CN114405491A - Preparation method and application of macroporous resin for VOCS adsorption - Google Patents

Preparation method and application of macroporous resin for VOCS adsorption Download PDF

Info

Publication number
CN114405491A
CN114405491A CN202210072179.6A CN202210072179A CN114405491A CN 114405491 A CN114405491 A CN 114405491A CN 202210072179 A CN202210072179 A CN 202210072179A CN 114405491 A CN114405491 A CN 114405491A
Authority
CN
China
Prior art keywords
resin
preparation
water
macroporous resin
dichloroethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210072179.6A
Other languages
Chinese (zh)
Other versions
CN114405491B (en
Inventor
毛瑞琪
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changguo Biomedical Technology Hebei Co ltd
Original Assignee
Changguo Biomedical Technology Hebei Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changguo Biomedical Technology Hebei Co ltd filed Critical Changguo Biomedical Technology Hebei Co ltd
Priority to CN202210072179.6A priority Critical patent/CN114405491B/en
Publication of CN114405491A publication Critical patent/CN114405491A/en
Application granted granted Critical
Publication of CN114405491B publication Critical patent/CN114405491B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J20/22—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a method for VOCSA preparation method and application of an adsorbed macroporous resin, belonging to the technical field of volatile organic compound adsorption resins; comprises the following steps: (1) preparing a water phase; (2) preparing an oil phase; (3) carrying out polymerization reaction; (4) and hanging double bonds for crosslinking. The invention adopts ternary polymerization of divinylbenzene, acrylonitrile and methyl acrylate to provide nitrile group and ester group for resin, and provides functional groups for sulfur-containing organic gas and chlorine-containing organic gas besides absorbing conventional nonpolar organic gas.

