CN104497250A - Method for producing high-concentration efficient naphthalene water reducer by virtue of binary azeotropic method - Google Patents
Method for producing high-concentration efficient naphthalene water reducer by virtue of binary azeotropic method Download PDFInfo
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- CN104497250A CN104497250A CN201410791512.4A CN201410791512A CN104497250A CN 104497250 A CN104497250 A CN 104497250A CN 201410791512 A CN201410791512 A CN 201410791512A CN 104497250 A CN104497250 A CN 104497250A
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Abstract
The invention provides a method of producing high-concentration efficient naphthalene water reducer by virtue of a binary azeotropic method. The method comprises the following steps of sulfonation, hydrolysis, condensation, neutralization and the like, wherein during sulfonation, much sulfonic acid as possible can be converted into sulfonic acid groups so that free sulfate ions in a product are decreased to the lowest level and the water phase in the product is reduced by virtue of binary azeotropic method, the production of 2-naphthalene sulfonic acid is increased and the yield is also increased; during condensation, a process for recovering formaldehyde is added and thus the cost is reduced, the emission of formaldehyde is decreased and the environment friendliness is achieved; furthermore, since the sulfate ions are controlled in the sulfonation stage, lime does not need to be added in the later process to remove the sulfate ions and thus the process is greatly simplified, the production time is shortened, the cost is saved again and no solid wastes can be generated which is conductive to environmental protection. The process provided by the invention is superior to the traditional process in terms of production efficiency, economic efficiency, environmental protection and the like.
Description
Technical field
The present invention relates to field of fine chemical, a kind of binary azeotropic method produces the method for high concentration and high efficiency naphthalene water reducer specifically.
Background technology
The development of construction industry blowout formula in recent years, result in concrete admixture and has also developed into an acme.Though have decline as the present sales volume of traditional naphthalene water reducer, but also there is very large advantage in it: one be the primary industry naphthalene used is the byproduct of Coal Chemical Industry coking industry, there is the useless function of profit, two is that product is to various cement, sandstone material has superpower adaptability, not available for other, so still by the favor of user.Traditional high concentration and high efficiency naphthalene water reducer, producing is all remove sulfate radical with unslaked lime, not only with whizzer, also produces a large amount of calcium sulphate solid waste materials.This waste material is very difficult, contaminate environment; Moreover the concentration of water reducer will be turned down in this technological process, the energy consumption in follow-up drying process is increased greatly, adds the cost of product virtually, the problem due to cost can not get applying widely.
Summary of the invention
The defect such as difficult for above-mentioned traditional high concentration and high efficiency naphthalene water reducer processing waste, technological process energy consumption is large, the invention provides a kind of method that binary azeotropic method produces high concentration and high efficiency naphthalene water reducer.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
Binary azeotropic method produces a method for high concentration and high efficiency naphthalene water reducer, comprises the following steps:
1) according to weight parts, in reactor, 160 ~ 200 parts of liquid industrial naphthalenes are added, when stirring and be warming up to 135 ~ 145 DEG C, starting to drip 120 ~ 160 parts of concentration is the sulfuric acid of 98%, controls to add speed, makes temperature be no more than 165 DEG C, insulation binary azeotropic backflow 4 ~ 5h, Controlled acidity is 25 ~ 27%;
2) step 1) gained material is cooled to 115 ~ 125 DEG C, then in reactor, adds 23 ~ 25 parts of water, be slowly warming up to 130 ~ 140 DEG C, utilize binary azeotropic method to reclaim naphthalene, Controlled acidity is 25.5 ~ 26.0% stopping hydrolysis;
3) by step 2) gained material is cooled to 110 DEG C, starts to drip 100 ~ 120 parts of formaldehyde, controls rate of addition, dropwises in 3 hours, and be then incubated condensation 5 hours, in this step process, reclaim formaldehyde simultaneously;
4) add 170 ~ 190 parts of alkali neutralizations to step 3) gained condenses, be then drying to obtain finished product;
In reactor, add 180 parts of liquid industrial naphthalenes in described step 1), when stirring and be warming up to 140 DEG C, starting to drip 140 parts of concentration is the sulfuric acid of 98%, controls to add speed, makes temperature be no more than 165 DEG C, insulation binary azeotropic backflow 4.5h, and Controlled acidity is 26%;
Described step 2) in step 1) gained material is cooled to 120 DEG C, then in reactor, add 24 parts of water, be slowly warming up to 135 DEG C, utilize binary azeotropic method to reclaim naphthalene, Controlled acidity is 25.5% stopping hydrolysis.
