CN105386364B - The method for reducing in pulping and paper-making production and removing organic pollutant deposition and ink - Google Patents

The method for reducing in pulping and paper-making production and removing organic pollutant deposition and ink Download PDF

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CN105386364B
CN105386364B CN201410449235.9A CN201410449235A CN105386364B CN 105386364 B CN105386364 B CN 105386364B CN 201410449235 A CN201410449235 A CN 201410449235A CN 105386364 B CN105386364 B CN 105386364B
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paper
polymer
ink
pulping
integer
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CN105386364A (en
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王祥槐
王焱
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Rui Xing Biotechnology (guangzhou) Co Ltd
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Rui Xing Biotechnology (guangzhou) Co Ltd
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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
    • 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
    • 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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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)

Abstract

A kind of method for being reduced in being produced the invention discloses pulping and paper-making and removing organic pollutant deposition and ink, belongs to pulp and paper technology field.This method uses molecular mass as 240 7000 multi-styrene phenol polyoxyethylene/propene/but-1-ene ether or its sulfuric acid, phosphoric acid, carboxylic acid esters polymer controls organic pollution and/or deinking as medicament, the polymer doses are added in aqueous cellulosic papermaking slurry material, it is set to be reacted with organic pollution or ink material surface, change the physics and chemical property of organic pollution and ink, this kind of material is set to be easier to be separated and remove in pulping process, the content of organic pollution and ink in reduction system, change simultaneously and even eliminate organic pollution viscosity, so as to eliminate deposition of the organic pollution in slurrying and paper-making process, reach the purpose for improving paper quality and improving paper production efficiency.

Description

The method for reducing in pulping and paper-making production and removing organic pollutant deposition and ink
Technical field
The present invention relates to pulp and paper technology field, and organic pollution is reduced in being produced more particularly to a kind of pulping and paper-making Deposition and ink foreign material, clean-keeping paper machine system, so as to improve the method for paper machine operation efficiency and product quality.
Background technology
It is well known that in paper-making process, the deposition (being called precipitation) of organic pollution is given birth to paper product quality and papermaking Production efficiency is all very unfavorable, and most important two concrete reasons of this problem are pitch deposition and Stickies deposit.Wherein, resin What the main component of deposit was naturally present in timber and discharged in slurrying and paper-making process.From physics angle For, " resin deposit " is generally formed by the microcosmic particle of adhesive material in slurry (natural or artificial) and accumulates and making On paper paper or pulping equipment.And " sicker precipitation " is typically the particulate in the slurry of regenerated fiber, it is mainly changed Learn the adhesives, also coating and ink etc. such as glue (adhesives) and the PUR (hot melts) that architectural feature is synthesis Composition.
In the past, the depositional phenomenon of resin and sicker has each typical embodiment in different system, and this is due to Papermaking at that time almost only uses protofibre or only uses regenerated fiber.The problem of in order to control these independent of one another, it will usually There are completely different processing chemicals and countermeasure.But trend in recent years is all gradually using again in all systems Raw fiber, therefore " Stickies deposit " can also occur while " pitch deposition " occurs, cause sicker to be sunk jointly with resin Long-pending organic pollutant deposition problem.
These deposits are easy in pulp storage tank wall, papermaking cabinet, u-shaped case, paper machine wires, wet press felts, drying cylinder Found in felt, drying chamber and calendar stacks.Organic pollutant deposition can be not only remained on the metal surface of system, can also Retain on plastics and synthetic surface, deleterious effect is caused to paper production.Such as in machine, woollen blanket, u-shaped case case and stream Starch on box part, be unfavorable for slurrying or papermaking, or even influence running efficiency, reduce production capacity etc..If organic pollution sinks On process equipment in paper manufacturing systems, the organic pollution being deposited on consistency regulator and other detection apparatuses can cause product These parts can not normal use, cause system operatio difficult.In addition, organic deposition can cause paper hole, dirt and its Its paper defects, these defects can make the Quality Down of paper, and be not used to subsequent handling, such as coating, printing and dyeing power day work or printing.
Although downtime can be carried out to paper machine, we are not intended to occur this shutdown and bought clearly, because this The corresponding loss of productivity ratio can be caused, and when these deposits fracture and are mixed into paper, the presence of these pollutants is again A meeting more step causes the deterioration of paper quality.It is therefore prevented that the organic deposition pole on pulping and papermaking equipmentses and vessel surface Its is important.
United States Patent (USP) US 3,992,249 discloses the anionic vinyl polymer using the hydrophobic group containing 25-85% Organic deposition is controlled, wherein hydrophobic group includes styrene, methyl styrene, long-chain fat alkyl etc., anionic group Including acrylic acid, methacrylic acid, styrene sulfonic acid etc..Nonionic polymeric detackifiers are as control resin and Stickies deposit Material be it is known in the art that its deposition for being used to control resin in slurrying and paper manufacturing systems and sicker.For example, It is proposed vinyl alcohol-acetate ethylene copolymer can control slurrying to United States Patent (USP) US 4,871,424 and US4,886,575 respectively With the resin and Stickies deposit in paper manufacturing systems.The nonionic of introduction hydrophobically modified in the Al of European patent EP 0568229 Association type polymer, such as the carboxyethyl cellulose ether (HMHEC) of hydrophobically modified, can prevent organic dirt in slurrying and paper manufacturing systems Dye thing deposits from paper pulp.United States Patent (USP) US 5,723,021 and US 7,166,192 discloses the ethene of non-ionic polyalcohol The combination of alcohol-acetate ethylene copolymer and HMHEC and cation type polymer.Recently, United States Patent (USP) US 8,048,268 disclosure With hydrophobically modified amino thickener (hydrophobically modified ethoxylated aminoplast Thickener-HEAT organic deposition problems) are controlled.But these methods really fully effective solution organic matter can not sink The problem of product, the defects of ineffective be present.
