Method of preventing or reducing aluminosilicate scale in industrial processes

The present invention relates to materials and methods that prevent or prevent the formation of scale on or in equipment used in industrial processes with alkaline process streams.

The problem of scale formation in and on equipment used in industrial processes, especially those with alkaline process streams, is very well known. Scales, when accumulated on the surface of the equipment in the process, cause serious problems and cause a decrease in heat transfer coefficient. Therefore, extra heat is required for the evaporator in these steps, resulting in increased cost.

An example of such an industrial process with an alkaline process flow is the Kraft paper recovery method in the paper industry, which has been known for 100 years and has many on this issue. It is explained in detail in the textbook (see Non-Patent Document 1). Recently, as a result of the development of a closed loop cycle in a kraft paper manufacturing plant, as described in Non-Patent Document 2, the accumulation of aluminum and silicon in the system results in the generation of scale in the equipment of the process. Problems are increasing. Therefore, it has long been well recognized that kraft paper mills need to provide methods and compositions that prevent the formation of aluminosilicate scales. Patent Document 1 describes that a ternary polymer of maleic acid, acrylic acid and hypophosphoric acid is used as a scale inhibitor in a kraft paper manufacturing factory. This type of polymer has been shown to be effective against the scale of calcium carbonate, but not against the scale of aluminosilicates.

The High Level Nuclear Waste Treatment Facility (HLNW) treats radioactive solid and liquid waste, minimizes volume, and immobilizes dangerous materials for long-term storage. To do. Recently, the treatment in HLNW is carried out through two steps, one of which is carried out under acidic conditions and the other one is carried out under alkaline conditions. Under alkaline treatment conditions, the formation of sodium aluminosilicate scale becomes a serious problem in the pretreatment stage prior to vitrification of waste.

Waste is evaporated, filtered, ion exchanged and further evaporated inside the pretreatment facility. During evaporation, aluminosilicate scales can form on the surface of the evaporator wall and on the heated surface. In addition, transfer pipes may also become clogged due to the accumulation of these scales and sediments, requiring closure for maintenance.

Pre-treated HLNW waste is transferred to a vitrification facility. The HLNW waste is transferred to a melt-making vessel, where silica and other glass-forming materials are added. The mixture is then heated and the melted mixture is poured into a large stainless steel container, cooled and transported to a temporary storage location until a permanent storage location is chosen.

A portion of the glass-forming material containing Si is circulated back from the vitrification unit operation to the evaporation unit (during the pre-operation). Dissolved aluminum and sodium silicate species in the form of sodium aluminate react gradually in solution to form complex hydrated sodium aluminate species. Among these chemical species, the types of amorphous aluminosilicate (hydrogel of aluminosilicate), zeolite, sodalite, and canclinite are collectively known as "sodium aluminosilicate". These nuclear waste logistics also have high concentrations of nitrate And OH containing nitrite ions (up to 2M for each ion) and very high concentration (up to 16M in some parts of the tank)^-Contains ions. These factors significantly increase the rate of aluminosilicate scale formation. The resulting sodium aluminosilicate scale has low solubility in alkaline HLNW solutions.

In addition, radioactive lanthanide and actinide enter the cage-like structure of the aluminosilicate scale and coprecipitate with sodium diuranate (Non-Patent Document 3), so sodium aluminosilicate is an undesired HLNW product. It is considered. Therefore, for HLNW facilities, it is desirable to minimize the volume of HLNW, including those resulting from these aluminosilicate scales. Thus, it can be seen that the scale growth of sodium aluminosilicate has a large negative economic and operational impact on the treatment of nuclear waste.

Therefore, it is desirable to solve the problem of sodium aluminosilicate scale when evaporating nuclear waste.

Conventionally, attempts to solve the above problems have not been very successful (see Non-Patent Document 4). These authors investigated methods of removing Si from the solution in the form of ferric salt precipitates using ferric nitrate to reduce or suppress the formation of aluminosilicate scales. Although this method has some advantages, the problem of discarding high concentrations of ferric precipitates still exists and requires extra filtration unit operation. In addition, Non-Patent Document 5 proposes a low molecular weight compound as an inhibitor of scale formation for HLNW, but it has been found that it is completely unsatisfactory.

Thus, it is economical to reduce the scale of aluminosilicates that accumulate in equipment used in industrial processes where accumulation of aluminosilicate scales is problematic, such as kraft paper manufacturing processes and nuclear waste treatment streams. There is a need for an effective method.<patcit num="1"><text>U.S. Pat. No. 5,409,571.</text></patcit><nplcit num="1"><text>GASmook, "Handbook for Pulp and paper technologists", 3rd edition.</text></nplcit><nplcit num="2"><text>PNWannamaker, WJ Frederick, "Application of solubility data to predicting the accumulation of aluminum and silicon in alkaline pulp mills", Minimum Effluent Mills Symposium (1996), p. 303.</text></nplcit><nplcit num="3"><text>Peterson, RA, Pierce, RA, (2000), "Sodium diuranate and sodium aluminosilicate precipitation testing results", WSRC-TR-2000-00156, Westinghouse Savannah River Company, Aiken, SC.</text></nplcit><nplcit num="4"><text>Wilmarth, WR, Mills, JT, Dukes, VH, Removal of silicon from high-level waste streams via ferric flocculation, Separation Sci. Technol., Vol. 40, pp. 1-11 (2005).</text></nplcit><nplcit num="5"><text>WRWilmarth, JTMills, "Results of Aluminosilicate Inhibitor Testing", WSRC-TR-2001-00230.</text></nplcit>

<u style="single">Outline of the present invention</u> In the present invention, as a terminal group or side chain (pendant) -Si (OR )₃(However, R = H, alkyl group, Na, K or NH₄On a scale of aluminosilicate in a process having an alkaline process stream, eg, a pulp manufacturing process or a process process stream of a high level nuclear waste evaporation process, using a polymer having at least 0.5 mol% of groups containing). Providing materials and methods to reduce or eliminate production solves the above and other problems. When the materials of the invention are added to these industrial process streams, the materials of the invention reduce, or even completely prevent, the formation of aluminosilicate scale on the surface of the device. Furthermore, the materials of the present invention are effective at economically feasible treatment concentrations.

