CN1009382B - Composition and method of deinking of recycled cellulosic material - Google Patents

Abstract

The present invention relates to a method for deinking recycled waste cellulosic material such as newsprint, which comprises the steps: waste material is made into paper pulp under the existence of the water dispersion of resin parent body; the resin parent body can be cured in the dispersion in the process of pulping operation.

Description

Composition and method of deinking of recycled cellulosic material

A large amount of day by day cellulose pulps that is used for paper industry is the waste cellulose material by reuse, makes especially that the newspaper of paper pulp and assorted attitude produce again.The paper pulp that contains any waste material in the above-mentioned waste material is all polluted by the pigment in the printing ink usually, in order to obtain appropriate brightness, just these pigment must be removed.

Usually, the particle of pigment is removed with froth flotation method, is that utilization naturally occurring surfactant in paper pulp promotes to form foam in the ordinary course of things, still, also can add other surfactant and/or foam improver again under a few cases.Another kind method is to use various solvent and/or surfactant, with pigment flush away from paper pulp.But these two kinds of methods all can not be removed the trace that waste paper is opened fully, so that attainable high-high brightness to be provided.

In order to improve the separating degree of trace, various suggestion had once been proposed, trace is assembled or with its be adsorbed on by floatation or even centrifugal process or the sieve method bigger particle that all is easy to separate on.But all these suggestions all have important disadvantages, thereby these suggestions can't be adopted in industrial production, and still adopt habitual washing and the flotation technology with generally acknowledged defective.

No. the 1379252nd, French Patent (FRP) and United States Patent (USP) had all been narrated for No. 337234 before system paper pulp, added surfactant in slurrying liquid earlier.This kind method can not be separated trace fully.United States Patent (USP) the 4013505th and narrated in pulper for No. 4147616 calcium soap precipitates is adsorbed trace is used the neat soap of centrifugal process resulting separation subsequently again.The only part success of this kind method.

United States Patent (USP) the 3846227th and narrated for No. 3963560 in the slurrying stage and used N-cyclohexyl pyrrolidones as solvent promotes to remove trace.This method need be approximately 73 ℃ the higher temperature of ratio, and in fact this increased the cost of energy of this method and caused unsafty solvent loss.

No. 2080354 suggestion of BP adds paper pulp with polymer under the temperature that is higher than the polymer softening point, so that remove adhesive from the paper pulp of reuse.This method needs high temperature, and does not propose effective de-inking method.

Secondary stock is a kind of on the chemical property and all be very complicated system on the physical property, and this kind system is carried out the variation of height in a kind of unpredictable mode.Mechanism for known de-inking method operation also is not fully aware of so far.Up to the present, de-inking method is by rule of thumb basically.

Therefore, we set about disclosing the reason of unsuitable operating characteristics of the method for prior art.

Far and away, the main pigment that in the paper of slurrying again, exists and be carbon black to the pigment that last brightness has the greatest impact, carbon black also is the pigment obstinate to the sensitiveness of de-inking method.In the content of the discussions below, take care of the discussion carbon black especially.But the explanation of being done generally also is applicable to other pigment.

We think the constraint of this kind view (but be not intended to be subjected to), and carbon black is to exist in the trace with the form that faintly is strapped in the particle in a kind of oily matrix, especially in the trace of newspaper.In pulping process, we think that this kind oily matrix will be disintegrated, thereby discharge little carbon black granules, and these carbon black granules can accumulate on the fibril surface of fiber.We think, when in a single day these carbon black granules are trapped, just are difficult to be removed with known Deinking Technology especially.

We have been found that now with waste paper a kind of fiber is not had substantial role, slurrying and this resin solidified in described water suspension in the water suspension of curable resin at room temperature, can obtain is the de-inking method that has improved in itself.We think, in the present invention, any granules of pigments can promptly be coated by uncured or partly solidified resin, uncured or the partly solidified resin of this kind can suppress that oily matrix is disintegrated and the carbon black granule that takes place subsequently is deposited on effect on the cellulose fibre again, and when this kind resin solidification, will cause carbon black granules to form aggregation, the more anti-fragmentation of this kind aggregation, and available customary way, method such as for example washing, flotation, centrifugal or screening is separated it from paper pulp.

