CN111111792A - Strong acid cation exchange resin for adsorbing iron and preparation method and application thereof - Google Patents
Strong acid cation exchange resin for adsorbing iron and preparation method and application thereof Download PDFInfo
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- CN111111792A CN111111792A CN202010012283.7A CN202010012283A CN111111792A CN 111111792 A CN111111792 A CN 111111792A CN 202010012283 A CN202010012283 A CN 202010012283A CN 111111792 A CN111111792 A CN 111111792A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000002253 acid Substances 0.000 title claims abstract description 48
- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 40
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001179 sorption measurement Methods 0.000 claims abstract description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 12
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000004088 foaming agent Substances 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229910000831 Steel Inorganic materials 0.000 claims description 10
- 239000010959 steel Substances 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 7
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 5
- 239000001095 magnesium carbonate Substances 0.000 claims description 5
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 description 5
- 229940023913 cation exchange resins Drugs 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/05—Processes using organic exchangers in the strongly acidic form
-
- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
-
- 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
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a strong acid cation exchange resin for adsorbing iron and a preparation method and application thereof, wherein monomer styrene and cross-linking agent divinylbenzene are subjected to suspension polymerization reaction in the presence of a pore-foaming agent, a dispersing agent and an initiator to obtain macroporous copolymerized white spheres with high specific surface area; the macroporous copolymerization white balls with high specific surface area are subjected to sulfonation reaction to obtain the strong acid cation exchange resin for adsorbing iron. The strong acid cation exchange resin with high specific surface area for adsorbing iron prepared by the invention is a strong acid cation exchange resin with a macroporous adsorption function, and the saturated adsorption capacity of the strong acid cation exchange resin is improved by more than 1 time compared with that of the conventional adsorption resin.
Description
Technical Field
The invention relates to a resin, a preparation method and application thereof, in particular to a strong acid cation exchange resin with high specific surface area for adsorbing iron, and a preparation method and application thereof.
Background
During the production and use of steel, a layer of oxide scale is generated on the surface due to corrosion. In order to improve the quality of steel, maintain good appearance of steel and prolong the service life, the surface of steel needs to be treated to a certain extent. The acid washing method is usually adopted for removing the acid, but acid washing waste acid water is generated, and the acid washing waste acid water is directly discharged without relevant treatment, so that the acid washing waste acid water has considerable harm to the environment and causes the loss of metal and acid in the waste water. Therefore, the recovery of the pickling waste acid water can bring economic benefits to enterprises and protect the environment. The pickling waste acid water is acidic, contains more iron ions, and is a subject with high industrial application value if metal iron and acid can be separated to realize recycling of the metal ions and the acid.
Many of the known cation exchange resins can be used for removing iron in steel pickling wastewater, but all of the cation exchange resins have the disadvantages of iron blocking resin micropores and difficult regeneration of iron poisoning, so that the cation exchange resins cannot be generally used for adsorbing steel pickling wastewater.
Disclosure of Invention
The invention aims to solve the technical problem of providing a strong acid cation exchange resin for adsorbing iron and a preparation method and application thereof aiming at the defects in the prior art; the strong acid cation exchange resin has high specific surface area, is a strong acid cation exchange resin with macroporous adsorption function, and has the saturated adsorption capacity improved by more than 1 time compared with the conventional adsorption resin.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a strong acid cation exchange resin for adsorbing iron comprises the following steps: carrying out suspension polymerization reaction on monomer styrene and a cross-linking agent divinylbenzene in the presence of a pore-foaming agent, a dispersing agent and an initiator to obtain a macroporous copolymerized white ball with a high specific surface area; the macroporous copolymerization white balls with high specific surface area are subjected to sulfonation reaction to obtain the strong acid cation exchange resin for adsorbing iron.
In the above technical scheme, the preparation method specifically comprises the following steps:
(1) suspension polymerization: firstly, heating 800 and 1200 parts of pure water to 40-50 ℃, and then adding 48-130 parts of dispersing agent and uniformly stirring to obtain a water phase; then 80-140 parts of monomer styrene, 80-140 parts of cross-linking agent divinylbenzene, 150-350 parts of pore-foaming agent and 2-5 parts of initiator are mixed and stirred for 10-60min to obtain an organic phase; adding the organic phase into the water phase, stirring to obtain spheres, heating until the particle size of the spheres is 0.3-1.2mm, heating to 65-98 ℃, and keeping the temperature for 2-15 hours to perform suspension polymerization reaction; after the heat preservation is finished, the temperature is reduced to 40-50 ℃, and after the pore-forming agent is distilled out, the product is sequentially washed, discharged, dried and screened to obtain macroporous copolymerized white balls with the particle size of 0.4-0.71mm and high specific surface area;
(2) and (3) sulfonation reaction: and (2) carrying out sulfonation reaction on 80-120 parts of the macroporous copolymerization white balls with high specific surface area obtained in the step (1) and 400 parts of sulfonating agent at 30-120 ℃ for 10-20 hours, cooling the product to 35 ℃, gradually diluting the product by dilute sulfuric acid, washing the product to be neutral, and discharging the product to obtain the strong acid cation exchange resin for adsorbing iron.
