CN104193107B - A kind for the treatment of process of tar and waste water - Google Patents
A kind for the treatment of process of tar and waste water Download PDFInfo
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- CN104193107B CN104193107B CN201410470158.5A CN201410470158A CN104193107B CN 104193107 B CN104193107 B CN 104193107B CN 201410470158 A CN201410470158 A CN 201410470158A CN 104193107 B CN104193107 B CN 104193107B
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- tar
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- containing wastewater
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- dimethyl
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- 239000002351 wastewater Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000011282 treatment Methods 0.000 title claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 31
- 239000003921 oil Substances 0.000 claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- 229920002545 silicone oil Polymers 0.000 claims abstract description 14
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 11
- 238000004062 sedimentation Methods 0.000 claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 7
- 230000020477 pH reduction Effects 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000012467 final product Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 241000894006 Bacteria Species 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 6
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 239000003245 coal Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- -1 comprise Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 239000011269 tar Substances 0.000 description 49
- 238000009288 screen filtration Methods 0.000 description 8
- 239000011280 coal tar Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 241000628997 Flos Species 0.000 description 4
- 241001148470 aerobic bacillus Species 0.000 description 4
- 239000010866 blackwater Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
Abstract
The invention discloses a kind of method for treating tar-containing wastewater, comprise, tar and waste water adds emulsion splitter and dimethyl silicone oil after filtering and removing solid in tar and waste water, through mixing, leaves standstill and the water layer being separated dimethyl-silicon oil reservoir and the bottom obtaining top.In described dimethyl-silicon oil reservoir, constantly pass into nitrogen and be heated to 120-180 DEG C of polycondensation 5-8h, being cooled to less than 10 DEG C filtrations and obtaining solid just polymers, by first for solid polymers under nitrogen protection in 300-400 DEG C of polyase 13-6h, obtain pitch.Water layer after acidification hydrolization, then gets final product qualified discharge through anaerobic treatment, aerobic treatment, sedimentation and absorption.The tar and waste water that the method is applicable to producing in oil or coal production processing processes, and removes the most of tar material in waste water, and makes water quality reach discharging standards.
Description
Technical field
The present invention relates to tar and waste water processing technology field, be specifically related to a kind for the treatment of process of tar and waste water.
Background technology
The process of manufacture of the mineral substance such as oil, coal often relates to washing process, easily produces a large amount of tar and waste water in water washing process.As its name suggests, the objectionable constituent in tar and waste water are mainly tar, and tar is a kind of complex compound containing 100 Multiple components, comprises the organism such as alkane, aromatic hydrocarbon and colloid; During washing process, part tar material is dissolved in water, becomes waste water.Outside tar removing, also containing aldehydes matter, ammonia nitrogen substances, prussiate and solid particulate matter in tar and waste water.
The process of tar and waste water, mainly for tar material, comprises gravity separation method, adsorption method etc.But the oils clearance of these methods is only 20-30wt.%, still there is a large amount of tar-like substance in water body; These tar-like substance can affect microbial growth, make the treatment effect of subsequent biochemical treatment system not good, and the ammonia nitrogen substances in waste water, aldehydes matter are difficult to remove, and water body COD degradation is incomplete, cannot reach national water quality standard requirement.
Summary of the invention
For this reason, technical problem to be solved by this invention is that the tar clearance of prior art to tar and waste water is low, causes water treatment effect not good, thus proposes the method for treating tar-containing wastewater that a kind of tar material clearance is high, water quality complies with the national standard requirements.
For solving the problems of the technologies described above, the invention discloses a kind of method for treating tar-containing wastewater, comprise the steps, (1) after tar and waste water filters and removes solid, in tar and waste water, add emulsion splitter and dimethyl silicone oil, through mixing, leave standstill and the water layer being separated dimethyl-silicon oil reservoir and the bottom obtaining top; (2) in described dimethyl-silicon oil reservoir, constantly pass into nitrogen and be heated to 120-180 DEG C of polycondensation 5-8h, being cooled to less than 10 DEG C filtrations and obtaining solid just polymers; (3) by solid just polymers under nitrogen protection in 300-400 DEG C of polyase 13-6h, obtain pitch; (4) water layer is after acidification hydrolization, then gets final product qualified discharge through anaerobic treatment, aerobic treatment, sedimentation and absorption.
The volume ratio of tar and waste water and dimethyl silicone oil is (14-35): 1.
In step (2), condensation temperature is 140-160 DEG C.
The polycondensation time is 7-8h.
In step (2), nitrogen flow is 30-100mL/min.
The polymerization temperature of the first polymers of solid is 360-380 DEG C.
Acidification hydrolization step in water layer, adds hydrolysis bacterium and acid-producing bacteria is mixed is incorporated in 30-35 DEG C of process 7-9h.
The sorbent material of adsorption step is the mixture of graphitized carbon black and gac.
Described emulsion splitter is polyoxyethylene polyoxypropylene stearyl alcohol ether.
Technique scheme of the present invention has the following advantages compared to existing technology,
(1) method for treating tar-containing wastewater of the present invention, first removing the solid impurity in tar and waste water and adding emulsion splitter makes emulsion be separated into aqueous phase and oil phase, use dimethyl silicone oil tar ingredients most of in waste water to be extracted, its tar clearance of measuring can up to more than 90% (weight percentage).Then, carry out just one-step polycondensation for the tar enclosed oxygen isolation in dimethyl-silicon oil reservoir and obtain solid just polymers, these solids just polymers can well be separated below 10 DEG C, and following polymerization further obtains the pitch that can directly use.In addition, extract remaining water and reach emission standard after acidification hydrolization, anaerobism, aerobic treatment, sedimentation, absorption.The tar clearance avoiding prior art tar and waste water is very low, the problem that water treatment effect is not good.And, can be the pitch that can directly use by a large amount of tar conversion in waste water by simple operation.
Wherein, nitrogen can avoid tar material oxidized in polycondensation process, can avoid dimethyl silicone oil deterioration by oxidation simultaneously, makes dimethyl silicone oil can continue to use.
(2) treatment process of tar and waste water of the present invention, the volume ratio of tar and waste water and dimethyl silicone oil is further defined to (14-35): 1, can under the consumption saving dimethyl silicone oil, make the tar clearance in water maintain the high level of more than 85% (weight percentage), thus finally obtain the water quality meeting GB.
(3) treatment process of tar and waste water of the present invention, hydrolysis bacterium and acid-producing bacteria mix and are incorporated in 30-35 DEG C of process 7-9h, thoroughly the larger molecular organics in waste water can be decomposed into small-molecule substance, then remove through subsequent handling.
Embodiment
embodiment 1
(1) black for 14L thick Coal Tar Wastewater 50-80 object screen filtration is removed solid, in tar and waste water, add 0.4g polyoxyethylene polyoxypropylene stearyl alcohol ether mixed, and left standstill and be separated the muddy look of dimethyl-silicon oil reservoir and bottom obtaining top black water layer I with 1L dimethyl silicone oil;
(2) in the dimethyl-silicon oil reservoir of black, constantly pass into nitrogen, the flow of nitrogen is 30mL/min, is heated to 140-160 DEG C of polycondensation 7-8h by airtight for dimethyl-silicon oil reservoir simultaneously, is separated obtains solid just polymers after being cooled to 8 DEG C with 150 object screen filtrations;
(3) first for solid polymers is continued at 360-380 DEG C of polymerization 5-6h under nitrogen protection, obtain bituminous matter I;
(4) in water layer, add hydrolysis bacterium and acid-producing bacteria is mixed is incorporated in 30 DEG C of process 9h, then through anerobe process and aerobic bacteria process, last sedimentation goes out solid, adopt in the mixture planar water of graphitized carbon black and gac and obtain water body I after floss.
embodiment 2
(1) black for 30L thick Coal Tar Wastewater 70-100 object screen filtration is removed solid, in tar and waste water, add 0.75g polyoxyethylene polyoxypropylene stearyl alcohol ether mixed, and left standstill and be separated the muddy look of dimethyl-silicon oil reservoir and bottom obtaining top black water layer II with 1L dimethyl silicone oil;
(2) in the dimethyl-silicon oil reservoir of black, constantly nitrogen is passed into, the flow of nitrogen is 60mL/min, be heated to 120-140 DEG C of polycondensation 6-7h by airtight for dimethyl-silicon oil reservoir simultaneously, be separated with 150 object screen filtrations after being cooled to 10 DEG C and obtain solid just polymers;
(3) first for solid polymers is continued at 300-350 DEG C of polyase 13-4h under nitrogen protection, obtain bituminous matter II;
(4) in water layer, add hydrolysis bacterium and acid-producing bacteria is mixed is incorporated in 32 DEG C of process 8h, then through anerobe process and aerobic bacteria process, last sedimentation goes out solid, adopt in the mixture planar water of graphitized carbon black and gac and obtain water body II after floss.
