CN107226636A - A kind of retarder and preparation method thereof - Google Patents
A kind of retarder and preparation method thereof Download PDFInfo
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- CN107226636A CN107226636A CN201710416076.6A CN201710416076A CN107226636A CN 107226636 A CN107226636 A CN 107226636A CN 201710416076 A CN201710416076 A CN 201710416076A CN 107226636 A CN107226636 A CN 107226636A
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
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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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
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Abstract
The present invention provides a kind of retarder being prepared from by corn starch wastewater, wherein it is 3~6 to be esterified substituted carbohydrate, protein and amino acids material, succinic acid starch ester, soluble cellulose, the mass ratio of aliphatic acid：10~20：50~100:20~30:1~3.Modified starch is succinic acid starch ester, and the glucide of esterification substitution reacts obtained derivative for glucide itself hydroxyl in production of corn starch waste water with esterifying reagent.The preparation method of the retarder of the present invention, including the component content of waste water determine, heat concentration, starch and the modification of glucide and pH value regulation.The present invention carries out recycling to production of corn starch waste water, and the retarder of preparation is with low cost, energy-conserving and environment-protective, and with good dispersiveness, retarding effect is good, hydration heat is uniform, bleed effect is good, be particularly suitable as concrete pump-feed agent and use.
Description
Technical field
The present invention relates to a kind of retarder and preparation method thereof, and in particular to a kind of to be prepared by production of corn starch waste water
Retarder and preparation method thereof, belongs to concrete additive technical field.
Background technology
Starch is a kind of very important raw material of industry, except edible with addition to processed food, being also widely used for weaving, making
The industries such as paper, medicine, fermentation, casting, gluing, chemical industry, machinery and drilling well.
At present, China is when carrying out Starch Production, and about 80% using corn as raw material, during production, can produce substantial amounts of
Organic wastewater, directly outer row not only makes Starch Production cost high, and water consumption is more, and corn loss is big, and due in production waste water
The corruption of the organic matters such as protein, aliphatic acid, makes water quality black smelly, and the dissolved oxygen in water can be consumed by being discharged into rivers, promote algae
Class and water plant breeding, occur anaerobism corruption, distribute stench, and the aquatic animal such as fish, shrimp, shellfish may therefore death by suffocation
Die.Accordingly, it would be desirable to handle corn starch wastewater.
At present, the processing method of starch production wastewater mainly has biological treatment, membrane separation process, flocculence etc..These methods
Although environmental pollution can be reduced to a certain extent, there is certain limitation, and beneficiating ingredient therein can not be returned
Receive.As anaerobic fermentation starts slow in Biochemical method, influenceed big, it is necessary to strict controller operating condition by pH value and temperature,
Operating cost is high；Active carbon adsorption technology limited sorption capacity, it is necessary to frequent regeneration when being adsorbed to high-concentration waste water；Film process
Technical finesse waste water, filter membrane is easily blocked；Flocculence handles waste water, and clearance is low.
Therefore, how the simple and effective recycling treatment for realizing starch is utilized, and is a current technical barrier.
Concrete retarder, is the additive for delaying concrete coagulating time and being had no significant effect to later strength, is applicable
In continuous concreting, mass concrete, ready-mixed concrete and pump concrete under hot conditions.Existing retarder has
Inorganic type, organic type, inorganic organic mixed, polymer-type.Inorganic type include sodium phosphate, sodium tripolyphosphate, hexa metaphosphoric acid
Sodium, sodium pyrophosphate etc., organic type include sodium gluconate, molasses, citric acid, 1-hydroxy ethylidene-1,1-diphosphonic acid, the methene phosphine of amino three
Acid, maltodextrin, sucrose, white sugar, tartaric acid etc.；Polymer-type：Polymer, acid anhydrides and the day of acrylic acid and hydroxy-ethyl acrylate
Polymer of the polymer of winter propylhomoserin, maleic acid and AMPS etc..It is increasingly deficient with the resource and the energy in the whole world, find new
, energy-conserving and environment-protective, the retarder that can turn waste into wealth, as a new problem.
To solve the recycling of production of corn starch waste water, inventor carries out recycling to production of corn starch waste water
Processing, be prepared for energy-conserving and environment-protective, with low cost, the retarder worked well.
