CN110368715B - Method and device for removing impurities from sulfonate anionic surfactant - Google Patents
Method and device for removing impurities from sulfonate anionic surfactant Download PDFInfo
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- CN110368715B CN110368715B CN201810324774.8A CN201810324774A CN110368715B CN 110368715 B CN110368715 B CN 110368715B CN 201810324774 A CN201810324774 A CN 201810324774A CN 110368715 B CN110368715 B CN 110368715B
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Abstract
The invention discloses a method for removing impurities of sulfonate anionic surfactants. The method is used for carrying out microporous material adsorption treatment on the acidic sulfonated substance obtained by sulfonation process treatment so as to remove sulfur trioxide, sulfuric acid and unsulfonated substance in the product; wherein the microporous material comprises a first microporous material with a pore size of 0.40-0.45nm and a second microporous material with a pore size greater than 0.45 nm. The first microporous material is loaded with cobalt chloride crystals, copper sulfate crystals or nickel sulfate crystals. The invention also discloses a device for realizing the method. The invention can effectively remove 30-70% of inorganic acid or inorganic salt in the sulfonated product of sulfonate anionic surfactant, and can remove 20-60% of unsulfonated substance, thereby improving the total active substance content of the product. The invention is used in the production process of sulfonate anionic surfactants, does not influence the productivity of the surfactants, and has lower equipment investment cost and production cost.
Description
Technical Field
The invention relates to a method and a device for removing impurities of sulfonate anionic surfactants.
Background
Currently, sulfonate anionic surfactants employ a sulfonation process in their preparation process and leave impurities such as inorganic acids or inorganic salts (mainly sulfuric acid or sulfates) and unsulfonated compounds (e.g., alkenes and alkanes, alkylbenzenes, and fatty acid esters) in the product. Moreover, the inorganic acid content of the product after the sulfonation process is high, so that the alkali consumption required in the subsequent neutralization step is increased, and the active matter content of the finished product is low.
Disclosure of Invention
The first purpose of the invention is to provide a method for removing impurities of sulfonate anionic surfactants, which effectively solves the defects of the prior art.
A second object of the invention is to provide a device for carrying out the above method.
In order to achieve the purpose, the invention adopts the following technical scheme:
the impurity removing method of sulfonate anionic surfactant includes adsorbing acid sulfonate with microporous material to eliminate sulfur trioxide, sulfuric acid and un-sulfonated matter; wherein the microporous material comprises a first microporous material with a pore size of 0.40-0.45nm and a second microporous material with a pore size greater than 0.45 nm.
Preferably, the first microporous material and the second microporous material are both inorganic microporous materials, including microporous aluminosilicate, microporous silica, microporous borophosphate, aluminum phosphate molecular sieves, and microporous ceramics.
Preferably, the first microporous material is loaded with cobalt chloride crystals, or copper sulfate crystals, or nickel sulfate crystals.
Preferably, after the crystal water loaded on the first microporous material is completely consumed, the first microporous material is subjected to a regeneration treatment, which includes an adsorbate desorption step and a crystal water generation step.
Alternatively, the pore diameter of the second microporous material is greater than 0.45 and less than or equal to 0.50nm, so as to remove the olefin and the alkane in the product; the ratio of the first microporous material to the second microporous material is 1: 0.8-1: 2; the two microporous materials are arranged in a mixing mode or in a sectional mode.
Alternatively, the pore diameter of the second microporous material is 0.70-0.80nm, so as to remove alkylbenzene and fatty acid ester in the product; the ratio of the first microporous material to the second microporous material is 1: 0.8-1: 2; the two microporous materials are arranged in a mixing mode or in a sectional mode.
In order to achieve the second purpose, the invention adopts the following technical scheme:
the impurity removing device of sulfonate anionic surfactant is arranged between a discharge pipeline and a finished product cylinder of sulfonation process equipment, and comprises: the adsorption pipeline is formed by connecting at least one adsorption pipe in parallel, and the total pipe diameter of the adsorption pipeline is 2-3 times of the pipe diameter of a discharge pipeline of the sulfonation process equipment; and the microporous material is filled in the adsorption pipeline, and the filling amount is 0.2-1 cubic meter.
Preferably, the microporous material comprises a first microporous material with a pore size of 0.40-0.45nm and a second microporous material with a pore size of more than 0.45 nm; the first microporous material and the second microporous material are both inorganic microporous materials and comprise microporous aluminosilicate, microporous silicon dioxide, microporous borophosphate, an aluminum phosphate molecular sieve and microporous ceramic; the first microporous material is loaded with cobalt chloride crystals, copper sulfate crystals or nickel sulfate crystals.
Preferably, the ratio of the first microporous material to the second microporous material is 1: 0.8-1: 2; the first microporous material and the first microporous material are filled in a mixing mode or are filled in a sectional mode.
Preferably, the pore diameter of the second microporous material is greater than 0.45 and equal to or less than 0.50 nm; or the pore diameter of the second microporous material is 0.70-0.80 nm.
The invention can effectively remove 30-70% of inorganic acid or inorganic salt in the sulfonated product of sulfonate anionic surfactant, and can remove 20-60% of unsulfonated substance, thereby improving the total active substance content of the product. The invention is used in the production process of sulfonate anionic surfactants, does not influence the productivity of the surfactants, and has lower equipment investment cost and production cost.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for removing impurities from a sulfonate anionic surfactant according to the present invention.
In the figure:
1-an adsorption tube; 11-a feed inlet; 12-a discharge port; 2 — a first microporous material; 3-a second microporous material.
The present invention will now be described in further detail with reference to the accompanying drawings and examples.
Detailed Description
As shown in fig. 1, the device for removing impurities from sulfonate anionic surfactants of the present invention comprises an adsorption pipeline, the adsorption pipeline is connected in parallel by at least one adsorption tube 1 (one in this embodiment), a feed inlet 11 of the adsorption pipeline is connected to a discharge pipeline of the sulfonation processing equipment, and a discharge outlet 12 of the adsorption pipeline is connected to a finished product cylinder; the total pipe diameter of the adsorption pipeline is 2-3 times of the pipe diameter of the discharge pipeline of the sulfonation process equipment. The adsorption pipeline is also filled with 0.2-1 cubic meter of microporous material.
The microporous material is inorganic microporous material (including microporous aluminosilicate, microporous silicon dioxide, microporous borophosphate, aluminum phosphate molecular sieve and microporous ceramic). The microporous material is divided into a first microporous material 2 and a second microporous material 3 which are filled in the adsorption tube 1 in sections; the filling ratio of the first microporous material to the second microporous material is 1: 0.8-1: 2. Wherein, the aperture of the first microporous material 2 is 0.40-0.45nm, and cobalt chloride crystals, or copper sulfate crystals, or nickel sulfate crystals are loaded for absorbing sulfur trioxide and sulfuric acid in the product. The second microporous material 2 is a microporous material with the pore diameter of more than 0.45 and less than or equal to 0.50nm and is used for removing olefin and alkane in the product; or the second microporous material 2 adopts a microporous material with the pore diameter of 0.70-0.80nm to remove alkylbenzene and fatty acid ester in the product.
It should be noted that the first microporous material and the second microporous material may also be mixed together and filled.
In addition, when the microporous material is used for a period of time, the adsorbate of the microporous material is saturated, and then the microporous material needs to be subjected to regeneration treatment, which is specifically as follows:
1. the regeneration treatment of the first microporous material:
the cobalt chloride crystals, or copper sulfate crystals, or nickel sulfate crystals supported by the first microporous material 2, in addition to being used to react with sulfur trioxide in the product in water to produce sulfuric acid, also have the characteristics of an indicator, i.e., cobalt chloride crystals are indicated as red, copper sulfate crystals are indicated as blue, and nickel sulfate crystals are indicated as blue. When the crystal water is completely consumed, the cobalt chloride indicates blue, the copper sulfate indicates white, and the nickel sulfate indicates yellow-green, and the first microporous material needs to be subjected to regeneration treatment. The first microporous material is subjected to the following steps of: firstly, taking out a first microporous material, soaking the first microporous material in deionized water, slowly adding a sodium hydroxide solution under the stirring state until the pH of the solution is 7.0-7.5 and the pH of the solution is H in micropores2SO4Completely neutralizing to obtain sodium sulfate, and desorbing in micropores; then, draining the moisture on the surface of the first microporous material, carrying out vacuum drying on the first microporous material, and evaporating the moisture in micropores; and finally, carrying out constant temperature and humidity treatment at the temperature of 35-40 ℃ and the humidity of 80-90% to ensure that the first microporous material shows the color of the loaded crystalline hydrate and has uniform color.
