CN1903778A - Preparation method of concrete high efficiency water reducer - Google Patents
Preparation method of concrete high efficiency water reducer Download PDFInfo
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- CN1903778A CN1903778A CN 200610048102 CN200610048102A CN1903778A CN 1903778 A CN1903778 A CN 1903778A CN 200610048102 CN200610048102 CN 200610048102 CN 200610048102 A CN200610048102 A CN 200610048102A CN 1903778 A CN1903778 A CN 1903778A
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Abstract
The present invention discloses a preparation method of concrete high-effective water-reducing agent. It is made up by using coal tar, residuum produced after the crude benzene is rectified in the coking plant or residuum of refinery as raw material through the processes of sulfonation, hydrolysis, condensation and neutralization.
Description
Technical field
The present invention relates to a kind of preparation method of concrete high efficiency water reducing agent, belong to build concrete admixture preparing technical field.
Background technology
In the concrete production process, water reducer is most important and the most frequently used concrete admixture, claims dispersion agent or dehydrating agent again.The main component of water reducer is a tensio-active agent, be by improving the character at solid, liquid interface, when significantly reducing the fresh concrete water consumption, still keep the workability of concrete mix, promptly improve a kind of the add chemical assistant of concrete in constructing operation performances such as mix, transportation, pouring, tampings.High efficiency water reducing agent claims superplasticizer again, can significantly reduce the fresh concrete water consumption, improve concrete performance, prolong concrete work-ing life, or keep concrete performance and reducing the chemical additive of cement consumption work-ing life on the basic basis of invariable by a relatively large margin.Adopt the high efficiency water reducing agent technology, both can prepare high performance concrete, be widely used in economic construction and social development, bringing into play significant role in the construction projects such as Highrise buildings, large-scale dykes and dams, highway, bridge, tunnel, national defence; Low cost, high water reducing rate, concrete flowability are good, degree of subsiding loss high-performance water reducing agent little, that compressive strength rate is high is the research direction that people pay attention to always and preparation has.In the prior art, naphthalene system, trimeric cyanamide system, modified lignin sulfonate high efficiency water reducing agent are to use the most general high efficiency water reducing agent, their water-reducing rate height, but because its raw material anxiety, price sharp rises, and has limited the development of high efficiency water reducing agent.So, it is low and water-reducing effect is good to seek a kind of raw materials cost, can strengthen the high efficiency water reducing agent new variety with various cement adaptabilities again, be not only an importance of high-strength high-performance concrete horizontal development, also just become a new problem of concrete material science.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of concrete high efficiency water reducing agent, solved present preparation high efficiency water reducing agent the raw material anxiety, cost an arm and a leg and cause the high problem of water reducer cost.
Design of the present invention is such.Coal tar, coke-oven plant's crude benzol rectified residue (are called the heavy benzol slag or the aromatic hydrocarbons mixture of weighing; together following) or the refinery residue; it is very complicated mixture of organic substance; mainly comprise multiple organic compositions such as trimethylbenzene, naphthalene, anthracene, indenes, phenanthrene; be mainly used in preparation pitch at present or it is added in the tar again and recycle; the former economical efficiency is lower, and the latter through regular meeting blocking pipe is taken place and caused stopping production, maintenance in operational process.Carrying out heavy aromatics synthetic study utilization, how to make full use of this part resource, promote its economic worth, be economic construction and enterprise development service, is a urgent and important research project.With coal tar, coke-oven plant's crude benzol rectified residue or refinery residue is raw material, and the preparation high efficiency water reducing agent both can reduce environmental pollution, can obtain high value-added product again.The applicant does not see that utilization is the report of feedstock production high efficiency water reducing agent with coal tar, coke-oven plant's crude benzol rectified residue or refinery residue by literature search.For this reason, the applicant is through a large amount of experimental studies, and having proposed with above three class waste materials is the method for feedstock production high efficiency water reducing agent, and, whole process of preparation does not have the discharging of any waste water,waste gas and industrial residue, therefore, this preparation technology be one clean, environmentally friendly technology.