The content of the invention
It is contemplated that carrying out recycling to production of corn starch waste water, production of corn starch waste water is carried out dense
Contracting, protein hydrolysis, starch conversion, glucide esterification substitution, obtain a kind of retarder, realize production of corn starch waste water
Recycling treatment, the retarder of preparation is with low cost, energy-conserving and environment-protective, and with good dispersiveness, retarding effect well, water
Change heat release is uniform, bleed effect is good, is particularly suitable as concrete pump-feed agent and uses.
Cornstarch is in production, by processes such as Feedstock treating, immersion, crushing, sieving, separating starch, washing, dryings
Composition.In production process, the carbohydrate that the main component in substantial amounts of organic wastewater, waste water is 0.3%~0.7% or so can be produced
Material, glucide is also containing 1.0%~2.0% or so egg in the mixed sugar of maltose, glucose, fructose etc., waste water
White matter, 5%~10% or so starch solid content, 2%~3% or so soluble cellulose, including cellulose, hemicellulose
And lignin, include 0.1%~0.3% or so aliphatic acid.
Prior art is when handling production of corn starch waste water, conventional method biological treatment, membrane separation process, wadding
Solidifying method etc., it is impossible to the utilization of recycling is carried out to starch production wastewater.Prior art also has to be carried out to production of corn starch waste water
Recycling treatment and prepare culture medium, liquid organic fertilizer, or the protein component in cornstarch is extracted.Not yet
It is found and recycling treatment is carried out to corn waste water, so as to obtains the prior art of retarder.
The invention provides a kind of retarder, be include soluble cellulose class material, protein and amino acids material,
Modified starch, esterification substitution glucide, and aliphatic acid mixed aqueous solution.
Further, the retarder that the present invention is provided is production of corn starch waste water by concentration, protein hydrolysis, shallow lake
The retarder that powder is modified, glucide esterification substitution is obtained.
Further, retarder of the invention, soluble cellulose class material is solvable in production of corn starch waste water
Cellulose, hemicellulose and the lignin of property.Due to the soluble cellulose class material in production of corn starch waste water be by
Water-soluble cellulose and hemicellulose after partial hydrolysis, also include partial lignin certainly.Above composition has the work of slow setting
With, and the other compositions cooperation in retarder, good retarding effect can be produced, so, the present invention does not give birth to cornstarch
Soluble cellulose in production waste water is modified processing.
Further, retarder of the invention, modified starch be production of corn starch waste water in obtained by starch conversion
Succinic acid starch ester.Starch can not be used separately as a kind of retarder, in order to obtain retarder, typically be carried out pre-
It is gelatinized, or is prepared into dextrin and use, Jiangsu Subotexin Material Co., Ltd's trial prepares dextrin-- starch composite junction
Structure material, is used as retarder.But, above method is not appropriate for production of corn starch waste water and prepares retarder practicality.
The present invention attempts the starch in corn starch wastewater and carbohydrate carrying out comprehensively modifying, using succinic anhydride in water
It is under alkalescence condition, by starch conversion, to generate succinic acid starch ester, the substitution value of succinic acid starch ester is 0.02~0.25.Together
When, the glucide in production of corn starch waste water, including glucose, maltose, sucrose, fructose mixture, also by succinic acid
Acid anhydride is esterified.Succinic acid starch ester has good dispersiveness, and water-reducing effect is good, and with deferred action.Carbohydrate thing after esterification
Matter, can reduce the hydration rate of accelerated period and deceleration period, reduce the aquation temperature rise of concrete, put so as to play good aquation
Hot regulating effect.
Protein is also one of material in production of corn starch waste water, in addition to conventional method of wastewater treatment, is also had
Recovery of the scholar to protein is studied, still, because content of the protein in production of corn starch waste water is not
Very high, it, which is carried out, to reclaim needs substantial amounts of cost, loses more than gain.Moreover, through recovery protein waste water need for into
Row environmental protection treatment, adds handling process, wastes time and energy.Protein is hydrolyzed the present invention, obtains amino acid, and incomplete
The protein of reaction together, as the aliphatic acid in Maize Production waste water, with good bleed effect.Match somebody with somebody with remaining composition
Close, a kind of good pumping admixture can be used as.
The retarder that the present invention is provided, be esterified substitution carbohydrate, protein and amino acids material, succinic acid starch ester,
Soluble cellulose, the mass ratio of aliphatic acid are 3~6：10~20：50~100:20~30:1~3.