In the above technical scheme, in the step (1), the dispersant is a mixture formed by mixing any one, two or more than two of polyvinyl alcohol, sodium chloride and basic magnesium carbonate in any proportion.
In the above technical scheme, in the step (1), when preparing the aqueous phase, preferably 800-1200 parts of pure water are heated to 40-50 ℃, then 3-10 parts of polyvinyl alcohol are added and stirred for 60-180min to be completely dissolved, then 40-100 parts of sodium chloride and 5-20 parts of basic magnesium carbonate are added and stirred uniformly to obtain the aqueous phase.
In the technical scheme, in the step (1), the mass fraction of solute in the cross-linking agent divinylbenzene is 80-98.5%, and the cross-linking degree of the cross-linking agent divinylbenzene is 30-74.5%.
In the above technical scheme, in the step (1), the pore-forming agent is a mixture of any one, two or more of toluene, ethylbenzene, propylbenzene, xylene and diethylbenzene mixed in any proportion.
In the above technical scheme, in the step (1), the initiator is a mixture of any one, two or more of benzoyl peroxide and azo in any proportion.
In the above technical solution, in the step (1), the suspension polymerization reaction preferably has the following reaction conditions: first heated to 80 ℃ and kept at that temperature for 2h, heated to 83 ℃ and kept at that temperature for 4 h, heated to 90 ℃ and kept at that temperature for 5 h, heated to 98 ℃ and kept at that temperature for 4 h.
In the technical scheme, in the step (1), after the suspension polymerization reaction is finished, the temperature is reduced to 80 ℃, and steam is introduced to distill the pore-forming agent; after distillation, washing the product for 3 times by using water at 80 ℃, washing the product for 3 times by using water at 60 ℃, washing the product by using normal temperature water until water is clear, and then discharging the material; the product is dried at 80-120 ℃ for 200-300min and then is sieved to obtain the macroporous copolymer white ball with the particle size of 0.4-0.71 mm.
In the above technical scheme, in the step (2), the sulfonating agent is a sulfuric acid solution of sulfur trioxide, and the mass fraction of solute in the sulfuric acid solution of sulfur trioxide is 20%, 40%, 60%, 80% or 100%.
In the above technical solution, in the step (2), the sulfonation reaction is preferably performed under the following reaction conditions: the macroporous copolymerized white balls with high specific surface area and the sulfonating agent are mixed for 2 hours at 30-40 ℃ (preferably 35 ℃), heated to 66 ℃ and kept at the temperature for 6 hours, heated to 83 ℃ and kept at the temperature for 2 hours, heated to 92 ℃ and kept at the temperature for 3 hours, heated to 116 ℃ and kept at the temperature for 3 hours.
In the above technical scheme, in the step (2), the dilute sulfuric acid is gradually diluted, and the specific operation steps are as follows: adding 500ml of dilute sulfuric acid with the specific gravity of 1.7, stirring for 1 hour, and sucking out the sulfuric acid; adding 500ml of dilute sulfuric acid with the specific gravity of 1.5, stirring for 1 hour, and sucking out the sulfuric acid; adding 500ml of dilute sulfuric acid with the mass fraction of 1.3, stirring for 1 hour, and sucking out the sulfuric acid; adding 400-500ml of dilute sulfuric acid with the mass fraction of 1.1, stirring for 1 hour, and sucking out the sulfuric acid.
The invention also provides a strong acid cation exchange resin for adsorbing iron, which is prepared by the preparation method, and the strong acid cation exchange resin for adsorbing iron has high specific surface area of 500m2More than one gram, and the exchange amount is more than 2.60 mmol/g.
The invention also provides application of the strong acid cation exchange resin for adsorbing iron in the adsorption of steel wastewater.
