WO2016034004A1 - Method for reducing and removing organic pollutant deposits and ink during pulp and paper production - Google Patents

Abstract

A method for reducing and removing organic pollutant deposits and ink during pulp and paper production, said method comprising adding polystyrene phenol polyoxyethylene/propylene/butylene ether or sulphate, phosphate and carboxylic ester polymers having a molecular weight of 240-7000 to aqueous cellulose papermaking slurry, said polymers comprising at least one polymer represented by formula I. Wherein: R¹ is selected from: hydrogen or C _1-4 alkyl; R², R³, and R⁴ are selected from: hydrogen, methyl, ethyl, propyl or phenyl, and the substituents of adjacent R² and R³ and R³ and R⁴ are from different radical groups; m is selected from: an integer between 0-70; n is selected from: an integer between 1-80; p is selected from: an integer between 0-30, and if one of R² or R³ is selected from phenyl, then the corresponding p value is zero; z is selected from: an integer between 1-3; X is selected from: hydrogen, R⁵OOH, a sulfuric acid group, a phosphoric acid group, acrylic acid, maleic acid, or fumaric acid, or a soluble salt of any one of R⁵OOH, a sulfuric acid group, a phosphoric acid group, acrylic acid, maleic acid, or fumaric acid; and R⁵ is selected from C _1-4 alkyl.

Description

Method for reducing and removing organic pollutant deposition and ink in pulp and paper production Technical field

The invention relates to the technical field of pulping and papermaking, in particular to a method for reducing organic pollutant deposition, ink impurities and clean paper machine system in pulp and paper production, thereby improving paper machine operating efficiency and product quality.

Background technique

It is well known that in the papermaking process, the deposition of organic pollutants (also known as precipitation) is very detrimental to the quality of paper products and paper production efficiency. The two main reasons for this problem are resin deposition and stickies deposition. Among them, the main component of the resin deposit is naturally present in the wood and released during the pulping and paper making process. From a physics point of view, "resin deposits" are typically formed by microscopic particles of binder material (natural or artificial) in the slurry that accumulate on papermaking paper or pulping equipment. The "sticker deposit" is usually a particle derived from a slurry of recycled fiber. Its main chemical structural features are synthetic adhesives such as adhesives and hot melts, as well as coatings and inks. And other ingredients.

In the past, the deposition of resins and stickies had their own typical manifestations in different systems, since papermaking used almost exclusively virgin fibers or only recycled fibers. In order to control these independent issues, there are often very different treatment chemicals and coping strategies. However, the trend in recent years is that recycled fibers are gradually used in all systems, so "sticker deposition" occurs at the same time as "resin deposition", which causes deposition of organic contaminants co-deposited with resin and resin. .

These deposits are easily found in the reservoir wall, paper making chassis, U-shaped box, paper machine wire, wet press felt, dryer felt, drying can and calender assembly. The deposition of organic contaminants will not only remain on the metal surface of the system, but will also remain on the plastic and synthetic surfaces, which will have a negative impact on paper production. For example, in machines, blankets, U-shaped boxes and headbox components, it is not conducive to pulping or papermaking, and even affects operating efficiency, reducing production capacity and the like. If organic contaminants are deposited on processing equipment in papermaking systems, organic contaminants deposited on consistency regulators and other detection equipment can cause these components to fail to function properly, making system operation difficult. In addition, organic deposits can cause paper face holes, dirt and its It is ill, and these defects can degrade the quality of the paper and cannot be used in subsequent processes such as coating, printing, or printing.

Although the paper machine can be shut down for cleaning, we do not want this kind of shutdown to be cleaned, as this will result in a corresponding loss of productivity, and when these deposits are broken and mixed into the paper, the presence of these contaminants will be even more One step causes deterioration in paper quality. Therefore, it is extremely important to prevent the deposition of organic matter on the surface of the pulp and paper making equipment and the container.

US Patent No. 3,992,249 discloses the use of an anionic vinyl polymer containing 25-85% of a hydrophobic group to control the deposition of organics, wherein the hydrophobic groups include styrene, methylstyrene, long chain fatty alkyl groups, etc., anionic groups Including acrylic acid, methacrylic acid, styrene sulfonic acid and the like. Nonionic polymeric release agents are well known in the art as materials for controlling the deposition of resins and stickies and are used to control the deposition of resins and stickies in pulp and papermaking systems. For example, U.S. Patent Nos. 4,871,424 and 4,886,575 each disclose the use of a vinyl alcohol-vinyl acetate copolymer to control the deposition of resins and stickies in pulp and paper systems. The use of hydrophobically modified nonionic associative polymers, such as hydrophobically modified carboxyethyl cellulose ethers (HMHEC), in European Patent EP 0 568 229 Al, prevents the deposition of organic contaminants from pulp in pulp and paper systems. . Combinations of vinyl alcohol-vinyl acetate copolymers of nonionic polymers and HMHEC with cationic polymers are disclosed in U.S. Patent Nos. 5,723,021 and 7,166,192. Recently, U.S. Patent No. 8,048,268 discloses the use of hydrophobically modified ethoxylated aminoplast thickener (HEAT) to control organic matter deposition problems. However, none of these methods can truly solve the problem of organic matter deposition completely and effectively, and there are defects of poor effect.