In routine techniques, often organic deposition, but its are controlled using DeTac (U.S.'s Hercules Inc. products) The problem of existing is effect difference and narrow application range, is deposited substantially to no effect especially for fatty acid soaps resinoid.
In addition, the organic pollution treatment technology in existing paper technology is typically all non-selectivity, without controlling With without Objective, therefore they interfere often with other beneficial additive for paper making effects, cause the significant of its effect Decline.
In addition, oneself knows the pollutant catabolic gene agent that enzyme can be effective as in slurrying and paper manufacturing systems.Its principle is：Fat Enzyme and esterase are protein catalysts, and they can promote the glycerine ester hydrolysis in resin Composition, can also be anti-with sicker Should, so that its viscosity reduces, eliminates and/or suppressed deposition.As United States Patent (USP) US 5,176,796 is elaborated with containing mechanical paper During slurry manufacture paper, using lipase by the main component of resin, i.e., nonpolar triglycerides, it is hydrolyzed to water-soluble sweet Oil and polarity aliphatic acid.United States Patent (USP) US5,507,952, US 5,356,800, US 6,471,826 B2, US patent publications Reported in No. 200610048908 and the A2 of International patent publications WO 02/095127 using lipolytic enzyme to hydrolyze containing vinegar The polymer of sour ethene, to reduce the viscosity of pollutant, the pollutant polyvinyl alcohol is the sicker in typical recycled writing paper Pollutant component.
But it not is the best approach for controlling organic pollution in slurrying and papermaking application that enzyme, which is used alone,.It is for example, many A well known problem is exactly that the aliphatic acid for decomposing resin using lipase and generating can react life with the metal ion in water Into slightly solubility fat soap, cause to deposit, and when resin content is higher, or even pitch deposition of the ratio without lipase treatment It is more serious.Fusing point after saponification of fats is higher than the fusing point of unconverted preceding resin, and viscosity is bigger, organic molten insoluble in general Agent, therefore be more difficult to control.Therefore, one kind is elaborated in United States Patent (USP) US 5,256,252 and US 5,667,634 in slurrying and is made The method that pitch deposition is controlled during paper, it includes lipase and cation type polymer is applied in combination, to reduce cellulose Fatty acid concentration in slurry aqueous phase.Similar method is disclosed in the B2 of United States Patent (USP) US 6,471,826, this method combination makes The organic pollution in recycled writing paper is controlled with an at least esterase and cation type polymer.U.S. Patent Application Publication A kind of method for reducing or preventing accumulation of pollutants is disclosed in 2004/0194903 Al, this method is using one kind Or a variety of enzymes and the liquid felt conditioner of non-enzymatic, the conditioner is by one or more surfactants and/or one kind or more Kind anionic or cationic dispersing agent or polymer are formed.It is public in the Al of U.S. Patent Application Publication 2006/0048908 A kind of method for improving removal or control to adhesive and adhesive contaminant in paper-making process is opened, it includes being applied in combination One or more enzymes and one or more absorbents or adsorbent.The absorbent or adsorbent are selected from natural or synthetic inorganic And organic granular, it includes cation, anion or the nonionic organic micro particles of crosslinking.
But up to the present, also without a kind of really fully effective method for solving organic deposition problems.And papermaking Industry very serious hope obtains a kind of cost-effective technology, and to solve the problems, such as organic deposition, this perplexs paper production for many years.
The content of the invention
Based on this, the defects of it is an object of the invention to overcome prior art, there is provided reduced in a kind of pulping and paper-making production With the method for removing organic pollutant deposition and ink, using this method, there is the advantages of effect is good, applied widely.
To achieve the above object, the present invention takes following technical scheme：
A kind of method for reducing in pulping and paper-making production and removing organic pollutant deposition and ink, makes in aqueous fiber Polymer doses are added in pulp material, the polymer doses is reacted with cellulosic papermaking slurry material, organic dirt in paper making pulp Dye thing and ink are modified, so as to be removed efficiently in pulping and papermaking processes；The polymer doses include Formulas I institute Show at least one of polymer：
Wherein：R1It is selected from：Hydrogen or C1-4Alkyl；
R2, R3And R4Optionally certainly：Hydrogen, methyl, ethyl, propyl group or phenyl, and adjacent R2And R3And adjacent R3And R4 Substituent is mutually different group；
M is selected from：Integer between 0-70；
N is selected from：Integer between 1-80；
P is selected from：Integer between 0-30, and the R2Or R3Any of which chooses phenyl, then it is zero to correspond to p value；
Z is selected from：Integer between 1-3；
X is selected from：Hydrogen, R5OOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid, or R5OOH, sulfuric acid Base, phosphate, acrylic acid, appoint in maleic acid, or fumaric acid
A kind of soluble-salt；
R5It is selected from：C1-4Alkyl；
The molecular weight of polymer shown in Formulas I is 240-7000 dalton.
