CN102180615A - Modified alkali lignin cement grinding aid and preparation method thereof - Google Patents
Modified alkali lignin cement grinding aid and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified alkali lignin cement grinding aid and a preparation method thereof. According to mass portions, the formula of the cement grinding aid includes the following ingredients: 200 portions of alkali lignin, 10-20 portions of oxidant, 10-20 portions of activating agent, and 20-50 portions of polar additive, wherein the alkali lignin is bamboo pulp or straw pulp papermaking black liquor alkali lignin treated by acidification, and the mass percentage of solid content in the alkali lignin is 95%. In the preparation method, the alkali lignin is taken as a main raw material, and the oxidant, the activating agent and the polar additive are added, thus obtaining the efficient alkali lignin cement grinding aid through activation and oxidation reactions. The product with low additive amount of 0.1% has good grinding aid and enhancing capabilities on cement clinker and admixture, and has less influence on the setting time of cement. The comprehensive performance of the modified alkali lignin cement grinding aid is far better than that of a traditional alkali lignin sulfonate grinding aid, and is comparable to the efficiency of a triethanolamine grinding aid. The product is wide in raw material sources, low in prices of raw materials, simple in process and low in production cost, thus being a novel green efficient cement grinding aid.
Description
Technical field
The present invention relates to cement grinding aid, particularly relate to the method that the oxidation modification of a kind of black liquid of straw pulp paper-making acid out alkali lignin prepares cement grinding aid.Be to be raw material specifically, under normal pressure, prepare a kind of modification alkali lignin high-efficiency concrete grinding aid through overactivation, oxidizing reaction with black liquid of straw pulp paper-making acid out alkali lignin.
Background technology
Cement grinding aid is a kind of chemical additive that improves cement grinding effect and performance, the grinding process that is used for cement material, adding a spot of grinding aid can significantly improve mill efficiency or cut down the consumption of energy, and significantly improve cement unit-hour output and every technical indicator, and don't the performance of infringement cement self.As a kind of chemical activator, grinding aid can improve the cement granules distribution and excite aquation power, thereby improves cement early strength and later strength.The energy consumption that China's Cement industry is produced accounts for 80% of building materials industry energy consumption, account for 8.7% of national industrial production total energy consumption, " energy-saving and emission-reduction " of the application feedwater bricklayer industry of cement grinding aid and the benefit that sustainable development of cement industry is brought, considerably beyond the value of itself, it has become the indispensable subsidiary material of Cement industry.
Industrial inorganic salt of domestic most employing and simple polymerisation organic salt are the main component of grinding aid.The addition height of mineral-type grinding aid, usefulness is low, and is big to the performance impact of cement itself; Organic Grinding Aid is mainly liquid agent, and based on amine, alcohols, alcamines, lipid acid and its esters, alkyl sulfonates, lignosulfonic acid salt isopolarity organism, addition is lower, and usefulness is higher, and is less to the performance impact of cement itself.Except sulfonated lignin, other Organic Grinding Aid mainly all derives from fossil class raw material, exists raw material sources to face exhaustion, problem that cost is high.Therefore, be that raw material is developed the problem that high-efficiency concrete grinding aid can effectively solve the in short supply of petroleum resources and paper industry environmental pollution with the alkali lignin in abundant, the cheap black liquid of originating, promote the development of recycling economy.
The patent No. is that 01128350 Chinese invention patent discloses a kind of hydramine series cement grinding aid of being made up of the mother liquor of 70%～80% trolamine and 20%～30%, and wherein mother liquor is mainly formulated by a certain percentage by sulfonated lignin, alkyl polyglycoside, sodium humate, Sodium dodecylbenzene sulfonate, fatty alcohol-polyoxyethylene ether isopolarity organism and water.The patent No. is that 200710055027 Chinese invention patent discloses and a kind ofly is made up of 10%～30% trolamine, 12%～30% tri-isopropanolamine, 5%～20% ethylene glycol, 3%～10% propylene glycol, 15%～40% water, 1%～5% Sodium dodecylbenzene sulfonate, 3%～10% xylogen, 2%～5% anhydrous sodium sulphate.
Korean Patent (KR 2006105954-A) " Grinding aid for mineral microgrinding which can improve grinding and hydration properties of miner
From present cement grinding aid patent both domestic and external, lignin derivative is existing the application in cement grinding aid, but is used for the liquid grinding aid prescription mainly as supplementary additive.Use more lignin derivative at present and be mainly sulfonated lignin, mainly come from the lignosulfonic acid salt that the acid system papermaking wastewater extracts, comprise sodium, calcium, magnesium and ammonia salt etc., have the source complexity, sulfonic group content is lower, the characteristics that range of molecular weight distributions is wide.Because sulfonated lignin are lower in the adsorptive power of cement surface, and because range of molecular weight distributions is wide, the molecule utilising efficiency of sulfonated lignin is lower, absorption fraction of coverage at cement particle surface is also lower, therefore these shortcomings of sulfonated lignin cause its grinding aid poor-performing in cement grinding, have also caused it to be difficult to be widely used in the cement grinding as a kind of high performance grinding aid.