Description

Preparation method and application of macroporous resin for VOCS adsorption
Technical Field
The invention belongs to the technical field of volatile organic compound adsorption resin, and particularly relates to a Volatile Organic Compound (VOC) adsorbentSA preparation method and application of the adsorbed macroporous resin.
Background
Volatile Organic Compounds (VOCs) are a large group of important atmospheric pollutants, and refer to organic compounds having a saturated vapor pressure of more than 70.91Pa at normal temperature and a boiling point of less than 260 ℃ at normal pressure, and the main components thereof are hydrocarbons, oxygen hydrocarbons, halogen-containing hydrocarbons, nitrogen hydrocarbons, sulfur hydrocarbons, and the like. The hazards of VOCs mainly include the generation of photochemical smog, the destruction of ozone layers, the harm to human health and the like. In recent years, the problem of air pollution caused by VOCs has become more severe, and therefore, it is of practical significance to develop a method for removing VOCs with excellent effect, low cost and simple process. In numerous VOCs treatment technologies, most VOCs can be recovered in the adsorption process, the operation is easy, the operation cost is low, and the method is widely applied to the field of VOCs pollution control. The activated carbon has developed micropores and large adsorption capacity, but has poor thermal and hydrothermal stability, is hydrophilic, is easy to block the pores, is difficult to regenerate, has flammable potential safety hazard problems in engineering application, and limits the application of the activated carbon to a certain extent. The inorganic molecular sieve pair has the defects of low selective adsorption on organic matters, limited adsorption capacity and the like. The organic framework of the adsorption resin can provide good selectivity for organic matters, and the developed pore structure and the high specific surface area of the adsorption resin can enable the adsorption resin to have higher adsorption capacity.
The macroporous adsorption resin is a macromolecular adsorption resin which does not contain exchange groups and has a macroporous structure, has a good macroporous network structure and a larger specific surface area, can selectively adsorb organic matters through physics, is a novel organic polymer adsorbent developed in the 60 th century, and has been widely applied to the fields of environmental protection, food, medicine and the like. The macroporous adsorption resin is originally used for adsorbing organic matters in aqueous solution, is gradually developed to the field of waste gas treatment in recent years, and is used for purifying VOCs.
At present, the research on the macroporous adsorption resin which can adsorb sulfur-containing organic gas and chlorine-containing organic gas besides conventional nonpolar organic gas is not reported in documents.
Disclosure of Invention
In order to solve the problems, the resin synthesized by divinylbenzene, acrylonitrile and methyl acrylate through ternary polymerization has nitrile group and ester group functional groups. Besides being capable of adsorbing conventional nonpolar organic gas, the adsorption adsorbent can also effectively adsorb sulfur-containing organic gas and chlorine-containing organic gas, and the invention adopts the technical scheme that:
1. for VOCSThe preparation method of the adsorbed macroporous resin comprises the following steps:
1) preparing a water phase: adding water into a reaction vessel, heating to 50-60 ℃, adding polyvinyl alcohol (PVA) and gelatin, stirring until the polyvinyl alcohol and the gelatin are completely dissolved, adding magnesium sulfate and sodium carbonate, stirring until the polyvinyl alcohol and the gelatin are completely dissolved, and preparing a water phase for later use;
2) preparing an oil phase: adding divinylbenzene into a reaction vessel, wherein the mass content of the divinylbenzene is 80%, acrylonitrile, methyl acrylate, dichloroethane, cyclohexane and Benzoyl Peroxide (BPO), and stirring uniformly to prepare an oil phase for later use;
3) polymerization reaction: slowly adding the prepared oil phase into the water phase, heating and stirring, preserving heat to form resin, extracting a pore-forming agent, and washing and drying the resin;
4) suspension double bond post-crosslinking: adding dichloroethane and methylcyclohexane into a reaction vessel, uniformly mixing to obtain a clear solution, putting the resin obtained in the step (3) into the clear solution for swelling and controlling the temperature, and adding anhydrous ferric trichloride serving as a catalyst after swelling is finished to carry out suspension double bond post-crosslinking reaction.
A certain amount of unreacted double bonds can remain on a benzene ring after one-time polymerization of divinylbenzene, the residual double bonds are polymerized in a post-crosslinking mode, so that the specific surface area of the resin is increased, more sites are provided for gas adsorption, dichloroethane and methylcyclohexane have certain swelling property on the resin, and the swelling of the resin is controlled according to different proportions to adjust the pore structure of the resin.
The weight part ratio of the water to the polyvinyl alcohol in the step (1) is 150-250: 1.
gelatin in the step (1): magnesium sulfate: sodium carbonate: the mass ratio of the polyvinyl alcohol is 0.4-0.8: 3-6: 1-3: 1.