<u style="single">Detailed description of the present invention</u> The present invention relates to methods and materials for reducing the scale of aluminosilicates in an industrial process with an alkaline process stream, such as a kraft paper manufacturing process stream or a high level nuclear waste treatment stream. The process flow to be treated is any process flow that has alkaline conditions in which scale formation occurs, such as black, green and white liquids in the kraft paper manufacturing process, or high level nuclear waste evaporation process flow. There can be.

This method is based on -Si (OR )₃, However, in the formula, R = H, C1 to C3 alkyl, aryl, Na, K or NH₄Is, A step of adding a polymer having at least 5 mol% of a side chain group or an end group containing (pendant thereof a group or an end group) to the process flow in an amount that prevents the formation of a scale containing aluminosilicate. Consists of including. -Si (OR ) present in this polymer₃The amount of functional groups is sufficient to achieve the desired result and can range from a minimum of 0.5 mol% to a maximum of 100 mol% of all monomeric groups present in the polymer. However, it would be most economical to use the minimum amount needed to obtain the desired result. This polymer is first a silyl ether derivative, polymer--Si (OR )₃It is preferable that it is made as. Here, R = H, C1 to C3 alkyl, aryl, for example, polymer--Si (OCH).₂CH₃)₃Or polymer--Si (OCH)₃)₃It is preferable that it is made as. Silyl ether derivatives can be added directly to the industrial stream or hydrolyzed prior to addition to the process stream to produce polymers with the following general structure: Polymer--Si (OH). )₃, Polymer--Si (ONa)₃, Polymer--Si (OK)₃, And polymer--Si (ONH)₄)₃.. It is a convenient feature of the present invention that any of these forms can be added to the process flow. The molecular weight of the polymer should be at least about 500, most preferably at least 1000.

In a preferred embodiment, -Si (OR )₃However, in the formula, R = H, C1 to C3 alkyl, aryl, Na, K or NH₄The groups containing, are --G--R--X--R'--Si (OR )₃Consists of including. Where G = non-existent, NH, NR "or O; R = non-existent, C = O, O, C1-C10 alkyl, or aryl; X = non-existent, NR, O, NH, amide, urethane, or urea R'= non-existent, O, C1-C10 alkyl, or aryl; and R "= H, C1-C3 alkyl, aryl, Na, K or NH₄Is.

In one embodiment, this group is --NH--R--X--R'--Si (OR ).₃Where R = non-existent, O, C1-C10 alkyl, or aryl; X = O, NH, amide, urethane, or urea; R'= non-existent, O, C1-C10 alkyl, or aryl; and R = H, C1-C3 alkyl, aryl, Na, K or NH₄Is.

In another embodiment, the polymer having the group as a side chain can be composed of at least one nitrogen to which the group of the side chain is attached. Examples of polymers containing at least one nitrogen to which side chain groups are attached include, but are not limited to, polymers according to the formula below:

<chemistry num="1"><img file="JP5100397B2_D0001.tif" /></chemistry>

Where x = 0.1 ~ 100%, y = 99.9 ~ 0%; and R = non-existent, C1 ~ C10 alkyl, aryl, or -COX-R'-where X = O or NH, R'= non-existent, C1-C10 alkyl, or aryl; R "= H, C1-C3 alkyl, aryl, Na, K or NH₄Is.

here

<chemistry num="2"><img file="JP5100397B2_D0002.tif" /></chemistry>

Polymers with x = 0.5 ~ 20%, y = 99.5 ~ 80% and according to R = C2 ~ C6 are suitable.

<chemistry num="3"><img file="JP5100397B2_D0003.tif" /></chemistry>

However, a polymer according to x = 0.5 to 20% and y = 99.5 to 80%. Is a specific example.

In another embodiment, -Si (OR )₃Polymers with side chain groups or terminal groups containing --Si (OR ")₃It is derived from an unsaturated polymerizable monomer containing, and is copolymerized with one or more other polymerizable monomers at any time. Where R = H, C1-C3 alkyl, aryl, Na, K or NH₄Is. Examples of such other polymerizable monomers are, but are not limited to, vinylpyrrolidone, (meth) acrylamide, N-substituted acrylamide, such as N-alkylacrylamide or acrylamide methylpropane sulphonic acid, (meth). ) Includes acrylic acids and their salts or esters, imide maleates, vinyl acetate, acrylonitrile, and styrene. --Si (OR )₃Particularly suitable unsaturated polymerizable monomers containing groups are monomers of formulas V and VI.

<chemistry num="4"><img file="JP5100397B2_D0004.tif" /></chemistry>

Here, P = H, C1 ~ C3 alkyl, -CO₂R ,-CONHR R = C_l~ C₁₀Alkyl, aryl, R'= H, C_l~ C₃Alkyl or aryl, X = O, NH, or NR, R = H, C1-C3 alkyl, aryl, Na, K or NH₄, Is. Examples of such polymers include trialkoxyvinylsilane, eg CH.₂= CHSi (OCH)₂CH₃)₃And homopolymers and copolymers of monomers of formula VII below:

<chemistry num="5"><img file="JP5100397B2_D0005.tif" /></chemistry>

Where P = H, R = -CH₂CH₂CH₂-, R'= H, X = NH, R = H, C1-C3 alkyl, aryl, Na, K or NH₄Is.