The present invention provides a kind of preparation method of retarder, comprises the following steps：
Step one：The component content of production of corn starch waste water is determined：
Starch production wastewater is collected first, determines soluble cellulose, glucide, egg in production of corn starch waste water
White matter, starch, the content of aliphatic acid, method of testing are carried out using traditional test methods.In general, production of corn starch waste water
In the weight/mass percentage compositions of various materials be：The glucide of 0.3%~0.6% weight/mass percentage composition, 1.0%~2.0%
The protein of weight/mass percentage composition, the starch of 5%~10% weight/mass percentage composition, the solubility of 2%~3% weight/mass percentage composition
Cellulose, the aliphatic acid of 0.1%~0.3% weight/mass percentage composition.After being completed, the Soluble Fiber in production waste water is calculated
Element, glucide, protein, starch, the quality of aliphatic acid.
Step 2：Heating concentration：
The production of corn starch waste water for carrying out concentration mensuration is concentrated, thickening temperature is 100~120 DEG C, during concentration
Between be 3~5h, until wherein protein mass concentration be 5%~10%, obtain the first mixed liquor.
Step 3：Protein is hydrolyzed：
The first mixed liquor after step 2 is concentrated uses the first pH value regulator, pH value is adjusted to 2~3, pH value is adjusted
It is soluble acid solution, preferably sulfuric acid or hydrochloric acid solution to save agent, and stirring is heated to 40~50 DEG C, then adds acidic protein
Enzyme, proceeds by hydrolysis, is incubated 8~20h, and hydrolysis is completed, and obtains the second mixed liquor, acid protease is preferably black song
Mould, the consumption of aspergillus niger is the 10% of protein wt.The hydrolysis of protein, generally requires longer time, still, due to step
Rapid two pairs of production of corn starch waste water has carried out heating concentration at 100~120 DEG C, not only makes mass concentration of the protein in water
A suitable scope is reached, and generates good thermal effectiveness, contributes to the hydrolysis of protein.
Step 4：The modification of starch and glucide：
The second mixed liquor that step 3 is obtained is adjusted using the second pH value regulator regulation pH value to 8~9, second pH value
The preferred sodium hydroxide solution of agent, stirring, keeping temperature is 25~30 DEG C, then in 2~3h, divides 2~3 times and fourth two is added portionwise
Acid anhydrides, the addition of succinic anhydride is the 2~12% of starch and glucide quality sum, then 3~5h of insulated and stirred, starch
Starch synthesis in waste water is succinic acid starch ester, and completes esterification substitution sugared in starch production wastewater, obtains the 3rd mixing
Liquid.Due in step 2, heating concentration having been carried out to production of corn starch waste water, now the weight/mass percentage composition of starch
25~50% or so, when also causing this step starch conversion, in a relatively good CONCENTRATION STATE, so that starch exists
Esterification under the conditions of aqueous alkaline is possibly realized, while also providing good condition for the esterification substitution of glucide.This hair
The bright modification for cleverly having carried out starch and glucide, and the modification of starch and glucide is carried out together, substantially reduce
While processing cost, good scattered and retarding effect is also played.
Step 5：PH value is adjusted：
The pH value for adjusting the 3rd mixed liquor using the first pH value regulator obtains retarder to 6.5~7.5.
The present invention is when pH value regulator is selected, from sulfuric acid, hydrochloric acid and sodium hydroxide solution.
The present invention uses above technical scheme, achieves following technique effect.
1st, the present invention uses simple and effective processing method, and production of corn starch waste water has been carried out into recycling, makes
For into concrete retarder, turn waste into wealth, be conducive to environmental protection.
2nd, retarder of the invention, through concrete experiments, its in concrete system setting time and 28d compression strength with
Quite, this is due to succinic acid starch ester present in the retarder of the present invention to commercial glucose saccharic acid sodium retarder, and is esterified
Substituted glucide and cellulose substances, above comprehensive function, so as to show good retarding effect.
3rd, retarder of the invention, in concrete system, its slump and divergence and holding capacity are substantially better than
The sour sodium of commercially available conventional glucose.This is because, the succinic acid starch ester in the retarder of the present invention has outstanding dispersiveness, carry
Supply good water-reducing rate, and protein and amino acid substance in retarder, and aliphatic acid, serve good bleed effect
Really, concrete system of the concrete 's air-containing higher than addition sodium gluconate retarder.
