CN103936186A - Method for treating crushed coal pressurization gasification process sewage through membrane technology - Google Patents
Method for treating crushed coal pressurization gasification process sewage through membrane technology Download PDFInfo
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- CN103936186A CN103936186A CN201410078008.XA CN201410078008A CN103936186A CN 103936186 A CN103936186 A CN 103936186A CN 201410078008 A CN201410078008 A CN 201410078008A CN 103936186 A CN103936186 A CN 103936186A
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Abstract
The present invention discloses a method for treating crushed coal pressurization gasification process sewage through a membrane technology. The method comprises that: (1) process sewage discharged from a phenol ammonia recovery apparatus is subjected to mechanical filtration and precise filtration to remove mechanical impurities so as to prevent membrane from clogging or injury; (2) the filtered process sewage is added with an alkali to adjust the pH value to 9-10.5 to make phenols in the sewage form phenol ammonia negative ions so as to prevent the membrane from pollution and clogging, and a two-stage or three-stage membrane system is adopted to remove the vast majority of the phenols and other organic matters; and (3) the fresh water discharged in the step (2) is added with an acid to adjust the pH value to 6-8 to make free ammonia form an ammonium salt, and a final-stage membrane is adopted to remove the vast majority of ammonia nitrogen in the sewage. According to the present invention, problems of high difficulty, high investment and high operation cost of the biological treatment of the high concentration phenol-containing wastewater produced during the crushed coal pressurization gasification process can be effectively solved.
Description
Technical field
The invention belongs to sewage treatment area, be specifically related to membrane technique and process crushed coal pressure gasifying process spent water.
Background technology
Crushed coal pressure gasifying belongs to fixed bed gasification technique, due to the existence of destructive distillation layer and drying layer, in the time of the young coal of gasification, raw gas contains the organic and inorganic impurities such as more tar, phenols, ammonia, prussic acid, along with the wash cooling process of raw gas, these impurity overwhelming majority are transferred in gas liquor.First traditional gas liquor treatment process passes through gas liquor tripping device and phenol ammonia recovery unit, comprises the series of physical sepn processes such as sedimentation, depickling, ammonia still process, extraction, and the process spent water of discharging is afterwards through biochemical treatment, then qualified discharge.Biochemical treatment crushed coal pressure gasifying process spent water, through putting into practice for many years and improving, technique is comparatively ripe, is widely applied.But crushed coal pressure gasifying sewage is as the industrial sewage of high phenol, ammonia content, wherein phenols has certain bio-toxicity to bacterium mud, particularly easily biochemical sewage treatment device is impacted when fluctuation of load, and time of recovery is longer, enterprise is produced and made a big impact continuously.Adopt in addition biochemical treatment, phenols and organism in sewage are decomposed by biochemistry, can not recycle.
Present method adopts embrane method to process crushed coal pressure gasifying process spent water, at home and abroad belongs to first and proposes, and its investment and running cost is all lower than biochemical processing process, and phenols and other organism in recoverable sewage.
Summary of the invention
The object of this invention is to provide a kind of membrane technique and process the method for crushed coal pressure gasifying process spent water,
For achieving the above object, the technical solution used in the present invention is as follows:
Membrane technique of the present invention is processed the method for crushed coal pressure gasifying process spent water, comprises the steps:
(1) first remove mechanical impurity through mechanical filter and secondary filter from the process spent water of phenol ammonia recovery unit discharge, prevent film result in blockage or damage;
(2) process spent water after filtration adds alkali adjusting pH value to 9 ~ 10.5, makes the phenols in sewage form phenol negative oxygen ion, prevents film to cause dirty blocking up, and then removes most phenols and other organism in sewage by two to three grades of film systems;
(3) fresh water that step (2) is discharged adds acid for adjusting pH to 6 ~ 8, makes free ammonia form ammonium salt, removes the most ammonia nitrogens in sewage by final stage film.
The film adopting in step (2) is reverse osmosis membrane or nanofiltration membrane.