the oil phase in the step (2) consists of the following components in percentage by weight: 20-30% of divinylbenzene, 3-8% of acrylonitrile, 3-4% of methyl acrylate, 10-15% of dichloroethane and 50-60% of cyclohexane, wherein the benzoyl peroxide accounts for 0.1-0.5% of the mass of the oil phase.
And (3) slowly adding the oil phase into the water phase, stirring at the rotating speed of 100r/min, stirring at a constant speed for 10min, heating to 75 ℃ at the speed of 5 ℃/10min, shaping the resin for 1-3 h, continuously heating to 85 ℃ at the speed of 5 ℃/10min, preserving heat for 3-6 h, condensing and refluxing dichloroethane in the process, continuously heating to 95 ℃ at the speed of 5 ℃/10min, preserving heat for 4-8 h, taking out, extracting the pore-forming agent by using acetone in a Soxhlet extractor, wherein the extraction time is 8h, and washing and drying by using water.
The step (4) comprises solution preparation, swelling and double bond suspension post-crosslinking, wherein the solution preparation comprises mixing dichloroethane and methylcyclohexane in a volume ratio of 3-5: 1 to obtain a clear solution.
Further, the swelling comprises the steps of adding resin into the clear solution for 10-14 hours, wherein the temperature is less than or equal to 25 ℃, and the volume ratio of the mass of the resin to the volume of the methylcyclohexane in the clear solution is 0.3-0.7: 1.
further, the suspension of double bonds and crosslinking comprises the steps of adding anhydrous ferric chloride catalyst for the first time after resin swelling is finished, reacting for 30min, adding anhydrous ferric chloride catalyst for the second time, reacting for 30min, heating to 80 ℃, reacting for 6h, adding water, heating to 95 ℃, condensing and recycling dichloroethane, adding 1% hydrochloric acid to wash off the anhydrous ferric chloride catalyst after distillation is finished, extracting organic residues with ethanol in a Soxhlet extractor, and taking out resin, purifying and washing with water to remove ethanol.
Further, the catalyst anhydrous ferric chloride with the same weight is added twice in the cross-linking process after the double bonds are hung, the weight part ratio of the added anhydrous ferric chloride to the resin in the mixture is 7-8:100, and the weight part ratio of the water to the resin in the mixture is 1: 1.
2. the macroporous resin of the invention is used for adsorbing VOCSThe use of (1).
Compared with the prior art, the invention has the following advantages:
1. the prior resin with high specific surface area is mainly crosslinked after chloromethylation, the production process is more complicated, the specific surface area of the resin is 1000-1200 square meters per gram, the average pore diameter is 3-5nm, and the pore diameter distribution is 2-15 nm. The resin is nonpolar macroporous adsorption resin which is mainly used for adsorbing micromolecular nonpolar organic matters such as phenol, toluene and the like, and is not good for adsorbing chlorine-containing and sulfur-containing polar organic matters. The resin of the invention can increase the specific surface area and simultaneously add partial functional groups, can increase the specific adsorption to partial polar organic matters, and has the specific surface area of 1200-1350 square meters per gram, the average pore diameter of 25-27nm and the pore diameter distribution of 4-60 nm.
2. The invention adopts divinylbenzene, acrylonitrile and methyl acrylate ternary polymerization, can provide nitrile group and ester group for resin, and can absorb conventional nonpolar organic gasAlso for specific adsorption of sulfur-containing organic gases and chlorine-containing organic gases, the resin of the present invention is useful for the treatment of CS2The adsorption of air can reach 98.9% at most, and the adsorption of air containing chlorobutadiene can reach 99.8% at most.
3. A certain amount of unreacted double bonds can remain on a benzene ring after one-time polymerization of the divinylbenzene, and the residual double bonds are polymerized in a post-crosslinking mode, so that the specific surface area of the resin is increased, a larger pore diameter is provided for transferring an adsorbed substance, more sites are provided for gas adsorption, and the adsorption capacity is improved. Dichloroethane and methylcyclohexane have certain swellability to the resin, and the swellability of the resin is controlled according to different proportions to adjust the pore structure of the resin.
Drawings
FIG. 1 shows the CS content in the resin treatment of example 12An air adsorption process;
wherein 1-CS2The device comprises a generating device, 2-a ventilating hole, 3-a resin adsorption column, 4-a gas guide pipe, 5-the resin adsorption column, 6-a gas collecting device, 7-the gas collecting device, 8-a pressure gauge and 9-a gas discharging device.
Detailed Description
The present invention is further illustrated by the following specific examples, but it should be understood by those skilled in the art that the specific examples of the present invention are not intended to limit the present invention in any way, and any equivalents based on the present invention are within the scope of the present invention.
Example 1:
1. preparation of the resin
1) Preparing a water phase: 1000ml of water was added to a 2000ml three-necked flask, the temperature was raised to 55 ℃, 5g of PVA and 3g of gelatin were added, and stirring was carried out for 20min to completely dissolve them, and 20g of magnesium sulfate and 10g of sodium carbonate were added and stirred for 0.5h to obtain an aqueous phase.
