CN111420642B - PT acid adsorption resin and preparation method thereof - Google Patents
PT acid adsorption resin and preparation method thereof Download PDFInfo
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- CN111420642B CN111420642B CN202010215600.5A CN202010215600A CN111420642B CN 111420642 B CN111420642 B CN 111420642B CN 202010215600 A CN202010215600 A CN 202010215600A CN 111420642 B CN111420642 B CN 111420642B
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- drying
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- 239000011347 resin Substances 0.000 title claims abstract description 32
- 229920005989 resin Polymers 0.000 title claims abstract description 32
- 239000002253 acid Substances 0.000 title claims abstract description 25
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 34
- 239000003463 adsorbent Substances 0.000 claims abstract description 29
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000460 chlorine Substances 0.000 claims abstract description 23
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 23
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 22
- 238000007265 chloromethylation reaction Methods 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004793 Polystyrene Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 229920002223 polystyrene Polymers 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 10
- 230000029936 alkylation Effects 0.000 claims abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims description 50
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 239000012442 inert solvent Substances 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 13
- 238000007670 refining Methods 0.000 abstract description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 29
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 23
- 238000003756 stirring Methods 0.000 description 18
- 238000001514 detection method Methods 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000012452 mother liquor Substances 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 238000012216 screening Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000002306 biochemical method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- -1 organic acid small molecules Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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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
- B01J20/22—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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/02—Alkylation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Polymers & Plastics (AREA)
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a PT acid adsorption resin, which is characterized in that: is a crosslinked polystyrene polymer, insoluble in water and organic solvents; brown to black particles in appearance; the density is 1.0-1.1 g/ml; the water content is 50-60%; specific surface area 900-2(ii)/g; the organic residue was less than 1500 ppm. The production method comprises the following steps of (1) polymerization: divinylbenzene and styrene are mixed according to a molar ratio of 1: (1-8) carrying out emulsion polymerization, and drying the polymer to obtain a white ball intermediate; (2) chloromethylation: carrying out chloromethylation reaction on the white ball intermediate by using a chloromethylation reagent, and drying to obtain an intermediate chlorine resin; (3) alkylation: and (3) carrying out alkylation reaction on the chlorine resin by using dichloroethane or nitrobenzene, and drying to obtain the PT acid adsorbent. The PT acid adsorption resin is used for recovering PT acid in PTA refining wastewater, and can reduce the PT acid in the wastewater to 1 ppm.
Description
Technical Field
The invention relates to a PT acid adsorption resin for recovering organic matters in refined wastewater in PTA industry.
Background
At present, most of PTA (purified terephthalic acid) production processes comprise the following stages: in the oxidation reaction stage, p-xylene is oxidized in an acetic acid solution to form terephthalic acid (hereinafter referred to as TA); obtaining a Crude Terephthalic Acid (CTA) crystal stage, and crystallizing, washing and drying to obtain a CTA crystal; a hydrorefining stage in which CTA is dissolved in hot water and subjected to hydrotreating for purification; a PTA crystallization stage, after the hydrogenation purification stage, crystallizing PTA in an aqueous solution; obtaining PTA crystal, and recovering PTA crystal; and a water washing and drying stage, wherein the obtained PTA particles are washed by water and then dried to obtain the product.
In the refining stage of PTA production, a large amount of waste water is produced, which contains PT acid (p-methyl benzoic acid), benzoic acid, acetic acid and other organic matters. If discharged directly into the environment, this waste water causes environmental pollution and must be treated to reduce the organic content thereof before discharge.
At present, the refined wastewater is mainly treated by a biochemical method, and organic matters in the wastewater are decomposed into carbon dioxide and water in a reaction tank, so that a water body is purified, but the organic matters are wasted. Therefore, the recovery of PT acid in the process of wastewater in the PTA refining stage becomes an important factor influencing the advancement and the economical efficiency of the PTA production process.
In "a method for treating wastewater from a refining process of a purified terephthalic acid production apparatus" disclosed in CN103241857A, PT acid is adsorbed by KX-I type adsorbent and then desorbed and recovered. However, this adsorbent relies on importation and is relatively costly.
