CN1269763C - Method for preparing water reducing agent for cement - Google Patents
Method for preparing water reducing agent for cement Download PDFInfo
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- CN1269763C CN1269763C CN 200410064511 CN200410064511A CN1269763C CN 1269763 C CN1269763 C CN 1269763C CN 200410064511 CN200410064511 CN 200410064511 CN 200410064511 A CN200410064511 A CN 200410064511A CN 1269763 C CN1269763 C CN 1269763C
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- phenanthrene
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- water
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Abstract
The present invention provides a method for preparing a water-reducing agent for cement, which has the synthesis technology that raw materials of phenanthrene sinter, sulphuric acid, formaldehyde and ethylenediamine or urea are added in a reaction kettle with the stirring function according to the raw material mole proportion of 1:1.5 to 2.5:0.8 to 1.2:0.001 to 0.01, and a product can be obtained by the reaction through the steps of vulcanization, hydrolyzed vulcanization, condensation, neutralization and re-condensation. In the method, the phenanthrene sinter is utilized as a raw material to solve the problems of high cost of a synthesized water-reducing agent and environment pollution by industrial waste slag; meanwhile, the method has the advantages of synthesis technology improvement, product performance enhancement, high water reducing rate of the synthesized product, less dosage, high flowability, good workability and concrete mechanical performance and durability improvement and enhancement. The product meets the national standard GB8076-1997 of a concrete additive. The water-reducing agent for cement produced by the method is suitable for concrete engineering, such as industry and civil architecture, road engineering, hydroelectric engineering, prefabricated components, cement products, etc.
Description
Technical field
The present invention relates to a kind of macromole and contain amino sodium sulfonate compound, particularly utilize luxuriant and rich with fragrance sulfonic acid and formaldehyde condensation and utilize quadrol or urea carries out the preparation method that a kind of cement water reducing agent is synthesized in condensation again.
Background technology
Along with the construction of Highrise buildings, people more and more pay attention to the quality and the life-span of buildings, and the urgent need water consumption is few, intensity is high, the good quality concrete of good fluidity, and generalized case is to add water reducer in concrete.In concrete, add water reducer and can when keeping concrete proportioning constant, improve concrete workability and flowability; When keeping workability constant, reduce water consumption, thereby improve concrete intensity; When keeping intensity constant, save cement consumption.The research of water reducer and application have greatly promoted the development of concrete material and technology, make the high performance concrete development of concrete technology to characteristics such as good fluidity, serviceability height, high strength and high-durabilities.Preparation has low cost, high water reducing rate, concrete flowability is good, slump-loss is little high-performance water reducing agent is the research direction that people pay attention to always.In the present disclosed report, relevant to coal tar converted products system water reducer, is raw material often with naphthalene, carbolineum, its synthesis technique adopts sulfonation, hydrolysis sulfonation again, condensation, neutralization to divide several steps to carry out, and owing to naphthalene, carbolineum price are more expensive, usually lose and strives power unexpectedly.Luxuriant and rich with fragrance slag is that coal tar processing crude anthracene separates the resistates in the system anthracene process, wherein mainly contain phenanthrene, carbazole and a spot of anthracene etc., because luxuriant and rich with fragrance slag does not also find the approach of effective utilization at present, often with the waste residue bulk deposition in plant area, serious environment pollution, if it is used, both turned waste into wealth, again environment purification.Because luxuriant and rich with fragrance slag is the resistates behind the crude anthracene recovery anthracene, difficult treatment wants to prepare high performance water reducer, needs improve synthesis technique, and the present invention dilutes raw material formaldehyde on the basis of above-mentioned synthesis technique, makes the condensation gentleness; Increase condensation again, in condensation product, introduced amino, improved the performance of water reducer.
Summary of the invention
The present invention is on the basis of original synthesis technique, mainly solve the synthesis technique problem of utilizing luxuriant and rich with fragrance slag system water reducer, luxuriant and rich with fragrance slag is to the pollution problem and the high problem of synthetic water reducer cost of environment, and this synthesis technique is a raw material with luxuriant and rich with fragrance slag, and a kind of preparation method of cement water reducing agent is provided.