embodiment 3
(1) black for 35L thick Coal Tar Wastewater 60-90 object screen filtration is removed solid, in tar and waste water, add 0.83g polyoxyethylene polyoxypropylene stearyl alcohol ether mixed, and left standstill and be separated the muddy look of dimethyl-silicon oil reservoir and bottom obtaining top black water layer III with 1L dimethyl silicone oil;
(2) in the dimethyl-silicon oil reservoir of black, constantly nitrogen is passed into, the flow of nitrogen is 100mL/min, be heated to 160-180 DEG C of polycondensation 5-6h by airtight for dimethyl-silicon oil reservoir simultaneously, be separated with 150 object screen filtrations after being cooled to 10 DEG C and obtain solid just polymers;
(3) first for solid polymers is continued at 380-400 DEG C of polymerization 4-5h under nitrogen protection, obtain bituminous matter III;
(4) in water layer, add hydrolysis bacterium and acid-producing bacteria is mixed is incorporated in 35 DEG C of process 7h, then through anerobe process and aerobic bacteria process, last sedimentation goes out solid, adopt in the mixture planar water of graphitized carbon black and gac and obtain water body III after floss.
embodiment 4
(1) black for 14L thick petroleum tar waste water 50-80 object screen filtration is removed solid, in tar and waste water, add 0.4g polyoxyethylene polyoxypropylene stearyl alcohol ether mixed, and left standstill and be separated the muddy look of dimethyl-silicon oil reservoir and bottom obtaining top black water layer IV with 1L dimethyl silicone oil;
(2) in the dimethyl-silicon oil reservoir of black, constantly pass into nitrogen, the flow of nitrogen is 30mL/min, is heated to 140-160 DEG C of polycondensation 7-8h by airtight for dimethyl-silicon oil reservoir simultaneously, is separated obtains solid just polymers after being cooled to 8 DEG C with 150 object screen filtrations;
(3) first for solid polymers is continued at 360-380 DEG C of polymerization 5-6h under nitrogen protection, obtain bituminous matter IV;
(4) in water layer, add hydrolysis bacterium and acid-producing bacteria is mixed is incorporated in 30 DEG C of process 9h, then through anerobe process and aerobic bacteria process, last sedimentation goes out solid, adopt in the mixture planar water of graphitized carbon black and gac and obtain water body IV after floss.
The character of the Coal Tar Wastewater related in above-described embodiment and petroleum tar waste water is as follows:
test case
1. adopt SK-100 coal tar device for testing water content (sale of Shenzhen Hua Qing instrument company limited) to detect the water content of Coal Tar Wastewater, petroleum tar waste water and water layer I-water layer IV, backwards calculation obtains the tar content of tar and waste water, petroleum tar waste water and water layer I-water layer IV, calculate the tar clearance of each embodiment according to the following formula, in table 1.
Tar clearance=100% × (waste water tar content-water layer tar content)/waste water tar content
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Tar clearance | 90.1％ | 85.7％ | 84.9％ | 87.6％ |
2. detect the penetration degree of bituminous matter I-IV, ductility and softening temperature, in table 2 according to the method for GB/T4509, GB/T4508, GB/T4507 respectively.
Table 2
3. after testing, every index of water body I-IV all meets the requirement of GB8978-1996 " integrated wastewater discharge standard ", can discharge.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (9)
1. a method for treating tar-containing wastewater, comprises the steps,
(1) after tar and waste water filters and removes solid, in tar and waste water, add emulsion splitter and dimethyl silicone oil, through mixing, leave standstill and the water layer being separated dimethyl-silicon oil reservoir and the bottom obtaining top;
(2) in described dimethyl-silicon oil reservoir, constantly pass into nitrogen and be airtightly heated to 120-180 DEG C of polycondensation 5-8h, being cooled to less than 10 DEG C and filtering and obtain solid just polymers;
(3) by solid just polymers under nitrogen protection in 300-400 DEG C of polyase 13-6h, obtain pitch;
(4) water layer is after acidification hydrolization, then gets final product qualified discharge through anaerobic treatment, aerobic treatment, sedimentation and absorption.
2. method for treating tar-containing wastewater according to claim 1, it is characterized in that, the volume ratio of tar and waste water and dimethyl silicone oil is (14-35): 1.
3. method for treating tar-containing wastewater according to claim 1 or 2, is characterized in that, in step (2), condensation temperature is 140-160 DEG C.
4. method for treating tar-containing wastewater according to claim 1 or 2, is characterized in that, in step (2), the polycondensation time is 7-8h.
5. method for treating tar-containing wastewater according to claim 3, it is characterized in that, in step (2), nitrogen flow is 30-100mL/min.
6. method for treating tar-containing wastewater according to claim 1 or 2, is characterized in that, the polymerization temperature of the first polymers of solid is 360-380 DEG C.
7. method for treating tar-containing wastewater according to claim 1 or 2, is characterized in that, acidification hydrolization step in water layer, adds hydrolysis bacterium and acid-producing bacteria is mixed is incorporated in 30-35 DEG C of process 7-9h.
8. method for treating tar-containing wastewater according to claim 1 or 2, is characterized in that, the sorbent material of adsorption step is the mixture of graphitized carbon black and gac.
9. method for treating tar-containing wastewater according to claim 1 or 2, is characterized in that, described emulsion splitter is polyoxyethylene polyoxypropylene stearyl alcohol ether.
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| CN201410470158.5A CN104193107B (en) | 2014-09-16 | 2014-09-16 | A kind for the treatment of process of tar and waste water |
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| CN201410470158.5A CN104193107B (en) | 2014-09-16 | 2014-09-16 | A kind for the treatment of process of tar and waste water |
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| CN104193107B true CN104193107B (en) | 2016-02-03 |
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| CN111135672A (en) * | 2019-01-06 | 2020-05-12 | 史光辉 | Environmental protection treatment process for tar smoke |
| CN109678295A (en) * | 2019-01-09 | 2019-04-26 | 青岛科信新能源技术有限公司 | A kind of environment-friendly type method for treating tar-containing wastewater |
| CZ309390B6 (en) * | 2021-09-21 | 2022-11-09 | Ivo Ing. Picek | Device and method of cleaning waste water polluted from cooling, scrubbing and gas cleaning |
Citations (4)
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| CN102585871A (en) * | 2012-01-09 | 2012-07-18 | 常州黑玛新型碳材料工程技术研究中心有限公司 | Mesophase pitch and preparation method thereof |
| CN102659287A (en) * | 2012-05-21 | 2012-09-12 | 哈尔滨工业大学 | Combination method of coal chemical industry wastewater treatment |
| CN102659204A (en) * | 2012-05-11 | 2012-09-12 | 青岛科技大学 | Method for treating waste water in coal chemical industry |
| CN102942172A (en) * | 2012-11-22 | 2013-02-27 | 长沙理工大学 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
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| CN100363268C (en) * | 2004-11-15 | 2008-01-23 | 华东理工大学 | Cool coking effluent treatment method and device |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585871A (en) * | 2012-01-09 | 2012-07-18 | 常州黑玛新型碳材料工程技术研究中心有限公司 | Mesophase pitch and preparation method thereof |
| CN102659204A (en) * | 2012-05-11 | 2012-09-12 | 青岛科技大学 | Method for treating waste water in coal chemical industry |
| CN102659287A (en) * | 2012-05-21 | 2012-09-12 | 哈尔滨工业大学 | Combination method of coal chemical industry wastewater treatment |
| CN102942172A (en) * | 2012-11-22 | 2013-02-27 | 长沙理工大学 | Raw material composition capable of being used for preparing mesocarbon microbeads (MCMB), preparation method thereof and preparation method of MCMB anode material |
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Effective date of registration: 20170427 Address after: 510653 Tianhe District, Guangdong Province, Da Ming Road, No. 504, No. 9, No. Patentee after: Guangzhou North Energy Environmental Protection Co Ltd Address before: 325025 Zhejiang City, Wenzhou Province Economic and Technological Development Zone, Binhai Road, Binhai District, No. 15, No. 2, No. 529 Patentee before: Wang Qianqian |