CN103936186B - The method of membrane technique process crushed coal pressure gasifying process spent water - Google Patents
The method of membrane technique process crushed coal pressure gasifying process spent water Download PDFInfo
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- CN103936186B CN103936186B CN201410078008.XA CN201410078008A CN103936186B CN 103936186 B CN103936186 B CN 103936186B CN 201410078008 A CN201410078008 A CN 201410078008A CN 103936186 B CN103936186 B CN 103936186B
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Abstract
The present invention discloses a kind of method of membrane technique process crushed coal pressure gasifying process spent water, comprising: the process spent water that (1) discharges from phenol ammonia recovery unit first removes mechanical impurity through mechanical filter and secondary filter, prevents from resulting in blockage to film or damaging; (2) process spent water after filtering adds alkali adjust ph to 9 ~ 10.5, makes the phenols in sewage form phenol negative oxygen ion, prevents from causing dirty blocking up to film, then removes most phenols and other organism in sewage by two to three grades of membranous system; (3) fresh water that step (2) is discharged adds acid for adjusting pH to 6 ~ 8, makes free ammonia form ammonium salt, is removed the most ammonia nitrogens in sewage by final stage film.The present invention effectively can solve the problem that high-concentration phenolic wastewater biochemical treatment difficulty is large, investment is large, running cost is high produced in crushed coal pressure gasifying process.
Description
Technical field
The invention belongs to sewage treatment area, be specifically related to membrane technique 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, when gasifying young coal, 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 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, the process spent water of discharging afterwards through biochemical treatment, then qualified discharge.Biochemical treatment crushed coal pressure gasifying process spent water, through to put into practice for many years and improve, 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 during fluctuation of load, and time of recovery is longer, enterprise's continuous seepage is made a big impact.Adopt biochemical treatment in addition, the phenols in sewage and organism, by biochemical decomposition, can not be recycled.
Present method adopts embrane method process crushed coal pressure gasifying process spent water, at home and abroad belongs to and proposes first, and its investment and running cost are all lower than biochemical processing process, and phenols in recoverable sewage and other organism.
Summary of the invention
The object of this invention is to provide a kind of method of membrane technique process crushed coal pressure gasifying process spent water,
For achieving the above object, the technical solution used in the present invention is as follows:
The method of membrane technique process crushed coal pressure gasifying process spent water of the present invention, 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 from resulting in blockage to film or damaging;
(2) process spent water after filtering adds alkali adjust ph to 9 ~ 10.5, makes the phenols in sewage form phenol negative oxygen ion, prevents from causing dirty blocking up to film, then removes most phenols and other organism in sewage by two to three grades of membranous system;
(3) fresh water that step (2) is discharged adds acid for adjusting pH to 6 ~ 8, makes free ammonia form ammonium salt, is removed the most ammonia nitrogens in sewage by final stage film.
The film adopted in step (2) is reverse osmosis membrane or nanofiltration membrane.
Described mechanical filter adopts vertical mechanical strainer, and quartz sand selected by filtrate, has unique water distribution uniformity mode, makes strainer reach maximum efficiency, can meet effluent quality requirement for a long time.
Described secondary filter adopts the effect of accurate filter to be the filler particles scratching film surface preventing from revealing, and filtering accuracy is 5 μm, 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 be separated to level Four membranous system by three, remove phenols wherein and ammonia, produce fresh water and carry out reuse, dense water cycle is to phenol ammonia recovery unit entrance or for the preparation of coal water slurry.
Face maximum problem with membrane technique process crushed coal pressure gasifying process spent water and be that the low-pole organism in waste water is easily adsorbed on film, cause dirty stifled to film, make Membrane cleaning too frequent, device cannot steady running have a strong impact on life-span of film.Show the analysis of crushed coal pressure gasifying sewage composition, organism is wherein various unit phenol and polyphenol mainly, and phenols is slightly acidic, exists, with phenol negative oxygen ion (RO under alkaline environment under sour environment with phenolic hydroxyl group (ROH) form
-) form existence.The present invention utilizes this character, and add the pH value that alkali regulates sewage in the ingress of one-level film, make the phenols negative ionization in sewage, polarity specific ionization phenol significantly strengthens, and greatly reduces the adsorption to film, thus the dirt that effectively prevent film is blocked up.But because one-level film ingress adds alkali, the ammonia in sewage exists with free ammonia form, and the removal effect of film to small molecules free ammonia is very poor, 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 is removed, and now acid adding reduces pH value again, can not cause dirty stifled to film.