The invention is provided in view of the above.
Disclosure of Invention
The invention aims to provide PT acid adsorption resin and a preparation method thereof, which are used for adsorbing and recovering PT acid in waste water in a PTA refining stage.
The PT acid adsorption resin is a crosslinked polystyrene polymer, and is insoluble in water and organic solvents; brown to black particles in appearance; the density is 1.0-1.1 g/ml; the water content is 50-60%; specific surface area 900-2(ii)/g; the organic residue was less than 1500 ppm.
The crosslinked polystyrene polymer is preferably a crosslinked polystyrene polymer obtained by copolymerizing and crosslinking divinylbenzene and styrene, and the crosslinking degree of the crosslinked polystyrene is adjusted by embedding styrene, and the size of micropores of a net structure is adjusted. Preferred mole ratios of divinylbenzene to styrene are 1: (1-8).
The invention also provides a production method of the PT acid adsorbent, which comprises the following steps:
(1) polymerization: using divinylbenzene or divinylbenzene and styrene, and mixing the divinylbenzene and the styrene according to a mol ratio of 1: (1-8) carrying out emulsion polymerization, and drying the polymer to obtain a white ball intermediate serving as a porous microspherical adsorbent framework;
(2) chloromethylation: chloromethylating the white ball intermediate with a chloromethylation reagent to replace the benzene ring with chloromethyl, and drying to obtain an intermediate chlorine resin;
(3) alkylation: and (3) performing alkylation reaction on the chlorine resin to change the molecular structure, further crosslinking the high molecular chains to realize tight connection, simultaneously reducing the surface polarity of the adsorbent, improving the adsorption capacity, and drying to obtain the PTA adsorbent.
Further, the emulsion polymerization in the step (1) may be carried out by first mixing the polymer monomer and the initiator benzoyl oxide in an inert solvent, adding into an aqueous solution containing a dispersant, reacting at 40-90 ℃ for 12-24 hours, and washing. The polymerization temperature is a key process condition, the microstructure of the adsorbent can be influenced by poor temperature control, and the polymerization temperature is preferably 60-90 ℃. Most preferably, the polymerization is carried out at 65 ℃ for about 1 hour and then at 85 ℃ for 16 hours.
The inert solvent can be one or more of toluene, xylene, liquid wax, octanol and mixed alcohol. The ratio of inert solvent to polymerized monomer has a large influence on the adsorption capacity of the adsorbent, and is generally calculated in a weight ratio of 1: preferably 1.
The dispersing agent can be one of carboxymethyl cellulose, polyvinyl alcohol and gelatin or a mixture of two of the carboxymethyl cellulose, the polyvinyl alcohol and the gelatin.
Further, the chloromethylation of the step (2) can be carried out by reacting chloromethyl ether with polymeric white spheres in the presence of a promoter at 35-55 ℃ for 10-40 hours, and then washing with methanol or ethanol. Preferably, the polymerized white spheres are counted by benzene rings, and the mole number of the chloromethyl ether is larger than that of the benzene rings, so that the reaction is favorably carried out in the forward direction.
During chloromethylation, dichloroethane can be added into the reaction system.
Further, the alkylation reaction in the step (3) is to react dichloroethane or nitrobenzene with chlorine resin in the presence of a promoter at the temperature of 80-150 ℃ for 10-40 hours, and then wash with methanol or ethanol.
The accelerant in the steps (2) and (3) is ferric chloride, zinc chloride, stannic chloride or aluminum chloride.
Furthermore, phenol or benzenediol is also added into the alkylation reaction system in the step (3).
The adsorbent is prepared by polymerizing monomers (styrene and divinylbenzene) with small dipole moment, is further crosslinked after chloromethylation and alkylation, adjusts the molecular structure of the polymer, reduces the polarity of the surface of a white ball to form nonpolar adsorption resin without any functional group and has stronger surface hydrophobicity, when PTA refined wastewater solution flows through the surface of the adsorbent, polar molecules such as water are far away from the surface of the adsorbent, and nonpolar organic acid small molecules are closer to the surface and then more easily enter pores on the surface, thereby realizing the purposes of adsorption and separation. The adsorbent provided by the invention is applied to recovery of PT acid in wastewater in a PTA refining stage, the recovery rate can reach 99%, and the PT acid content in the treated wastewater can reach 1 ppm.