Particularly, technical scheme of the present invention is such, and method of the present invention may further comprise the steps:
(1) feeds intake
Coal tar, crude benzol rectified residue or the refinery residue of metering are dropped in the reactor, stir, be warming up to 90 ℃-110 ℃, by residue: the sulfuric acid mass ratio is 1: 0.5-0.9 drips the vitriol oil that massfraction is 95%-98% in the thread mode;
(2) sulfonation
Be warmed up to 110 ℃ of-140 ℃ of sulfonation insulation 1-4h, be warmed up to 160 ℃ of-180 ℃ of sulfonation insulation 1-3h again, afterwards, by residue: the quality ratio is 1: the 0.3-0.7 thin up, and insulation 20-60min, sulfonation acidity is surveyed in sampling, get final product to 20%-50%, at 100 ℃ of-140 ℃ of hydrolysis 20-60min;
(3) condensation
Be cooled to 80 ℃-100 ℃, by residue: the material mass ratio that contains aldehyde radical is 1: 0.1-0.4 slowly drips the material that contains aldehyde radical, whole dropping time 40-180min, then, in 85 ℃ of-120 ℃ of condensation reaction 2-7h;
When material viscosity is big, should in time in still, replenishes less water and regulate;
Dropping contains in the aldehyde radical material process very fast if find that material heats up, in time the logical cooling water temperature of chuck in still;
Sudden and violent poly-for preventing, drip again after can in the material that contains aldehyde radical that drips, adding water earlier, amount of water is by the material that contains aldehyde radical: the quality ratio is 1: 0.2-0.8;
The described material that contains aldehyde radical is more suitable with formaldehyde, acetaldehyde or furfural;
(4) neutralization
The material that condensation is good is put into neutralizing well, adds alkaline solution earlier, adds the milk of lime neutralization again, makes material pH value be 6-10, then, material filtering is removed calcium sulfate precipitation, gets brown thick liquid product;
Used alkaline solution is that sodium hydroxide, yellow soda ash, ammoniacal liquor or other are alkaline substance solution;
The alkaline solution add-on is in residue: the solute mass ratio in the alkaline solution is 1: the ratio of 0.2-0.8 adds;
It is the most first-selected with the hydro-oxidation sodium solution that institute adds alkaline solution, and the massfraction of institute's hydro-oxidation sodium solution is that 10%-60% is suitable;
Liquid product is made pulvis through spraying drying, and the pulvis finished product is a Vandyke brown.
The positively effect that the present invention obtains is: both solved water reducer and synthesized the high problem of cost (from the price of raw material, coal tar, heavy aromatics, petroleum residue are compared low many of price with naphthalene), solved residue (waste residue) pollution on the environment problem again.The high efficiency water reducing agent of preparation, its every index all meets or exceeds GB GB8076-1997 requirement.The present invention not only makes residue turn waste into wealth, and has also increased new variety for cement uses industry, has reached the purpose of " turning waste into wealth environment purification ", has great environment protection significance, social benefit and economic benefit.
Embodiment
Following examples are used to illustrate the present invention.