4th, retarder of the invention, synthetic method is ingenious.The step of heating concentration, not only protein is set to be easy in one kind
The concentration of enzyme hydrolysis, moreover, serving good pre-heat effect, realizes the hydrolysis of protein in acid condition.And heat dense
The step of contracting, the concentration of starch is also controlled in good scope, under the conditions of aqueous alkaline, generated succinic acid starch
Ester, meanwhile, glucide is esterified, helps to reduce the heat of hydration, the modification of starch and carbohydrate carries out simultaneously, it is to avoid multistep is anti-
Answer waste of manpower and resource.
Embodiment
In order that the purpose of the present invention, technical scheme and beneficial effect are more clearly understood, with reference to embodiments, to this
Invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, and without
It is of the invention in limiting.As long as in addition, technical characteristic involved in each embodiment of invention described below is each other
Between do not constitute conflict can just be mutually combined.
In order to carry out the recycling of production of corn starch waste water, turned waste into wealth, be used as a kind of concrete retarding
Agent is used, and the present invention provides a kind of retarder prepared by production of corn starch waste water.Retarder is to include soluble cellulose
The mixed liquor of the glucide of class material, protein and amino acids material, modified starch and esterification substitution.
Protein and amino acid therein, are the product of protein hydrolysis in corn starch wastewater or partial hydrolysis；
Modified starch is the succinic acid starch ester obtained by butanedioic anhydride modification；The glucide of esterification substitution is production of corn starch
Glucide itself hydroxyl in waste water and esterifying reagent react obtained derivative, wherein glucide be include glucose,
The mixture of maltose, sucrose, fructose etc.；Soluble cellulose class material is the Soluble Fiber in production of corn starch waste water
Element, hemicellulose and lignin.
The retarder that the present invention is provided, be esterified substitution carbohydrate, protein and amino acids material, succinic acid starch ester,
Soluble cellulose, the mass ratio of aliphatic acid are 3~6：10~20：50~100:20~30:1~3.
The production method of the production of corn starch waste water of the present invention, collects production of corn starch waste water, test is wherein first
Soluble cellulose, glucide, protein, the content of starch and aliphatic acid.Method of testing is traditional test methods.Through surveying
Try, the content range of each material in production of corn starch waste water is：The glucide of 0.3%~0.6% weight/mass percentage composition,
The protein of 1.0%~2.0% weight/mass percentage composition, the starch of 5%~10% weight/mass percentage composition, 2%~3% mass percentage
The soluble cellulose of content, the aliphatic acid of 0.1%~0.3% weight/mass percentage composition.
Embodiment 1
A kind of preparation method of retarder, comprises the following steps：
Step one：The component content of production of corn starch waste water is determined：
Collect production of corn starch waste water 1L, determine soluble cellulose therein, glucide, protein, starch and
The content of aliphatic acid, method of testing is carried out using traditional test methods.Calculate soluble cellulose, glucide, protein, shallow lake
The quality of powder and aliphatic acid.
Step 2：Heating concentration：
The production of corn starch waste water for carrying out concentration mensuration is concentrated, thickening temperature is 100 DEG C, and concentration time is 3
~5h, when the mass concentration of test wherein protein is 5%, stops concentration, obtains the first mixed liquor.
Step 3：Protein is hydrolyzed：
The first mixed liquor after step 2 is concentrated is adjusted its pH value to 2 with sulfuric acid solution, and stirring is heated to 40 DEG C,
Then aspergillus niger is added, the addition of aspergillus niger is the 10% of the protein quality that step one is calculated, proceeds by hydrolysis anti-
Should, 8h is incubated, the second mixed liquor is obtained.
Step 4：The modification of starch and glucide：
The second mixed liquor that step 3 is obtained adjusts pH value to 8 using sodium hydroxide solution, stirs, keeping temperature is 25
DEG C, then within 2 hours, point 2 addition succinic anhydrides, the addition of succinic anhydride is mixed equal to step one is calculated second
2% of starch and the mass fraction of glucide quality sum in liquid is closed, then insulated and stirred 3h, Starch synthesis is succinic acid shallow lake
Powder ester, and esterification substitution sugared in starch production wastewater is completed, obtain the 3rd mixed liquor.After tested, the Replacement rate of starch is
0.02。
Step 5：PH value is adjusted：
The pH value of the 3rd mixed liquor is adjusted to 6.5 using sulfuric acid, retarder is obtained.
