Method for Preparing Dispersant using Lignin Degradation Products

Abstract

A method for preparing dispersant using lignin degradation products includes preparation of lignin degradation products: degrading lignin which are used as raw materials using alkali through microwave-assisted activation at the presence of a metal oxide catalyst to obtain the lignin degradation products; and preparation of dispersant: preparing dispersant by molecularly reforming and chemically modifying the lignin degradation products obtained in the step of preparation of lignin degradation products.

Claims

1. A method for preparing dispersant using lignin degradation products, comprising the steps of: (1) preparation of lignin degradation products: degrading lignin which are used as raw materials using alkali through microwave-assisted activation at the presence of a metal oxide catalyst to obtain the lignin degradation products; and (2) preparation of dispersant: preparing dispersant by molecularly reforming and chemically modifying the lignin degradation products obtained in step (1).

2. The method of claim 1, wherein step (1) comprises the sub-steps of: 1A) mixing lignin, an alkaline activator and the metal oxide catalyst by a mass ratio, suspending the mixed materials in an aqueous solution, and blending the mixture well; 1B) letting the mixed substances to react for 0.5 to 2 h at a temperature within the range of 120-200° C. and microwave power within a range of 200-400 W; and 1C) performing suction filtration after the reaction liquid gets cool to remove solid residues and obtain the lignin degradation products; and wherein step (2) comprises the sub-steps of: 2A) adding monomers to the lignin degradation products obtained in step (1), letting the mixed materials to react for 30-50 min at a temperature within a range of 50-70° C., then slowly adding a cross-linking agent, stirring the substances to let a reaction proceed for 2.5-4.5 h at a temperature within the range of 80-100° C., and after the reaction ends, adding urea and isocyanate to let condensation reaction proceed for 4 h; and 2B) adjusting the pH value of the liquid obtained after the condensation reaction to 9.5-10.5, and cooling the liquid to room temperature to obtain the dispersant.

3. The method of claim 2, wherein in step (1), preparation of the lignin degradation products, the following ingredients are added in percentage by mass: 8.0%-12.0% of lignins; 4.0%-16.0% of alkaline activator; 0.1%-0.5% of catalyst; and 75.5%-85.6% of water; in step (2), preparation of the dispersant, the following ingredients are added in percentage by mass: 7.5%-12.5% of monomers; 80.0%-86.0% of lignin degradation products; 2.5%-6.25% of cross-linking agent; 1.25%-2.5% of urea; and 0.25%-1.25% of isocyanate.

4. The method of claim 3, wherein the lignins comprise organic solvent lignin, enzymolysis lignin, milled wood lignin, Kraft lignin, sulfate lignin, alkaline lignin and natural lignin prepared using one or a mixture of several ones of bamboos, corn cobs, maize straw, bagasse, cotton straw, straw, wheat straw, Manchurian ash, Chinese silver grass, cottonwood, reeds, eucalyptuses, xylosmas, birches and Chinese red pines by means of solvent extraction, enzymolysis, mechanical process, sulfite process or alkaline process.

5. The method of claim 3, wherein the alkaline activator is any one or a mixture of several ones of NaOH, KOH, LiOH, Na.sub.2CO.sub.3, K.sub.2CO.sub.3 and NaAlO.sub.2 at any ratio.

6. The method of claim 3, wherein the catalyst is any one or a mixture of several ones of zirconia, molybdenum oxide, zinc oxide, titanium oxide and columbium oxide at any ratio.

7. The method of claim 3, wherein the monomers are any one or a mixture of several ones of aminosulfonic acid, p-aminobenzenesulfonic acid, sodium p-aminobenzenesulfonate, sodium cyclohexylsulfamate and calcium cyclamate at any ratio.

8. The method of claim 3, wherein the cross-linking agent is any one or a mixture of several ones of formaldehyde, acetaldehyde, glutaraldehyde, acraldehyde and trioxymethylene at any ratio.

9. A dispersant prepared by the method of claim 1, having a relative molecular weight Mn of 6000-30000.

10. An application of the dispersant of claim 9 as a ceramic additive, a concrete water reducer, a dye dispersant and a coal water slurry additive.

