WO2005110941A1 - 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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- WO2005110941A1 WO2005110941A1 PCT/AU2005/000629 AU2005000629W WO2005110941A1 WO 2005110941 A1 WO2005110941 A1 WO 2005110941A1 AU 2005000629 W AU2005000629 W AU 2005000629W WO 2005110941 A1 WO2005110941 A1 WO 2005110941A1
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- Prior art keywords
- molasses
- treatment
- acid
- molassperse
- alkali
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- 235000013379 molasses Nutrition 0.000 title claims abstract description 69
- 239000004568 cement Substances 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000000227 grinding Methods 0.000 title claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 11
- 239000000654 additive Substances 0.000 title claims abstract description 10
- 239000008032 concrete plasticizer Substances 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000010306 acid treatment Methods 0.000 claims abstract description 4
- 230000007062 hydrolysis Effects 0.000 claims abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 235000005985 organic acids Nutrition 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 235000000346 sugar Nutrition 0.000 abstract description 20
- 230000004048 modification Effects 0.000 abstract description 17
- 238000012986 modification Methods 0.000 abstract description 17
- 150000003839 salts Chemical class 0.000 abstract description 8
- JTXJZBMXQMTSQN-UHFFFAOYSA-N amino hydrogen carbonate Chemical class NOC(O)=O JTXJZBMXQMTSQN-UHFFFAOYSA-N 0.000 abstract description 7
- 150000007513 acids Chemical class 0.000 abstract description 6
- 150000008163 sugars Chemical class 0.000 abstract description 6
- 239000002270 dispersing agent Substances 0.000 abstract description 4
- 239000004615 ingredient Substances 0.000 abstract description 4
- 150000002772 monosaccharides Chemical class 0.000 abstract description 4
- 239000000344 soap Substances 0.000 abstract description 4
- 150000002170 ethers Chemical class 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 239000004567 concrete Substances 0.000 description 13
- 229920001732 Lignosulfonate Polymers 0.000 description 12
- 239000004117 Lignosulphonate Substances 0.000 description 12
- 235000019357 lignosulphonate Nutrition 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000011575 calcium Substances 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 239000011083 cement mortar Substances 0.000 description 8
- 238000000855 fermentation Methods 0.000 description 8
- 230000004151 fermentation Effects 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000011122 softwood Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000019750 Crude protein Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- -1 acids salts Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
Definitions
- Molasses (see molasses typical analysis in Appendix 1) is traditionally used as a retarding agent in concrete admixtures [1,4]. It allows increased settings and as a result slightly reducing water consumption in concrete mixes.
- This invented setting-retardant type high-early strength water reducing agent is prepared as follows: after molasses is diluted to 1.22-1.25 Baum'e degrees and heated to 70-80 deg.C, lime of 1-2 wt. % of that of diluted molasses is added for reaction to make a portion of sugar react with calcium oxide to form soluble calcium sugar which can produce optimum effect of water reduction.
- the result is that the product after reaction still retains a portion of sugar component so that the said product not only possesses the effect of water reduction, but also that of setting retarding, meanwhile, the addition of anhydrous sodium sulphate in a certain proportion makes it have the effect of high-early strength.
- “Molasses fermentation byproducts” essentially are spent waste liquor after fermentation of molasses sugars and extraction of fermentation products (mainly alcohol and yeast) from the "mother liquor”.
- This molasses spent waste liquor in comparison with original molasses contains a relatively small quantity of the byproducts from the sugar fermentation process mainly in the form of different organic acids. These acids slightly increase the surfactant properties of molasses spent waste liquor in comparison with original molasses.
- the main disadvantage (problem) of the "molasses fermentation byproducts” molasses spent waste liquor
- “molasses fermentation byproducts” contain too many variables. Therefore these byproducts are seldom used in concrete admixtures application.
- talc is a much softer material than cement clinker and gets ground significantly thinner than clinker.
- the very fine particles of talc in the complex with molasses (as adhesive agent) hypothetically can envelope cement particles averting them from (against) aggregation.
- the main disadvantage of this method is that molasses is not used as a surfactant- dispersant.
- Molasses in the series is treated in acid and alkali environments at temperatures higher than ambient.