2. And (3) regeneration treatment of the second microporous material:
firstly, taking out the second microporous material, and soaking the second microporous material in an organic solvent (such as alcohol, ether, ketone and ester solvents, such as ethanol, acetone, diethyl ether and ethyl acetate) with the total carbon number less than or equal to 4 to remove the non-sulfonated monomer from the second microporous material; finally, the solvent of the second microporous material is drained, and the solvent in the micropores is evaporated by carrying out reduced pressure distillation on the second microporous material.
3. Mixed regeneration treatment of the first microporous material and the second microporous material;
firstly, taking out the microporous material (the first microporous material and the second microporous material are mixed and filled), soaking in deionized water, and stirringSlowly adding sodium hydroxide solution in a stirring state until the pH of the solution is 7.0-7.5 and the H in the micropores2SO4Completely neutralizing to obtain sodium sulfate, and desorbing in micropores; then, draining off the water on the surface of the microporous material; then, soaking the microporous material with an organic solvent (such as alcohol, ether, ketone, ester solvent, such as ethanol, acetone, diethyl ether, ethyl acetate, etc.) with a total carbon number of less than or equal to 4 to remove the non-sulfonated monomer from the microporous material; then, carrying out vacuum drying on the microporous material, and evaporating the solvent and water in the micropores; and finally, carrying out constant temperature and humidity treatment at the temperature of 35-40 ℃ and the humidity of 80-90% to ensure that the first microporous material in the microporous material shows the color of the loaded crystalline hydrate and has uniform color.
The following is a description of the present invention in terms of removing impurities from four major sulfonate anionic surfactants.
Example 1
Alkylbenzene sulfonate anionic surfactant:
the capacity of the sulfonation equipment for producing the surfactant is 3 tons/hour, and the total pipe diameter of the adsorption pipeline is 2 times of the pipe diameter of a discharge pipe of the sulfonation equipment. The filling amount of the microporous materials is 0.5 cubic meter, wherein the filling amount of the first microporous material is 0.2 cubic meter, the filling amount of the second microporous material is 0.3 cubic meter, and the first microporous material and the second microporous material are filled in a segmented mode. The pore diameter of the second microporous material is 0.70-0.75 nm. The impurity removal effect is shown in the following table:
| before adsorption | After adsorption | |
| Total active content/%) | 96.3 | 97.8 |
| Inorganic acid/%) | 1.48 | 0.5 |
| Free oil/% | 1.8 | 0.9 |
| color/Klett | 48 | 28 |
Example 2
Alpha-olefin sulfonate anionic surfactant:
the capacity of the sulfonation equipment for producing the surfactant is 5 tons/hour, and the total pipe diameter of the adsorption pipeline is 3 times of the pipe diameter of a discharge pipe of the sulfonation equipment. The filling amount of the microporous material is 1m3Wherein the filling amount of the first microporous material is 0.45m3The filling amount of the second microporous material is 0.55m3And the two are filled in sections. The pore diameter of the second microporous material is greater than 0.45 and equal to or less than 0.50 nm. The impurity removal effect is shown in the following table:
example 3
Fatty acid methyl ester sulfonate anionic surfactant:
the capacity of the sulfonation equipment for producing the surfactant is 1 ton/hour, and the total pipe diameter of the adsorption pipeline is 2.5 times of the pipe diameter of a discharge pipe of the sulfonation equipment. The filling amount of the microporous material is 0.2m3Wherein the filling amount of the first microporous material is 0.1m3The filling amount of the second microporous material is 0.1m3And the two are filled in sections. First, theThe aperture of the two microporous materials is 0.75-0.80 nm. The impurity removal effect is shown in the following table:
example 4
Alkane sulfonate anionic surfactant:
the capacity of the sulfonation equipment for producing the surfactant is 3 tons/hour, and the total pipe diameter of the adsorption pipeline is 2.5 times of the pipe diameter of a discharge pipe of the sulfonation equipment. The filling amount of the microporous material is 0.8m3Wherein the filling amount of the first microporous material is 0.27m3The filling amount of the second microporous material is 0.53m3And the two are filled in sections. The pore diameter of the second microporous material is greater than 0.45 and equal to or less than 0.50 nm. The impurity removal effect is shown in the following table:
Claims (8)
1. the impurity removing method of sulfonate anionic surfactant is characterized in that acid sulfonated substance obtained by sulfonation process is subjected to microporous material adsorption treatment to remove sulfur trioxide, sulfuric acid and unsulfonated substance in the product; wherein the microporous material comprises a first microporous material with a pore size of 0.40-0.45nm and a second microporous material with a pore size of more than 0.45 nm; the first microporous material and the second microporous material are both inorganic microporous materials and comprise microporous aluminosilicate, microporous silicon dioxide, microporous borophosphate, an aluminum phosphate molecular sieve and microporous ceramic; the first microporous material is loaded with cobalt chloride crystals, copper sulfate crystals or nickel sulfate crystals.