Described mechanical filter adopts vertical mechanical strainer, and filtrate is selected quartz sand, has unique water distribution uniformity mode, makes strainer reach maximum efficiency, can meet for a long time effluent quality requirement.
It is the filler particles scratching film surface that prevents leakage that described secondary filter adopts the effect of accurate filter, and filtering accuracy is 5 μ m, and filter core is PP cotton or wire-wound filter core.
Below the present invention is elaborated:
The waste water that crushed coal pressure gasifying produces is after phenol ammonia recovery unit reclaims most of tar, middle oil, crude phenols and ammonia, then separate to level Four film system by three, remove phenols and ammonia wherein, the fresh water that produces carries out reuse, and dense water cycle is to phenol ammonia recovery unit entrance or for the preparation of coal water slurry.
Process crushed coal pressure gasifying process spent water with membrane technique and face maximum problem and be that the low-pole organism in waste water is easily adsorbed on film, film is caused dirty stifled, film is cleaned too frequent, device cannot steady running and is had a strong impact on life-span of film.Analysis to crushed coal pressure gasifying sewage composition shows, organism is wherein mainly various unit phenol and polyphenol, and phenols is slightly acidic, under sour environment, exist with phenolic hydroxyl group (ROH) form, under alkaline environment with phenol negative oxygen ion (RO
-) form existence.The present invention utilizes this character, adds the pH value of alkali adjusting sewage in the ingress of one-level film, makes the phenols negative ionization in sewage, and polarity specific ionization phenol significantly strengthens, and greatly reduces the adsorption to film, thereby has effectively prevented that the dirt of film is stifled.But because one-level film ingress adds alkali, the ammonia in sewage exists with free ammonia form, and film is very poor to the removal effect of small molecules free ammonia, the present invention, in final stage film entrance acid adding, makes the free ammonia in sewage form ammonium salt, is easy to tunicle and removes.Sewage is after two to three grades of films, and most phenols are removed, and now acid adding reduces pH value again, can not cause film dirty stifled.
The invention discloses membrane technique and process the method for crushed coal pressure gasifying process spent water, can effectively solve the problem that high-concentration phenolic wastewater biochemical treatment difficulty is large, investment is large, running cost is high producing in crushed coal pressure gasifying process.Crushed coal pressure gasifying process spent water first passes through gas liquor tripping device and phenol ammonia recovery unit, reclaim wherein after most of tar, middle oil, crude phenols and ammonia, pass through again mechanical filter and secondary filter, then separate to level Four film system by three, remove phenols and ammonia wherein, the fresh water that produces can be back to circulating water system or other user, and dense water cycle is to phenol ammonia recovery unit entrance or for the preparation of coal water slurry.Embrane method is processed crushed coal pressure gasifying process spent water and is had advantages of that investment is little, running cost is low.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1
As shown in Figure 1, membrane technique of the present invention is processed the method for crushed coal pressure gasifying process spent water, and concrete implementation step is as follows:
1, as follows from the process spent water index of phenol ammonia recovery unit discharge:
CODcr:3000 ~ 4500 mg/l, phenols: 800-1200mg/L, NH3-N:150～250 mg/l, oils: 200 mg/l, temperature: 35 ~ 45 DEG C, pH value: 7.0 ~ 9.5.
2, process spent water is first removed mechanical impurity through mechanical filter and secondary filter, prevents the film of rear system result in blockage or damage.
Described mechanical filter adopts vertical mechanical strainer, and filtrate is selected quartz sand, has unique water distribution uniformity mode, makes strainer reach maximum efficiency, can meet for a long time effluent quality requirement.
It is the filler particles scratching film surface that prevents leakage that described secondary filter adopts the effect of accurate filter, and filtering accuracy is 5 μ m, and filter core is PP cotton or wire-wound filter core.
3, the process spent water after filtration adds alkali adjusting pH value to 9.5, then enters one-level low-pressure membrane (one-level A), is separated into one-level A fresh water and the dense water of one-level A, and the dense water of one-level A enters the concentrated film (one-level B) of one-level, is separated into one-level B fresh water and the dense water of one-level B.Remove most of phenols in sewage by one-level film, the effect that one-level film entrance adds alkali has two, and one is to prevent that sewage from causing dirty blocking up to film, and another is to be more conducive to removing of phenols.
