CN1089581A - Igredient for cement raw material used as high-efficiency agent for dilution and grinding aid - Google Patents
Igredient for cement raw material used as high-efficiency agent for dilution and grinding aid Download PDFInfo
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- CN1089581A CN1089581A CN 93121287 CN93121287A CN1089581A CN 1089581 A CN1089581 A CN 1089581A CN 93121287 CN93121287 CN 93121287 CN 93121287 A CN93121287 A CN 93121287A CN 1089581 A CN1089581 A CN 1089581A
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Abstract
Igredient for cement raw material used as high-efficiency agent for dilution and grinding aid.Adopting peat, brown coal or weathered coal is raw material, after the pulverizing,, filter residue is alkalized through oxidation, filtration, or alkalization and sulfonation, removal of impurities promptly obtains required high-efficiency agent for dilution grinding aid.Raw material of the present invention is easy to get, cost is low, humic acids in the brown coal is after oxidation, the strongest to the cement raw slurry diluting effect, so consumption is little and effect is obvious, alkalization can be carried out in a step with sulfonation, save energy, shortened processing step, introduced hydrophilic radical, the grinding aid dilution function of humic acids is effectively strengthened.Can utilize sulfurous gas and paper plant's black liquor in the stack gas, help environment protection, turn waste into wealth.
Description
The invention belongs to the technical field of cement additire, specifically is a kind of when being used for wet production cement, can play the efficient additive of dilution grinding aid effect to cement raw slurry.
Wet-process cement production has many advantages, convenient as slip with pipe-line transportation, the wet grinding dust is few, quality product equilibrium etc., but a disadvantage of wet-process cement production is exactly the energy consumption height, and 35-38% is arranged in institute's thermal losses is the water evaporates that is used for slip, the general every reduction of slip moisture content 1%(wet basis), unit heat consumption can reduce 1-2%, and kiln output can increase by 2%, therefore, in the wet production of cement, should reduce the moisture content of slip as much as possible.In order to reduce the moisture content of slip, people have adopted some materials to make additive, but existing additive such as tripoly phosphate sodium STPP, water glass etc. are because efficient is low, and the cost height fails to apply industrial.
In order to seek a kind of additive efficiently, the contriver has carried out deep research to adopting humic acids as cement dilution grinding aid.The humic acid that contains 10-80% in brown coal, peat (peat composed of rotten mosses), the weathered coal, humic acid is not the simplification compound, but molecular size is different and the mixture of the multiple compound that the structure composition differs, these compounds contain elements such as nitrogen, oxygen, carbon, they are the polyfunctional group chain-like macromolecule compounds that contain aromatic nucleus and ethylene linkage, there are carboxyl, alcoholic extract hydroxyl group, phenolic hydroxyl group, methoxyl group etc. in these functional groups, and wherein, what mainly play diluting effect is carboxyl, phenolic hydroxyl group and methoxyl group etc.Humic acids divides Ulmic acids, ulmic acid and xanthohumic acid.Evidence, what diluting effect was the strongest is ulmic acid, and energy of oxidation makes Ulmic acids change into ulmic acid and humic acids.Carboxyl, phenolic hydroxyl group methoxyl group increase, and sulfonation or sulfomethylation make the interior hydrophilic radical-CH-SO of introducing of humic acids make the humic acids modification generate the high-efficiency agent for dilution agent.The black liquor serious environment pollution of the sulfurous gas in the stack gas, paper mill discharging; in black liquor, contain alkali, S-WAT and xylogen, if can utilize sulfur in smoke and paper plant's black liquor production dilution grinding aid, both helped environment protection; can reduce production costs again, turn waste into wealth.
The purpose of this invention is to provide that a kind of raw material is easy to get, cost is low, and the good Igredient for cement raw material used as high-efficiency agent for dilution and grinding aid of dilution grinding-aid effect.
Technology contents of the present invention is:
Igredient for cement raw material used as high-efficiency agent for dilution and grinding aid, main component are a kind of through oxidation and sulfonated modified humic acid, can adopt following method manufacturing:
The present invention is a raw material with peat, brown coal or weathered coal, after the pulverizing, through oxidation, filtration, filter residue is alkalized and sulfonation, or alkalization and sulfonation carries out simultaneously, and removal of impurities promptly obtains required high-efficiency agent for dilution grinding aid.Grinding particle size is the 20-200 order, adopt nitric acid or nitric acid+potassium permanganate to make oxygenant during oxidation, ratio of components (weight percent) is brown coal: nitric acid (or nitric acid+potassium permanganate): water=1: 0.05-3: 1-10(or water=1: 0.05-3: 0.001-0.02: 1-10), oxidizing temperature 75-100 ℃, heated 1.5-2.5 hour.Filter residue is added alkali (or black liquor) alkalization, and ratio of components is a filter residue: alkali: water=1: 0.05-2: 1-10(or filter residue: alkali: black liquor=1: 0.05-2: 0.5-10) alkalization temperature is 70-95 ℃, heats 1-2 hour.The sulphonating agent that adopts is S-WAT or Sodium Pyrosulfite or sulfurous gas, and ratio of components is filter residue: S-WAT: alkali: water=1: 0.05-2: 0.05-2: 0.05-10, sulfonation temperature are 75-100 ℃, 1-2 hour heat-up time.Described sulfurous gas can be the sulfurous gas in the stack gas.The dilution grinding aid that the present invention makes also can be used as the additive of cement water reducing agent or coal water slurry.