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

[0038] FIG. 1 is a flow chat of the method for preparing dispersant using lignin degradation products;

[0039] FIG. 2 is a relative molecular mass diagram of the dispersant prepared in embodiment 3.

DETAILED DESCRIPTION OF THE INVENTION

[0040] A method for preparing dispersant using lignin degradation products includes the following steps:

[0041] (1) preparation of lignin degradation products: degrading lignins with alkali through microwave-assisted activation at the presence of a metal oxide catalyst to obtain the lignin degradation products;

[0042] (2) preparation of dispersant: preparing the dispersant by molecularly reforming and chemically modifying the lignin degradation products.

[0043] According to the method for preparing dispersant using lignin degradation products, the preparation of the lignin degradation products in step (1) includes the following specific sub-steps:

[0044] 1) suspending the lignins, an alkaline activator and the metal oxide catalyst by a mass ratio in an aqueous solution, and blending the mixed substances well;

[0045] 2) letting the mixed substances to react for 0.5 to 2 h at a temperature within the range of 120-200° C. and a microwave power within a range of 200-400 W;

[0046] 3) performing suction filtration after the reaction liquid gets cool to remove solid residues and obtain degradation products;

[0047] wherein preparation of the dispersant in step (2) specifically includes the following sub-steps:

[0048] 1) adding water into the lignin degradation products obtained in step (1), blending the mixed substances well, then adding monomers, letting the mixed materials to react for 30-50 min at a temperature within a range of 50-70° C., then slowly adding a cross-linking agent, stirring the substances to let the reaction proceed for 2.5-4.5 h at a temperature within the range of 80-100° C., and after the reaction ends, adding urea and isocyanate to let the condensation reaction proceed for 4 h;

[0049] 2) adjusting the pH value of the liquid obtained after the condensation reaction to 9.5-10.5, and cooling the liquid to room temperature to obtain the dispersant.

[0050] According to the method, in step (1), preparation of the lignin degradation products, the following ingredients are added in percentage by mass:

[0051] 8.0%-12.0% of lignins;

[0052] 4.0%-16.0% of alkaline activator;

[0053] 0.1%-0.5% of catalyst;

[0054] 75.5%-85.6% of water;

[0055] in step (2), preparation of the dispersant, the following ingredients are added in percentage by mass:

[0056] 7.5%-12.5% of monomers;

[0057] 80.0%-86.0% of lignin degradation products;

[0058] 2.5%-6.25% of cross-linking agent;

[0059] 1.25%-2.5% of urea; and,

[0060] 0.25%-1.25% of isocyanate.

[0061] Further, the lignins include organic solvent lignin, enzymolysis lignin, milled wood lignin, Kraft lignin, sulfate lignin, alkaline lignin and natural lignin prepared using one or a mixture of several ones of bamboos, corn cobs, maize straw, bagasse, cotton straw, straw, wheat straw, Manchurian ash, Chinese silver grass, cottonwood, reeds, eucalyptuses, xylosmas, birches and Chinese red pines by means of solvent extraction, enzymolysis, mechanical process, sulfite process or alkaline process.

[0062] Further, the alkaline activator is any one or a mixture of several ones of NaOH, KOH, LiOH, Na.sub.2CO.sub.3, K.sub.2CO.sub.3 and NaAlO.sub.2 at any ratio.

[0063] Further, the catalyst is any one or a mixture of several ones of zirconia, molybdenum oxide, zinc oxide, titanium oxide and columbium oxide at any ratio.

[0064] Further, the monomers are any one or a mixture of several ones of aminosulfonic acid, p-aminobenzenesulfonic acid, sodium p-aminobenzenesulfonate, sodium cyclohexylsulfamate and calcium cyclamate at any ratio.

[0065] Further, the cross-linking agent is any one or a mixture of several ones of formaldehyde, acetaldehyde, glutaraldehyde, acraldehyde and trioxymethylene at any ratio.

[0066] The relative molecular weight Mn of the dispersant prepared using the method is 6000-30000.