Embodiment 2
A kind of preparation method of retarder, comprises the following steps：
Step one：The component content of production of corn starch waste water is determined：
Collect production of corn starch waste water 1L, determine soluble cellulose therein, glucide, protein, starch and
The content of aliphatic acid, method of testing is carried out using traditional test methods.Calculate soluble cellulose, glucide, protein, shallow lake
The quality of powder and aliphatic acid.
Step 2：Heating concentration：
The production of corn starch waste water for carrying out concentration mensuration is concentrated, thickening temperature is 120 DEG C, and concentration time is 3
~5h, when the mass concentration of test wherein protein is 10%, stops concentration, obtains the first mixed liquor.
Step 3：Protein is hydrolyzed：
The first mixed liquor hydrochloric acid solution after step 2 is concentrated, pH value is adjusted to 3, stirring is heated to 50 DEG C, so
After add aspergillus niger, the addition of aspergillus niger is 10% of the protein quality in the first mixed liquor, proceeds by hydrolysis,
20h is incubated, the second mixed liquor is obtained.
Step 4：The modification of starch and glucide：
The second mixed liquor that step 3 is obtained adjusts pH value to 9 using sodium hydroxide solution, stirs, keeping temperature is 30
DEG C, then within 3 hours, point 3 addition succinic anhydrides, the addition of succinic anhydride is mixed equal to step one is calculated second
12% of starch and the mass fraction of glucide quality sum in liquid is closed, then insulated and stirred 5h, the starch in starch wastewater
Succinic acid starch ester is synthesized, and completes esterification substitution sugared in starch production wastewater, the 3rd mixed liquor is obtained.After tested, form sediment
The Replacement rate of powder is 0.25.
Step 5：PH value is adjusted：
PH value is adjusted to 7.5 using hydrochloric acid, retarder is obtained.
Embodiment 3
A kind of preparation method of retarder, comprises the following steps：
Step one：The component content of production of corn starch waste water is determined：
Collect production of corn starch waste water 1L, determine soluble cellulose therein, glucide, protein, starch and
The content of aliphatic acid, method of testing is carried out using traditional test methods.Calculate soluble cellulose, glucide, protein, shallow lake
The quality of powder and aliphatic acid.
Step 2：Heating concentration：
The production of corn starch waste water for carrying out concentration mensuration is concentrated, thickening temperature is 115 DEG C, and concentration time is 3
~5h, when the mass concentration of test wherein protein is 6%, stops concentration, obtains the first mixed liquor.
Step 3：Protein is hydrolyzed：
The first mixed liquor sulfuric acid solution after step 2 is concentrated, pH value is adjusted to 2, stirring is heated to 45 DEG C, so
After add aspergillus niger, the addition of aspergillus niger is 10% of the protein quality in the first mixed liquor, proceeds by hydrolysis,
12h is incubated, the second mixed liquor is obtained.
Step 4：The modification of starch and glucide：
The second mixed liquor that step 3 is obtained adjusts pH value to 8 using sodium hydroxide solution, stirs, keeping temperature is 27
DEG C,
Then within 2 hours, point 3 addition succinic anhydrides, the addition of succinic anhydride is equal to what step one was calculated
The 2% of starch and the mass fraction of glucide quality sum in second mixed liquor, then insulated and stirred 4h, Starch synthesis is fourth
Diacid starch ester, and esterification substitution sugared in starch production wastewater is completed, obtain the 3rd mixed liquor.After tested, the substitution of starch
Rate is 0.08.
Step 5：PH value is adjusted：
PH value is adjusted to 7 using sulfuric acid, retarder is obtained.
Embodiment 4
A kind of preparation method of retarder, comprises the following steps：
Step one：The component content of production of corn starch waste water is determined：
Collect production of corn starch waste water 1L, determine soluble cellulose therein, glucide, protein, starch and
The content of aliphatic acid, method of testing is carried out using traditional test methods.Calculate soluble cellulose, glucide, protein, shallow lake
The quality of powder and aliphatic acid.