Fig. 1 is a process flow diagram of the present invention.
Embodiment 1: with brown coal (containing HA62%) is that 25 grams are raw material, adds 10% HNO
3200 milliliters, heated 1 hour, filter.Filter residue 20 grams add 5 gram NaOH5 gram NaSO
3, add 200 milliliters in water, to boil 2 hours, oven dry obtains diluting grinding aid product 29.5 grams; It is 9 that filtrate is adjusted pH with NaOH, adds gac 10 grams, and adsorption filtration is that 10 buck cleans with pH again, and evaporate to dryness gets SODLUM FULVATE 1.5 and restrains.
During use, in cement raw slurry, add 0.3% above-mentioned dilution grinding aid, moisture 18% o'clock of cement raw slurry, degree of mobilization is 170mm.
Embodiment 2: with brown coal 25 grams, add 5% HNO
3200 milliliters, KMnO
42.5 gram boiled 1 hour, filtered, and got filter residue 19.8 grams, added 100 milliliters of black liquors, added 5 gram NaOH, 5 restrain NaSO
3Boiled 2 hours, and dried to such an extent that product 22 restrains.
During use, add this thinner of 0.3% in cement raw slurry, during slip moisture content 18%, degree of mobilization is 210mm.
Embodiment 3: restrain with brown coal 25, add 50 milliliters of industrial nitric acids, boiled 2 hours, filter to such an extent that filter residue 24 restrains, add the NaOH7.5 gram and boiled 1 hour, get the dilution grinding aid products of 31.3 grams.
During use, add this dilution grinding aid of 0.3% in cement raw slurry, during slip moisture content 18%, degree of mobilization is 190mm.
Embodiment 4: with brown coal 25 grams, 200 milliliters in the nitric acid of adding 5%, boiled 1 hour, and filtered, filtrate is returned usefulness through charcoal absorption, use the alkali liquid washing gac, dry that SODLUM FULVATE 1.3 restrains, filter residue adds sodium hydroxide 7.5 grams, adds 100 milliliters of black liquor again, 400 ℃ of gas dryings get product 33.4 grams.
During use, in 0.3% adding cement slurry, during slip moisture content 18%, degree of mobilization 160mm.
Embodiment 5: with brown coal 25 grams, add 100 milliliters in 5% nitric acid, add Potcrate 2 grams, boiled 1 hour, filter identical with embodiment 4; Filter residue adds 7.5 gram sodium hydroxide, adds 100 milliliters in water, feeds sulfur dioxide gas 20 minutes, and the dry grinding aid product 32.6 that must dilute restrains.
The dilution grinding aid of adding 0.3% in cement raw slurry, cement slurry moisture content 18%, degree of mobilization 165mm.
Compared with prior art, the present invention has the following advantages:
1, the brown coal equal size of occurring in nature is abundant, so raw material of the present invention is easy to get, and cost is low, The humic acid that contains in the brown coal makes the humic acid chain rupture after oxidation, ulmic acid content increases greatly, and ulmic acid is the strongest to the cement raw slurry diluting effect, so the little and successful of consumption. The present invention can extract again the very high fulvic acid of value as byproduct simultaneously from brown coal.
2, alkalization and one step of sulfonation carry out, and energy savings has shortened processing step, introduces hydrophilic radical, and the grinding aid dilution function of humic acid is effectively strengthened.
4, fluid product can use after drying after the alkalization, carries out drying as adopting flue gas, both can saving heat energy, and dry sulfonated product, but the sulfur dioxide in the absorption from flue gas again provide a new way for reducing sulfur dioxide to the pollution of environment; The present invention also can utilize paper plant's black liquor also to turn waste into wealth, and is conducive to environmental protection. Therefore, the present invention has good Social benefit and economic benefit.
Claims (6)
1, a kind of main component is the Igredient for cement raw material used as high-efficiency agent for dilution and grinding aid of modified humic acid, it is characterized in that adopting following method manufacturing, with peat, brown coal or weathered coal is raw material, after the pulverizing, through oxidation, filtration, filter residue is alkalized and sulfonation, or alkalization and sulfonation are carried out simultaneously, removal of impurities promptly obtains required high-efficiency agent for dilution grinding aid.