Embodiment 1
In 4 mouthfuls of flasks, add Coking Plant, Shijiazhuang's crude benzol workshop rectified residue (heavy benzol slag or heavy aromatics mixture) 200g, composition mainly comprises trimethylbenzene, naphthalene, anthracene, indenes, phenanthrene etc., stir, be warming up to 80 ℃-115 ℃, slowly drip 98% dense H2SO4140g, be warmed up between 120 ℃-125 ℃ and be incubated 2h, be warmed up to again between 160 ℃-165 ℃ and be incubated 1h.Afterwards, add water 100ml dilution, add 98% vitriol oil 25g again, controlled temperature drips formaldehyde 40g between 90-95 ℃, and is sudden and violent poly-for preventing, adds water 20ml in formaldehyde.The whole dropping time should not be less than 50min.Add in the formaldehyde process if find that material heats up very fast, should the logical cold water cooling of chuck in still in time.Afterwards, be warming up to 97 ℃-105 ℃, insulation 3.5h-4h.In insulating process, in reactor, add the dilution of 20 ml waters every half an hour, add about 140 milliliters in water altogether.After the cooling, the NaOH liquid caustic soda with 30% neutralizes behind the pH=7.5, and discharging promptly gets brown slime body product.The product that makes with the present invention, two leading indicators of water-reducing rate and compressive strength rate have reached 20.9% (GB is 〉=12%) and 169,163,159,116 (GB is 1d 〉=130,3d 〉=120,7d 〉=115) respectively through Hebei Prov. Architecture Science Academy's detection.
Embodiment 2
In 4 mouthfuls of flasks, add Coking Plant, Shijiazhuang's crude benzol workshop rectified residue (heavy benzol slag or heavy aromatics mixture) 100g, stir, be warming up to 100 ℃-105 ℃, slowly drip 98% dense H2SO470g, start the sour gas that the water film dust removal device absorption reaction produces simultaneously; Be warmed up between 120 ℃-125 ℃ and be incubated 2h, be warmed up to again between 160 ℃-165 ℃ and be incubated 1h.Afterwards, add water 50ml dilution, insulation 30min, controlled temperature drips formaldehyde 20g between 90-95 ℃, sudden and violent poly-for preventing, adds water 10ml in formaldehyde, and the whole dropping time should not be less than 60min.It is very fast if find that material heats up to add the formaldehyde process, should the logical cold water cooling of chuck in still in time.Afterwards, be warming up to 97 ℃-105 ℃, insulation 3.5h-4h.In insulating process, in reactor, add the dilution of 10 ml waters every half an hour, add about 70 milliliters in water altogether.After the cooling, the NaOH liquid caustic soda with 30% neutralizes behind the pH=8, concentrates discharging.
Embodiment 3
In 4 mouthfuls of flasks, add Coking Plant, Shijiazhuang's crude benzol workshop rectified residue (heavy benzol slag or heavy aromatics mixture) 100g, stir, be warming up to 100 ℃-105 ℃, slowly drip 98% dense H2SO480g, start the sour gas that the water film dust removal device absorption reaction produces simultaneously; Be warmed up between 120 ℃-125 ℃ and be incubated 1h, be warmed up to again between 160 ℃-165 ℃ and be incubated 2h.Afterwards, add water 100ml dilution, controlled temperature drips formaldehyde 20g between 90-95 ℃, and is sudden and violent poly-for preventing, adds water 10ml in formaldehyde, whole dropping time 70min.It is very fast if find that material heats up to add the formaldehyde process, should the logical cold water cooling of chuck in still in time.Afterwards, be warming up to 97 ℃-105 ℃, insulation 3.5h-4h.After viscosity reached prescribed value, dilute with water after the cooling, neutralized behind the pH=9 with liquid caustic soda NaOH.Promptly get Vandyke brown thick liquid product, discharging.
Claims (5)
1, a kind of preparation method of concrete high efficiency water reducing agent is characterized in that may further comprise the steps:
(1) feeds intake
Coal tar, crude benzol rectified residue or the refinery residue of metering are dropped in the reactor, stir, be warming up to 90 ℃-110 ℃, by residue: the sulfuric acid mass ratio is 1: 0.5-0.9 drips the vitriol oil that massfraction is 95%-98% in the thread mode; Start the sour gas that the water film dust removal device absorption reaction produces simultaneously;
(2) sulfonation
Be warmed up to 110 ℃ of-140 ℃ of sulfonation insulation 1-4h, be warmed up to 160 ℃ of-180 ℃ of sulfonation insulation 1-3h again, afterwards, by residue: the quality ratio is 1: the 0.3-0.7 thin up, and insulation 20-60min, sulfonation acidity is surveyed in sampling, get final product to 20%-50%, at 100 ℃ of-140 ℃ of hydrolysis 20-60min;
(3) condensation
Be cooled to 80 ℃-100 ℃, by residue: the material mass ratio that contains aldehyde radical is 1: 0.1-0.4 slowly drips the material that contains aldehyde radical, whole dropping time 40-180min, then, in 85 ℃ of-120 ℃ of condensation reaction 2-7h;
(4) neutralization
The material that condensation is good is put into neutralizing well, adds alkaline solution earlier, adds the milk of lime neutralization again, makes material pH value be 6-10, then, material filtering is removed calcium sulfate precipitation, gets brown thick liquid product;
Liquid product is made the pulvis finished product through spraying drying.