Step 2：Heating concentration：
The production of corn starch waste water for carrying out concentration mensuration is concentrated, thickening temperature is 110 DEG C, and concentration time is 3
~5h, the mass concentration of test wherein protein is 5%, obtains the first mixed liquor.
Step 3：Protein is hydrolyzed：
The first mixed liquor hydrochloric acid solution after step 2 is concentrated, pH value is adjusted to 3, stirring is heated to 40 DEG C, so
After add aspergillus niger, the addition of aspergillus niger is 10% of the protein quality in the first mixed liquor, proceeds by hydrolysis,
16h is incubated, the second mixed liquor is obtained.
Step 4：The modification of starch and glucide：
The second mixed liquor that step 3 is obtained adjusts pH value to 8 using sodium hydroxide solution, stirs, keeping temperature is 25
DEG C, then within 2 hours, point 2 addition succinic anhydrides, the addition of succinic anhydride is equal to starch and sugar in the second mixed liquor
The 8% of the mass fraction of class material mass sum., time for adding is 2h, then insulated and stirred 3h, and the starch in starch wastewater is closed
As succinic acid starch ester, and esterification substitution sugared in starch production wastewater is completed, obtain the 3rd mixed liquor.After tested, starch
Replacement rate be 0.12.
Step 5：PH value is adjusted：
PH value is adjusted to 6.5 using hydrochloric acid, retarder is obtained.
Embodiment 5
A kind of preparation method of retarder, comprises the following steps：
Step one：The component content of production of corn starch waste water is determined：
Collect production of corn starch waste water 1L, determine soluble cellulose therein, glucide, protein, starch and
The content of aliphatic acid, method of testing is carried out using traditional test methods.Calculate soluble cellulose, glucide, protein, shallow lake
The quality of powder and aliphatic acid.
Step 2：Heating concentration：
The production of corn starch waste water for carrying out concentration mensuration is concentrated, thickening temperature is 120 DEG C, and concentration time is 3
~5h, the mass concentration of test wherein protein is 10%, obtains the first mixed liquor.
Step 3：Protein is hydrolyzed：
The first mixed liquor sulfuric acid solution after step 2 is concentrated, pH value is adjusted to 2, stirring is heated to 50 DEG C, so
After add aspergillus niger, the addition of aspergillus niger is 10% of the protein quality in the first mixed liquor, proceeds by hydrolysis,
18h is incubated, the second mixed liquor is obtained.
Step 4：The modification of starch and glucide：
The second mixed liquor that step 3 is obtained adjusts pH value to 9 using sodium hydroxide solution, stirs, keeping temperature is 30
DEG C, then within 3 hours, point 3 addition succinic anhydrides, the addition of succinic anhydride is equal to starch and sugar in the second mixed liquor
Starch synthesis in the 10% of the mass fraction of class material mass sum, then insulated and stirred 4h, starch wastewater is that succinic acid forms sediment
Powder ester, and esterification substitution sugared in starch production wastewater is completed, obtain the 3rd mixed liquor.After tested, the Replacement rate of starch is
0.18。
Step 5：PH value is adjusted：
PH value is adjusted to 7 using sulfuric acid, retarder is obtained.
Experimental example
In order to examine the effect of the retarder of the invention prepared, using commercially available conventional retarder sodium gluconate as comparative example,
Comparative example and each embodiment 1 are determined to the concrete experiments data of the retarder of embodiment 5.It is tested in concrete system
Setting time, air content, compression strength, the slump, divergence and its retention property shown.
Concrete mix is, cement：Flyash：Sand：Stone：Water=280：80：790：1061：180.Retarder folding is solid
Volume is 0.6%, and the volume of sodium gluconate is 0.6%, and cement is the new PO42.5 cement of China.Test result is shown in Table 1.
The testing concrete performance result of table 1
The retarder prepared using the inventive method embodiment 1 to embodiment 5 is can be seen that from the test result of table 1, with
Commercially available conventional retarder sodium gluconate is compared, and both setting time and 28d compression strength are similar in concrete system, performance
Good retarding effect is gone out.This is due to succinic acid starch ester present in the retarder of the present invention, and is esterified substitution
Glucide and cellulose substances, above comprehensive function, so as to show good retarding effect.