Beneficial effect of the present invention:
In sulfonation reaction, sulfuric acid conversion as much as possible can be become sulfonic acid group, the free sulfuric acid radical ion in resultant is made to have dropped to minimum stage, decreased the aqueous phase of resultant by binary azeotropic, thus the growing amount of 2-sulfonic acid naphthalene is increased, this also just improves yield; Add one recovery formaldehyde technique in condensation course, which decrease cost, and the discharge decreasing formaldehyde protects environment; Moreover control sulfate ion so just there is no need to add unslaked lime sulfate radical ion in technique below due to sulfonation stage; technique is simplified greatly; contracting has been broken the production time; another has saved cost, does not produce solid waste again simultaneously, is conducive to environmental protection again; technological process of the present invention; no matter from production efficiency, economic benefit, the aspects such as environment protection are all superior to traditional technique.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated.
Embodiment 1
Binary azeotropic method produces a method for high concentration and high efficiency naphthalene water reducer, comprises the following steps:
1) according to weight parts, in reactor, 180 parts of liquid industrial naphthalenes are added, when stirring and be warming up to 140 DEG C, starting to drip 140 parts of concentration is the sulfuric acid of 98%, controls to add speed, makes temperature be no more than 165 DEG C, insulation binary azeotropic backflow 4.5h, Controlled acidity is 26%;
2) step 1) gained material is cooled to 120 DEG C, then in reactor, adds 24 parts of water, be slowly warming up to 135 DEG C, utilize binary azeotropic method to reclaim naphthalene, Controlled acidity is 25.5% stopping hydrolysis;
3) by step 2) gained material is cooled to 110 DEG C, starts to drip 110 parts of formaldehyde, controls rate of addition, dropwises in 3 hours, and be then incubated condensation 5 hours, in this step process, reclaim formaldehyde simultaneously;
4) add 180 parts of alkali neutralizations to step 3) gained condenses, be then drying to obtain finished product;
Above each material and supplies add all with weight parts, all parts by weight are according to same ratio standard.
Embodiment 2
Binary azeotropic method produces a method for high concentration and high efficiency naphthalene water reducer, comprises the following steps:
1) according to weight parts, in reactor, 160 parts of liquid industrial naphthalenes are added, when stirring and be warming up to 135 DEG C, starting to drip 120 parts of concentration is the sulfuric acid of 98%, controls to add speed, makes temperature be no more than 165 DEG C, insulation binary azeotropic backflow 4h, Controlled acidity is 25%;
2) step 1) gained material is cooled to 115 DEG C, then in reactor, adds 23 parts of water, be slowly warming up to 130 DEG C, utilize binary azeotropic method to reclaim naphthalene, Controlled acidity is 26% stopping hydrolysis;
3) by step 2) gained material is cooled to 110 DEG C, starts to drip 100 parts of formaldehyde, controls rate of addition, dropwises in 3 hours, and be then incubated condensation 5 hours, in this step process, reclaim formaldehyde simultaneously;
4) add 170 parts of alkali neutralizations to step 3) gained condenses, be then drying to obtain finished product;
Above each material and supplies add all with weight parts, all parts by weight are according to same ratio standard.
Embodiment 3
Binary azeotropic method produces a method for high concentration and high efficiency naphthalene water reducer, comprises the following steps:
1) according to weight parts, in reactor, 200 parts of liquid industrial naphthalenes are added, when stirring and be warming up to 145 DEG C, starting to drip 160 parts of concentration is the sulfuric acid of 98%, controls to add speed, makes temperature be no more than 165 DEG C, insulation binary azeotropic backflow 5h, Controlled acidity is 27%;
2) step 1) gained material is cooled to 125 DEG C, then in reactor, adds 25 parts of water, be slowly warming up to 140 DEG C, utilize binary azeotropic method to reclaim naphthalene, Controlled acidity is 26% stopping hydrolysis;
3) by step 2) gained material is cooled to 110 DEG C, starts to drip 120 parts of formaldehyde, controls rate of addition, dropwises in 3 hours, and be then incubated condensation 5 hours, in this step process, reclaim formaldehyde simultaneously;
4) add 190 parts of alkali neutralizations to step 3) gained condenses, be then drying to obtain finished product;
Above each material and supplies add all with weight parts, all parts by weight are according to same ratio standard.
Sulfonation reaction formula:
Hydrolysis reaction formula:
Condensation reaction is a macromolecular forming process, and do not have a fixing molecular weight, the scope of molecular weight is about 1500 ~ 2000.
