CN103073688A - Method for preparing redoxite for removing sulfur from waste water - Google Patents
Method for preparing redoxite for removing sulfur from waste water Download PDFInfo
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- CN103073688A CN103073688A CN2012105789931A CN201210578993A CN103073688A CN 103073688 A CN103073688 A CN 103073688A CN 2012105789931 A CN2012105789931 A CN 2012105789931A CN 201210578993 A CN201210578993 A CN 201210578993A CN 103073688 A CN103073688 A CN 103073688A
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- polyoxymethylene
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Abstract
The invention discloses a method for preparing redoxite for removing sulfur from waste water. The method comprises the following steps: preparing polyformaldehyde into a solution, adding paradioxybenzene and sodium hydroxide and performing heating reaction to prepare a linear prepolymer A, wherein the polyformaldehyde and the paradioxybenzene serve as raw materials; preparing polyformaldehyde into a solution, adding phenol and sodium hydroxide and performing heating reaction to prepare a linear prepolymer B, wherein the polyformaldehyde and the phenol serve as raw materials; mixing the linear prepolymer A and the linear prepolymer B, heating and performing crosslinking reaction to obtain a water-containing resin product; and drying and crushing the water-containing resin product to obtain the product redoxite for removing sulfur from waste water. The paradioxybenzene has an excellent quinone type and phenol type transformation function, and resin groups are connected by a covalent bond, so that the service life of the synthetic product redoxite is prolonged. According to the product obtained by the preparation method, the stability and the recycling times are greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method of redox resin, particularly relate to a kind of preparation method of the redox resin for the waste water sulphur removal.
Background technology
Redox resin is the macromolecular compound that a class has redox property.Because they can reversible electron exchange reaction occur with other molecules or ion under suitable reaction conditions, so be also referred to as electron exchange resin.
Redox resin has a wide range of applications at industrial sectors such as wastewater treatment, gas sweetening and the desulfurizations of fuel oil.Utilize its electronics transfer characteristic, can be as redox catalyst in many treating processess.
Existing redox resin roughly is divided into four classes: organic functional group type, mineral ion type, metal mold and coordination compound type.Wherein organic functional group type redox resin is easy to preparation, but oxidation-reduction capacity is less, can't satisfy the large scale industry requirement; The redox ability of inorganic metal ion type redox resin is better, but because metal ion and organic resin reactive force are not enough, wash-out lost efficacy easily.The synthetic comparatively complexity of metal mold resin and cost are high, are not suitable for industrial scale operation.The redox ability of corrdination type redox resin is more stable, but each use needs manipulation of regeneration just can reuse after finishing, and using method comparatively bothers, and reusability is just had a greatly reduced quality.
Wherein, Resorcinol type " gabion " redox resin is comparatively common.The characteristics that it is little owing to environmental pollution, oxidation-reduction capacity is higher receive an acclaim.But this resin take the strong basicity quaternary ammonium type anion exchange resin as skeleton still has its deficiency, as: because the chain of Resorcinol interts on anion frame, but do not form stable chemical bond, thereby cause the easy wash-out of this resin, life-span short.
Summary of the invention
The technical problem to be solved in the present invention is for the existing weak point of present redox resin, and the preparation method of the redox resin that is used for the waste water sulphur removal after a kind of improve is provided.Technical solution of the present invention adopts Resorcinol as redox-active group, and phenol is as effective linking agent, and formaldehyde is as polymerization agent, and sodium hydroxide provides alkaline environment to synthesize, and prepares product redox resin of the present invention.The present invention utilizes Resorcinol to have the transition function of good quinoid and phenol type, will link to each other with covalent linkage between the resin group, and prolonged the work-ing life of its synthetic product redox resin.The product stability, the recycling number of times that obtain by preparation method of the present invention all are greatly improved.
