CN102001841A - Preparation method of zymolytic lignin modified water reducing agent - Google Patents
Preparation method of zymolytic lignin modified water reducing agent Download PDFInfo
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- CN102001841A CN102001841A CN 201010534951 CN201010534951A CN102001841A CN 102001841 A CN102001841 A CN 102001841A CN 201010534951 CN201010534951 CN 201010534951 CN 201010534951 A CN201010534951 A CN 201010534951A CN 102001841 A CN102001841 A CN 102001841A
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- solid
- solid acid
- lignin
- enzymolysis xylogen
- reducing agent
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/18—Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
Abstract
The invention provides a preparation method of zymolytic lignin modified water reducing agent. In the method, zymolytic lignin is used as raw material; solid acid and solid alkali generate catalytic and sulfonation reactions to prepare a cement water reducing agent. By using the advantages of strong chemical activity, high purity and the like of the zymolytic lignin and using a zymolytic lignin derivative sulfonated by the solid acid and the solid alkali as the cement water reducing agent, the performance of the zymolytic lignin modified water reducing agent is obviously superior to that of lignin sulfonate of a traditional byproduct of paper making industry. Used catalysts of the solid acid and the solid alkali can be repeatedly used; renewable resources can be thoroughly used; the consumption of petrochemicals is reduced; the cost of the preparation method is low so that great social and economic benefits are generated; and the process of preparing the cement water reducing agent has the advantages of simplicity, easy implementation and good effect.
Description
Technical field
The invention belongs to novel material exploitation, preparation field, relate more specifically to a kind of enzymolysis xylogen that utilizes and be modified feedstock
The method for preparing cement water reducing agent.
Background technology
As far back as nineteen thirty-five, cement water reducing agent is done with regard to bringing into use the sulfonated lignin that extract in the papermaking wastewater by the U.S., and many afterwards countries have also carried out research and vigorously promoted the use, and China produces this series products since the seventies in 20th century.Lignosulfonic acid salt water reducer mostly belongs to coventional type, but because its wide material sources are with low cost, has become the important concrete additive of a class now.At present, the application of domestic sulfonated lignin water reducer mainly contains two fields: 1) be used alone as the water reducer concrete batching; 2) be used for the formulation components of compound additives such as various hardening accelerator, early strength water-reducing agent, retardation water reducing agent, efficient retarding and water reducing agent, pumping agent, water-resisting agent.When the xylogen water reducer uses separately, water-reducing effect is also not really desirable, the sulfonated lignin water reducer is being recommended volume 0.2%～0.3% o'clock, its water-reducing rate in concrete is 8%～12%, be lower than naphthalene water reducer (〉=14%) and poly carboxylic acid series water reducer (〉=25%), use in engineering and be subjected to certain restriction.But naphthalene water reducer and poly carboxylic acid series water reducer all are the products of petroleum chemistry, coal chemical industry, and resource is progressively depleted, and costs an arm and a leg.Thereby in recent years, many scholars study the modification of sulfonated lignin, in the hope of improving its water-reducing property, enlarge the range of application of sulfonated lignin.
Enzymolysis xylogen is to extract from the biomass material enzymolysis prepares the residue of bio-natural gas, functional polysaccharide or bio-ethanol, biological butanol, and whole leaching process all is to carry out under gentle relatively condition.A lot of functional groups of natural lignin as phenolic hydroxyl group, alcoholic extract hydroxyl group and methoxyl group etc., are all kept preferably, and foreign matter content is low, and narrow molecular weight distribution has higher using value than the lignin product of traditional paper industry.Rationally utilize enzymolysis xylogen, can not only promote effective utilization of natural resources, reduce and pollute, and can bring considerable economic interests for biological energy industry.
Solid catalyst has high reactivity, highly selective, low burn into is pollution-free and easily and reactants separate, can reuse, characteristics such as Heat stability is good, be a kind of green catalyst.
The present inventor carried out for many years research to the lignin modification derivative, and the achievement in research that obtains novelty is (as enzymolysis xylogen or its derivative modified pnenolic aldehyde foam material and preparation method thereof, national inventing patent ZL200810071003.9; The composition of raw materials of enzymolysis xylogen or its derivative modified hot melt type phenolic resin and preparation method, national inventing patent application number 200810072174.3; ); On above-mentioned research basis, explore that a kind of employing is low-cost, reproducible enzymolysis xylogen substitutes the part petroleum chemicals and prepares cement water reducing agent, reduce cost and environment protection on will have very big advantage, and good economic benefit and social benefit.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing enzymolysis xylogen to prepare cement water reducing agent for modified feedstock.Utilize the xylogen sulfonation derivative of this method preparation to have better water reducer performance than traditional sulfonated lignin, can directly add or use as the batching of composite water-reducing agent, renewable resources can be made full use of, the consumption of petroleum chemicals can be reduced again.