- Inorganic and organic acids can be used for acidification of molasses up to pH 0.8
- Inorganic and organic alkalis can be used for alkalization of molasses up to pH14.0
- Temperature of acid and alkali treatment can be 50-200°C at ambient, positive and negative pressure
- Catalysts of acid and alkali hydrolysis (oxidation) can be used for the treatment
- Solids content of molasses can be 5.0-90.0%
- Acid treatment provides: - converting of polysaccharides to monosaccharides (reducing sugars) converting of the part of monosaccharides to aldonic acids - decomposition of proteins to aminocarbonic acids with a relatively high quantity of carboxyl and amino groups
- Alkali treatment provides: - converting of monosaccharides (reducing sugars) to saccharinic acids and their salts converting of aldonic acids to their salts decomposition of the residuary proteins to aminocarbonic acids - converting of aminocarbonic acids to their salts - converting (saponification) of wax ethers to the soluble soaps
- the salts of saccharinic and aldonic acids are quite strong anionic surfactants with high dispersion properties.
- the salts of aminocarbonic acids and wax soaps are effective wetting agents and detergents [7].
- the produced complex of the surfactants provides a relatively high effectiveness of the treated molasses as concrete plasticizers (water reducing admixtures) and clinker grinding additives.
- the modified molasses was tested as a plasicizer in cement mortars in comparison with the best general European softwood Na and Ca lignosulphonates.
- Ratio Cement : Sand : Water was 1 : 3 : 0.55.
- Fluidity of cement mortars was determined with Flow Table.
- Air entrainment was determined by a volumetric method.
- NA and CA Lignosulphonates are typical middle range water reducers and retarders.
- Compressive strength of all cement mortars with the molasses modifications is a slightly higher in comparison with the mortars with lignosulphonates.
- the molasses modifications are compatible with the best general European softwood Na and Ca lignosulphonates
- the molasses modifications can be characterized as middle range water reducers with a low air entrainment.
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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
Application for Invention
Title: Molasses treatment for the "Molassperse" surfactant production for concrete plasticizers (water reducing admixtures) and cement clinker grinding additives application
1. Background
1.1. Concrete admixtures
Molasses (see molasses typical analysis in Appendix 1) is traditionally used as a retarding agent in concrete admixtures [1,4]. It allows increased settings and as a result slightly reducing water consumption in concrete mixes.
Chinese patent titled: "PROCESS FOR PREPARING SETTING RETARDANT TYPE-HIGH- EARLY STRENGTH WATER-REDUCING AGENT AND PRODUCTS THEREOF" [2] is close to our presented invention.
This invented setting-retardant type high-early strength water reducing agent is prepared as follows: after molasses is diluted to 1.22-1.25 Baum'e degrees and heated to 70-80 deg.C, lime of 1-2 wt. % of that of diluted molasses is added for reaction to make a portion of sugar react with calcium oxide to form soluble calcium sugar which can produce optimum effect of water reduction. The result is that the product after reaction still retains a portion of sugar component so that the said product not only possesses the effect of water reduction, but also that of setting retarding, meanwhile, the addition of anhydrous sodium sulphate in a certain proportion makes it have the effect of high-early strength.
It is known that sugar (molasses sugar) added to the concrete mix immediately react with calcium oxide (which is produced in the process of cement hydration) and form "soluble calcium sugar".
The difference of this Chinese method, in comparison with traditional molasses using (direct molasses addition in concrete mix), is that a relatively small part molasses sugar is converted to "calcium sugar". The disadvantages in this method are: from a position of molasses modification: practically nothing is changed in the ingredients of concrete mix; just the process of formation of a small quantity of "calcium sugar" is slightly intensified "calcium sugar" starts to precipitate [3] at temperature lower than 20 deg. C misbalancing the hardening of concrete - sodium sulfate is used for reduction of traditionally strong molasses sugar retardation effect
The closest to the presented invention is the traditional Soviet Union's method [4] which is covered by Korean patent [5] titled: CONCRETE ADMIXTURES CONTAINING MOLASSES FERMENTATION BYPRODUCTS.
"Molasses fermentation byproducts" essentially are spent waste liquor after fermentation of molasses sugars and extraction of fermentation products (mainly alcohol and yeast) from the "mother liquor".
This molasses spent waste liquor in comparison with original molasses contains a relatively small quantity of the byproducts from the sugar fermentation process mainly in the form of different organic acids. These acids slightly increase the surfactant properties of molasses spent waste liquor in comparison with original molasses. The main disadvantage (problem) of the "molasses fermentation byproducts" (molasses spent waste liquor) is their still lower surfactant properties in comparison with traditional water reducing agents such as lignosulphonates. Also "molasses fermentation byproducts" contain too many variables. Therefore these byproducts are seldom used in concrete admixtures application.