Drawings
FIG. 1 is a flow diagram of the production of PTA adsorbent.
Detailed Description
The invention is further described below in conjunction with the drawings and the detailed description of the invention to assist in understanding the content of the invention.
As shown in fig. 1, the whole production process comprises:
raw material detection: various raw materials used for production are detected, qualified raw materials are used for adsorbent production, and unqualified raw materials are returned or replaced.
Polymerization reaction: and (3) carrying out emulsion polymerization reaction on the polymerized monomers by using the qualified raw materials to obtain the polymer white balls.
White ball washing: the polymer white balls are washed to remove unreacted monomers.
Drying: and drying the polymer white balls.
Chloromethylation reaction: the polymer white ball and chloromethylation reagent are subjected to chloromethylation reaction.
And (3) performing alkylation reaction, namely performing alkylation reaction after the chloromethylation intermediate control detection is qualified, and removing chlorine.
And (3) finished product detection: and detecting the water content, the specific surface area, the appearance and the like of the finished product.
Packaging: and packaging qualified products, marking the qualified products to be qualified, and warehousing the qualified products.
The following description will be given with reference to specific examples.
Example 1
First, polymerization reaction
1. Oil phase
100 kg of styrene, 100 kg of divinylbenzene (namely the molar ratio of the divinylbenzene to the styrene is 1: 1.62), 5kg of benzoyl peroxide, 80 kg of liquid wax and 120 kg of toluene are weighed in a batching tank, and are stirred and mixed fully and uniformly.
2. Aqueous phase
500 kg of water is added into a 1000L reaction kettle, and 50 kg of dissolved 10% (wt%) carboxymethyl cellulose solution is added.
3. Reaction of
Adding oil phase at 30-45 deg.C, stirring, adjusting oil droplet size to 0.5-1.0mm, heating to 65 deg.C, reacting for 1 hr, and heating to 85 deg.C for 16 hr.
4. Washing machine
Cooling to room temperature, washing with water for 3 times, washing with methanol or ethanol for 8 times, and washing with water for 3 times.
5. Drying
And (4) putting the white balls into a boiling dryer, drying for 4 hours by hot air, and discharging.
6. Sieving
Screening the dried white balls by a screening machine to obtain intermediate white balls with the particle size of 0.5-1.0 mm.
Chlorination reaction
1. Adding 1500 kg of chloromethyl ether and 500 kg of dichloroethane into a 3000L reaction kettle, adding 500 kg of white balls and 600 kg of ferric chloride, controlling the temperature to be 35 ℃, reacting for 2 hours, adjusting the kettle temperature to be 50 ℃ to enable reaction liquid to flow back, reacting for 20 hours, draining mother liquor, stirring and washing for four times by using methanol at normal temperature, and drying to obtain an intermediate chlorine resin.
Three, alkylation reaction
2000 kg of dichloroethane is added into a 3000L reaction kettle, stirring is started, 500 kg of chlorine resin and 80 kg of zinc chloride are added, the temperature is heated to 83 ℃, and the dichloroethane is refluxed and reacted for 20 hours. Cooling, extracting mother liquor, and draining as much as possible; washing the solid with ethanol for 6 times, washing with water for 4 times, draining free water, and packaging to obtain the final adsorbent.
And (3) detection: the detection by an infrared spectrometer is that the crosslinked polystyrene spectrum is met, and the density is 1.0 g/ml; the water content is 53 percent; specific surface area 981m2(ii)/g; the organic residue was less than 1500 ppm.
Example 2:
first, polymerization reaction
1. Oil phase
164 kg of styrene, 36 kg of divinylbenzene (namely the molar ratio of the divinylbenzene to the styrene is 1: 7.4), 5kg of benzoyl peroxide, 100 kg of mixed alcohol and 100 kg of toluene are weighed in a batching tank, and are stirred fully and uniformly mixed.
