CN105384151A - Comprehensive utilization and treatment method of waste sulfuric acid - Google Patents
Comprehensive utilization and treatment method of waste sulfuric acid Download PDFInfo
- Publication number
- CN105384151A CN105384151A CN201510903429.6A CN201510903429A CN105384151A CN 105384151 A CN105384151 A CN 105384151A CN 201510903429 A CN201510903429 A CN 201510903429A CN 105384151 A CN105384151 A CN 105384151A
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- Prior art keywords
- sulfuric acid
- waste sulfuric
- comprehensive utilization
- utilization method
- coupler
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/905—Removal of organic impurities
Abstract
The invention relates to the field of waste liquid purification treatment, and provides a comprehensive utilization and treatment method of waste sulfuric acid. The method comprises the following steps: (1) filtering: filtering waste sulfuric acid to remove impurities such as floccule, particles, and the like; (2) coupling and adsorption: adding a coupling agent into the effluent obtained in the step (1), wherein the addition amount is 10 to 100 grams for each liter, and fully stirring to carry out reactions for 2 to 3 hours at a temperature of 30 to 60 DEG C; (3) suction filtration: subjecting the effluent obtained in the step (2) to suction filtration so as to separate the coupling agent and sulfuric acid. The provided method can effectively reduce COD and chroma of waste sulfuric acid, and guarantees the concentration of final sulfuric acid product. The procedure and operation are both very simple.
Description
Technical field
The present invention relates to effluent purifying process field, particularly relate to a kind of Comprehensive utilization method of Waste Sulfuric Acid.
Background technology
In the chemical intermediate production process of dyestuff, medicine and other fields, often can produce a large amount of Waste Sulfuric Acids, usually up to 1000-5000 doubly, COD content is also higher, and pH is even lower about 1 for the colourity of these Waste Sulfuric Acids.Treatment process conventional in current industrial production has distillation method, chemical oxidization method etc.Distillation method cost is lower, but energy consumption is higher, in chemical oxidization method, Fenton oxidation effect better still needs to regulate pH to about 3, the product sulfur acid concentration is had a certain impact, and larger molecular organics is oxidized to small organic molecule, still need supporting subsequent disposal, and resource cannot be fully utilized.Therefore, research and develop and a kind ofly effectively can remove COD in Waste Sulfuric Acid and colourity and ensure that the concentration of final sulfuric acid product, process Waste Sulfuric Acid Comprehensive utilization method simple and easy to operate seems particularly important.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind ofly effectively can be removed COD in Waste Sulfuric Acid and colourity and ensure the Waste Sulfuric Acid Comprehensive utilization method that the concentration of final sulfuric acid product, process are simple and easy to operate.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
Waste Sulfuric Acid Comprehensive utilization method of the present invention, comprises following concrete steps:
(1) filter: Waste Sulfuric Acid is filtered, remove the impurity such as floss, particulate matter wherein contained;
(2) coupling absorption: add coupler in step (1) gained water outlet, add-on is 10-100g/L, abundant stirring reaction 2-3h at 30-60 DEG C;
(3) suction filtration: suction filtration is carried out in step (2) gained water outlet, coupler is separated with sulfuric acid.
Waste Sulfuric Acid Comprehensive utilization method of the present invention, further, filters in step (1) and uses acidproof filter cloth to filter.
Waste Sulfuric Acid Comprehensive utilization method of the present invention, further, described acidproof selection of filter cloth 80-150 order.
Waste Sulfuric Acid Comprehensive utilization method of the present invention, further, the coupler used in step (2) comprises following component (mass percent):
Gac 10% ~ 30%, polymeric adsorbent 30% ~ 70%, polymeric coupler 15% ~ 50%.
Waste Sulfuric Acid Comprehensive utilization method of the present invention, further, described polymeric adsorbent is hypercrosslinked polymeric resin.
Waste Sulfuric Acid Comprehensive utilization method of the present invention, further, described polymeric coupler comprises following component (mass percent): divinylbenzene 20-69.7%, vinylbenzene 30-79.8% and dispersion agent 0.1-0.5%.
Waste Sulfuric Acid Comprehensive utilization method of the present invention, further, described dispersion agent selects one or more in polyvinyl alcohol, gelatin, hydroxylated cellulose, calcium carbonate, talcum powder, diatomite.
Waste Sulfuric Acid Comprehensive utilization method of the present invention, further, described polymeric coupler adopts following methods to be prepared from: by divinylbenzene, vinylbenzene and dispersant, at 60-150 DEG C, with the stirring velocity of 20-100rad/min, polyreaction 12-36h.
Waste Sulfuric Acid Comprehensive utilization method of the present invention, further, described polyreaction is carried out under 0.1-0.5MP pressure.
Waste Sulfuric Acid Comprehensive utilization method of the present invention, further, in step (3), suction filtration uses the acidproof filter cloth of 120-200 object.
Waste Sulfuric Acid Comprehensive utilization method of the present invention compared with prior art, has following beneficial effect:
Waste Sulfuric Acid Comprehensive utilization method of the present invention have employed the method that physical filtering combines with coupler, filter and eliminate the floss and granular precipitate material that contain in Waste Sulfuric Acid, and add compound coupler, not only adsorb most COD in Waste Sulfuric Acid, the clearance of COD can reach 60-90%, and the chromonic material of adsorbing greatly in Waste Sulfuric Acid, be separated with sulfuric acid by the coupler of vacuum pump suction filtration by compound again, thus reach the object of sulfuric acid purification, the clearance for the treatment of process of the present invention to the coloring matter in Waste Sulfuric Acid is higher, chroma removal rate is up to more than 98%, the sulfuric acid product obtained is transparent, can be used as industrial production raw material directly to send in production system and use.This method avoids and in treating processes, introduce other reagent dilution is caused to sulfuric acid, change the acidity of sulfuric acid product, it also avoid other inorganic salt of introducing and cause secondary pollution, or increase other treatment process, reduce the quantity discharged of the by product such as acid, salt, on the basis that ensure that higher COD, chroma removal rate, simplify technical process greatly, the disposal of resources cost of process Waste Sulfuric Acid of the present invention is about 60-90 yuan/ton, make that method is simple and easy to operate, cost is low, pollution is few, resource recycling rate is high.
Waste Sulfuric Acid Comprehensive utilization method of the present invention utilizes divinylbenzene, vinylbenzene and dispersion agent carry out suspension polymerization, obtained polymeric coupler, this polymeric coupler is macroporous type rigid structural, inner containing certain space, to hydroxyl under strong acidic condition, Selective adsorption that is amino and derivative is stronger, applied range, reaction efficiency is high, be applicable to the removal of the coloring matter in different substrates, still higher adsorption efficiency can be kept in strong acidic environment, also obvious to organic removal effect, and and more easily separated between substrate fluid, new material can not be introduced in matrix, easy and simple to handle, running cost is lower.
Embodiment
Embodiment 1
Waste Sulfuric Acid Comprehensive utilization method of the present invention comprises following concrete steps:
(1) filter: use the acidproof filter cloth of 80 object to filter Waste Sulfuric Acid, remove the impurity such as floss, particulate matter wherein contained;
(2) coupling absorption: add coupler in step (1) gained water outlet, add-on is 10g/L, abundant stirring reaction 3h at 60 DEG C;
The coupler used comprises following component (mass percent): gac 15%, polymeric adsorbent 35%, polymeric coupler 50%;
Wherein, polymeric adsorbent is hypercrosslinked polymeric resin, select the modified superhigh crosslinked macroporous resin of commercially available NDA150 oxygen, polymeric coupler is adopted and is prepared with the following method: added in reactor by divinylbenzene 20%, vinylbenzene 79.8% and polyvinyl alcohol 0.2% and mix, 60 DEG C, under 0.5MP, with the stirring velocity of 50rad/min, suspension polymerization 36h obtains.
(3) suction filtration: use 120 object acidproof filter cloth that suction filtration is carried out in step (2) gained water outlet, coupler is separated with sulfuric acid, the vitriol oil be purified, can be used as industrial production raw material.
The present embodiment method is as shown in table 1 for the treatment of the treatment effect of the Waste Sulfuric Acid produced in medicine intermediate production process:
The treatment effect of table 1 embodiment 1 method process Waste Sulfuric Acid
| CODcr(mg/L) | Colourity | Acidity | |
| Former water | 12500 | 2500 | 9.0mol/L |
| After reaction suction filtration | 4600 | 40 | 9.0mol/L |
Shown in table 1, Waste Sulfuric Acid is after coupler absorption, coupling, COD clearance in Waste Sulfuric Acid is 63.2%, and the clearance of colourity is up to 98.4%, simultaneously owing to not using any adjustment acidity or dilution means in treating processes, so Waste Sulfuric Acid acidity after coupling and suction filtration remains unchanged, directly can deliver in industrial production as industrial raw material and apply.
Embodiment 2
Waste Sulfuric Acid Comprehensive utilization method of the present invention comprises following concrete steps:
(1) filter: use the acidproof filter cloth of 150 object to filter Waste Sulfuric Acid, remove the impurity such as floss, particulate matter wherein contained;
(2) coupling absorption: add coupler in step (1) gained water outlet, add-on is 100g/L, abundant stirring reaction 2h at 30 DEG C;
The coupler used comprises following component (mass percent): gac 30%, polymeric adsorbent 55%, polymeric coupler 15%;
Wherein, polymeric adsorbent is hypercrosslinked polymeric resin, select the HYA-106 hypercrosslinked polymeric resin that Xi'an Han Yu resin Science and Technology Ltd. produces, the preparation method of polymeric coupler is as follows: mix after divinylbenzene 69.5%, vinylbenzene 30%, calcium carbonate 0.4% and diatomite 0.1% is added reactor, 150 DEG C, under 0.1MP, with the stirring velocity of 100rad/min, suspension polymerization 12h obtains.
(3) suction filtration: use 160 object acidproof filter cloth that suction filtration is carried out in step (2) gained water outlet, coupler is separated with sulfuric acid, the vitriol oil be purified, can be used as industrial production raw material.
The present embodiment method is as shown in table 2 for the treatment of the treatment effect of the Waste Sulfuric Acid produced in dyestuff intermediate production process:
The treatment effect of table 2 embodiment 2 method process Waste Sulfuric Acid
| CODcr(mg/L) | Colourity | Acidity | |
| Former water | 25700 | 1500 | 6.0mol/L |
| After reaction suction filtration | 6800 | 30 | 6.0mol/L |
Shown in table 2, Waste Sulfuric Acid is after coupler absorption, coupling, COD clearance in Waste Sulfuric Acid is 73.5%, and the clearance of colourity is up to 98%, simultaneously owing to not using any adjustment acidity or dilution means in treating processes, so Waste Sulfuric Acid acidity after coupling and suction filtration remains unchanged, directly can deliver in industrial production as industrial raw material and apply.
Embodiment 3
Waste Sulfuric Acid Comprehensive utilization method of the present invention comprises following concrete steps:
(1) filter: use the acidproof filter cloth of 110 object to filter Waste Sulfuric Acid, remove the impurity such as floss, particulate matter wherein contained;
(2) coupling absorption: add coupler in step (1) gained water outlet, add-on is 50g/L, abundant stirring reaction 2.5h at 40 DEG C;
The coupler used comprises following component (mass percent): gac 10%, polymeric adsorbent 70%, polymeric coupler 20%;
Wherein, polymeric adsorbent is hypercrosslinked polymeric resin, what select is the XAD-1 series hypercrosslinked polymeric resin that Hebei Kairui Chemical LLC produces, the preparation method of polymeric coupler is as follows: mix after divinylbenzene 48%, vinylbenzene 51.9% and calcium carbonate 0.1% is added reactor, 100 DEG C, under 0.3MP, with the stirring velocity of 20rad/min, suspension polymerization 24h obtains.
(3) suction filtration: use 200 object acidproof filter cloth that suction filtration is carried out in step (2) gained water outlet, coupler is separated with sulfuric acid, the vitriol oil be purified, can be used as industrial production raw material.
The present embodiment method is as shown in table 3 for the treatment of the treatment effect of the Waste Sulfuric Acid produced in medicine intermediate production process:
The treatment effect of table 3 embodiment 3 method process Waste Sulfuric Acid
| CODcr(mg/L) | Colourity | Acidity | |
| Former water | 18400 | 3000 | 8.0mol/L |
| After reaction suction filtration | 3300 | 40 | 8.0mol/L |
Shown in table 3, Waste Sulfuric Acid is after coupler absorption, coupling, COD clearance in Waste Sulfuric Acid is 82.1%, and the clearance of colourity is up to 98.7%, simultaneously owing to not using any adjustment acidity or dilution means in treating processes, so Waste Sulfuric Acid acidity after coupling and suction filtration remains unchanged, directly can deliver in industrial production as industrial raw material and apply.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.
Claims (10)
1. Waste Sulfuric Acid Comprehensive utilization method, is characterized in that: comprise following concrete steps:
(1) filter: Waste Sulfuric Acid is filtered, remove the impurity such as floss, particulate matter wherein contained;
(2) coupling absorption: add coupler in step (1) gained water outlet, add-on is 10-100g/L, abundant stirring reaction 2-3h at 30-60 DEG C;
(3) suction filtration: suction filtration is carried out in step (2) gained water outlet, coupler is separated with sulfuric acid.
2. Waste Sulfuric Acid Comprehensive utilization method according to claim 1, is characterized in that: filter in step (1) and use acidproof filter cloth to filter.
3. Waste Sulfuric Acid Comprehensive utilization method according to claim 2, is characterized in that: described acidproof selection of filter cloth 80-150 order.
4. Waste Sulfuric Acid Comprehensive utilization method according to claim 1, is characterized in that: the coupler used in step (2) comprises following component (mass percent):
Gac 10% ~ 30%, polymeric adsorbent 30% ~ 70%, polymeric coupler 15% ~ 50%.
5. Waste Sulfuric Acid Comprehensive utilization method according to claim 4, is characterized in that: described polymeric adsorbent is hypercrosslinked polymeric resin.
6. Waste Sulfuric Acid Comprehensive utilization method according to claim 4, is characterized in that: described polymeric coupler comprises following component (mass percent): divinylbenzene 20-69.7%, vinylbenzene 30-79.8% and dispersion agent 0.1-0.5%.
7. Waste Sulfuric Acid Comprehensive utilization method according to claim 6, is characterized in that: described dispersion agent selects one or more in polyvinyl alcohol, gelatin, hydroxylated cellulose, calcium carbonate, talcum powder, diatomite.
8. Waste Sulfuric Acid Comprehensive utilization method according to claim 6, it is characterized in that: described polymeric coupler adopts following methods to be prepared from: by divinylbenzene, vinylbenzene and dispersant, at 60-150 DEG C, with the stirring velocity of 20-100rad/min, polyreaction 12-36h.
9. Waste Sulfuric Acid Comprehensive utilization method according to claim 8, is characterized in that: described polyreaction is carried out under 0.1-0.5MP pressure.
10. the Waste Sulfuric Acid Comprehensive utilization method according to claim 1-9 any one, is characterized in that: in step (3), suction filtration uses the acidproof filter cloth of 120-200 object.
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| CN201510903429.6A CN105384151A (en) | 2015-12-09 | 2015-12-09 | Comprehensive utilization and treatment method of waste sulfuric acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108405552A (en) * | 2018-02-08 | 2018-08-17 | 兰州康顺石化有限责任公司 | Chemical industry acid sludge Neutralisation treatment method |
| CN113460974A (en) * | 2021-08-14 | 2021-10-01 | 淄博点石环保科技有限公司 | Purification treatment process for high-concentration waste sulfuric acid |
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| US7837880B2 (en) * | 2004-02-06 | 2010-11-23 | Exxonmobil Research And Engineering Company | Acid tolerant polymeric membrane and process for the recovery of acid using polymeric membranes |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108405552A (en) * | 2018-02-08 | 2018-08-17 | 兰州康顺石化有限责任公司 | Chemical industry acid sludge Neutralisation treatment method |
| CN113460974A (en) * | 2021-08-14 | 2021-10-01 | 淄博点石环保科技有限公司 | Purification treatment process for high-concentration waste sulfuric acid |
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Application publication date: 20160309 |