In the conventional art, DeTac (product of Hercules Inc., USA) is often used to control the deposition of organic matter, but the problem is that the effect is poor and the application range is narrow, and in particular, it is substantially ineffective for the deposition of the fatty acid soap resin.

In addition, the organic pollutant treatment technologies in the existing papermaking technology are generally non-selective, non-controllable and non-targeting, so they often act with other beneficial papermaking additives, causing interference, resulting in significant effects. Falling.

In addition, enzymes are known to be effective as contaminant control agents in pulp and papermaking systems. Principle Yes: Lipases and esterases are protein catalysts that promote the hydrolysis of glycerides in the resin component, as well as react with stickies to reduce, eliminate and/or inhibit deposition. For example, in U.S. Patent No. 5,176,796, the use of lipase to hydrolyze the main component of the resin, i.e., non-polar triglycerides, to water-soluble glycerol and polar fatty acids is used in the manufacture of paper from mechanical pulp. U.S. Patent No. 5,507,952, US Pat. No. 5,356,800, US Pat. The viscosity of the contaminant polyvinyl alcohol is a typical contaminant component of recycled paper.

However, the use of enzymes alone is not the best way to control organic contaminants in pulp and paper applications. For example, a well-known problem is that a fatty acid formed by decomposing a resin with a lipase reacts with a metal ion in water to form a poorly soluble fat soap, resulting in deposition, and even at a higher resin content, even than without lipase treatment. Resin deposition is more serious. The melting point of the fat after saponification is higher than the melting point of the resin before unconversion, the viscosity is larger, and it is insoluble in a common organic solvent, so it is more difficult to control. To this end, a method for controlling resin deposition in a pulping and papermaking process is described in U.S. Patent Nos. 5,256,252 and 5,667,634, which incorporate the use of a combination of a lipase and a cationic polymer to reduce the aqueous phase of the cellulose slurry. Fatty acid concentration. A similar process is disclosed in U.S. Patent No. 6,471,826 B2, which uses a combination of at least one esterase and a cationic polymer to control organic contaminants in recycled paper. A method for reducing or preventing the deposition of contaminants is disclosed in U.S. Patent Application Publication No. 2004/0194903 Al, which comprises the use of one or more enzymes and a non-enzymatic liquid felt conditioner, said conditioning agent being It is composed of one or more surfactants and/or one or more anionic or cationic dispersants or polymers. A method of increasing the removal or control of adhesives and viscous contaminants in a papermaking process, comprising combining one or more enzymes with one or more, is disclosed in US Patent Application Publication No. 2006/0048908 Al. Absorbent or adsorbent. The absorbent or adsorbent is selected from natural or synthetic inorganic and organic particles comprising crosslinked cationic, anionic or nonionic organic microparticles.

However, so far, there is no way to truly solve the problem of organic matter deposition completely. The paper industry is eager to get a cost-effective technology to solve the problem of organic matter deposition that has plagued papermaking for many years.

Summary of the invention

Based on this, the object of the present invention is to overcome the defects of the prior art and to provide a method for reducing and removing organic pollutant deposition and ink in pulp and paper production. The method has the advantages of good effect and wide application range.

To achieve the above object, the present invention adopts the following technical solutions:

A method for reducing and removing organic pollutant deposition and ink in pulp and paper production, adding a polymer agent to an aqueous fiber papermaking slurry to react the polymer agent with a cellulose papermaking pulp, in a papermaking slurry The organic contaminants and inks are modified to be effectively removed during the pulping and papermaking process; the polymeric agents comprise at least one of the polymers of Formula I:

Wherein: R ^{1 is} selected from the group consisting of: hydrogen or C _1-4 alkyl;

R ² , R ³ and R ^{4 are each selected} from the group consisting of hydrogen, methyl, ethyl, propyl or phenyl, and the adjacent R ² and R ³ and the adjacent R ³ and R ⁴ substituents are different from each other. Group

m is selected from: an integer between 0 and 70;

n is selected from the group consisting of: an integer between 1 and 80;

p is selected from: an integer between 0 and 30, and wherein any one of R ² or R ^{3 is} a phenyl group, the corresponding p value is zero;

z is selected from: an integer between 1-3;

X is selected from the group consisting of: hydrogen, R ⁵ OOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid, or R ⁵ OOH, sulfate, phosphate, acrylic acid, maleic acid, or fubutene a soluble salt of any of the diacids;

R ^{5 is} selected from the group consisting of: C _1-4 alkyl;

The polymer of formula I has a molecular weight of from 240 to 7000 Daltons.