1.2. Cement clinker grinding additives
Traditionally molasses is not used as a grinding additive because of its low dispersant properties (low properties surfactant). However Chinese patent [6] titled: METHOD FOR
USING TALC & MOLASSES AS CEMENT GRINDIG AID suggests to use molasses for this application in combination with talc in approximate proportion, accordingly, 1 :10.
It seems that in this composition molasses is used as a well known adhesive agent.
In the process of grinding, talc is a much softer material than cement clinker and gets ground significantly thinner than clinker. The very fine particles of talc in the complex with molasses (as adhesive agent) hypothetically can envelope cement particles averting them from (against) aggregation.
This method is not widely used because of its low effectiveness.
The main disadvantage of this method is that molasses is not used as a surfactant- dispersant.
2. Idea of the Suggested Molasses Treatment
Deep modification of the molasses ingredients, converting them to the effective surfactants with plasticizer (water reducing) and dispersant properties.
3. Description of the Treatment (Invention)
3.1. Essence of the treatment
Molasses in the series is treated in acid and alkali environments at temperatures higher than ambient.
This means the ingredients of molasses are exposed to acid and alkali hydrolysis.
3.2. Regimes and parameters of the treatment
3.2.1. Inorganic and organic acids can be used for acidification of molasses up to pH 0.8
3.2.2. Inorganic and organic alkalis can be used for alkalization of molasses up to pH14.0
3.2.3. Temperature of acid and alkali treatment can be 50-200°C at ambient, positive and negative pressure
3.2.4. Catalysts of acid and alkali hydrolysis (oxidation) can be used for the treatment
3.2.5. Solids content of molasses can be 5.0-90.0%
3.2.6. Time of the treatment:
- acid treatment 10min-24 hours alkali treatment 10min-24 hours 3.2.7. After both the acid and alkali treatment, the pH of molasses can be adjusted to the required levels.
4. Treatment effect on molasses properties
4.1. Acid treatment provides: - converting of polysaccharides to monosaccharides (reducing sugars) converting of the part of monosaccharides to aldonic acids - decomposition of proteins to aminocarbonic acids with a relatively high quantity of carboxyl and amino groups
4.2. Alkali treatment provides: - converting of monosaccharides (reducing sugars) to saccharinic acids and their salts converting of aldonic acids to their salts decomposition of the residuary proteins to aminocarbonic acids - converting of aminocarbonic acids to their salts - converting (saponification) of wax ethers to the soluble soaps
5. Properties of the new formations of the treated molasses
5.1. The salts of saccharinic and aldonic acids are quite strong anionic surfactants with high dispersion properties.
The salts of aminocarbonic acids and wax soaps are effective wetting agents and detergents [7].
5.2. Content of the produced complex of the surfactants: - domination of saccharinic and aldonic acids salts - a small part of aminocarbonic acids salts and wax soaps
5.3. The produced complex of the surfactants provides a relatively high effectiveness of the treated molasses as concrete plasticizers (water reducing admixtures) and clinker grinding additives.
6. Application tests of the treated molasses
6.1. The modified molasses was tested as a plasicizer in cement mortars in comparison with the best general European softwood Na and Ca lignosulphonates.
The test results are shown in Appendix 2.
6.2. The modified molasses was also tested as a clinker grinding additive.
The test results are shown in Appendix 3.
7. Conclusion
The results of the tests show that the molasses modifications can be effectively used for concrete plasticizers (water reducing admixtures) and cement clinker grinding additives application.
Appendix 1
Mill Molasses - Typical Analysis
Solids by Drying (%) 70-80 Total Sugar (%) 40-65 Sucrose (%) 30-40 (Jackson & Gillis method) Reducing Sugars (%) 10-20 (Lane & Eynon method) Unfermentable Sugars (%) 2-5 Crude Protein (%) 2-5 (Kjeldalh N) Ash (%) 10-15 (double sulphation)
Major Elements: Potassium 3.5-5.5 % Calcium 0.5-1.2 % Sodium 0.05-0.10 %
Trace Elements: Iron ppm Max 250 Copper ppm Max 10 Zinc ppm Max 15 Lead ppm Max 1.0 Arsenic less than ppm 1.0 Cadmium less than ppm 0.02
Appendix 2
Investigations of "Molassperse" Modified Molasses for Concrete Applications
Modifications
Three modifications of the raw molasses were done in the AIA laboratory.
The modifications were named Molassperse P-l, Molassperse P-2 and Molassperse P-3.
Testing in cement mortars
The best general European softwood Na and Ca lignosulphonates were used as control samples.
