CN105985527B - A kind of new technique for synthesizing of high substituted degree ligno-sulfate based plasticizer - Google Patents
A kind of new technique for synthesizing of high substituted degree ligno-sulfate based plasticizer Download PDFInfo
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- CN105985527B CN105985527B CN201510078510.5A CN201510078510A CN105985527B CN 105985527 B CN105985527 B CN 105985527B CN 201510078510 A CN201510078510 A CN 201510078510A CN 105985527 B CN105985527 B CN 105985527B
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Abstract
The suspension reaction system for the lignin sodium raw material of industry and sulfur trioxide and the non-protonic solvent composition that the present invention is spray-dried using pulping waste liquor successfully synthesizes high substituted degree ligno-sulfate based plasticizer, the problem of overcoming existing lignosulfonates diminishing and enhancing poor performance, develop simple process, of low cost, energy conservation and environmental protection, industrial new process is completely suitable for, realizes the high value added utilization of slurrying by-product lignin.Product Green environmental protection, of low cost without poisonous and harmful substance, not only exclusive use effect is good, and use cost can be greatly reduced with polycarboxylic acids, cellulose sulfonate water reducer compounding use.
Description
Technical field
Patent of the present invention is related to a kind of lignin using black liquor of pulp making source as Material synthesis high substituted degree lignin sulfonic acid
The water-reducing agent new process of salt.
Background technology
It is growing day by day to the dosage and demand of concrete with the fast development of construction industry, the research of concrete admixture
Receive more and more extensive concern, water-reducing agent is a kind of the moon as the important component that a kind of additive is concrete
Ionic surfactant.Water-reducing agent is mixed in concrete can significantly reduce the ratio of mud of mixed concrete, and raising is newly mixed
Workability, the mobility of concrete, and improve the intensity of concrete.Therefore, it is various improvement water-reducing agent to be mixed in concrete
The economical and effective method of its performance.
The principal item of existing water-reducing agent has ligno-sulfate based plasticizer, naphthalene water reducer, poly carboxylic acid series water reducer, three
Poly cyanamid based water reducer, aminosulfonic water-reducing agent etc..Lignosulfonates currently used in the market are sulphite process lifes
Produce the by-product of paper pulp, have it is of low cost, raw material sources extensively etc., the features such as concrete strength can be increased.Existing wood
Mahogany sulfonate water-reducing agent is just applied in concrete from early 20th century, since high temperature and highly basic slurrying cause lignin to drop
Solution, for average molecular weight less than 10,000, water-reducing rate only has 8%-9%, belongs to plain edition cement water reducing agent.
In order to further improve the water-reducing rate of lignosulfonates, meet the requirement of high performance concrete, United States Patent (USP)
US2680113 is reported carries out lignin high temperature sulfonation and condensation at 150 DEG C using formaldehyde and sodium sulfite, but diminishing is imitated
Rate improves little；Patent CN1434068 is employed and is first added in formaldehyde, and then adding in sulphite heating reaction reduces reaction temperature
The method for producing lignosulfonates, though product sulfonation degree and water reducing ability have improvement, and it is still not high；Patent CN1202027C is reported
A kind of preparation method for aoxidizing sulfonation in road, sequentially add alkaline conditioner, strong oxidizer, sulfonating agent and molecular weight regulator into
The method that row oxidation sulfonating reaction prepares modified lignin mahogany sulfonate.But lignosulfonates prepared by above method can only only reach
To ordinary water-reducing agent using effect, it is necessary to greatly improve its performance.
The content of the invention
The present invention is based on our breakthroughs in terms of cleaning pulping and biology base sulfonation synthesis technology early period, utilize new system
The lignin sodium and process for sulfonation in sizing process source, which have developed, greatly improves sulfonation degree lignosulfonates, and product uses result
Show that water-reducing rate and concrete strength are largely increased.
This production technology provides the alkali wood being spray-dried with the pulp waste of patent CN102337687A methods production
Quality is raw material, in non-protonic solvent, with SO3For sulfonated reagent, high conversion synthesis high substituted degree, high molecular weight are wooden
The new process of plain sulfonate.New product is at low cost, environmentally protective, water-soluble fine with synthesizing, and shows to subtract well
Water and enhancing performance.
Specific implementation step is：
1.SO3The preparation of solution
By SO3Gas, liquid or solid be dissolved in non-protonic solvent 1 in the cooling condition, in 2- dichloroethanes.