Above-mentioned R5OOH, sulfate, phosphate, acrylic acid, any soluble-salt in maleic acid, or fumaric acid Can be sylvite, sodium salt or ammonia salt etc., it is only necessary to polymer shown in the Formulas I is ionized in aqueous and produce anion.Work as X For hydrogen when, the polymer is neutral ether；When X chooses R5OOH, sulfate, phosphate, acrylic acid, maleic acid, or anti-butylene two When acid and its soluble-salt, the polymer is anionic ester class formation.
Organic pollutant deposition and the method for removing ink are reduced in the pulping and paper-making production of the present invention, using shown in Formulas I Polymer as control organic pollution and/or deinking medicament, the polymer be multi-styrene phenol polyoxyethylene/propylene/ Butylene ether or its sulfuric acid, phosphoric acid, carboxylate, its molecular mass are 240-7000Dalton.In pulping and paper-making production, this is gathered Compound is added in the slurry containing organic pollution, and what it can be selective reacts simultaneously with organic pollution or ink material surface Change the physics and chemical property of organic pollution and ink, make this kind of material be easier to be separated and remove in pulping process Go, the content of organic pollution and ink in reduction system, reduce and even eliminate organic pollution viscosity, or divide them Dissipate, so as to eliminate deposition of the organic pollution in slurrying and paper-making process, reaching improves paper quality and raising paper production The purpose of efficiency.
The method of the present invention can reduce and remove organic pollutant deposition and the principle of ink is：Above-mentioned polymeric oxidizer Property absorption in organic pollution or ink pellet surface, this part surface is covered, decreases or even eliminates its interaction, so as to The surface nature of organic pollution and ink can be selectively changed, reaches the effect for efficiently reducing organic pollutant deposition and deinking Fruit.
Also, the polymer can also coordinate the mixture of any one or two kinds in esterase and surfactant common Use, the polymer can be compatible with other slurrying and additive for paper making or its mixture, wherein described slurrying and papermaking adds Add the one kind of agent for starch, filler, defoamer, wet strengthening resin, cation type polymer, anionic polymer and glue sizing auxiliary agent Or more than one mixture.Described polymer can be powder, aqueous dispersion, be mixed in one with activating agent/emulsifying agent Any form of the solution risen.
Above-mentioned polymer has different chemical names in the literature, such as polystyrene phenol polyoxy alkyl polyoxy styrene (polystyrylphenol poly(alkyl oxide)poly(styrene oxide)),styrenated alkoxylated phenols,alkoxykated polystyrylphenols,styrenated poly(ethyl oxide),polystyrylphenol alkoxylates,ethoxlated styrenated phenols,styrenated Phenol ethoxlates, and tri-or di-styrylphenol ethoxylates etc..
The preparation method of above-mentioned polymer may be referred to following document：US 4,842,776, US 6,736,892, US7, 205,352, US 7,271,2311, US 8,211,837, US 6,455,471, US 4,904,695, WO2007/110355, US 2010/0016155, US 4,240,918, US 7,030,078, US 8,372,788, US2011/0190174, US 5,035, 785, US 6,736,892 and Surfactants in Agricultural Formulations (Karsa, Chapter 2, " Recent Developments in the Technology of Surfactants",edited by M.R.Porter, Elsevier,1990).In those references, such polymer is used in formulation of pesticide, detergent compositions and Petroleum Production, but It is so far, to be disclosed without any application on these polymer in paper pulp papermaking.
Paper production is carried out using the method for the present invention, the polymer is added into aqueous cellulosic papermaking slurry material Reaction is mixed, can subsequently be carried out according to conventional production process, specific steps can be：
(1) water and cellulose papermaking dry pulp are mixed, is configured to aqueous cellulosic papermaking slurry material, be placed in slurry supply dress It is stirred in the blender put；
(2) under conditions of stirring, the polymer doses are added in the cellulosic papermaking slurry material obtained toward step (1), Reacted to obtain mixing paper making pulp；
(3) the mixing paper making pulp that step (2) obtains is served into screen pack, filters out water therein, by mixing paper making pulp Solid constituent formed page；
(4) page that step (3) obtains by squeezing and is dried, obtains paper product.
In one of the embodiments, the R4For phenyl.
In one of the embodiments, the R2And R3Optionally certainly：Hydrogen, methyl.
In one of the embodiments, the X is sulfate or phosphate.
In one of the embodiments, the z is 2 or 3, and preferably z is 3.
In above-mentioned one of embodiment, m is selected from：Integer between 5-50；N is selected from：Integer or 70- between 1-50 Integer between 80；P is selected from：Integer between 0-20.
In one of the embodiments, the molecular weight of polymer shown in the Formulas I is 500-2000 dalton or 4000- 7000 dalton.
