CN114832789B - Method for removing polymerization inhibitor in acrylic acid by replacing activated carbon adsorption and adsorbent - Google Patents
Method for removing polymerization inhibitor in acrylic acid by replacing activated carbon adsorption and adsorbent Download PDFInfo
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- CN114832789B CN114832789B CN202210290035.8A CN202210290035A CN114832789B CN 114832789 B CN114832789 B CN 114832789B CN 202210290035 A CN202210290035 A CN 202210290035A CN 114832789 B CN114832789 B CN 114832789B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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Abstract
The invention provides a preparation method of an adsorbent for replacing activated carbon to adsorb a polymerization inhibitor in acrylic acid and the adsorbent, relates to the field of chemical industry, and improves the adsorption performance of bentonite by modifying acrylic acid-acrylamide-styrene-hydroxypropyl acrylate tetrapolymer, can replace the activated carbon in the prior art, has low cost, can be regenerated and continuously used, greatly reduces the production cost of enterprises, and has good significance for energy conservation and environmental protection.
Description
Technical Field
The invention relates to the technical field of chemistry and chemical engineering, in particular to a method for removing polymerization inhibitor in acrylic acid by replacing activated carbon adsorption and an adsorbent.
Background
It has been a popular problem to remove the polymerization inhibitor from the acrylic monomer to obtain a high performance polyacrylic acid product. Typical methods for removing the polymerization inhibitor include a reduced pressure distillation method, a low temperature recrystallization method, an ion exchange resin method, a molecular sieve or an activated carbon adsorption separation method. The vacuum distillation method and the low-temperature recrystallization method have the advantages of expensive equipment, high investment, high energy consumption and high cost, and only large factories can consider the use of the method, and the tail liquid (acrylic acid liquid with high polymerization inhibitor content) prepared by the distillation method is further treated. The ion exchange resin method has simple equipment, but has small treatment capacity, and the regeneration treatment of the resin has great difficulty and high cost. So that the prior middle and small factories mostly adopt an active carbon adsorption method to remove polymerization inhibitor in acrylic acid. Along with the higher and higher environmental protection requirements, the waste residues of the activated carbon in the factories are strictly controlled, and besides the waste residues of the activated carbon are required to be treated uniformly by related departments, the quantity of the waste residues of the activated carbon produced in the factories is strictly controlled, and the quantity of the waste residues produced is not allowed to exceed the standard, so that certain difficulty is brought to the factories.
Disclosure of Invention
The invention aims at overcoming the defects and shortcomings of the prior art, and provides a method for removing polymerization inhibitor in acrylic acid by replacing activated carbon adsorption and an adsorbent, which solve the problem that the waste residue of the activated carbon exceeds the standard in the prior art, and the novel mineral adsorbent can be automatically regenerated, so that the cost is reduced and the secondary pollution is reduced.
In order to achieve the above object, the present invention provides the following solutions: the invention provides a preparation method of an adsorbent for removing polymerization inhibitor in acrylic acid by replacing activated carbon adsorption, which comprises the following steps:
s1, bentonite is taken and dried for standby;
s2, dissolving the acrylic acid-acrylamide-styrene-hydroxypropyl acrylate tetrapolymer in water to prepare an aqueous solution with the concentration of 2-5%;
s3, mixing bentonite in the S1 and the solution in the S2 according to the mass ratio of 1:1, uniformly stirring to form mud, and standing at the temperature of 25-35 ℃ for 48 hours;
s4, putting the slurry in the step S3 into a baking oven for baking and crushing to obtain the adsorbent finished product.
As a preferred embodiment of the invention, the preparation method of the acrylic acid-acrylamide-styrene-hydroxypropyl acrylate tetrapolymer comprises the steps of adding acrylic acid and acrylamide into pure water to be dissolved into aqueous solution, wherein the mass ratio of the acrylic acid to the acrylamide is 4:3:1:1; adding styrene into hydroxypropyl acrylate to dissolve to obtain oil phase solution; then the oil phase solution is added into the water phase solution in a dropwise manner, and the mixture is stirred rapidly at the same time, so that the emulsion phase solution is uniform. Then adding initiator potassium persulfate with the mass of 0.5-0.8 percent and sodium sulfite with the mass of 0.2-0.4 percent into the mixture, reacting the mixture for 4-6 hours at the temperature of 25-30 ℃ to obtain a gel product, and then granulating, drying, crushing and sieving the gel product.
As a preferred embodiment of the present invention, bentonite is sieved through 200 mesh in step S1.
The invention also provides the adsorbent prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
the method can solve the problem of exceeding standard of the active carbon waste residue and the problem of removing polymerization inhibitor in the acrylic acid, and the new mineral adsorbent can reduce the cost and secondary pollution through regeneration treatment.