2. the preparation of alkali lignin raw material
Water content of the pulping waste liquor by spray drying is less than 0.5% alkali lignin powder.
3. Sulfation/sulfonation
The alkali lignin powder being spray-dried in step 2 is put into slowly uniform stirring in 1,2- dichloroethanes, in temperature
It spends to be slowly added to the SO that step 1 has configured at 20-35 DEG C3/ 1,2- dichloroethane solution, add SO3With alkali lignin powder
Mass ratio is 0.3-1, and 1-6h is stirred in the case where stir speed (S.S.) is 100-1000rad/min；When reaction time preferred 4-5 is small, reaction temperature
Preferred 29-31 DEG C is spent, SO3Mass ratio with alkali lignin powder is preferably 0.5-0.8, the preferred 300-500rad/min of stir speed (S.S.).
4. post-processing approach
By solid/liquid mixture after reaction, 1,2- of filtered recycling dichloroethanes filters for recycling
In obtained -10-0 DEG C of aqueous alkalis of solid input, pH=7-9 is neutralized to, precipitation is removed by filtration, lignosulfonates can be arrived
1,2- dichloroethanes in crude product, liquid separation or the further recovered material of distillation can obtain needing the lignin sulfonic acid brine of concentration
Insoluble products.
This product can be solid or liquid.
Raw materials used lignin, the lignin sodium salt to be extracted in pulping waste liquor of patent of the present invention, pulping waste liquor
Spray-dried obtained alkali lignin and rich in lignin plant etc..
Non-protonic solvent used in the present invention is to promote SO3 dissolvings, not react with SO3, easily separated from reaction system
Solvent.Non-protonic solvent can be the small molecules aliphatic halogenated hydrocarbon such as dichloroethanes, dichloropropane, dichloromethane, preferably
1,2- dichloroethanes.
Neutralization of the present invention is with hydroxide, oxide or the salt that alkali is sodium, calcium, magnesium and zinc or can also be ammonia or has
Machine amine or be amino-containing macromolecule can also be the mixture of above two or many kinds of substance, comprehensive cost and diminishing effect
Fruit is best as neutralization alkali using calcium hydroxide.
To avoid hydrolyzing, product stability is influenced, neutralization reaction need to cooled down and carried out under sinking temperature, neutralize pH to alkalescent.
Research shows：It can be smoothed out by raw material sulfonation/Sulfation of alkali lignin powder, since lignin sodium can
To be automatically converted to sodium lignin sulfonate, it is therefore desirable to which the alkali number of neutralization can substantially reduce.And it can use a small amount of cheap
Calcium hydroxide is neutralized into the complex salt of calcium salt and sodium salt, and sulfonation degree significantly improves, and average molecular weight can reach 1,110,000.
The experimental results showed that：The product that calcium salt is neutralized into through calcium hydroxide after using alkali lignin as raw material sulfonation/esterification is being mixed
Water-reducing rate can reach the diminishing standard (14%) of high efficiency water reducing agent when measuring 1.2% for cement quality.Working performance of concrete changes
Kind, 3 days, 7 days and 28 days intensity is significantly increased with being not added with the comparison of sample concrete.
The experimental results showed that：The production of calcium salt is neutralized into after using alkali lignin powder as raw material sulfonation/Sulfation through calcium hydroxide
Product can reduce volume with poly carboxylic acid series water reducer compounding, increase by 3 days, 7 days and 28 days compression strength, while reduce polycarboxylic-acid and subtract
The dosage and use cost of aqua.The compound proportion of preferred ligno-sulfate based plasticizer and poly carboxylic acid series water reducer is 1: 1.
The experimental results showed that：After using alkali lignin as raw material sulfonation/esterification through calcium hydroxide be neutralized into the product of calcium salt with
Cellulose sulfuric acid ester salt water-reducing agent compounds, and can make up the shortcomings that ligno-sulfate based plasticizer water-reducing rate is low, reduces usage amount
And use cost.The compound proportion of preferred ligno-sulfate based plasticizer and cellulose sulfuric acid ester salt water-reducing agent is 7: 3.Cause
This, using alkali lignin powder as raw material sulfonation/Sulfation after through calcium hydroxide be neutralized into sodium calcium salt-mixture product be used alone
In the case of higher dosage, good water-reducing rate and intensity can be reached, due to being with the very low by-product lignin of cost
Sodium is simply synthesized with cheap raw materials such as sulfur trioxide, lime, therefore, still with cost advantage.With cellulose sulfuric acid ester calcium salt
Water-reducing agent compounds, and can reduce volume, and can make up the shortcomings that ligno-sulfate based plasticizer water-reducing rate is relatively low, compounding use
Economic technique superiority become apparent from.