2, by the preparation method of the described concrete high efficiency water reducing agent of claim 1, it is characterized in that: in step (3), drip after containing of dropping adds water in the aldehyde radical material, amount of water is by containing the aldehyde radical material: the quality ratio is 1: 0.2-0.8 again.
3, by the preparation method of claim 1 or 2 described concrete high efficiency water reducing agents, it is characterized in that: in step (3), the aldehyde radical material that contains of dropping is formaldehyde, acetaldehyde or furfural.
4, by the preparation method of the described concrete high efficiency water reducing agent of claim 1, it is characterized in that: in step (4), used alkaline solution is sodium hydroxide, yellow soda ash, ammoniacal liquor or is alkaline substance solution.
5, by the preparation method of claim 1 or 4 described concrete high efficiency water reducing agents, it is characterized in that: in step (4), the alkaline solution add-on is by residue: the solute mass ratio in the alkaline solution is 1: the ratio adding of 0.2-0.8.
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| CNB2006100481026A CN100386282C (en) | 2006-08-02 | 2006-08-02 | Preparation method of concrete high efficiency water reducer |
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| CNB2006100481026A CN100386282C (en) | 2006-08-02 | 2006-08-02 | Preparation method of concrete high efficiency water reducer |
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| CN1903778A true CN1903778A (en) | 2007-01-31 |
| CN100386282C CN100386282C (en) | 2008-05-07 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101913792A (en) * | 2010-08-24 | 2010-12-15 | 中南林业科技大学 | Method for producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer |
| CN101560074B (en) * | 2008-04-16 | 2012-11-21 | 万方 | Water reducer produced by utilizing zirconium silica residues and production method thereof |
| CN111825364A (en) * | 2020-06-15 | 2020-10-27 | 安徽鑫固环保股份有限公司 | Preparation method of environment-friendly naphthalene water reducer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8802780D0 (en) * | 1988-02-08 | 1988-03-09 | Ti Corporate Services | Vehicle exhaust gas catalysts |
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2006
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560074B (en) * | 2008-04-16 | 2012-11-21 | 万方 | Water reducer produced by utilizing zirconium silica residues and production method thereof |
| CN101913792A (en) * | 2010-08-24 | 2010-12-15 | 中南林业科技大学 | Method for producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer |
| CN101913792B (en) * | 2010-08-24 | 2012-07-11 | 中南林业科技大学 | Method for producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer |
| CN111825364A (en) * | 2020-06-15 | 2020-10-27 | 安徽鑫固环保股份有限公司 | Preparation method of environment-friendly naphthalene water reducer |
| CN111825364B (en) * | 2020-06-15 | 2022-06-14 | 安徽鑫固环保股份有限公司 | Preparation method of environment-friendly naphthalene water reducer |
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| CN100386282C (en) | 2008-05-07 |
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Assignee: Hebei Tieyuan Science & Technology Development Co., Ltd. Assignor: Shijiazhuang College Contract record no.: 2010130000044 Denomination of invention: Preparation method of concrete high efficiency water reducer Granted publication date: 20080507 License type: Exclusive License Open date: 20070131 Record date: 20100701 |
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