2, dilution grinding aid according to claim 1, it is characterized in that grinding particle size is the 20-200 order, adopt nitric acid or nitric acid+potassium permanganate to make oxygenant during oxidation, ratio of components (weight percent) is brown coal: nitric acid (or nitric acid+potassium permanganate): water=1: 0.05-3: 1-10(or water=1: 0.05-3: 0.001-0.02: 1-10), oxidizing temperature 75-100 ℃, heated 1.5-2.5 hour.
3, dilution grinding aid according to claim 1, it is characterized in that filter residue is added alkali (or black liquor) alkalization, ratio of components is a filter residue: alkali: water=1: 0.05-2: 1-10(or filter residue: alkali: black liquor=1: 0.05-2: 0.5-10) alkalization temperature is 70-95 ℃, heats 1-2 hour.
4, dilution grinding aid according to claim 1, it is characterized in that the sulphonating agent that adopts is S-WAT or Sodium Pyrosulfite or sulfurous gas, ratio of components is, filter residue: S-WAT: alkali: water=1: 0.05-2: 0.05-2: 0.05-10, sulfonation temperature is 75-100 ℃, 1-2 hour heat-up time.
5, dilution grinding aid according to claim 4 is characterized in that described sulfurous gas can be the sulfurous gas in the stack gas.
6, application rights requires 1 described dilution grinding aid, also can be used as the additive of cement water reducing agent or coal water slurry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93121287A CN1037764C (en) | 1993-12-30 | 1993-12-30 | Igredient for cement raw material used as high-efficiency agent for dilution and grinding aid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93121287A CN1037764C (en) | 1993-12-30 | 1993-12-30 | Igredient for cement raw material used as high-efficiency agent for dilution and grinding aid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1089581A true CN1089581A (en) | 1994-07-20 |
| CN1037764C CN1037764C (en) | 1998-03-18 |
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ID=4993647
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93121287A Expired - Fee Related CN1037764C (en) | 1993-12-30 | 1993-12-30 | Igredient for cement raw material used as high-efficiency agent for dilution and grinding aid |
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| Country | Link |
|---|---|
| CN (1) | CN1037764C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453492C (en) * | 2003-06-09 | 2009-01-21 | 黑龙江省永新煤炭化工有限责任公司 | Cement grinding aids and production process thereof |
| CN102001840A (en) * | 2010-12-10 | 2011-04-06 | 甘肃省建材科研设计院 | Powder composite cement grinding additive and preparation method thereof |
| CN105130261A (en) * | 2015-08-25 | 2015-12-09 | 建华建材（蚌埠）有限公司 | Cement grinding aid for building and preparation method for cement grinding aid |
| CN105130260A (en) * | 2015-08-25 | 2015-12-09 | 建华建材（蚌埠）有限公司 | Special diluting grinding aid for cement production and preparation method for special diluting grinding aid |
| CN106753679A (en) * | 2016-11-14 | 2017-05-31 | 中海油天津化工研究设计院有限公司 | A kind of energy-saving material in New Type Dry-process Cement Production |
| CN109824284A (en) * | 2017-11-23 | 2019-05-31 | 湖南昌迪环境科技有限公司 | A kind of cement slurry additive and its application and cement production process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3954491A (en) * | 1974-10-21 | 1976-05-04 | Diamond Shamrock Corporation | Process for production of raw mix cement slurries having reduced water content |
| US4175975A (en) * | 1975-12-29 | 1979-11-27 | The Dow Chemical Company | Aqueous suspensions |
-
1993
- 1993-12-30 CN CN93121287A patent/CN1037764C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453492C (en) * | 2003-06-09 | 2009-01-21 | 黑龙江省永新煤炭化工有限责任公司 | Cement grinding aids and production process thereof |
| CN102001840A (en) * | 2010-12-10 | 2011-04-06 | 甘肃省建材科研设计院 | Powder composite cement grinding additive and preparation method thereof |
| CN102001840B (en) * | 2010-12-10 | 2013-01-30 | 甘肃省建材科研设计院 | Powder composite cement grinding additive and preparation method thereof |
| CN105130261A (en) * | 2015-08-25 | 2015-12-09 | 建华建材（蚌埠）有限公司 | Cement grinding aid for building and preparation method for cement grinding aid |
| CN105130260A (en) * | 2015-08-25 | 2015-12-09 | 建华建材（蚌埠）有限公司 | Special diluting grinding aid for cement production and preparation method for special diluting grinding aid |
| CN106753679A (en) * | 2016-11-14 | 2017-05-31 | 中海油天津化工研究设计院有限公司 | A kind of energy-saving material in New Type Dry-process Cement Production |
| CN109824284A (en) * | 2017-11-23 | 2019-05-31 | 湖南昌迪环境科技有限公司 | A kind of cement slurry additive and its application and cement production process |
| CN109824284B (en) * | 2017-11-23 | 2021-08-27 | 湖南昌迪环境科技有限公司 | Cement raw material additive, application thereof and cement production process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1037764C (en) | 1998-03-18 |
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