Sulfur trioxide used in the present invention be synthesize sulfuric acid intermediate raw material, at low cost, used solvent and raw material
Toxicity is low, can be fully converted to product or recycle.
The lignin sodium raw material of industry being spray-dried using pulping waste liquor and sulfur trioxide and aprotic of the invention
The suspension reaction system of solvent composition successfully synthesizes Novel wooden quality sulfonate water reducer, overcomes existing lignosulfonates
The problem of water-reducing property is poor develops simple process, of low cost, energy conservation and environmental protection, and height can be obtained by being completely suitable for industrial production
The new process of degree of substitution product realizes the high value added utilization of pulping byproducts lignin.Product Green environmental protection, without toxic
Harmful substance, of low cost, not only exclusive use effect is good, and can make with polycarboxylic acids, cellulose sulfonate water reducer compounding
With being greatly reduced use cost, improve using effect.
Description of the drawings
Attached drawing 1 is that the infrared spectrum of product and raw material compares figure.
Specific embodiment
Embodiment 1
The alkali lignin that 500g is spray-dried stirs low suspension in 2500mL1,2- dichloroethanes, is slowly added to
940.0mL SO3Concentration is the SO of 4.0mol/L3/ dichloroethane solution keeps reaction temperature between 29-31 DEG C, stirring, instead
4h is answered to be filtered to remove solvent afterwards, 910g solids (the dichloroethanes 160g containing 1,2-) material is slowly added to 5 DEG C of NaOH containing 221g
Solution in, adjust pH to alkalescent, centrifuging and taking supernatant is denoted as L-1, product design 33.3%.
With reference to product analysis method GB/T 8077-2012《Methods for testing uniformity of concrete admixture》It is tested not
With the benchmark mortar fluidity under additive amount.Measuring unit：Industrial technology research institute of Xiamen University
| Sample | Incorporation/% | Water-reducing rate/% | Flow angle value/mm |
| L-1 | 0.6 | 8 | 181 |
| L-1 | 0.7 | 8 | 191 |
| L-1 | 1.0 | 14 | 170 |
| L-1 | 1.1 | 14 | 183 |
| L-1 | 1.2 | 14 | 200 |
From test result, when volume reaches 0.6%, sodium lignin sulfonate water-reducing rate is 8%, reaches common diminishing
The water-reducing effect of agent；When volume reaches 1.1%, sodium lignin sulfonate water-reducing rate is 14%, reaches the standard of high efficiency water reducing agent.
Concrete slump is tested with reference to product analysis method (GBT_50080-2002 concrete admixtures)；With reference to product
Analysis method (GBT_8076-2008 concrete admixtures) tests concrete strength.
Embodiment 2
The 500g alkali lignin powder being spray-dried is suspended in 2500mL1, in 2- dichloroethanes, is slowly added to 940.0mL
SO3Concentration is the SO of 4.0mol/L3/ dichloroethane solution keeps reaction temperature between 29-31 DEG C, stirring, after reaction 4h
Solvent is filtered to remove, 910g solids (the dichloroethanes 160g containing 1,2-) material is slowly added to 5 DEG C of (OH) containing 204gCa2Lime
In water, pH is adjusted to alkalescent, centrifuging and taking supernatant is denoted as L-2, product design 37.6%.
With reference to product analysis method GB/T 8077-2012《Methods for testing uniformity of concrete admixture》It is tested not
With the benchmark mortar fluidity under additive amount.Measuring unit：Industrial technology research institute of Xiamen University
| Sample | Incorporation/% | Water-reducing rate/% | Flow angle value/mm |
| L-2 | 0.6 | 8 | 175 |
| L-2 | 0.7 | 8 | 181 |
| L-2 | 0.8 | 8 | 192 |
| L-2 | 1.2 | 14 | 175 |
| L-2 | 1.3 | 14 | 184 |
| L-2 | 2.0 | 20 | 170 |
| L-2 | 2.1 | 20 | 175 |
| L-2 | 2.2 | 20 | 181 |
Concrete slump test method is tested with reference to product analysis method (GBT_50080-2002 concrete admixtures)；
Concrete strength is tested with reference to product analysis method (GBT_8076-2008 concrete admixtures).