Summary of the invention
The objective of the invention is to strengthen the relatively poor shortcoming of ability and develop a kind of high performance alkali lignin base cement grinding aid and preparation method thereof at the grinding aid of existing lignosulfonic acid salt cement grinding aid.
Alkali lignin base cement grinding aid is through overactivation and oxidation modification and have lower molecular weight distribution, hydroxy-acid group content in the molecule is higher, has stronger adsorptive power at cement particle surface, and the absorption fraction of coverage because molecular weight is lower at cement particle surface also improves greatly, and the molecule utilising efficiency also greatly improves.This grinding aid is a main component with the xylogen, has overcome the shortcoming of lignin-base grinding aid poor-performing, under lower addition cement is had good grinding aid and strengthens ability.
Purpose of the present invention realizes by the following method:
A kind of preparation method of modification alkali lignin cement grinding aid may further comprise the steps and processing condition:
(1) alkali lignin is mixed with water to obtain mass percent concentration be 25～35% suspension, stir down and regulate pH to 10～12, be heated to 60～90 ℃ of dissolvings fully, add the activator in the prescription, under 70～90 ℃, carry out priming reaction 0.5～1.5 hour, and got reaction solution;
(2) oxygenant being mixed with mass percent concentration is 10～20% solution, is added drop-wise under 60～90 ℃ in step (1) the gained reaction solution, then 70 ~ 90 ℃ of reactions 2～4 hours down; Add polar additive again, reacted 1～2 hour down at 70 ~ 90 ℃; Reaction finishes postcooling to room temperature and obtains modification alkali lignin cement grinding aid liquid product;
In mass fraction, the consumption of alkali lignin, oxygenant, activator and polar additive is respectively 200 parts, 10～20 parts, 10～20 parts and 20～50 parts;
Described alkali lignin is bamboo pulp or black liquid of straw pulp paper-making acid out alkali lignin, its solid content mass percent 93% ~ 97%;
Described oxygenant is one or more in potassium permanganate, hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Sodium peroxoborate and the clorox;
Described activator is one or more in diacetone alcohol, diethylene glycol monobutyl ether, n-Octanol, lauryl alcohol, nonylcarbinol and the phenylcarbinol;
Described polar additive is one or more in Diethylene Glycol, dipropylene glycol, glycerol, hydroxy acid sodium, Sunmorl N 60S and the Trisodium Citrate.
For further realizing the object of the invention, the preferred NaOH of employing regulates the pH value in the step (1).
The oxygenant of step (2) preferably was added drop-wise in 30～60 minutes in step (1) the gained reaction solution.
Described polar additive is preferably one or both in Diethylene Glycol, dipropylene glycol, glycerol, hydroxy acid sodium, Sunmorl N 60S and the Trisodium Citrate.
A kind of modification alkali lignin cement grinding aid is by method for preparing.
The present invention except that alkali lignin all by pure content.
The present invention compared with prior art has following outstanding advantage and effect:
1, production process of the present invention is carried out under atmospheric low-temperature, and easy handling control has the advantage that technology is simple, efficient is high, production cost is low.Product good water solubility, free from extraneous odour, nontoxic, belong to green chemical.The present invention is applicable to that industrial alkali paper-making black liquor acid out alkali lignin prepares cement grinding aid, also can offer reference for black liquor such as industrial soda method wood pulp, bamboo pulp, bagasse pulp prepare cement grinding aid.
2, lignin-base high-efficiency concrete grinding aid of the present invention has good grinding aid to cement clinker and blended material and strengthens the property, under 0.1% addition, 45 μ m of cement clinker and blended material are tailed over reduce per-cent and reach 37.37%, make 28 days intensity of cement improve 5%, very little to the influence of cement setting time simultaneously, the high-efficiency concrete grinding aid that belongs to a kind of grinding aid enhancement type, its grinding aid is strengthened the property considerably beyond the plain sulfonate cement grinding aid of conventional wooden, has reached the level of hydramine series cement grinding aid (mainly being trolamine).