In order to address the above problem, the technical solution used in the present invention is:
The invention provides a kind of preparation method of the redox resin for the waste water sulphur removal, described preparation method may further comprise the steps:
A, the preparation of linear pre-polymer A: take polyoxymethylene [30525-89-4] and Resorcinol [123-31-9] as raw material, described polyoxymethylene and Resorcinol between the two the mol ratio of add-on be that 0.85～1.0(is in formaldehyde): 1, take by weighing raw material polyoxymethylene and Resorcinol according to the proportioning ratio, at first the polyoxymethylene that takes by weighing is mixed with mass percentage concentration and is 36～38% formaldehyde solution, then the Resorcinol that takes by weighing is added in the formaldehyde solution of preparation, then add sodium hydroxide, sodium hydroxide and Resorcinol between the two the mol ratio of add-on be 0.015～0.02:1, then being heated to 60～70 ℃ reacts, react 25～30min after the Resorcinol solid dissolves fully, obtaining linear pre-polymer A after reaction finishes is formaldehyde Resorcinol linear resin again;
B, the preparation of linear pre-polymer B: take polyoxymethylene and phenol [108-95-2] as raw material, described polyoxymethylene and phenol between the two the mol ratio of add-on be that 6.5～7(is in formaldehyde): 6, take by weighing raw material polyoxymethylene and phenol according to the proportioning ratio, at first the polyoxymethylene that takes by weighing is mixed with mass percentage concentration and is 36～38% formaldehyde solution, then the phenol that takes by weighing is dissolved in the formaldehyde solution, and adding sodium hydroxide carries out catalyzed reaction, sodium hydroxide and the phenol mol ratio between the two is 0.015～0.02:1, being heated to 60～70 ℃ reacts, react 20～25min after the phenol solid dissolves fully, obtaining linear pre-polymer B after reaction finishes is linear phenolic resin again;
The mol ratio of the polyoxymethylene that adopts among the polyoxymethylene that adopts among the step a and the step b between the two is 6～6.5:7;
C, linear pre-polymer A and linear pre-polymer B that step a and step b are obtained respectively mix according to the ratio of mol ratio 0.9～1.1:1, be heated to 80～100 ℃ and carry out crosslinking reaction, reaction times is 1.5～2h, and reaction obtains the aqueous resins product after finishing;
D, the aqueous resins product that step c is obtained are dried, and pulverize after the oven dry, and making particle size range is 1～2mm, obtain the redox resin that product is used for the waste water sulphur removal after the pulverizing.
According to the above-mentioned preparation method who is used for the redox resin of waste water sulphur removal, described in the step a take polyoxymethylene and Resorcinol as raw material, described polyoxymethylene and Resorcinol between the two the mol ratio of add-on be that 1(is in formaldehyde): 1.
According to the above-mentioned preparation method who is used for the redox resin of waste water sulphur removal, described in the step b take polyoxymethylene and phenol as raw material, described polyoxymethylene and phenol between the two the mol ratio of add-on be that 7(is in formaldehyde): 6.
According to the above-mentioned preparation method who is used for the redox resin of waste water sulphur removal, the linear pre-polymer A and the linear pre-polymer B that described in the step c step a and step b are obtained respectively mix according to the ratio of mol ratio 1:1.
According to the preparation method of the above-mentioned redox resin that is used for the waste water sulphur removal, the aqueous resins product that described in the steps d step c is obtained is dried, and its bake out temperature is 90～100 ℃, and drying time is 8～10h.
According to the preparation method of the above-mentioned redox resin that is used for the waste water sulphur removal, the oxidation-reduction capacity that product described in the steps d is used for the redox resin of waste water sulphur removal is 4.00～5.00 mmol/g.
The product redox resin of the present invention's preparation is the brownish black solid, and quality is hard, is brown after pulverizing.Product oxidized form of the present invention and reduced form infrared spectrum see for details respectively shown in accompanying drawing 1 and the accompanying drawing 2, can find out its functional group.
Positive beneficial effect of the present invention:
1, utilize the redox resin oxidation-reduction capacity of technical solution of the present invention preparation high: redox resin of the present invention with resol as skeleton, and with the crosslinked linear side chain that contains Resorcinol of C-C.Utilize iodometric determination, its oxidation-reduction capacity is 4.00 ~ 5.00 mmol/g.
2, utilize the redox resin catalysis of technical solution of the present invention preparation strong except the sulfonium ion ability: test
The result is by dynamics calculation, and under top condition (high temperature, resin demand is moderate, low basicity), novel redox resin of the present invention can improve 45 times with the speed of reaction of sulfonium ion oxidation by air; On the other hand, in the test duration scope, sulfonium ion solution is only had about 37% by the degree of air natural oxidation, and after adding redox resin of the present invention, sulfur-containing anion hardly in the solution after the processing, sulfonium ion all is oxidizing to the high oxidation state acid ion, and this has shown that redox resin of the present invention not only can improve the speed of reaction of sulfonium ion oxidation by air, has also improved the level of response of sulfonium ion oxidation by air greatly.