Acidity detection method in sulfonation and hydrolytic process:
Claim 0.1 gram, sulfonation (hydrolysis) sample (precision 0.0001) m, add water 100 milliliters and dissolve, add 2-3, phenolphthalein sodium hydroxide 0.1N reference liquid v milliliter and be titrated to colourless, then by following formulae discovery:
Acidity a=(N1*v*49/ (m*1000)) * 100%
Note: N1 is the equivalent concentration of sodium hydroxide, and v is the titration volumes of sodium hydroxide, and 49 is gram molecular weights of sulfuric acid, and m is the quality of sample.
Sulfuric acid and naphthalene react generation 2-naphthene sulfonic acid and this sulfonation reaction of water is a pyroreaction, and is reversible reaction.This reversible reaction has a characteristic: just move to favourable direction if increase arbitrary concentration-response in reactant, if reduce the concentration of arbitrary material of resultant one side, react and move to favourable direction.Increase according to the concentration of this principle by the NAPTHALENE FLAKES. (INDUSTRIAL GRADE） of reaction object space, as far as possible object allows sulfuric acid transform fully, and what the free sulfate ion taking next reaction to was tried one's best lacks, and prepares like this for high dense production; Reduced by the water concentration generating object space, the realization of this scheme just make use of binary azeotropic method, and in this process, naphthalene and water meeting azeotropic, so just can remove water, then reclaimed by naphthalene and turn back in reactor, reaction is carried out to required direction.By this process, the transformation efficiency of sulfuric acid is improved, the growing amount of 2-naphthene sulfonic acid also improves, then next step hydrolysis is entered, the object of this step is removed by the by product 1-naphthalene sulfonic aicd in reaction, still binary azeotropic principle is utilized water and naphthalene to be removed and control the acidity of material among process, next condensation reaction is entered, the condensation problem of Low acid is mainly solved in this process, improve condensation temp, increase the reaction times, also added the link reclaiming formaldehyde in this process, finally neutralize, drying goes out finished product.
Claims (3)
1. binary azeotropic method produces a method for high concentration and high efficiency naphthalene water reducer, it is characterized in that, comprises the following steps:
1) according to weight parts, in reactor, 160 ~ 200 parts of liquid industrial naphthalenes are added, when stirring and be warming up to 135 ~ 145 DEG C, starting to drip 120 ~ 160 parts of concentration is the sulfuric acid of 98%, controls to add speed, makes temperature be no more than 165 DEG C, insulation binary azeotropic backflow 4 ~ 5h, Controlled acidity is 25 ~ 27%;
2) step 1) gained material is cooled to 115 ~ 125 DEG C, then in reactor, adds 23 ~ 25 parts of water, be slowly warming up to 130 ~ 140 DEG C, utilize binary azeotropic method to reclaim naphthalene, Controlled acidity is 25.5 ~ 26.0% stopping hydrolysis;
3) by step 2) gained material is cooled to 110 DEG C, starts to drip 100 ~ 120 parts of formaldehyde, controls rate of addition, dropwises in 3 hours, and be then incubated condensation 5 hours, in this step process, reclaim formaldehyde simultaneously;
4) add 170 ~ 190 parts of alkali neutralizations to step 3) gained condenses, be then drying to obtain finished product.
2. binary azeotropic method as claimed in claim 1 produces the method for high concentration and high efficiency naphthalene water reducer, it is characterized in that: in described step 1), in reactor, add 180 parts of liquid industrial naphthalenes, when stirring and be warming up to 140 DEG C, starting to drip 140 parts of concentration is the sulfuric acid of 98%, control adds speed, make temperature be no more than 165 DEG C, insulation binary azeotropic backflow 4.5h, Controlled acidity is 26%.
3. binary azeotropic method as claimed in claim 1 produces the method for high concentration and high efficiency naphthalene water reducer, it is characterized in that: described step 2) in step 1) gained material is cooled to 120 DEG C, 24 parts of water are added again in reactor, slowly be warming up to 135 DEG C, utilize binary azeotropic method to reclaim naphthalene, Controlled acidity is 25.5% stopping hydrolysis.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464464A (en) * | 2010-11-09 | 2012-05-23 | 浙江龙盛集团股份有限公司 | Preparation method of naphthalene series water reducer |
| CN104176968A (en) * | 2014-08-21 | 2014-12-03 | 广东瑞安科技实业有限公司 | Production method for naphthalene high-concentration water reducer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464464A (en) * | 2010-11-09 | 2012-05-23 | 浙江龙盛集团股份有限公司 | Preparation method of naphthalene series water reducer |
| CN104176968A (en) * | 2014-08-21 | 2014-12-03 | 广东瑞安科技实业有限公司 | Production method for naphthalene high-concentration water reducer |
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