The soluble salt of any of the above R ⁵ OOH, sulfate group, phosphate group, acrylic acid, maleic acid, or fumaric acid may be a potassium salt, a sodium salt or an ammonium salt, etc., and only the formula I is required. The polymer can be ionized in an aqueous solution to produce an anion. When X is hydrogen, the polymer is a neutral ether; when X is selected from R ⁵ OOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid and soluble salts thereof, the polymer is Anionic ester structure.

The method for reducing organic pollutant deposition and removing ink in the pulp and paper production of the invention adopts the polymer of the formula I as a medicament for controlling organic pollutants and/or deinking, the polymer being polystyrene phenol polyoxyl Ethylene/propylene/butene ether or its sulfuric acid, phosphoric acid, carboxylic acid ester, and its molecular mass is 240-7000 Dalton. In pulp and paper production, the polymer is added to a slurry containing organic contaminants that selectively react with organic contaminants or ink materials and alter the physical and chemical properties of organic contaminants and inks. These materials are more easily separated and removed during the pulping process, reducing the amount of organic contaminants and inks in the system, reducing or even eliminating the viscosity of organic contaminants, or dispersing them, thereby eliminating organic pollutants in the pulping and papermaking process. The deposition in the paper achieves the goal of improving paper quality and improving paper production efficiency.

The method of the present invention is capable of reducing and removing organic contaminant deposits and inks by selectively adsorbing the above-mentioned polymer on the surface of organic contaminants or inks, covering the surface of the portion, reducing or even eliminating the interaction thereof, thereby enabling selectivity. The surface properties of organic pollutants and inks are changed to achieve the effect of effectively reducing the deposition and deinking of organic pollutants.

Moreover, the polymer may also be used in combination with any one or a mixture of an esterase and a surfactant, which may be compatible with other pulping and papermaking additives or mixtures thereof, wherein the polymer is prepared. The pulp and papermaking additives are one or more mixtures of starch, fillers, defoamers, wet strength resins, cationic polymers, anionic polymers, and sizing aids. The polymer may be in the form of a powder, an aqueous dispersion, or a solution mixed with an active agent/emulsifier.

The above polymers have different chemical names in the literature, such as 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 et al.

The preparation of the above-mentioned polymers can be referred to the following documents: US 4,842,776, US 6,736,892, US 7,205,352, 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, US 2011/0190174, 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 MR Porter, Elsevier, 1990). In these documents, such polymers are used in pesticide formulations, detergent formulations and petroleum production, but to date, no application for these polymers in pulp papermaking has been disclosed.

The papermaking process is carried out by the method of the invention, and the polymer is added to the aqueous cellulose papermaking pulp to be mixed and reacted, and then can be carried out according to a conventional production process, and the specific steps can be:

(1) mixing water and cellulose papermaking dry pulp, preparing into an aqueous cellulose papermaking slurry, and stirring and mixing in a mixer of the slurry supply device;

(2) adding the polymer agent to the cellulose papermaking slurry obtained in the step (1) under stirring to carry out a reaction to obtain a mixed papermaking slurry;

(3) sending the mixed papermaking slurry obtained in the step (2) to a filter screen, filtering out the water therein, and forming a paper sheet from the solid components of the mixed papermaking slurry;

(4) The sheet obtained in the step (3) is pressed and dried to obtain a paper product.

In one embodiment, the R ⁴ is phenyl.

In one embodiment, the R ² and R ^{3 are selected} from the group consisting of hydrogen, methyl.

In one embodiment, the X is a sulfate group or a phosphate group.

In one embodiment, the z is 2 or 3, preferably z is 3.

In one of the above embodiments, m is selected from the group consisting of: an integer between 5 and 50; n is selected from: 1 to 50. An integer or an integer between 70 and 80; p is selected from: an integer between 0 and 20.

In one embodiment, the polymer of Formula I has a molecular weight of from 500 to 2000 Daltons or from 4000 to 7000 Daltons.

In one embodiment, the polymeric agent is a different at least two polymers of the polymer of Formula I, wherein R ⁴ in one polymer is phenyl and X in the other polymer is Sulfate group.

In one embodiment, one or more biological enzymes are added to the aqueous cellulose papermaking slurry, the biological enzymes being cellulases, hemicellulases and esterases; the polymer: biological enzymes The weight ratio is 10:0.5-1.5.

