CN103864332B - A kind of preparation method of collapse protection type naphthalene water reducer - Google Patents
A kind of preparation method of collapse protection type naphthalene water reducer Download PDFInfo
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- CN103864332B CN103864332B CN201410066495.8A CN201410066495A CN103864332B CN 103864332 B CN103864332 B CN 103864332B CN 201410066495 A CN201410066495 A CN 201410066495A CN 103864332 B CN103864332 B CN 103864332B
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Abstract
The invention discloses a kind of preparation method of collapse protection type naphthalene water reducer, adopt and comprise the starting material such as the naphthalene derivatives such as NAPTHALENE FLAKES. (INDUSTRIAL GRADE）, methylnaphthalene, the vitriol oil, formaldehyde, liquid caustic soda, water, prepare naphthalene water reducer by sulfonation, hydrolysis, condensation, neutralization procedure.This production technique introduces other monomer substituents such as methylnaphthalene, acenaphthene, and adopts organic solvent azeotropic method to synthesize, and in finally carrying out with Starso and adjust ph to 7 ~ 10, obtain final naphthalene water reducer.Prepare collapse protection type naphthalene water reducer by embodiments of the present invention, replace NAPTHALENE FLAKES. (INDUSTRIAL GRADE） with part naphthalene derivatives, propose the effective way reduced costs, naphthalene steam and solvent form naphthalene solution circulated through condensation and utilize, and improve product yield and reduce environmental pollution.
Description
Technical field
The invention belongs to the technical field of material of construction, particularly relate to a kind of preparation method of collapse protection type naphthalene water reducer.
Background technology
Along with the fast development of China's economy, foundation construction facility constantly perfect, increasing to the consumption demand of concrete admixture.Concrete admixture add the performance such as mobility, workability can improving fresh concrete, obviously can reduce the consumption of water simultaneously, improve concrete intensity.The advantages such as it is low that naphthalene water reducer has cost, and adaptability is good are the concrete admixture that in high efficiency water reducing agent, usage quantity is maximum, turnout is maximum at present.The production method of naphthalene water reducer is in the stage of maturity, is generally divided into sulfonation, hydrolysis, condensation, neutralization stage.
But NAPTHALENE FLAKES. (INDUSTRIAL GRADE） price volalility is obviously seasonal, as the prices of raw and semifnished materials are higher, NAPTHALENE FLAKES. (INDUSTRIAL GRADE） amount of increase is brought to industrial production naphthalene water reducer and be had a strong impact on.In addition, the naphthalene steam produced in sulfonation process directly discharge can to environment.
Summary of the invention
Technical problem to be solved by this invention is the preparation method providing a kind of collapse protection type naphthalene water reducer, the method replaces NAPTHALENE FLAKES. (INDUSTRIAL GRADE） with part naphthalene derivatives, can reduce costs, naphthalene steam and solvent form naphthalene solution circulated through condensation and utilize, and carry high product yield and reduce environmental pollution.
For solving the problems of the technologies described above, technical solution of the present invention is:
A preparation method for collapse protection type naphthalene water reducer, comprises the following steps:
(1) sulfonation: by mass parts, in the closed reactor A being connected to cooling and reflux device, add 100 ~ 130 parts of NAPTHALENE FLAKES. (INDUSTRIAL GRADE）, 20 ~ 40 parts of polycyclic aromatic hydrocarbon, when heating to 120 ~ 130 DEG C, start to drip 110 ~ 150 parts of vitriol oils and 50 ~ 70 parts of organic solvents respectively, dropwised in 0.5 ~ 1 hour; When the vitriol oil dropwises, temperature in the kettle is controlled at 155 ~ 170 DEG C, continue insulation 1 ~ 2 hour; In reaction process, at the bottom UNICOM steam-pipe of sulfonation reaction still A, pass into steaming time 0.5 ~ 1h, lower boiling organic solvent enters the cooling and reflux device heat exchange condensation on reactor A top with naphthalene steam, naphthalene steam and solvent form cooling fluid and send constantly into reactor again and continue circulating reaction after condensation, until reaction terminates, the part cooling fluid remaining in cooling and reflux device the most at last reclaims or continues the reaction of next still, finally carry high product yield because naphthalene steam refrigeration cycle utilizes, and reduce environmental pollution;
(2) be hydrolyzed: after sulfonation reaction terminates, cool to 120 ~ 130 DEG C, add 30 ~ 45 parts of water, be hydrolyzed reaction 10 ~ 30 minutes;
(3) condensation: after hydrolysis reaction terminates, adds the sulfonate of 10 ~ 20 parts, cools to 85 ~ 95 DEG C, drips 60 ~ 80 parts of formaldehyde, dropwises in 2 ~ 4 hours; Be warming up to 105 ~ 115 DEG C, be incubated 2 ~ 6 hours; Divide in insulating process and respectively add 10 ~ 15 parts of water for 3 times, finally dilute with 120 ~ 140 parts of water;
(4) neutralize: after water injection, in being transferred to by material and in still B, regulate pH to 7 ~ 10, after cooling, namely obtain product to room temperature.