The technical key of the invention is modification treatment of bentonite. As is well known, bentonite is mainly of montmorillonite structure, na 0.7 (Al 3.3 ˙Mg 0.7 )Si 8 O 2 (0H) 4 ˙nH 2 The O crystal structure shows that the upper layer and the lower layer are S i-O tetrahedrons, and the middle layer is an Al-O octahedron, so that the O crystal has larger specific surface, good adsorptivity, volume expansion, ion exchange property and cohesiveness. The acrylic acid-acrylamide-styrene-hydroxypropyl acrylate tetrapolymer is a good adsorbent and has good adsorption effect on various metal ions and some organic matters. When the two are mixed, the modified bentonite is easy to attach to the surface of the bentonite, so that the bentonite is modified and the adsorption performance is greatly improved. In addition, slits are arranged between the upper layer Si-O tetrahedron and the lower layer Si-O tetrahedron of the bentonite, if the slits are enlarged, the adsorption capacity of the bentonite is further improved, so that cationic surfactants such as cetyl ammonium bromide or stearyl trimethyl ammonium chloride and the like can be added in the process of treating the bentonite to replace Na+ in the slits to enlarge the slits, and the adsorption performance of the bentonite is further improved.
The method and the adsorbent for removing the polymerization inhibitor in the acrylic acid by replacing activated carbon adsorption can completely replace the activated carbon in the prior art, have low cost, can be regenerated and used continuously, greatly reduce the production cost of enterprises, and have good popularization significance on energy conservation and environmental protection.
Detailed Description
The invention provides a preparation method of an adsorbent for removing polymerization inhibitor in acrylic acid by replacing activated carbon adsorption, which comprises the following steps:
s1, bentonite is taken and dried for standby;
s2, dissolving the acrylic acid-acrylamide-styrene-hydroxypropyl acrylate tetrapolymer in water to prepare an aqueous solution with the concentration of 2-5%;
s3, mixing bentonite in the S1 and the solution in the S2 according to the mass ratio of 1:1, uniformly stirring to form mud, and standing at the temperature of 25-35 ℃ for 48 hours;
s4, putting the slurry in the step S3 into a baking oven for baking and crushing to obtain the adsorbent finished product.
The preparation method of the acrylic acid-acrylamide-styrene-hydroxypropyl acrylate tetrapolymer comprises the steps of adding acrylic acid and acrylamide into pure water to be dissolved into aqueous phase solution, wherein the mass ratio of the acrylic acid to the acrylamide to the hydroxypropyl acrylate tetrapolymer is 4:3:1:1; adding styrene into hydroxypropyl acrylate to dissolve to obtain oil phase solution; then slowly dripping the oil phase solution into the water phase solution, and rapidly stirring while dripping to form uniform emulsion phase solution. Then adding initiator potassium persulfate with the mass of 0.5-0.8 percent and sodium sulfite with the mass of 0.2-0.4 percent into the mixture, reacting the mixture for 4-6 hours at the temperature of 25-30 ℃ to obtain a gel product, and then granulating, drying, crushing and sieving the gel product.
As a preferable embodiment of the invention, a cationic surfactant such as cetylammonium bromide or octadecyltrimethylammonium chloride is further added in the step S1.
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
Example 1
Synthesis of tetrapolymer: adding 15g of acrylamide into 30g of pure water to fully dissolve the acrylamide, and then adding 20g of acrylic acid to prepare an aqueous phase solution; in addition, 5g of styrene was weighed and 5g of hydroxypropyl acrylate was added to prepare an oil phase solution. Under the stirring state, slowly adding the oil phase solution into the water phase solution, stirring for 30 minutes after the dripping is finished to form a uniform solution, then adding 0.18g of potassium persulfate and 0.10 g of sodium sulfite, reacting for 4 hours at the temperature of 30 ℃ to obtain the tetrapolymer, and sieving the tetrapolymer with a 200-mesh sieve powder for standby after granulating and drying at the temperature of 105 ℃.
Preparing an adsorbent: sieving commercial Na-bentonite with a 200-mesh sieve, putting into a baking oven, drying at 105 ℃ to constant weight, preparing the quadripolymer into 4% aqueous solution concentration, adding the quadripolymer into the dried bentonite according to the weight ratio of 1:1, stirring into slurry, standing at 30 ℃ for 48 hours, putting into the baking oven, and drying at 105 ℃ to obtain powder blocks.
Adsorption polymerization inhibitor removal MEHQ (4-methoxyphenol) test: the adsorption is carried out by selecting basic acrylic acid, neutralizing acrylic acid with NaOH, adding into adsorbent at 5 per mill (based on total sodium acrylate), standing and stirring for 8 hours, filtering, measuring MEHQ content of filtrate by spectrophotometry, and converting into PPM concentration. In addition, sodium acrylate after adsorption treatment is used as a raw material, polymerized into a thickener according to a given formula, prepared into water solution glue with concentration of 2 per mill, measured by a rotary viscometer NDJ-1 type, the viscosity of the water solution glue is required to be more than 800 mpa.s, and the measured data are listed in an attached table.
Example two
The adsorption test was performed by using acid clay, i.e., H-bentonite, instead of Na-bentonite in example I to prepare an adsorbent, and the other steps were the same as in example I.
Example III
The adsorbent was prepared by using organic bentonite instead of sodium bentonite in example one, and the adsorption test was performed in the same manner as in example one.