In one embodiment, the polymeric agent is added in an amount of from 0.01 to 10 kilograms per ton of dry cellulosic papermaking pulp, preferably from 0.1 to 5 kilograms per ton of dry cellulosic papermaking pulp. The reaction temperature of the polymer agent with the cellulose papermaking pulp is 10-80 ° C, preferably 20-60 ° C, more preferably 50-60 ° C, the reaction pH is 3-10, preferably 4-7, and the reaction time is 5 - 1200 minutes, preferably 20-400 minutes. Among them, the pH was adjusted with hydrochloric acid or sodium hydroxide having a mass concentration of 1%.

The invention also discloses an application of the polymer of the formula I for reducing and removing organic pollutant deposition and ink in pulp and paper production,

Wherein: R ^{1 is} selected from the group consisting of: hydrogen or C _1-4 alkyl;

R ² , R ³ and R ^{4 are each selected} from the group consisting of hydrogen, methyl, ethyl, propyl or phenyl, and the adjacent R ² and R ³ and the adjacent R ³ and R ⁴ substituents are different from each other. Group

m is selected from: an integer between 0 and 70;

n is selected from the group consisting of: an integer between 1 and 80;

p is selected from: an integer between 0 and 30, and wherein any one of R ² or R ^{3 is} a phenyl group, the corresponding p value is zero;

z is selected from: an integer between 1-3;

X is selected from the group consisting of hydrogen, R ⁵ OOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid, or R ⁵ OOH, sulfate, phosphate, acrylic acid, maleic acid, or fubutene a soluble salt of any of the diacids;

R ^{5 is} selected from the group consisting of: C _1-4 alkyl;

The polymer of formula I has a molecular weight of from 240 to 7000 Daltons.

In one embodiment, the R ⁴ is phenyl.

In one embodiment, the R ² and R ^{3 are selected} from the group consisting of hydrogen, methyl.

In one embodiment, the X is a sulfate group or a phosphate group.

In one embodiment, the z is 2 or 3, preferably z is 3.

In one embodiment, m is selected from: an integer between 5 and 50; n is selected from: an integer between 1 and 50 or an integer between 70 and 80; p is selected from the group consisting of: an integer between 0 and 20 .

In one embodiment, the polymer of Formula I has a molecular weight of from 500 to 2000 Daltons or from 4000 to 7000 Daltons.

Compared with the prior art, the present invention has the following beneficial effects:

A method for reducing and removing organic contaminant deposits and inks in a pulp and paper production of the present invention, using the polymer of Formula I to modify the surface physical and chemical properties of organic contaminants and inks, thereby reducing, removing, preventing, and even Eliminate the problem of depositing organic pollutants (stickies) in the pulp and paper system during pulping and papermaking, and reduce the amount of ink in the system. Thereby improving the efficiency of paper production and product quality.

Moreover, the polymer used in the present invention has wide applicability, regardless of whether the source of the organic pollutant is chemical pulp, mechanical pulp, sulfite pulp or the like, or the recycled fiber slurry of MOW, OCC, ONP, OMG, etc., whether acidic or not. It is also an alkaline condition. Under the industrial conditions of low temperature or high temperature, the polymer has the effect of effectively reducing the precipitation of organic pollutants, and also has a high-efficiency effect on the deposition of fatty acid soap resin which is ineffective with DeTac.

At the same time, the polymer in the present invention selectively adsorbs on the surface of the hydrophobic particles and does not act on the fibers, thereby selectively changing only the surface of the organic contaminants or inks, thereby achieving efficient control of the stickies and deinking. As a result, there is no negative impact on paper machine production and paper product quality.

DRAWINGS

1 is a pulping process for producing corrugated paper by OCC in Example 2;

Figure 2 is a comparative bar graph of the total paper break time of the paper machine before baking (before coating) in Example 3 at various stages before and after the addition of the polymer.

detailed description

The present invention is described in detail below with reference to the accompanying drawings and specific embodiments, but without restricting the invention.

The polymer structure described in the following examples is as shown in Formula II:

Table 1 specific polymer products in the specific examples

among them:

First, the preparation methods of the polymers A, B, D, E, G and H are as follows: the synthesis method of the polyoxystyrene includes:

(1) adding tri-styrene phenol and ethylene oxide to the reaction vessel according to the molar ratio required for the target product, and mixing uniformly; then adding the catalyst zinc dihydride (zinc diethyl) And water, the weight of which is based on water: zinc diethyle: ethylene oxide ratio of 1:1.10:13; then adding a large amount of dioxane (dioxan) as a reaction solvent The reaction vessel was evacuated, and after the high vacuum was reached, the above reactant was warmed to 80 ° C, and continuously stirred and mixed for 240 hours.