The technical scheme of the invention has the advantages that: the strong acid cation exchange resin with high specific surface area for adsorbing iron prepared by the invention is a strong acid cation exchange resin with a macroporous adsorption function, and the saturated adsorption capacity of the strong acid cation exchange resin is improved by more than 1 time compared with that of the conventional adsorption resin.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:
example 1:
a strong acid cation exchange resin for adsorbing iron is prepared by the following method:
(1) suspension polymerization:
adding 1000ml of pure water into a three-necked bottle, heating to 45 ℃, weighing 5g of polyvinyl alcohol, stirring for 120 minutes to completely dissolve the polyvinyl alcohol, adding 50g of sodium chloride and 6.5g of basic magnesium carbonate into the three-necked bottle, and uniformly stirring to obtain a water phase. The organic phase was prepared by mixing 100g of styrene, 100g of divinylbenzene (80% by mass), 200g of toluene, 25g of ethylbenzene and 3.6g of benzoyl peroxide and stirring for 15 minutes. Adding the uniformly stirred organic phase into a water phase, adjusting the granularity of the ball to 0.3-1.2mm, heating, keeping the temperature for 2 hours at 80 ℃ after shaping, heating to 83 ℃ and keeping the temperature for 4 hours, heating to 90 ℃ and keeping the temperature for 5 hours, and heating to 98 ℃ and keeping the temperature for 4 hours. Cooling to 80 deg.C, and introducing steam to distill the pore-forming agent. Washing with 80 deg.C water for 3 times, 60 deg.C water for 3 times, washing with normal temperature water until the water is clear, discharging, drying at 105 deg.C for 4 hr, sieving with 0.4-0.71mm sieve, and sieving to obtain 0.4-0.71mm macroporous copolymer white ball.
(2) And (3) sulfonation reaction:
adding 500g of sulfur trioxide with the concentration of 20% into a three-necked bottle at the temperature of 35 ℃, adding 95g of the macroporous copolymerized white ball obtained in the step (1), heating to 66 ℃ after 2 hours, preserving heat for 6 hours, heating to 83 ℃ and preserving heat for 2 hours, heating to 92 ℃ and preserving heat for 3 hours, and heating to 116 ℃ and preserving heat for 3 hours. Cooling to below 35 deg.C, gradually diluting with dilute sulfuric acid, washing with water to neutral, and discharging. Obtaining the strong acid cation exchange resin which adsorbs the iron and is marked as adsorption resin A.
Example 2:
a strong acid cation exchange resin for adsorbing iron was prepared in substantially the same manner as in example 1, except that in the step (1), there were 57.1g of styrene, 143.9g of 97g ethylbenzene in divinylbenzene (98% by mass), and 54g of xylene; the sulfur trioxide concentration in the step (2) is 60 percent; obtaining the strong acid cation exchange resin for adsorbing the iron, and marking as the adsorption resin B.
Example 3:
a strong acid cation exchange resin for adsorbing iron was prepared in substantially the same manner as in example 1, except that in the step (1), 59.3g of styrene, 140.7g of divinylbenzene (85.3% by mass), 89g of propylbenzene and 55g of diethylbenzene; the sulfur trioxide concentration in the step (2) is 80 percent; to obtain the strong acid cation exchange resin for adsorbing iron, which is marked as adsorption resin C.
The physical and chemical indexes of the adsorption resin obtained in the embodiments 1 to 3 of the invention are shown in Table 1:
TABLE 1 index for high specific surface area strongly acidic cation exchange resins
The application example is as follows: evaluation experiment for passing steel wastewater through column
50mL of the resin was measured and charged into an exchange column which was purged of air bubbles under the sand core with pure water, and the steel wastewater was added to the exchange column. The column passing space velocity is 150 mL/h. Effluent COD was measured 1 time every 8 hours. The results of the column chromatography are shown in Table 2.
TABLE 2 high specific surface area strong acid cation exchange resin column test results
As can be seen from the table, the high specific surface area strong acid cation exchange resin prepared by the method of the present invention has a lower exchange capacity but a larger specific surface area than the strong acid cation exchange resin prepared by the known method, but the method of the present invention increases the specific surface area of the resin, so that the strong acid cation exchange resin of the present invention has an enhanced adsorption effect, and the saturated adsorption capacity of iron is improved by more than 1 time compared with the conventional adsorption resin.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The preparation method of the strong acid cation exchange resin for adsorbing iron is characterized by comprising the following steps of: carrying out suspension polymerization reaction on monomer styrene and a cross-linking agent divinylbenzene in the presence of a pore-foaming agent, a dispersing agent and an initiator to obtain a macroporous copolymerized white ball with a high specific surface area; the macroporous copolymerization white balls with high specific surface area are subjected to sulfonation reaction to obtain the strong acid cation exchange resin for adsorbing iron.