According to a kind of embodiment of the present invention, the aqueous dispersion of we provide at least a liquid, that can solidify in aqueous dispersion, do not have substantial role to fiber resin precursor and a kind of curing catalysts that said composition is cured in this dispersion of being enough to.

Be preferably, said composition contains a kind of dispersant that resin precursor is disperseed.We further find, with the extender or the mixing diluents of said composition and a kind of inertia, can in fact reduce the ratio of needed curable resin, thereby improve the economic benefit of this method.

According to second kind of embodiment of the present invention, so we provide a kind of composition, said composition comprise a kind of for said composition weight 10 to 85% liquid, that can in aqueous dispersion, solidify, to fiber do not have the resin precursor of substantial role, at least a 5% inertia for composition weight, fiber is not had the liquid diluent of substantial role and a kind of dispersant that is used for disperseing said composition of effective dose.

According to another embodiment of the present invention, we provide a kind of method that will pollute the reclaimed fibre cellulosic material slurrying of trace, this method comprises floods this cellulosic material in the aqueous dispersion of the liquid that contains a kind of q.s, that can solidify, as fiber not had substantial role resin precursor in aqueous dispersion, to promote the deinking of carrying out subsequently and described resin precursor solidified.

According to the present invention, this resin precursor can be in water suspension, and is preferably any liquid that fiber is not had substantial role curable in alkaline aqueous suspension.Especially, this resin precursor preferably is being lower than under 50 ℃ the temperature, and is preferably at room temperature, should be curable.Be preferably, this resin precursor is a kind of abundant hydrophobic material that is not easy to be attracted on the cellulose fibre, but again preferably can be compatible with trace.Each molecule that typical resin precursor contains a kind of liquid all have the prepolymer of at least two active function groups and under the situation that has at least a kind of suitable catalyst to exist can with the crosslinking agent of described reacted with functional groups.Under the situation that this polymeric system can solidify in pulper, when no a kind of catalyst exists, this resin precursor can be formed in pulper usually, crosslinking agent adds in the prepolymer before then can or being about to add pulper when adding pulper.

Best is that this resin is a kind of polymolecular of curable organic at room temperature silicon ether.What especially be suitable for is the mixture of poly-(dialkylsiloxane) polymer of a kind of dihydroxy and a kind of poly-(alkyl hydride siloxane) crosslinking agent.Be preferably, under each situation, alkyl all is rudimentary (for example 1 to 4 carbon atom) alkyl, is typically methyl.Be used for a kind of cured resin system of Gong selecting for use of the present invention and contain a kind of and the crosslinked oligomeric hydroxy acrylic ester prepolymer of vulcabond, for example, a kind of hydroxy ethyl methacrylate resin that mixes with the 1.6-di-isocyanate.

This kind prepolymer generally has by 5,000 to 70,000, and is preferably by 10,000 to 50,000, for example 30,000 to 45,000 mean molecule quantity.We particularly preferably are the prepolymer that comprises that a kind of molecular weight distribution is wide, and for example a kind of molecular weight is that 3,000 to 12,000 short chain prepolymer and a kind of molecular weight are the mixture of 50,000 to 70,000 long-chain polymer.

This kind crosslinking agent generally has by 1,000 to 5,000 mean molecule quantity.In the ordinary course of things, the ratio of this kind crosslinking agent and two functional polymers is 1: 10 to 10: 1, is preferably 1: 2 to 2: 1, and best be 3: 4 to 4: 3, for example 1: 1(weight).

Can use any water-soluble or can with water miscible but also miscible surfactant or the dispersant of resin precursor that can be more hydrophobic with this kind.Be applicable to that disperseing the dispersant of organopolysiloxane resins precursor is the surfactant of nonionic, for example poly-alkoxyl organopolysiloxane, for example a kind of poly-(dimethyl siloxane) poly-(ethylene glycol) ether, with polyethoxy sorbitan list alkanoic acid ester, and cationic surface active agent.Anionic surfactant is not preferred.