(2) The product obtained by the above reaction is dissolved in a benzene liquid, and then a catalyst Zinc Diethyl is precipitated by adding methanol to terminate the polymerization reaction; then, the solid matter is separated and removed by centrifugation.

(3) Polymers D and H also need to evolve the sulfonation reaction in a conventional manner, while other polymers do not require a sulfonation step.

(4) The benzene and water are removed by a freeze-drying method to obtain a pure product.

2. The preparation method of the polymer C is as follows: the basic steps are the same as the above-mentioned polymer A and polymer B products, first synthesizing polyoxypropylene, and then polymerizing polyoxyethylene. The specific steps include:

(1) adding tri-styrene phenol and propylene oxide to the reaction vessel according to the desired molar ratio of the target product, and mixing uniformly; then adding the catalyst zinc dichloride and Water, its weight is in accordance with water: zinc diethyl: zinc oxide The ratio of propylene oxide is 1:1.10:13, then a large amount of dioxane is added as a reaction solvent, and the reaction kettle is evacuated, and the above reactant is heated after reaching a high vacuum. The mixture was stirred at 80 ° C for 24 hours.

(2) Then, ethylene oxide and zinc dihydride are added in a molar ratio of the desired product, and the weight is in accordance with water: zinc diethyle: ethylene oxide ratio 1:1.10:13 feeding; then adding a large amount of dioxane (dioxan) as a reaction solvent, after reaching a high vacuum, the above reactants were warmed to 80 ° C, and continuously stirred and mixed for 240 hours. ;

(3) The product obtained by the above reaction is dissolved in a benzene liquid, and then the catalyst Zinc Diethyle is precipitated by adding methanol to terminate the polymerization reaction; then, the solid matter is separated and removed by centrifugation.

(4) The benzene and water were removed by freeze-drying to obtain a pure product polymer C.

3. The preparation method of the polymer F is as follows: the basic steps are the same as those of the above polymer C product, that is, polyoxypropylene, polyoxyethylene, and then polyoxystyrene are first synthesized. The specific steps include:

(1) adding tri-styrene phenol and propylene oxide to the reaction vessel according to the desired molar ratio of the target product, and mixing uniformly; then adding the catalyst zinc dichloride and Water, the weight of which is based on water: zinc diethyl: propylene oxide ratio of 1:1.10:13, and then a large amount of dioxane (dioxan) is added as a reaction solvent. The autoclave was evacuated, and after the high vacuum was reached, the above reactant was warmed to 80 ° C, and continuously stirred and mixed for 240 hours.

(2) Then, ethylene oxide and zinc dihydride are added in a molar ratio of the desired product, and the weight is in accordance with water: zinc diethyle: ethylene oxide ratio 1:1.10:13 feeding; then adding a large amount of dioxane (dioxan) as a reaction solvent, after reaching a high vacuum, the above reactants were warmed to 80 ° C, and continuously stirred and mixed for 240 hours. ;

(3) Then, according to the desired number of moles of styrene oxide required to be added to the reaction vessel, the mixture is uniformly mixed; then, the catalyst zinc diethylene and water are added. The weight is in accordance with water: zinc diethyle: styrene oxide ratio is 1:1.25:40; the feed is then added with a large amount of dioxane (dioxan) as a reaction solvent, the reaction The kettle was evacuated, and after the high vacuum was reached, the above reactant was warmed to 60 ° C, and continuously stirred and mixed for 240 hours.

(4) The product obtained by the above reaction is dissolved in a benzene liquid, and then the catalyst Zinc Diethyle is precipitated by adding methanol to terminate the polymerization; then, the solid is separated and removed by centrifugation.

(5) The benzene and water were removed by freeze-drying to obtain a pure product polymer F.

Example 1

A method for reducing deposition of organic pollutants in pulp and paper production, which is mainly used for controlling organic pollutants (stickies) in the process of producing newsprint by recycling used newspapers.

First, the material

The dry cellulose pulp of deinked waste newspaper pulp (ONP) was obtained from a paper mill in the south.

做参考对比。Conventional Adhesive Control Agents are registered trademarks of Ashland Corporation of the United States.

Make a reference comparison.

Other polymer products are shown in Table 1.

Second, the method

模拟制浆造纸生产中的工序中的纸浆混合和烘干流程，测定在不同条件下胶粘物在混合缸和搅拌叶瓣表面的沉积量，然后比较各种组分对有机物沉积的影响。Using a food mixer

The pulp mixing and drying process in the process of simulating pulp and paper production was carried out to determine the deposition amount of the stickies on the surface of the mixing tank and the stirring vane under different conditions, and then the effects of various components on the deposition of organic matter were compared.