Consumption of the molasses modifications and lignosulphonates were 0.1, 0.2 and 0.3% of cement mass.
Blue Circle Southern Cement was used for making the cement mortars.
Two river sands (coarse and fine) were used in the tests (ratio 1:1).
Water/Cement ratio for all cement mortars was constant - 0.55.
Ratio Cement : Sand : Water was 1 : 3 : 0.55.
Fluidity of cement mortars was determined with Flow Table.
Air entrainment was determined by a volumetric method.
Cement mortar ISO prisms 40x40x160mm were made for compressive strength determination.
The results of the tests have shown in Table 1.
Discussion
NA and CA Lignosulphonates (control) are typical middle range water reducers and retarders.
Cement mortars with Molassperse P-l, Molassperse P-2 and Molassperse P-3 in comparison with NA Lignosulphonate and CA Lignosulphonate have a higher fluidity at low consumption 0.1 %.
At the middle consumption 0,2% and high consumption 0.3%- the mortar fluidity is similar for the molasses modifications and lignosulphonates.
Compressive strength of all cement mortars with the molasses modifications is a slightly higher in comparison with the mortars with lignosulphonates.
This can be explained by a higher air entrainment of lignosulphonates.
Conclusions The molasses modifications are compatible with the best general European softwood Na and Ca lignosulphonates The molasses modifications can be characterized as middle range water reducers with a low air entrainment.
Table 1. Comparison tests of molasses modifications Molassperse P-l, Molassperse P-2 and Molassperse P-3 with NA and CA Lignosulphonates
Investigations of "Molassperse" Modified Molasses for Cement Clinker Grinding Applications
Modifications Two modifications of the raw molasses were done in the AIA laboratory. The modifications were named Molassperse G-1 and Molassperse G-2. Testing in laboratory cement grinding mill Laboratory grinding mill with 2700 revolutions per hour and standard equipment were used. Cement clinker was ground with gypsum at a ratio of 95:5. The results of the tests are shown in Table 1.
Table 1. Clinker grinding tests of molasses modifications Molassperse G-1, and Molassperse G-2
Conclusion Both Molassperse G-1 and Molassperse G-2 can be used as effective cement clinker grinding additives.
Reference Literature
1. B.J.Addis, D.E.Davis FULTON'S CONCRETE TECHNOLOGY Portland Cement Institute Midrand, South Africa, 1986
2. WANG RUBIN, QU ZHENBIN PROCESS FOR PREPARING SETTING RETARDANT TYPE-HIGH- EARLY STRENGTH WATER-REDUCING AGENT AND PRODUCTS 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 Korea CONCRETE ADMIXTURES CONTAINING MOLASSES FERMENTATION BYPRODUCTS Patent: KR3037597A
6. BAI XIANMING, SHAO ZHONGJUN; China METHOD FOR USING TALK & MOLASSES AS CEMENT GRINDIG AID Patent: CN1089245A
7. A.M.Schwartz, J.W.Perry SURFACE ACTIVE AGENTS THEIR CHEMISTRY AND TECHNOLOGY New York - London , 1949, 545 p
Claims
8. We claim:
A molasses treatment for the surfactant production for concrete plasticizers (water reducing admixtures) and cement clinker grinding additives application, the method comprising:
8.1. Molasses is in the series treated in acid and alkali environments at temperature higher than ambient
8.
2. Inorganic and organic acids can be used for acidification of molasses up to pH 0.8
8.
3. Inorganic and organic alkalis can be used for alkalization of molasses up to pH14.0
8.
4. Temperature of acid and alkali treatment can be 50-200°C at ambient, positive and negative pressure
8.
5. Catalysts of acid and alkali hydrolysis (oxidation) can be used for the treatment
8.
6. Solids content of molasses can be 5.0-90.0%)
8.