2) Preparing an oil phase: 75g of divinylbenzene (80%), 15g of acrylonitrile, 10g of methyl acrylate, 38g of dichloroethane, 162g of cyclohexane and 1g of BPO are added into a beaker and mixed by ultrasound to obtain an oil phase.
3) Polymerization reaction: slowly adding the oil phase into the water phase, stirring at a controlled rotation speed of 120r/min until the mixture is stirred constantly, and stirring at a constant speed for 10 min. The temperature was raised from 55 ℃ to 75 ℃ at a rate of 5 ℃/10 min. After the resin is shaped for 2h, the temperature is continuously raised from 75 ℃ to 85 ℃ at the speed of 5 ℃/10min, the heat preservation is carried out for 4h, dichloroethane is condensed and refluxed in the process, the temperature is continuously raised from 85 ℃ to 95 ℃ at the speed of 5 ℃/10min, the heat preservation is carried out for 6h, and then the dichloroethane is taken out. Washing the surface of the resin with warm water to remove polyvinyl alcohol, putting the resin into a Soxhlet extractor, extracting the resin with acetone for 8 hours to extract a pore-forming agent, washing the resin with water and drying the resin.
4) Suspension double bond post-crosslinking: adding 800ml dichloroethane and 200ml methylcyclohexane into a three-neck flask, placing 100g of resin into the three-neck flask for swelling for 12 hours, and controlling the temperature in the kettle to be not more than 25 ℃ in the swelling process. After swelling, 7.5g of anhydrous ferric trichloride is added and stirred uniformly, after 30min, 7.5g of anhydrous ferric trichloride is added and stirred for 30min, and then the temperature is slowly raised to 80 ℃ for reaction for 6 h. Adding 100ml water, heating to 95 deg.C, condensing and recovering dichloroethane, adding 1% hydrochloric acid to wash off catalyst after distillation, extracting organic residue with ethanol in Soxhlet extractor, taking out resin, purifying, and washing with water to remove ethanol.
2. Measuring physical and chemical indexes of the resin (see Table 1)
Moisture content: the resin white balls were soaked with purified water for 24 hours, then centrifuged and the resin moisture was measured using a rapid moisture meter.
Granularity: the measurements were performed using sieves of different pore sizes.
Average pore diameter and specific surface area: measured using a BET aperture specific surface area analyzer.
Content of functional group: measured using a semer flying infrared spectrometer.
Measurement of adsorbed amount of phenol: taking 1g of dry resin (wet resin is converted into dry resin after centrifugation) and putting the dry resin into a 50ml conical flask, adding 25ml of phenol solution with the concentration of 50mg/ml, sealing the cover, putting the conical flask into a constant temperature oscillator, oscillating the conical flask at 25 ℃ for 12h, measuring the light absorption value at 270nm by using an ultraviolet spectrophotometer, and calculating the content of phenol after adsorption. The phenol adsorption capacity is generally used for evaluating the specific surface area, active sites, effective pore structure and the like of the resin in the aspect of macroporous resin detection, the higher phenol adsorption capacity indicates that the performance of the resin is better, generally, the phenol adsorption capacity is better when the phenol adsorption capacity is more than 600mg/g, and the phenol adsorption capacity of the embodiment is 602.3 mg/g.
Table 1 shows VOC synthesized in example 1 of the present inventionSPhysical and chemical indexes of adsorbed macroporous resin
Figure BDA0003482501580000061
Example 2:
1. preparation of the resin
1) Preparing a water phase: in a 2000ml three-necked flask, 750ml of water was added, the temperature was raised to 55 ℃, 5g of PVA and 2g of gelatin were added, and stirring was carried out for 20min to completely dissolve them, and 15g of magnesium sulfate and 5g of sodium carbonate were added and stirred for 0.5h to obtain an aqueous phase.
2) Preparing an oil phase: 60g of divinylbenzene (80%), 9g of acrylonitrile, 9g of methyl acrylate, 24g of dichloroethane, 150g of cyclohexane and 0.3g of BPO are added into a beaker and mixed by ultrasound to obtain an oil phase.
3) Polymerization reaction: slowly adding the oil phase into the water phase, stirring at a controlled rotation speed of 120r/min until the mixture is stirred constantly, and stirring at a constant speed for 10 min. The temperature was raised from 55 ℃ to 75 ℃ at a rate of 5 ℃/10 min. After the resin is shaped for 2h, the temperature is continuously raised from 75 ℃ to 85 ℃ at the speed of 5 ℃/10min, the heat preservation is carried out for 4h, dichloroethane is condensed and refluxed in the process, the temperature is continuously raised from 85 ℃ to 95 ℃ at the speed of 5 ℃/10min, the heat preservation is carried out for 6h, and then the dichloroethane is taken out. Washing the surface of the resin with warm water to remove polyvinyl alcohol, putting the resin into a Soxhlet extractor, extracting the resin with acetone for 8 hours to extract a pore-forming agent, washing the resin with water and drying the resin.