4, one-level A fresh water and one-level B fresh water enter secondary film after merging, and further remove phenols, are separated into the dense water of secondary fresh water and secondary, and secondary concentrate recirculation is to one-level low-pressure membrane entrance.
5, secondary fresh water adds acid for adjusting pH value to 6.5, then enters three grades of film removal of ammonia and nitrogen, is separated into final fresh water and three grades of dense water.The effect of acid adding is for the free ammonia in water is converted into ammonium ion, thereby removes.
One-level low-pressure membrane and one-level concentrate HL8040 film or the ESNA1-K1 film of Hydranautics company product, the AD8040 film of secondary film, three grades of films employing GE products or the SWC film that Hydranautics company produces that film adopts GE company to produce.
Final fresh water index is as follows:
| Sequence number | Project | Numerical value | Sequence number | Project | Numerical value |
| 1 | pH | 6~8 | 7 | COD（mg/L） | 40 |
| 2 | Colourity | 10 | 8 | NH3-N（mg/L） | 5 |
| 3 | Electricity is led (μ s/cm) | <50 | 9 | SO 4 2-(mg/L) | <20 |
| 4 | Turbidity (mg/L) | Do not detect | 10 | Na +（mg/L） | <10 |
| 5 | Cl -（mg/L） | <10 | 11 | Suspended substance (mg/L) | Do not detect |
| 6 | Total hardness (mg/L) is (with CaCO 3Meter) | <20 | ? | ? | ? |
6, the dense water that membrane separation unit is discharged is for the preparation of coal water slurry, and final fresh water is back to coal water slurry ash water system.
7, when film cleans, adopt the alkali lye of NaOH preparation to carry out on-line cleaning, alkali lye pH value is controlled between 11 ~ 13.
Embodiment 2
As shown in Figure 1, membrane technique of the present invention is processed the method for crushed coal pressure gasifying process spent water, and concrete implementation step is as follows:
1, as follows from the process spent water index of phenol ammonia recovery unit discharge:
CODcr:3500 ~ 4500 mg/l, phenols: 900-1200mg/L, NH3-N:150～250 mg/l, oils: 200 mg/l, temperature: 35 ~ 45 DEG C, pH value: 7.0 ~ 9.5.
2, process spent water is first removed mechanical impurity through mechanical filter and secondary filter, prevents the film of rear system result in blockage or damage.
Described mechanical filter adopts vertical mechanical strainer, and filtrate is selected quartz sand, has unique water distribution uniformity mode, makes strainer reach maximum efficiency, can meet for a long time effluent quality requirement.
It is the filler particles scratching film surface that prevents leakage that described secondary filter adopts the effect of accurate filter, and filtering accuracy is 5 μ m, and filter core is PP cotton or wire-wound filter core.
3, the process spent water after filtration adds alkali adjusting pH value to 9.0, then enters one-level low-pressure membrane (one-level A), is separated into one-level A fresh water and the dense water of one-level A, and the dense water of one-level A enters the concentrated film (one-level B) of one-level, is separated into one-level B fresh water and the dense water of one-level B.Remove most of phenols in sewage by one-level film, the effect that one-level film entrance adds alkali has two, and one is to prevent that sewage from causing dirty blocking up to film, and another is to be more conducive to removing of phenols.
4, one-level A fresh water and one-level B fresh water enter secondary film after merging, and further remove phenols, are separated into the dense water of secondary fresh water and secondary, and secondary concentrate recirculation is to one-level low-pressure membrane entrance.
5, secondary fresh water adds acid for adjusting pH value to 6.0, then enters three grades of film removal of ammonia and nitrogen, is separated into final fresh water and three grades of dense water.The effect of acid adding is for the free ammonia in water is converted into ammonium ion, thereby removes.
One-level low-pressure membrane and one-level concentrate HL8040 film or the ESNA1-K1 film of Hydranautics company product, the AD8040 film of secondary film, three grades of films employing GE products or the SWC film that Hydranautics company produces that film adopts GE company to produce.