[0067] Applications of the dispersant prepared using the method as a ceramic additive, a concrete water reducer, a dye dispersant and a coal water slurry additive are provided.

[0068] The flow chat of the method for preparing dispersant using lignin degradation products can be seen in FIG. 1.

Embodiment 1

[0069] A method for preparing dispersant using lignin degradation products includes the following specific steps:

[0070] (1) mixing 40 kg alkaline lignin obtained from bamboo pulp, 30 kg of NaOH and 10 kg of NaAlO.sub.2, 1.2 kg of zirconia catalyst and 418.8 kg of water, then blending the mixed solution well;

[0071] (2) pouring the mixed solution into a microwave reactor, setting the reaction temperature at 180° C. and the microwave power at 300 W, letting the reaction proceed for 1 h, cooling the reaction products, discharging materials, and filtering the materials to remove solid residues and obtain the lignin degradation products;

[0072] (3) adding 40 kg of sodium p-aminobenzenesulfonate into 430 g of lignin degradation product obtained in step (3), and letting the solution react for 40 min at the temperature of 60° C. and the revolving speed of 250 rpm;

[0073] (4) adding 20 kg of formaldehyde (effective content) into the solution obtained after the reaction in step (4), stirring for reaction for 3 h at the temperature of 95° C., then slowly adding 6.25 kg of urea and 3.75 kg of isocyanate to let the condensation reaction proceed for 4 h;

[0074] (5) adjusting the pH value of the liquid product obtained after the condensation reaction ends to 10.0, cooling the product, and discharging the product to obtain the dispersant with a relative molecular weight of 17600.

Embodiment 2

[0075] A method for preparing dispersant using lignin degradation products includes the following specific steps:

[0076] (1) mixing 50 kg of lignin obtained rice hulls using an organic solvent, 15 kg of NaOH and 5 kg of KOH, 2 kg of molybdenum oxide catalyst and 428 kg of water, then blending the mixed solution well;

[0077] (2) pouring the mixed solution into a microwave reactor, setting the reaction temperature at 160° C. and the microwave power at 200 W, letting the reaction proceed for 2 h, cooling the reaction products, discharging materials, and filtering the materials to remove solid residues and obtain the lignin degradation products;

[0078] (3) adding 62.5 kg of amido-sulfonic acid into 400 g of lignin degradation product obtained in step 3), and letting the solution react for 30 min at the temperature of 50° C. and at the revolving speed of 250 rpm;

[0079] (4) adding 27.5 kg of aldehyde (effective content) into the solution obtained after the reaction in step (4), stirring for reaction for 4 h at the temperature of 90° C., then slowly adding 7.5 kg of urea and 2.5 kg of isocyanate to let the reaction continue for 4 h;

[0080] (5) adjusting the pH value of the liquid product obtained after the condensation reaction ends to 9.5, cooling the product, and discharging the product to obtain the dispersant with a relative molecular weight of 10500.

Embodiment 3

[0081] A method for preparing dispersant using lignin degradation products includes the following steps:

[0082] (1) mixing 60 kg milled wood lignin of eucalyptuses, 30 kg of NaOH and 10 kg of Na.sub.2CO.sub.3, 0.5 kg of zinc oxide catalyst and 379.5 kg of water, then blending the mixed solution well;

[0083] (2) pouring the mixed solution into a microwave reactor, setting the reaction temperature at 120° C. and the microwave power at 400 W, letting the reaction proceed for 0.5 h, cooling the reaction products, discharging materials, and filtering the materials to remove solid residues and obtain the lignin degradation products;

[0084] (3) adding 50 kg of p-aminobenzenesulfonic acid into 410 kg of lignin degradation product obtained in step (3), and letting the solution react for 50 min at the temperature of 70° C. and at the revolving speed of 250 rpm;

[0085] (4) adding 25 kg of glutaraldehyde (effective content) into the solution obtained after the reaction in step (4), stirring for reaction for 3 h at the temperature of 85° C., then slowly adding 8.75 kg of urea and 6.25 kg of isocyanate to let the condensation reaction proceed for 4 h;

[0086] (5) adjusting the pH value of the liquid product obtained after the condensation reaction ends to 10.5, cooling the product, and discharging the product to obtain the dispersant with a relative molecular weight of 8800.