4) Suspension double bond post-crosslinking: 600ml of dichloroethane and 200ml of methylcyclohexane are added into a three-mouth bottle, 60g of resin is taken and put into the three-mouth bottle to swell for 12 hours, and the temperature in the kettle is controlled not to exceed 25 ℃ in the swelling process. After swelling, adding 4.2g of anhydrous ferric trichloride, stirring uniformly, adding 4.2g of anhydrous ferric trichloride after 30min, stirring for 30min, slowly heating to 80 ℃ and reacting for 6 h. Adding 60ml of water, heating to 95 ℃, simultaneously condensing and recovering dichloroethane, adding 1% hydrochloric acid to wash off the catalyst after distillation is finished, putting the catalyst into a Soxhlet extractor to extract organic residues by using ethanol, taking out resin, purifying and washing the organic residues by using water to remove the ethanol.
2. And (3) determining the physical and chemical indexes of the resin: the procedure is as in example 1 (see Table 2)
Table 2 synthesized in example 2 of the present inventionFor VOCSPhysical and chemical indexes of adsorbed macroporous resin
Figure BDA0003482501580000071
Example 3:
1. preparation of the resin
1) Preparing a water phase: 1250ml of water is added into a 2000ml three-neck flask, the temperature is raised to 55 ℃, 5g of PVA and 4g of gelatin are added, stirring is carried out for 20min, complete dissolution is carried out, 30g of magnesium sulfate and 15g of sodium carbonate are added, and stirring is carried out for 0.5h, thus obtaining a water phase.
2) Preparing an oil phase: 90g of divinylbenzene (80%), 24g of acrylonitrile, 12g of methyl acrylate, 36g of dichloroethane, 180g of cyclohexane and 1.5g of BPO are added into a beaker and mixed by ultrasound to obtain an oil phase.
3) Slowly adding the oil phase into the water phase, stirring at a controlled rotation speed of 120r/min until the mixture is stirred constantly, and stirring at a constant speed for 10 min. The temperature was raised from 55 ℃ to 75 ℃ at a rate of 5 ℃/10 min. After the resin is shaped for 2h, the temperature is continuously raised from 75 ℃ to 85 ℃ at the speed of 5 ℃/10min, the heat preservation is carried out for 4h, dichloroethane is condensed and refluxed in the process, the temperature is continuously raised from 85 ℃ to 95 ℃ at the speed of 5 ℃/10min, the heat preservation is carried out for 6h, and then the dichloroethane is taken out. Washing the surface of the resin with warm water to remove polyvinyl alcohol, putting the resin into a Soxhlet extractor, extracting the resin with acetone for 8 hours to extract a pore-forming agent, washing the resin with water and drying the resin.
4) Suspension double bond post-crosslinking: 1000ml of dichloroethane and 200ml of methylcyclohexane are added into a three-necked flask, 140g of resin is taken out and put into the three-necked flask for swelling for 12 hours, and the temperature in the kettle is controlled not to exceed 25 ℃ in the swelling process. After swelling, 9.8g of anhydrous ferric trichloride is added and stirred uniformly, and after 30min, 9.8g of anhydrous ferric trichloride is added and stirred for 30min, and then the temperature is slowly raised to 80 ℃ for reaction for 6 h. Adding 140ml of water, heating to 95 ℃, simultaneously condensing and recovering dichloroethane, adding 1% hydrochloric acid to wash off the catalyst after distillation is finished, putting the catalyst into a Soxhlet extractor to extract organic residues by using ethanol, taking out resin, purifying and washing the organic residues by using water to remove the ethanol.
2. And (3) determining the physical and chemical indexes of the resin: same as example 1 (see Table 3)
Table 3 shows the VOC synthesized in example 3 of the present inventionSAdsorbed macroporous resin physicochemical meansSign board
Figure BDA0003482501580000081
Example 4:
1. treatment of CS-containing Using the resin of example 12Air: 100ml of resin is weighed and loaded into A, B, C, D four adsorption columns, 10mg/L of carbon disulfide gas circuit is respectively connected into the lower port of A, B adsorption column, and 15mg/L of carbon disulfide gas circuit is connected into the lower port of C, D adsorption column. Different volumes of column breakthrough adsorption were performed at the same gas flow rate. 300L of gas passes through A, C adsorption column and 500L of gas B, D adsorption column, and is collected by sealed plastic bags respectively. The carbon disulphide concentration is determined by gas chromatography. The resin adsorption efficiency was calculated by calculating the volume and concentration of gas in the plastic bag (see table 4).
Resin adsorption rate Cr ═ 1-V2C2/V1C1) X 100% where V1Is the intake volume (L), C1Is intake air concentration (mg/L), V2Gas volume (L), C after passing through adsorption column2Gas concentration (mg/L) after passing through the adsorption column.
2. Chloroprene-containing air was treated with the resin of example 1: the method also treats the C-containing gas2Air (see table 5).
Table 4 shows the adsorption treatment of the resin containing CS2Result of air
Figure BDA0003482501580000082
Figure BDA0003482501580000091
Table 5 shows the results of resin adsorption treatment of chloroprene-containing air
Numbering Number 1 Number 2 No. 3 Number 4
State of resin Drying Drying Wet state Wet state
Volume of intake air/L 300 500 300 500
Intake air concentration/(mg. L-1) 30 55 30 55
Gas volume/L after passing through adsorption column 297.72 493.21 297.78 482.23
Gas concentration/(mg. L-1) after passing through adsorption column 0.061 1.338 0.813 1.79
Total efficiency of resin adsorption% 99.8 97.6 97.31 96.86
As can be seen from tables 4 and 5, the dry resin has a good adsorption efficiency, and the adsorption efficiency of the resin, which is improved by a relatively low initial concentration, to CS2The adsorption of air can reach 98.9% at most, and the adsorption of air containing chlorobutadiene can reach 99.8% at most.