Embodiment 3
Product L-2 in embodiment 1 is answered with the poly carboxylic acid series water reducer TS-80 provided with glad building materials Co., Ltd
Match somebody with somebody, compound proportion and code name are as follows：
| Sample | Compound proportion (L-2: TS-80) |
| H-1 | 3∶7 |
| H-2 | 1∶1 |
| H-3 | 7∶3 |
Concrete slump is tested with reference to product analysis method (GBT_50080-2002 concrete admixtures)；With reference to product
Analysis method (GBT_8076-2008 concrete admixtures) tests concrete strength.
Embodiment 4
By product L-2 in embodiment 2 and this seminar production cellulose sulfate calcium (during volume 0.5%, water-reducing rate
14%) C-1 is compounded, and compound proportion and code name are as follows：
| Sample | Compound proportion (L-2: C-1) |
| H-4 | 3∶7 |
| H-5 | 1∶1 |
| H-6 | 7∶3 |
Concrete slump test method is tested with reference to product analysis method (GBT_50080-2002 concrete admixtures)；
Concrete strength is tested with reference to product analysis method (GBT_8076-2008 concrete admixtures).
Reference examples
Reference examples 1
Methylolation, process for sulfonation：The 500g alkali lignin powder being spray-dried is added in 1500ml water, stirs 30 points
For the pH value of Zhong Houyong dilute sulfuric acids (10%Wt) adjustment solution to 3, filtering, sediment adds in 2.5wt%NaOH solution 2000g, adds
Enter formaldehyde (37.5%) solution of 25g, heat 60 DEG C and react 80 minutes, add in the sodium sulfite of 15g, react 100 points at 95 DEG C
Clock.Product is denoted as Y-1.
Concrete slump test method is tested with reference to product analysis method (GBT_50080-2002 concrete admixtures)；
Concrete strength is tested with reference to product analysis method (GBT_8076-2008 concrete admixtures).
Reference examples 2
Oxidation, sulfomethylation technique：500g alkali lignins are weighed, add in distilled water 1500g, with dilute sulphur after stirring 30 minutes
For the pH value of sour (10%Wt) adjustment solution to 3, filtering, sediment adds in 2.5wt%NaOH solution 2000g, adds in 75g peroxidating
Hydrogen, 5g ferrous sulfate, heat 60 DEG C reaction, reaction 1 it is small when after, be warming up to 75 DEG C, then add in 75g formaldehyde (37.5%) it is molten
Liquid, when isothermal reaction 2 is small.90 DEG C are continuously heating to, 10g anhydrous sodium sulfites are added in, when isothermal reaction 3 is small.Product is denoted as Y-2.
Concrete slump test method is tested with reference to product analysis method (GBT_50080-2002 concrete admixtures)；
Concrete strength is tested with reference to product analysis method (GBT_8076-2008 concrete admixtures).
Sodium lignin sulfonate sulfur content compares after alkali lignin sulfonation under different technology conditions：
| Product | Technique is sketched | S (%) |
| Alkali lignin | - | 0.871 |
| Embodiment 1 | Alkali lignin/SO 3 sulfonated system | 6.645 |
| Embodiment 2 | Alkali lignin/SO 3 sulfonated system | 5.787 |
| Reference examples 1 | Methylolation, process for sulfonation | 1.735 |
| Reference examples 2 | Oxidation, sulfomethylation technique | 2.900 |
As it can be seen that new process can greatly improve degree of substitution, product sulfur content and water solubility are dramatically increased.
Foundation《Design of common concrete proportioning regulation》(JGJ55-2000) (J64-2000) and《Construction calculates
Handbook》
Design concrete mix is C30
Comparative example 1 is matched using the C30 of the holy extraordinary building materials Co., Ltd in Chongqing three, and comparative example 2 is refined prosperous using Sichuan Chengtong
The C30 proportionings of construction material Co., Ltd
Concrete slump is tested with reference to product analysis method (GBT_50080-2002 concrete admixtures), with reference to product
Analysis method (GBT_8076-2008 concrete admixtures) tests concrete strength.