This type of monomer can be copolymerized with any other polymerizable monomer, such as the above-mentioned monomer. Particularly suitable copolymerizable monomers include vinylpyrrolidone, (meth) acrylamide, N-substituted (meth) acrylamide, (meth) acrylic acid and salts or esters thereof, and imide maleate. N-substituted acrylamide with 4 to 20 carbon atoms, such as N-methylacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-amylacrylamide, N-hexylacrylamide, N -Includes phenylacrylamide and N-octylacrylamide.

In a suitable embodiment, the following equation

<chemistry num="6"><img file="JP5100397B2_D0006.tif" /></chemistry>

Polymer is used. Where w = 0 ~ 99%, x = 1 ~ 99%, y = l ~ 99%, z = 0.5 ~ 20%; M = H, Na, K, NH₄R = H, C1-10 alkyl, aryl, Na, K or NH₄; P = H or CH₃, L = H, or C1 ~ C10 alkyl, aryl, or aralkyl, F = --G--R--X--R'--Si (OR )₃Where G = non-existent, NH, NR "or O; R = non-existent, C = O, O, C1-C10 alkyl, or aryl; X = non-existent, NR, O, NH, amide, urethane , Or urea; R'= non-existent, O, C1-C10 alkyl, or aryl; and R "= H, C1-C3 alkyl, aryl, Na, K or NH₄VPD is the moiety derived from vinylpyrrolidone with or without substituents. An exemplary polymer is a copolymer or copolymer of one or more copolymerizable monomers of the formula VII below:

<chemistry num="7"><img file="JP5100397B2_D0007.tif" /></chemistry>

Where P = H, R = -CH₂CH₂CH₂-, R'= H, X = NH, and R = H, C1-C3 alkyl, aryl, Na, K or NH₄And the polymer is based on the following formula,

<chemistry num="8"><img file="JP5100397B2_D0008.tif" /></chemistry>

Here, a polymer having w = 0 to 90%, x = 0 to 50%, y = 0 to 90%, and z = 2 to 50 mol% is a specific example.

In another embodiment, the polymer of the following formula:

<chemistry num="9"><img file="JP5100397B2_D0009.tif" /></chemistry>

Here, w = 1 ~ 99.9%, x = 0.1 ~ 50%, y = 0 ~ 50%, z = 0 ~ 50%; Q = C1 ~ C10 alkyl, aryl, amide, acrylate, ether, COXR. With X = O or NH; also R = H, Na, K, NH₄, C1 to C10 alkyl or aryl, or any other substituent; X = NH, NP, where P = C1 to C3 alkyl or aryl, or O; R'= C1 to 10 alkyl or aryl; V = H, C1 ~ C3 alkyl, aryl, Na, K or NH₄Or form an anhydrous ring; R = H, C1-C3 alkyl, aryl, Na, K or NH₄; D = NR1₂Or OR1, where R1 = H, C1-C20 alkyl, C1-C20 alkenyl or aryl, but R, R ", V" and R1 groups do not all have to be the same, are used. , Polymers according to the following formula:

<chemistry num="10"><img file="JP5100397B2_D0010.tif" /></chemistry>

Where w = 1-99.9%, x = 0.1-50%, y = 0-50%, z = 0-50%; and Q is phenyl, and

<chemistry num="11"><img file="JP5100397B2_D0011.tif" /></chemistry>

However, w = 1 ~ 99.9%, x = 0.1 ~ 50%, y1 + y2 = 0 ~ 50%, y1 and y2 = 0 ~ 50%, z = 0 ~ 50%, and Q is phenyl. Is a specific example.

In other embodiment, the polymer of the following formula is used.

<chemistry num="12"><img file="JP5100397B2_D0012.tif" /></chemistry>

Where x = 5-100% (as mol%), y and z = 0-100%, and at least one A and / or B unit is the group --Si (OR ).₃Is a group containing, where R = H, C1-C3 alkyl, aryl, Na, K or NH₄Is. Examples of such polymers include those of the following formula.

<chemistry num="13"><img file="JP5100397B2_D0013.tif" /></chemistry>

However, A and / or B = R-Si (OR )₃, X = 5 ~ 50%, y = 5 ~ 95%, z = 0 ~ 50%, That is, -Si (OR )₃Copolymers of ethylene oxide and propylene oxide substituted with groups: and

<chemistry num="14"><img file="JP5100397B2_D0014.tif" /></chemistry>

However, A and / or B = R-Si (OR )₃, X = 100%, y = 0%, z = 0%, that is, R-Si (OR )₃A homopolymer of polyethylene oxide substituted with a group.

In other embodiment, polymers made from polysaccharides or polysaccharide derivatives are used. Became a side chain--Si (OR )₃Any polypeptide capable of attaching groups can be used. Preferably the polysaccharide must be soluble in the process stream of kraft pulp and paper production, or in an industrial process stream such as a high level nuclear waste treatment stream. Polysaccharides used in the present invention include, but are not limited to, cellulose and derivatives thereof such as hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydroxybutyl cellulose, carboxymethyl cellulose, starch and starch derivatives such as cationic starch. , Guar, dextran, dextrin, xanthan, agar, carrageenan, etc. are included. Especially suitable Starch and cellulose derivatives, a particular example of which is the reaction product of hydroxyethyl cellulose with 3-glycidoxypropyltrimethylsilane.