Described polycyclic aromatic hydrocarbon is the one in methylnaphthalene, acenaphthene, anthracene.
Described organic solvent is the one in hexanaphthene, acetic acid, methylene dichloride.
Described sulfonate is the one in Sodium styrene sulfonate, sodium naphthalene sulfonate, p-hydroxy benzenyl sulfonate sodium.
In described step (4), adjust ph adopts 25 ~ 45 parts of Starsos.
Because the present invention adds suitable organic solvent recovered steam in sulfonation process, recycle, makes tail gas discharging pollutant reduce, and is conducive to economizing on resources, protection of the environment.In addition, the naphthalene derivativess such as the present invention's methylnaphthalene, anthracene, acenaphthene suitably replace part NAPTHALENE FLAKES. (INDUSTRIAL GRADE）, can alleviate a part of pressure, improve the market competitiveness of naphthalene water reducer.In addition, the present invention also introduces sulfonate component, and the molecular structure controllability in the condensation stage by the naphthalene water reducer synthesized with formaldehyde condensation strengthens, and suitable introducing sulfonate also can improve its over-all properties, improves the application of naphthalene water reducer.
In a word, the present invention replaces NAPTHALENE FLAKES. (INDUSTRIAL GRADE） with part naphthalene derivatives, and propose the effective way reduced costs, naphthalene steam and solvent form naphthalene solution circulated through condensation and utilize, and improve product yield and reduce environmental pollution.
Embodiment
Below in conjunction with specific embodiment, the inventive method is described in further detail, makes the person skilled of this area have more deep understanding to the present invention.
Embodiment 1
(1) sulfonation: in the closed reactor A being connected to cooling and reflux device, adds 100kg NAPTHALENE FLAKES. (INDUSTRIAL GRADE）, 20kg methylnaphthalene, when heating to 120 ~ 130 DEG C, starts to drip the 110kg vitriol oil and 50kg hexanaphthene respectively, dropwises in 0.5 hour.When the vitriol oil dropwises, temperature in the kettle is controlled at 160 ~ 170 DEG C, continue insulation 1.5 hours.In reaction process, at the bottom UNICOM steam-pipe of sulfonation reaction still A, pass into steaming time 0.5 ~ 1h, hexanaphthene enters the cooling and reflux device heat exchange condensation on reactor A top with naphthalene steam, naphthalene steam and hexanaphthene form cooling fluid and send constantly into reactor and continue circulating reaction after condensation, until reaction terminates, the part cooling fluid remaining in cooling and reflux device the most at last reclaims or continues the reaction of next still.
(2) be hydrolyzed: after sulfonation reaction terminates, cool to 125 DEG C, add 30kg water, be hydrolyzed reaction 20 minutes.
(3) condensation: after hydrolysis reaction terminates, adds the Sodium styrene sulfonate of 10kg, cools to 85 ~ 95 DEG C, drips 60kg formaldehyde, dropwises in 2 hours.Be warming up to 105 DEG C, be incubated 3 hours.Divide in insulating process and respectively add 10kg water 3 times, finally dilute with 120kg water.
(4) neutralize: after water injection, in being transferred to by material and in still B, add 25kg Starso, adjust ph to 7 ~ 10, after cooling, namely obtain product to room temperature.
Embodiment 2
(1) sulfonation: in the closed reactor A being connected to cooling and reflux device, adds 130kg NAPTHALENE FLAKES. (INDUSTRIAL GRADE）, 40kg acenaphthene, when heating to 130 DEG C, starts to drip the 150kg vitriol oil and 60kg acetic acid respectively, dropwises in 0.5 hour.When the vitriol oil dropwises, temperature in the kettle is controlled at 155 ~ 165 DEG C, continue insulation 2 hours.In reaction process, at the bottom UNICOM steam-pipe of sulfonation reaction still A, pass into steaming time 0.5 ~ 1h, acetic acid enters the cooling and reflux device heat exchange condensation on reactor A top with naphthalene steam, naphthalene steam and acetic acid form cooling fluid and send constantly into reactor and continue circulating reaction after condensation, until reaction terminates, the part cooling fluid remaining in cooling and reflux device the most at last reclaims or continues the reaction of next still.
