CN101913792B - Method for producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer - Google Patents
Method for producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer Download PDFInfo
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- CN101913792B CN101913792B CN2010102602286A CN201010260228A CN101913792B CN 101913792 B CN101913792 B CN 101913792B CN 2010102602286 A CN2010102602286 A CN 2010102602286A CN 201010260228 A CN201010260228 A CN 201010260228A CN 101913792 B CN101913792 B CN 101913792B
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Abstract
The invention discloses a method for producing a bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer, which adopts the following steps of: (1) determining a ratio of replacing phenol by utilizing the separated crude phenol of a bamboo tar; and (2) determining a process of producing the bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer. The method for producing the bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer solves the problems of complicated components, low content of single component and no effective utilization of the bamboo tar produced in the bamboo charcoal firing process, produces the modified aminosulfonic acid-based superplasticzer by obtaining the high-content crude phenol through a simple and economic separation method and replacing part of the phenol by the crude phenol, and is an effective method for effectively treating and utilizing the bamboo tar and reducing the utilization of nonrenewable resources.
Description
Technical field
The present invention relates to a kind of method of crude phenols modified amido sulfoacid series high-efficiency water reducer, particularly relate to the method for crude phenols modified amido sulfoacid series high-efficiency water reducer in a kind of bamboo tar.
Background technology
Along with the continuous development of construction business with science and technology, large-scale or super-huge building constantly occurs, and like subway engineering, bridge spanning the sea, water power dam etc., requires also increasingly high to concrete performance.Current general method through interpolation admixture in concrete is improved concrete performance; And simple and easy to do construction technology is provided; Nearly recent decades, all wideling popularize the use of using all kinds concrete admixture, particularly cement water reducing agent both at home and abroad; The level of a national building materials and operating technique is being represented in the technology of water reducer and application thereof, and cement water reducing agent is divided into ordinary water-reducing agent and high efficiency water reducing agent.Water-reducing rate is called ordinary water-reducing agent greater than 5% less than 12% water reducer, like sodium abietate, sodium lignosulfonate and stearate soap etc.; Water-reducing rate is called high efficiency water reducing agent greater than 12% water reducer, like trimeric cyanamide system, naphthalene system, modified lignin resin sulfonic acid system, amido sulfoacid series and polycarboxylic acid series etc.At present; Concrete admixture becomes in the concrete indispensable the 5th component except that cement, sand, stone and water gradually; Especially when preparing high-strength or super high strength concrete, the contribution of high efficiency water reducing agent and high-performance water reducing agent can not be ignored, and usage quantity is bigger; According to statistics in 2007, the whole nation more than 1500 families of existing admixture manufacturing enterprise.High efficiency water reducing agent such as naphthalene series high-efficiency water-reducing agent, aliphatic high-efficiency water reducing agent, trimeric cyanamide series high-efficiency water-reducing agent and modified lignin sulfonate water reducer etc., water-reducing rate is higher, generally at 12%-20%.And high-performance water reducing agent has sulfamate high-effective water-reducing agent and polycarboxylic acid series high efficiency water reducing agent, and water-reducing rate is high, generally at 20%-35%.Along with the development of construction industry, as in the construction such as railway engineering, bridge construction and hydroelectric project, the usage quantity of high-performance water reducing agent will increase year by year in the particularly serious at home engineering.
The polycarboxylic acid series high efficiency water reducing agent water-reducing rate is high; Mainly form through unsaturated monomer copolymerization under the initiator effect, used unsaturated monomer mainly contains at present: polymerisable carboxylic acids such as unsaturated acid and acid anhydrides thereof such as toxilic acid, maleic anhydride and (methyl) vinylformic acid; Polyolefine and contain the verivate of different functional groups is like ether, alcohol, sulphonate etc.; Poly styrene sulfonate and (methyl) acrylate, ester etc.Raw material monomer is wide in variety, and synthesis technique is complicated, and present domestic raw material supply is not enough, and main dependence on import cause the products production cost higher, and the product water-reducing property of different material production differs.In Large-scale Railway engineering, bridge spanning the sea engineering, hydroelectric project etc. are built, use morely at present, polycarboxylic acid series high efficiency water reducing agent mainly relies on import, and domestic have a produced in small quantities.And amido sulfoacid series high-efficiency water reducer is the product that phenyl-sulfamic acid salt, phenols and aldehydes is carried out condensation, and water-reducing rate is high, and synthesis technique is simpler; Domestic production producer is prone to produce; But owing to be prone to cause the concrete water bleeding segregation, workability is relatively poor, in use is difficult to control; Add that raw materials for production are as being mainly derived from petrochemical materials to phenylamino sulfamate and phenols; At present price is higher, has limited it the promoting the use of of market, thereby has caused domestic production amount and usage quantity all less.For improving the application performance and the use cost of amido sulfoacid series high-efficiency water reducer; General employing is carried out the composite method of physics with other cement water reducing agents or other admixtures and is improved its serviceability; Avoid concrete bleeding segregation; Or use other low cost raw material to replace or part substituted phenol raw material production modified amido sulfoacid series high-efficiency water reducer, and reduce production costs, improve market demand.