Final fresh water index is as follows:
| Sequence number | Project | Numerical value | Sequence number | Project | Numerical value |
| 1 | pH | 6~8 | 7 | COD（mg/L） | 40 |
| 2 | Colourity | 10 | 8 | NH3-N（mg/L） | 5 |
| 3 | Electricity is led (μ s/cm) | <50 | 9 | SO 4 2-(mg/L) | <20 |
| 4 | Turbidity (mg/L) | Do not detect | 10 | Na +（mg/L） | <10 |
| 5 | Cl -（mg/L） | <10 | 11 | Suspended substance (mg/L) | Do not detect |
| 6 | Total hardness (mg/L) is (with CaCO 3Meter) | <20 | ? | ? | ? |
8, the dense water that membrane separation unit is discharged is for the preparation of coal water slurry, and final fresh water is back to coal water slurry ash water system.
9, when film cleans, adopt the alkali lye of NaOH preparation to carry out on-line cleaning, alkali lye pH value is controlled between 11 ~ 13.
Embodiment 3
As shown in Figure 1, membrane technique of the present invention is processed the method for crushed coal pressure gasifying process spent water, and concrete implementation step is as follows:
1, as follows from the process spent water index of phenol ammonia recovery unit discharge:
CODcr:3500 ~ 4500 mg/l, phenols: 900-1200mg/L, NH3-N:150～250 mg/l, oils: 200 mg/l, temperature: 35 ~ 45 DEG C, pH value: 7.0 ~ 9.5.
2, process spent water is first removed mechanical impurity through mechanical filter and secondary filter, prevents the film of rear system result in blockage or damage.
Described mechanical filter adopts vertical mechanical strainer, and filtrate is selected quartz sand, has unique water distribution uniformity mode, makes strainer reach maximum efficiency, can meet for a long time effluent quality requirement.
It is the filler particles scratching film surface that prevents leakage that described secondary filter adopts the effect of accurate filter, and filtering accuracy is 5 μ m, and filter core is PP cotton or wire-wound filter core.
3, the process spent water after filtration adds alkali adjusting pH value to 10.5, then enters one-level low-pressure membrane (one-level A), is separated into one-level A fresh water and the dense water of one-level A, and the dense water of one-level A enters the concentrated film (one-level B) of one-level, is separated into one-level B fresh water and the dense water of one-level B.Remove most of phenols in sewage by one-level film, the effect that one-level film entrance adds alkali has two, and one is to prevent that sewage from causing dirty blocking up to film, and another is to be more conducive to removing of phenols.
4, one-level A fresh water and one-level B fresh water enter secondary film after merging, and further remove phenols, are separated into the dense water of secondary fresh water and secondary, and secondary concentrate recirculation is to one-level low-pressure membrane entrance.
5, secondary fresh water adds acid for adjusting pH value to 8.0, then enters three grades of film removal of ammonia and nitrogen, is separated into final fresh water and three grades of dense water.The effect of acid adding is for the free ammonia in water is converted into ammonium ion, thereby removes.
One-level low-pressure membrane and one-level concentrate HL8040 film or the ESNA1-K1 film of Hydranautics company product, the AD8040 film of secondary film, three grades of films employing GE products or the SWC film that Hydranautics company produces that film adopts GE company to produce.
Final fresh water index is as follows:
| Sequence number | Project | Numerical value | Sequence number | Project | Numerical value |
| 1 | pH | 6~8 | 7 | COD（mg/L） | 40 |
| 2 | Colourity | 10 | 8 | NH3-N（mg/L） | 5 |
| 3 | Electricity is led (μ s/cm) | <50 | 9 | SO 4 2-(mg/L) | <20 |
| 4 | Turbidity (mg/L) | Do not detect | 10 | Na +（mg/L） | <10 |
| 5 | Cl -（mg/L） | <10 | 11 | Suspended substance (mg/L) | Do not detect |
| 6 | Total hardness (mg/L) is (with CaCO 3Meter) | <20 | ? | ? | ? |
10, the dense water that membrane separation unit is discharged is for the preparation of coal water slurry, and final fresh water is back to coal water slurry ash water system.