(2) be hydrolyzed: after sulfonation reaction terminates, cool to 120 DEG C, add 30kg water, be hydrolyzed reaction 30 minutes.
(3) condensation: after hydrolysis reaction terminates, adds the sodium naphthalene sulfonate of 20kg, cools to 85 ~ 95 DEG C, drips 80kg formaldehyde, dropwises in 3 hours.Be warming up to 115 DEG C, be incubated 5 hours.Divide in insulating process and respectively add 10kg water 3 times, finally dilute with 140kg water.
(4) neutralize: after water injection, in being transferred to by material and in still B, add 45kg Starso, adjust ph to 7 ~ 10, after cooling, namely obtain product to room temperature.
Embodiment 3
(1) sulfonation: in the closed reactor A being connected to cooling and reflux device, adds 120kg NAPTHALENE FLAKES. (INDUSTRIAL GRADE）, 25kg anthracene, when heating to 125 DEG C, starts to drip the 150kg vitriol oil and 70kg methylene dichloride respectively, dropwises in 1 hour.When the vitriol oil dropwises, temperature in the kettle is controlled at 160 ~ 170 DEG C, continue insulation 2 hours.In reaction process, at the bottom UNICOM steam-pipe of sulfonation reaction still A, pass into steaming time 0.5 ~ 1h, methylene dichloride enters the cooling and reflux device heat exchange condensation on reactor A top with naphthalene steam, naphthalene steam and methylene dichloride form cooling fluid and send constantly into reactor and continue circulating reaction after condensation, until reaction terminates, the part cooling fluid remaining in cooling and reflux device the most at last reclaims or continues the reaction of next still.
(2) be hydrolyzed: after sulfonation reaction terminates, cool to 125 DEG C, add 30kg water, be hydrolyzed reaction 20 minutes.
(3) condensation: after hydrolysis reaction terminates, adds the 4-Vinyl phenol sodium sulfonate of 15kg, cools to 85 ~ 95 DEG C, drips 70kg formaldehyde, dropwises in 3 hours.Be warming up to 110 DEG C, be incubated 5 hours.Divide in insulating process and respectively add 10kg water 3 times, finally dilute with 140kg water.
(4) neutralize: after water injection, in being transferred to by material and in still B, add 30kg Starso, adjust ph to 7 ~ 10, after cooling, namely obtain product to room temperature.
Embodiment 1 ~ 3 is synthesized the sample obtained and common naphthalene water reducer contrasts, measure the slump and each age strength of concrete.
Table 1 embodiment concrete contrast properties
Test-results illustrates, the concrete initial fluidity using product of the present invention to prepare and function of slump protection are all better than common naphthalene water reducer performance in the market, and do not affect other workabilities.
The above is only preferred embodiment of the present invention, not imposes any restrictions technical scope of the present invention, therefore the change in every case done according to claim of the present invention and specification sheets or modification, all should belong within scope that patent of the present invention contains.