Claims (10)

1. For VOCSThe preparation method of the adsorbed macroporous resin is characterized by comprising the following steps:
1) preparing a water phase: adding water into a reaction vessel, heating to 50-60 ℃, adding polyvinyl alcohol and gelatin, stirring until the polyvinyl alcohol and the gelatin are completely dissolved, adding magnesium sulfate and sodium carbonate, stirring until the magnesium sulfate and the sodium carbonate are completely dissolved, and preparing a water phase for later use;
2) preparing an oil phase: adding divinylbenzene, acrylonitrile, methyl acrylate, dichloroethane and cyclohexane into a reaction vessel, uniformly mixing, adding an initiator benzoyl peroxide, and uniformly stirring to obtain an oil phase for later use;
3) polymerization reaction: slowly adding the prepared oil phase into the water phase, heating and stirring, preserving heat to form resin, extracting a pore-forming agent, and washing and drying the resin;
4) suspension double bond post-crosslinking: adding dichloroethane and methylcyclohexane into a reaction vessel, uniformly mixing to obtain a clear solution, putting the resin obtained in the step (3) into the clear solution for swelling and controlling the temperature, and adding anhydrous ferric trichloride serving as a catalyst after swelling is finished to carry out suspension double bond post-crosslinking reaction.
2. For VOC according to claim 1SThe preparation method of the adsorbed macroporous resin is characterized in that the weight part ratio of water to polyvinyl alcohol in the step (1) is 150-250: 1.
3. for VOC according to claim 1SThe preparation method of the adsorbed macroporous resin is characterized in that the gelatin in the step (1): magnesium sulfate: sodium carbonate: the mass ratio of the polyvinyl alcohol is 0.4-0.8: 3-6: 1-3: 1.
4. for VOC according to claim 1SThe preparation method of the adsorbed macroporous resin is characterized in that the oil phase in the step (2) consists of the following components in percentage by weight: 20-30% of divinylbenzene, 3-8% of acrylonitrile, 3-4% of methyl acrylate, 8-12% of dichloroethane and 50-60% of cyclohexane, wherein the benzoyl peroxide accounts for 0.1-0.5% of the mass of the oil phase.
5. For VOC according to claim 1SThe preparation method of the adsorbed macroporous resin is characterized in that the polymerization reaction in the step (3) comprises the steps of slowly adding an oil phase into a water phase, stirring at a rotating speed of 100r/min, stirring at a constant speed for 10min, heating to 75 ℃ at a speed of 5 ℃/10min, shaping the resin for 1-3 h, continuing heating to 85 ℃ at a speed of 5 ℃/10min, preserving heat for 3-6 h, condensing and refluxing dichloroethane in the process, continuing heating to 95 ℃ at a speed of 5 ℃/10min, preserving heat for 4-8 h, taking out, extracting a pore-forming agent with acetone in a Soxhlet extractor, extracting for 8h, washing with water and drying.
6. For VOC according to claim 1SThe preparation method of the adsorbed macroporous resin is characterized in that the step (4) comprises the steps of solution preparation, swelling and crosslinking after double bond suspension, wherein the solution preparation comprises the step of mixing dichloroethane and methylcyclohexane in a volume ratio of 3-5: 1 to obtain clarified solutionAnd (4) clearing the solution.
7. For VOC according to claim 6SThe preparation method of the adsorbed macroporous resin is characterized in that the swelling comprises the steps of adding the resin into a clear solution for 10-14 hours at the temperature of less than or equal to 25 ℃, wherein the volume ratio of the mass of the resin to the volume of methylcyclohexane in the clear solution is 0.3-0.7: 1.
8. for VOC according to claim 6SThe preparation method of the adsorbed macroporous resin is characterized in that suspension of double bonds and crosslinking comprise the steps of adding anhydrous ferric chloride catalyst for the first time after the resin is swelled, reacting for 30min, adding anhydrous ferric chloride catalyst for the second time, reacting for 30min, heating to 80 ℃, reacting for 6h, adding water, heating to 95 ℃, condensing and recycling dichloroethane, adding 1% hydrochloric acid to wash off the anhydrous ferric chloride catalyst after distillation is completed, extracting organic residues with ethanol in a Soxhlet extractor, and taking out the resin, purifying and washing off the ethanol with water.
9. The method of claim 8 for VOCSThe preparation method of the adsorbed macroporous resin is characterized in that the catalyst anhydrous ferric chloride with the same weight is added twice in the cross-linking process after the double bonds are suspended, the weight part ratio of the added anhydrous ferric chloride to the resin in the mixture is 7-8:100, and the weight part ratio of the water to the resin in the mixture is 1: 1.
10. the macroporous resin of claim 1 in VOCSApplication in adsorption.
CN202210072179.6A 2022-01-21 2022-01-21 Preparation method and application of macroporous resin for VOCS adsorption Active CN114405491B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210072179.6A CN114405491B (en) 2022-01-21 2022-01-21 Preparation method and application of macroporous resin for VOCS adsorption