Above-mentioned purpose of the present invention realizes by following processing method, in having the reactor of stirring, by the feed molar proportioning be: phenanthrene: sulfuric acid: formaldehyde: quadrol or urea=1: 1.5～2.5: 0.8～1.2: 0.001～0.01 adds raw material, follows these steps to successively react:
1) sulfonation: at first by the phenanthrene in the luxuriant and rich with fragrance slag, in reactor, add luxuriant and rich with fragrance slag by above-mentioned ratio of components, heat temperature raising, treat to begin to stir after the luxuriant and rich with fragrance slag fusion, under 120 ℃～160 ℃, slowly add the vitriol oil in 60 minutes, keep temperature of reaction then at 120 ℃～160 ℃, sulfonation reaction 2～4 hours, sulfonation finishes;
2) hydrolysis sulfonation again: being cooled to 110 ℃～120 ℃, is to add entry at 1: 3.92 by phenanthrene than water mol ratio, and hydrolysis 30 minutes then is warming up to 140 ℃～160 ℃, and sulfonation is 30 minutes again;
3) condensation: after sulfonation finishes again, be cooled to 70 ℃～80 ℃, in 60 minutes, slowly the adding mass percent is 37% formalin, in formalin, be 1: 19.6 than water mol ratio, allocate certain amount of solvent water again into by formaldehyde, add formaldehyde after, keep temperature of reaction at 70 ℃～90 ℃, condensation 3～4 hours;
4) neutralization: condensation finishes the back and adds the saturated NaOH aqueous solution, makes pH=7～8 of solution;
5) condensation again: add quadrol or urea at 70 ℃～90 ℃, condensation is 30 minutes again, vacuumized 30 minutes under 70 ℃～90 ℃ of temperature of reaction at last, steam suitable quantity of water and promptly get red-brown slime body product, the finished product effective constituent mass percent is greater than 37%.
The present invention had compared with prior art both solved the high problem of the synthetic cost of water reducer (from the price of raw material, luxuriant and rich with fragrance slag and naphthalene are compared low many of price with carbolineum), had solved luxuriant and rich with fragrance slag environmental pollution problem again.Improve synthesis technique simultaneously, increased condensation again, promptly in condensation product, introduced amino, improved product performance.Product is that a kind of macromole contains amino sodium sulfonate compound, is the red-brown slime body, pH=7～8, and good to cement and adulterant adaptability, dissemination is strong, and product meets concrete admixture standard GB 8076-1997.
Its synthesis technique advantage is: add aqueous solvent during (1) condensation and make condensation become gentle in formalin, can prevent implode; (2) add a small amount of quadrol or urea condensation again, make and introduce the amino performance that has increased tensio-active agent in the product; (3) synthesis technique is simple, less investment, and this technological process major equipment only needs a band stirs, band heats reactor, a vacuum pump and a condensing equipment to get final product; (4) synthetic cost is low, and from the price of raw material, luxuriant and rich with fragrance slag and naphthalene are compared low many of price with carbolineum, thereby is the synthetic water reducer of raw material with luxuriant and rich with fragrance slag, can reduce cost greatly.
Its sintetics performance is: (1) water-reducing rate height, in effective constituent, add 3 kilograms of this product by cement per ton, and water-reducing rate can reach 16～18%, adds 5 kilograms of water-reducing rate 〉=20%; (2) consumption is few, and by one ton of cement, this product add-on is 0.3%; (3) can make concrete slump bring up to 200mm by 30～50mm; (4) can save cement 10%～20%; (5) mobile big, workability is good, can improve mechanical performance of concrete and weather resistance.
Its environment protection significance is: luxuriant and rich with fragrance slag is the resistates of crude anthracene process for preparation of refined anthracene, also do not find the approach that effectively utilizes at present, generally be deposited in plant area as waste residue, serious environment pollution, thereby be the synthetic water reducer of raw material with luxuriant and rich with fragrance slag, both prepared a kind of high efficiency water reducing agent, reached the purpose of " turning waste into wealth; environment purification " again, have great environment protection significance, social benefit and economic benefit.
Embodiment
Embodiment 1
In having the reactor of stirring by the feed molar proportioning be: phenanthrene: sulfuric acid: formaldehyde: quadrol or urea=1: 1.5～2.5: 0.8～1.2: 0.001～0.01 adds raw material, follows these steps to successively react:
1) sulfonation: at first by the phenanthrene in the luxuriant and rich with fragrance slag, in reactor, add luxuriant and rich with fragrance slag by above-mentioned ratio of components, heat temperature raising, treat to begin to stir after the luxuriant and rich with fragrance slag fusion, under 120 ℃～160 ℃, slowly add the vitriol oil in 60 minutes, keep temperature of reaction then at 120 ℃～160 ℃, sulfonation reaction 2～4 hours, sulfonation finishes;
2) hydrolysis sulfonation again: being cooled to 110 ℃～120 ℃, is to add entry at 1: 3.92 by phenanthrene than water mol ratio, and hydrolysis 30 minutes then is warming up to 140 ℃～160 ℃, and sulfonation is 30 minutes again;
3) condensation: after sulfonation finishes again, be cooled to 70 ℃～80 ℃, in 60 minutes, slowly adding mass percent and be 37% formalin, prevent implode for making the condensation reaction gentleness, is 1: 19.6 by formaldehyde than water mol ratio in formalin, allocate certain amount of solvent water again into, after adding formaldehyde, keep temperature of reaction at 70 ℃～90 ℃, condensation 3～4 hours;
4) neutralization: condensation finishes the back and adds the saturated NaOH aqueous solution, makes pH=7～8 of solution;
5) condensation again: add quadrol or urea at 70 ℃～90 ℃, condensation is 30 minutes again, vacuumized 30 minutes under 70 ℃～90 ℃ of temperature of reaction at last, steam suitable quantity of water and promptly get red-brown slime body product, the finished product effective constituent mass percent is greater than 37%.