The conditions of the deposition test were: dry cellulose pulp 100 g (dry pulp weight), water was added to adjust the slurry to 10% aqueous cellulose paper pulp, using different polymer agents (as shown in Table 2) and fibers. The papermaking pulp reaction, the reaction temperature is 65 ° C, the reaction time is 120 minutes, and the stirring strength is medium.

Third, the results

At the end of the deposition test, the deposition amount of the stickies on the surfaces of the mixing cylinder and the stirring vane under different conditions was measured, as shown in Table 2 below.

Table 2 Deposition of stickies on the surface of mixing cylinder and stirring vane under different conditions

Note: "Stirring flap surface" is the area covered by the stickies divided by the ratio of the total surface area of the stirring flap;

"Container surface deposit" is the ratio of the area covered by the stickies divided by the total area of the inner surface of the container.

具有更好的效果。特别是当选用2个不同化学结构的聚合物产品的组合使用时，其表现的效果是最佳的，与对比产品

相比，只需20-30％的

用药量就能达到相同的胶粘物控制效果。As can be seen from the above table, all the polymers of the present invention have better effect in controlling the deposition of stickies than the comparative products.

Has a better effect. Especially when using a combination of two polymer products with different chemical structures, the performance is the best, and the comparison product

Compared to 20-30%

The same amount of glue control can be achieved with the dose.

Example 2

A method for reducing the deposition of organic contaminants in the production of pulp and paper. The method is mainly used for controlling organic pollutants (stickies) in the process of producing corrugated paper by using recycled cardboard (OCC).

First, the material

The dry cellulose pulp of the recycled boxboard pulp (OCC) was obtained from a paper mill in the south.

Biological enzyme composition (cellulase, hemicellulase and esterase), wherein: cellulase is a commercial product of Dyadic, FiberZyme G200, hemicellulose enzyme is a commercially available product, and esterase is Guangzhou Ruichen Shengda Biological Technology Co., Ltd.'s Clean ^EnzymeTM product, model SC-3000, is derived from Aspergillus, expressed in E. coli after recombination, and has a relative activity ratio of 10 to 3 for the reaction substrate triglyceride and ethyl acetate. between.

Other polymer products used are shown in Table 1.

Second, the method

According to the production process shown in Figure 1, corrugated paper was produced by recycling cardboard (OCC), and the polymers D and F in Table 1 were combined (where the weight ratio of D and F was 1:1) as a control for organic pollutant deposition. The polymer is added to the pulper in an amount ranging from 50 to 300 g/T (addition of dry pulp per ton). Then, a bio-enzyme composition (cellulase, hemicellulase and esterase) is added to the good slurry discharge tank of the multi-plate concentrator, wherein the weight ratio of the polymer:bio-enzyme composition is 10:1, the biological enzyme The weight ratio of cellulase, hemicellulase and esterase in the composition was 1:1:1. The total amount of total polymer and biological enzymes ranges from 100 to 400 g/T (addition of dry pulp per ton). And run for 4 weeks before adding the polymer, and regularly check the total paper-breaking time before the paper machine is baked (before coating). After 4 weeks of operation, the above polymer is added in an amount of 100 g/T, run for 2 weeks, and the paper is regularly inspected. The total paper-breaking time before machine drying (before coating), then adding the above polymer in the amount of 400g/T at the third week, running for 5 weeks, and regularly checking the total paper break before the paper machine was baked (before coating) time.

Third, the results

During the test, we found that the surface of the guide roll accumulated many years of stickies/waste before using the polymer of the present invention, and the polymer of the present invention was used at a low level in the initial stage of the test to facilitate the slow cleaning of the system. . After the addition of a high amount of polymer, the deposition of the stickies is rapidly reduced.

Moreover, after the end of the test, we took the total paper break time of the paper machine before baking (before coating) as the ordinate and the running time as the abscissa, as shown in Figure 2.

Figure 2 compares the total paper break time of the paper machine before baking (before coating) at various time periods before and after the test. As can be seen from Fig. 2, after the use of the polymer of the present invention in the paper machine, the total paper break time for drying before the paper machine is correspondingly reduced due to the reduction of the stickies. After the use of the polymer of the present invention is stopped, the deposition of the stickies in the paper machine is gradually increased, and the paper break of the paper machine is gradually increased. It is indicated that the method of the invention can improve the quality of the paper in addition to reducing the precipitation of organic pollutants on the equipment system.

Example 3

A method for removing and recycling waste paper ink in pulp and paper production, the method is mainly used for removing ink and other contaminants in the process of producing coated white paper by recycling mixed waste paper, improving whiteness of paper and reducing dust point (ink point).