The data before and after adsorption in the above examples are as follows:
the MEHQ content of the polymerization inhibitor is determined according to the method specified in GB/T17530.5-1998 for determining polymerization inhibitors in industrial acrylic acid and esters, and the measured content of the MEHQ [ mu ] g is converted into ppm content.
From the above data, it can be seen that the three adsorbents of the present invention can be used to replace activated carbon when the inhibitor is removed by adsorption in alkaline sodium acrylate solution to the level of activated carbon adsorption.
And (3) adsorbent regeneration: the used adsorbent can be attached with sodium acrylate and MEHQ on the surface, can be washed or soaked twice by low-concentration alkali liquor such as (15%) NaOH aqueous solution, is washed once by tap water and pure water, is then put into an oven for drying at 105 ℃, is then added with a tetrapolymer aqueous solution to prepare the modified adsorbent thereof according to the method for preparing the adsorbent, and is subjected to next adsorption to remove polymerization inhibitor, so that the adsorbent can be repeatedly used for 3-4 times, and although the capacity of removing MEHQ of the regenerated adsorbent is slightly reduced each time, the reduction amplitude is smaller, and the effective rate of removing the polymerization inhibitor can still reach 70% -80% of the original level after being regenerated to the end.
The principles and embodiments of the present invention have been described in detail with reference to specific examples, which are provided to facilitate understanding of the present invention and its core ideas; also, it is within the scope of the present invention to be modified by those of ordinary skill in the art in light of the present teachings. In view of the foregoing, this description should not be construed as limiting the invention.
Claims (6)
1. The application of the adsorbent for replacing activated carbon to adsorb polymerization inhibitor in acrylic acid in removing the polymerization inhibitor is characterized in that the preparation method comprises the following steps:
s1, bentonite is taken and dried for standby;
s2, dissolving the acrylic acid-acrylamide-styrene-hydroxypropyl acrylate tetrapolymer in water to prepare an aqueous solution with the concentration of 2-5%; the mass ratio of the acrylic acid to the acrylamide to the styrene to the hydroxypropyl acrylate is 4:3:1:1;
s3, mixing bentonite in the S1 and the solution in the S2, uniformly stirring to form a mud shape, and standing for 48 hours;
s4, putting the slurry in the step S3 into a baking oven for baking and crushing to obtain the adsorbent finished product.
2. The use according to claim 1, wherein in step S1 the bentonite is sieved through 200 mesh.
3. The use according to claim 1, wherein the mass ratio of the mixing in step S3 is 1:1.
4. The use according to claim 1, wherein in step S2, acrylic acid and acrylamide are added into pure water to be dissolved into aqueous solution; adding styrene into hydroxypropyl acrylate to dissolve to obtain oil phase solution; then dripping the oil phase solution into the water phase solution, and rapidly stirring while dripping to form a uniform emulsion; then adding initiator potassium persulfate with the mass of 0.5-0.8 percent and sodium sulfite with the mass of 0.2-0.4 percent into the mixture, reacting the mixture for 4-6 hours at the temperature of 25-30 ℃ to obtain a gel product, and then granulating, drying, crushing and sieving the gel product.
5. The use according to claim 1, wherein step S1 further comprises adding a cationic surfactant to the bentonite.
6. The use according to claim 5, wherein the cationic surfactant is one or both of cetylammonium bromide and octadecyltrimethylammonium chloride.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310580273.7A CN116586046A (en) | 2022-03-23 | 2022-03-23 | Polymerization inhibitor adsorbent for removing acrylic acid |
| CN202210290035.8A CN114832789B (en) | 2022-03-23 | 2022-03-23 | Method for removing polymerization inhibitor in acrylic acid by replacing activated carbon adsorption and adsorbent |
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| CN202210290035.8A CN114832789B (en) | 2022-03-23 | 2022-03-23 | Method for removing polymerization inhibitor in acrylic acid by replacing activated carbon adsorption and adsorbent |
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| CN202310580273.7A Division CN116586046A (en) | 2022-03-23 | 2022-03-23 | Polymerization inhibitor adsorbent for removing acrylic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4530766A (en) * | 1983-04-15 | 1985-07-23 | Rohm And Haas Company | Method of inhibiting scaling in aqueous systems with low molecular weight copolymers |
| US4566973A (en) * | 1984-08-06 | 1986-01-28 | The B. F. Goodrich Company | Scale inhibition in water systems |
| JP3682990B2 (en) * | 1994-07-13 | 2005-08-17 | ジーイー東芝シリコーン株式会社 | Method for removing polymerization inhibitor |
| CN1268657C (en) * | 2003-08-13 | 2006-08-09 | 河北科技大学 | High elasticity acetal phenyl propyl soapless copolymerized emulsion and its preparation |
| CN103055824B (en) * | 2013-01-07 | 2015-01-07 | 河北工业大学 | Calcium bentonite -AA- (AA-Na) composite cadmium ion adsorbent |
| CN110420626A (en) * | 2019-08-14 | 2019-11-08 | 徐州工程学院 | Acrylic acid/acrylamide/styrene terpolymer hydrogel and its preparation method and application |
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