7. Time of the treatment: - acid treatment 10min-24 hours - alkali treatment 10min-24 hours
8.8. After the both acid and alkali treatment, the pH of molasses is adjusted up to the necessary value using inorganic and organic acids and alkalis.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007511765A JP2007537117A (en) | 2004-05-14 | 2005-04-28 | Molasses treatment method for producing "Molasspers" surfactant for use in concrete fluidizer (water reducing agent) and cement clinker grinding admixture |
| NZ551941A NZ551941A (en) | 2004-05-14 | 2005-04-28 | Molasses treatment for the ômolassperseö surfactant production for concrete plasticizers (water reducing admixtures) and cement clinker grinding additives applications |
| AU2005244022A AU2005244022B2 (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 |
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 |
|---|---|
| WO2005110941A1 true WO2005110941A1 (en) | 2005-11-24 |
Family
ID=35394106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/AU2005/000629 WO2005110941A1 (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) |
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| WO2012155342A1 (en) | 2011-05-17 | 2012-11-22 | Construction Research & Technology Gmbh | Process for preparing additive for cementitious materials, additive and mixture comprising additive |
| EP2559675A1 (en) | 2011-08-16 | 2013-02-20 | Sika Technology AG | Enzymatically inverted saccharose as dispersing agent |
| US8460460B2 (en) | 2011-06-24 | 2013-06-11 | Construction Research & Technology Gmbh | Cementitious composition and admixture |
| WO2013160158A1 (en) | 2012-04-23 | 2013-10-31 | Sika Technology Ag | Enzymatically inverted sucrose as a grinding aid |
| US8657953B2 (en) | 2011-06-24 | 2014-02-25 | Construction Research & Technology Gmbh | Cement additive |
| EP2862625A1 (en) * | 2013-10-18 | 2015-04-22 | Sika Technology AG | Alkaline treated inverted molasses as a dispersant 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 |
| CN115180868A (en) * | 2022-08-16 | 2022-10-14 | 贵州石博士科技股份有限公司 | Modified liquid concrete retarder and preparation method and application thereof |
| RU2795848C1 (en) * | 2022-05-11 | 2023-05-12 | Мехманович Тагиев Сенан | Coal dust wetting agent |
| WO2024052077A1 (en) | 2022-09-09 | 2024-03-14 | Sika Technology Ag | A novel chromium reducing agent used in a cement |
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| 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 |
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| 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 |
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- 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 CN CNA2005800234179A patent/CN101006025A/en active Pending
- 2005-04-28 WO PCT/AU2005/000629 patent/WO2005110941A1/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014519466A (en) * | 2011-05-17 | 2014-08-14 | コンストラクション リサーチ アンド テクノロジー ゲーエムベーハー | Method for producing additive for cementitious material, additive, and mixture containing additive |
| WO2012155342A1 (en) | 2011-05-17 | 2012-11-22 | Construction Research & Technology Gmbh | Process for preparing additive for cementitious materials, additive and mixture comprising additive |
| US9133059B2 (en) | 2011-06-24 | 2015-09-15 | Construction Research & Technology Gmbh | Cementitious composition and admixture |
| US8460460B2 (en) | 2011-06-24 | 2013-06-11 | Construction Research & Technology Gmbh | Cementitious composition and admixture |
| US8657953B2 (en) | 2011-06-24 | 2014-02-25 | Construction Research & Technology Gmbh | Cement additive |
| US8920556B2 (en) | 2011-06-24 | 2014-12-30 | Construction Research & Technology Gmbh | Cementitious composition and admixture |
| EP2559675A1 (en) | 2011-08-16 | 2013-02-20 | Sika Technology AG | Enzymatically inverted saccharose as dispersing agent |
| WO2013024138A1 (en) | 2011-08-16 | 2013-02-21 | Sika Technology Ag | Enzymatically inverted saccharose as a dispersant |
| WO2013160158A1 (en) | 2012-04-23 | 2013-10-31 | Sika Technology Ag | Enzymatically inverted sucrose as a grinding aid |
| EP2862625A1 (en) * | 2013-10-18 | 2015-04-22 | Sika Technology AG | Alkaline treated inverted molasses as a dispersant for mineral suspensions |
| WO2015055725A1 (en) | 2013-10-18 | 2015-04-23 | Sika Technology Ag | Alkaline-treated inverted molasses as dispersants for mineral suspensions |
| US9981875B2 (en) | 2013-10-18 | 2018-05-29 | Sika Technology Ag | Alkaline-treated inverted molasses as dispersants 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 |
| RU2795848C1 (en) * | 2022-05-11 | 2023-05-12 | Мехманович Тагиев Сенан | Coal dust wetting agent |
| CN115180868A (en) * | 2022-08-16 | 2022-10-14 | 贵州石博士科技股份有限公司 | Modified liquid concrete retarder and preparation method and application thereof |
| 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 |
| WO2024052077A1 (en) | 2022-09-09 | 2024-03-14 | Sika Technology Ag | A novel chromium reducing agent used in a cement |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007537117A (en) | 2007-12-20 |
| CN101006025A (en) | 2007-07-25 |
| NZ551941A (en) | 2009-10-30 |
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