2. Aqueous phase
500 kg of water is added into a 1000L reaction kettle, and 25 kg of dissolved 10% (wt%) polyvinyl alcohol solution is added.
3. Reaction of
Adding oil phase at 30-45 deg.C, stirring, adjusting oil droplet size to 0.5-1.0mm, heating to 65 deg.C, reacting for 1 hr, and heating to 85 deg.C for 16 hr.
4. Washing machine
Cooling to room temperature, washing with water for 3 times, washing with methanol or ethanol for 8 times, and washing with water for 3 times.
5. Drying
And (4) putting the white balls into a boiling dryer, drying for 4 hours by hot air, and discharging.
6. Sieving
Screening the dried white balls by a screening machine to obtain intermediate white balls with the particle size of 0.5-1.0 mm.
Chlorination reaction
1. 1000 kg of chloromethyl ether and 1000 kg of dichloroethane are added into a 3000L reaction kettle, 500 kg of white balls and 500 kg of zinc chloride are added, the temperature is controlled at 35 ℃, the reaction is carried out for 2 hours, the kettle temperature is adjusted to 55 ℃, reaction liquid is refluxed and reacted for 20 hours, mother liquor is drained, methanol is used for stirring and washing for four times at normal temperature, and the intermediate chlorine resin is obtained after drying.
Three, alkylation reaction
2000 kg of nitrobenzene is added into a 3000L reaction kettle, stirring is started, 500 kg of chlorine resin, 50 kg of stannic chloride and 100 kg of phenol are added, the temperature is heated to 150 ℃, and dichloroethane is refluxed and reacted for 12 hours. Cooling, extracting mother liquor, and draining as much as possible; washing the solid with ethanol for 4-6 times, washing with water for 4 times, draining free water, and packaging to obtain the final adsorbent.
And (3) detection: the detection by an infrared spectrometer shows that the crosslinked polystyrene spectrum is satisfied, and the density is 1.1 g/ml; the water content is 56 percent; specific surface area 1037m2(ii)/g; the organic residue was less than 1500 ppm.
Example 3
First, polymerization reaction
1. Oil phase
160 kg of styrene, 50 kg of divinylbenzene (namely the molar ratio of the divinylbenzene to the styrene is 1: 5.2), 5kg of benzoyl peroxide, 50 kg of liquid wax and 100 kg of toluene are weighed in a batching tank, and are stirred and mixed fully and uniformly.
2. Aqueous phase
500 kg of water is added into a 1000L reaction kettle, and 50 kg of dissolved 10% (wt%) carboxymethyl cellulose solution is added.
3. Reaction of
Adding oil phase at 30-45 deg.C, stirring, adjusting oil droplet size to 0.5-1.0mm, heating to 65 deg.C, reacting for 1 hr, and heating to 85 deg.C for 16 hr.
4. Washing machine
Cooling to room temperature, washing with water for 3 times, washing with methanol or ethanol for 8 times, and washing with water for 3 times.
5. Drying
And (4) putting the white balls into a boiling dryer, drying for 4 hours by hot air, and discharging.
6. Sieving
Screening the dried white balls by a screening machine to obtain intermediate white balls with the particle size of 0.5-1.0 mm.
Chlorination reaction
1. Adding 1500 kg of chloromethyl ether and 500 kg of dichloroethane into a 3000L reaction kettle, adding 500 kg of white balls and 600 kg of ferric chloride, controlling the temperature to be 35 ℃, reacting for 2 hours, adjusting the kettle temperature to be 55 ℃, refluxing the reaction liquid, reacting for 20 hours, draining the mother liquor, stirring and washing for four times by using methanol at normal temperature, and drying to obtain the intermediate chlorine resin.