The invention discloses the method for membrane technique process crushed coal pressure gasifying process spent water, effectively can solve the problem that high-concentration phenolic wastewater biochemical treatment difficulty is large, investment is large, running cost is high produced in crushed coal pressure gasifying process.Crushed coal pressure gasifying process spent water is first through gas liquor tripping device and phenol ammonia recovery unit, reclaim wherein after most of tar, middle oil, crude phenols and ammonia, again through mechanical filter and secondary filter, then be separated to level Four membranous system by three, remove phenols wherein and ammonia, produce fresh water and can be back to circulating water system or other user, dense water cycle is to phenol ammonia recovery unit entrance or for the preparation of coal water slurry.Embrane method process crushed coal pressure gasifying process spent water has the advantage that investment is little, running cost is low.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
Embodiment
Embodiment 1
As shown in Figure 1, the method for membrane technique process crushed coal pressure gasifying process spent water of the present invention, 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 through mechanical filter and secondary filter removing mechanical impurity, prevents from resulting in blockage to the film of rear system or damaging.
Described mechanical filter adopts vertical mechanical strainer, and quartz sand selected by filtrate, has unique water distribution uniformity mode, makes strainer reach maximum efficiency, can meet effluent quality requirement for a long time.
Described secondary filter adopts the effect of accurate filter to be the filler particles scratching film surface preventing from revealing, and filtering accuracy is 5 μm, and filter core is PP cotton or Wire-wound filter core.
3, the process spent water after filtering adds alkali adjust ph to 9.5, and then enter one-level low-pressure membrane (one-level A), be separated into one-level A fresh water and the dense water of one-level A, the dense water of one-level A enters primary concentration film (one-level B), 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 prevent sewage from causing dirty blocking up to film, and another is more conducive to removing of phenols.
4, one-level A fresh water and one-level B fresh water enter secondary membrane after merging, and remove phenols further, be separated into secondary fresh water and the dense water of secondary, 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 in order to the free ammonia in water is converted into ammonium ion, thus removes.
The HL8040 film that one-level low-pressure membrane and primary concentration film adopt GE company to produce or the ESNA1-K1 film that Hydranautics company produces, the SWC film that secondary membrane, three grades of films adopt the AD8040 film of GE product or Hydranautics 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 | Conductance (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 of membrane separation unit discharge is for the preparation of coal water slurry, and final fresh water is back to coal water slurry ash water system.
7, adopt the alkali lye of NaOH preparation to carry out on-line cleaning during Membrane cleaning, alkali lye pH value controls between 11 ~ 13.
Embodiment 2
As shown in Figure 1, the method for membrane technique process crushed coal pressure gasifying process spent water of the present invention, 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 through mechanical filter and secondary filter removing mechanical impurity, prevents from resulting in blockage to the film of rear system or damaging.
Described mechanical filter adopts vertical mechanical strainer, and quartz sand selected by filtrate, has unique water distribution uniformity mode, makes strainer reach maximum efficiency, can meet effluent quality requirement for a long time.
Described secondary filter adopts the effect of accurate filter to be the filler particles scratching film surface preventing from revealing, and filtering accuracy is 5 μm, and filter core is PP cotton or Wire-wound filter core.
3, the process spent water after filtering adds alkali adjust ph to 9.0, and then enter one-level low-pressure membrane (one-level A), be separated into one-level A fresh water and the dense water of one-level A, the dense water of one-level A enters primary concentration film (one-level B), 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 prevent sewage from causing dirty blocking up to film, and another is more conducive to removing of phenols.
4, one-level A fresh water and one-level B fresh water enter secondary membrane after merging, and remove phenols further, be separated into secondary fresh water and the dense water of secondary, 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 in order to the free ammonia in water is converted into ammonium ion, thus removes.