3, technical solution of the present invention compared with prior art (prior art use transition metal as the redox center), the present invention be with the carbonyl of quinone with and the hydroxyl of corresponding phenol between mutual conversion, redox functional group as the electronics transmission, harm to environment is less, more be conducive to environmental protection, have significant Social benefit and economic benefit.
4, technical solution of the present invention adopts Resorcinol as redox-active group, and phenol is as effective linking agent, and formaldehyde is as polymerization agent, and sodium hydroxide provides alkaline environment to synthesize, and prepares product redox resin of the present invention.The present invention utilizes Resorcinol to have the transition function of good quinoid and phenol type, will link to each other with covalent linkage between the resin group, and prolonged the work-ing life of its synthetic product redox resin.The product stability, the recycling number of times that obtain by preparation method of the present invention all are greatly improved.
Four, description of drawings:
The infrared spectrogram of Fig. 1 product of the present invention under oxide morphology;
Show among Fig. 1 and since carbonyl on phenyl ring with two key conjugation, so divide 1583.77 cm
-1The peak, thereby Resorcinol is that form with quinone exists in the proof oxidized form.
The infrared spectrogram of Fig. 2 product of the present invention under oxide morphology;
Show among Fig. 2: 1580cm
-1The place does not divide the peak that, and illustrate does not have carbonyl to exist on the phenyl ring, thereby proves that Resorcinol in the reduced form is that form with phenol exists.
Curve is compared in the reaction of Fig. 3 product of the present invention under different variable conditions.
This is measured with S
2-The solutions simulate trade effluent arranges three factors according to orthogonal experiment method: temperature, basicity and catalytic amount.And the S in set time mensuration solution
2O
3 2-Growing amount, with reaction than representing, i.e. the ratio of the amount of substance of the actual sulphur products (in Sulfothiorine) that generates and the amount of substance of theory generation Sulfothiorine.Wherein, the x axle represents reaction times/min, and the y axle represents reaction ratio/%.Every curve all with (temperature/℃, resin demand/g, basicity/molL
-1) form mark.As: 26 ℃ of curve 1 expression temperature, 0.00g resin catalysis (being blank), the reaction ratio of the reaction soln of 0mol/L NaOH (basicity).This Fig. 3 is illustrated under the different condition, the catalytic performance of this resin: reaction is than larger, and then level of response is larger; Rate of curve is higher, and then speed of response is faster.
Five, embodiment:
Further set forth the present invention below in conjunction with embodiment, but do not limit content of the present invention.
Embodiment 1:
The present invention is used for the preparation method of the redox resin of waste water sulphur removal, and this preparation method's detailed step is as follows:
The preparation of a, linear pre-polymer A: take by weighing raw material polyoxymethylene 4.5g and Resorcinol 16.5g (mol ratio is 1:1) according to the proportioning ratio, at first the polyoxymethylene that takes by weighing is mixed with mass percentage concentration and is 37% formaldehyde solution, then the Resorcinol that takes by weighing is added in the formaldehyde solution of preparation, then add sodium hydroxide 0.1g and carry out catalysis, then being heated to 65 ℃ reacts, react 30min after the Resorcinol solid dissolves fully, obtaining linear pre-polymer A after reaction finishes is formaldehyde Resorcinol linear resin again;
The preparation of b, linear pre-polymer B: take by weighing raw material polyoxymethylene 5.3g and phenol 14.1g (mol ratio is 7:6) according to the proportioning ratio, at first the polyoxymethylene that takes by weighing is mixed with mass percentage concentration and is 37% formaldehyde solution, then the phenol that takes by weighing is dissolved in the formaldehyde solution, and adding sodium hydroxide 0.1g carries out catalysis, being heated to 65 ℃ reacts, react 25min after the phenol solid dissolves fully, obtaining linear pre-polymer B after reaction finishes is linear phenolic resin again;
C, linear pre-polymer A and linear pre-polymer B that step a and step b are obtained respectively mix, at this moment, the mol ratio of linear pre-polymer A and linear pre-polymer B is 1:1, is heated to 100 ℃ and carries out crosslinking reaction, reaction times is 1.5h, and reaction obtains the aqueous resins product after finishing;
D, the aqueous resins product that step c is obtained are dried, and bake out temperature is 100 ℃, and drying time is 8h, pulverize after the oven dry, and the product that obtains particle size range 1～2mm namely is used for the redox resin 17.4g of waste water sulphur removal.The oxidation-reduction capacity of products therefrom is 4.76mmol/g.