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210072179.6A CN114405491B (en) 2022-01-21 2022-01-21 Preparation method and application of macroporous resin for VOCS adsorption

Publications (2)

Publication Number Publication Date
CN114405491A true CN114405491A (en) 2022-04-29
CN114405491B CN114405491B (en) 2023-07-04

Family

ID=81275634

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210072179.6A Active CN114405491B (en) 2022-01-21 2022-01-21 Preparation method and application of macroporous resin for VOCS adsorption

Country Status (1)

Country Link
CN (1) CN114405491B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001300307A (en) * 2000-02-16 2001-10-30 Sekisui Chem Co Ltd Volatile organic compound adsorbent
JP2003193410A (en) * 2001-12-27 2003-07-09 Sk Kaken Co Ltd Method for forming patterned paved surface
CN101088598A (en) * 2006-06-12 2007-12-19 天津协成昌国际贸易有限公司 Prepn and product of adsorbing material
CN106008790A (en) * 2016-06-20 2016-10-12 立邦涂料（中国）有限公司 Low-solvent hydroxyl-containing polyacrylate aqueous dispersion and preparation method thereof
CN112011000A (en) * 2020-09-03 2020-12-01 昌果生物医药科技河北有限公司 Method for performing secondary reinforcement on chloromethylated resin by using crosslinking reaction
CN112125992A (en) * 2020-09-11 2020-12-25 昌果生物医药科技河北有限公司 Synthetic method of acrylic resin

