CN101006025A - Molasses treatment for the 'molassperse' surfactant production for concrete plasticizers (water reducing admixtures) and cement clinker grinding additives applications - Google Patents
Molasses treatment for the 'molassperse' surfactant production for concrete plasticizers (water reducing admixtures) and cement clinker grinding additives applications Download PDFInfo
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- CN101006025A CN101006025A CNA2005800234179A CN200580023417A CN101006025A CN 101006025 A CN101006025 A CN 101006025A CN A2005800234179 A CNA2005800234179 A CN A2005800234179A CN 200580023417 A CN200580023417 A CN 200580023417A CN 101006025 A CN101006025 A CN 101006025A
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- molasses
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- cement clinker
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
- C13B50/00—Sugar products, e.g. powdered, lump or liquid sugar; Working-up of sugar
- C13B50/006—Molasses; Treatment of molasses
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/10—Carbohydrates or derivatives thereof
-
- 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
-
- 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
- C04B2103/52—Grinding aids; Additives added during grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Food Science & Technology (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
A method of treating molasses in which the molasses is modified to yield surfactants with plasticizer (water reducing) and dispersant properties. The essence of the treatment is that the molasses in the series is treated in acid and alkali environments at temperatures higher than ambient. This means that the ingredients of molasses are exposed to acid and alkali hydrolysis. The acid treatment provides the production of monosaccharides (reducing sugars), aldonic and aminocarbonic acids. The alkali treatment provides the forming of saccharinic acids and their salts, aldonic acid salts, aminocarbonic acids and their salts, and soluble soaps of wax ethers. The molasses modifications can be effectively used for concrete plasticizers (water reducing admixtures) and cement clinker grinding additives application.
Description
1.
Background
1.1 concrete additives
Molasses (seeing the canonical analysis of molasses in the appendix 1) are usually as the retardant [1,4] in the concrete additives.Its enhancing is condensed and has therefore been reduced the water loss in the concrete mixture slightly.
The Chinese patent [2] that is entitled as " setting retardant type-high-early strength water-reducing agent preparation method and product " approaches our invention.The setting retardant type-high-early strength water-reducing agent of this invention is prepared as follows: molasses are diluted to the 1.22-1.25 degree Beaume, be heated to after 70～80 ℃, adding dilution back molasses weight is the lime reaction of 1-2%, makes part sugar and calcium oxide reaction generate the soluble sugar calcium that can produce best water-reducing effect.The result is the composition that still keeps part sugar in the reacted product, makes this product both have water-reducing effect, has delayed coagulation again, adds anhydrous sodium sulphate simultaneously by a certain percentage and makes it have potent fruit early.
The known sugar (tangerine sugar) that joins in the concrete mixture also forms " soluble sugar calcium " with calcium oxide (it produces) react with immediately in the cement hydration process.
Compare with utilizing conventional molasses (directly adding molasses in concrete mixture), the difference of this Chinese patent method is that the tangerine sugar of relative small portion is converted into " sugared calcium "
The shortcoming of this method is:
-from the angle of molasses modification, in fact the composition of concrete mixture does not change; It only is the forming process of having strengthened a small amount of " sugared calcium " slightly
-" sugared calcium " begins precipitation being lower than under 20 ℃ the temperature, make concrete sclerosis unbalanced [3]
-sodium sulfate is used to reduce strong traditionally tangerine sugar slow setting effect.
Of the present invention is to be entitled as included conventional Soviet Union method [4] in the Korean Patent [5] of " CONCRETE ADMIXTURESCONTAINING MOLASSES FERMENTATION BYPRODUCTS " near prior art.
" molasses fermented byproduct " be basically the tangerine sugar-fermenting and from " mother liquor " extractive fermentation product (mainly being alcohol and yeast) waste liquid afterwards.
Compare with the primary molasses, this molasses waste liquid comprises the byproduct of relatively small amount, and this byproduct derives from the fermenting process of sugar, and it mainly is to exist with different organic acid forms.Compare with original molasses, these acid have improved the surfactivity of molasses waste liquids slightly.
With conventional water reducer for example Sulfite lignin compare, the main drawback of " molasses fermented byproduct " (molasses waste liquid) is still lower surfactivity.In addition, " molasses fermented byproduct " comprises too much variant.Therefore these byproducts seldom are used for the concrete additives application.
1.2 cement clinker interground addition
Because its low dispersed (lower performance tensio-active agent), molasses be not traditionally as interground addition.But the Chinese patent CN 1089245A suggestion that is entitled as " with the method for talcum or molasses as cement grinding aid " is used from this application with about 1: 10 ratio with molasses and talcum one.
As if in said composition, molasses are used as known tackiness agent.In process of lapping, talcum is the material that manys softer than cement clinker, and grinds thinlyyer than slag.In the mixture with molasses (as tackiness agent), very the talcum of particulate can coat cement granules by inference, thereby prevents their gatherings.
Because this method poor efficiency is not so it is widely used.
The main drawback of this method is that molasses need not make tensio-active agent-dispersion agent.
2. the design that the molasses of being advised are handled
Degree of depth molasses modifications composition makes it be converted into the effective tensio-active agent of have softening agent (water reducing ability) and dispersion agent character.
3. (the present invention) stated in arranging of handling
3.1 the key of handling
Be higher than under the temperature of envrionment temperature, in acid and alkaline environment, handling molasses continuously.
This means that the molasses composition carries out acidic hydrolysis and alkaline hydrolysis.
3.2 mode and the parameter handled
3.2.1 mineral acid and organic acid can be used for molasses are acidified to pH0.8;
3.2.2 mineral alkali and organic bases can be used for molasses are alkalized to pH14.0;
3.2.3 under environmental stress, malleation and negative pressure, the temperature of acid treatment and alkaline purification can be 50-200 ℃;
3.2.4 the catalyzer of acidic hydrolysis and alkaline hydrolysis (oxidation) can be used for described processing;
3.2.5 the solids content of molasses can be 5.0-90.0%;
3.2.6 the treatment time:
-acid treatment: 10 minutes-24 hours
-alkaline purification: 10 minutes-24 hours
3.2.7 after acid treatment and the alkaline purification, can be with the pH regulator of molasses to desired level.
4. handle influence to molasses character
4.1 acid treatment provides:
-polysaccharide is converted into monose (reducing sugar);
-part monose is converted into glyconic acid;
-protein is decomposed into has relatively large carboxyl and amino amino carbonic acid.
4.2 alkaline purification provides:
-monose (reducing sugar) is converted into saccharinic acid and salt thereof;
-glyconic acid is converted into their salt;
-protein of remnants is decomposed into amino carbonic acid;
-amino carbonic acid is converted into their salt;
-wax ether is transformed (saponification) is soluble soaps.
5. the character of the newly-generated thing of the molasses of handling
5.1 the salt of saccharinic acid and glyconic acid is the great anion surfactant with polymolecularity.
The salt and the wax soap of amino carbonic acid are effective wetting agent and sanitising agent [7].
5.2 the inclusion in the surfactant complex that is produced
-be mainly the salt of saccharinic acid and glyconic acid;
-small portion is amino-carbon hydrochlorate and wax soap.
5.3 the surfactant complex that is produced provides the molasses of processing of more efficient as concrete plasticizers (diminishing adulterating agent) and slag interground addition.
6. the molasses of handling are carried out application testing
6.1 molasses modifications is tested as the softening agent in the sand-cement slurry, with best common European softwood tree lignin sulfonic acid Na and lignosulfonic acid Ca relatively.Test result is shown in the appendix 2.
6.2 also molasses modifications is tested as the slag interground addition.Test result is shown in the appendix 3.
7. conclusion
Test result shows: molasses modifications can be effective to concrete plasticizers (diminishing adulterating agent) and the cement clinker interground addition is used.
Appendix 1
Grind molasses-canonical analysis
Drying solid (%) 70-80
Total reducing sugar (%) 40-65
Sucrose (%) 30-40 (Jackson﹠amp; The Gillis method)
Reducing sugar (%) 10-20 (Lane﹠amp; The Eynon method)
The sugar that can not ferment (%) 2-5
Crude protein (%) 2-5 (Kjeldalh N)
Ash (%) 10-15 (disulfonic acidization)
Principal element:
Potassium 3.5-5.5%
Calcium 0.5-1.2%
Sodium 0.05-0.10%
Trace element:
Iron ppm maximum 250
Copper ppm maximum 10
Zinc ppm maximum 15
Plumbous ppm maximum 1.0
Arsenic is less than ppm 1.0
Cadmium is less than ppm 0.02
Appendix 2
" Molassperse " molasses modifications is used for the research that concrete is used
Modification
In the AIA laboratory to three modifications of carrying out of raw sugar honey.Molasses modifications is called Molassperse P-1, Molassperse P-2 and Molassperse P-3.
In sand-cement slurry, test
Use best common European softwood tree lignin sulfonic acid Na and lignosulfonic acid Ca sample in contrast.
The consumption of molasses modifications and Sulfite lignin is 0.1%, 0.2% and 0.3% of concrete qualities.
Blue Circle Southern Cement is used to prepare sand-cement slurry.
In test, use two kinds of river sand (thick with thin) (ratio 1: 1).
Water in all sand-cement slurry/concrete ratio is a constant 0.55.
Concrete: sand: the ratio of water is 1: 3: 0.55.
Determine the flowability of sand-cement slurry with drift station.
Determine the air entrainment amount by volumetric method.
Preparation sand-cement slurry ISO prism 40 * 40 * 160mm is used for determining ultimate compression strength.
Test result is shown in table 1.
Discuss
Lignosulfonic acid NA and lignosulfonic acid CA (reference) are typical middle water reducer and the retardant of imitating.
Compare with the sand-cement slurry of lignosulfonic acid CA with having lignosulfonic acid NA, the sand-cement slurry with Molassperse P-1, Molassperse P-2 and Molassperse P-3 has higher flowability under 0.1% low consumption.
Under medium consumption 0.2% and 0.3% the high flow rate, for molasses modifications and Sulfite lignin, mortar mobile similar.
Compare with the mortar with Sulfite lignin, all have the ultimate compression strength of the sand-cement slurry of molasses modifications and all omit high.This can be explained by the higher air entrainment amount of Sulfite lignin.
Conclusion
Therefore, molasses modifications and best common European softwood tree lignin sulfonic acid Na and lignosulfonic acid Ca are suitable.
Molasses modifications can qualitative middle effect water reducer for having low air entrainment amount.
The compare test of table 1 molasses modifications Molasspcrse P-1, Molassperse P-2 and Molassperse P-3 and lignosulfonic acid NA and lignosulfonic acid CA
| N | The adulterating agent title | The flowability of grout, mm | The air entrainment amount, % | Ultimate compression strength, MPa | |||
| 5min | 60min | 1 day | 7 days | 28 days | |||
| 1 | Common molasses (cement quality 0.2% consumption) | 155 | 150 | 2 | 21.4 | 31.7 | 40.9 |
| The adulterating agent consumption of cement quality 0.1% | |||||||
| 2 | Molassperse P-1 | 182 | 158 | 2 | 20.3 | 32.1 | 43.3 |
| 3 | Molasspcrse P-2 | 182 | 160 | 2 | 21.3 | 33.2 | 44.1 |
| 4 | Molassperse P-3 | 183 | 159 | 2 | 21.4 | 33.5 | 44.4 |
| 5 | Lignosulfonic acid NA | 178 | 148 | 3 | 21.5 | 29.4 | 40.4 |
| 6 | Lignosulfonic acid CA | 179 | 162 | 3 | 20.5 | 30.1 | 41.1 |
| The adulterating agent consumption of cement quality 0.2% | |||||||
| Molassperse P-1 | 181 | 162 | 2 | 20.2 | 33.9 | 45.0 | |
| 7 | Molassperse P-2 | 186 | 163 | 2 | 20.6 | 34.3 | 45.1 |
| 8 | Molassperse P-3 | 188 | 169 | 2 | 20.9 | 34.7 | 45.3 |
| 9 | Lignosulfonic acid NA | 186 | 164 | 4 | 20.3 | 32.6 | 43.2 |
| 10 | Lignosulfonic acid CA | 188 | 168 | 4 | 19.6 | 32.8 | 43.9 |
| The adulterating agent consumption of cement quality 0.3% | |||||||
| 11 | Molassperse P-1 | 193 | 162 | 3 | 20.3 | 34.1 | 44.9 |
| 12 | Molassperse P-2 | 190 | 160 | 3 | 20.1 | 33.1 | 43.5 |
| 13 | Molassperse P-3 | 198 | 168 | 3 | 20.5 | 33.6 | 43.9 |
| 14 | Lignosulfonic acid NA | 200 | 170 | 7 | 19.5 | 31.2 | 41.4 |
| 15 | Lignosulfonic acid CA | 195 | 168 | 7 | 19.3 | 31.5 | 41.9 |
Appendix 3
" Molassperse " molasses modifications is used for the research of cement clinker abrasive application
Modification
In the AIA laboratory, raw sugar honey is carried out twice modification.Molasses modifications is called Molassperse G-1 and Molassperse G-2.
In the concrete shredder of laboratory, test
Using 2700 changes/hour laboratory shredder and standard equipment.
Cement clinker and gypsum grind with 95: 5 ratio.
Test result is shown in table 1.
The slag of table 1. molasses modifications Molassperse G-1 and Molassperse G-2 grinds test
| The title of interground addition | Dosage range, % slag quality (Gu Gu /) | Output under identical cement fineness, % |
| Do not have | - | 100 |
| Molassperse G-1 | 0.02-0.04 0.06-0.08 | 106-111 109-116 |
| Molassperse G-2 | 0.02-0.04 0.06-0.08 | 108-114 112-121 |
Conclusion
Molassperse G-1 and Molassperse G-2 can be used as effective cement clinker interground addition.
Reference
1.B.J.Addis，D.E.Davis
FULTON′S CONCRETE TECHNOLOGY
Portland Cement Institute
Midrand，South Africa，1986
2.WANG RUBIN.QU ZHENBIN
PROCES S FOR PREPARING SETTING RETARDANTTYPE-HIGH-EARLY STRENGTH WATER-REDUCING AGENT ANDPRODUCTS THEREOF
INST.OF LOW-TEMP.ARCHITECTURAL SCIENCE，HEILONGJIANG PROV.China
Patent：CN 1067231 A
3.Schoenrock，Karlheinz W.R.；Ogden，UT
Hsieh，Chia-Lung；Ogden，UT
Rounds，Hugh G.；Ogden，UT
Continuous process for the recovery of sugar from molasses
Patent：US3997357
4.Admixtures for Concrete
Soviet Union′s State Standard：24211-91
Moscow，1991
5.KIM SEUNG JIN，PARK JEE WON；Republic of KoreaCONCRETE ADMIXTURES CONTAINING MOLASSESFERMENTATION BYPRODUCTS
Patent：KR3037597A
6.BAI XIANMING，SHAO ZHONGJUN；China
METHOD FOR USING TALK&MOLASSES AS CEMENTGRINDlG AID
Patent：CN 1089245A
7.A.M.Schwartz，J.W.Perry
SURFACE ACTIVE AGENTS
THEIR CHEMISTRY AND TECHNOLOGY
New York-London，1949，545p
Claims (1)
1. handle molasses for one kind, produce the method for the tensio-active agent that is used for concrete plasticizers (diminishing adulterating agent) and the application of cement clinker interground addition, this method comprises:
-be higher than under the temperature of envrionment temperature, in acid and alkaline environment, handle molasses continuously;
-can use mineral acid and organic acid that molasses are acidified to pH0.8;
-can use mineral alkali and organic bases that molasses are alkalized to pH14.0;
-under environmental stress, malleation and negative pressure, the temperature of acid treatment and alkaline purification can be 50-200 ℃;
The catalyzer of-acidic hydrolysis and alkaline hydrolysis (oxidation) can be used for described processing;
The solids content of-molasses can be 5.0-90.0%;
-the treatment time:
-acid treatment: 10 minutes-24 hours
-alkaline purification: 10 minutes-24 hours
After-acid treatment and the alkaline purification, utilize inorganic and organically bronsted lowry acids and bases bronsted lowry with the pH regulator of molasses to desirable value.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2004902556A AU2004902556A0 (en) | 2004-05-14 | Molasses treatment for the "Molassperse" surfactant production for concrete plasticizers (water reducing admixtures) and cement clinker grinding additives | |
| AU2004902556 | 2004-05-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101006025A true CN101006025A (en) | 2007-07-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800234179A Pending CN101006025A (en) | 2004-05-14 | 2005-04-28 | Molasses treatment for the 'molassperse' surfactant production for concrete plasticizers (water reducing admixtures) and cement clinker grinding additives applications |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2007537117A (en) |
| CN (1) | CN101006025A (en) |
| NZ (1) | NZ551941A (en) |
| WO (1) | WO2005110941A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229478A (en) * | 2011-04-08 | 2011-11-02 | 江苏博特新材料有限公司 | Preparation method of molasses retarding water reducer and application thereof |
| CN103534222A (en) * | 2011-05-17 | 2014-01-22 | 建筑研究和技术有限公司 | Process for preparing additive for cementitious materials, additive and mixture comprising additive |
| CN103732556A (en) * | 2011-08-16 | 2014-04-16 | Sika技术股份公司 | Enzymatically inverted saccharose as a dispersant |
| CN106182881A (en) * | 2016-06-30 | 2016-12-07 | 潘洁萍 | A kind of sugar machine squeezes roller and manufacture method thereof |
| CN110143777A (en) * | 2019-03-19 | 2019-08-20 | 江西万年青工程有限公司 | A kind of high-efficiency concrete grinding aid |