But, particularly preferably be film forming dispersant and especially polymer-type protecting colloid, for example polyvinyl alcohol, carboxymethyl cellulose, polyvinyl pyrrolones or cellulose acetate.

The consumption of dispersant should be enough to make this resin precursor to form a kind of stable dispersion in water.According to the viewpoint of business accounting, preferably avoid adding above the needed minimum dispersant of dispersion resin precursor.In general, the consumption of dispersant is 0.1 to a 20%(weight of resin precursor), 3 to 7%(weight for example).We do not get rid of and do not use dispersant or utilize the accidental dispersant that exists in the normal components of the paper pulp in the pulper to be used for possibility with the resin precursor dispersion.

Can optionally add diluent, its consumption reaches as high as the about 95% of said composition weight, is preferably 5 to 90%, for example 55 to 80%, and best be 65 to 75%.

This diluent can be any inert oil, and this kind oil is fully hydrophobic, thereby become fiber is not had substantial role and can be miscible with resin precursor.The exemplary of diluent comprises dimethyl silicone polymer and hydrocarbon ils with terminal methyl.This diluent is preferably has sufficient flowability; so that making said composition can incline to; protect trace particle in the paper pulp effectively but have sufficient viscosity again, so that the particle that prevents trace was broken and/or holds back and guarantee to form a kind of carbon black granules aggregation with curing of mechanical strength at the slurrying initial stage.

This catalyst can be any can the catalytic resin precursor in water suspension, and the catalyst that preferably at room temperature is cured.Particularly preferably be organotin catalysts, for example dioxane acid dialkyl tin.Being preferably these two alkyl is to have; 2 to 4 carbon atoms for example, and the low alkyl group of 4 carbon atoms preferably, these two alkanoyls are to have 2 to 20 carbon atoms; have 8 to 14 carbon atoms and be preferably, for example two (thylhexoic acid) dibutyl tin or dibutyl tin laurates.

This activity of such catalysts and volatility increase with the minimizing of the carbon number of this alkanoyl.Our preferred catalyst is a kind of in normal slurrying period, and for example in 15 to 40 minutes, its activity is enough to make the completely crued catalyst of this resin precursor.Active higher catalyst, for example dibutyltin diacetate though also can use, is preferred.

This catalyst can be with a kind of in organic solvent, for example the formation of the solution in the trichloro-ethylene is used, but, our preferential the use is the aqueous emulsion of catalyst, the aqueous emulsion of this kind catalyst can have been bought on market, and has been found that in pulping water solution better activity can be provided.

In general, we think that the brightness of paper pulp can reach a maximum after curing is finished period, and if continue slurrying, then the brightness of paper pulp will reduce.Therefore, our preferred catalyst is that the catalyst that approximates the slurrying time greatly can be provided hardening time, rather than those initial stages at pulping process can provide and come down to completely crued catalyst.

Even for those in the system with regard to being cured under the situation that catalyst-free exists and under the temperature that in pulper, is reached, we also pay the utmost attention to applications catalyst, but, for the present invention, this situation is not main.

Be preferably, under the situation that has catalyst to exist (or when not needing catalyst, then be under the situation that the crosslinking agent that adding is arranged exists), resin precursor is dispersed in the water, and before adding waste material,, make one period short time of its precuring being preferably under 8 to 12 the pH value, for example 10 seconds to 5 minutes, and be preferably 0.5 to 1 minute.In general, this precuring time is 1 to 10% of total precuring time.Be preferably, press the weight of paper pulp solid and calculate, the used amount of resin precursor is 0.1 to 10%, and is more preferably 1 to 5%, for example 1.5 to 4%.

Press the weight of resin precursor and calculate, catalyst consumption is 0.1 to 50%, and is preferably 0.5 to 20%, for example 1 to 10%.