Embodiment 2
According to the processing method of embodiment 1, the mole proportioning of its raw material is: phenanthrene: sulfuric acid: formaldehyde: quadrol=1: 1.5: 0.8: 0.001.
Embodiment 3
According to the processing method of embodiment 1, the mole proportioning of its raw material is: phenanthrene: sulfuric acid: formaldehyde: urea=1: 1.5: 0.8: 0.001.
Embodiment 4
According to the processing method of embodiment 1, the mole proportioning of its raw material is: phenanthrene: sulfuric acid: formaldehyde: quadrol=1: 2.0: 1.0: 0.005.
Embodiment 5
According to the processing method of embodiment 1, the mole proportioning of its raw material is: phenanthrene: sulfuric acid: formaldehyde: urea=1: 2.0: 1.0: 0.005.
Embodiment 6
According to the processing method of embodiment 1, the mole proportioning of its raw material is: phenanthrene: sulfuric acid: formaldehyde: quadrol=1: 2.5: 1.2: 0.01.
Embodiment 7
According to the processing method of embodiment 1, the mole proportioning of its raw material is: phenanthrene: sulfuric acid: formaldehyde: urea=1: 2.5: 1.2: 0.01.
Claims (4)
1. the preparation method of a cement water reducing agent, it is characterized in that in having the reactor of stirring, mole proportioning by raw material is: phenanthrene: sulfuric acid: formaldehyde: quadrol or urea=1: 1.5～2.5: 0.8～1.2: 0.001～0.01, add raw material, and follow these steps to successively react:
1) sulfonation: at first by the phenanthrene in the luxuriant and rich with fragrance slag, in reactor, add luxuriant and rich with fragrance slag by above-mentioned ratio of components, heat temperature raising, treat to begin to stir after the luxuriant and rich with fragrance slag fusion, under 120 ℃～160 ℃, slowly add the vitriol oil in 60 minutes, keep temperature of reaction then at 120 ℃～160 ℃, sulfonation reaction 2～4 hours, sulfonation finishes;
2) hydrolysis sulfonation again: being cooled to 110 ℃～120 ℃, is to add entry at 1: 3.92 by phenanthrene than the mol ratio of water, and hydrolysis 30 minutes then is warming up to 140 ℃～160 ℃, and sulfonation is 30 minutes again;
3) condensation: after sulfonation finishes again, be cooled to 70 ℃～80 ℃, in 60 minutes, slowly the adding mass percent is 37% formalin, in formalin, be 1: 19.6 than water mol ratio, allocate certain amount of solvent water again into by formaldehyde, add formaldehyde after, keep temperature of reaction at 70 ℃～90 ℃, condensation 3～4 hours;
4) neutralization: condensation finishes the back and adds the saturated NaOH aqueous solution, makes pH=7～8 of solution;
5) condensation again: add quadrol or urea at 70 ℃～90 ℃, condensation is 30 minutes again, vacuumized 30 minutes under 70 ℃～90 ℃ of temperature of reaction at last, steam suitable quantity of water and promptly get red-brown slime body product, the finished product effective constituent mass percent is greater than 37%.
2. the preparation method of a kind of cement water reducing agent according to claim 1 is characterized in that the feed molar proportioning of this method is: phenanthrene: sulfuric acid: formaldehyde: quadrol or urea=and 1: 1.5: 0.8: 0.001.
3. the preparation method of a kind of cement water reducing agent according to claim 1 is characterized in that the feed molar proportioning of this method is: phenanthrene: sulfuric acid: formaldehyde: quadrol or urea=and 1: 2.0: 1.0: 0.005.
4. the preparation method of a kind of cement water reducing agent according to claim 1 is characterized in that the feed molar proportioning of this method is: phenanthrene: sulfuric acid: formaldehyde: quadrol or urea=and 1: 2.5: 1.2: 0.01.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410064511 CN1269763C (en) | 2004-10-20 | 2004-10-20 | Method for preparing water reducing agent for cement |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410064511 CN1269763C (en) | 2004-10-20 | 2004-10-20 | Method for preparing water reducing agent for cement |
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| Publication Number | Publication Date |
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| CN1600734A CN1600734A (en) | 2005-03-30 |
| CN1269763C true CN1269763C (en) | 2006-08-16 |
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| CN 200410064511 Expired - Fee Related CN1269763C (en) | 2004-10-20 | 2004-10-20 | Method for preparing water reducing agent for cement |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1299803C (en) * | 2005-06-09 | 2007-02-14 | 太原理工大学 | Process for preparing flue gas desulfurization agent |
| CN104446097A (en) * | 2014-11-14 | 2015-03-25 | 浙江建研科之杰新材料有限公司 | Preparation method of dye dispersant and concrete naphthalene water reducer |
| CN108081447A (en) * | 2017-12-01 | 2018-05-29 | 福州市鸿生建材有限公司 | A kind of pile pile production technology |
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