Bamboo tar is a kind of main by product that is produced in the bamboo charcoal production process; Account for about 10% of whole bamboo charcoal output; Be a kind of black, heavy-gravity oily liquids, contain nearly hundred kinds of organic cpds, can be applied to the manufacturing of the series product in fields such as agricultural, chemical industry, medical and health.See that from the group composition classification fatty compounds of group has 9 kinds in the bamboo tar, relative content is 7.31%, is mainly cyclopentenone and organic acid derivatives.Aromatics has kind more than 80, and relative content is 75.24%, is mainly alkylphenol, korenyl, heterocyclic and substituent thereof.And in the bamboo tar hydroxy derivatives-aldehydes matter of phenol as 2; 6-dimethyl oxygen base phenol (9.63%), 4-ethylphenol (6.08%), 2-ethylphenol (4.76%), phenol (4.35%), 4-ethyl-2-methoxyphenol (2.63%), 2-methoxyl group-4-methylphenol (2.23%) account for 43.63% of total identification number altogether.They all are very important Organic Chemicals, are widely used in synthetic important intermediate such as spices, plastics, dyestuff and medicine.
But present, a lot of important components are not exploited as yet in the bamboo tar, and owing to its complicated component, the content of single component is all lower simultaneously, obtains wherein a certain component if separate, and the separation cost for purification is high, loses more than gain.Inquiring into how to utilize bamboo tar, is an important content of bamboo wood chemical field research.This experiment is hoped to pass through with the crude phenols compounds in the certain density alkali lye separation and Extraction bamboo tar; Partly substitute phenol synthesizing amino sulfonic acid series high-efficiency water-reducing agent with crude phenols; To reduce cost, improve its application performance simultaneously, for the development and use of bamboo tar good try is provided simultaneously.
Summary of the invention
Technical problem to be solved by this invention provides a kind of by product that can effectively utilize the renewable resources bamboo wood---bamboo tar; Reduce the usage quantity of Nonrenewable resources; The protection environment; Can reduce simultaneously the production cost of amido sulfoacid series high-efficiency water reducer, improve the diminishing dispersing property and the serviceability of thionamic acid based water reducer, enlarge the method for the producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer of engineering usage quantity.
In order to solve the problems of the technologies described above, the method for producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer provided by the invention, adopt following steps:
(1), utilize bamboo tar crude phenols fortified phenol determination of ratio, change the ratio synthesizing amino sulfonic acid series high-efficiency water-reducing agent of bamboo tar crude phenols fortified phenol, according to the mensuration of product diminishing dispersing property, substitute proportion is confirmed as 10%-30%;
(2), part bamboo tar crude phenols, phenol and Sodium sulfanilate and formolite reaction prepare modified amido sulfoacid series high-efficiency water reducer; Synthesis technique is: temperature of reaction 80-95 ℃; The pH value of solution value is controlled between the 9.5-13.5; Reaction times 1.5-4.5h, reaction ratio are Sodium sulfanilate (g): always phenol (phenol+bamboo tar crude phenols) (g): formaldehyde (ml)=(10-14): 10: (24-36).
The preparation technology of the bamboo tar crude phenols described in the above-mentioned steps (1) is: the flue gas comb with cooling water circulation pipe is installed on the bamboo charcoal baking apparatus; In the bamboo charcoal sintering procedure, use the water quench flue gas; Collect the liquid that flue gas produces; Clarification separates, and liquid level is the bamboo vinegar layer, and the thickness beds of precipitation are bamboo tar; With the mass concentration is the alkali liquid washing bamboo tar of 1%-6%, and separate the clarification back, and the gained liquid level is bamboo tar crude phenols.