The polymer used in the present invention can be produced by various methods. For example-Si (OR )₃However, in the formula, R = H, C1 to C3 alkyl, aryl, Na, K or NH₄It can be made by polymerizing a monomer containing, for example, a silane monomer, or by copolymerizing such a monomer with one or more copolymerization monomers. Suitable silane monomers for use in the present invention are, but are not limited to, vinyltriethoxysilane, vinyltrimethoxysilane, allyltriethoxysilane, butenyltriethoxysilane, γ-N-acrylamidepropyl. Triethoxysilane, p-triethoxysilylstyrene, 2- (methyltrimethoxysilyl) acrylic acid, 2- (methyltrimethoxysilyl) -1,4-butadiene, N-triethoxysilylpropyl maleate imide, and maleic acid -Si (OR ) with anhydrides and other unsaturated anhydrides₃Includes other reaction products with amino compounds, including. These monomers can be hydrolyzed with aqueous bases before or after polymerization. Suitable copolymerization monomers for use in the present invention include, but are not limited to, vinyl acetate, acrylonitrile, styrene, (meth) acrylic acid and salts and esters thereof, (meth) acrylamide, and substituted acrylamide. , For example, acrylamide methylpropan sulphonic acid, N-methyl acrylamide, N, N-dimethyl acrylamide, N-ethyl acrylamide, N-propyl acrylamide, N-butyl acrylamide, N-amyl acrylamide, N-hexyl acrylamide, N-phenyl acrylamide, Contains N-octyl acrylamide. The copolymers can also be graft copolymers, such as polyacrylic acid-g-poly (vinyltriethoxysilane) and poly (vinyl acetate-co-crotonic acid) -g-poly (vinyltriethoxysilane). .. These polymers can be made in various solvents. Suitable solvents for this include, but are not limited to, acetone, tetrahydrofuran, toluene, xylene and the like. In some cases, the polymer is dissolved in a reaction solvent and the solvent is removed for recovery. Alternatively, if the polymer is insoluble in the reaction solvent, the product is recovered by filtration. Suitable reaction initiators for use in the present invention include, but are not limited to, 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2-azobisisobutyronitrile, benzoyl. Includes peroxide, and cumenehydroperoxide.

In another embodiment, -Si (OR )₃A polymer useful for the present invention can be produced by reacting a compound containing a group and a group that reacts with either a side chain group or a skeletal atom of an existing polymer. For example, polyamines and polysaccharides-Si (OR )₃Compounds useful in the present invention can be obtained by reacting with various compounds containing groups. Suitable reactive groups include, but are not limited to, alkyl halide groups such as chloropropyl, bromoethyl, chloromethyl, and bromoundecyl.

-Si (OR )₃Compounds may include epoxy functional groups such as glycidoxypropyl, 1,2-epoxyamyl, 1,2-epoxydecyl or 3,4-epoxycyclohexylethyl. 3-glycidoxypropyltrimethoxysilane is a particularly suitable compound.

Reactive groups can also be a combination of hydroxyl groups and halides, such as 3-chloro-2-hydroxypropyl. This reactive moiety can also contain isocyanate groups, such as isocyanatopropyl or isocyanatomethyl, which react to form a urea bond. In addition to this, silanes containing anhydride groups, such as triethoxysilylpropyl succinic anhydride, are suitable for making the polymers of the present invention. This reaction can be carried out in a neat state or in a suitable solvent. Also other amino groups, or nitrogen atoms on the polymer, are alkyl halides, epoxides or isocyanates. By reacting with, other functional groups such as alkyl groups can be added. Polyamines can be made in a variety of ways. Polyamines can be made by ring-opening polymerization of aziridine or similar compounds. It can also be produced by condensation of amines such as ammonia, methylamine, dimethylamine, ethylenediamine and the like with reactive compounds such as 1,2-dichloroethane, epichlorohydrin, epibromohydrin and similar compounds.

Polymers containing anhydride groups are -Si (OR )₃A polymer suitable for use in the present invention can be prepared by reacting with various compounds including. Polymers containing suitable anhydride groups include maleic anhydride and ethylene unsaturated monomers such as styrene, ethylene, α-olefins such as octadecene, meta (acrylamide), (meth) acrylic acid, acrylic acid esters. For example, copolymers of methyl (meth) acrylate, ethyl (meth) acrylate, butyl acrylate, and methyl vinyl ether are included. The polymer can also be a graft polymer, such as poly (1,4-butadiene) -g-maleic anhydride or polyethylene-g-maleic anhydride. Other suitable anhydride monomers include, but are not limited to, itaconic acid and citraconic acid anhydrides. Suitable reactive silane compounds include, but are not limited to, γ-aminopropyltriethoxysilane, bis (γ-triethoxysilylpropyl) amine, N-phenyl-γ-aminopropyltriethoxysilane, p- Includes aminophenyltriethoxysilane, 3- (m-aminophenoxypropyl) -trimethoxysilane, and γ-aminobutyltriethoxysilane. Other functional groups can be added to the polymer by reacting the polymer with amines, alcohols, and other compounds. In a suitable polymer suitable for use in the present invention, the anhydride is maleic anhydride and the copolymerization monomer is styrene. A suitable silane is γ-aminopropyltriethoxysilane. It is also advantageous to react some anhydride with other amines such as diethylamine.

-Si (OR )₃Amino compounds of the same type include, but are not limited to, copolymers containing side chain isocyanate groups, such as isopropenyldimethylbenzyl isocyanate and vinyl isocyanate, and but not limited to vinyl acetate, styrene, acrylic acid, and acrylamide. It can be reacted with a copolymer with a monomer. In addition, these polymers can be reacted with other compounds such as amines to enhance their performance.

Like γ-isocyanatopropyltrimethoxysilane-Si (OR )₃The isocyanate functional compound having a group can also react with a polymer containing a hydroxyl group, for example, hydrolyzed polyvinyl acetate, and a copolymer of vinyl acetate with another monomer. Other hydroxyl-containing polymers suitable for use include, but are not limited to, polymers containing polysaccharide and N-methylolacrylamide.

In the method of the present invention, the amount of the polymer added to the process flow can depend on the composition of the industrial process flow (eg, kraft paper pulp manufacturing process or treatment stream involved in high-level nuclear waste), and the amount thereof. Is all that is generally required to be an amount that blocks scales containing aluminosilicates. It is generally preferred to add the polymer to the process stream at a concentration that is economical and practically advantageous. Suitable concentrations are above about 0 ppm up to about 300 ppm, more preferably over about 0 ppm up to about 50 ppm, and it is best to add the polymer to the process stream at a concentration above about 0 ppm up to about 10 ppm. Suitable.