Three, alkylation reaction
2000 kg of dichloroethane is added into a 3000L reaction kettle, stirring is started, 500 kg of chlorine resin and 80 kg of zinc chloride are added, the temperature is heated to 100 ℃, and the dichloroethane is refluxed and reacted for 20 hours. Cooling, extracting mother liquor, and draining as much as possible; washing the solid with ethanol for 6 times, washing with water for 4 times, draining free water, and packaging to obtain the final adsorbent.
And (3) detection: the detection by an infrared spectrometer shows that the crosslinked polystyrene spectrum is satisfied, and the density is 1.1 g/ml; the water content is 58%; specific surface area 1175m2(ii)/g; the organic residue was less than 1500 ppm.
Example 4
First, polymerization reaction
1. Oil phase
In a batching tank, 20 kg of styrene, 80 kg of divinylbenzene (namely the molar ratio of the divinylbenzene to the styrene is 1: 0.41), 5kg of benzoyl peroxide, 50 kg of octanol and 50 kg of toluene are weighed and stirred to be mixed fully and uniformly.
2. Aqueous phase
500 kg of water is added into a 1000L reaction kettle, and 50 kg of dissolved 10% (wt%) carboxymethyl cellulose solution is added.
3. Reaction of
Adding oil phase at 30-45 deg.C, stirring, adjusting oil droplet size to 0.5-1.0mm, heating to 65 deg.C, reacting for 1 hr, and heating to 85 deg.C for 16 hr.
4. Washing machine
Cooling to room temperature, washing with water for 3 times, washing with methanol or ethanol for 8 times, and washing with water for 3 times.
5. Drying
And (4) putting the white balls into a boiling dryer, drying for 4 hours by hot air, and discharging.
6. Sieving
Screening the dried white balls by a screening machine to obtain intermediate white balls with the particle size of 0.5-1.0 mm.
Chlorination reaction
1. Adding 1500 kg of chloromethyl ether into a 3000L reaction kettle, adding 500 kg of white balls and 600 kg of ferric chloride, controlling the temperature to be 35 ℃, reacting for 2 hours, adjusting the temperature of the reaction kettle to be 55 ℃, refluxing reaction liquid, reacting for 20 hours, pumping out mother liquor, stirring and washing for four times by using methanol at normal temperature, and drying to obtain an intermediate chlorine resin.
Three, alkylation reaction
2000 kg of dichloroethane is added into a 3000L reaction kettle, stirring is started, 500 kg of chlorine resin and 80 kg of zinc chloride are added, the temperature is heated to 83 ℃, and the dichloroethane is refluxed and reacted for 20 hours. Cooling, extracting mother liquor, and draining as much as possible; washing the solid with ethanol for 6 times, washing with water for 4 times, draining free water, and packaging to obtain the final adsorbent. And (3) detection: the detection by an infrared spectrometer is that the crosslinked polystyrene spectrum is met, and the density is 1.0 g/ml; the water content is 55 percent; specific surface area 950m2(ii)/g; the organic residue was less than 1500 ppm.
Example 5
First, polymerization reaction
1. Oil phase
In a batching tank, 110 kg of styrene, 10 kg of divinylbenzene (namely the molar ratio of the divinylbenzene to the styrene is 1: 18.1), 5kg of benzoyl peroxide, 60 kg of liquid wax and 60 kg of toluene are weighed and stirred to be mixed fully and uniformly.
2. Aqueous phase
500 kg of water is added into a 1000L reaction kettle, and 50 kg of dissolved 10% (wt%) carboxymethyl cellulose solution is added.
3. Reaction of
Adding oil phase at 30-45 deg.C, stirring, adjusting oil droplet size to 0.5-1.0mm, heating to 65 deg.C, reacting for 1 hr, and heating to 85 deg.C for 16 hr.
4. Washing machine
Cooling to room temperature, washing with water for 3 times, washing with methanol or ethanol for 8 times, and washing with water for 3 times.
5. Drying
And (4) putting the white balls into a boiling dryer, drying for 4 hours by hot air, and discharging.
6. Sieving
Screening the dried white balls by a screening machine to obtain intermediate white balls with the particle size of 0.5-1.0 mm.