Described alkali lye is sodium hydroxide solution or sodium carbonate solution or ammoniacal liquor or triethanolamine solution.
The adjusting of pH value is regulated with sodium hydroxide solution or sodium carbonate solution or ammoniacal liquor or trolamine in the described step (2).
Adopt the method for the producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer of technique scheme; Through utilizing the crude phenols class material in the by product bamboo tar in the certain density alkali lye Separation and Recovery bamboo charcoal sintering procedure; To carry out part through the bamboo tar crude phenols Pyrogentisinic Acid that separation obtains and replace effectively to utilize by product---the bamboo tar of renewable resources bamboo wood, reduce the usage quantity of Nonrenewable resources to produce modified amido sulfoacid series high-efficiency water reducer; The protection environment; Can reduce simultaneously the production cost of amido sulfoacid series high-efficiency water reducer, improve the diminishing dispersing property and the serviceability of thionamic acid based water reducer, enlarge the engineering usage quantity.
The present invention replaces the phenol raw material production modified amido sulfoacid series high-efficiency water reducer of 10%-30% with bamboo tar crude phenols; Its water-reducing rate and the approaching even slightly raising with the water-reducing rate of phenol synthetic amido sulfoacid series high-efficiency water reducer fully; Cost decline 8%-25%; And the bleeding quantity of modified amido sulfoacid series high-efficiency water reducer descends, and concrete workability ability and serviceability improve, and to enlarging its work usage quantity positive meaning are arranged.
Embodiment
Below in conjunction with specific embodiment the present invention is done further explain.
Embodiment 1:
(1) separating of the collection of bamboo tar and contained crude phenols, the flue gas comb with cooling water circulation pipe is installed on the bamboo charcoal baking apparatus, in the bamboo charcoal sintering procedure, use the water quench flue gas; Collect the liquid that flue gas produces; Clarification separates, and liquid level is the bamboo vinegar layer, and the thickness beds of precipitation are bamboo tar; With mass concentration 4% alkali lye of (down together)--sodium hydroxide solution washing bamboo tar, separate the clarification back, and the gained liquid level is bamboo tar crude phenols;
(2) utilize separating obtained bamboo tar crude phenols fortified phenol determination of ratio, change the ratio synthesizing amino sulfonic acid series high-efficiency water-reducing agent of bamboo tar crude phenols fortified phenol, according to the mensuration of product diminishing dispersing property, substitute proportion confirms as 10%;
(3) part bamboo tar crude phenols and phenol and Sodium sulfanilate and formolite reaction prepare modified amido sulfoacid series high-efficiency water reducer; Synthesis technique is: 95 ℃ of temperature of reaction; The pH value of solution value is controlled between 13.1; Reaction times 2.5h, reaction ratio are Sodium sulfanilate (g): always phenol (phenol+bamboo tar crude phenols) (g): formaldehyde (ml)=12: 10: 30.
Embodiment 2:
(1) separating of the collection of bamboo tar and contained crude phenols, the flue gas comb with cooling water circulation pipe is installed on the bamboo charcoal baking apparatus, in the bamboo charcoal sintering procedure, use the water quench flue gas; Collect the liquid that flue gas produces, clarification separates, and liquid level is the bamboo vinegar layer; The thickness beds of precipitation are bamboo tar; Alkali lye with 2%--sodium hydroxide solution washing bamboo tar, separate the clarification back, and the gained liquid level is bamboo tar crude phenols;
(2) utilize separating obtained bamboo tar crude phenols fortified phenol determination of ratio, change the ratio synthesizing amino sulfonic acid series high-efficiency water-reducing agent of bamboo tar crude phenols fortified phenol, according to the mensuration of product diminishing dispersing property, substitute proportion confirms as 15%;
(3) part bamboo tar crude phenols and phenol and Sodium sulfanilate and formolite reaction prepare modified amido sulfoacid series high-efficiency water reducer; Synthesis technique is: 95 ℃ of temperature of reaction; The pH value of solution value is controlled between 13.1; Reaction times 2.5h, reaction ratio are Sodium sulfanilate (g): always phenol (phenol+bamboo tar crude phenols) (g): formaldehyde (ml)=12: 10: 30.