[0087] The relative molecular weight of the dispersant prepared in this embodiment is determined with a gel permeation chromatograph (Waters2414, Waters Corporation in USA) by using polystyrene (PS) as the guide sample and THF as the flow phase. See FIG. 1 for results.

Embodiment 4

[0088] A method for preparing dispersant using lignin degradation products includes the following steps:

[0089] (1) mixing 40 kg of lignin obtained by enzymolysis of corn cobs, 60 kg of NaOH and 20 kg of K.sub.2CO.sub.3, 2.5 kg of titanium oxide catalyst and 377.5 kg of water, then blending the mixed solution well;

[0090] (2) pouring the mixed solution into a microwave reactor, setting the reaction temperature at 200° C. and the microwave power at 300 W, letting the reaction proceed for 1 h, cooling the reaction products, discharging materials, and filtering the materials to remove solid residues and obtain the lignin degradation products;

[0091] (3) adding 55 kg of sodium cyclohexylsulfamate into 420 kg of lignin degradation product obtained in step (3), and letting the solution react for 40 min at the temperature of 60° C. and at the revolving speed of 250 rpm;

[0092] (4) adding 15 kg of aldehyde (effective content) into the solution obtained after the reaction in step (4), stirring for reaction for 3.5 h at the temperature of 80° C., then slowly adding 8.0 kg of urea and 2.0 kg of isocyanate to let the reaction continue for 4 h;

[0093] (5) adjusting the pH value of the liquid obtained after the condensation reaction to 10.0, cooling the liquid, and discharging the liquid to obtain the dispersant with a relative molecular weight of 12300.

Embodiment 5

[0094] A method for preparing dispersant using lignin degradation products includes the following steps:

[0095] (1) mixing 50 kg of sulfate ligni of Chinese red pines, 50 kg of NaOH, 1.5 kg of columbium oxide catalyst and 398.5 kg of water, then blending the mixed solution well;

[0096] (2) pouring the mixed solution into a microwave reactor, setting the reaction temperature at 140° C. and the microwave power at 200 W, letting the reaction proceed for 0.5 h, cooling the reaction products, discharging materials, and filtering the materials to remove solid residues and obtain the lignin degradation products;

[0097] (3) adding 45 kg of calcium cyclamate into 410 kg of lignin degradation products obtained in step (3), and letting the solution react for 30 min at the temperature of 55° C. and at the revolving speed of 250 rpm;

[0098] (4) adding 31.25 kg of trioxymethylene (effective content) into the solution obtained after the reaction in step (4), stirring for reaction for 4.5 h at the temperature of 100° C., then slowly adding 10.0 kg of urea and 3.75 kg of isocyanate to let the reaction continue for 4 h;

[0099] (5) adjusting the pH value of the liquid product obtained after the condensation reaction ends to 10.5, cooling the product, and discharging the product to obtain the dispersant with a relative molecular weight of 11500.

Embodiment 6

[0100] A method for preparing dispersant using lignin degradation products includes the following specific steps:

[0101] (1) mixing 60 kg of sulfonate lignin of cotton straw, 30 kg of NaOH, 10 kg of NaAlO.sub.2, 1.0 kg of columbium oxide catalyst and 399 kg of water, then blending the mixed solution well;

[0102] (2) pouring the mixed solution into a microwave reactor, setting the reaction temperature at 150° C. and the microwave power at 400 W, letting the reaction proceed for 2 h, cooling the reaction products, discharging materials, and filtering the materials to remove solid residues and obtain the lignin degradation products;

[0103] (3) adding 50 kg of sodium p-aminobenzenesulfonate into 420 kg of lignin degradation product obtained in step (3), and letting the solution react for 50 min at the temperature of 50° C. and at the revolving speed of 250 rpm;

[0104] (4) adding 12.5 kg of formaldehyde (effective content) into the solution obtained after the reaction in step (4), stirring for reaction for 3.5 h at the temperature of 95° C., then slowly adding 12.5 kg of urea and 5.0 kg of isocyanate to let the condensation reaction proceed for 4 h;

[0105] (5) adjusting the pH value of the liquid product obtained after the condensation reaction ends to 9.5, cooling the liquid, and discharging the liquid to obtain the dispersant with a relative molecular weight of 10980.