Comparative example 1
The naphthalene water reducer that testing example 1, embodiment 2 are provided with the holy extraordinary building materials Co., Ltd in Chongqing three, is denoted as
The working performance of concrete of FDN-O.Measuring unit：Chongqing Sansheng Building Materials Co., Ltd.
Comparative example 2
Testing example 1, embodiment 2 and the coagulation of the poly carboxylic acid series water reducer TS-80 provided with glad building materials Co., Ltd
Native working performance.Measuring unit：Sichuan Chengtong Ya Xin construction materials Co., Ltd
It can be seen that be used alone in the case of higher dosage, good water-reducing rate and intensity can be reached, due to be with into
This very low by-product lignin sodium is simply synthesized with cheap raw materials such as sulfur trioxide, lime, therefore, still excellent with cost
Gesture.As can be seen that the economic technique superiority of compounding becomes apparent from.
Comparative example 3
Reference examples 1, the test of the working performance of concrete of reference examples 2, measuring unit：Chengtong refined prosperous construction material in Sichuan is limited
Company
As it can be seen that the intensity and water-reducing effect of control sample are all very poor.
Claims (7)
- A kind of 1. method for synthesizing high substituted degree ligno-sulfate based plasticizer, it is characterised in that：It is dry using pulping waste liquor spraying The suspension reaction system of the dry obtained lignin sodium raw material of industry and sulfur trioxide and non-protonic solvent composition synthesizes to obtain height Degree of substitution ligno-sulfate based plasticizer, concrete technology are characterized as：Dried powder material is suspended in non-protonic solvent, under stiring, is added in dissolved with SO3Non-protonic solvent, Stir speed (S.S.) 100-1000rad/min, at a temperature of 20-35 DEG C react 1-6 it is small when after, be filtered to remove solvent, solid is slow Add in the alkali water-soluble liquid of sub-cooled, it is 7-9 to carry out acid-base neutralization to pH, is filtered to remove precipitation insoluble matter, liquid separation or Remaining non-protonic solvent is distilled off, obtains the excellent environmentally protective water-reducing agent of water-reducing property；SO3With alkali lignin powder Mass ratio is 0.3-1.
- 2. according to the method described in claim 1, wherein, SO3It is 0.5-0.8 with alkali lignin powder quality ratio, reaction temperature is 29-31 DEG C, when the reaction time is 4-5 small, stir speed (S.S.) 300-500rad/min.
- 3. according to the method described in claim 1, wherein non-protonic solvent is to promote SO3Dissolving, not with SO3Reaction, Yi Cong Separated solvent in reaction system；The non-protonic solvent is small molecule aliphatic halogenated hydrocarbon.
- 4. the method according to claim 1 or 3, wherein, non-protonic solvent is dichloroethanes, dichloropropane or dichloromethane Alkane.
- 5. according to the method described in claim 1, it is characterized in that, neutralize the hydroxide that alkaline matter is sodium, calcium, magnesium and zinc Object ammonia or organic amine or be amino-containing macromolecule or above two or many kinds of substance mixture.
- 6. according to the method described in claim 5, wherein, alkaline matter is calcium hydroxide.
- 7. according to the method for claim 1 synthesis product, wherein, the product respectively with poly carboxylic acid series water reducer, fibre The plain sulfuric acid based water reducer compounding of dimension；The compound proportion of ligno-sulfate based plasticizer and poly carboxylic acid series water reducer for 1: 1 or The compound proportion of person's ligno-sulfate based plasticizer and cellulose sulfuric acid ester salt water-reducing agent is 7: 3.
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| CN111072991A (en) * | 2019-12-24 | 2020-04-28 | 鞍钢集团矿业有限公司 | Preparation method of bio-based sulfonate for improving saline-alkali soil |
| CN115180862B (en) * | 2022-08-09 | 2023-08-08 | 佛山建发东方雨虹建材科技有限公司 | Preparation method of high-quality lignosulfonate water reducer |
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| CN103360499A (en) * | 2012-04-11 | 2013-10-23 | 厦门大学 | Simple synthesis process of cellulose sulfate |
| CN103539952A (en) * | 2012-07-10 | 2014-01-29 | 厦门大学 | Novel humic acid sulfonatiion process |
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| CN103360499A (en) * | 2012-04-11 | 2013-10-23 | 厦门大学 | Simple synthesis process of cellulose sulfate |
| CN103539952A (en) * | 2012-07-10 | 2014-01-29 | 厦门大学 | Novel humic acid sulfonatiion process |
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