Embodiment 2: substantially the same manner as Example 1, difference is:
Among the step a: the mol ratio of add-on is 0.95:1 between polyoxymethylene and the Resorcinol, namely takes by weighing polyoxymethylene 4.3g and Resorcinol 16.5g; Then being heated to 70 ℃ reacts;
Among the step b: polyoxymethylene and phenol between the two the mol ratio of add-on be 6.8:6, namely take by weighing raw material polyoxymethylene 5.1g and phenol 14.1g; Being heated to 70 ℃ reacts;
In the steps d: the aqueous resins product that step c obtains is dried, and bake out temperature is 90 ℃, and drying time is 9h, pulverizes the redox resin 14.3g that the product that obtains particle size range 1～2mm namely is used for the waste water sulphur removal after the oven dry.The oxidation-reduction capacity of products therefrom is 4.34mmol/g.
Embodiment 3: substantially the same manner as Example 1, difference is:
Among the step b: polyoxymethylene and phenol between the two the mol ratio of add-on be 7:6, namely take by weighing polyoxymethylene 4.2g and phenol 11.3g;
Among the step c: linear pre-polymer A and linear pre-polymer B that step a and step b are obtained respectively mix, at this moment, the mol ratio of linear pre-polymer A and linear pre-polymer B is 1.25:1, be heated to 100 ℃ and carry out crosslinking reaction, reaction times is 1.5h, and reaction obtains the aqueous resins product after finishing;
In the steps d: the aqueous resins product that step c obtains is dried, and bake out temperature is 100 ℃, and drying time is 8h, pulverizes after the oven dry, and the product that obtains particle size range 1～2mm namely is used for the redox resin 13.8g of waste water sulphur removal.The oxidation-reduction capacity of products therefrom is 4.68mmol/g.
Embodiment 4: substantially the same manner as Example 1, difference is:
The present invention is used for the preparation method of the redox resin of waste water sulphur removal, and its detailed step is as follows:
A, the preparation of linear pre-polymer A: take polyoxymethylene and Resorcinol as raw material, described polyoxymethylene and Resorcinol between the two the mol ratio of add-on be 1 (in formaldehyde): 1, take by weighing raw material polyoxymethylene 136g and Resorcinol 500g according to the proportioning ratio, at first the polyoxymethylene that takes by weighing is mixed with mass percentage concentration and is 37% formaldehyde solution, then the Resorcinol that takes by weighing is added in the formaldehyde solution of preparation, then add sodium hydroxide 1g and carry out catalysis, then being heated to 65 ℃ reacts, react 30min after the Resorcinol solid dissolves fully, obtaining linear pre-polymer A after reaction finishes is formaldehyde Resorcinol linear resin again;
The preparation of b, linear pre-polymer B: take polyoxymethylene and phenol as raw material, described polyoxymethylene and phenol between the two the mol ratio of add-on be 7:6, take by weighing raw material polyoxymethylene 160 and phenol 430g according to the proportioning ratio, at first the polyoxymethylene that takes by weighing is mixed with mass percentage concentration and is 37% formaldehyde solution, then the phenol that takes by weighing is dissolved in the formaldehyde solution, and adding sodium oxide 1g carries out catalysis, being heated to 65 ℃ reacts, react 25min after the phenol solid dissolves fully, obtaining linear pre-polymer B after reaction finishes is linear phenolic resin again;
C, linear pre-polymer A and linear pre-polymer B that step a and step b are obtained respectively mix, at this moment, the mol ratio of linear pre-polymer A and linear pre-polymer B is 1:1, is heated to 100 ℃ and carries out crosslinking reaction, reaction times is 1.5h, and reaction obtains the aqueous resins product after finishing;
D, the aqueous resins product that step c is obtained are dried, bake out temperature is 100 ℃, drying time is 8h, process with shearing crusher after the oven dry, the product that obtains particle size range 1 ~ 2mm namely is used for the redox resin 533g of waste water sulphur removal, after measured, the oxidation-reduction capacity of products therefrom is 4.72mmol/g.