Technical scheme of the present invention is as follows:
It is that raw material obtains enzymatic hydrolysis (EH) lignin modified water reducer through the catalysis sulfonation reaction that the present invention adopts enzymolysis xylogen.
Described enzymolysis xylogen is to adopt solvent method directly to extract or adopt solvent method to extract the natural macromolecular material that obtains from wood chip, bamboo or vegetation stalk fermentation prepare the residue of ethanol, functional polysaccharide or bio-natural gas from the biomass material that contains lignin component.
The catalyzer of described sulfonation reaction is with ZrOCl
28H
2O is the solid acid and the solid base catalyst of feedstock production, and described Preparation of catalysts method is as follows:
1) with ZrOCl
28H
2O is dissolved in the distilled water, makes it to be made into the solution that massfraction is 8-10%, slowly drips strong aqua under the agitation condition in solution, regulates pH=8.5-9.5, forms gel;
2) gel ageing at room temperature suction filtration after 24 hours does not have Cl with distilled water repetitive scrubbing filter residue to washings
-
3) filter residue after will washing places baking oven 80-120 ℃, and dry 12-30h grinds to form fine powder, crosses 80-120 mesh sieve, obtains powder;
4) above-mentioned powder is divided into two parts, a with 0.5 mol/L dilute sulphuric acid dipping, a sodium nitrate solution dipping with 1mol/L carries out suction filtration respectively behind the dipping;
5) with the gained filter cake respectively at 80-120 ℃ of dry 12-30 hour, ZrO
2/ SO
4 2-And Na
2O/ZrO
2Initial sample respectively 620-700 ℃ of following roasting 4 hours, promptly obtains ZrO at last
2/ SO
4 2-Solid acid catalyst and Na
2O/ZrO
2Solid base catalyst.
Described enzymolysis xylogen is the preparation method that modified feedstock prepares cement water reducing agent, and concrete steps are:
Enzymolysis xylogen, 100 weight parts waters, 2-4 weight part sodium hydroxide, 2-5 weight part Na with the 10-15 weight part
2SO
3Add in the there-necked flask with 2-5 weight part solid acid catalyst, react 3.0-5.0h under 85-95 ℃ of condition, suction filtration reclaims solid acid catalyst after cooling, obtains the enzymolysis xylogen derivative solution of solid acid catalysis; The enzymolysis xylogen derivative solution of getting above-mentioned solid acid catalysis then adds 10-25 weight part 37%(weight ratio in there-necked flask) formaldehyde solution, 3-6 weight part Na
2SO
3With 4-6 weight part solid base catalyst, react 2.5-3.5h under 85-95 ℃ of condition, after the cooling, suction filtration reclaims solid base catalyst, obtain the enzymolysis xylogen derivative solution of solid acid, catalyzed by solid base, underpressure distillation, oven dry obtain Powdered enzymatic hydrolysis (EH) lignin modified water reducer.
The principle for preparing enzymatic hydrolysis (EH) lignin modified water reducer with solid acid, catalyzed by solid base sulfonation enzymolysis xylogen:
Sulfonation reaction is the important chemical property of xylogen, helps to improve the water-soluble and surfactivity of xylogen, and xylogen sulfonation reaction mainly contains two kinds, and a kind of is Direct Sulfonation (formula I), and a kind of is sulfomethylation (formula II).Under acidic conditions, the lignin structure unit of phenol type and non-phenol type all helps C
αSulfonation reaction on the carbon sometimes also may be at C
γOn carry out.The sulfomethylation of xylogen then will just can carry out under alkaline condition.Therefore the present invention adopts the direct catalysis sulfonation of solid acid enzymolysis xylogen earlier, obtains the enzymolysis xylogen derivative (being called for short SEHL) of solid acid catalysis.Because SEHL has kept the phenol type structure of enzymolysis xylogen, thereby can use catalyzed by solid base sulfomethylation SEHL again, makes enzymolysis xylogen obtain abundant sulfonation, obtain the enzymolysis xylogen derivative (being called for short SH-SEHL) of solid acid, catalyzed by solid base.
The mechanism of xylogen generation sulfonation reaction has following two types:
The Direct Sulfonation reaction mechanism of formula I xylogen
Formula II sulfomethylated lignin methylation reaction mechanism
The present invention adopts solid catalyst to come the catalysis enzymolysis xylogen to carry out sulfonation and sulfomethylation, and enzymolysis xylogen is carried out modification, obtains xylogen sulfonation and sulfomethylated derivative, improves its water-reducing property, has enlarged the range of application of xylogen.