Chlorination reaction
1. Adding 1500 kg of chloromethyl ether and 500 kg of dichloroethane into a 3000L reaction kettle, adding 500 kg of white balls and 600 kg of ferric chloride, controlling the temperature to be 35 ℃, reacting for 2 hours, adjusting the kettle temperature to be 55 ℃, refluxing the reaction liquid, reacting for 20 hours, draining the mother liquor, stirring and washing for four times by using methanol at normal temperature, and drying to obtain the intermediate chlorine resin.
Three, alkylation reaction
2000 kg of dichloroethane is added into a 3000L reaction kettle, stirring is started, 500 kg of chlorine resin and 80 kg of zinc chloride are added, the temperature is heated to 83 ℃, and the dichloroethane is refluxed and reacted for 20 hours. Cooling, extracting mother liquor, and draining as much as possible; washing the solid with ethanol for 6 times, washing with water for 4 times, draining free water, and packaging to obtain the final adsorbent. And (3) detection: the detection by an infrared spectrometer is that the crosslinked polystyrene spectrum is met, and the density is 1.0 g/ml; the water content is 59 percent; specific surface area 1005m2(ii)/g; the organic residue was less than 1500 ppm.
Comparative example 1
First, polymerization reaction
1. Oil phase:
310 kg of divinylbenzene (which is equivalent to the total benzene mole number of 2.38 in example 3), 5kg of benzoyl peroxide, 80 kg of liquid wax and 120 kg of toluene are weighed in a batching tank and stirred and mixed evenly.
2. Aqueous phase
500 kg of water is added into a 1000L reaction kettle, and 50 kg of dissolved 10% (wt%) carboxymethyl cellulose solution is added.
3. Reaction of
Adding oil phase at 30-45 deg.C, stirring, adjusting oil droplet size to 0.5-1.0mm, heating to 65 deg.C, reacting for 1 hr, and heating to 85 deg.C for 16 hr.
4. Washing machine
Cooling to room temperature, washing with water for 3 times, washing with methanol or ethanol for 8 times, and washing with water for 3 times.
5. Drying
And (4) putting the white balls into a boiling dryer, drying for 4 hours by hot air, and discharging.
6. Sieving
Screening the dried white balls by a screening machine to obtain intermediate white balls with the particle size of 0.5-1.0 mm.
Chlorination reaction
1. Adding 1500 kg of chloromethyl ether (benzene: chloromethyl ether molar ratio is 1: 7.8) and 500 kg of dichloroethane into a 3000L reaction kettle, adding 500 kg of white balls and 600 kg of ferric chloride, controlling the temperature to be 35 ℃, reacting for 2 hours, adjusting the kettle temperature to 55 ℃, refluxing reaction liquid, reacting for 20 hours, pumping out mother liquor, stirring and washing for four times by using methanol at normal temperature, and drying to obtain an intermediate chlorine resin.
Three, alkylation reaction
2000 kg of dichloroethane is added into a 3000L reaction kettle, stirring is started, 500 kg of chlorine resin and 80 kg of zinc chloride are added, the temperature is heated to 83 ℃, and the dichloroethane is refluxed and reacted for 20 hours. Cooling, extracting mother liquor, and draining as much as possible; washing the solid with ethanol for 6 times, washing with water for 4 times, draining free water, and packaging to obtain the final adsorbent. And (3) detection: the density is 1.0 g/ml; the water content is 50 percent; specific surface area 761m2(ii)/g; the organic residue was less than 1500 ppm.
Comparative example 2
The polymeric white spheres of example 1 were used directly as adsorbents.
Test examples
The adsorbents 075kg of examples 1 to 5 and comparative examples 1 and 2 were charged in adsorption tanks having a diameter of 60mm, respectively. The feed water containing 464ppm PT acid enters an adsorption tank from an inlet, flows through an adsorbent bed at the flow rate of 15m/h, flows out from an outlet of the adsorption tank, and detects the PT acid content in the effluent, so that the PT acid content in the solution after adsorption treatment by the adsorbents of examples 1-4 can be reduced to 1ppm, and the PT acid content in example 5 and comparative examples 1 and 2 is more than 1 ppm. After the accumulated flow reaches a set value, desorbing with 90 wt% acetic acid, washing residual acetic acid with desalted water, and detecting and calculating the adsorption amount. The adsorption capacities of the adsorbents of examples 1 to 6 were calculated and the results are shown in Table 1.