Embodiment 5: the application example of product of the present invention
Oxide catalyst with product of the present invention is processed as aerating wastewater is used for the waste water sulphur removal, and detailed step is as follows:
The 0.05mol/L Na of a, usefulness 500mL
2S solutions simulate sulfur-bearing trade effluent according to orthogonal experiment method, arranges three factors: temperature, basicity and catalytic amount, and totally 9 groups of experiment conditions, such as following table 1:
B, air pump is connected into Na
2The container of S solution as aeration source, adds redox resin (the being called for short RR) catalyzer that product of the present invention is used for the waste water sulphur removal according to different experiment conditions, NaOH, and regulate temperature.Whole process stirs with mechanical stirrer.Under each condition, arrange 5 measurement point, be respectively: 0,30min, 60min, 90min and 120min.In each measurement point, extract water sample 5.00mL.
After c, water sample were processed through the acetic acid zinc solution of 0.02mol/mL first, centrifugation went out precipitation, and the stillness of night is used iodometric titrationiodimetry titration.When calculating the sulphur products that generates by measuring result, with S
2O
3 2-Concentration represents.The amount of substance of the actual sulphur products (in Sulfothiorine) that generates is called for short the reaction ratio with the ratio that theory generates the amount of substance of Sulfothiorine, calculates under each condition, and the reaction of each measurement point ratio, and the time mapped.Such as accompanying drawing 3, every slope of a curve is the speed of sulfonium ion in the atmospheric oxidation waste water.
E, find out from the result that at 65 ℃, in the sulfur-containing waste water of 0.10mol/L, add the 0.50gRR catalyzer, the speed of atmospheric oxidation sulfonium ion is about 26 ℃, i.e. room temperature, during catalyst-free, 45 times of the speed of air natural sulfur oxide ion.
Embodiment 6: product application implementation of the present invention
Product of the present invention is removed for the treatment of sulphur in certain fertilizer plant's gasification wastewater.Detailed step is as follows:
A, in the small-sized fluidized bed reactor, add in advance RR 12.0 g with atmospheric oxidation.To test with actual waste water in the top introducing fluidized-bed reactor of lower gas grid distributor with small-sized impeller pump, making its mean residence time in reactor with needle valve control wastewater flow is 30min.Change the pressurized air flow velocity that enters reactor, temperature of reaction is normal temperature.After 1h is stablized in system's running, the S of sampling and measuring reactor water outlet
2-Content.Experiment waste water S
2-Content 1.78mg/L is 0.30～0.56mg/L after the processing, S
2-Clearance is 68.5～83.1%.
B, fixed air liquor ratio are 13, and the mean residence time of waste water in fluidized-bed is 30min, change the add-on of RR, at normal temperatures after 1h is stablized in system's running, and the S of sampling and measuring reactor water outlet
2-Content.Experiment waste water S
2-Content 3.78mg/L is 0.08～0.049mg/L after the processing, S
2-Clearance is 87.0～98.0%
C, as can be seen from the results, RR has kept the oxidation catalytic property of phenol-quinonyl in liquid phase basically.Can think that the immobilization of this homogeneous catalyst is successfully, it can be used as the catalyzer of gasification wastewater aeration oxide treatment fully.The present invention not only can make discharged wastewater met the national standard aspect treatment effect, and the treatment time is shorter than existing method.