Remarkable advantage of the present invention:
1. the enzymolysis xylogen that adopts of the present invention is the xylogen that directly extracts or adopt the solvent method separation and Extraction from biomass material with solvent method from biorefinery prepares the residue of bio-natural gas, functional polysaccharide or biological alcohol, leaching process does not pass through operations such as high temperature, high pressure, the chemically reactive that has kept natural lignin preferably, the xylogen purity height that obtains, its ash oontent is less than 3%, the calcium lignin sulphonate or the alkali lignin that obtain well below paper industry.The raw material of enzymolysis xylogen can utilize the waste residue of agriculture and forestry organic waste material or biomass refining industry, and manufacturing cost is lower, can effectively utilize these wastes again simultaneously, helps environment protection.
2. because enzymolysis xylogen has kept the chemically reactive of natural lignin preferably, under the condition of solid acid that the present invention uses, catalyzed by solid base, enzymolysis xylogen can with sulphite, formaldehyde reaction, obtain xylogen sulfonation derivative, because xylogen is the natural polymer of three-dimensional structure, contain relatively abundanter polar group again, the enzymolysis xylogen derivative of solid acid, solid alkali sulfonation modifying is as cement water reducing agent, and is more effective than traditional sulfonated lignin.
3. solid acid, catalyzed by solid base sulfonated enzymolysis xylogen derivative are as cement water reducing agent, and its performance not only substantially exceeds the sulfonated lignin that traditional paper industry obtains, and performance also surmounts naphthalene water reducer.The solid catalyst secondary still keeps catalytic activity preferably when using, and can reuse.Use catalysis sulfonated enzymolysis xylogen derivative of the present invention as cement water reducing agent, can substitute, reduce the consumption of petroleum chemistry, coal chemistry product, not only can reduce the cost of cement water reducing agent, can also make full use of the xylogen renewable resources in the waste of biorefinery, help developing low-carbon economy.
Description of drawings
Fig. 1 is calcium lignosulfonate (LS), embodiment 1(SEHL) and embodiment 2(SH-SEHL) sulfonated products is in the adsorptive capacity of cement particle surface.
Embodiment
1. raw material and plant and instrument:
The enzymolysis xylogen that solid acid, catalyzed by solid base sulfonation are used is equipped with by Shandong dragon Lik-Sang thing science and technology joint-stock company according to the method (separating and extracting method of patent of invention enzymolysis xylogen, national inventing patent ZL200510099747.8) that patent proposed; Calcium lignin sulphonate: the paper mill, Guangzhou provides; Formaldehyde: analytical pure, the huge industry chemical industry in Jinan company limited; S-WAT, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group; ZrOCl
28H
2O, strong aqua, sulfuric acid and SODIUMNITRATE, analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group.Reference cement is provided by Beijing Chinese Research Institute for Building Sciences, and the cement sample of brand such as iso standard sand, conch, Taurus, star stone, evergreen and Yongan has Fuzhou Building Scientific Research Inst. to provide.
Agitator: JJ-1, Changzhou Guohua Electric Appliance Co., Ltd.; Digital display thermostat water bath: XMT-DA, Yuyao City digital display instrument instruments and meters company limited; Electric heating constant temperature air dry oven: DHG-9036A, the grand experimental installation of last Nereid company limited; Ultraviolet-visible pectrophotometer: 756PC type, Shanghai Spectrum Apparatus Co., Ltd.; Fourier infrared spectrograph: FTIR-8400S type, day island proper Tianjin company; Electrophoresis apparatus: JS94H type, Shanghai Zhongchen digital technology equipment Co., Ltd.Dialysis tubing: green bird MW1000 type, go up sea green bird development in science and technology company limited.
2. performance measurement
(1) mensuration of flowing degree of net paste of cement: take by weighing the 300g cement sample, water cement ratio is 0.35 and 0.29, adds water preparation cement paste, and the water reducer volume is that the 0.5%(of cement consumption all calculates with solids content).To starch only and pour back cut diameter 36mm into, lower port diameter 60mm, high 60mm(volume is about 75mL) test cup in, test by GB/T 8077-2000 " Methods for testing uniformity of concrete admixture ".
(2) mensuration of flowing degree of net paste of cement loss: after measuring clean slurry degree of mobilization, will starch only and change back cut diameter 36mm over to, lower port diameter 60mm, high 60mm(volume is about 75mL) test cup in, put into maintaining box.Once starch degree of mobilization only every 60 min mensuration.Stir evenly during mensuration, measure 120min altogether.
(3) sand-cement slurry performance measurement: the sand-cement slurry water-reducing rate is tested by GB/T 8077-2000 " Methods for testing uniformity of concrete admixture ", and used cement is reference cement, and the water reducer volume is that the 0.25%(of cement consumption is all in powder).The ultimate compression strength of sclerosis mortar is then measured according to GB177-85 " Test method for strength of hydraulic cement mortar ".