TABLE 1 adsorption Effect of the different examples
As can be seen from the above examples, the adsorption amounts of examples 1 to 4 are significantly better than those of example 5 and comparative examples 1 and 2, and are more advantageous than those of examples 1 to 3. Therefore, the adsorbent obtained by copolymerizing styrene and divinylbenzene has more outstanding adsorption capacity than divinylbenzene polymerization. And when the molar ratio of divinylbenzene to styrene is 1: (1-8), that is, the adsorption amounts in examples 1-3 are superior to those in examples 4 and 5 in which the styrene content is too high or too low. After chloromethylation and alkylation treatment, the adsorption capacity is multiplied compared with that of the white spherogen.
Claims (8)
1. A PT acid adsorption resin is characterized in that: is a crosslinked polystyrene polymer, insoluble in water and organic solvents; brown to black particles in appearance; the density is 1.0-1.1 g/ml; the water content is 50-60%; specific surface area 900-2(ii)/g; the organic residue is less than 1500 ppm; is prepared by the following steps:
(1) polymerization: using divinylbenzene and styrene, and mixing the raw materials according to a mol ratio of 1: (1-8) mixing the mixture and an initiator benzoyl oxide in an inert solvent uniformly, adding the mixture into an aqueous solution containing a dispersing agent, polymerizing for about 1 hour at 65 ℃, heating to 85 ℃ for polymerizing for 16 hours, and drying the polymer to obtain a white ball intermediate; the inert solvent is one or a mixture of more of toluene, xylene, liquid wax, octanol and mixed alcohol;
(2) chloromethylation: carrying out chloromethylation reaction on the white ball intermediate by using a chloromethylation reagent, and drying to obtain an intermediate chlorine resin;
(3) alkylation: and (3) carrying out alkylation reaction on the chlorine resin by using dichloroethane or nitrobenzene, and drying to obtain the PT acid adsorbent.
2. A method for producing the PT acid adsorption resin of claim 1, comprising the steps of:
(1) polymerization: mixing divinylbenzene and styrene according to a molar ratio of 1: (1-8) mixing the mixture and an initiator benzoyl oxide in an inert solvent uniformly, adding the mixture into an aqueous solution containing a dispersing agent, polymerizing for about 1 hour at 65 ℃, heating to 85 ℃ for polymerizing for 16 hours, washing, and finally drying to obtain a white ball intermediate; the inert solvent is one or a mixture of more of toluene, xylene, liquid wax, octanol and mixed alcohol;
(2) chloromethylation: carrying out chloromethylation reaction on the white ball intermediate by using a chloromethylation reagent, and drying to obtain an intermediate chlorine resin;
(3) alkylation: and (3) carrying out alkylation reaction on the chlorine resin by using dichloroethane or nitrobenzene, and drying to obtain the PT acid adsorbent.
3. The method of claim 2, wherein: the dispersing agent is one or two of carboxymethyl cellulose, polyvinyl alcohol and gelatin.
4. The method of claim 2, wherein: chloromethylating in the step (2), reacting chloromethyl ether with the polymerized white ball in the presence of an accelerator at 35-55 ℃ for 10-40 hours, and then washing with methanol or ethanol.
5. The method of claim 4, wherein: in the chloromethylation reaction system, dichloroethane is also added.
6. The method of claim 2, wherein: the alkylation reaction in the step (3) is to react dichloroethane or nitrobenzene with chlorine resin at the temperature of 80-150 ℃ for 10-40 hours in the presence of an accelerant, and then wash with methanol or ethanol.
7. The method of claim 4, wherein: the accelerant is ferric chloride, zinc chloride, stannic chloride or aluminum chloride.
8. The method of claim 6, wherein: phenol or benzenediol is also added into the alkylation reaction system.
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