11, when film cleans, adopt the alkali lye of NaOH preparation to carry out on-line cleaning, alkali lye pH value is controlled between 11 ~ 13.
Claims (3)
1. membrane technique is processed a method for crushed coal pressure gasifying process spent water, it is characterized in that comprising the steps:
First remove mechanical impurity through mechanical filter and secondary filter from the process spent water of phenol ammonia recovery unit discharge, prevent film result in blockage or damage;
Process spent water after filtration adds alkali and regulates pH value to 9 ~ 10.5, makes the phenols in sewage form phenol negative oxygen ion, prevents film to cause dirty blocking up, and then removes most phenols and other organism in sewage by two to three grades of film systems;
The fresh water that step (2) is discharged adds acid for adjusting pH to 6 ~ 8, makes free ammonia form ammonium salt, removes the most ammonia nitrogens in sewage by final stage film.
2. membrane technique according to claim 1 is processed the method for crushed coal pressure gasifying process spent water, it is characterized in that: the film adopting in step (2) is reverse osmosis membrane or nanofiltration membrane.
3. membrane technique according to claim 1 is processed the method for crushed coal pressure gasifying process spent water, it is characterized in that: described mechanical filter adopts vertical mechanical strainer, and filtrate is selected quartz sand.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860467A (en) * | 2015-05-27 | 2015-08-26 | 张世文 | Method for recycling coal tar, ammonia and phenol in semi-coke wastewater |
| CN105836964A (en) * | 2016-03-31 | 2016-08-10 | 煤科集团杭州环保研究院有限公司 | Biological treatment system and method for fixed-bed gasification waste water |
| CN117865420A (en) * | 2024-03-11 | 2024-04-12 | 中天合创能源有限责任公司 | Equipment and method for treating ammonia nitrogen in sewage of coal chemical gasification process by membrane technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238670A (en) * | 2006-03-06 | 2007-09-20 | Mitsubishi Heavy Ind Ltd | Gas purifying equipment and process, gasification system, and gasification/power generation system |
| CN103204602A (en) * | 2012-01-11 | 2013-07-17 | 中国海洋石油总公司 | Coal gasification wastewater processing method |
| CN103288308A (en) * | 2013-07-01 | 2013-09-11 | 大唐国际化工技术研究院有限公司 | Slack coal pressure gasification wastewater recycling treatment method and treatment system as well as application |
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2014
- 2014-03-05 CN CN201410078008.XA patent/CN103936186B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238670A (en) * | 2006-03-06 | 2007-09-20 | Mitsubishi Heavy Ind Ltd | Gas purifying equipment and process, gasification system, and gasification/power generation system |
| CN103204602A (en) * | 2012-01-11 | 2013-07-17 | 中国海洋石油总公司 | Coal gasification wastewater processing method |
| CN103288308A (en) * | 2013-07-01 | 2013-09-11 | 大唐国际化工技术研究院有限公司 | Slack coal pressure gasification wastewater recycling treatment method and treatment system as well as application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104860467A (en) * | 2015-05-27 | 2015-08-26 | 张世文 | Method for recycling coal tar, ammonia and phenol in semi-coke wastewater |
| CN105836964A (en) * | 2016-03-31 | 2016-08-10 | 煤科集团杭州环保研究院有限公司 | Biological treatment system and method for fixed-bed gasification waste water |
| CN105836964B (en) * | 2016-03-31 | 2018-08-17 | 煤科集团杭州环保研究院有限公司 | A kind of fixed bed gasification biological treatment of waste water system and method |
| CN117865420A (en) * | 2024-03-11 | 2024-04-12 | 中天合创能源有限责任公司 | Equipment and method for treating ammonia nitrogen in sewage of coal chemical gasification process by membrane technology |
| CN117865420B (en) * | 2024-03-11 | 2024-05-10 | 中天合创能源有限责任公司 | Equipment and method for treating ammonia nitrogen in sewage of coal chemical gasification process by membrane technology |
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