Slurrying liquid is alkalescence preferably, and under general situation, the pH value of the material in the pulper should be 8 to 12.5, and for example 9 to 10.Application examples such as NaOH, sodium carbonate, sodium metasilicate or its mixture can reach this pH value.Can directly resin precursor and catalyst be suspended in the preparation liquid, perhaps can prepare a kind of denseer suspended substance in addition, then it be added in the slurrying liquid before being about to slurrying.

The raw material of paper pulp can comprise the cellulose wastes of newspaper and/or magazine and/or other ink pollutions.This paper pulp raw material preferably comprises the mixture of newspaper and magazine, for example comprises 10 to 60%(weight) magazine.But this method also is applicable to 100% newspaper, and this is a kind of raw material that is difficult to especially with the deinking satisfactorily of existing technology.Waste material is generally 5 to 60 ℃ in temperature, and is preferably 20 to 50 ℃, for example under 35 ℃ the situation, flooded 10 to 60 minutes with slurrying liquid, and be preferably 15 to 40 minutes.This paper pulp can contain 2 to 25% solid, more commonly contains 5 to 15% solid.

We have found that, according to the present invention, the especially chelating agent of calcium, for example ethylenediamine tetra-acetic acid in that a kind of alkaline-earth metal is arranged; Or phosphate, condensed phosphate or phosphonate, especially tripolyphosphate or silicate, slurrying liquid situation about existing under, the brightness that can improve the paper pulp of deinking significantly.This discovery is the aspect that the present invention recommends.We are top-priority to be, but by the total of the alkaline-earth metal ions of the chelating that exists in the paper pulp, the consumption of chelating agent should reach stoichiometric amount.

It would be desirable the resin particle of this kind curing, should have a kind of physical form that is easy to from paper pulp, separate.For example, they can have the density that obviously is different from aqueous medium, preferably in fact low weight, so that carry out centrifugation or they can have enough sizes, so that effectively sieve.The previous case is that they are passable, for example by selecting a kind of low-density extender, perhaps forms by add a kind of foaming agent in resin precursor.Latter event is, it can be a kind of volatile liquid, for example a kind of carbon fluoride, and this kind carbon fluoride is formed the particle that expands by the evaporation of the curing reaction of heat release.

Another kind method is, no matter is that size or density can be controlled by the solid particle or the particulate that add a kind of polymer.Be preferably, this kind particle is a kind of low-density material, for example expanded polystyrene (EPS) and/or be a kind of have enough sizes can be by sieving the particle that separates.These particles are preferably has a kind of resin precursor and pigment all is easy to assemble superincumbent surface.

We are also special to find, the coarse granule of separating, no matter be the coarse granule of assembling the polymer of the other adding that trace is arranged in its surface, or coarse granule that solidify and resin itself gathering, all can advantageously be recirculated in the pulper, so that make the trace of gathering separate more fully.

Therefore, according to another embodiment of the invention, with the pollution of reuse the cellulosic material of trace, have a kind of dispersion, that cellulose do not had substantial role, but trace is then had in the presence of the curable resin of substantial role, thereby under the condition that is suitable for resin is cured and trace is assembled, in a pulper, make paper pulp again; This paper pulp is emitted from pulper; The resin that solidifies is separated from paper pulp; Be recirculated into pulper with the resin that a part is solidified.

In pulper, can add surfactant, foam stabiliser or defoamer, thus the formation of promotion or control foam.

Use any known method, the trace of assembling can be separated from paper pulp, specifically use the physical form which kind of method then depends on the particle of curing.

Use habitual froth flotation method, the particle separation of this curing can be come out.Where necessary, can in paper pulp, add foam improver and/or foam inhibitor, the degree of regulating foaming.In addition, the method for available washing for example with dewatering of pulp with make slurry again, is removed the trace of gathering.

When if the density of the density of this particle and paper pulp is very inequality, then it can be separated with centrifugal separation, the then available sieve method of sizable particle separates.

In general, paper pulp can be diluted to solids content and be less than 2%(weight) and with its screening, to remove big particle.Then, any particle of staying in the paper pulp that contains printing ink can be used washing, centrifugal and/or floatation is separated.

Now the present invention is described with following example:

Except that illustrating separately, following each example is all used following condition:

Resin precursor:

50%(weight) hydroxyl-functional group's dimethyl silicone polymer

45%(weight) Si-H functional group dimethyl silicone polymer prepolymer

5%(weight) polyethyleneoxy-/polypropylene oxygen base-functional group's dimethyl silicone polymer

Pulp density: 4%

The initial pH value of pulper: 10.5

Pulper initial temperature: 30 ℃

The slurrying time: 25 minutes

Resin addition: 2% of fibre weight

Resin adding method: before adding fiber, caustic soda and catalyst, elder generation adds resin compound in the entry and makes its dispersion.

Raw material: 100% newspaper

Example 1

2% the dibutyl tin laurate of using fibre weight is tested in the laboratory as catalyst, is 41% to compare with brightness under the no resin existence, and the brightness of pulp that goes out pulper is 49%.

Example 2

Repeat the test of example 1, but use 100% magazine replacement newspaper.With brightness under no resin exists is 54% to compare, and the brightness of pulp that goes out pulper is 57%.

Example 3

Repeat the test of example 1, but use 50%(weight) newspaper, 50%(weight) magazine as raw material.With brightness under no resin exists is 47% to compare, and the brightness of pulp that goes out pulper is 52%.

Example 4-6

Use 1.5% different catalyst of fibre weight, consequently:

No resin-brightness of pulp is 45%;

Example 4-adds dibutyltin diacetate, and brightness of pulp is 55.5%;

Example 5-adds dibutyl tin laurate, and brightness of pulp is 56.5%;

Example 6-adds two (2 ethyl hexanoic acid) dibutyl tin (in ethanol), and brightness of pulp is 58%.

Example 7

Fig. 1 represents, in shop test, uses dibutyltin diacetate catalyst and 1 ton of newspaper, and pulp density is 12 to 15% o'clock, and brightness of pulp over time.The curve of below is the contrast experiment's curve that does not add resin.Middle curve is, the empirical curve of 2% resin that adds that the weight of press fiber calculates and 0.25% catalyst, and the curve of the top is adds 4% the resin of the weight calculating of pressing fiber and the empirical curve of 0.5% catalyst.

Example 8

Fig. 2 represents, adds the 4%(weight of the weight calculating of press fiber) resin and 1.5%(weight) dibutyltin diacetate, variations in temperature is to the influence of 6 laboratory tests.

Example 9

Fig. 3 represents, adds the 1.5%(weight that the weight of press fiber is calculated) dibutyltin diacetate, the increase resin concentration is to the influence of brightness.

Example 10

Repeating the test of example 1, before being about to add fiber, is in the resin precursor that add to disperse of 1 to 10 millimeter expanded polystyrene bead material with diameter.These bead materials are easy to separate from paper pulp, and have substantially improved the aggtegation and the centrifugation of trace.The application diameter is that the bead material of 1-2 millimeter can obtain optimal results.The bead material of being separated is recycled in the pulper and repeats experimentize.The bead material that recirculation is used is equivalent to the improvement that aggtegation provided of original unpolluted bead material to trace in fact to the improvement that aggtegation provided of trace.

Example 11

Repeat the test of example 1.The particle of the trace assembled is separated from paper pulp, and the particle of being separated is recycled to pulper and repeats the test of this example 1 once more.According to test for the second time, can be observed the aggtegation of having improved and separate with easier.

Example 12 and 13

Add a kind of acrylic resin precursor in example 12 and 13, its composition is:

%(weight) material function carrier trade mark

65% hydroxy ethyl methacrylate prepolymer, 50% butyl acetate " DURASOL " 346

30% hexamethylene diisocyanate crosslinking agent dimethylbenzene " DESMODUR " N75

5% ethylene glycol/propylene glycol dispersant " GLYCOL B "

The methylol silicone copolymers

Be the result's of application siloxanes resin precursor in the result that uses this kind acrylic resin precursor and the example 1 comparison below:

Example 12

Raw material 100% newspaper

Catalyst dibutyl tin laurate (fiber addition 1%)

Brightness R goes out the unlimited washing of paper pulp of pulper

Only add caustic alkali 37 49

3% acrylate/caustic alkali 45 51 1/2

2% siloxanes/caustic alkali 47 55 1/2

Example 13

Raw material 50/50 newspaper/magazine

Catalyst dibutyl tin laurate (fiber addition 1%)

After brightness R goes out the paper pulp flotation of pulper

Only add caustic alkali 50 54 1/2

2% acrylate RTV(cold curing)/caustic alkali 52 63 1/2

2% siloxanes RTV(cold curing)/caustic alkali 56 62

Example 14

To contain a kind of influence of not having functional group's extender in order illustrating in resin, to repeat the test of example 1, in the prepolymer that the methyl dimethyl silicone polymer adding of different proportion is active, its result is as follows:

Active prepolymer, %(weight) go out the brightness of pulp of pulper

95 51.5

45 51.8

25 51.9

10 50.0

Contrast (no resin) 40.7

Example 15

Prepare a kind of prepolymer emulsion that contains following material:

Dihydroxy gathers (dimethyl siloxane) n=49-144(mean molecule quantity=7566) 10 grams

Dihydroxy gathers (dimethyl siloxane) n=850(mean molecule quantity=63066) poly-(hydrogenated methyl siloxanes) n=40(mean molecule quantity=2562 of 40 grams) 45 grams

5% polyvinyl alcohol water solution, 165 grams

The catalyst emulsion of solid a kind of 33%(weight that contains of independent again preparation), wherein contain:

Dibutyl tin laurate 60 grams

Polyvinyl alcohol 7 grams

Water 133 grams

With 1900 ml waters and 6 gram prepolymer emulsion (be calculated as by fibre weight 1% resin) in pulper with the catalyst emulsion (being calculated as 0.05%) of 13 milliliters of strong caustics and 0.3 milliliter by fibre weight, at room temperature stir precuring time in 30 seconds.Disregard message paper with 2.36 grams adds then, and the concentration that makes paper pulp is 11%.

, compare after 25 minutes in slurrying with pulp washing and with the contrast test of only using sodium hydroxide solution.

Go out the brightness after the brightness washing of paper pulp of pulper

Comparison example 36.5 42.8

Example 5 46.3 51

Claims (26)

1, a kind of composition, this kind composition comprises:

(i) a kind of moisture, reclaimed fibre cellulose fiber paper pulp;

(ii) be dispersed in the paper pulp, by the weight of paper pulp solid be calculated as 0.1 to 10% curable, fiber is not had the resin precursor of the solid polymer of substantial role, this resin precursor comprises that mainly a kind of each molecule all has the liquid prepolymer of at least two active function groups and a kind of mixture of the crosslinking agent that can react with this functional group; With

The (iii) curing catalysts that this resin precursor is solidified in this kind dispersion.

2, according to the composition of claim 1, wherein contain a kind of diluent that is used for diluting this resin precursor mixture, this diluent is a kind of inertia, fiber is not had the liquid of substantial role, and the content of this resin precursor mixture and diluent is respectively at least 5% of the 10-85% of described composition weight and described composition weight.

3,, wherein contain a kind of dispersant that is used for disperseing this resin precursor mixture according to the composition of claim 2.

4, require the composition of any one claim in 1,2 and 3 according to aforesaid right, wherein said resin precursor can solidify being lower than under 50 ℃ the temperature.

5, according to the composition of claim 4, wherein said resin precursor can at room temperature solidify.

6, according to the composition of claim 1, wherein this resin precursor comprises the mixture of poly-(dialkylsiloxane) polymer of a kind of dihydroxy and a kind of poly-(alkyl hydride siloxane) crosslinking agent.

7, according to the composition of claim 6, wherein each alkyl all has 1 to 4 carbon atom.

8, according to the composition of claim 7, wherein said alkyl is a methyl.

9, according to the composition of claim 1, wherein this resin precursor comprises the mixture of a kind of oligomeric hydroxy acrylic ester prepolymer and a kind of diisocyanate cross-linking agent.

10, according to the composition of claim 1, the part by weight of wherein said crosslinking agent and this prepolymer is 1: 10 to 10: 1.

11, according to the composition of claim 3, wherein this dispersant is a kind of polymer-type protecting colloid.

12, according to the composition of aforesaid right requirement 3, wherein the consumption of this dispersant is the 0.1-20% of the weight of this resin precursor.

13, according to the composition of claim 2, the consumption of wherein said diluent is the 55-80% of said composition.

14, according to the composition of claim 2, wherein said diluent is a kind of dimethyl silicone polymer or a kind of hydrocarbon ils with terminal methyl.

15, according to the composition of aforesaid right requirement 1, wherein said curing catalysts is a kind of dioxane acid dialkyl tin.

16, according to the composition of claim 15, wherein said catalyst is the two alkanoic acid dibutyl tins that a kind of wherein each dioxane acid moieties all has 8 to 14 carbon atoms.

17, according to the composition of claim 1, wherein said catalyst consumption is the 0.1-50% of the weight of this resin precursor.

18, the method of the reclaimed fibre cellulosic material manufacturing paper pulp of trace has been polluted in a kind of application, this method comprise with this kind material the weight by the paper pulp solid be calculated as 0.1% to 10% curable, fiber is not had in the aqueous dispersion of resin precursor of solid polymer of substantial role and flood, this resin precursor comprises that mainly a kind of each molecule all has the liquid prepolymer of at least two active function groups and a kind of mixture of the crosslinking agent that can react with this functional group, with deinking in order to promote to carry out subsequently, the catalyst that this resin precursor is solidified with a kind of effective dose solidifies this resin precursor.

19, according to the method for claim 18, wherein, in a kind of aqueous dispersion of the resin precursor that comprises a kind of curable, solid polymer of fiber not had substantial role, add a kind of curing catalysts that this resin precursor is solidified in this aqueous dispersion, this resin precursor comprises that mainly a kind of each molecule all has the liquid prepolymer of at least two active function groups and a kind of mixture of the crosslinking agent that can react with this functional group, this aqueous dispersion precuring of Schilling is no more than 20 minutes, and then it is added in this cellulosic material.

20, according to the method for claim 18 or 19, wherein the consumption of this resin precursor is the 0.1-10% of this paper pulp solid weight.

21, according to the method for claim 18, the pH value of wherein said aqueous dispersion in described dipping process is 8 to 12.5.

22,,, be 5 to 60 ℃ and be under the condition of 2-25% that in temperature dipping is 10 to 60 minutes in slurrying liquid in solids content wherein with described cellulosic material according to claim 18,19 or 21 method.

23, according to claim 18,19 or 21 method, wherein said slurrying liquid contains the chelating agent that makes the calcium ion chelating.

24, according to claim 18,19 or 21 method, wherein this resin precursor contains a kind of foaming agent.

25, according to claim 18,19 or 21 method, wherein this paper pulp contains the solid particle of polymer.

26, a kind of method of making paper pulp, wherein with the pollution of reuse the cellulosic material of trace, under the condition that the curable resin that a kind of dispersion is arranged exists, in a pulper, make paper pulp again, the curable resin of this dispersion does not have substantial role to fiber, but to trace have substantial role and comprise weight by the paper pulp solid be calculated as 0.1% to 10% curable, the resin precursor that fiber is not had the solid polymer of substantial role, this resin precursor comprises that mainly a kind of each molecule all has the liquid prepolymer of at least two active function groups and a kind of mixture of the crosslinking agent that can react with this functional group

Thereby this makes process of pulp again is to carry out under the condition of the catalyst existence that this resin is cured and this trace is assembled that a kind of effective dose is arranged;

Paper pulp is emitted from pulper;

The resin that solidifies is separated from paper pulp; With

The resin that a part is solidified is recirculated in this pulper.

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