Embodiment 3:
(1) separating of the collection of bamboo tar and contained crude phenols, the flue gas comb with cooling water circulation pipe is installed on the bamboo charcoal baking apparatus, in the bamboo charcoal sintering procedure, use the water quench flue gas; Collect the liquid that flue gas produces, clarification separates, and liquid level is the bamboo vinegar layer; The thickness beds of precipitation are bamboo tar; Alkali lye with 1%--sodium hydroxide solution washing bamboo tar, separate the clarification back, and the gained liquid level is bamboo tar crude phenols;
(2) utilize separating obtained bamboo tar crude phenols fortified phenol determination of ratio, change the ratio synthesizing amino sulfonic acid series high-efficiency water-reducing agent of bamboo tar crude phenols fortified phenol, according to the mensuration of product diminishing dispersing property, substitute proportion confirms as 20%;
(3) part bamboo tar crude phenols and phenol and Sodium sulfanilate and formolite reaction prepare modified amido sulfoacid series high-efficiency water reducer; Synthesis technique is: 95 ℃ of temperature of reaction; The pH value of solution value is controlled between 13.1; Reaction times 2.5h, reaction ratio are Sodium sulfanilate (g): always phenol (phenol+bamboo tar crude phenols) (g): formaldehyde (ml)=12: 10: 30.
Embodiment 4:
(1) separating of the collection of bamboo tar and contained crude phenols, the flue gas comb with cooling water circulation pipe is installed on the bamboo charcoal baking apparatus, in the bamboo charcoal sintering procedure, use the water quench flue gas; Collect the liquid that flue gas produces, clarification separates, and liquid level is the bamboo vinegar layer; The thickness beds of precipitation are bamboo tar; Alkali lye with 4%--sodium hydroxide solution washing bamboo tar, separate the clarification back, and the gained liquid level is bamboo tar crude phenols;
(2) utilize separating obtained bamboo tar crude phenols fortified phenol determination of ratio, change the ratio synthesizing amino sulfonic acid series high-efficiency water-reducing agent of bamboo tar crude phenols fortified phenol, according to the mensuration of product diminishing dispersing property, substitute proportion confirms as 10%;
(3) part bamboo tar crude phenols and phenol and Sodium sulfanilate and formaldehyde-prepared in reaction modified amido sulfoacid series high-efficiency water reducer; Synthesis technique is: 85 ℃ of temperature of reaction; The pH value of solution value is controlled between 13.1; Reaction times 4.5h, reaction ratio are Sodium sulfanilate (g): always phenol (phenol+bamboo tar crude phenols) (g): formaldehyde (ml)=12: 10: 30.
Embodiment 5:
(1) separating of the collection of bamboo tar and contained crude phenols, the flue gas comb with cooling water circulation pipe is installed on the bamboo charcoal baking apparatus, in the bamboo charcoal sintering procedure, use the water quench flue gas; Collect the liquid that flue gas produces, clarification separates, and liquid level is the bamboo vinegar layer; The thickness beds of precipitation are bamboo tar, the alkali lye with 4%--sodium hydroxide solution or sodium carbonate solution or ammoniacal liquor or triethanolamine solution, washing bamboo tar; Separate the clarification back, and the gained liquid level is bamboo tar crude phenols;
(2) utilize separating obtained bamboo tar crude phenols fortified phenol determination of ratio, change the ratio synthesizing amino sulfonic acid series high-efficiency water-reducing agent of bamboo tar crude phenols fortified phenol, according to the mensuration of product diminishing dispersing property, substitute proportion confirms as 10%;
(3) part bamboo tar crude phenols and phenol and Sodium sulfanilate and formolite reaction prepare modified amido sulfoacid series high-efficiency water reducer; Synthesis technique is: 95 ℃ of temperature of reaction; The pH value of solution value is controlled between 11.5; Reaction times 3.5h, reaction ratio are Sodium sulfanilate (g): always phenol (phenol+bamboo tar crude phenols) (g): formaldehyde (ml)=12: 10: 30.