The polymer can be added directly to the scale-forming process stream, for example, in the black liquid evaporator of the kraft pulp and paper manufacturing process, and in the green and white liquid evaporators of the process. However, it is preferable to add the polymer to the feed stream or circulating stream, or to the process stream leading to the evaporator of the black liquid. It is preferable to add the polymer at any point in the process in an industrial process. Is. The polymer is usually added just before the evaporator.

[Example]<u style="single">High level nuclear waste</u>(Control Example A) The reaction product of the styrene / maleic anhydride copolymer and butylamine (control polymer A) is made as follows: M with a molar ratio of styrene to maleic anhydride of about 1.1._wAbout 16,000 dry styrene / maleine anhydride copolymers (SMA) 10.0 g are suspended in 100 ml of toluene. A solution containing 1.72 g of butylamine in 10 ml of toluene is added at ambient temperature. Reflux the mixture for 3 hours. The solid product is filtered off, washed and dried. This gives a polymer containing 53 mol% styrene, 24 mol% N-butyl semiamide obtained from maleic anhydride, and 23 mol% maleic anhydride.

(Control Example B) The reaction product of the styrene / maleic anhydride copolymer and tallow (tallow, tallow) amine (control polymer B) is made as follows: M with a molar ratio of styrene to maleic anhydride of about 1.1._wSuspension 100.0 g of about 16,000 dried SMAs in 941.7 g of toluene. A solution containing 25.2 g taroamine and 27.5 g diethylamine in 35.2 g of toluene is added at ambient temperature and the mixture is refluxed for 30 minutes. The resulting toluene slurry is cooled to room temperature, then about 700 ml of a 2% caustic soda aqueous solution is added. The toluene layer is separated and the toluene remaining in the aqueous phase is removed by evaporation. The aqueous solution is further purified by ultrafiltration using a 0.2 μm hydrophilic polyether sulfone filter and lyophilized to obtain a dried polymer. This gives a polymer containing 53 mol% styrene, 38 mol% N-butyl semiamide obtained from maleic anhydride, and 9 mol% N-taroamide obtained from maleic anhydride.

(Control Example C) The reaction product of Nt-octylacrylamide and acrylic acid (control polymer C) is made as follows: 2.81 g acrylic acid, 2.52 g Nt-octylacrylamide, and 0.14 g 2-mercaptoethanol 12.5 g. Dissolves in DMF and 13.87 g of dioxane and expels air through nitrogen. The mixture is heated to 75 ° C and 0.16 g of 2,2'-azobis (2,4-dimethylvaleronitrile) contained in 3 g of dioxane is added. After 6 hours at 75 ° C., the mixture was cooled to give the desired polymer in solution. This gives a polymer containing 73.7 mol% acrylic acid and 26.3 mol% Nt-octylylamide.

Polymer i To obtain a polymer with 1 mol% silane-containing monomeric unit (polymer i), the reaction product of SMA with butylamine and (3-aminopropyl) triethoxysilane is made as follows: The molar ratio of styrene to maleic anhydride is about 1.1 and M_wSuspension of 10.0 g of about 16,000 dried SMAs in 100 ml of toluene. A solution containing 1.72 g of butylamine and 0.21 g of (3-aminopropyl) triethoxysilane in 10 ml of toluene is added at ambient temperature. Reflux the mixture for 3 hours. The solid product is filtered off, washed and dried. This resulted in 53 mol% styrene, 23.9 mol% N-butyl semi-amide from maleic anhydride, 1 mol% N- (3-aminoethoxysilyl) semi-amide from maleic anhydride, and 22.1 mol maleic anhydride. A polymer containing% is obtained.

Polymer ii To obtain a polymer with 3.8 mol% silane-containing monomeric units (polymer ii), the reaction product of SMA with butylamine and (3-aminopropyl) triethoxysilane is made as follows: The molar ratio of styrene to maleic anhydride is about 1.1 and M_wSuspension of 10.0 g of about 16,000 dried SMAs in 100 ml of toluene. A solution containing 1.72 g of butylamine and 0.83 g of (3-aminopropyl) triethoxysilane in 10 ml of toluene is added at ambient temperature. Reflux the mixture for 3 hours. The solid product is filtered off, washed and dried. This resulted in 53 mol% styrene, 23.9 mol% N-butyl semi-amide from maleic anhydride, 3.8 mol% N- (3-aminoethoxysilyl) semi-amide from maleic anhydride, and 19.3 mol maleic anhydride. A polymer containing% is obtained.

Polymer iii To obtain a polymer with 7.6 mol% silane-containing monomeric units (polymer iii), the reaction product of SMA with butylamine and (3-aminopropyl) triethoxysilane is made as follows: The molar ratio of styrene to maleic anhydride is about 1.1 and M_wSuspension of 10.0 g of about 16,000 dried SMAs in 100 ml of toluene. A solution containing 1.72 g of butylamine and 1.66 g of (3-aminopropyl) triethoxysilane in 10 ml of toluene is added at ambient temperature. Reflux the mixture for 3 hours. The solid product is filtered off, washed and dried. This resulted in 53 mol% styrene, 23.9 mol% N-butyl semi-amide from maleic anhydride, 7.6 mol% N- (3-aminoethoxysilyl) semi-amide from maleic anhydride, and 15.5 mol maleic anhydride. A polymer containing% is obtained.

Polymer iv To obtain a polymer with 3.8 mol% silane-containing monomeric units (polymer iv), the reaction product of SMA with butylamine, tallowamine, diethylamine, and (3-aminopropyl) triethoxysilane was Made in this way: M with a molar ratio of styrene to maleic anhydride of about 1.1_wSuspension 100.0 g of about 16,000 dried SMAs in 941.7 g of toluene. A solution containing 25.2 g taroamine, 27.5 g diethylamine, and 8.3 g (3-aminopropyl) triethoxysilane in 38.9 g of toluene is added at ambient temperature and the mixture is refluxed for 30 minutes. The resulting toluene slurry is cooled to room temperature, then about 700 ml of a 2% caustic soda aqueous solution is added. The toluene layer is separated and the toluene remaining in the aqueous phase is removed by evaporation. The aqueous solution is further purified by ultrafiltration using a 0.2 μm hydrophilic polyether sulfone filter and lyophilized to obtain a dried polymer. This resulted in 53 mol% styrene, 3.8 mol% N- (3-triethoxysilyl) propyl semiamide from maleic anhydride, 9.4 mol% N-taro semiamide of maleic anhydride, and N of maleic anhydride. A polymer containing 33.8 mol% of N-diethyl semi-amide is obtained.

Polymer v To obtain a polymer with 7.5 mol% silane-containing monomeric units (polymer v), the reaction product of SMA with butylamine, tallowamine, diethylamine, and (3-aminopropyl) triethoxysilane was Made in this way: M with a molar ratio of styrene to maleic anhydride of about 1.1_wSuspension 100.0 g of about 16,000 dried SMAs in 941.7 g of toluene. 20.2 g of tallowamine in 40.2 g of toluene, 23 A solution containing .4 g of diethylamine and 16.7 g of (3-aminopropyl) triethoxysilane is added at ambient temperature and the mixture is refluxed for 30 minutes. The resulting toluene slurry is cooled to room temperature, then about 700 ml of a 2% caustic soda aqueous solution is added. The toluene layer is separated and the toluene remaining in the aqueous phase is removed by evaporation. The aqueous solution is further purified by ultrafiltration using a 0.2 μm hydrophilic polyether sulfone filter and lyophilized to obtain a dried polymer. This resulted in 53 mol% styrene, 7.5 mol% N- (3-triethoxysilyl) propyl semiamide from maleic anhydride, 7.5 mol% N-taro semiamide of maleic anhydride, and N of maleic anhydride. A polymer containing 30 mol% of N-diethyl semi-amide is obtained.

Polymer vi To obtain a polymer with 3.8 mol% silane-containing monomeric units (polymer vi), the reaction product of SMA with taroamine, diethylamine, and (3-aminopropyl) triethoxysilane is as follows: Make: M with a molar ratio of styrene to maleic anhydride of about 1.1_wSuspension 100.0 g of about 16,000 dried SMAs in 941.7 g of toluene. A solution containing 10.1 g taroamine, 28.9 g diethylamine, and 8.3 g (3-aminopropyl) triethoxysilane in 31.3 g of toluene is added at ambient temperature and the mixture is refluxed for 30 minutes. The resulting toluene slurry is cooled to room temperature, then about 700 ml of a 2% caustic soda aqueous solution is added. The toluene layer is separated and the toluene remaining in the aqueous phase is removed by evaporation. The aqueous solution is further purified by ultrafiltration using a 0.2 μm hydrophilic polyether sulfone filter and lyophilized to obtain a dried polymer. This resulted in 53 mol% styrene, 3.8 mol% N- (3-triethoxysilyl) propyl semiamide from maleic anhydride, 3.8 mol% N-taro semiamide of maleic anhydride, and N of maleic anhydride. A polymer containing 39.4 mol% of N-diethyl semi-amide is obtained.

To make N- (3-triethoxysilyl) propylacrylamide (TESPA) as follows: Dissolve 197.4 g of N- (3-triethoxysilyl) propylacrylamide and 89.9 g of triethylamine in 300 g of THF. Evacuate air through nitrogen and cool to 0 ° C. 83.9 g of acryloyl chloride is added dropwise with mixing and the mixture is heated to 40 ° C for 2 hours after addition. The mixture is cooled to room temperature and the salts are filtered off. The resulting solution of TESPA (42% in THF) is used without further formation.

Polymer vii To obtain a polymer with 5 mol% silane-containing monomeric units (polymer vii), the following quaternary polymers of Nt-octylacrylamide, acrylic acid, 1-vinyl-2-pyrrolidone, and TESPA were added. 1.89 g of 1-vinyl-2-pyrrolidone, 0.66 g of acrylic acid, 2.21 g of Nt-octylacrylamide, 1.30 g of TESPA (42% in THF), and 0.14 g of 2-mercaptoethanol. Dissolve in 14 g of DMF and 11.64 g of dioxane and expel air with nitrogen. The mixture is heated to 75 ° C and 0.16 g of 2,2'-azobis (2,4-dimethylvaleronitrile) contained in 3 g of dioxane is added. After 6 hours at 75 ° C, the mixture is cooled to give the desired polymer as a solution. The polymer is further purified by precipitation with isopropyl alcohol, washed and dried. This results in a polymer containing 42.5 mol% 1-vinyl-2-pyrrolidone, 22.5 mol% acrylic acid, 5 mol% TESPA, and 30 mol% Nt-octylacrylamide.

Polymer viii To obtain a polymer with 5 mol% silane-containing monomeric units (polymer viii), a copolymer of 1-vinyl-2-pyrrolidone and TESPA is made as follows: 1.69 g 1- Dissolve vinyl-2-pyrrolidone, 1.44 g TESPA (42% in THF), and 0.14 g 2-mercaptoethanol in 12.5 g DMF and 13.07 g dioxane and expel air with nitrogen. The mixture is heated to 75 ° C and 0.16 g of 2,2'-azobis (2,4-dimethylvaleronitrile) contained in 3 g of dioxane is added. After 6 hours at 75 ° C., the mixture is cooled to give the desired polymer as a solution at a concentration of 15%. This gives a polymer containing 95 mol% 1-vinyl-2-pyrrolidone and 5 mol% TESPA.