Embodiment 7

[0106] A method for preparing dispersant using lignin degradation products includes the following specific steps:

[0107] (1) mixing 40 kg of lignin obtained through an alkaline process (reeds and wheat straw mixed at a ratio of 1:2), 30 kg of KOH and 10 kg of LiOH, 1.8 kg of zirconia catalyst and 418.2 kg of water, then blending the mixed solution well;

[0108] (2) pouring the mixed solution into a microwave reactor, setting the reaction temperature at 170° C. and the microwave power at 300 W, letting the reaction proceed for 1 h, cooling the reaction products, discharging materials, and filtering the materials to remove solid residues and obtain the lignin degradation products;

[0109] (3) adding 37.5 kg of p-aminobenzenesulfonic acid into 430 kg of lignin degradation product obtained in step (3), and letting the solution react for 40 min at the temperature of 70° C. and the revolving speed of 250 rpm;

[0110] (4) adding 22.5 kg of formaldehyde (effective content) into the solution obtained after the reaction in step (4), stirring for reaction for 3 h at the temperature of 90° C., then slowly adding 8.75 kg of urea and 1.25 kg of isocyanate to let the condensation reaction proceed for 4 h;

[0111] (5) adjusting the pH value of the liquid product obtained after the condensation reaction ends to 10.0, cooling the product, and discharging the product to obtain the dispersant with a relative molecular weight of 14900.

[0112] Property Test

[0113] 1. Ceramic Additive

[0114] A ceramic additive was taken as an example. Raw materials of pottery clay smashed and milled at different grades were placed in ball millers; the prepared dispersant which accounted for 0.6 wt % of the total mass of the pottery clay was added; a proper amount of water was added to adjust the water content of the slurry to 40 wt %; the slurry was milled for 10 min using a fast mill; after ball milling, the mobility of the slurry was tested, and the blank was prepared into test samples with a size of 120 mm×60 mm×5 mm to undergo the rupture strength test for green bodies. The test results can be seen in Table 1.

Contrast to the Embodiment

[0115] Raw materials of pottery clay smashed and milled at different grades were placed in ball millers; sodium tripolyphosphate ceramic additive which accounted for 0.6 wt % of the total mass of the pottery clay was added; a proper amount of water was added to adjust the water content of the slurry to 40 wt %; the slurry was milled for 10 min using a fast mill; after ball milling, the mobility and viscosity of the slurry were tested, and the blank was prepared into test samples with a size of 120 mm×60 mm×5 mm to undergo the rupture strength test for green bodies.

[0116] The test results of the above-mentioned embodiments 1-7 and the contrast to the embodiments can be seen in Table 1 below. From the results shown in Table 1 it can be seen that, under the condition of the same additive quantity, the product of the invention can well disperse ceramic slurry, is superior to sodium tripolyphosphate in the aspect of enhancement property, and can meet the pulping requirements of the ceramic industry.

TABLE-US-00001 Rupture Amount Flow strength of used Viscosity time green body Product (wt %) (mPa .Math. s) (s) (MPa) Contrast 0.6 78.0 17.2 0.55 Embodiment 1 0.6 55.2 17.6 0.66 Embodiment 2 0.6 85.2 21.8 0.59 Embodiment 3 0.6 89.0 23.5 0.56 Embodiment 4 0.6 62.2 18.5 0.59 Embodiment 5 0.6 65.3 20.0 0.58 Embodiment 6 0.6 77.0 21.1 0.55 Embodiment 7 0.6 58.3 18.3 0.62

[0117] 2. Concrete Water Reducer

[0118] A concrete water reducer was taken as an example. In accordance with GBT8077-2012 Methods for Testing Uniformity of Concrete Admixture and GB50119 Code for Concrete Admixture Application, the comparison between effects of the dispersant prepared by the invention and other similar products on mobility (mm) of the cement paste can be seen in Table 2. From the results shown in table 2 it can be seen that the product of the invention achieves good water reduction and dispersion effects on different varieties of concrete.