Embodiment 6:
(1) separating of the collection of bamboo tar and contained crude phenols, the flue gas comb with cooling water circulation pipe is installed on the bamboo charcoal baking apparatus, in the bamboo charcoal sintering procedure, use the water quench flue gas; Collect the liquid that flue gas produces, clarification separates, and liquid level is the bamboo vinegar layer; The thickness beds of precipitation are bamboo tar; Alkali lye with 4%--sodium hydroxide solution washing bamboo tar, separate the clarification back, and the gained liquid level is bamboo tar crude phenols;
(2) utilize separating obtained bamboo tar crude phenols fortified phenol determination of ratio, change the ratio synthesizing amino sulfonic acid series high-efficiency water-reducing agent of bamboo tar crude phenols fortified phenol, according to the mensuration of product diminishing dispersing property, substitute proportion confirms as 10%;
(3) part bamboo tar crude phenols and phenol and Sodium sulfanilate and formolite reaction prepare modified amido sulfoacid series high-efficiency water reducer.Synthesis technique is: 95 ℃ of temperature of reaction, and the pH value of solution value is controlled between 13.1, and reaction times 3.0h, reaction ratio are Sodium sulfanilate (g): always phenol (phenol+bamboo tar crude phenols) is (g): formaldehyde (ml)=10: 10: 24.
Claims (4)
1. the method for a producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer is characterized in that: adopt following steps:
(1), utilize bamboo tar crude phenols fortified phenol determination of ratio, change the ratio synthesizing amino sulfonic acid series high-efficiency water-reducing agent of bamboo tar crude phenols fortified phenol, according to the mensuration of product diminishing dispersing property, substitute proportion is confirmed as 10%-30%;
(2), part bamboo tar crude phenols, phenol and Sodium sulfanilate and formolite reaction prepare modified amido sulfoacid series high-efficiency water reducer; Synthesis technique is: temperature of reaction 80-95 ℃; The pH value of solution value is controlled between the 9.5-13.5; Reaction times 1.5-4.5h, reaction ratio are Sodium sulfanilate g: total phenol g: formaldehyde mL=(10-14): 10: (24-36), described total phenol is phenol+bamboo tar crude phenols.
2. the method for producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer according to claim 1; It is characterized in that: the preparation technology of the bamboo tar crude phenols described in the above-mentioned steps (1) is: the flue gas comb with cooling water circulation pipe is installed on the bamboo charcoal baking apparatus; In the bamboo charcoal sintering procedure, use the water quench flue gas, collect the liquid that flue gas produces, clarification separates; Liquid level is the bamboo vinegar layer, and the thickness beds of precipitation are bamboo tar; With the mass concentration is the alkali liquid washing bamboo tar of 1%-6%, and separate the clarification back, and the gained liquid level is bamboo tar crude phenols.
3. the method for producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer according to claim 2, it is characterized in that: described alkali lye is sodium hydroxide solution or sodium carbonate solution or ammoniacal liquor or triethanolamine solution.
4. the method for producing bamboo tar crude phenol-modified aminosulfonic acid-based superplasticzer according to claim 1 and 2 is characterized in that: the adjusting of pH value is regulated with sodium hydroxide solution or sodium carbonate solution or ammoniacal liquor or triethanolamine solution in the described step (2).
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| CN102584084A (en) * | 2012-02-29 | 2012-07-18 | 哈尔滨工业大学强石混凝土技术开发有限责任公司 | Sulfamate water reducer and synthesizing device |
| CN103723943B (en) * | 2013-12-19 | 2015-12-02 | 江苏苏博特新材料股份有限公司 | A kind of utilize industrial by-products to prepare cement dispersants method and application |
| CN114478197A (en) * | 2022-02-11 | 2022-05-13 | 福建竹家女炭业科技有限公司 | Extraction process of bamboo tar phenolic compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1083030A (en) * | 1993-04-30 | 1994-03-02 | 崔玉璞 | Efficient non-basic dewatering agent |
| CN1903778A (en) * | 2006-08-02 | 2007-01-31 | 石家庄学院 | Preparation method of concrete high efficiency water reducer |
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| CN1234637C (en) * | 2000-12-20 | 2006-01-04 | 武汉科技大学 | Water-reducing agent preparing from coking acid and tar and its preparing process |
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| CN1083030A (en) * | 1993-04-30 | 1994-03-02 | 崔玉璞 | Efficient non-basic dewatering agent |
| CN1903778A (en) * | 2006-08-02 | 2007-01-31 | 石家庄学院 | Preparation method of concrete high efficiency water reducer |
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