(4) solid acid catalysis sulfonation enzymolysis xylogen (SEHL) and solid acid, catalyzed by solid base sulfonation enzymolysis xylogen (SH-SEHL) are measured in the cement surface adsorptive capacity:
Solid acid catalysis sulfonation enzymolysis xylogen (SEHL) and solid acid, catalyzed by solid base sulfonation enzymolysis xylogen (SH-SEHL) are mixed with serial solution such as 5mg/L, 10 mg/L, 20 mg/L, 40 mg/L, 60 mg/L, 80 mg/L respectively, measure the light absorption value of each solution with ultraviolet spectrophotometer, concentration and corresponding light absorption value data drafting pattern, the line linearity match of going forward side by side obtains the typical curve of SEHL and SH-SEHL solution and light absorption value.SEHL and the SH-SEHL solution of getting different concns mixes (solid-to-liquid ratio is 4:1) with reference cement, stir 3min after, leave standstill 1 hour after, measure light absorption value, and calculate the concentration of absorption back water reducer solution.Change calculations adsorptive capacity according to concentration before and after the absorption.
(5) Zeta potential is measured:
Getting the 0.1g reference cement is the water reducer solution 50ml stirring 5min of 0.5g/L, 10.0g/L with concentration respectively, measures the carried charge of cement granules with JS94H type electrophoresis apparatus.
The enzymolysis xylogen derivative of embodiment 1. solid acid catalysis
With 50gZrOCl
28H
2O is dissolved in the distilled water, makes it to be made into massfraction and be 8% solution, and under agitation slow Dropwise 55 ml strong aquas in solution are regulated pH ≈ 9.0, form gel.Heavyization suction filtration after 24 hours at room temperature, repetitive scrubbing is to there not being Cl
-(the silver nitrate solution check of 0.1 mol/L).Solids is placed 105 ℃ of dryings of baking oven 24 hours, grind to form fine powder, cross 100 mesh sieve, resulting 28.6 g powder are divided into two parts, a with 214ml 0.5 mol/L dilute sulphuric acid dipping, a sodium nitrate solution dipping with 214ml 1mol/L, suction filtration does not wash.With the gained filter cake 105 ℃ of dryings 24 hours, ZrO
2/ SO
4 2-And Na
2O/ZrO
2Initial sample 680 ℃ of following roastings 4 hours, promptly obtains 17.6 g ZrO at last
2/ SO
4 2-Solid acid catalyst and 15.8 g Na
2O/ZrO
2Solid base catalyst.
10g enzymolysis xylogen, 100ml water and 3g sodium hydroxide added under 63 ℃ of conditions have in the there-necked flask of heating, whipping appts, stir 25min, dissolving evenly, add S-WAT 3 g, add the 3g solid acid catalyst again, when being warming up to 85 ℃, 4.0h is carried out in reaction, sample is cooled to room temperature after-filtration separate solid acid catalyst, obtain the sulfonated lignin modification derivant solution of solid content 20.1%, underpressure distillation, oven dry obtain enzymolysis xylogen derivative (SEHL) powder 12.8 g of solid acid catalysis.
The enzymolysis xylogen derivative of embodiment 2. solid acids, catalyzed by solid base
With the 10g enzymolysis xylogen, 100ml water and 3g sodium hydroxide add under 65 ℃ of conditions and have heating, in the there-necked flask of whipping appts, stir 25min, dissolving evenly, add S-WAT 3 g, the solid acid catalyst that adds 3g embodiment 1 preparation again, when being warming up to 90 ℃, 4.0h is carried out in reaction, sample is cooled to room temperature after-filtration separate solid acid catalyst, obtain the enzymolysis xylogen derivative solution of the solid acid catalysis of solid content 20.1%, add 10g concentration again and be 37% formaldehyde, be warming up to 70 ℃ of reaction 2.0h, add the solid base catalyst 4g of S-WAT 3 g and embodiment 1 preparation again, when being warming up to 90 ℃, 3.0h is carried out in reaction, sample is cooled to room temperature after-filtration separate solid alkaline catalysts, obtain the sulfonated lignin modification derivant solution of solid content 21.2%, underpressure distillation, oven dry obtains solid acid, enzymolysis xylogen derivative (SH-SEHL) powder 14.8 g of catalyzed by solid base.
Embodiment 3.
10g enzymolysis xylogen, 100ml water and 3g sodium hydroxide added under 65 ℃ of conditions have in the there-necked flask of heating, whipping appts, stir 25min, dissolving evenly, add S-WAT 3 g, add the solid acid catalyst 3g that embodiment 1 reclaims again, when being warming up to 90 ℃, 4.0h is carried out in reaction, sample is cooled to room temperature after-filtration separate solid acid catalyst, obtain the sulfonated lignin modification derivant solution of solid content 20.0%, underpressure distillation, oven dry obtain enzymolysis xylogen derivative (SEHL) powder 12.7 g of solid acid catalysis.
Embodiment 4.