In one of the embodiments, the polymer doses are at least two polymerizations different in polymer shown in Formulas I Thing, the R in one of which polymer4For phenyl, the X in another polymer is sulfate.
In one of the embodiments, one or more biology enzymes, institute are additionally added in aqueous cellulosic papermaking slurry material It is cellulase, hemicellulase and esterase to state biology enzyme；The polymer：The weight ratio of biology enzyme is 10:0.5-1.5.
In one of the embodiments, the addition of the polymer doses is to be added in dry cellulosic paper making pulp per ton 0.01-10 kilograms, 0.1-5 kilograms is added in dry cellulosic paper making pulp preferably per ton.The polymer doses are made with cellulose The temperature of pulp material reaction is 10-80 DEG C, preferably 20-60 DEG C, more preferably 50-60 DEG C, pH value in reaction 3-10, preferably 4-7, instead It it is 5-1200 minutes, preferably 20-400 minutes between seasonable.Wherein, pH is adjusted with the hydrochloric acid or sodium hydroxide that mass concentration is 1% Value.
Reduced the invention also discloses polymer shown in a kind of Formulas I in pulping and paper-making production and go removal organic polluter to sink The application of product and ink,
Wherein：R1It is selected from：Hydrogen or C1-4Alkyl；
R2, R3And R4Optionally certainly：Hydrogen, methyl, ethyl, propyl group or phenyl, and adjacent R2And R3And adjacent R3And R4 Substituent is mutually different group；
M is selected from：Integer between 0-70；
N is selected from：Integer between 1-80；
P is selected from：Integer between 0-30, and the R2Or R3Any of which chooses phenyl, then it is zero to correspond to p value；
Z is selected from：Integer between 1-3；
X is selected from：Hydrogen, R5OOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid, or R5OOH, sulfuric acid Base, phosphate, acrylic acid, any soluble-salt in maleic acid, or fumaric acid；
R5It is selected from：C1-4Alkyl；
The molecular weight of polymer shown in Formulas I is 240-7000 dalton.
In one of the embodiments, the R4For phenyl.
In one of the embodiments, the R2And R3Optionally certainly：Hydrogen, methyl.
In one of the embodiments, the X is sulfate or phosphate.
In one of the embodiments, the z is 2 or 3, and preferably z is 3.
In one of the embodiments, m is selected from：Integer between 5-50；N is selected from：Integer or 70-80 between 1-50 it Between integer；P is selected from：Integer between 0-20.
In one of the embodiments, the molecular weight of polymer shown in the Formulas I is 500-2000 dalton or 4000- 7000 dalton.
Compared with prior art, the invention has the advantages that：
The method for reducing in a kind of pulping and paper-making production of the present invention and removing organic pollutant deposition and ink, using formula Polymer shown in I changes the surface physics of organic pollution and ink and chemical property, so as to reducing, removing, preventing even The problem of middle organic pollutant (sicker) of elimination paper pulp papermaking system deposits in pulping and papermaking processes, and reduce system The content of middle ink.And then improve the efficiency and product quality of paper production.
Also, the polymer applicability used in the present invention is wide, no matter the source of organic pollutant is chemical pulp, machinery Original Pulp or MOW, OCC, ONP, the OMG such as slurry, sulfurous wintercherry, etc. recycled fiber pulp, either acid or alkalescence condition, Either under the industrial condition of low temperature or high temperature, the polymer plays the role of efficiently to reduce organic pollution precipitation, also right Also possess efficient reduction with the invalid fatty acid soaps resinoid depositions of DeTac to act on.
Meanwhile the polymer in the present invention is selective absorption on hydrophobic particle surface, will not with fibration, from And the surface of organic pollution or ink is only selectively changed, and reach the result of efficient control sicker and deinking, and it is right Paper machine produces and paper product quality has no adverse effect.
Brief description of the drawings
Fig. 1 is that OCC produces corrugated paper slurrying flow in embodiment 2；
Fig. 2 is always disconnected paper time each phase contrast before and after polymer is added of paper machine front baking (before coating) in embodiment 3 Column diagram.
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments, but any restrictions is not caused to the present invention.
Shown in polymer architecture below formula II described in following examples：
Each polymeric articles in the specific embodiment of table 1
Wherein：
First, polymer A, B, D, E, G and H preparation method is：The synthetic method of polyoxy styrene includes：
(1) by tristyryl phenol (tri-styrene phenol) and ethylene oxide (ethylene oxide) according to mesh Mark the molal quantity proportioning needed for product and add reactor, be well mixed；Then catalyst diethyl alkanisation zinc (zinc is added ) and water, diethyl its weight is according to water：Diethyl alkanisation zinc (zinc diethyle):Ethylene oxide (ethylene oxide) Ratio be 1:1.10:13 feed intake；Then add substantial amounts of dioxane (dioxan) and be used as reaction dissolvent, to reactor Vacuumize, above reactant is heated 80 DEG C after condition of high vacuum degree is reached, and it is continuously stirred mixing, react 240 hours.