| CN110746135A (en) * | 2019-06-06 | 2020-02-04 | 青岛筑建海绵城市科技有限公司 | Application of inorganic permeable concrete modifier in ecological city construction |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2723695B1 (en) | 2011-06-24 | 2017-01-04 | Construction Research & Technology GmbH | Cement additive |
| MX388135B (en) | 2011-06-24 | 2025-03-12 | Construction Research & Technology Gmbh | COMPOSITION OF CEMENT AND MIXTURE. |
| WO2013160158A1 (en) | 2012-04-23 | 2013-10-31 | Sika Technology Ag | Enzymatically inverted sucrose as a grinding aid |
| ES2625102T3 (en) | 2013-10-18 | 2017-07-18 | Sika Technology Ag | Inverted molasses treated under alkaline conditions as a dispersing agent for mineral suspensions |
| CN106220024A (en) * | 2016-08-26 | 2016-12-14 | 广西勤德科技股份有限公司 | A kind of cane molasses produces the method for cement grinding aid |
| RU2770264C1 (en) * | 2021-10-04 | 2022-04-14 | Акционерное общество "СУЭК-Кузбасс" | Composition for fixing dusty surfaces |
| CN115180868B (en) * | 2022-08-16 | 2023-05-16 | 贵州石博士科技股份有限公司 | Modified liquid concrete retarder and preparation method and application thereof |
| CN117720300A (en) | 2022-09-09 | 2024-03-19 | Sika技术股份公司 | Novel chromium reducing agent for cement |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1276753A (en) * | 1960-10-12 | 1961-11-24 | Ile D Etudes Et De Rech S Phar | Process for the production of food, diet and similar products from vinasses |
| JPS5229772B2 (en) * | 1972-10-18 | 1977-08-04 | ||
| JPS5240330B2 (en) * | 1974-01-25 | 1977-10-12 | ||
| JPS5338731B2 (en) * | 1974-06-04 | 1978-10-17 | ||
| US4058403A (en) * | 1975-11-12 | 1977-11-15 | Hooker Chemicals & Plastics Corporation | Refractory compositions |
| SU983254A1 (en) * | 1981-07-29 | 1982-12-23 | Филиал Северо-Кавказского Государственного Научно-Исследовательского И Проектного Института Нефтяной Промышленности | Composition for cementing high-temperature oil and gas wells |
| JPS63285138A (en) * | 1987-05-15 | 1988-11-22 | Nissan Chem Ind Ltd | Grinding aid for cement clinker and blast furnace slag |
| KR100448343B1 (en) * | 2001-11-06 | 2004-09-13 | 조석호 | Admixture for concrete comprising molasses fermentation by-product |
| EP1494990A4 (en) * | 2002-03-13 | 2010-05-26 | Grace W R & Co | Beneficiated water reducing compositions |
-
2005
- 2005-04-28 CN CNA2005800234179A patent/CN101006025A/en active Pending
- 2005-04-28 NZ NZ551941A patent/NZ551941A/en not_active IP Right Cessation
- 2005-04-28 JP JP2007511765A patent/JP2007537117A/en active Pending
- 2005-04-28 WO PCT/AU2005/000629 patent/WO2005110941A1/en active Application Filing
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229478A (en) * | 2011-04-08 | 2011-11-02 | 江苏博特新材料有限公司 | Preparation method of molasses retarding water reducer and application thereof |
| CN102229478B (en) * | 2011-04-08 | 2013-07-03 | 江苏博特新材料有限公司 | Preparation method of molasses retarding water reducer and application thereof |
| CN103534222A (en) * | 2011-05-17 | 2014-01-22 | 建筑研究和技术有限公司 | Process for preparing additive for cementitious materials, additive and mixture comprising additive |
| CN103732556A (en) * | 2011-08-16 | 2014-04-16 | Sika技术股份公司 | Enzymatically inverted saccharose as a dispersant |
| CN103732556B (en) * | 2011-08-16 | 2016-09-07 | Sika技术股份公司 | Sucrose as the Enzymatic transformation of dispersant |
| CN106182881A (en) * | 2016-06-30 | 2016-12-07 | 潘洁萍 | A kind of sugar machine squeezes roller and manufacture method thereof |
| CN106182881B (en) * | 2016-06-30 | 2017-10-27 | 潘洁萍 | A kind of sugared machine squeezes roller and its manufacture method |
| CN110143777A (en) * | 2019-03-19 | 2019-08-20 | 江西万年青工程有限公司 | A kind of high-efficiency concrete grinding aid |
| CN110746135A (en) * | 2019-06-06 | 2020-02-04 | 青岛筑建海绵城市科技有限公司 | Application of inorganic permeable concrete modifier in ecological city construction |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007537117A (en) | 2007-12-20 |
| WO2005110941A1 (en) | 2005-11-24 |
| NZ551941A (en) | 2009-10-30 |
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