2. The preparation method according to claim 1, comprising the following steps:
(1) suspension polymerization: firstly, heating 800 and 1200 parts of pure water to 40-50 ℃, and then adding 48-130 parts of dispersing agent and uniformly stirring to obtain a water phase; then 80-140 parts of monomer styrene, 80-140 parts of cross-linking agent divinylbenzene, 150-350 parts of pore-foaming agent and 2-5 parts of initiator are mixed and stirred for 10-60min to obtain an organic phase; adding the organic phase into the water phase, stirring to obtain spheres, heating until the particle size of the spheres is 0.3-1.2mm, heating to 65-98 ℃, and keeping the temperature for 2-15 hours to perform suspension polymerization reaction; after the heat preservation is finished, the temperature is reduced to 40-50 ℃, and after the pore-forming agent is distilled out, the product is sequentially washed, discharged, dried and screened to obtain macroporous copolymerized white balls with the particle size of 0.4-0.71mm and high specific surface area;
(2) and (3) sulfonation reaction: and (2) carrying out sulfonation reaction on 80-120 parts of the macroporous copolymerization white balls with high specific surface area obtained in the step (1) and 400 parts of sulfonating agent at 30-120 ℃ for 10-20 hours, cooling the product to 35 ℃, gradually diluting the product by dilute sulfuric acid, washing the product to be neutral, and discharging the product to obtain the strong acid cation exchange resin for adsorbing iron.
3. The preparation method according to claim 2, wherein in the step (1), the dispersant is a mixture of any one, two or more of polyvinyl alcohol, sodium chloride and basic magnesium carbonate mixed in any proportion; in the step (1), the mass fraction of solute in the cross-linking agent divinylbenzene is 80-98.5%, and the cross-linking degree of the cross-linking agent divinylbenzene is 30-74.5%; in the step (1), the pore-foaming agent is a mixture formed by mixing any one, two or more than two of toluene, ethylbenzene, propyl benzene, dimethylbenzene and diethylbenzene in any proportion; in the step (1), the initiator is a mixture formed by mixing any one, two or more than two of benzoyl peroxide and azo in any proportion; in the step (2), the sulfonating agent is sulfuric acid solution of sulfur trioxide, and the mass fraction of solute in the sulfuric acid solution of sulfur trioxide is 20%, 40%, 60%, 80% or 100%.
4. The preparation method as claimed in claim 2, wherein in the step (1), when preparing the aqueous phase, firstly, 800-1200 parts of pure water are heated to 40-50 ℃, then 3-10 parts of polyvinyl alcohol are added and stirred for 60-180min to be completely dissolved, then 40-100 parts of sodium chloride and 5-20 parts of basic magnesium carbonate are added and stirred uniformly to obtain the aqueous phase.
5. The process according to claim 2, wherein in the step (1), the suspension polymerization is carried out under the following reaction conditions: first heated to 80 ℃ and kept at that temperature for 2h, heated to 83 ℃ and kept at that temperature for 4 h, heated to 90 ℃ and kept at that temperature for 5 h, heated to 98 ℃ and kept at that temperature for 4 h.
6. The preparation method according to claim 2, wherein in the step (1), after the suspension polymerization reaction is finished, the temperature is reduced to 80 ℃, and steam is introduced to distill the pore-forming agent; after distillation, washing the product for 3 times by using water at 80 ℃, washing the product for 3 times by using water at 60 ℃, washing the product by using normal temperature water until water is clear, and then discharging the material; the product is dried at 80-120 ℃ for 200-300min and then is sieved to obtain the macroporous copolymer white ball with the particle size of 0.4-0.71 mm.
7. The method according to claim 2, wherein in the step (2), the sulfonation is carried out under the following reaction conditions: mixing the macroporous copolymer white balls with high specific surface area and a sulfonating agent at 30-40 ℃ for 2 hours, heating to 66 ℃ and preserving heat at the temperature for 6 hours, heating to 83 ℃ and preserving heat at the temperature for 2 hours, heating to 92 ℃ and preserving heat at the temperature for 3 hours, heating to 116 ℃ and preserving heat at the temperature for 3 hours.
8. The preparation method according to claim 2, wherein in the step (2), the dilute sulfuric acid is gradually diluted, and the specific operation steps are as follows: adding 500ml of dilute sulfuric acid with the specific gravity of 1.7, stirring for 1 hour, and sucking out the sulfuric acid; adding 500ml of dilute sulfuric acid with the specific gravity of 1.5, stirring for 1 hour, and sucking out the sulfuric acid; adding 500ml of dilute sulfuric acid with the mass fraction of 1.3, stirring for 1 hour, and sucking out the sulfuric acid; adding 400-500ml of dilute sulfuric acid with the mass fraction of 1.1, stirring for 1 hour, and sucking out the sulfuric acid.
9. A strong acid cation exchange resin for adsorbing iron, characterized by passing through the following claims1-9, said strong acid cation exchange resin adsorbing iron having a high specific surface area of 500m2More than one gram, and the exchange amount is more than 2.60 mmol/g.
10. Use of the strong acid cation exchange resin for the adsorption of iron according to claim 9 for the adsorption of steel wastewater.
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