(2) product that above-mentioned reaction obtains is dissolved in benzene liquid, then adds methanol by catalyst diethyl alkanisation zinc (Zinc Diethyl) is precipitated out, and allows polymerisation to terminate；Then solids separation is removed with centrifugal separation.
(3) polymer D and H also needs sulfonating reaction of evolving according to a conventional method, and other polymer need not then carry out sulfonation procedure.
(4) benzene and water are removed with freeze-drying, obtains pure product.
2nd, polymer C preparation method is：Basic step is identical with above-mentioned polymer A and polymer B product, first closes Into polyoxypropylene, then it polymerize polyoxyethylene again.Specific steps include：
(1) by tristyryl phenol (tri-styrene phenol) and propylene oxide (propylene oxide) according to Molal quantity proportioning adds reactor needed for target product, is well mixed；Then catalyst diethyl alkanisation zinc (zinc is added ) and water, diethyl its weight is according to water：Diethyl alkanisation zinc (zinc diethyl):Propylene oxide (propylene oxide) Ratio be 1:1.10:13 feed intake, and then add substantial amounts of dioxane (dioxan) and are used as reaction dissolvent, to reactor Vacuumize, above reactant is warmed to 80 DEG C after condition of high vacuum degree is reached, and it is continuously stirred mixing, reaction 240 is small When.
(2) then, ethylene oxide (ethylene oxide) and bisethane are added according to molar ratio needed for target product Change zinc, its weight is according to water：Diethyl alkanisation zinc (zinc diethyle):The ratio of ethylene oxide (ethylene oxide) is 1:1.10:13 feed intake；Then add substantial amounts of dioxane (dioxan) and be used as reaction dissolvent, reach condition of high vacuum degree it Above reactant is warmed to 80 DEG C afterwards, and it is continuously stirred mixing, is reacted 240 hours；
(3) product that above-mentioned reaction obtains is dissolved in benzene liquid, then adds methanol by catalyst diethyl alkanisation zinc (Zinc Diethyle) is precipitated out, and polymerisation is terminated；Then solids separation is removed with centrifugal separation.
(4) benzene and water are removed with freeze-drying, obtains pure product polymer C.
3rd, polymer F preparation method is：Basic step is identical with above-mentioned polymer C products, i.e., first synthesizes polyoxy third Alkene, polyoxyethylene, then it polymerize polyoxy styrene again.Specific steps include：
(1) by tristyryl phenol (tri-styrene phenol) and propylene oxide (propylene oxide) according to Molal quantity proportioning adds reactor needed for target product, is well mixed；Then catalyst diethyl alkanisation zinc (zinc is added ) and water, diethyl its weight is according to water：Diethyl alkanisation zinc (zinc diethyl):Propylene oxide (propylene oxide) Ratio be 1:1.10:13 feed intake, and then add substantial amounts of dioxane (dioxan) and are used as reaction dissolvent, to reactor Vacuumize, above reactant is warmed to 80 DEG C after condition of high vacuum degree is reached, and it is continuously stirred mixing, reaction 240 is small When.
(2) then, ethylene oxide (ethylene oxide) and bisethane are added according to molar ratio needed for target product Change zinc, its weight is according to water：Diethyl alkanisation zinc (zinc diethyle):The ratio of ethylene oxide (ethylene oxide) is 1:1.10:13 feed intake；Then add substantial amounts of dioxane (dioxan) and be used as reaction dissolvent, reach condition of high vacuum degree it Above reactant is warmed to 80 DEG C afterwards, and it is continuously stirred mixing, is reacted 240 hours；
(3) then, matched according to styrene oxide needed for target product (styrene oxide) molal quantity and add reaction Kettle, it is well mixed；Then catalyst diethyl alkanisation zinc (zinc diethylene) and water are added, its weight is according to water：Bisethane Change zinc (zinc diethyle):The ratio of styrene oxide (styrene oxide) is 1:1.25:40；Feed intake and then add and be big The dioxane (dioxan) of amount is used as reaction dissolvent, and reactor is vacuumized, after condition of high vacuum degree is reached by more than Reactant is warmed to 60 DEG C, and it is continuously stirred mixing, reacts 240 hours.
(4) product that above-mentioned reaction obtains is dissolved in benzene liquid, then adds methanol by catalyst diethyl alkanisation zinc (Zinc Diethyle) is precipitated out, and is that polymerisation terminates；Then solid is separated off with centrifugal separation.
(5) benzene and water are removed with freeze-drying, obtains pure product polymer F.
Embodiment 1
A kind of method that organic pollutant deposition is reduced in pulping and paper-making production, this method are mainly used in reclaim waste and old report Control during paper production newsprint to organic pollution (sicker).
First, material
The dry cellulosic slurry of deinking old and useless newspaper slurry (ONP) is obtained by a southern paper plant.
Conventional stickies control agent uses the registration mark product of Ashland companies of the U.S.Make reference pair Than.
Other polymeric articles are shown in Table 1.
2nd, method
Using food mixer () simulation pulping and paper-making production in process in paper pulp mixing and dry Mainstream journey, measure at different conditions sicker in the deposition on mixed cylinder and stirring flap surface, then more various components Influence to organic deposition.
The condition of deposition test is：100 grams of dry cellulosic slurry (dry pulp weight), add water by the aqueous of slurry regulation to 10% Cellulosic papermaking slurry material, is reacted using different polymer doses (as shown in table 2) and cellulosic papermaking slurry material, and reaction temperature is 65 DEG C, the reaction time is 120 minutes, and stirring intensity is medium.
3rd, result
Deposition test terminates, measure at different conditions sicker in the deposition on mixed cylinder and stirring flap surface, tool Body is as shown in table 2 below.
Deposition conditions of the sicker on mixed cylinder and stirring flap surface under the different condition of table 2
Note：" stirring valve surface " is the area for being glued thing covering divided by the ratio for stirring valve total surface area；
" vessel surface deposition " is the ratio of the area divided by the inner surface of container gross area that are glued thing covering.
All polymer of the present invention compare contrast product in the effect of control Stickies deposit it can be seen from upper tableWith more preferable effect.Particularly when from when being applied in combination of polymeric articles of 2 different chemical structures, Its effect showed is optimal, with contrast productCompare, only need 20-30%'sDosage is with regard to energy Reach identical stickies control effect.
Embodiment 2
A kind of method that organic pollutant deposition is reduced in pulping and paper-making production, this method are mainly used in reclaim boxboard (OCC) control during production corrugated paper to organic pollution (sicker).
First, material
The dry cellulosic slurry of recovery boxboard slurry (OCC) is obtained by a southern paper plant.
Biological enzymatic compositions (cellulase, hemicellulase and esterase), wherein：Cellulase is the business of Dyadic companies Industry product F iberZyme G200, hemicellulase are commercially available prod, and esterase is the auspicious occasion Sheng Da Bioisystech Co., Ltd in Guangzhou Clean enzymeTMProduct, model SC-3000, from black-koji mould (Aspergillus), expressed after restructuring in E.Coli, to anti- Answer between the ester of substrate glycerol three and the relative activity ratio 10~3 of ethyl acetate.
Other polymeric articles used are shown in Table 1.
2nd, method
According to production procedure shown in Fig. 1, to reclaim boxboard (OCC) production corrugated paper, by polymer D and the F group in table 1 (wherein D and F weight ratio are 1 for conjunction:1), the polymer as control organic pollutant deposition is added in pulper, amount ranges For 50-300g/T (oven dry stock addition per ton).Then add biological enzymatic compositions (fine again in the good slurry blowpit of polydisc thickener Tie up plain enzyme, hemicellulase and esterase), wherein polymer：The weight ratio of biological enzymatic compositions is 10：1, biological enzymatic compositions In, cellulase, the weight ratio of hemicellulase and esterase is 1：1：1.Total polymer and the total amount ranges 100- of biology enzyme 400g/T (oven dry stock addition per ton).And run 4 weeks before polymer is added, periodically investigate paper machine front baking (before coating) The always disconnected paper time, after running 4 weeks, above-mentioned polymer is added by 100g/T amount, is run 2 weeks, paper machine front baking is periodically investigated and (is coated with Before) the always disconnected paper time, then add above-mentioned polymer in the 3rd week amount by 400g/T, run to 5 weeks, regular investigation paper machine The always disconnected paper time of front baking (before coating).
3rd, result
During experiment, it has been found that before the polymer using the present invention, guide roller surface have accumulated glue for many years Viscous thing/rubbish, for polymer of the invention at the initial stage of experiment, dosage is relatively low, in order to slowly purging system.Add high dosage After polymer, the rapid reduction of Stickies deposit.
Also, after experiment investigation terminates, we using the always disconnected paper time of the paper machine front baking (before coating) of different phase as Ordinate, mapped run time as abscissa, as shown in Figure 2.
Fig. 2 compared for each time phase before and after experiment, the change of total disconnected paper time of paper machine front baking (before coating).From Fig. 2 As can be seen that paper machine, after the polymer using the present invention, because sicker is reduced, what is dried before paper machine always breaks the paper time Correspondingly reduce.After the polymer of the present invention is stopped using, sicker slowly increases in paper machine deposition, the disconnected paper of paper machine Slowly increase.Illustrate that the method for the present invention in addition to it can reduce the precipitation of the organic pollution on device systems, can also improve paper Quality.
Embodiment 3
A kind of method that reclaimed waste paper ink is removed in pulping and paper-making production, this method are mainly used in reclaim mixed waste paper The pollutants such as removal ink are removed during producing coated manila, the whiteness of paper is improved and reduces dust point (ink point).
First, material
Mixed waste paper (office waste, waste and old books etc.) is reclaimed to obtain from Guangdong Jiangmen paper mill.
Other polymeric articles used are shown in Table 1.
2nd, method
Test products are that polymer C and F in table 1 are independent or it combines (1:1), i.e. polymer C, polymer F, polymerization Thing (C+F).
Test method is：Waste paper is first taken, is put into hydrabrusher, then adds laboratory simulation plain boiled water (containing 400PPM's CaCl2The aqueous solution) to starching dense about 12%, then add deinking bleaching chemical (NaOH and H2O2), it is eventually adding Reference Product Or the polymer of the present invention is as deinking agent.Again after pulping 15min, paper pulp is taken out, adds simulation plain boiled water to be diluted to pulp weight Percentage is 3%, places 60min, and then sampling is placed on Denver formula flotation devices, and adding simulation plain boiled water, to be diluted to 1.0% slurry dense, After stirring, start flotation, flotation 3-6min, after flotation, take the pan feeding of flotation and good slurry (discharging), make handsheet respectively, Test handsheet whiteness and dust point.
3rd, result
Table 3 is to deinking effect to two polymer in original deinking agent (reference) and the present invention and combinations thereof Compare.Original Reference Product deinking agent is the deinking chemical medicament of a Switzerland Co., Ltd (Rhodia), and it is mainly formed as polyoxy second Alkene fatty alcohol.As can be seen from the table, the floatation and ink removing effect of the original deinking chemicals of polymer C and F ratio of the invention Number much better, not only the whiteness of good slurry is high, and dust point is low, and can significantly reduce chemicals usage, is advantageous to the environmental protection of paper plant.
The contrast of the floatation and ink removing effect of table 3 (reference combines for original paper plant's deinking agent)
Embodiment 4
A kind of method that reclaimed waste paper ink is removed in pulping and paper-making production, this method are mainly used in reclaim mixed waste paper The pollutants such as removal ink are removed during producing toilet paper, the whiteness of paper is improved and reduces dust point (ink point).
First, material
Mixed waste paper (office waste, waste and old books etc.) is reclaimed to obtain from one paper plant of Dongguan, Guangdong.
Other polymeric articles used are shown in Table 1.
2nd, method
Test products are that the polymer in table 1 is independent or it combines (1:1).
Test method is：Waste paper is first taken, is put into hydrabrusher, then adds laboratory simulation plain boiled water (containing 400PPM's CaCl2The aqueous solution) to starching dense about 12%, then add deinking bleaching chemical (NaOH and H2O2), it is eventually adding Reference Product Or the polymer of the present invention is as deinking agent.Again after pulping 15min, paper pulp is taken out, adds simulation plain boiled water to be diluted to pulp weight Percentage is 3%, places 60min, and then sampling is placed in handsheet machine, and adding simulation plain boiled water, to be diluted to 0.5% slurry dense, and stirring is equal After even, water is bled off, running water is then added and is starched to identical dense, then water bled off；Running water is eventually adding to about 1% Slurry it is dense, be made handsheet, test handsheet whiteness and dust point.
3rd, result
Table 4 is to comparison of the polymer and combinations thereof to deinking effect in original deinking agent (reference) and the present invention. Original Reference Product deinking agent is market routine deinking agent, and it is mainly formed as phosphate, as can be seen from the table, this hair Deinking efficiency number of the bright all polymeric articles all than original deinking chemicals is much better, and not only the whiteness of good slurry is high, dust Point is low, and can significantly reduce chemicals usage, is advantageous to the environmental protection of paper plant.
Table 4 washs the contrast of deinking efficiency (reference combines for original paper plant's deinking agent)
Embodiment described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but simultaneously Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention Protect scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.

Claims (21)

1. the method for reducing in a kind of production of pulping and paper-making and removing organic pollutant deposition and ink, it is characterised in that containing Polymer doses are added in the cellulosic papermaking slurry material of water, the polymer doses is reacted with fibrous paper making pulp, papermaking Organic pollution and ink in slurry are modified, so as to be removed efficiently in pulping and papermaking processes；The polymer Medicament includes formulaAt least one of shown polymer：
Wherein：R1It is selected from：Hydrogen or C1-4Alkyl;
R2, R3And R4Optionally certainly：Hydrogen, methyl, ethyl, propyl group or phenyl, and adjacent R2And R3And adjacent R3And R4Take The mutually different groups of Dai Jiwei；And R2, R3And R4In at least one be selected from phenyl；
M is selected from：Integer between 0-70；
N is selected from：Integer between 1-80；
P is selected from：Integer between 0-30, and the R2Or R3Any of which chooses phenyl, then it is zero to correspond to p values；When R4For phenyl when, p value is not zero；
Z is selected from：Integer between 1-3;
X is selected from：Hydrogen, R5COOH, sulfonic group, phosphate, acrylic, maleic, or fumaric acid base, or R5COOH, sulfonic group, phosphate, acrylic, any soluble-salt in maleic, or fumaric acid base；
R5It is selected from：C1-4Alkylidene；
FormulaThe molecular weight of shown polymer is 240-7000 dalton.
2. the method for reducing in pulping and paper-making production according to claim 1 and removing organic pollutant deposition and ink, Characterized in that, the R4For phenyl.
3. the method for reducing in pulping and paper-making production according to claim 1 and removing organic pollutant deposition and ink, Characterized in that, the R2And R3Optionally certainly：Hydrogen, methyl.
4. the method for reducing in pulping and paper-making production according to claim 1 and removing organic pollutant deposition and ink, Characterized in that, the X is sulfonic group or phosphate.
5. the method for reducing in pulping and paper-making production according to claim 1 and removing organic pollutant deposition and ink, Characterized in that, the z is 2 or 3.
6. the method for reducing in pulping and paper-making production according to claim 1 and removing organic pollutant deposition and ink, Characterized in that, m is selected from：Integer between 5-50；N is selected from：The integer between integer or 70-80 between 1-50；P is selected from： Integer between 0-20.
7. the method for reducing in pulping and paper-making production according to claim 1 and removing organic pollutant deposition and ink, Characterized in that, the formulaThe molecular weight of shown polymer is 500-2000 dalton or 4000-7000 dalton.
8. the method for reducing in pulping and paper-making production according to claim 1 and removing organic pollutant deposition and ink, Characterized in that, the polymer doses are formulaAt least two different polymer, one of which polymer in shown polymer In R4For phenyl, the X in another polymer is sulfonic group.
9. reduce and remove organic pollutant deposition and ink in the pulping and paper-making production according to claim any one of 1-8 Method, it is characterised in that one or more biology enzymes are additionally added in aqueous cellulosic papermaking slurry material, the biology enzyme is Cellulase, hemicellulase and esterase；The polymer doses：The weight ratio of biology enzyme is 10:0.5-1.5.
10. reduce and remove organic pollutant deposition and oil in the pulping and paper-making production according to claim any one of 1-8 The method of ink, it is characterised in that the addition of the polymer doses is to add 0.01-10 in dry cellulosic paper making pulp per ton Kilogram；The temperature of the polymer doses and cellulosic papermaking slurry material reaction is 10-80 DEG C, pH value in reaction 3-10, during reaction Between be 5-1200 minutes.
11. the method for reducing in a kind of production of pulping and paper-making and removing organic pollutant deposition and ink, it is characterised in that containing Polymer doses are added in the cellulosic papermaking slurry material of water, the polymer doses is reacted with fibrous paper making pulp, papermaking Organic pollution and ink in slurry are modified, so as to be removed efficiently in pulping and papermaking processes；The polymer Medicament includes polymer F, and the structural formula of the polymer F is as follows：
。
12. the side of organic pollutant deposition and ink is reduced and removed in pulping and paper-making production according to claim 11 Method, it is characterised in that one or more biology enzymes are additionally added in aqueous cellulosic papermaking slurry material, the biology enzyme is fiber Plain enzyme, hemicellulase and esterase；The polymer doses：The weight ratio of biology enzyme is 10:0.5-1.5.
13. the side of organic pollutant deposition and ink is reduced and removed in pulping and paper-making production according to claim 11 Method, it is characterised in that the addition of the polymer doses is that 0.01-10 kilograms is added in dry cellulosic paper making pulp per ton； The polymer doses and the temperature of cellulosic papermaking slurry material reaction are 10-80 DEG C, pH value in reaction 3-10, reaction time 5- 1200 minutes.
14. formulaShown polymer reduces and removed the application of organic pollutant deposition and ink in pulping and paper-making production,
Wherein：R1It is selected from：Hydrogen or C1-4Alkyl;
R2, R3And R4Optionally certainly：Hydrogen, methyl, ethyl, propyl group or phenyl, and adjacent R2And R3And adjacent R3And R4Take The mutually different groups of Dai Jiwei；And R2, R3And R4In at least one be selected from phenyl；
M is selected from：Integer between 0-70；
N is selected from：Integer between 1-80；
P is selected from：Integer between 0-30, and the R2Or R3Any of which chooses phenyl, then it is zero to correspond to p values；When R4For phenyl when, p value is not zero；
Z is selected from：Integer between 1-3;
X is selected from：Hydrogen, R5COOH, sulfonic group, phosphate, acrylic, maleic, or fumaric acid base, or R5COOH, sulfonic group, phosphate, acrylic, any soluble-salt in maleic, or fumaric acid base；
R5It is selected from：C1-4Alkylidene；
FormulaThe molecular weight of shown polymer is 240-7000 dalton.
15. formula according to claim 14Shown polymer reduces in pulping and paper-making production and goes removal organic polluter to sink The application of product and ink, it is characterised in that the R4For phenyl.
16. formula according to claim 14Shown polymer reduces in pulping and paper-making production and goes removal organic polluter to sink The application of product and ink, it is characterised in that the R2And R3Optionally certainly：Hydrogen, methyl.
17. formula according to claim 14Shown polymer reduces in pulping and paper-making production and goes removal organic polluter to sink The application of product and ink, it is characterised in that the X is sulfonic group or phosphate.
18. formula according to claim 14Shown polymer reduces in pulping and paper-making production and goes removal organic polluter to sink The application of product and ink, it is characterised in that the z is 2 or 3.
19. formula according to claim 14Shown polymer reduces in pulping and paper-making production and goes removal organic polluter to sink The application of product and ink, it is characterised in that m is selected from：Integer between 5-50；N is selected from：Integer or 70-80 between 1-50 it Between integer；P is selected from：Integer between 0-20.
20. formula according to claim 14Shown polymer reduces in pulping and paper-making production and goes removal organic polluter to sink The application of product and ink, it is characterised in that the formulaThe molecular weight of shown polymer is 500-2000 dalton or 4000- 7000 dalton.
21. polymer F reduces and removed the application of organic pollutant deposition and ink, the polymer in pulping and paper-making production F structural formula is as follows：
。
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