2. The method of claim 1, wherein the first microporous material is subjected to a regeneration treatment after the crystal water supported by the first microporous material is completely consumed, and the regeneration treatment comprises an adsorbate desorption step and a crystal water generation step.
3. The method of claim 1, wherein the second microporous material has a pore size of 0.45nm or more and 0.50nm or less for removing the olefin and the alkane from the product; the ratio of the first microporous material to the second microporous material is 1: 0.8-1: 2; the two microporous materials are arranged in a mixing mode or in a sectional mode.
4. The method of claim 1, wherein the second microporous material has a pore size of 0.70 to 0.80nm for removing alkylbenzene and fatty acid ester from the product; the ratio of the first microporous material to the second microporous material is 1: 0.8-1: 2; the two microporous materials are arranged in a mixing mode or in a sectional mode.
5. The impurity removing device of sulfonate anionic surfactant is arranged between a discharge pipeline and a finished product cylinder of sulfonation processing equipment, and is characterized by comprising:
the adsorption pipeline is formed by connecting at least one adsorption pipe in parallel, and the total pipe diameter of the adsorption pipeline is 2-3 times of the pipe diameter of a discharge pipeline of the sulfonation process equipment; and
the microporous material is filled in the adsorption pipeline, and the filling amount is 0.2-1 cubic meter; the microporous material comprises a first microporous material with the pore diameter of 0.40-0.45nm and a second microporous material with the pore diameter of more than 0.45 nm; the first microporous material is loaded with cobalt chloride crystals, copper sulfate crystals or nickel sulfate crystals.
6. The device of claim 5, wherein the first microporous material and the second microporous material are both inorganic microporous materials, and comprise microporous aluminosilicate, microporous silica, microporous borophosphate, aluminum phosphate molecular sieves, and microporous ceramic.
7. The device for removing impurities from a sulfonate anionic surfactant according to claim 6, wherein the ratio of the first microporous material to the second microporous material is 1:0.8 to 1: 2; the first microporous material and the second microporous material are filled in a mixing mode or in a sectional filling mode.
8. The apparatus for removing impurities from a sulfonate-type anionic surfactant as claimed in claim 7, wherein the pore diameter of the second microporous material is greater than 0.45nm and not greater than 0.50 nm; or the pore diameter of the second microporous material is 0.70-0.80 nm.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5319117A (en) * | 1989-10-28 | 1994-06-07 | Henkel Kommanditgesellschaftr Auf Aktien | Process for the sulfonation of unsaturated fatty acid glycerol esters |
| CN102190605A (en) * | 2010-03-03 | 2011-09-21 | 北京中石大节能科技发展有限责任公司 | Petroleum sulfonate anionic surfactant and preparation method thereof |
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| US6773490B2 (en) * | 2001-05-04 | 2004-08-10 | E. I. Du Pont De Nemours And Company | Sulfur trioxide delivery system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5319117A (en) * | 1989-10-28 | 1994-06-07 | Henkel Kommanditgesellschaftr Auf Aktien | Process for the sulfonation of unsaturated fatty acid glycerol esters |
| CN102190605A (en) * | 2010-03-03 | 2011-09-21 | 北京中石大节能科技发展有限责任公司 | Petroleum sulfonate anionic surfactant and preparation method thereof |
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