With the 10g enzymolysis xylogen, 100ml water and 3g sodium hydroxide add under 63 ℃ of conditions and have heating, in the there-necked flask of whipping appts, stir 25min, dissolving evenly, add S-WAT 3 g, the solid acid catalyst that adds 3g embodiment 1 preparation again, when being warming up to 90 ℃, 4.0h is carried out in reaction, sample is cooled to room temperature after-filtration separate solid acid catalyst, obtain the enzymolysis xylogen derivative solution of the solid acid catalysis of solid content 20%, adding 10g concentration is 37% formaldehyde, be warming up to 70 ℃ of reaction 2.0h, add the solid base catalyst 4g that S-WAT 3 g and embodiment 2 reclaim again, when being warming up to 90 ℃, 3.0h is carried out in reaction, sample is cooled to room temperature after-filtration separate solid alkaline catalysts, obtain the sulfonated lignin modification derivant solution of solid content 21.2%, underpressure distillation, oven dry obtains solid acid, enzymolysis xylogen derivative (SH-SEHL) powder 14.6 g of catalyzed by solid base.
Embodiment 5.
With the 13g enzymolysis xylogen, the sodium hydroxide of 100ml water and 4g adds under 65 ℃ of conditions and has heating, in the there-necked flask of whipping appts, stir 25min, dissolving evenly, add S-WAT 4 g, the solid acid catalyst that adds 4g embodiment 1 preparation again, when being warming up to 88-90 ℃, 4.0h is carried out in reaction, sample is cooled to room temperature after-filtration separate solid acid catalyst, obtain the enzymolysis xylogen derivative solution of the solid acid catalysis of solid content 20.5%, adding 12g concentration is 37% formaldehyde, be warming up to 70 ℃ of reaction 2.0h, add the solid base catalyst 5g of S-WAT 3 g and embodiment 1 preparation again, when being warming up to 90 ℃, 3.0h is carried out in reaction, sample is cooled to room temperature after-filtration separate solid alkaline catalysts, obtain the sulfonated lignin modification derivant solution of solid content 22.8%, underpressure distillation, oven dry obtains solid acid, enzymolysis xylogen derivative (SH-SEHL) powder 16.8 g of catalyzed by solid base.
Embodiment 6.
With 50gZrOCl
28H
2O is dissolved in the distilled water, makes it to be made into massfraction and be 10% solution, under agitation slowly drips strong aqua in solution, regulates pH ≈ 9.0, forms gel.Heavyization suction filtration after 24 hours at room temperature, repetitive scrubbing is to there not being Cl
-(the silver nitrate solution check of 0.1 mol/L).Solids was placed 120 ℃ of dryings of baking oven 12 hours, grind to form fine powder, cross 120 mesh sieve, resulting powder is divided into two parts, a with 0.5 mol/L dilute sulphuric acid dipping, a sodium nitrate solution dipping with 1mol/L, suction filtration does not wash.With the gained filter cake 120 ℃ of dryings 12 hours, ZrO
2/ SO
4 2-And Na
2O/ZrO
2Initial sample 620 ℃ of following roastings 4 hours, promptly obtains ZrO at last
2/ SO
4 2-Solid acid catalyst and Na
2O/ZrO
2Solid base catalyst.
With 15g enzymolysis xylogen, 100ml water, 4g sodium hydroxide, 5gNa
2SO
3Add in the there-necked flask with the 5g solid acid catalyst, react 3.0h under 95 ℃ of conditions, suction filtration reclaims solid acid catalyst after cooling, obtains the enzymolysis xylogen derivative solution of solid acid catalysis; Adding 25g concentration then is the 37%(weight ratio) formaldehyde solution, 6gNa
2SO
3With the 6g solid base catalyst, under 95 ℃ of conditions, react 2.5h, after the cooling, suction filtration reclaims solid base catalyst, obtain the enzymolysis xylogen derivative solution of solid acid, catalyzed by solid base, underpressure distillation, oven dry obtain the acid of 36.1g pulverulent solids, catalyzed by solid base sulfonation enzymolysis xylogen derivative (SH-SEHL), enzymatic hydrolysis (EH) lignin modified water reducer promptly of the present invention.
Embodiment 7.
With 50gZrOCl
28H
2O is dissolved in the distilled water, makes it to be made into massfraction and be 9% solution, under agitation slowly drips strong aqua in solution, regulates pH ≈ 9.0, forms gel.Heavyization suction filtration after 24 hours at room temperature, repetitive scrubbing is to there not being Cl
-(the silver nitrate solution check of 0.1 mol/L).Solids was placed 80 ℃ of dryings of baking oven 30 hours, grind to form fine powder, cross 80 mesh sieve, resulting powder is divided into two parts, a with 0.5 mol/L dilute sulphuric acid dipping, a sodium nitrate solution dipping with 1mol/L, suction filtration does not wash.With the gained filter cake 80 ℃ of dryings 30 hours, ZrO
2/ SO
4 2-And Na
2O/ZrO
2Initial sample 620 ℃ of following roastings 4 hours, promptly obtains ZrO at last
2/ SO
4 2-Solid acid catalyst and Na
2O/ZrO
2Solid base catalyst.
With 10g enzymolysis xylogen, 100ml water, 2g sodium hydroxide, 2gNa
2SO
3Add in the there-necked flask with the 2g solid acid catalyst, react 5.0h under 85 ℃ of conditions, suction filtration reclaims solid acid catalyst after cooling, obtains the enzymolysis xylogen derivative solution of solid acid catalysis; Adding 15g concentration then is the 37%(weight ratio) formaldehyde solution, 3gNa
2SO
3With the 4g solid base catalyst, under 85 ℃ of conditions, react 3.5h, after the cooling, suction filtration reclaims solid base catalyst, obtain the enzymolysis xylogen derivative solution of solid acid, catalyzed by solid base, underpressure distillation, oven dry obtain the acid of 20.3g pulverulent solids, catalyzed by solid base sulfonation enzymolysis xylogen derivative (SH-SEHL), enzymatic hydrolysis (EH) lignin modified water reducer promptly of the present invention.
The comparative example 1.Solid acid catalysis sulfonated lignin calcium sulphonate derivative
10g calcium lignin sulphonate, 100ml water and 3g sodium hydroxide added under 65 ℃ of conditions have in the there-necked flask of heating, whipping appts, stir 25min, dissolving evenly, add S-WAT 3 g, add the 3g solid acid catalyst again, when being warming up to 90 ℃, 4.0h is carried out in reaction, sample is cooled to room temperature after-filtration separate solid acid catalyst, obtain the catalysis sulfonated lignin calcium sulphonate derivative solution of solid content 20.1%, underpressure distillation, oven dry obtain solid acid catalysis sulfonated lignin calcium sulphonate derivative powder 12.7 g.
The comparative example 2.
With the 10g calcium lignin sulphonate, 100ml water and 3g sodium hydroxide add under 62 ℃ of conditions and have heating, in the there-necked flask of whipping appts, stir 10min, dissolving evenly, add S-WAT 3 g, the solid acid catalyst 3g that adds embodiment 1 preparation again, when being warming up to 90 ℃, 4.0h is carried out in reaction, sample is cooled to room temperature after-filtration separate solid acid catalyst, obtain the sulfonated lignin modification derivant solution of solid content 20.1%, add 6ml, percentage concentration is 37% formaldehyde, be warming up to 70 ℃ of reaction 2.0h, add the solid base catalyst 4g of S-WAT 3 g and embodiment 1 preparation again, when being warming up to 90 ℃, 3.0h is carried out in reaction, sample is cooled to room temperature after-filtration separate solid alkaline catalysts, obtain the catalysis sulfonated lignin calcium sulphonate solution of solid content 21.2%, underpressure distillation, oven dry obtains solid acid, catalyzed by solid base sulfonated lignin calcium sulphonate derivative powder 14.6 g.
The performance test of embodiment and comparative example's product and comparison
(1) mensuration of flowing degree of net paste of cement: test by GB/T 8077-2000 " Methods for testing uniformity of concrete admixture ".Specific practice is to take by weighing 300g cement, is 0.35 to be mixed with cement paste according to water cement ratio, and the foregoing description or comparative example's product is added as water reducer, and volume is that the 0.5%(of cement consumption is all with solid weight meter).
(2) mensuration of flowing degree of net paste of cement loss: after measuring clean slurry degree of mobilization, will starch only and pour back cut diameter 36mm into, lower port diameter 60mm, high 60mm(volume is about 75mL) test cup in, put into maintaining box.Once starch degree of mobilization only every 60 min mensuration.Stir evenly during mensuration, measure 120min altogether.
(3) sand-cement slurry performance measurement: the sand-cement slurry water-reducing rate is tested by GB/T 8077-2000 " Methods for testing uniformity of concrete admixture ", and used cement is reference cement, and the water reducer volume is that the 0.25%(of cement consumption is all with solid weight meter).The ultimate compression strength of sclerosis mortar is then measured according to GB177-85 " Test method for strength of hydraulic cement mortar ".
(4) solid acid, catalyzed by solid base sulfonated derivative are measured in the cement surface adsorptive capacity
The foregoing description or comparative example's product is made into serial solution such as 5mg/L, 10 mg/L, 20 mg/L, 40 mg/L, 60 mg/L, 80 mg/L, measure the light absorption value of each solution with ultraviolet spectrophotometer, concentration and corresponding light absorption value data drafting pattern, the line linearity match of going forward side by side obtains the typical curve of solid acid, catalyzed by solid base sulfonated derivative solution and light absorption value.Solid acid, the catalyzed by solid base sulfonated derivative solution of getting different concns mix (solid-to-liquid ratio is 4:1) with reference cement, stir 3min after, leave standstill 1 hour after, measure light absorption value, and calculate the concentration of absorption back water reducer solution.Change calculations adsorptive capacity according to concentration before and after the absorption.