3, cement grinding aid of the present invention is main raw material with the alkali lignin, raw material sources are wide, production technique is simple, cheap, the raw material that not composite any hydramine is a grinding aid in the product, thus product of the present invention to belong to truly be the lignin-base high-efficiency concrete grinding aid of main raw material with the xylogen.Preparation method of the present invention above the modification that can be applied in black liquid of straw pulp paper-making acid out alkali lignin, can also offer reference for the modification of industrial alkali technique pulp, bamboo pulp, bagasse black liquor acid out alkali lignin.Improved the utility value of alkali paper-making black liquor, thereby increased the enthusiasm that factory utilizes black liquor recovery, therefore, the present invention has economy and environmental protection double effect.
Description of drawings
Fig. 1 is the molecular weight distribution gel chromatography figure of modification alkali lignin cement grinding aid.
Fig. 2 is the surface tension figure of modification alkali lignin cement grinding aid.
Embodiment
The invention will be further described below in conjunction with specific embodiments and the drawings.
Embodiment 1
Get 200 gram alkaline process straw pulp black liquor acid out alkali lignin (weight percent meters, solid content is 95%) be mixed in the 400 gram water, add sodium hydroxide and regulate pH to 10.5, it is abundant to be heated to 60 ℃ of stirring and dissolving then, add 10 gram diethylene glycol monobutyl ethers, under 70 ℃, carry out priming reaction 1.5 hours, and got reaction solution.10 gram ammonium persulphates are dissolved in the 60 gram water, under 60 ℃, in 30 minutes, slowly are added drop-wise in the reaction solution, under 80 ℃, carried out oxidizing reaction 2 hours then.Add 20 gram glycerol then, reacted 1 hour down at 85 ℃.Reaction finishes postcooling to room temperature and obtains modification alkali lignin cement grinding aid liquid product.
Embodiment 2
Get 200 gram alkali lignin alkaline process straw pulp black liquor acid out alkali lignin (weight percent meters, solid content is 95%) be mixed in the 433 gram water, add sodium hydroxide and regulate pH to 10, it is abundant to be heated to 70 ℃ of stirring and dissolving then, add 15 gram n-Octanols, under 80 ℃, carry out priming reaction 1 hour, and got reaction solution.The hydrogen peroxide of 30 grams, 50% content are dissolved in the 120 gram water, under 70 ℃, in 45 minutes, slowly are added drop-wise in the reaction solution, under 70 ℃, carried out oxidizing reaction 3 hours then.Add 30 gram Diethylene Glycols then, reacted 2 hours down at 70 ℃.Reaction finishes postcooling to room temperature and obtains modification alkali lignin cement grinding aid liquid product.
Embodiment 3
Get 200 gram alkali lignin alkaline process straw pulp black liquor acid out alkali lignin (weight percent meters, solid content is 95%) be mixed in the 560 gram water, add sodium hydroxide and regulate pH to 11, it is abundant to be heated to 80 ℃ of stirring and dissolving then, add 20 gram nonylcarbinols, under 90 ℃, carry out priming reaction 1.5 hours, and got reaction solution.20 gram Sodium peroxoborate are dissolved in the 80 gram water, under 80 ℃, in 60 minutes, slowly are added drop-wise in the reaction solution, under 90 ℃, carried out oxidizing reaction 4 hours then.Add 30 gram Sunmorl N 60Ss and 10 gram dipropylene glycol mixtures then, reacted 1.5 hours down at 90 ℃.Reaction finishes postcooling to room temperature and obtains modification alkali lignin cement grinding aid liquid product.
Embodiment 4
Get 200 gram alkali lignin alkaline process bamboo pulp black liquor acid out alkali lignin (weight percent meters, solid content is 93%) be mixed in the 342 gram water, add sodium hydroxide and regulate pH to 12, it is abundant to be heated to 90 ℃ of stirring and dissolving then, add 10 gram diacetone alcohols and 8 gram lauryl alcohol mixtures, under 85 ℃, carry out priming reaction 1 hour, and got reaction solution.5 gram potassium permanganate and 7 gram Sodium Persulfate mixtures are dissolved in the 70 gram water, under 90 ℃, in 30 minutes, slowly are added drop-wise in the reaction solution, under 85 ℃, carried out oxidizing reaction 4 hours then.Add 50 gram hydroxy acid sodiums then, reacted 1.5 hours down at 85 ℃.Reaction finishes postcooling to room temperature and obtains modification alkali lignin cement grinding aid liquid product.