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001300307A (en) * 2000-02-16 2001-10-30 Sekisui Chem Co Ltd Volatile organic compound adsorbent
JP2003193410A (en) * 2001-12-27 2003-07-09 Sk Kaken Co Ltd Method for forming patterned paved surface
CN101088598A (en) * 2006-06-12 2007-12-19 天津协成昌国际贸易有限公司 Prepn and product of adsorbing material
CN106008790A (en) * 2016-06-20 2016-10-12 立邦涂料（中国）有限公司 Low-solvent hydroxyl-containing polyacrylate aqueous dispersion and preparation method thereof
CN112011000A (en) * 2020-09-03 2020-12-01 昌果生物医药科技河北有限公司 Method for performing secondary reinforcement on chloromethylated resin by using crosslinking reaction
CN112125992A (en) * 2020-09-11 2020-12-25 昌果生物医药科技河北有限公司 Synthetic method of acrylic resin

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JINGYU SUN: ""A theoretical study on gas-phase reactions of acrylic acid with chlorine atoms: mechanism, kinetics, and insights"", 《ENVIRONMENTAL SCIENECE AND POLLUTION RESEARCH》, vol. 27, pages 15772 - 15784, XP037108563, DOI: 10.1007/s11356-020-08100-z *
邵谦: ""无机纳米粒子改性复合乳液的制备及在水性涂料中的应用"", 《中国博士学位论文全文数据库工程科技Ⅰ辑》, no. 03 *

Also Published As

Publication number Publication date
CN114405491B (en) 2023-07-04

Similar Documents

Publication Publication Date Title
Cooney et al. Solvent regeneration of activated carbon
US4470829A (en) Solid adsorbent for carbon monoxide and process for separation from gas mixture
US4810266A (en) Carbon dioxide removal using aminated carbon molecular sieves
CN101314124B (en) Hydrophobic high-micropore polymeric adsorbent, preparation and uses thereof
Zeng et al. Enhanced adsorption of phenol from water by a novel polar post-crosslinked polymeric adsorbent
CN105504128B (en) A kind of absorption resin and its preparation method and application for Phenol-Containing Wastewater Treatment
CN102974322B (en) Hydrophobic silica gel composite resin-based VOC adsorbent
CN104226274B (en) Remove sorbent material and its preparation method of environmental water sample PetroChina Company Limited. pollutant
CN108273477B (en) Porous polyion liquid adsorbent and application thereof
JPH02274702A (en) Preparation of absorbent porous resin beads
CN111793176B (en) Lignin-based hypercrosslinked polymer with hierarchical pore structure and preparation method and adsorption application thereof
CN102942701B (en) Phenolic hydroxyl group containing ultra-high cross-linking adsorbent resin, preparation method and application thereof
CN113372524B (en) Non-reversible thiourea-linked covalent organic framework capable of rapidly removing mercury, and preparation method and application thereof
CN112076726A (en) Mesoporous molecular sieve loaded with ionic liquid and preparation method and application thereof
CN104927063A (en) Method for adsorbing and recycling phenolic compounds in industrial wastewater and method for manufacturing adsorption materials
CN102125823B (en) Adsorption resin with large specific surface area and large pore volume for removing volatile organic pollutants
US20170066987A1 (en) Improved adsorption process for recovering condensable components from a gas stream
CN114672036A (en) Metal organic framework material with basic functional group and preparation method thereof
CN114405491B (en) Preparation method and application of macroporous resin for VOCS adsorption
CN114870601A (en) Method for treating waste gas of extraction workshop to reach emission standard and recycling organic solvent
CN101496978A (en) Method for recycling halogenated hydrocarbon compound in gas using hydrophobic high-crosslinking adsorption resin
US4239508A (en) Cumene recovery
JPS6021128B2 (en) How to remove vinyl chloride from a gas stream
CN110755991B (en) Styrene waste gas treatment method
JPS60225641A (en) Regeneration of fibrous activated carbon

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant