CN1285533C - Method for preparing high efficient concrete water reducing agent using heavy washing oil - Google Patents
Method for preparing high efficient concrete water reducing agent using heavy washing oil Download PDFInfo
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- CN1285533C CN1285533C CN 200410041156 CN200410041156A CN1285533C CN 1285533 C CN1285533 C CN 1285533C CN 200410041156 CN200410041156 CN 200410041156 CN 200410041156 A CN200410041156 A CN 200410041156A CN 1285533 C CN1285533 C CN 1285533C
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Abstract
The present invention discloses a method for preparing a high-efficiency water-reducing agent by using heavy washing oil, which comprises the steps: the amount of substances is calculated firstly, the weight of components, containing fluorene, dibenzofuran, methyl dibenzofuran, anthracene phenanthrene, acenaphthene, and the like in the heavy washing oil is converted into respective mole number, and the statistical mole number M of the washing oil is calculated; then the heavy washing oil is heated and put into sulphuric acid by a sulfonation reaction; the cooling and hydrolysis reaction is carried out, and the condensed acidity is adjusted by adding the sulphuric acid; a pH value is adjusted by dripping formaldehyde through a condensation reaction and a neutralization reaction, and the water-reducing agent is obtained by the steps of cooling, filtration and drying finally. The water-reducing agent for concrete prepared by the method not only has the water-reducing rate as high as 20 to 30% but also greatly increases the folding strength and the compressive strength of the prepared concrete; in addition, the production cost is low, and the method is favorable for solving the problem of pollution by the heavy washing oil and is also suitable for the plasticizing use of white slime sinter-calcium carbide sludge in chemical industry.
Description
One technical field
The present invention relates to a kind of preparation method of novel concrete water reducing agent, particularly a kind of method of utilizing heavy wash oil to prepare efficient cement water reducing agent.
Two background technologies
Water reducer claims superplasticizer again, is a kind of anion surfactant, itself not with cement generation chemical reaction, but by tensio-active agent be used for improve concrete workability energy, have diminishing enhanced effect significantly.Existing water reducer mainly contains sulfonated lignin system, naphthene sulfonic acid system and sweet ammoniacal liquor soluble resin system.The raw material majority that above-mentioned water reducer adopts is the product of Chemical Manufacture, and the starting material of preparation naphthalene series high-efficiency water-reducing agent also lack day by day, thereby the production cost height, and its output is subjected to the restriction of Chemical Manufacture.On the other hand, the further raising that high performance concrete keeps performance requriements to water-reducing property, dispersing property and the slump of high efficiency water reducing agent, people pay attention to more to amido sulfoacid series, poly-research preparation by sour series high-efficiency water-reducing agent.Quantity such as amido sulfoacid series, poly carboxylic acid series water reducer is increasing; The quantity of naphthalene system, trimeric cyanamide system is reducing, and the application maximum of polycarboxylic acid series.But polycarboxylic acid series, naphthalene system, melamine system water reducer are not broken away from the cost of material height yet, and the product price height is unfavorable for application.
Heavy wash oil is the cut of coal tar between 280 ℃～300 ℃, and its main component is fluorenes (50.42wt%), dibenzofuran (23.03wt%), methyl dibenzofuran (4.09wt%), anthracene phenanthrene (13.80wt%) and acenaphthene (2.26wt%).The report about related manufacturing processes such as the sulfonation that utilizes heavy wash oil, hydrolysis, condensation, neutralizations is not seen in the process online information retrieval, does not see with the report of heavy wash oil as the synthetic water reducer of raw material yet.
Three summary of the invention
The purpose of this invention is to provide a kind of method of utilizing heavy wash oil to prepare efficient cement water reducing agent, solving the coking industry environmental pollution problems, and provide a kind of cement water reducing agent efficiently for building trade.
The technical scheme that realizes the object of the invention is: a kind of method of utilizing heavy wash oil to prepare high efficiency water reducing agent comprises the following steps:
The first step: the amount of substance for calculation, fluorenes, dibenzofuran, methyl dibenzofuran, anthracene phenanthrene and acenaphthene content in the heavy wash oil are converted into separately mole number greater than the weight of 2.0% component, and the statistics mole number M that its summation is added up and draws heavy wash oil
Washing oil
Second step: sulfonation reaction, press heavy wash oil statistics mole number M
Washing oilWith vitriol oil mole number M
SulphurMol ratio be that 1: 1.30～1.40 ratio is added to the vitriol oil in 80～90 ℃ the heavy wash oil, be warmed up to 115～125 ℃ then and carry out sulfonation, be incubated 2～3 hours;
The 3rd step: hydrolysis reaction, sulfonation postcooling to 105～115 ℃ added the water hydrolysis 20～40 minutes, press heavy wash oil and added up mole number M
Washing oilWith water mole number M
WaterMol ratio be 1: 1～2 to add water to regulate the hydrolysis total acidity be 26～29%;
The 4th step: condensation reaction, adding sulfuric acid adjustment condensation acidity is 28～32%, perhaps presses heavy wash oil statistics mole number M
Washing oilWith vitriol oil mole number M
SulphurMol ratio is 1: 0.133～0.100 to add the vitriol oil, when temperature is reduced to 95～85 ℃, presses heavy wash oil statistics mole number M
Washing oilWith formaldehyde mole number M
FormaldehydeMol ratio be 1: 0.7～0.9 ratio to add concentration be 35～37% formaldehyde solution, condensation temp is controlled at 90～100 ℃ of reactions 2～3 hours down;
The 5th step: neutralization reaction, add concentration and be 40～30% caustic soda soln, the re-adjustment pH value cools off at last, filters and promptly get water reducer between 7～9, and its principal reaction is:
Sulfonation reaction:
Hydrolysis reaction: fluorenes, dibenzofuran are in the α position under cold condition
Condensation reaction: the condensation reaction after the fluorenes sulfonation
Condensation reaction after the dibenzofuran sulfonation
Neutralization reaction: liquid caustic soda is poured into adjusted pH value 2～3 in the condensated liquid earlier, add milk of lime then and adjust pH value 8～9.
The present invention utilizes heavy wash oil to prepare in the heavy wash oil that the vitriol oil in the sulfonation reaction of method of high efficiency water reducing agent joins 90 ℃, and add-on is pressed heavy wash oil statistics mole number M
Washing oilWith vitriol oil mole number M
SulphurMol ratio is 1: 1.4, and sulfonation temperature is controlled at 120 ℃, sulfonation insulation 2.5 hours.
The sulfonation postcooling to 110 that the present invention utilizes heavy wash oil to prepare the method for high efficiency water reducing agent ℃ added the water hydrolysis 30 minutes, pressed heavy wash oil statistics mole number M in the hydrolysis reaction
Washing oilWith water mole number M
WaterMol ratio be to add water at 1: 1.5 to regulate the hydrolysis total acidity be 28%.
It is 30% that the present invention utilizes heavy wash oil to prepare to add in the condensation reaction of method of high efficiency water reducing agent sulfuric acid to adjust condensation acidity, when temperature is reduced to 85 ℃, press heavy wash oil and adds up mole number M
Washing oil: formaldehyde mole number M
FormaldehydeIt is 36% formaldehyde solution that=1: 0.8 ratio adds concentration, and condensation temp is controlled at 95 ℃, and condensation 3 hours adds the viscosity of water management material in the reaction process.
The present invention utilizes heavy wash oil to prepare the method for high efficiency water reducing agent, and with the neutralizer solid-liquid separation of making, liquid dried obtains powdery high density water reducer.
Adopt the remarkable advantage of the cement water reducing agent of method of the present invention preparation to be: with the high efficiency water reducing agent of heavy wash oil preparation not only water-reducing rate can reach 20～30%, make concrete folding strength and the ultimate compression strength made increase substantially, and production cost is low, the pollution problem of favourable solution heavy wash oil, and the plasticizing that is suitable for chemical clay-slag-calcium carbide body refuse is used.
Four description of drawings:
Accompanying drawing is that the present invention utilizes heavy wash oil to prepare the process flow sheet of the method for high efficiency water reducing agent.
Five embodiments
Below in conjunction with accompanying drawing the present invention is further described.
Embodiment 1: in conjunction with the accompanying drawings, dropping into 100g in the there-necked flask of 500ml is the heavy wash oil of 0.5545mol, is heated to 90 ℃; Mol ratio by the heavy wash oil and the vitriol oil is 1: 1.4 adding 77.63g, and promptly the vitriol oil of 42ml reacted 2.5 hours under 120 ℃ of temperature; Being cooled to 110 ℃ then, is to add water 20ml at 1: 2 to make acidity reach 28% by the mol ratio of heavy wash oil and water, and vitriol oil 4ml is added in hydrolysis 0.5 hour again, makes acidity reach 30%; Being cooled to 85 ℃, is to add 33.3g at 1: 0.8 by the mol ratio of heavy wash oil and formaldehyde, i.e. the formaldehyde solution of 33.3ml, and reaction is 3 hours under 95 ℃ of temperature; The caustic soda soln that adds concentration 40% at last, regulating pH value is 8, can obtain water reducer through cooling, filtration and drying again.When water cement ratio is 0.3, add 1～1.5% water reducer in the cement, flowing degree of net paste of cement reaches 240mm.Volume in the concrete is 1 of cement consumption～1.5% o'clock, and water-reducing rate can reach 20～25%.Cement mortar folding strength and ultimate compression strength all improve about 20%.
Embodiment 2: in conjunction with the accompanying drawings, dropping into 100g in the there-necked flask of 500ml is the heavy wash oil of 0.5545mol, is heated to 85 ℃; The mol ratio 1 to 1.30 of pressing heavy wash oil and the vitriol oil adds 72g, i.e. the 42ml vitriol oil, and reaction is 3 hours under 120 ℃ of temperature; Be cooled to 110 ℃ then, by heavy wash oil and water mol ratio be to add water 10ml at 1: 1 to make acidity reach 28%, vitriol oil 4ml is added in hydrolysis 0.5 hour again, makes acidity reach 31%; Be cooled to 85 ℃, the mol ratio of pressing heavy wash oil and formaldehyde adds 37.3g at 1: 0.9, and promptly the formaldehyde solution of 33.3ml was reacted 3 hours under 95 ℃ of temperature; Add caustic soda soln at last, regulating pH value is 7, can obtain water reducer through cooling, drying again.When water cement ratio is 0.3, add 1～1.5% water reducer in the cement, flowing degree of net paste of cement reaches 240mm.Volume in the concrete is 1 of cement consumption～1.5% o'clock, and water-reducing rate can reach 20～25%.Cement mortar folding strength and ultimate compression strength all improve about 20%.