Polymer ix To obtain a polymer with 5 mol% silane-containing monomeric units (polymer ix), a ternary polymer of Nt-octylacrylamide, acrylic acid, and TESPA is made as follows: 2.46 g Acrylic acid, 2.21 g Nt-octylacrylamide, 1.56 g TESPA (42% in THF), and 0.14 g 2-mercaptoethanol were dissolved in 12.5 g DMF and l2.97 g dioxane and aired with nitrogen. Kick out. The mixture is heated to 75 ° C and 0.16 g of 2,2'-azobis (2,4-dimethylvaleronitrile) contained in 3 g of dioxane is added. After 6 hours at 75 ° C., the mixture is cooled to give the desired polymer as a solution at a concentration of 15%. This results in a polymer containing 70 mol% acrylic acid, 5 mol% TESPA and 25 mol% Nt-octylacrylamide.

Polymer x To obtain a polymer with 2.2 mol% silane-containing monomeric units (polymer x), the reaction product of polyethylene oxide with 3-glycidoxypropyltrimethoxysilane is made as follows: 20.0 g polyethylene oxide (M_nApproximately 2000) is dissolved in 10.0 g of DMSO and air is expelled with nitrogen. To this mixture is added 2.63 g of 3-glycidoxypropyltrimethoxysilane, followed by 1.36 g of 45% KOH. The resulting mixture is heated to 80 ° C. for 1 hour to give the desired polymer as a solution at a concentration of 65.8%. This gives a polymer containing about 97.8 mol% ethylene oxide and 2.2 mol% 3-glycidoxypropyltrimethoxysilane.

Polymer xi Poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) and 3-glycid to obtain a polymer (polymer xi) with 3.1 mol% silane-containing monomer units The reaction product with xypropyltrimethoxysilane is made as follows: 30.0 g of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) (ethylene oxide 50% by weight, M)_nApproximately 1900) is mixed with 4.52 g of 3-glycidoxypropyltrimethoxysilane under nitrogen. Add 2.34 g of 45% KOH and heat the resulting mixture to 80 ° C for 1 hour to give the desired polymer at a concentration of 92.6%. This gives a polymer containing about 55.1 mol% ethylene oxide, 41.8 mol% propylene oxide, and 3.1 mol% 3-glycidoxypropyltrimethoxysilane.

Polymer xii Poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) and 3-glycid to obtain a polymer (polymer xii) with 3.0 mol% silane-containing monomer units The reaction product with xypropyltrimethoxysilane is made as follows: 30.0 g of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) (ethylene oxide 10% by weight, M)_nApproximately 2000) is mixed with 4.3 g of 3-glycidoxypropyltrimethoxysilane under nitrogen. Add 2.22 g of 45% KOH and heat the resulting mixture to 80 ° C for 1 hour to give the desired polymer at a concentration of 92.9%. This gives a polymer containing about 12.3 mol% ethylene oxide, 84.7 mol% propylene oxide, and 3.0 mol% 3-glycidoxypropyltrimethoxysilane.

Polymer xiii To obtain a polymer with 0.5 mol% silane-containing monomeric units (polymer xiii), the reaction product of polyethyleneimine with 3-glycidoxypropyltrimethoxysilane is made as follows: 25.4 g Polyethyleneimine (M_wAbout 25,000) is mixed with 0.7 g of 3-glycidoxypropyltrimethoxysilane and the resulting mixture is heated to 70 ° C. for 16 hours to give the desired polymer as a soft, brittle gel.

Polymer xiv To obtain a polymer with 1.0 mol% silane-containing monomeric units (polymer xiv), the reaction product of polyethyleneimine with 3-glycidoxypropyltrimethoxysilane is made as follows: 25.72 g Polyethyleneimine (M_wAbout 25,000) is mixed with 1.43 g of 3-glycidoxypropyltrimethoxysilane and the resulting mixture is heated to 70 ° C. for 16 hours to give the desired polymer as a soft, brittle gel.

Polymer xv To obtain a polymer with 2.0 mol% silane-containing monomeric units (polymer xv), the reaction product of polyethyleneimine with 3-glycidoxypropyltrimethoxysilane is made as follows: 11.39 g Polyethyleneimine (M_wAbout 25,000) is mixed with 1.28 g of 3-glycidoxypropyltrimethoxysilane and the resulting mixture is heated to 70 ° C. for 16 hours to give the desired polymer as a soft, brittle gel.

Polymer xvi In order to obtain a polymer (polymer xvi) having 4.0 mol% silane-containing monomer unit, the reaction product of polyethyleneimine and 3-glycidoxypropyltrimethoxysilane is prepared as follows: 10.0 g Polyethyleneimine (M_wAbout 25,000) is mixed with 2.29 g of 3-glycidoxypropyltrimethoxysilane and the resulting mixture is heated to 70 ° C. for 16 hours to give the desired polymer as a soft, brittle gel.

Polymer xvii In order to obtain a polymer (polymer xvii) having a high (about 30 mol%) silane-containing monomer unit, the reaction product of hydroxyethyl cellulose and 3-glycidoxypropyltrimethoxysilane was prepared as follows. Tsukuru: 8.0 g of dried hydroxyethyl cellulose (molecular weight of about 24,000 to 27,000), 2.0 g of 3 in 5 g of acetone. -Mix with glycidoxypropyltrimethoxysilane. Evaporation to remove acetone and heating the resulting mixture to 100 ° C. for 16 hours gives the desired polymer.

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Test method By adding sodium carbonate, sodium sulphate, sodium hydroxide, sodium aluminate solution (produced by warming alumina trihydrate in caustic soda), sodium silicate, sodium nitrate, and sodium nitrite to deionized water. Create high-level synthetic nuclear waste treatment liquid. The final composition of the liquid is shown in Table 2.