First, the material

Recycling mixed waste paper (office waste paper, used books, etc.) was obtained from a paper mill in Jiangmen, Guangdong.

Other polymer products used are shown in Table 1.

Second, the method

The test products were the polymers C and F in Table 1 alone or in combination (1:1), namely Polymer C, Polymer F, Polymer (C+F).

The test method is: first take the waste paper, put it into the hydraulic pulper, and then add the laboratory to simulate white water (containing 400PPM of CaCl ₂ aqueous solution) to the pulp concentration of about 12%, then add deinking bleaching chemicals (NaOH and H ₂ O ₂ Finally, the reference product or the polymer of the invention is added as a deinking agent. After 15 minutes of pulping, the pulp was taken out, diluted with simulated white water to a weight percentage of 3% of the pulp, placed for 60 minutes, then sampled and placed in a Denver-type flotation machine, diluted with simulated white water to 1.0% pulp concentration, and stirred evenly, starting Flotation, flotation 3-6min, after flotation, take the flotation feed and the good pulp (discharge), respectively, for the sheet, test the whiteness and dust point of the sheet.

Third, the results

Table 3 is a comparison of the deinking effect of the original deinking agent (reference) and the two polymers of the present invention and combinations thereof on the waste paper. The original reference product deinking agent is a deinking chemical of the Swiss company (Rhodia), whose main component is polyoxyethylene fatty alcohol. It can be seen from the data in the table that the polymers C and F of the present invention are much better than the flotation deinking effect of the original deinking chemicals, and not only the whiteness of the good pulp is high, the dust point is low, and it can be significantly reduced. The amount of chemicals is conducive to the environmental protection of paper mills.

Table 3 Comparison of flotation deinking effects (reference is the original paper mill deinking agent combination)

Example 4

A method for removing and recycling waste paper ink in pulp and paper production, the method is mainly used for removing contaminants such as ink during the process of producing mixed toilet paper to produce toilet paper, improving whiteness of paper and reducing dust point (ink point).

First, the material

Recycling mixed waste paper (office waste paper, used books, etc.) was obtained from a paper factory in Dongguan, Guangdong.

Other polymer products used are shown in Table 1.

Second, the method

The test products were the polymers in Table 1 alone or in combination (1:1).

The test method is: first take the waste paper, put it into the hydraulic pulper, and then add the laboratory to simulate white water (containing 400PPM of CaCl ₂ aqueous solution) to the pulp concentration of about 12%, then add deinking bleaching chemicals (NaOH and H ₂ O ₂ Finally, the reference product or the polymer of the invention is added as a deinking agent. After 15 minutes of pulping, the pulp was taken out, diluted with simulated white water to a weight percentage of 3% of the pulp, placed for 60 minutes, then sampled and placed in a sheeting machine, diluted with simulated white water to a concentration of 0.5%, and evenly stirred. Let go, then add tap water to the same pulp concentration, then let the water go; finally add tap water to about 1% pulp to make a sheet, test the whiteness and dust point of the sheet.

Third, the results

Table 4 is a comparison of the deinking effect of the original deinking agent (reference) and the polymer of the present invention and combinations thereof on the waste paper. The original reference product deinking agent is a market conventional deinking agent, and its main component is phosphate ester. It can be seen from the data that all the polymer products of the present invention have much better deinking effect than the original deinking chemicals, and not only the whiteness of the good pulp is high, the dust point is low, and the amount of chemicals can be significantly reduced. Conducive to the environmental protection of paper mills.

Table 4 Comparison of washing deinking effects (reference is the original paper mill deinking agent combination)

The above-mentioned embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims (17)

A method for reducing and removing organic contaminant deposits and inks in pulp and paper production, characterized in that a polymer agent is added to an aqueous cellulose papermaking pulp to react the polymer agent with a fiber-containing papermaking slurry The organic contaminants and inks in the papermaking slurry are modified to be effectively removed during the pulping and papermaking process; the polymeric agent comprises at least one of the polymers of Formula I:

Wherein: R ^{1 is} selected from the group consisting of: hydrogen or C _1-4 alkyl; R ² , R ³ and R ^{4 are each selected} from the group consisting of hydrogen, methyl, ethyl, propyl or phenyl, and the adjacent R ² and R ³ and the adjacent R ³ and R ⁴ substituents are different from each other. Group m is selected from: an integer between 0 and 70; n is selected from the group consisting of: an integer between 1 and 80; p is selected from: an integer between 0 and 30, and wherein any one of R ² or R ^{3 is} a phenyl group, the corresponding p value is zero; z is selected from: an integer between 1-3; X is selected from the group consisting of hydrogen, R ⁵ OOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid, or R ⁵ OOH, sulfate, phosphate, acrylic acid, maleic acid, or fubutene a soluble salt of any of the diacids; R ^{5 is} selected from the group consisting of: C _1-4 alkyl; The polymer of formula I has a molecular weight of from 240 to 7000 Daltons. A method of reducing and removing organic contaminant deposits and inks in a pulp and paper production according to claim 1, wherein said R ⁴ is a phenyl group. A method of reducing and removing organic contaminant deposits and inks in a pulp and paper production according to claim 1 wherein said R ² and R ^{3 are selected} from the group consisting of hydrogen and methyl. A method of reducing and removing organic contaminant deposits and inks in a pulp and paper production according to claim 1, wherein said X is a sulfate group or a phosphate group. A method of reducing and removing organic contaminant deposits and inks in a pulp and paper production according to claim 1 wherein said z is 2 or 3. A method for reducing and removing organic contaminant deposits and inks in a pulp and paper production according to claim 1 wherein m is selected from the group consisting of: an integer between 5 and 50; n is selected from the group consisting of: 1 to 50. An integer or an integer between 70-80; p is selected from: an integer between 0-20. A method of reducing and removing organic contaminant deposits and inks in a pulp and paper production according to claim 1 wherein said polymer of formula I has a molecular weight of from 500 to 2000 Daltons or from 4000 to 7000 channels. Lton. A method of reducing and removing organic contaminant deposits and inks in a pulp and paper production according to claim 1 wherein said polymeric agent is a different one of at least two polymers of the polymer of formula I, wherein R ^{4 in} one polymer is a phenyl group, and X in the other polymer is a sulfate group. A method for reducing and removing organic contaminant deposits and inks in a pulp and paper production according to any of claims 1-8, characterized in that one or more organisms are added to the aqueous cellulose papermaking slurry. The enzyme, the biological enzyme is a cellulase, a hemicellulase and an esterase; and the weight ratio of the polymer agent: biological enzyme is 10:0.5-1.5. A method for reducing and removing organic contaminant deposits and inks in a pulp and paper production according to claim 1, wherein the amount of the polymer agent added is 0.01-10 per ton of dry cellulose papermaking pulp. The reaction temperature of the polymer agent and the cellulose papermaking slurry is 10-80 ° C, the reaction pH is 3-10, and the reaction time is 5-120 minutes. The polymer of Formula I reduces and removes the deposition of organic contaminants and inks in pulp and paper production,

Wherein: R ^{1 is} selected from the group consisting of: hydrogen or C _1-4 alkyl; R ² , R ³ and R ^{4 are each selected} from the group consisting of hydrogen, methyl, ethyl, propyl or phenyl, and the adjacent R ² and R ³ and the adjacent R ³ and R ⁴ substituents are different from each other. Group m is selected from: an integer between 0 and 70; n is selected from the group consisting of: an integer between 1 and 80; p is selected from: an integer between 0 and 30, and wherein any one of R ² or R ^{3 is} a phenyl group, the corresponding p value is zero; z is selected from: an integer between 1-3; X is selected from the group consisting of hydrogen, R ⁵ OOH, sulfate, phosphate, acrylic acid, maleic acid, or fumaric acid, or R ⁵ OOH, sulfate, phosphate, acrylic acid, maleic acid, or fubutene a soluble salt of any of the diacids; R ^{5 is} selected from the group consisting of: C _1-4 alkyl; The polymer of formula I has a molecular weight of from 240 to 7000 Daltons. Use of a polymer of formula I according to claim 11 for the reduction and removal of organic contaminant deposits and inks in pulp and paper production, characterized in that said R ⁴ is a phenyl group. Use of a polymer of formula I according to claim 11 for the reduction and removal of organic contaminant deposits and inks in pulp and paper production, characterized in that said R ² and R ^{3 are selected} from the group consisting of: hydrogen, methyl . Use of a polymer of formula I according to claim 11 for the reduction and removal of organic contaminant deposits and inks in pulp and paper production, characterized in that said X is a sulphate or phosphate group. Use of a polymer of formula I according to claim 11 for the reduction and removal of organic contaminant deposits and inks in pulp and paper production, characterized in that said z is 2 or 3. Use of a polymer of formula I according to claim 11 for reducing and removing organic contaminant deposits and inks in pulp and paper production, characterized in that m is selected from the group consisting of: an integer between 5 and 50; n is selected from An integer between 1-50 or an integer between 70-80; p is selected from: an integer between 0-20. Use of a polymer of formula I according to claim 11 for the reduction and removal of organic contaminant deposits and inks in pulp and paper production, characterized in that the molecular weight of the polymer of formula I is from 500 to 2000 Lton or 4000-7000 Daltons.

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