TABLE-US-00002 TABLE 2 Effects of the dispersant prepared by the invention and other similar products on mobility (mm) of the cement paste Mobility of cement Amount paste of different varieties Water used Lianshi Tapai Jinniu reducer (wt %) cement cement cement Embodiment 1 0.7 156 168 161 Embodiment 7 0.7 150 160 155 Calcium 0.7 143 162 157 lignosulphonate (powder, industrial) Amido-sulfonic 0.7 155 165 160 acid series efficient water reducer (powder, industrial)

[0119] 3. Dye Dispersant

[0120] Dye dispersant was taken as an example. The thermal stability of the dispersant prepared by the invention in the vat dye and the disperse dye was tested by reference to HG/T3507-2008 Sodium Lignie Sulphonate Dispersing Agent and GB/T27597-2011 Dyestuff-Determination of Diffusibility. From the test results shown in Table 3 and Table 4 it can be seen that the product of the present can well disperse the dye and has high thermal stability.

TABLE-US-00003 TABLE 3 Thermal stability of the dispersant applied to vat olive at different temperatures Thermal stability Product 100° C. 130° C. 150° C. Embodiment 1 Grade 5 Grade 5 Grade 5 Embodiment 2 Grade 5 Grade 4 Grade 4 Embodiment 3 Grade 5 Grade 4 Grade 4 Embodiment 4 Grade 5 Grade 5 Grade 5 Embodiment 5 Grade 5 Grade 5 Grade 4 Embodiment 6 Grade 5 Grade 5 Grade 4 Embodiment 7 Grade 5 Grade 5 Grade 5

TABLE-US-00004 TABLE 4 Thermal stability of the dispersant applied to different types of dye at the temperature of 150° C. Thermal stability Product Vat black Vat olive Disperse red 191 Disperse violet Embodiment 1 Grade 5 Grade 5 Grade 5 Grade 5 Embodiment 2 Grade 4 Grade 4 Grade 4 Grade 5 Embodiment 3 Grade 4 Grade 4 Grade 4 Grade 4 Embodiment 4 Grade 5 Grade 4 Grade 5 Grade 5 Embodiment 5 Grade 5 Grade 4 Grade 5 Grade 4 Embodiment 6 Grade 5 Grade 4 Grade 5 Grade 4 Embodiment 7 Grade 5 Grade 5 Grade 5 Grade 5

[0121] 4. Coal Water Slurry Additive

[0122] Take the coal water slurry additive. The dispersity and thermal stability of the dispersant prepared by the invention in coal water slurry were tested. Coal of China Shenghua was selected as the study object. The coal was smashed, milled, screened and graded, and then added with a certain amount of water and dispersant (added by 0.4 wt %). The mixture was uniformly stirred to obtain coal water slurry with different concentrations. The viscosity of the coal water slurry was determined using a viscosimeter, and the stability of the coal water slurry was tested by the rod-drop method. From the test results shown in Table 5 it can be seen that the product of the present can well disperse the coal water slurry and has high stability.

TABLE-US-00005 Property of coal water slurry Maximum slurry Viscosity/ Slurry Slurry Product concentration/% mPa .Math. s mobility stability Embodiment 1 64.9 750  A.sup.+ A Embodiment 2 66.6 980  A.sup.− B Embodiment 3 66.9 1050  A.sup.− B Embodiment 4 65.5 880  A.sup.+ A Embodiment 5 65.8 910 A A Embodiment 6 66.0 990 A A Embodiment 7 65.3 870  A.sup.+ A

[0123] The above are preferred embodiments of the invention. All equivalent changes, amendments, replacements and modifications made by those ordinarily skilled in the field according to the principle and concept of the invention shall fall within the protective scope of the invention.

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