Embodiment 5
Get 200 gram alkali lignin alkaline process bamboo pulp black liquor acid out alkali lignin (weight percent meters, solid content is 93%) be mixed in the 450 gram water, add sodium hydroxide and regulate pH to 11.5, it is abundant to be heated to 75 ℃ of stirring and dissolving then, add 12 gram phenylcarbinols, under 80 ℃, carry out priming reaction 0.5 hour, and got reaction solution.The chlorine bleach liquor of 160 grams, 10% content slowly is added drop-wise in the reaction solution under 85 ℃, in 45 minutes, under 90 ℃, carried out oxidizing reaction 2.5 hours then.Add 20 gram dipropylene glycols and 15 gram Trisodium Citrate mixtures then, reacted 2 hours down at 75 ℃.Reaction finishes postcooling to room temperature and obtains modification alkali lignin cement grinding aid liquid product.
The comparative example
Table 1 is that embodiment 3 products are carried out carrying out structural characterization behind the ultrafiltration purification.Select the ultra-filtration membrane of 1000 molecular weight and 100000 molecular weight, product earlier by the film of 100000 molecular weight, is removed undissolved solid substance impurity; By the film of 1000 molecular weight, remove the small molecular weight impurity by film then, the component by film is not the back product of purifying.The back product of will purifying adopts hcl acidifying, and the low temperature vacuumizing and drying obtains the product powder then.After testing, it is as shown in table 1 to record the functional group content data of modification alkali lignin.
Adopt crusher that grog and gypsum are crushed to 1 ~ 2mm particle diameter, proportionally (95% grog, 5% gypsum) mixes, and adds 0.1% grinding aid (accounting for the butt mass percent of total material), drops into grinding 16min in the SM500 test mill.Take by weighing sample 10g(then and be accurate to 0.01 g), place clean negative pressure screen analyzer (45 μ m sieve) screen analysis 2 min continuously, the quality of the screenings that weighs with scale is calculated 45 microns mass percents that tail over.The result is as showing 2(embodiment 3 products and the trolamine grinding aid performance comparison data to grog and blended material) shown in.
Take by weighing grinding gained cement 400g, according to GB/ T1 7671-1999 with water cement ratio 0.55 sample preparation, cement and sand mass ratio are 1/3, measure the folding strength and the ultimate compression strength of preparation cement block sample, the result is as showing 3(embodiment 3 products and the trolamine correlation data of strengthening the property to grog and blended material) shown in.
Take by weighing grinding gained cement 400g, use Vicat apparatus according to measuring cement setting time according to GB/T 1346-2001, the result is as showing 4(embodiment 3 products and the trolamine correlation data to the cement setting time influence) shown in.
As shown in table 1, carboxylic acid group's content of the product after embodiment 3 products are purified through ultrafiltration is 8.69%, be higher than the raw material alkali lignin 5.58% and sodium lignosulfonate 6.36%; The content of phenolic hydroxyl groups of embodiment 3 products is 2.82%, be higher than the raw material alkali lignin 1.96% and sodium lignosulfonate 0.97%.As seen, the oxidation modification reaction is greatly improved the carboxylic acid group of alkali lignin and phenolic hydroxyl group isopolarity group content tool.Carboxylic acid group and phenolic hydroxyl group belong to strong polar functional group, in cement pulverizing course, can be adsorbed on the newborn active site of cement and prevent that reassembling of cement granules is agglomerating, so the raising of carboxylic acid group and content of phenolic hydroxyl groups helps the raising of alkali lignin grinding aid performance.
Table 1
Table 2
Table 3
Table 4
As shown in table 2, embodiment 3 products tail over by barren 7.76% 45 μ m of grinding to drop to 4.86%, and the decline ratio is 37.37%; Trolamine tails over by barren 7.76% 45 μ m to drop to 4.96%, and the decline ratio is 36.08%.From table 2 data as can be seen, embodiment 3 products and trolamine are suitable to the grinding aid performance of grog and blended material, slightly are better than trolamine.
As shown in table 3, embodiment 3 products make cement folding strength was by blank in 28 days the time 7.3 MPa bring up to 8.7MPa, trolamine make cement folding strength was by blank in 28 days the time 7.8 MPa bring up to 7.8MPa; Embodiment 3 products make cement ultimate compression strength was by blank in 28 days the time 36.0MPa bring up to 37.8MPa, and trolamine make cement ultimate compression strength was by blank in 28 days the time 36.0 MPa bring up to 37.4MPa.From table 3 data results as can be seen embodiment 3 products strengthening the property of cement slightly is better than trolamine.
As shown in table 4, embodiment 3 products make the presetting period of cement become 81min by 61min, make the final setting time of cement become 126min by 105min, so embodiment 3 products are slightly influential to cement setting time, but influence lessly, be lower than in the 30min scope of industry standard regulation.Trolamine is very little to the influence of the slow setting time of cement.