Claims (5)
1, a kind of method of utilizing heavy wash oil to prepare high efficiency water reducing agent comprises the following steps:
The first step: the amount of substance for calculation, fluorenes, dibenzofuran, methyl dibenzofuran, anthracene phenanthrene and acenaphthene content in the heavy wash oil are converted into separately mole number greater than the weight of 2.0% component, and the statistics mole number M that its summation is added up and draws heavy wash oil
Washing oil
Second step: sulfonation reaction, press heavy wash oil statistics mole number M
Washing oilWith vitriol oil mole number M
SulphurMol ratio be that 1: 1.30～1.40 ratio is added to the vitriol oil in 80～90 ℃ the heavy wash oil, be warmed up to 115～125 ℃ then and carry out sulfonation, be incubated 2～3 hours;
The 3rd step: hydrolysis reaction, sulfonation postcooling to 105～115 ℃ added the water hydrolysis 20～40 minutes, press heavy wash oil and added up mole number M
Washing oilWith water mole number M
WaterMol ratio be 1: 1～2 to add water to regulate the hydrolysis total acidity be 26～29%;
The 4th step: condensation reaction, adding sulfuric acid adjustment condensation acidity is 28～32%, perhaps presses heavy wash oil statistics mole number M
Washing oilWith vitriol oil mole number M
SulphurMol ratio is 1: 0.133～0.100 to add the vitriol oil, when temperature is reduced to 95～85 ℃, presses heavy wash oil statistics mole number M
Washing oilWith formaldehyde mole number M
FormaldehydeMol ratio be 1: 0.7～0.9 ratio to add concentration be 35～37% formaldehyde solution, condensation temp is controlled at 90～100 ℃ of reactions 2～3 hours down;
The 5th step: neutralization reaction, add concentration and be 40～30% caustic soda soln, the re-adjustment pH value cools off at last, filters and promptly get water reducer between 7～9.
2, the method for utilizing heavy wash oil to prepare high efficiency water reducing agent according to claim 1 is characterized in that the vitriol oil in the sulfonation reaction joins in 90 ℃ the heavy wash oil, and add-on is pressed heavy wash oil statistics mole number M
Washing oilWith vitriol oil mole number M
SulphurMol ratio is 1: 1.4, and sulfonation temperature is controlled at 120 ℃, sulfonation insulation 2.5 hours.
3, the method for utilizing heavy wash oil to prepare high efficiency water reducing agent according to claim 1 and 2 is characterized in that sulfonation postcooling to 110 ℃ added the water hydrolysis 30 minutes, presses heavy wash oil statistics mole number M in the hydrolysis reaction
Washing oilWith water mole number M
WaterMol ratio be to add water at 1: 1.5 to regulate the hydrolysis total acidity be 28%.
4, the method for utilizing heavy wash oil to prepare high efficiency water reducing agent according to claim 1 and 2, it is characterized in that adding in the condensation reaction sulfuric acid adjustment condensation acidity is 30%, when temperature is reduced to 85 ℃, presses heavy wash oil statistics mole number M
Washing oil: formaldehyde mole number M
FormaldehydeIt is 36% formaldehyde solution that=1: 0.8 ratio adds concentration, and condensation temp is controlled at 95 ℃, and condensation 3 hours adds the viscosity of water management material in the reaction process.
5, the method for utilizing heavy wash oil to prepare high efficiency water reducing agent according to claim 1 and 2 is characterized in that the neutralizer solid-liquid separation that will make, and liquid dried obtains powdery high density water reducer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410041156 CN1285533C (en) | 2004-07-02 | 2004-07-02 | Method for preparing high efficient concrete water reducing agent using heavy washing oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410041156 CN1285533C (en) | 2004-07-02 | 2004-07-02 | Method for preparing high efficient concrete water reducing agent using heavy washing oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1715236A CN1715236A (en) | 2006-01-04 |
| CN1285533C true CN1285533C (en) | 2006-11-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200410041156 Expired - Fee Related CN1285533C (en) | 2004-07-02 | 2004-07-02 | Method for preparing high efficient concrete water reducing agent using heavy washing oil |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100567197C (en) * | 2007-09-24 | 2009-12-09 | 杭州华冠建材有限公司 | Utilize industrial acenaphthylene to prepare the method for efficient cement water reducing agent |
| CN102351458B (en) * | 2011-07-14 | 2013-08-07 | 兰州大学 | Method for preparing water reducer by using low distillate section of neutral wash oil instead of industrial naphthalene |
| CN102786249B (en) * | 2012-08-21 | 2014-06-25 | 武汉格瑞林建材科技股份有限公司 | Efficient polycarboxylic water reducer modified from illegal cooking oil |
| CN103880315A (en) * | 2013-11-06 | 2014-06-25 | 东南大学 | Raw material and method for preparing concrete water reducer |
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