CN1071152A - Utilize spent pulping liquor to make cement water reducing agent - Google Patents
Utilize spent pulping liquor to make cement water reducing agent Download PDFInfo
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- CN1071152A CN1071152A CN91108840A CN91108840A CN1071152A CN 1071152 A CN1071152 A CN 1071152A CN 91108840 A CN91108840 A CN 91108840A CN 91108840 A CN91108840 A CN 91108840A CN 1071152 A CN1071152 A CN 1071152A
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- Prior art keywords
- reducing agent
- water reducing
- polyoxyethylene
- pulping liquor
- cement water
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- 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
- C04B40/0042—Powdery mixtures
-
- 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
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of method of utilizing spent pulping liquor or chemical fibre waste fluid to make cement water reducing agent.The cement water reducing agent that adopts the inventive method to make is compared with other spent pulping liquor series concrete water-reducing agent, and to concrete water-reducing rate and ultimate compression strength, particularly early anti pressured intension increases significantly, and can be used widely in steam-curing concrete.Cement water reducing agent of the present invention, its raw material sources are abundant, and cheap, volume is low, and production technique is simple, is a kind of very rising cement water reducing agent.
Description
The present invention relates to the technology category of preparation cement water reducing agent, specifically, relate to the technology category that utilizes spent pulping liquor or chemical fibre waste fluid to make concrete high efficiency water reducing agent.
Along with developing rapidly of construction industry, the application of concrete admixture more and more obtains paying attention to, and it has become one of important composition of modern concrete.Cement water reducing agent is a kind of main kind of concrete admixture.At present, the cement water reducing agent of producing is various in style both at home and abroad, and the cement water reducing agent of domestic present production mainly contains spent pulping liquor series concrete water-reducing agent and sulfonated coal tar series concrete water-reducing agent two big classes by the raw material classification.From the performance index of cement water reducing agent, the sulfonated coal tar series concrete water-reducing agent belongs to concrete high efficiency water reducing agent, and the spent pulping liquor series concrete water-reducing agent belongs to the concrete ordinary water-reducing agent.The major ingredient of sulfonated coal tar series concrete water-reducing agent is aromatic sulphonate or aromatic sulphonate formaldehyde condensation products and a part of heterogeneous ring compound.The better performances of this class cement water reducing agent is high efficiency water reducing agent.But because they are all produced by route of synthesis, the variety of raw material of use is also many, and wherein many materials are starting material of Chemical Manufacture, and complex manufacturing.Therefore the cost of this class cement water reducing agent is higher, and simultaneously, required starting material are subjected to the restriction that the chemical plant produces often when producing this class cement water reducing agent.
The effective constituent that mainly contains of spent pulping liquor series concrete water-reducing agent is all kinds of lignin derivatives in the spent pulping liquor, it is as the cement dispersants history of existing five more than ten years, is what directly to use with lignin salt to the spent pulping liquor of major ingredient as cement water reducing agent in early days.The sixties bring into use the spent pulping liquor after taking off candy (fermentation proposes alcohol) to prepare cement water reducing agent, and its technical process is as follows:
Spent pulping liquor → fermented extracted alcohol → concentrate → spraying drying → finished product
Or vanillin food grade,1000.000000ine mesh contains solid 10～50% 200 ℃
Directly use with lignin salt to the spent pulping liquor of major ingredient as cement water reducing agent no matter be, or the cement water reducing agent of spent pulping liquor preparation through taking off candy, its performance index are all at the category of concrete ordinary water-reducing agent, its shortcoming is that the concrete mix water-reducing rate is low, only reach 7～9% scopes, concrete crushing strength improves fewly, and especially early anti pressured intension is mixed the blank concrete of admixture and compared (ultimate compression strength ratio) 1 day: 80～90% with the end of term of the same age; 3 days: 100～110%; 7 days: 105～115%; 28 days: 100～110%.Therefore the range of application of spent pulping liquor series concrete water-reducing agent is restricted.Late nineteen seventies, the eighties since as concrete high efficiency water reducing agents such as sulfonated coal tar series concrete water-reducing agents because of its shortage of raw materials, price is higher and influenced applying of concrete high efficiency water reducing agent.Be to enlarge the production kind of concrete high efficiency water reducing agent, various countries' technological approaches that how that the starting material source is abundant, inexpensive the spent pulping liquor that contains lignin salt or chemical fibre waste fluid be prepared into concrete high efficiency water reducing agent that begins one's study in succession.People generally believe at present, and spent pulping liquor series concrete water-reducing agent water-reducing rate reason low and that concrete crushing strength improves fewly is because slow setting and bleed effect that the spent pulping liquor series concrete water-reducing agent itself has cause.Therefore, spent pulping liquor series concrete water-reducing agent performance be improved, its slow setting and bleed shortcoming must be overcome.For addressing this problem, utilize ultrafiltration apparatus to remove low molecular weight carbohydrate and low-molecular weight lignin salt in the method that Britain adopts; Adopt the ion exchange method preparation to receive salt; Improve the sulfonation degree of lignin salt in process of production as far as possible; Strengthen its volume and do the concrete high efficiency water reducing agent use.Also have in addition spent pulping liquor and no chlorine setting accelerator and do the concrete high efficiency water reducing agent use after compound.Reasonable two kinds of method of modifying have been explored with the study on the modification of spent pulping liquor making concrete high efficiency water reducing agent by the Soviet Union:
1. utilize calcium hydroxide or various ionogen to make precipitation agent, make a part of high molecular component adsorption precipitation in the spent pulping liquor,, reach the purpose that reduces its slow setting to reduce the lignin salt of high molecular component in the cement water reducing agent.Soviet Union's HN Л-20 cement water reducing agent carries out modification with this method to spent pulping liquor, and the sorbent material of employing is a portland cement.Removed high molecular sulfonated lignin, made it have efficient plasticizing function, and can reduce slow setting.But wherein the bleed of low-molecular-weight component is excessive, and makes this method that certain limitation be arranged.
2. reduce bleed.Two kinds of approach are arranged: (1) removes low-molecular-weight component; (2) add a small amount of (be about enriching agent dry weight 1～3%) properties-correcting agent (regulating amount of air entrainment reagent), to reduce amount of air entrainment.As Soviet Union HN Л-21 cement water reducing agent promptly is that properties-correcting agent is prepared from the propyl carbinol, and its performance is similar to concrete high efficiency water reducing agent.
In addition, also useful formaldehyde, potassium bichromate modified pulp waste liquid; With physico-chemical process modified pulp waste liquid, be about to its aqueous solution and make concrete high efficiency water reducing agent with the caustic soda violent stirring; Or the association composition of the lignin salt in the separating pulp waste liquid, and be converted into and receive salt, to carry out modification; The spent pulping liquor volume is strengthened, and with compound use of sodium sulphate or the like.
In the above-mentioned method of improving spent pulping liquor series concrete water-reducing agent performance, and though be take to reduce slow setting might as well, still reduce bleed might as well, not only make complex manufacturing, and the cement water reducing agent performance do not significantly improved.According to present retrieval data searching, employing contains the spent pulping liquor of lignin salt or the cement water reducing agent of chemical fibre waste fluid preparation, and its performance does not all reach the standard-required of concrete high efficiency water reducing agent among China GB8076-87.Especially the concrete early anti pressured intension is not improved a lot.
Purpose of the present invention will improve the spent pulping liquor series concrete water-reducing agent exactly to concrete water-reducing rate and ultimate compression strength, particularly early strength.
Realize that concrete grammar of the present invention is:
At first select the spent pulping liquor or the chemical fibre waste fluid that contain lignin salt for use, polyoxyethylene carboxylate, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyxyethylated alkylphenol, castor oil polyoxyethylene ether, polyethers, alkylol amide, sugar is close, calglucon, tartrate, tartrate is received, citric acid, citric acid is received, gluconic acid, Whitfield's ointment, sodium sulphate, the sulfuration sodium sulphate, nitrite natrium, Tai-Ace S 150, chromic salt, calcium formiate, urea is preparation of raw material cement water reducing agent of the present invention.Its production technique is: the spent pulping liquor or the chemical fibre waste fluid (preferably through carrying the waste liquid of candy) that will contain lignin salt are concentrated into solid content 40～60%, adding by the concentration any or multiple and that water is mixed with in polyoxyethylene carboxylate, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyxyethylated alkylphenol, castor oil polyoxyethylene ether, polyethers and the alkylol amide is 10～40 the aqueous solution again, mix to stir 0.5～2 hour, operating period temperature be controlled at 5～70 ℃ of scopes.So promptly make the cement water reducing agent of liquid.Also its oven dry can be made pulverous cement water reducing agent.If making the raising slow setting as required (compares with blank concrete, can delay the cement water reducing agent of 2～4 hours time of coagulation, sugared close (available calglucon, tartrate, tartrate are received, citric acid, citric acid are received, one or more replacements in gluconic acid and the Whitfield's ointment) that can add solid content 50% in making the cement water reducing agent of liquid again stirred 0.5～1 hour.If make as required improve the early age strength of concrete performance (with blank concrete ratio mutually: 1 day 160～200%; 3 days 130～180%; 7 days 120～140%; 28 days 110～130%) water reducer, should the cement water reducing agent that will make liquid be dried into Powdered after, add sodium sulphate (one or more replacements in available sodium thiosulfate, nitrite natrium, Tai-Ace S 150, chromic salt, calcium formiate and the urea) mix grinding mix again and evenly get final product.
The prescription of spent pulping liquor series concrete water-reducing agent of the present invention following (weight ratio):
Example 1:
The spent pulping liquor or the chemical fibre that contain lignin salt
Waste liquid (solid content 40～60%) 30～90%;
Polyoxyethylene carboxylate (available polyoxyethylene sorbitol fatty acid ester, polyoxyethylene Fatty Alcohol(C12-C14 and C12-C18)
One or more replacements in ether, polyxyethylated alkylphenol, castor oil polyoxyethylene ether, polyethers and the alkylol amide) 1～10%;
Water 0～69%.
Example 2:
The spent pulping liquor or the chemical fibre waste fluid that contain lignin salt
(solid content 40～60%) 24～86%;
Polyoxyethylene carboxylate (one or more replacements in available polyoxyethylene sorbitol fatty acid ester, polyoxyethylene aliphatic alcohol ether or polyxyethylated alkylphenol, castor oil polyoxyethylene ether, polyethers and the alkylol amide) 1～9.6%;
Water 0～72%;
Sugar close (solid content 50%) (available calglucon, tartrate are received, citric acid, citric acid are received, one or more replacements in gluconic acid and the Whitfield's ointment) 1～20%.
Example 3:
The spent pulping liquor or the chemical fibre waste fluid that contain lignin salt
(solid content 40～60%) 7.5～31.5%;
Polyoxyethylene carboxylate (one or more replacements in available polyoxyethylene sorbitol fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyxyethylated alkylphenol, castor oil polyoxyethylene ether, polyethers and the alkylol amide) 0.2～3.5%;
Water 0～17.2%;
Sodium sulphate (available sodium thiosulfate, nitrite natrium, Tai-Ace S 150, chromic salt, calcium formiate, and urea in one or more replacements) 65～85%.
The spent pulping liquor series concrete water-reducing agent that adopts the inventive method to make, its index can reach high efficiency water reducing agent standard-required among the GB8076-87.But be characterized in efficient, slow setting, impervious, and the growth of accelerate concrete intensity.
The water reducer that employing example 1 prescription is made and as follows with the concrete performance of its preparation:
1. proportion: 1.23 ± 0.02(20 ℃)
2. amount of air entrainment: 1～2%(depends on sand allotment and water consumption)
3. water mixing: 0.3～0.6%(cement weight meter)
4. water-reducing rate: concrete eight～15%;
Mortar 15～25%.
5. freezing point: after the freeze thawing, still can use through stirring.
6. increase substantially the slump of concrete mix, be approximately 10 centimetres.
7. workability is good, even during 22 centimetres of the slumps, mortar and stone be also not stratified, do not disintegrate.
8. improve concrete strength (with blank concrete in length of time ratio mutually)
Onsite concrete: 1 day 120～150%;
3 days 120～140%;
7 days 120～140%;
28 days 110～130%.
Steam-curing concrete: steam-cured back 120～140%;
Steam-cured back maintenance 28 days 110～130%.
9. keep the onsite concrete of the identical slump and intensity can save cement 10～15%; Steam-curing concrete can be saved cement 10%.
10. compare with blank concrete, can delay 1～2 hour time of coagulation.
11. mix liquid concrete water reducer of the present invention, need not take grading of aggregate method and other measure just can prepare general water-tight concrete.
12. when mix 0.5% cement water reducing agent of the present invention in mortar, 3 days intensity can improve 30～50%, 7 days intensity and improve intensity raising 20～40% in 20～40%, 28 days.
Adopt water reducer that example 2 prescriptions make and with the concrete salient features of its preparation:
1. water-reducing rate: concrete eight～15%;
Mortar 15～25%.
2. improve concrete crushing strength (with blank concrete in length of time ratio mutually)
Onsite concrete: 3 days 120～140%;
7 days 120～140%;
28 days 110～130%.
3. compare with blank concrete, can delay 2～4 hours time of coagulation.
Adopt water reducer that example 3 prescriptions make and with the concrete salient features of its preparation:
1. water-reducing rate: concrete eight～15%.
2. improve concrete crushing strength (with blank concrete in length of time ratio mutually).
Onsite concrete: 1 day 160～200%;
3 days 130～180%;
7 days 120～140%;
28 days 110～130%.
Steam-curing concrete: steam-cured back 120～150%;
Steam-cured back maintenance 28 days 110～130%.
Cement water reducing agent of the present invention is that cement water reducing agent is compared with existing spent pulping liquor, concrete compression strength, particularly early strength and water-reducing rate is increased significantly, and can be used widely in steam-cured concrete. Cement water reducing agent of the present invention, its raw material is abundant, Cheap, production technology also simple, be a kind of very rising cement water reducing agent.
Claims (6)
1, a kind of cement water reducing agent that utilizes spent pulping liquor or chemical fibre waste fluid to make, the production technique that it is characterized in that it is: the spent pulping liquor or the chemical fibre waste fluid (preferably through carrying the waste liquid of candy) that will contain lignin salt are concentrated into solid content 40～60%, add again by polyoxyethylene carboxylate, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyxyethylated alkylphenol, castor oil polyoxyethylene ether, concentration any or multiple and that water is mixed with in polyethers and the alkylol amide is 10～40% the aqueous solution, mix to stir 0.5～2 hour, operating period temperature be controlled at 5～70 ℃ of scopes.So promptly make the cement water reducing agent of liquid.
2, the production technique of utilizing spent pulping liquor or chemical fibre waste fluid to make cement water reducing agent according to claim 1 is characterized in that: sugared close (available calglucon, tartrate, tartrate are received, citric acid, citric acid are received, one or more replacements in gluconic acid and the Whitfield's ointment) that add solid content 50% in making the cement water reducing agent of liquid again stirred 0.5～1 hour.
3, the production technique of utilizing spent pulping liquor or chemical fibre waste fluid to make cement water reducing agent according to claim 1, it is characterized in that: the cement water reducing agent that will make liquid is dried into Powdered, and it is even to add sodium sulphate (one or more replacements in available sulfo-sulphur sodium sulphate, nitrite natrium, Tai-Ace S 150, chromic salt, calcium formiate and the urea) mix grinding mix again.
4, cement water reducing agent according to claim 1 is characterized in that prescription is (weight ratio):
The spent pulping liquor or the chemical fibre waste fluid that contain lignin salt
(solid content 40～60%) 30～90%;
Polyoxyethylene carboxylate (one or more replacements in available sorbitol polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyxyethylated alkylphenol, castor oil polyoxyethylene ether, polyethers and the alkylol amide) 1～10%;
Water 0～69%
5, cement water reducing agent according to claim 2 is characterized in that prescription is (weight ratio):
The spent pulping liquor or the chemical fibre waste fluid (solid content 40～60%) that contain lignin salt
24～86%;
Polyoxyethylene carboxylate (one or more replacements in available polyoxyethylene sorbitol fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyxyethylated alkylphenol, castor oil polyoxyethylene ether, polyethers and the alkylol amide) 1～9.6%;
Water 0～72%;
Sugared close (available calglucon, tartrate are received, citric acid, citric acid are received, one or more replacements in gluconic acid and the Whitfield's ointment) 1～20% of solid content 50%.
6, cement water reducing agent according to claim 3 is characterized in that prescription is (weight ratio):
The spent pulping liquor or the chemical fibre waste fluid that contain lignin salt
(solid content 40～60%) 7.5～31.5%;
Polyoxyethylene carboxylate (one or more replacements in available polyoxyethylene sorbitol fatty acid ester, polyoxyethylene aliphatic alcohol ether, polyxyethylated alkylphenol, castor oil polyoxyethylene ether, polyethers and the alkylol amide) 0.2～3.5%;
Water 0～17.2%;
Sodium sulphate (one or more replacements in available sodium thiosulfate, nitrite natrium, Tai-Ace S 150, chromic salt, calcium formiate and the urea) 65～85%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91108840A CN1071152A (en) | 1991-09-16 | 1991-09-16 | Utilize spent pulping liquor to make cement water reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN91108840A CN1071152A (en) | 1991-09-16 | 1991-09-16 | Utilize spent pulping liquor to make cement water reducing agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1071152A true CN1071152A (en) | 1993-04-21 |
Family
ID=4909513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91108840A Pending CN1071152A (en) | 1991-09-16 | 1991-09-16 | Utilize spent pulping liquor to make cement water reducing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1071152A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173643A (en) * | 2011-01-18 | 2011-09-07 | 延边石岘白麓纸业股份有限公司 | Concrete water-reducing agent and preparation method thereof |
| CN107572960A (en) * | 2017-09-21 | 2018-01-12 | 镇江市太浪新材料科技有限公司 | A kind of preparation method of efficiently build concrete |
| CN107746201A (en) * | 2017-09-21 | 2018-03-02 | 镇江市太浪新材料科技有限公司 | A kind of efficient preparation technology of the special water reducer of concrete |
| CN107746220A (en) * | 2017-09-21 | 2018-03-02 | 镇江市太浪新材料科技有限公司 | A kind of novel architecture concrete |
| CN107793064A (en) * | 2017-09-21 | 2018-03-13 | 镇江市太浪新材料科技有限公司 | A kind of special water reducer of concrete |
-
1991
- 1991-09-16 CN CN91108840A patent/CN1071152A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173643A (en) * | 2011-01-18 | 2011-09-07 | 延边石岘白麓纸业股份有限公司 | Concrete water-reducing agent and preparation method thereof |
| CN102173643B (en) * | 2011-01-18 | 2013-01-30 | 延边石岘白麓纸业股份有限公司 | Concrete water-reducing agent and preparation method thereof |
| CN107572960A (en) * | 2017-09-21 | 2018-01-12 | 镇江市太浪新材料科技有限公司 | A kind of preparation method of efficiently build concrete |
| CN107746201A (en) * | 2017-09-21 | 2018-03-02 | 镇江市太浪新材料科技有限公司 | A kind of efficient preparation technology of the special water reducer of concrete |
| CN107746220A (en) * | 2017-09-21 | 2018-03-02 | 镇江市太浪新材料科技有限公司 | A kind of novel architecture concrete |
| CN107793064A (en) * | 2017-09-21 | 2018-03-13 | 镇江市太浪新材料科技有限公司 | A kind of special water reducer of concrete |
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