9A CN201410449235A CN105386364A CN 105386364 A CN105386364 A CN 105386364A CN 201410449235 A CN201410449235 A CN 201410449235A CN 105386364 A CN105386364 A CN 105386364A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/02—Working-up waste paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
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Abstract
The present invention discloses a method for reducing and removing organic pollutant deposition and ink during pulping papermaking production, and belongs to the technical field of pulping papermaking. According to the method, polystyrene phenol polyoxyethylene having a molecular mass of 240-7000/propylene/butene ether or sulfuric acid or a sulfuric acid, phosphoric acid and carboxylic ester polymer thereof is used as an agent to control organic pollutants and/or deinking, and the polymer agent is added to a water-containing cellulose papermaking pulp to make the polymer agent react with the organic pollutants or ink substance surface, such that the physical and chemical properties of the organic pollutants and the ink are changed, the substances in the pulping process are easily separated and removed, the contents of the organic pollutants and the ink in the system are reduced, and the viscosity of the organic pollutants is changed even eliminated so as to eliminate the deposition of the organic pollutants in the pulping and papermaking process and achieve the purposes of paper quality improving and papermaking production efficiency improving.
Description
Technical field
The present invention relates to pulp and paper technology field, particularly relate to during a kind of pulping and paper-making is produced and reduce organic pollutant deposition and ink foreign material, clean-keeping paper machine system, thus improve the method for paper machine operation efficiency and product quality.
Background technology
As everyone knows, in paper-making process, the deposition (being again precipitation) of organic pollution to paper product quality and paper efficiency all very unfavorable, topmost two concrete reasons of this problem are pitch deposition and Stickies deposit.Wherein, the main component of resin deposit to be naturally present in timber and to discharge in slurrying and paper-making process.From physics angle, " resin deposit " is usually formed by the microcosmic particle of adhesive material in slurry (natural or artificial) and is accumulated on papermaking paper or pulping equipment.And " sicker precipitation " normally derives from the particulate in the slurry of regenerated fiber, its general chemical structure feature is glue (adhesives) and the adhesive such as hot melt adhesive (hotmelts) of synthesis, the composition such as coating and ink in addition.
In the past, the depositional phenomenon of resin and sicker has typical separately embodiment in different system, and this almost only uses protofibre due to papermaking at that time or only uses regenerated fiber.In order to control these problems independent of each other, usually have distinct process chemicals and countermeasure.But trend in recent years uses regenerated fiber all gradually in all systems, therefore also can occur " Stickies deposit " while generation " pitch deposition ", cause sicker and resin consedimental organic pollutant deposition problem altogether.
These deposits are easy to find in pulp storage tank wall, papermaking cabinet, U-shape case, paper machine wires, wet press felts, dryer felts, drying chamber and calendar stacks.Organic pollutant deposition not only can remain on the metal surface of system, also can retain on plastics and synthetic surface, cause bad impact to paper.Such as on machine, woollen blanket, U-shape case case and head box components, be unfavorable for slurrying or papermaking, even affect running efficiency, reduce production capacity etc.If on the process equipment of organic pollutant deposition in paper manufacturing systems, the organic pollution be deposited on consistency regulator and other detection apparatus can cause these parts normally to use, and causes Dynamic System difficulty.In addition, organic deposition can cause paper hole, dirt and other paper defects, and these defects can make the Quality Down of paper, and cannot be used for subsequent handling, such as, be coated with, power of printing and dyeing day work or printing.
Although downtime can be carried out to paper machine; but we do not wish that this shutdown occurs buys clearly; because this can cause the corresponding loss of productivity ratio, and when these deposits fracture and are mixed in paper, the existence of these pollutants more a step can cause the deterioration of paper quality again.Therefore, prevent the organic deposition on pulping and papermaking equipments and vessel surface of crucial importance.
US Patent No. 3,992,249 disclose the anionic vinyl polymer controls organic deposition used containing 25-85% hydrophobic group, wherein hydrophobic group comprises styrene, methyl styrene, long-chain fat alkyl etc., and anionic group comprises acrylic acid, methacrylic acid, styrene sulfonic acid etc.Nonionic polymeric detackifiers is well known in the art as the material controlling resin and Stickies deposit, and it is used to control the deposition of resin in slurrying and paper manufacturing systems and sicker.Such as, US Patent No. 4,871,424 and US4,886,575 respectively proposition vinyl alcohol-acetate ethylene copolymer can control resin in slurrying and paper manufacturing systems and Stickies deposit.The non-ionic associative type polymer of introduction hydrophobically modified in European patent EP 0568229Al, the carboxyethyl cellulose ether (HMHEC) of such as hydrophobically modified, can prevent organic pollution in slurrying and paper manufacturing systems from depositing from paper pulp.US Patent No. 5,723,021 and US7,166,192 disclose the vinyl alcohol-acetate ethylene copolymer of non-ionic polyalcohol and the combination of HMHEC and cation type polymer.Recently, US Patent No. 8,048,268 disclose and control organic deposition problems with the amino thickener (hydrophobicallymodifiedethoxylatedaminoplastthickener-HE AT) of hydrophobically modified.But these methods all can not the problem of real fully effective solution organic deposition, there is the defect of poor effect.
In routine techniques, often use DeTac (U.S. HerculesInc. product) to control organic deposition, but its Problems existing is weak effect and narrow application range, particularly for fatty acid soaps resinoid deposition substantially to no effect.
In addition, the organic pollution treatment technology in existing paper technology be all generally non-selectivity, without controlling with driftlessness, therefore they are often with other useful additive for paper making effect, cause interference, cause showing of its effect to decline.
In addition, oneself knows that enzyme can be effective as the pollutant catabolic gene agent in slurrying and paper manufacturing systems.Its principle is: lipase and esterase are protein catalyst, and they can promote the glycerine ester hydrolysis in resin Composition, also can react with sicker, reduces, eliminate and/or suppress deposition to make its viscosity.As US Patent No. 5,176,796 have set forth manufacturing in the process of paper with containing mechanical pulp, utilize lipase by the main component of resin, i.e. nonpolar triglycerides, are hydrolyzed to water-soluble glycerol and polarity aliphatic acid.US Patent No. 5,507,952, US5,356,800, the polymer utilizing lipolytic enzyme to be hydrolyzed containing vinyl acetate is reported in US6,471,826B2, No. 200610048908, US patent publications and International patent publications WO02/095127A2, to reduce the viscosity of pollutant, described pollutant polyvinyl alcohol is the stickies contaminant composition in typical recycled writing paper.
But being used alone enzyme is not the best approach controlling organic pollution in slurrying and papermaking application.Such as, a well-known problem is exactly, use lipase decompose resin and the aliphatic acid that generates can and water in the slightly solubility fat soap that generates of metal ion reaction, cause depositing, and when resin content is higher, even more serious than the pitch deposition without lipase treatment.Fusing point after saponification of fats is higher than the fusing point of unconverted front resin, and viscosity is larger, is insoluble to general organic solvent, therefore more difficult control.For this reason, US Patent No. 5,256,252 and US5,667, set forth a kind of method controlling pitch deposition in slurrying and paper-making process in 634, it comprises and combinationally uses lipase and cation type polymer, to reduce the fatty acid concentration in cellulose paste aqueous phase.Disclose similar method in US Patent No. 6,471,826B2, the method combinationally uses at least one esterase and cation type polymer to control the organic pollution in recycled writing paper.Disclose a kind of for the method reduced or preventing pollution thing deposits in U.S. Patent application publication 2004/0194903Al, the method comprises the liquid felt conditioner utilizing one or more enzymes and non-enzymatic, and described conditioner is made up of one or more surfactants and/or one or more anionics or cationic dispersing agent or polymer.Disclose a kind of raising in U.S. Patent application publication 2006/0048908Al to the adhesive in paper-making process and the removal of adhesive contaminant or the method for control, it comprises and combinationally uses one or more enzymes and one or more absorbents or adsorbent.Described absorbent or adsorbent are selected from inorganic and organic granular that is natural or synthesis, and it comprises crosslinked CATION, anion or nonionic organic micro particles.
But, up to the present, also there is no a kind of method of real fully effective solution organic deposition problems.And paper industry is thirsted for obtaining a kind of cost-effective technology and is solved this puzzlement paper of organic deposition problem for many years very much.
Summary of the invention
Based on this, the object of the invention is to the defect overcoming prior art, reduce and remove the method for organic pollutant deposition and ink in providing a kind of pulping and paper-making to produce, adopt the method, have effective, advantage applied widely.
For achieving the above object, the present invention takes following technical scheme:
A kind of pulping and paper-making reduces and removes the method for organic pollutant deposition and ink in producing, polymer doses is added in moisture fiber papermaking slurry, this polymer doses and cellulosic papermaking slurry material are reacted, organic pollution in paper making pulp and ink generation modification, thus be removed efficiently in pulping and papermaking processes; Described polymer doses includes at least one in polymer shown in formula I:
Wherein: R
1be selected from: hydrogen or C
1-4alkyl;
R
2, R
3and R
4certainly optional: hydrogen, methyl, ethyl, propyl group or phenyl, and adjacent R
2and R
3and adjacent R
3and R
4substituting group is mutually different group;
M is selected from: the integer between 0-70;
N is selected from: the integer between 1-80;
P is selected from: the integer between 0-30, and described R
2or R
3wherein any one chooses phenyl, then corresponding p value is zero;
Z is selected from: the integer between 1-3;
X is selected from: hydrogen, R
5oOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid, or R
5oOH, sulfate, phosphate, acrylic acid, maleic acid, or appoint in fumaric acid
A kind of soluble-salt;
R
5be selected from: C
1-4alkyl;
The molecular weight of polymer shown in formula I is 240-7000 dalton.
Above-mentioned R
5oOH, sulfate, phosphate, acrylic acid, maleic acid, or in fumaric acid, the soluble-salt of any one can be sylvite, sodium salt or ammonia salt etc., only needs that polymer shown in this formula I can be ionized in aqueous and produces anion.When X is hydrogen, this polymer is neutral ether; When X chooses R
5oOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid and soluble-salt time, this polymer is anionic ester class formation.
Pulping and paper-making of the present invention reduces organic pollutant deposition and removes the method for ink in producing, polymer shown in employing formula I is as the medicament controlling organic pollution and/or deinking, this polymer is multi-styrene phenol polyoxyethylene/propene/but-1-ene ether or its sulfuric acid, phosphoric acid, carboxylic acid ester, and its molecular mass is 240-7000Dalton.In pulping and paper-making is produced, this polymer is joined in the slurry containing organic pollution, it optionally can change the physics and chemistry character of organic pollution and ink with organic pollution or ink material surface reaction, make the more easily separated and removing in pulping process of this kind of material, the content of organic pollution and ink in reduction system, reduce and even eliminate organic pollution viscosity, or make them disperse, thus eliminate the deposition of organic pollution in slurrying and paper-making process, reach the object improved paper quality and improve paper efficiency.
The principle that method of the present invention can reduce and remove organic pollutant deposition and ink is: above-mentioned polymer selective be adsorbed on organic pollution or ink pellet surface, this part surface is covered, reduce and even eliminate its interaction, thus optionally can change the surface nature of organic pollution and ink, reach the efficient effect reducing organic pollutant deposition and deinking.
And, described polymer also can coordinate the mixture of any one or two kinds in esterase and surfactant jointly to use, this polymer can with other slurrying and additive for paper making or its mixture compatible, wherein said slurrying and additive for paper making are one or more mixture of starch, filler, defoamer, wet strengthening resin, cation type polymer, anionic polymer and glue sizing auxiliary agent.Described polymer can be powder, aqueous dispersion, any one form of solution that mixes with activating agent/emulsifying agent.
Above-mentioned polymer has different chemical names in the literature, as polystyrene phenol polyoxy alkyl polyoxy styrene (polystyrylphenolpoly (alkyloxide) poly (styreneoxide)), styrenatedalkoxylatedphenols, alkoxykatedpolystyrylphenols, styrenatedpoly (ethyloxide), polystyrylphenolalkoxylates, ethoxlatedstyrenatedphenols, styrenatedphenolethoxlates, andtri-ordi-styrylphenolethoxylates etc.
The preparation method of above-mentioned polymer can with reference to such as Publication about Document: US4, 842, 776, US6, 736, 892, US7, 205, 352, US7, 271, 2311, US8, 211, 837, US6, 455, 471, US4, 904, 695, WO2007/110355, US2010/0016155, US4, 240, 918, US7, 030, 078, US8, 372, 788, US2011/0190174, US5, 035, 785, US6, 736, 892 and SurfactantsinAgriculturalFormulations (Karsa, Chapter2, " RecentDevelopmentsintheTechnologyofSurfactants ", editedbyM.R.Porter, Elsevier, 1990).In those references, this base polymer is used in formulation of pesticide, detergent compositions and Petroleum Production, but, up to now, be disclosed without any about the application of these polymer in paper pulp papermaking.
Adopt method of the present invention to carry out paper, be added to by described polymer in moisture cellulosic papermaking slurry material to mix and react, follow-uply can conveniently production technology to carry out, concrete steps can be:
(1) by water and the mixing of cellulose papermaking dry pulp, be mixed with moisture cellulosic papermaking slurry material, the blender being placed in slurry feedway is uniformly mixed;
(2) under the condition stirred, in the cellulosic papermaking slurry material that step (1) obtains, add described polymer doses, carry out being obtained by reacting mixing paper making pulp;
(3) the mixing paper making pulp that step (2) obtains is served screen pack, filtering water wherein, form page by the solid constituent of mixing paper making pulp;
(4) page step (3) obtained, through pressing and drying, obtains paper product.
Wherein in an embodiment, described R
4for phenyl.
Wherein in an embodiment, described R
2and R
3certainly optional: hydrogen, methyl.
Wherein in an embodiment, described X is sulfate or phosphate.
Wherein in an embodiment, described z is 2 or 3, and preferred z is 3.
In one of them embodiment above-mentioned, m is selected from: the integer between 5-50; N is selected from: the integer between 1-50 or the integer between 70-80; P is selected from: the integer between 0-20.
Wherein in an embodiment, the molecular weight of polymer shown in described formula I is 500-2000 dalton or 4000-7000 dalton.
Wherein in an embodiment, described polymer doses is at least two kinds of polymer different in polymer shown in formula I, the R wherein in a kind of polymer
4for phenyl, the X in another kind of polymer is sulfate.
Wherein in an embodiment, in moisture cellulosic papermaking slurry material, also add one or more biology enzymes, described biology enzyme is cellulase, hemicellulase and esterase; Described polymer: the weight ratio of biology enzyme is 10:0.5-1.5.
Wherein in an embodiment, the addition of described polymer doses is add 0.01-10 kilogram in dry cellulosic paper making pulp per ton, adds 0.1-5 kilogram in preferred dry cellulosic paper making pulp per ton.The temperature that described polymer doses and cellulosic papermaking slurry material react is 10-80 DEG C, preferred 20-60 DEG C, more preferably 50-60 DEG C, and pH value in reaction is 3-10, preferred 4-7, and the reaction time is 5-1200 minute, preferred 20-400 minute.Wherein, by mass concentration be 1% hydrochloric acid or NaOH adjust ph.
The invention also discloses the application that polymer shown in a kind of formula I reduces and removes organic pollutant deposition and ink in pulping and paper-making is produced,
Wherein: R
1be selected from: hydrogen or C
1-4alkyl;
R
2, R
3and R
4certainly optional: hydrogen, methyl, ethyl, propyl group or phenyl, and adjacent R
2and R
3and adjacent R
3and R
4substituting group is mutually different group;
M is selected from: the integer between 0-70;
N is selected from: the integer between 1-80;
P is selected from: the integer between 0-30, and described R
2or R
3wherein any one chooses phenyl, then corresponding p value is zero;
Z is selected from: the integer between 1-3;
X is selected from: hydrogen, R
5oOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid, or R
5oOH, sulfate, phosphate, acrylic acid, maleic acid, or any one soluble-salt in fumaric acid;
R
5be selected from: C
1-4alkyl;
The molecular weight of polymer shown in formula I is 240-7000 dalton.
Wherein in an embodiment, described R
4for phenyl.
Wherein in an embodiment, described R
2and R
3certainly optional: hydrogen, methyl.
Wherein in an embodiment, described X is sulfate or phosphate.
Wherein in an embodiment, described z is 2 or 3, and preferred z is 3.
Wherein in an embodiment, m is selected from: the integer between 5-50; N is selected from: the integer between 1-50 or the integer between 70-80; P is selected from: the integer between 0-20.
Wherein in an embodiment, the molecular weight of polymer shown in described formula I is 500-2000 dalton or 4000-7000 dalton.
Compared with prior art, the present invention has following beneficial effect:
A kind of pulping and paper-making of the present invention reduces and removes the method for organic pollutant deposition and ink in producing, polymer shown in employing formula I changes surface physics and the chemical property of organic pollution and ink, thus the problem reducing, remove, prevent the middle organic pollutant (sicker) even eliminating paper pulp papermaking system to deposit in pulping and papermaking processes, and reduce the content of ink in system.And then improve efficiency and the product quality of paper.
And, the polymer applicability adopted in the present invention is wide, source regardless of organic pollutant is Original Pulp or the MOW such as chemical pulp, mechanical pulp, sulfurous wintercherry, OCC, ONP, OMG, no matter etc. recycled fiber pulp, be no matter acid or alkali condition, be under low temperature or the industrial condition of high temperature, this polymer all has the efficient effect reducing organic pollution precipitation, still possesses efficient reducing effect to the fatty acid soaps resinoid deposition invalid with DeTac.
Simultaneously, polymer in the present invention is optionally adsorbed on hydrophobic particle surface, can not with fibration, thus only optionally change the surface of organic pollution or ink, reach the result controlling sicker and deinking efficiently, and negative effect is not had to the production of paper machine and paper product quality.
Accompanying drawing explanation
Fig. 1 is that in embodiment 2, OCC produces corrugated paper slurrying flow process;
Fig. 2 is each phase contrast's column diagram before and after interpolation polymer of total disconnected paper time of paper machine front baking (before coating) in embodiment 3.
Detailed description of the invention
Describe the present invention in detail below in conjunction with the drawings and specific embodiments, but any restriction is not caused to the present invention.
Shown in the following general formula I I of polymer architecture described in following examples:
Each polymeric articles in table 1 specific embodiment
Wherein:
One, polymer A, the preparation method of B, D, E, G and H is: the cinnamic synthetic method of polyoxy comprises:
(1) tristyryl phenol (tri-styrenephenol) and ethylene oxide (ethyleneoxide) are added reactor according to the molal quantity proportioning needed for target product, mix; Then add catalyst diethyl alkanisation zinc (zincdiethyl) and water, its weight is according to water: diethyl alkanisation zinc (zincdiethyle): the ratio of ethylene oxide (ethyleneoxide) is that 1:1.10:13 feeds intake; Then add a large amount of dioxanes (dioxan) as reaction dissolvent, reactor is vacuumized, after reaching condition of high vacuum degree, above reactant is heated 80 DEG C, and make it be uniformly mixed continuously, react 240 hours.
(2) the above-mentioned product be obtained by reacting is dissolved in benzene liquid, then adds methyl alcohol and catalyst diethyl alkanisation zinc (ZincDiethyl) is precipitated out, allow polymerisation stop; Then by centrifugal separation, solids separation is removed.
(3) polymer D and H also needs sulfonating reaction of evolving according to a conventional method, and other polymer is then without the need to carrying out sulfonation procedure.
(4) with freeze-drying, benzene and water are removed, obtain pure product.
Two, the preparation method of polymer C is: basic step is identical with polymer B product with above-mentioned polymer A, first synthesizes polyoxypropylene, and then is polymerized polyoxyethylene.Concrete steps comprise:
(1) tristyryl phenol (tri-styrenephenol) and propylene oxide (propyleneoxide) are added reactor according to molal quantity proportioning needed for target product, mix; Then catalyst diethyl alkanisation zinc (zincdiethyl) and water is added, its weight is according to water: diethyl alkanisation zinc (zincdiethyl): the ratio of propylene oxide (propyleneoxide) is that 1:1.10:13 feeds intake, then a large amount of dioxanes (dioxan) is added as reaction dissolvent, reactor is vacuumized, after reaching condition of high vacuum degree, above reactant is warmed to 80 DEG C, and make it be uniformly mixed continuously, react 240 hours.
(2) then, add ethylene oxide (ethyleneoxide) and diethyl alkanisation zinc according to molar ratio needed for target product, its weight is according to water: diethyl alkanisation zinc (zincdiethyle): the ratio of ethylene oxide (ethyleneoxide) is that 1:1.10:13 feeds intake; Then add a large amount of dioxanes (dioxan) as reaction dissolvent, after reaching condition of high vacuum degree, above reactant is warmed to 80 DEG C, and makes it be uniformly mixed continuously, react 240 hours;
(3) the above-mentioned product be obtained by reacting is dissolved in benzene liquid, then adds methyl alcohol and catalyst diethyl alkanisation zinc (ZincDiethyle) is precipitated out, polymerisation is stopped; Then by centrifugal separation, solids separation is removed.
(4) with freeze-drying, benzene and water are removed, obtain pure product polymer C.
Three, the preparation method of polymer F is: basic step is identical with above-mentioned polymer C product, namely first synthesizes polyoxypropylene, polyoxyethylene, and then is polymerized polyoxy styrene.Concrete steps comprise:
(1) tristyryl phenol (tri-styrenephenol) and propylene oxide (propyleneoxide) are added reactor according to molal quantity proportioning needed for target product, mix; Then catalyst diethyl alkanisation zinc (zincdiethyl) and water is added, its weight is according to water: diethyl alkanisation zinc (zincdiethyl): the ratio of propylene oxide (propyleneoxide) is that 1:1.10:13 feeds intake, then a large amount of dioxanes (dioxan) is added as reaction dissolvent, reactor is vacuumized, after reaching condition of high vacuum degree, above reactant is warmed to 80 DEG C, and make it be uniformly mixed continuously, react 240 hours.
(2) then, add ethylene oxide (ethyleneoxide) and diethyl alkanisation zinc according to molar ratio needed for target product, its weight is according to water: diethyl alkanisation zinc (zincdiethyle): the ratio of ethylene oxide (ethyleneoxide) is that 1:1.10:13 feeds intake; Then add a large amount of dioxanes (dioxan) as reaction dissolvent, after reaching condition of high vacuum degree, above reactant is warmed to 80 DEG C, and makes it be uniformly mixed continuously, react 240 hours;
(3) then, add reactor according to styrene oxide needed for target product (styreneoxide) molal quantity proportioning, mix; Then add catalyst diethyl alkanisation zinc (zincdiethylene) and water, its weight is according to water: diethyl alkanisation zinc (zincdiethyle): the ratio of styrene oxide (styreneoxide) is 1:1.25:40; Feed intake and then add a large amount of dioxanes (dioxan) as reaction dissolvent, reactor is vacuumized, after reaching condition of high vacuum degree, above reactant is warmed to 60 DEG C, and make it be uniformly mixed continuously, react 240 hours.
(4) being dissolved in benzene liquid by the above-mentioned product be obtained by reacting, then adding methyl alcohol and be precipitated out by catalyst diethyl alkanisation zinc (ZincDiethyle), is that polymerisation stops; Then by centrifugal separation, solid is separated removing.
(5) with freeze-drying, benzene and water are removed, obtain pure product polymer F.
Embodiment 1
Pulping and paper-making reduces the method for organic pollutant deposition in producing, and the method is mainly used in reclaiming old and useless newspaper and produces control to organic pollution (sicker) in the process of newsprint.
One, material
The dry cellulosic slurry of deinking old and useless newspaper slurry (ONP) is obtained by a southern paper plant.
Conventional stickies control agent adopts the registration mark product of Ashland company of the U.S.
make reference contrast.
Other polymeric articles is in table 1.
Two, method
Use food mixer (
) simulation pulping and paper-making produce in operation in paper pulp mixing and dry flow process, measure the deposition on mixed cylinder and paddle lobe surface of sicker at different conditions, then more various component is on the impact of organic deposition.
The condition of deposition test is: 100 grams, dry cellulosic slurry (dry pulp weight), add water slurry is adjusted to 10% aqueous cellulosic paper making pulp, different polymer doses (as shown in table 2) and cellulosic papermaking slurry material is adopted to react, reaction temperature is 65 DEG C, reaction time is 120 minutes, and stirring intensity is medium.
Three, result
Deposition test terminates, and measures the deposition on mixed cylinder and paddle lobe surface of sicker at different conditions, shown in table 2 specific as follows.
Under table 2 different condition, sicker is in the deposition conditions on mixed cylinder and paddle lobe surface
Note: " stirring lobe surface " is for the area covered by sicker is divided by the ratio stirring lobe total surface area;
" vessel surface deposition " is for the area that covered by sicker is divided by the ratio of the inner surface of container gross area.
As can be seen from upper table, all polymer of the present invention compare contrast product in the effect controlling Stickies deposit
there is better effect.Particularly when selecting the combinationally using of the polymeric articles of 2 different chemical structures, effect of its performance is best, with contrast product
compare, only need 20-30%'s
dosage just can reach identical stickies control effect.
Embodiment 2
Pulping and paper-making reduces the method for organic pollutant deposition in producing, and the method is mainly used in producing control to organic pollution (sicker) in the process of corrugated paper with collection box paperboard (OCC).
One, material
The dry cellulosic slurry of collection box paperboard slurry (OCC) is obtained by a southern paper plant.
Biology enzyme composition (cellulase, hemicellulase and esterase), wherein: cellulase is the commercial product FiberZymeG200 of Dyadic company, and hemicellulase is commercially available prod, esterase is the clean enzyme of Guangzhou Rui Chenshengda Bioisystech Co., Ltd
tMproduct, model is SC-3000, is derived from black-koji mould (Aspergillus), expresses, between reaction substrate triglycerides and the relative activity ratio 10 ~ 3 of ethyl acetate after restructuring at E.Coli.
Other polymeric articles used is in table 1.
Two, method
According to production procedure shown in Fig. 1, corrugated paper is produced with collection box paperboard (OCC), polymer D and F in table 1 is combined (wherein the weight ratio of D and F is 1:1), be added on pulper as the polymer controlling organic pollutant deposition, amount ranges is 50-300g/T (oven dry stock addition per ton).Then biology enzyme composition (cellulase is added again at the good slurry blowpit of polydisc thickener, hemicellulase and esterase), wherein polymer: the weight ratio of biology enzyme composition is 10:1, in biology enzyme composition, cellulase, the weight ratio of hemicellulase and esterase is 1:1:1.Total polymer and the total amount ranges 100-400g/T of biology enzyme (oven dry stock addition per ton).And 4 weeks were run before interpolation polymer, the total disconnected paper time of regular investigation paper machine front baking (before coating), after running 4 weeks, above-mentioned polymer is added by the amount of 100g/T, run 2 weeks, regularly investigate the total disconnected paper time of paper machine front baking (before coating), added above-mentioned polymer at the 3rd week by the amount of 400g/T subsequently, move to 5 weeks, regularly investigate the total disconnected paper time of paper machine front baking (before coating).
Three, result
In process of the test, we find, before use polymer of the present invention, guide roller surface have accumulated sicker/rubbish for many years, and polymer of the present invention is when the initial stage of test, and consumption is lower, so that slowly scavenger system.After adding the polymer of high consumption, the rapid minimizing of Stickies deposit.
Further, after experiment investigation terminates, running time as ordinate, maps as abscissa, as shown in Figure 2 by we by the total disconnected paper time of the paper machine front baking (before coating) of different phase.
Fig. 2 compared for each time phase before and after test, the change of the total disconnected paper time of paper machine front baking (before coating).As can be seen from Figure 2, paper machine is after use polymer of the present invention, and because sicker reduces, the total disconnected paper time of drying before paper machine also correspondingly reduces.After stopping using polymer of the present invention, sicker slowly increases in paper machine deposition, and the disconnected paper of paper machine also slowly increases.Method of the present invention is described except the organic pollution precipitation that can reduce on device systems, also can improves the quality of paper.
Embodiment 3
Pulping and paper-making removes a method for reclaimed waste paper ink in producing, the method is mainly used in reclaiming mixed waste paper and produces except pollutants such as removal inks in the process of coated manila, improves the whiteness of paper and reduces dust point (ink point).
One, material
Reclaim mixed waste paper (office waste, waste and old books etc.) to obtain from Guangdong Jiangmen paper mill.
Other polymeric articles used is in table 1.
Two, method
Test products be polymer C and F in table 1 separately or its combination (1:1), i.e. polymer C, polymer F, polymer (C+F).
Test method is: first get waste paper, puts into hydrabrusher, then adds laboratory simulation plain boiled water (containing the CaCl of 400PPM
2the aqueous solution) to starching dense about 12%, then add deinking bleaching chemical (NaOH and H
2o
2), finally add Reference Product or polymer of the present invention as deinking agent.Again after pulping 15min, paper pulp is taken out, adding simulation plain boiled water, to be diluted to pulp weight percentage be 3%, place 60min, then sampling is placed on Denver formula flotation device, and to be diluted to 1.0% slurry dense, after stirring to add simulation plain boiled water, start flotation, flotation 3-6min, after flotation, gets pan feeding and the good slurry (discharging) of flotation, make handsheet respectively, test handsheet whiteness and dust point.
Three, result
Table 3 is the comparisons to deinking effect to two polymer in original deinking agent (reference) and the present invention and combination thereof.Original Reference Product deinking agent is the deinking chemical medicament of a Switzerland Co., Ltd (Rhodia), and it mainly consists of polyoxyethylene fatty alcohol.As can be seen from the table, polymer C and F of the present invention is number more much better than the floatation and ink removing effect of original deinking chemicals, and not only the whiteness of good slurry is high, and dust point is low, and significantly can reduce chemicals usage, is conducive to the environmental protection of paper plant.
The contrast (reference is the deinking agent combination of original paper plant) of table 3 floatation and ink removing effect
Embodiment 4
Pulping and paper-making removes a method for reclaimed waste paper ink in producing, the method is mainly used in reclaiming mixed waste paper and produces except pollutants such as removal inks in the process of toilet paper, improves the whiteness of paper and reduces dust point (ink point).
One, material
Reclaim mixed waste paper (office waste, waste and old books etc.) to obtain from Dongguan, Guangdong paper plant.
Other polymeric articles used is in table 1.
Two, method
Test products be polymer in table 1 separately or its combination (1:1).
Test method is: first get waste paper, puts into hydrabrusher, then adds laboratory simulation plain boiled water (containing the CaCl of 400PPM
2the aqueous solution) to starching dense about 12%, then add deinking bleaching chemical (NaOH and H
2o
2), finally add Reference Product or polymer of the present invention as deinking agent.Again after pulping 15min, paper pulp is taken out, adding simulation plain boiled water, to be diluted to pulp weight percentage be 3%, place 60min, then sampling is placed in handsheet machine, and adding simulation plain boiled water, to be diluted to 0.5% slurry dense, after stirring, water is bled off, and then it is dense to identical slurry to add running water, then water is bled off; The slurry finally adding running water to about 1% is dense, makes handsheet, test handsheet whiteness and dust point.
Three, result
Table 4 is the comparisons to deinking effect to polymer in original deinking agent (reference) and the present invention and combination thereof.Original Reference Product deinking agent is the conventional deinking agent in market, it mainly consists of phosphate, as can be seen from the table, all polymeric articles of the present invention are all number much better than the deinking efficiency of original deinking chemicals, not only the whiteness of good slurry is high, dust point is low, and significantly can reduce chemicals usage, is conducive to the environmental protection of paper plant.
Table 4 washs the contrast (reference is the deinking agent combination of original paper plant) of deinking efficiency
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (17)
1. a pulping and paper-making reduces and removes the method for organic pollutant deposition and ink in producing, it is characterized in that, polymer doses is added in moisture cellulosic papermaking slurry material, this polymer doses and fibrous paper making pulp are reacted, organic pollution in paper making pulp and ink generation modification, thus be removed efficiently in pulping and papermaking processes; Described polymer doses includes at least one in polymer shown in formula I:
Wherein: R
1be selected from: hydrogen or C
1-4alkyl;
R
2, R
3and R
4certainly optional: hydrogen, methyl, ethyl, propyl group or phenyl, and adjacent R
2and R
3and adjacent R
3and R
4substituting group is mutually different group;
M is selected from: the integer between 0-70;
N is selected from: the integer between 1-80;
P is selected from: the integer between 0-30, and described R
2or R
3wherein any one chooses phenyl, then corresponding p value is zero;
Z is selected from: the integer between 1-3;
X is selected from: hydrogen, R
5oOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid, or R
5oOH, sulfate, phosphate, acrylic acid, maleic acid, or any one soluble-salt in fumaric acid;
R
5be selected from: C
1-4alkyl;
The molecular weight of polymer shown in formula I is 240-7000 dalton.
2. pulping and paper-making according to claim 1 reduces and removes the method for organic pollutant deposition and ink in producing, and it is characterized in that, described R
4for phenyl.
3. pulping and paper-making according to claim 1 reduces and removes the method for organic pollutant deposition and ink in producing, and it is characterized in that, described R
2and R
3certainly optional: hydrogen, methyl.
4. pulping and paper-making according to claim 1 reduces and removes the method for organic pollutant deposition and ink in producing, and it is characterized in that, described X is sulfate or phosphate.
5. pulping and paper-making according to claim 1 reduces and removes the method for organic pollutant deposition and ink in producing, and it is characterized in that, described z is 2 or 3.
6. pulping and paper-making according to claim 1 reduces and removes the method for organic pollutant deposition and ink in producing, and it is characterized in that, m is selected from: the integer between 5-50; N is selected from: the integer between 1-50 or the integer between 70-80; P is selected from: the integer between 0-20.
7. pulping and paper-making according to claim 1 reduces and removes the method for organic pollutant deposition and ink in producing, and it is characterized in that, the molecular weight of polymer shown in described formula I is 500-2000 dalton or 4000-7000 dalton.
8. pulping and paper-making according to claim 1 reduces and removes the method for organic pollutant deposition and ink in producing, and it is characterized in that, described polymer doses is at least two kinds of polymer different in polymer shown in formula I, the R wherein in a kind of polymer
4for phenyl, the X in another kind of polymer is sulfate.
9. the pulping and paper-making according to any one of claim 1-8 reduces and removes the method for organic pollutant deposition and ink in producing, it is characterized in that, in moisture cellulosic papermaking slurry material, also add one or more biology enzymes, described biology enzyme is cellulase, hemicellulase and esterase; Described polymer doses: the weight ratio of biology enzyme is 10:0.5-1.5.
10. pulping and paper-making according to claim 1 reduces and removes the method for organic pollutant deposition and ink in producing, and it is characterized in that, the addition of described polymer doses is add 0.01-10 kilogram in dry cellulosic paper making pulp per ton; The temperature that described polymer doses and cellulosic papermaking slurry material react is 10-80 DEG C, and pH value in reaction is 3-10, and the reaction time is 5-1200 minute.
Polymer shown in 11. formula I reduces and removes the application of organic pollutant deposition and ink in pulping and paper-making is produced,
Wherein: R
1be selected from: hydrogen or C
1-4alkyl;
R
2, R
3and R
4certainly optional: hydrogen, methyl, ethyl, propyl group or phenyl, and adjacent R
2and R
3and adjacent R
3and R
4substituting group is mutually different group;
M is selected from: the integer between 0-70;
N is selected from: the integer between 1-80;
P is selected from: the integer between 0-30, and described R
2or R
3wherein any one chooses phenyl, then corresponding p value is zero;
Z is selected from: the integer between 1-3;
X is selected from: hydrogen, R
5oOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid, or R
5oOH, sulfate, phosphate, acrylic acid, maleic acid, or any one soluble-salt in fumaric acid;
R
5be selected from: C
1-4alkyl;
The molecular weight of polymer shown in formula I is 240-7000 dalton.
Polymer shown in 12. formula I according to claim 11 reduces and removes the application of organic pollutant deposition and ink in pulping and paper-making is produced, and it is characterized in that, described R
4for phenyl.
Polymer shown in 13. formula I according to claim 11 reduces and removes the application of organic pollutant deposition and ink in pulping and paper-making is produced, and it is characterized in that, described R
2and R
3certainly optional: hydrogen, methyl.
Polymer shown in 14. formula I according to claim 11 reduces and removes the application of organic pollutant deposition and ink in pulping and paper-making is produced, and it is characterized in that, described X is sulfate or phosphate.
Polymer shown in 15. formula I according to claim 11 reduces and removes the application of organic pollutant deposition and ink in pulping and paper-making is produced, and it is characterized in that, described z is 2 or 3.
Polymer shown in 16. formula I according to claim 11 reduces and removes the application of organic pollutant deposition and ink in pulping and paper-making is produced, and it is characterized in that, m is selected from: the integer between 5-50; N is selected from: the integer between 1-50 or the integer between 70-80; P is selected from: the integer between 0-20.
Polymer shown in 17. formula I according to claim 11 reduces and removes the application of organic pollutant deposition and ink in pulping and paper-making is produced, it is characterized in that, the molecular weight of polymer shown in described formula I is 500-2000 dalton or 4000-7000 dalton.
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| PCT/CN2015/081323 WO2016034004A1 (en) | 2014-09-04 | 2015-06-12 | Method for reducing and removing organic pollutant deposits and ink during pulp and paper production |
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Cited By (2)
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| CN107254793A (en) * | 2017-08-08 | 2017-10-17 | 山西强伟纸业有限公司 | A kind of production technology of high-cleanness, high protecting paper of gypsum board |
| CN115538208A (en) * | 2022-10-08 | 2022-12-30 | 江西省芦林纸业股份有限公司 | Preparation process of environment-friendly recycled paper |
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| JP2002327384A (en) * | 2001-04-25 | 2002-11-15 | Toho Chem Ind Co Ltd | Deinking agent |
| US7205352B2 (en) * | 2003-12-17 | 2007-04-17 | Ethox Chemicals, Llc | Dispersions containing fatty acid esters of styrenated phenol alkoxylates |
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| CN104262606B (en) * | 2014-09-04 | 2017-08-25 | 瑞辰星生物技术（广州）有限公司 | Polystyrene phenol polyoxy alkyls polymer and its preparation method and application |
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| US5651861A (en) * | 1995-12-18 | 1997-07-29 | Rhone-Poulenc Inc. | Process for removing inks from waste paper |
| JP2007063699A (en) * | 2005-08-30 | 2007-03-15 | Toho Chem Ind Co Ltd | Deinking agent for hard-to-deink waste paper |
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| CN115538208A (en) * | 2022-10-08 | 2022-12-30 | 江西省芦林纸业股份有限公司 | Preparation process of environment-friendly recycled paper |
| CN115538208B (en) * | 2022-10-08 | 2023-11-24 | 江西省芦林纸业股份有限公司 | Preparation process of environment-friendly recycled paper |
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| CN105386364B (en) | 2018-02-06 |
| WO2016034004A1 (en) | 2016-03-10 |
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