Claims (6)
1. preparation method who is used for the redox resin of waste water sulphur removal is characterized in that described preparation method may further comprise the steps:
A, the preparation of linear pre-polymer A: take polyoxymethylene and Resorcinol as raw material, described polyoxymethylene and Resorcinol between the two the mol ratio of add-on be that 0.85～1.0(is in formaldehyde): 1, take by weighing raw material polyoxymethylene and Resorcinol according to the proportioning ratio, at first the polyoxymethylene that takes by weighing is mixed with mass percentage concentration and is 36～38% formaldehyde solution, then the Resorcinol that takes by weighing is added in the formaldehyde solution of preparation, then add sodium hydroxide, sodium hydroxide and Resorcinol between the two the mol ratio of add-on be 0.015～0.02:1, then being heated to 60～70 ℃ reacts, react 25～30min after the Resorcinol solid dissolves fully, obtaining linear pre-polymer A after reaction finishes is formaldehyde Resorcinol linear resin again;
B, the preparation of linear pre-polymer B: take polyoxymethylene and phenol as raw material, described polyoxymethylene and phenol between the two the mol ratio of add-on be that 6.5～7(is in formaldehyde): 6, take by weighing raw material polyoxymethylene and phenol according to the proportioning ratio, at first the polyoxymethylene that takes by weighing is mixed with mass percentage concentration and is 36～38% formaldehyde solution, then the phenol that takes by weighing is dissolved in the formaldehyde solution, and adding sodium hydroxide carries out catalyzed reaction, sodium hydroxide and the phenol mol ratio between the two is 0.015～0.02:1, being heated to 60～70 ℃ reacts, react 20～25min after the phenol solid dissolves fully, obtaining linear pre-polymer B after reaction finishes is linear phenolic resin again;
The mol ratio of the polyoxymethylene that adopts among the polyoxymethylene that adopts among the step a and the step b between the two is 6～6.5:7;
C, linear pre-polymer A and linear pre-polymer B that step a and step b are obtained respectively mix according to the ratio of mol ratio 0.9～1.1:1, be heated to 80～100 ℃ and carry out crosslinking reaction, reaction times is 1.5～2h, and reaction obtains the aqueous resins product after finishing;
D, the aqueous resins product that step c is obtained are dried, and pulverize after the oven dry, and making particle size range is 1～2mm, obtain the redox resin that product is used for the waste water sulphur removal after the pulverizing.
2. the preparation method of the redox resin for the waste water sulphur removal according to claim 1, it is characterized in that: described in the step a take polyoxymethylene and Resorcinol as raw material, described polyoxymethylene and Resorcinol between the two the mol ratio of add-on be that 1(is in formaldehyde): 1.
3. the preparation method of the redox resin for the waste water sulphur removal according to claim 1, it is characterized in that: described in the step b take polyoxymethylene and phenol as raw material, described polyoxymethylene and phenol between the two the mol ratio of add-on be that 7(is in formaldehyde): 6.
4. the preparation method of the redox resin for the waste water sulphur removal according to claim 1 is characterized in that: the linear pre-polymer A and the linear pre-polymer B that described in the step c step a and step b are obtained respectively mix according to the ratio of mol ratio 1:1.
5. the preparation method of the redox resin for the waste water sulphur removal according to claim 1, it is characterized in that: the aqueous resins product that described in the steps d step c is obtained is dried, and its bake out temperature is 90～100 ℃, and drying time is 8～10h.
6. the preparation method of the redox resin for the waste water sulphur removal according to claim 1, it is characterized in that: the oxidation-reduction capacity that product described in the steps d is used for the redox resin of waste water sulphur removal is 4.00～5.00 mmol/g.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929846A (en) * | 2021-10-22 | 2022-01-14 | 西北工业大学 | High-carbon-formation-rate water-soluble phenolic resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5578011A (en) * | 1979-10-08 | 1980-06-12 | Hokuetsu Seishi Kk | Quinone-type crosslinked redox resin and its preparation |
| JPS55147516A (en) * | 1979-10-08 | 1980-11-17 | Hokuetsu Seishi Kk | Preparation of quinone-type crosslinked redox resin |
| CN1298891A (en) * | 2000-12-15 | 2001-06-13 | 霍银坤 | Process for preparing spherical hydrazine coordinated sulfonated phenolic type redex resin |
-
2012
- 2012-12-28 CN CN201210578993.1A patent/CN103073688B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5578011A (en) * | 1979-10-08 | 1980-06-12 | Hokuetsu Seishi Kk | Quinone-type crosslinked redox resin and its preparation |
| JPS55147516A (en) * | 1979-10-08 | 1980-11-17 | Hokuetsu Seishi Kk | Preparation of quinone-type crosslinked redox resin |
| CN1298891A (en) * | 2000-12-15 | 2001-06-13 | 霍银坤 | Process for preparing spherical hydrazine coordinated sulfonated phenolic type redex resin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929846A (en) * | 2021-10-22 | 2022-01-14 | 西北工业大学 | High-carbon-formation-rate water-soluble phenolic resin and preparation method thereof |
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