Even, retarder of the invention is in concrete system, and its slump and divergence and holding capacity are substantially excellent
In the sour sodium of commercially available conventional glucose.This is because, the succinic acid starch ester in the retarder of the present invention has outstanding dispersiveness,
There is provided good water-reducing rate, and protein and amino acid substance in retarder, and aliphatic acid, serve good bleed
Effect, concrete system of the concrete 's air-containing higher than addition sodium gluconate retarder.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (9)
1. a kind of retarder, it is characterised in that：The retarder is to include soluble cellulose class material, protein and amino acid
Class material, modified starch, esterification substitution glucide, and aliphatic acid mixed aqueous solution.
2. retarder according to claim 1, it is characterised in that：The retarder is production of corn starch waste water through overrich
The retarder that contracting, protein hydrolysis, starch conversion, glucide esterification substitution and pH value regulation are obtained.
3. retarder according to claim 2, it is characterised in that：The soluble cellulose class material is given birth to for cornstarch
Produce soluble cellulose, hemicellulose and the lignin in waste water.
4. retarder according to claim 2, it is characterised in that：The modified starch be production of corn starch waste water in pass through
The succinic acid starch ester that starch conversion is obtained is crossed, the substitution value of the succinic acid starch ester is 0.02~0.25.
5. retarder according to claim 2, it is characterised in that：The glucide of the esterification substitution is given birth to for cornstarch
Glucide itself hydroxyl in production waste water reacts obtained derivative with esterifying reagent.
6. retarder according to claim 5, it is characterised in that：The glucide be glucose, maltose, sucrose,
The mixture of fructose, the esterifying reagent is succinic anhydride.
7. according to any described retarder of claim 1 to 6, it is characterised in that：In the retarder, the sugar of substitution is esterified
Class, protein and amino acids material, succinic acid starch ester, soluble cellulose, the mass ratio of aliphatic acid are 3~6：10~
20：50~100:20~30:1~3.
8. a kind of preparation method of retarder, it is characterised in that comprise the following steps：
Step one：The component content of production of corn starch waste water is determined：
Soluble cellulose, carbohydrate quality in collection starch production wastewater, measure production of corn starch waste water, protein, shallow lake
The content of powder, aliphatic acid；
Step 2：Heating concentration：
The starch production wastewater for carrying out concentration mensuration is concentrated, thickening temperature is 100~120 DEG C, concentration time for 3~
5h, until the mass concentration of wherein protein reaches 5%~10%, obtains the first mixed liquor；
Step 3：Protein is hydrolyzed：
The first pH value regulator of the first mixed liquor after step 2 is concentrated, pH value is adjusted to 2~3, stirring is heated to 40
~50 DEG C, acid protease is then added, hydrolysis is proceeded by, 8~20h is incubated, hydrolysis is completed, and obtains the second mixing
Liquid；
Step 4：The modification of starch and glucide：
The second mixed liquor that step 3 is obtained adjusts pH value to 8~9 using the second pH value regulator, stirs, and keeping temperature is
25~30 DEG C, 2~3 addition succinic anhydrides are then divided in 2~3h, succinic anhydride addition is starch and the total matter of glucide
The 2~12% of amount, are protected and then temperature 3~5h of stirring, Starch synthesis is succinic acid starch ester, and complete the esterification substitution of sugar, are obtained
3rd solution；
Step 5：PH value is adjusted：
The pH value for adjusting the 3rd solution using the first pH value regulator obtains retarder to 6.5~7.5.
9. the preparation method of retarder according to claim 8, it is characterised in that：First pH value regulator is sulfuric acid
Or hydrochloric acid, second pH value regulator is sodium hydroxide.
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| CN110128081A (en) * | 2019-06-15 | 2019-08-16 | 广东腾基建设有限公司 | A kind of concrete and preparation method thereof |
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| CN113121149B (en) * | 2021-03-01 | 2022-09-16 | 交通运输部公路科学研究所 | Cement-based hydration heat inhibitor and preparation method of cement hydration heat inhibiting concrete |
| CN118026618A (en) * | 2024-04-15 | 2024-05-14 | 天津市辰青金属制品有限公司 | Slow adhesive and application thereof in steel bar |
| CN118026618B (en) * | 2024-04-15 | 2024-06-07 | 天津市辰青金属制品有限公司 | Slow adhesive and application thereof in steel bar |
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