The HL8040 film that one-level low-pressure membrane and primary concentration film adopt GE company to produce or the ESNA1-K1 film that Hydranautics company produces, the SWC film that secondary membrane, three grades of films adopt the AD8040 film of GE product or Hydranautics 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 | Conductance (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 of membrane separation unit discharge is for the preparation of coal water slurry, and final fresh water is back to coal water slurry ash water system.
9, adopt the alkali lye of NaOH preparation to carry out on-line cleaning during Membrane cleaning, alkali lye pH value controls between 11 ~ 13.
Embodiment 3
As shown in Figure 1, the method for membrane technique process crushed coal pressure gasifying process spent water of the present invention, 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 through mechanical filter and secondary filter removing mechanical impurity, prevents from resulting in blockage to the film of rear system or damaging.
Described mechanical filter adopts vertical mechanical strainer, and quartz sand selected by filtrate, has unique water distribution uniformity mode, makes strainer reach maximum efficiency, can meet effluent quality requirement for a long time.
Described secondary filter adopts the effect of accurate filter to be the filler particles scratching film surface preventing from revealing, and filtering accuracy is 5 μm, and filter core is PP cotton or Wire-wound filter core.
3, the process spent water after filtering adds alkali adjust ph to 10.5, and then enter one-level low-pressure membrane (one-level A), be separated into one-level A fresh water and the dense water of one-level A, the dense water of one-level A enters primary concentration film (one-level B), 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 prevent sewage from causing dirty blocking up to film, and another is more conducive to removing of phenols.
4, one-level A fresh water and one-level B fresh water enter secondary membrane after merging, and remove phenols further, be separated into secondary fresh water and the dense water of secondary, 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 in order to the free ammonia in water is converted into ammonium ion, thus removes.
The HL8040 film that one-level low-pressure membrane and primary concentration film adopt GE company to produce or the ESNA1-K1 film that Hydranautics company produces, the SWC film that secondary membrane, three grades of films adopt the AD8040 film of GE product or Hydranautics 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 | Conductance (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 of membrane separation unit discharge is for the preparation of coal water slurry, and final fresh water is back to coal water slurry ash water system.
11, adopt the alkali lye of NaOH preparation to carry out on-line cleaning during Membrane cleaning, alkali lye pH value controls between 11 ~ 13.
Claims (3)
1. a method for membrane technique process crushed coal pressure gasifying process spent water, is characterized in that comprising 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 from resulting in blockage to film or damaging;
(2) process spent water after filtering adds alkali adjust ph to 9 ~ 10.5, the phenols in sewage is made to form phenol negative oxygen ion, prevent from causing dirty blocking up to film, then one-level low-pressure membrane is entered, be separated into one-level A fresh water and the dense water of one-level A, the dense water of one-level A enters primary concentration film, is separated into one-level B fresh water and the dense water of one-level B; Most of phenols in sewage is removed by one-level film; Enter secondary membrane after one-level A fresh water and one-level B fresh water merge, remove phenols further, be separated into secondary fresh water and the dense water of secondary, secondary concentrate recirculation is to one-level low-pressure membrane entrance;
(3) fresh water that step (2) is discharged adds acid for adjusting pH to 6 ~ 8, makes free ammonia form ammonium salt, then enters three grades of film removal of ammonia and nitrogen, be separated into final fresh water and three grades of dense water.
2. the method for membrane technique process crushed coal pressure gasifying process spent water according to claim 1, is characterized in that: the film adopted in step (2) is reverse osmosis membrane or nanofiltration membrane.
3. the method for membrane technique process crushed coal pressure gasifying process spent water according to claim 1, is characterized in that: described mechanical filter adopts vertical mechanical strainer, and quartz sand selected by filtrate.
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| CN104860467A (en) * | 2015-05-27 | 2015-08-26 | 张世文 | Method for recycling coal tar, ammonia and phenol in semi-coke wastewater |
| 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 |
| 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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| 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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| JP2007238670A (en) * | 2006-03-06 | 2007-09-20 | Mitsubishi Heavy Ind Ltd | Gas purifying equipment and process, gasification system, and gasification/power generation system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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