By above-mentioned data as can be seen, embodiment 3 products have good grinding aid and enhancing ability to cement clinker and blended material, have reached the usefulness of hydramine series cement grinding aid, and less to the influence of presetting period of cement and final setting time.
Because alkali lignin belongs to macromolecular compound, too high molecular weight is unfavorable for the molecule utilising efficiency of alkali lignin, breaks the bodily form macromolecular structure of alkali lignin by chemical reaction, reduces its molecular weight distribution, helps improving its grinding aid performance.As shown in Figure 1, adopt gel chromatography (GPC) method to measure the molecular weight distribution of embodiment 3 products, and compare with the raw material alkali lignin.As can be seen from Figure 1, the weight average molecular mass (Mw) of embodiment 3 products is 4505, and number average molecular mass (Mn) is 1240, and polydispersity index (Mw/ Mw) is 3.63; The Mw of raw material alkali lignin is 6636, and Mn is 2679, and polydispersity index (Mw/ Mw) is 2.48.Modified-reaction slightly reduces the molecular weight of raw material alkali lignin as can be seen, the polydispersity index of product also tool is greatly improved, therefore embodiment 3 products are greatly improved as the molecule utilising efficiency tool of grinding aid, strengthen the property also to the grinding aid of cement that tool has greatly improved, strengthening data results from the grinding aid of table 2 and table 3 also can prove.
A kind of good grinding aid must have the surface of good activity, because in cement pulverizing course, have surface-active grinding aid molecule and be penetrated into easily in the newborn crack of cement, produce " chock " effect, and therefore the grinding of acceleration cement granules produces the grinding aid effect.Embodiment 3 products just have stronger interfacial activity, and as shown in Figure 2, embodiment 3 products have the ability of strong reduction solution surface tension in the aqueous solution, and the lowest surface tension of its aqueous solution can reach 26mN.m
-1About, and the lowest surface tension of unmodified alkali lignin in the aqueous solution is 42mN.m
-1About.This explanation embodiment 3 products have stronger interfacial activity, and are better in the wetting and spreading ability of cement particle surface, therefore cement had grinding-aid effect preferably.
After tested, embodiment 1,2,4,5 products obtained therefrom performances and embodiment 3 basically identicals do not repeat one by one.
Claims (5)
1. the preparation method of a modification alkali lignin cement grinding aid is characterized in that may further comprise the steps and processing condition:
(1) alkali lignin is mixed with water to obtain mass percent concentration be 25～35% suspension, stir down and regulate pH to 10～12, be heated to 60～90 ℃ of dissolvings fully, add the activator in the prescription, under 70～90 ℃, carry out priming reaction 0.5～1.5 hour, and got reaction solution;
(2) oxygenant being mixed with mass percent concentration is 10～20% solution, is added drop-wise under 60～90 ℃ in step (1) the gained reaction solution, then 70 ~ 90 ℃ of reactions 2～4 hours down; Add polar additive again, reacted 1～2 hour down at 70 ~ 90 ℃; Reaction finishes postcooling to room temperature and obtains modification alkali lignin cement grinding aid liquid product;
In mass fraction, the consumption of alkali lignin, oxygenant, activator and polar additive is respectively 200 parts, 10～20 parts, 10～20 parts and 20～50 parts;
Described alkali lignin is bamboo pulp or black liquid of straw pulp paper-making acid out alkali lignin, its solid content mass percent 93% ~ 97%;
Described oxygenant is one or more in potassium permanganate, hydrogen peroxide, ammonium persulphate, Sodium Persulfate, Sodium peroxoborate and the clorox;
Described activator is one or more in diacetone alcohol, diethylene glycol monobutyl ether, n-Octanol, lauryl alcohol, nonylcarbinol and the phenylcarbinol;
Described polar additive is one or more in Diethylene Glycol, dipropylene glycol, glycerol, hydroxy acid sodium, Sunmorl N 60S and the Trisodium Citrate.
2. the preparation method of modification alkali lignin cement grinding aid according to claim 1 is characterized in that adopting in the step (1) NaOH to regulate the pH value.
3. the preparation method of modification alkali lignin cement grinding aid according to claim 1, the oxygenant that it is characterized in that step (2) is to be added drop-wise in 30～60 minutes in step (1) the gained reaction solution.
4. the preparation method of modification alkali lignin cement grinding aid according to claim 1 is characterized in that described polar additive is one or both in Diethylene Glycol, dipropylene glycol, glycerol, hydroxy acid sodium, Sunmorl N 60S and the Trisodium Citrate.
5. a modification alkali lignin cement grinding aid is characterized in that: by the described method preparation of claim 1.
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