(5) Zeta potential is measured
Get the water reducer solution stirring 5min of 0.1g reference cement and 50mL different concns, measure the carried charge of cement granules with JS94H type electrophoresis apparatus.
In order to estimate the foregoing description and comparative example's buck effect, test respectively above-mentioned product according to the rules ratio be added on clean slurry degree of mobilization in the cement paste, cement adaptability, solid acid, the reusable effect of solid base catalyst, sulfonated products the cement particle surface adsorptive capacity with add of the Zeta potential influence of different water reducers to cement granules.
The clean slurry degree of mobilization of table 1 embodiment and the corresponding various cement of comparative example
As shown in table 1, embodiment has higher clean slurry degree of mobilization, better dispersing property and to the adaptability of various cement than calcium lignosulfonate and comparative example.Because enzymolysis xylogen (EHL) is different with the molecular structure of calcium lignosulfonate (LS), EHL compares with LS that to have range of molecular weight distributions little, characteristics such as the residual sugar amount is low, ash content is few, and molecular weight distribution and residual sugar amount are dispersing property and the adaptive two big factors of restriction LS.Ash content after a little while, when the water reducer addition is identical, the enzymolysis xylogen derivative (SH-SEHL) of the enzymolysis xylogen derivative (SEHL) of solid acid catalysis and solid acid, catalyzed by solid base is more than LS as the effective constituent of water reducer, thereby SEHL and SH-SEHL have dispersing property preferably and to the adaptability of different varieties cement.The data of the clean slurry degree of mobilization of embodiment 1 and embodiment 3, embodiment 2 and embodiment 4 are close, and after this also showed solid acid, catalyzed by solid base reaction, solid catalyst still had catalytic activity preferably.Therefore, solid catalyst can be reused in enzymolysis xylogen catalysis sulfonation and catalysis sulfomethylation.
Table 2 time is to the variable effect of clean slurry degree of mobilization
Table 2 has been enumerated calcium lignosulfonate, comparative example 1, embodiment 1 and embodiment 2 has been added in the clean slurry of reference cement, the interpolation time is to the variation of clean slurry degree of mobilization, clean slurry degree of mobilization passes in time that variation is more little to help engineering construction more, and the data presentation SEHL of table 2, SH-SEHL have excellent more performance as water reducer than traditional calcium lignosulfonate or calcium lignosulfonate catalysis sulfonated products.
As shown in Figure 1, the adsorption curve of SEHL is almost linear, and adsorptive capacity increases along with the increase of concentration, and adsorptive capacity is all big than LS under each concentration, and absorption does not yet reach capacity when concentration arrives 8g/L; And the LS adsorbed state that when concentration is 4g/L, just reached capacity; Also there is the state of saturated absorption in SH-SEHL, but the overall adsorption amount is the twice of LS.SEHL may be because EHL itself has superior adsorptive power in cement surface good adsorption performance, a large amount of SEHL molecular adsorption are at cement particle surface, make the effect that produces sterically hindered and electrostatic repulsion between the cement granules, and have good dispersing property.The adsorptive capacity of SH-SEHL decreases than SEHL, and from clean slurry data, the dispersing property of SH-SEHL is better than SEHL, but the sulfonation degree of SH-SEHL is than SEHL height, a large amount of SO
3 2-Form the hydration shell that one deck has physical strength with water, hindered the further absorption of SH-SEHL at cement particle surface.
Shown in the table 3 is to be mixed with different xylogen sulfonation products as the comparison of water reducer to the water-reducing rate and the compressive strength rate of sand-cement slurry, the water-reducing rate that is mixed with the mortar of 0.25% SEHL and SH-SEHL as can be seen from the table is respectively 17.0% and 20.5%, with how the water-reducing rate of based water reducer is suitable, is better than LS(11.6%); Be mixed with SEHL and SH-SEHL can obviously improve the sclerosis mortar ultimate compression strength, wherein 28 days the sclerosis mortar compressive strength rate be respectively 112.4% and 122.7%, obviously be better than being mixed with the sclerosis mortar (87.3%) of LS.
The different water reducers of table 3 are to the sand-cement slurry Effect on Performance
It can also be seen that from table 3 the water reducer effect of the calcium lignosulfonate derivative of traditional paper industry by product calcium lignin sulphonate and solid acid catalysis can not show a candle to and SEHL, SH-SEHL.Further can improve the ultimate compression strength of the water-reducing rate of its product in sand-cement slurry and sclerosis mortar with the catalyzed by solid base sulfomethylation to SEHL.The mortar water-reducing rate that is mixed with embodiment 2 has improved 20.6% than the mortar water-reducing rate that is mixed with embodiment 1, and the ultimate compression strength that is mixed with the sclerosis mortar of embodiment 2 frequently be mixed with embodiment 1 sclerosis mortar height 10.3%.This is because behind the catalyzed by solid base sulfomethylation, the sulfonation degree of enzymolysis xylogen is further enhanced.