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Before adding to the nuclear waste treatment solution, all of the polymer sample was dissolved in a 2% aqueous solution of NaOH, the previously unreacted anhydrides and trialkoxysilane groups were hydrolyzed, and the trialkoxysilane groups were converted to silanol groups. Or change to sodium salt. Place the scale-reducing additive (if used) in a 125 ml polyethylene jar. It is used as a 0.5% solution in 2% NaOH aqueous solution for low doses and as a 3% solution in the same aqueous solution for high doses. Next, 120 ml of the above-mentioned stored synthetic high-level nuclear waste treatment solution is added to the bottle while mixing. Heat the closed jar to 102 ° C for 18 ± 2 hours with stirring. Perform up to 24 such tests (using bottles) at the same time. After 18 hours, open the bottle and filter the solution (0.45 μm filter). It was observed that a significant amount of aluminosilicate scale was generated in the liquid as loose aluminosilicate (this was initially). It seems to have occurred on the surface of polyethylene). In the examples below, the weight of scales produced in this test is expressed as a percentage of the average weight of scales produced in two control blank tests (without additives) that are part of the same set.

Using the test method outlined above, the ability of a series of SMA-type polymers containing varying amounts of silane to react with butylamine to block the formation of aluminosilicate scales was examined and the results are shown in Table 3. Shown.

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Using the test method outlined in Example 19, the ability of a series of SMA-type polymers with varying amounts of silane to react with taroamine and diethylamine to block the formation of aluminosilicate scales was tested and said. The results are shown in Table 4.

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Using the test method outlined in Example 19, the ability of a series of polymers made with silanes containing the monomeric TESPA to block the formation of aluminosilicate scales was tested and the results are shown in Table 5. Shown.

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Using the test method outlined in Example 19, the ability of a series of polyester-type polymers containing varying amounts of silane to block the formation of aluminosilicate scales was tested and the results are shown in Table 6.

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Using the test method outlined in Example 19, the ability of a series of polyethyleneimine-type polymers containing varying amounts of silane to block the formation of aluminosilicate scales was examined and the results are shown in Table 7.

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Using the test method outlined in Example 19, the ability of hydroxyethyl cellulose containing silane to block the formation of aluminosilicate scales was examined and the results are shown in Table 8.

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<u style="single">Testing to prevent scale formation in the kraft pulp and paper manufacturing process</u>

In order to simulate the conditions found in the black liquor of a typical kraft pulp and paper manufacturing process, a synthetic process liquor that resembles a typical black liquor is prepared by the following method.

A solution of basic aluminate according to the following formulation is prepared by adding the aluminate and NaOH solution to water and stirring overnight. The solution is then filtered through a 3 μm filtration membrane (Pall Versapor-3000 T w / wa, 47 mm).

Na₂O.Al₂O₃.3H₂O 100.0g 50% NaOH 146.6g Deionized water 753.4g --------- 1000.0g in total

This basic aluminate solution is used to make a simulated black solution according to the formulation and method below. Sodium acetate is added to obtain the desired sodium ion concentration. Unless otherwise specified, the quantity is in grams and% is w / w.

Sodium carbonate 121.9 Sodium sulphate 32.7 Sodium thiosulfate 36.4 Sodium hydrosulfide, 60% 70.9 Sodium acetate 445.3 50% sodium hydroxide 290.7 29.55% SiO₂ 14.0 Basic aluminate solution 25.1 Deionized water 1746 --------- Total 2783g = 2.30 liters Calculated concentration [CO₃^2-] = 0.5M [SO₄^2-] = 0.1M [S₂O₃^2-] = 0.1M [SH^-] = 0.33M [Na⁺] = 5.7M [OH^-] = 1.6M [Si] = 0.03M [Al] = 0.01M

This solution is made by adding sodium carbonate, sodium sulphate, sodium thiosulfate, sodium hydrosulfide, and sodium acetate to water with rapid stirring. After stirring for 30 minutes, the solution is filtered through a coarse glass frit to remove small amounts of insoluble material. After adding each, add the sodium hydroxide solution, the silica solution, and finally the basic aluminate solution while stirring. This solution is used immediately as follows.

For each of Examples 26 to 33, polymers iii (Example 3), v (Example 5), vii (Example 8), viii (Example 9), x (Example 11), xi Each polymer of (Example 12), xvi (Example 17) and xvii (Example 18) is diluted in advance to a concentration of 1% (w / w) in 2% NaOH before use.

Add 1.45 g of the polymer solution (or 1.45 g of water for the control test) to a labeled 4 oz HDPE wide-mouthed bottle. A solution of 145 g (120 ml) of simulated kraft paper black liquor is then added to each bottle, then stoppered and shaken. At this time, each bottle contains a "test solution". The dose of the polymer is 100 ppm.

Next, loosen the stopper of the bottle so that the pressure can be released, place the bottle on the floor at 102 ° C of the oven, and perform a simulation to heat the kraft paper process liquid. After 1.5 hours, close the stopper and place the jar on a rotating hot plate inside the oven. After rotating the rotary heating plate in the oven overnight (16.5 hours), each sample is filtered using a pre-weighed 3 μm filtration membrane (Pall Versapor-3000 T w / wa, 47 mm). Rinse each membrane and collected solids with approximately 5 ml of water and place on a 2.5 inch diameter watch glass. Place the watch glass and steel dish containing the entire membrane in an oven at 102 ° C for 30 minutes to dry the filtered solids. Weigh the entire membrane and solids, respectively, and calculate the weight of the solids from the difference. Next, the scale generation inhibition rate (%) is calculated by the following method.

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Table 9 shows the results of the test in which the polymers of Examples 26 to 33 were present at 100 ppm.

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