Claims (4)
1. a preparation method for collapse protection type naphthalene water reducer, is characterized in that comprising the following steps:
(1) sulfonation: by mass parts, in the airtight reactor A being connected to cooling and reflux device, add 100 ~ 130 parts of NAPTHALENE FLAKES. (INDUSTRIAL GRADE）, 20 ~ 40 parts of polycyclic aromatic hydrocarbon, described polycyclic aromatic hydrocarbon is the one in methylnaphthalene, acenaphthene, anthracene, when heating to 120 ~ 130 DEG C, start to drip 110 ~ 150 parts of vitriol oils and 50 ~ 70 parts of organic solvents respectively, dropwised in 1 hour; When the vitriol oil dropwises, temperature in the kettle is controlled at 155 ~ 170 DEG C, continue insulation 1 ~ 2 hour; In sulfonation reaction process, the bottom UNICOM steam-pipe of reactor A, pass into steaming time 0.5 ~ 1h, lower boiling organic solvent enters the cooling and reflux device heat exchange condensation on reactor A top with naphthalene steam, naphthalene steam and solvent form cooling fluid and send constantly into reactor again and continue circulating reaction after condensation, until reaction terminates, the part cooling fluid remaining in cooling and reflux device the most at last reclaims or continues the reaction of next still;
(2) be hydrolyzed: after sulfonation reaction terminates, cool to 120 ~ 130 DEG C, by mass parts, add 30 ~ 45 parts of water, be hydrolyzed reaction 10 ~ 30 minutes;
(3) condensation: after hydrolysis reaction terminates, by mass parts, adds the sulfonate of 10 ~ 20 parts, cools to 85 ~ 95 DEG C, drips 60 ~ 80 parts of formaldehyde, dropwises in 4 hours; Be warming up to 105 ~ 115 DEG C, be incubated 2 ~ 6 hours; Divide in insulating process and respectively add 10 ~ 15 parts of water for 3 times, finally use 120 ~ 140 parts of water to dilute;
(4) neutralize: after water injection, in being transferred to by material and in still B, regulate pH to 7 ~ 10, after cooling, namely obtain product to room temperature.
2. the preparation method of a kind of collapse protection type naphthalene water reducer according to claim 1, is characterized in that: described organic solvent is the one in hexanaphthene, acetic acid, methylene dichloride.
3. the preparation method of a kind of collapse protection type naphthalene water reducer according to claim 1, is characterized in that: described sulfonate is the one in Sodium styrene sulfonate, sodium naphthalene sulfonate, p-hydroxy benzenyl sulfonate sodium.
4. the preparation method of a kind of collapse protection type naphthalene water reducer according to claim 1, is characterized in that: in described step (4), by mass parts, and adjust ph adopts 25 ~ 45 parts of Starsos.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104176968B (en) * | 2014-08-21 | 2015-12-02 | 广东瑞安科技实业有限公司 | The production method of the high dense water reducer of a kind of naphthalene system |
| CN105884238B (en) * | 2015-08-18 | 2017-12-22 | 科之杰新材料集团有限公司 | A kind of naphthalene system pulvis water reducer and preparation method thereof |
| CN106117481B (en) * | 2016-06-24 | 2018-06-08 | 山东省莱芜市汶河化工有限公司 | A kind of solvent method concentrates the production method of sulfonation separate mealing type condensation production naphthalene water reducer |
| CN106117482B (en) * | 2016-06-29 | 2018-05-18 | 南京瑞迪高新技术有限公司 | A kind of modified high-thin arch dam naphthalene water reducer and preparation method thereof |
| CN106632938B (en) * | 2016-09-20 | 2019-01-01 | 江苏苏博特新材料股份有限公司 | A kind of energy saving preparation method and its special equipment of naphthalene water reducer |
| CN107200817B (en) * | 2017-07-07 | 2019-07-19 | 科之杰新材料集团有限公司 | A kind of preparation method of stable type concrete slump controlling agent |
| CN108033706B (en) * | 2017-12-28 | 2020-10-09 | 科之杰新材料集团浙江有限公司 | Synthetic method of modified naphthalene sulfonate water reducer |
| CN110156368A (en) * | 2019-05-24 | 2019-08-23 | 莱芜市兆信新材料股份有限公司 | A kind of preparation method of gypsum water-reducing agent |
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| US4662942A (en) * | 1983-08-01 | 1987-05-05 | Idemitsu Petrochemical Co., Ltd. | Cement additives |
| JPS61148130A (en) * | 1984-12-21 | 1986-07-05 | Kawasaki Steel Corp | Collection of naphthalene |
| CN101314556A (en) * | 2007-05-28 | 2008-12-03 | 重庆达华砼外加剂科技发展有限公司 | Process for recovering residual naphthalin in naphthalin series water reducing agent synthesis |
| RU2007136392A (en) * | 2007-10-03 | 2009-04-10 | Открытое акционерное общество "Полипласт" (ОАО "Полипласт") (RU) | SUPERPLASTICIZER |
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Effective date of registration: 20170327 Address after: 710500 Lantian County, Shaanxi Province, industrial park, the first phase of the planning of the southern section of the two phase of the Patentee after: SHAANXI KZJ NEW MATERIALS CO., LTD. Address before: 361004 Fujian province Xiamen torch hi tech Zone (Xiangan) Industrial Park Wai Road No. 169 Patentee before: Kezhijie New Material Group Co., Ltd. |
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