The different water reducers of table 4 are to the Zeta potential influence of cement granules
Shown in the table 4 be four kinds of water reducers under low concentration and two kinds of situations of higher concentration, the changing conditions of cement granules Zeta potential, the order of magnitude of the Zeta potential of four kinds of water reducers is in proper order as can be seen: SH-SEHL〉SEHL LS.The cement granules that has adsorbed SH-SEHL has big electrostatic repulsion, thereby has better dispersing property.Three kinds of water reducers all are to have the stronger SO of electronegativity
3 2-, the size of Zeta potential absolute value is mainly determined jointly by the height and the adsorptive capacity of sulfonation degree.SEHL is big in the adsorptive capacity of cement surface, and sulfonation degree is lower; The SH-SEHL adsorptive capacity is big not as SEHL, and sulfonation degree is higher, produces powerful electrostatic repulsion effect after being adsorbed on cement surface.
The foregoing description and comparative example result show, the water reducer effect of the enzymolysis xylogen derivative of solid acid, catalyzed by solid base is different with traditional calcium lignin sulphonate, utilize the enzymolysis xylogen derivative of solid acid, catalyzed by solid base to make full use of reproducible xylogen resource as cement water reducing agent, both substituted the part petrochemical materials, reduced production cost, and the water reducer performance of the solid acid that obtains, catalyzed by solid base sulfonation enzymolysis xylogen derivative is better, preparation technology is simple, has important use to be worth.
Claims (4)
1. the preparation method of an enzymatic hydrolysis (EH) lignin modified water reducer is characterized in that: described method uses enzymolysis xylogen to obtain enzymatic hydrolysis (EH) lignin modified water reducer as raw material through the catalysis sulfonation reaction.
2. enzymolysis xylogen according to claim 1 is the preparation method that modified feedstock prepares cement water reducing agent, it is characterized in that:
Described enzymolysis xylogen is to adopt solvent method directly to extract or adopt solvent method to extract the natural macromolecular material that obtains from wood chip, bamboo or vegetation stalk fermentation prepare the residue of ethanol, functional polysaccharide or bio-natural gas from the biomass material that contains lignin component.
3. enzymolysis xylogen according to claim 1 is the preparation method that modified feedstock prepares cement water reducing agent, it is characterized in that:
The catalyzer of described sulfonation reaction is with ZrOCl
28H
2O is the solid acid and the solid base catalyst of feedstock production, and described Preparation of catalysts method is as follows:
With ZrOCl
28H
2O is dissolved in the distilled water, makes it to be made into the solution that massfraction is 8-10%, slowly drips strong aqua under the agitation condition in solution, regulates pH=8.5-9.5, forms gel;
Gel ageing at room temperature suction filtration after 24 hours does not have Cl with distilled water repetitive scrubbing filter residue to washings
-
Filter residue after the washing is placed baking oven 80-120 ℃, and dry 12-30h grinds to form fine powder, crosses 80-120 mesh sieve, obtains powder;
Above-mentioned powder is divided into two parts, and a with 0.5 mol/L dilute sulphuric acid dipping, a sodium nitrate solution dipping with 1mol/L carries out suction filtration respectively behind the dipping;
5) with the gained filter cake respectively at 80-120 ℃ of dry 12-30 hour, ZrO
2/ SO
4 2-And Na
2O/ZrO
2Initial sample respectively 620-700 ℃ of following roasting 4 hours, promptly obtains ZrO at last
2/ SO
4 2-Solid acid catalyst and Na
2O/ZrO
2Solid base catalyst.
4. be the preparation method that modified feedstock prepares cement water reducing agent according to claim 1,2 or 3 described enzymolysis xylogens, it is characterized in that: described preparation method's concrete steps are:
Enzymolysis xylogen, 100 weight parts waters, 2-4 weight part sodium hydroxide, 2-5 weight part Na with the 10-15 weight part
2SO
3Add in the there-necked flask with 2-5 weight part solid acid catalyst, react 3.0-5.0h under 85-95 ℃ of condition, suction filtration reclaims solid acid catalyst after cooling, obtains the enzymolysis xylogen derivative solution of solid acid catalysis; The enzymolysis xylogen derivative solution of getting above-mentioned solid acid catalysis then adds 10-25 weight part 37%(weight ratio in there-necked flask) formaldehyde solution, 3-6 weight part Na
2SO
3With 4-6 weight part solid base catalyst, react 2.5-3.5h under 85-95 ℃ of condition, after the cooling, suction filtration reclaims solid base catalyst, obtain the enzymolysis xylogen derivative solution of solid acid, catalyzed by solid base, underpressure distillation, oven dry obtain Powdered enzymatic hydrolysis (EH) lignin modified water reducer.
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