CN107445374A - A kind of improvement handling process of MTO alkali cleanings spent lye - Google Patents
A kind of improvement handling process of MTO alkali cleanings spent lye Download PDFInfo
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- CN107445374A CN107445374A CN201610377879.0A CN201610377879A CN107445374A CN 107445374 A CN107445374 A CN 107445374A CN 201610377879 A CN201610377879 A CN 201610377879A CN 107445374 A CN107445374 A CN 107445374A
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- spent lye
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The present invention provides a kind of improvement handling process of MTO alkali cleanings spent lye, and the improvement handling process comprises the following steps：(1) oil wash deaerates：MTO spent lyes are washed using washing oil, it is preliminary to remove entrained oil class in spent lye, reduced pressure treatment is carried out afterwards, its pressure is reduced to 0.15MPaG~flare pressure；(2) storage tank is stood：By the spent lye after preliminary removing oils and reduced pressure treatment, stop standing is carried out in storage tank, oil slick is further removed after profit layering；(3) neutralize：Inorganic acid is added into the spent lye after stewing process, it is 79 to control pH value；(4) air lift organic matter：By the spent lye after neutralization, air lift is carried out in air lift Tower System, removes the organic matter being dissolved in spent lye.After present invention process is handled, COD clearances can reach more than 92%；The organic oxygen compound that sewage plant is difficult to degrade is removed to below 20mg/l, can meet traditional wastewater processing requirement.
Description
Technical field
The present invention relates to petrochemical wastewater process field, is given up more particularly, to a kind of MTO alkali cleanings
The improvement handling process of alkali lye.
Background technology
Contain CO in MTO device product gas2Deng sour gas, technological process requirement is by product gas
CO2It is removed to 10-6(VOL) below.Current widely used setting caustic wash tower, passes through NaOH solution
The method of cleaning product gas removes CO2.In washing process, with NaOH chemistry occurs for sour gas
React and remove, while produce spent lye.
From ethylene unit caused by spent lye it is different, not sulfur-bearing in MTO spent lyes, but contain diformazan
The organic oxygen compounds such as ether, methanol.The presence of organic matter can cause spent lye COD very high, and rear
In continuous processing procedure, such organic oxygen compound of degrading is difficult to using traditional biochemical sewage processing, to dress
Put operation and bring very big environmental protection pressure.If the organic matter in spent lye can be removed to reduce COD,
It then can directly neutralize the sewage plant processing of Hou Songquan factories.
At present, the processing method of domestic spent lye (slag) mainly includes burning method, neutralisation, oxidation
Method and the major class of biological treatment four.
Burning method belongs to direct facture, organic matter is generated CO under high temperature and normal pressure2And H2O,
NaOH changes into Na2CO3, sulfate and carbonate are remained dissolved in treated waste liquid.The method
It is a kind of feasible processing method, it is simple to operate.Its shortcoming is that energy consumption is big, and running cost is high；Meanwhile
The sodium carbonate that burning is formed at high temperature can be serious to refractory corrosion in stove, also easily in fast cooling device
With fouling in pipeline.This method needs to set up a whole set of complicated fume treatment flow, to meet flue gas
Qualified discharge requirement.Therefore, the use of burning method is restricted.
Neutralisation is with concentrated sulfuric acid neutralisation and CO2Neutralisation is representative.Sulfuric acid disappears in concentrated sulfuric acid neutralisation
Consumption is big, and financial cost is high, serious to equipment corrosion.CO2Neutralisation needs stable CO2Gas
Source, general petrochemical plant are not easy to provide.
Oxidizing process includes wet oxidation (WAO) and CWO (CWAO)；MTO salkali waste
Not sulfur-bearing in liquid, therefore, when handling MTO spent lyes, WAO and CWAO are inapplicable.
Biological treatment is with QBR (Quick Bioreactor) high-concentration sewage disposal technologies and South Korea SK
Biological reinforcing technology is representative, is a kind of biological oxidation technology.Biological treatment inevitably has
Have that long flow path, floor space are big, treatment effeciency is low, operating cost (needing regular replenishment strain) is higher
The shortcomings of, the application of bioanalysis is limited to a certain extent.Meanwhile one can be produced using bioanalysis
Quantitative sludge, the processing to sludge are also increasingly restricted.
To sum up analyze, for MTO spent lyes, current various processing methods exist it is inapplicable,
The problems such as investment is big, operating cost is high, efficiency is low.
The content of the invention
It is an object of the invention to provide a kind of improvement handling process of MTO alkali cleanings spent lye, for MTO
Spent lye not sulfur-bearing, content of organics is high, causes simultaneously containing organic oxygen compounds such as dimethyl ether, methanol
COD it is high the features such as, efficiently reduce MTO spent lyes in COD, reclaim spent lye in it is valuable
Hydro carbons, realize low cost, the efficient process of MTO spent lyes.
To achieve these goals, the present invention provides a kind of improvement processing work of MTO alkali cleanings spent lye
Skill, the improvement handling process comprise the following steps：
(1) oil wash deaerates：MTO spent lyes are washed using washing oil, tentatively remove spent lye
Middle entrained oil class；Reduced pressure treatment is carried out to the spent lye after oil wash, reduces to its pressure
0.15MPaG~flare pressure；
(2) storage tank is stood：By the spent lye after preliminary removing oils and reduced pressure treatment, enter in storage tank
Row, which stops, to be stood, and oil slick is further removed after profit layering；
(3) neutralize：Inorganic acid is added into the spent lye after stewing process, it is 7-9 to control pH value；
(4) air lift organic matter：By the spent lye after neutralization, air lift is carried out in air lift Tower System,
Remove the organic matter being dissolved in spent lye.
In step (1), described oil wash is directed to inject washing oil in spent lye, utilizes washing oil and salkali waste
Liquid tentatively dissolves into the oils in spent lye to being present in the different solubility of the oils in spent lye
In washing oil, by stratification, washing oil and spent lye are separated, reach the purpose of spent lye de-oiling.
According to improvement handling process provided by the invention, it is preferable that in step (1), the washing oil be containing
The gasoline of benzene.
Spent lye comes from caustic wash tower, and pressure is about 0.5-1.8MPaG, at improvement provided by the invention
Science and engineering skill, it is preferable that in step (1), reduced pressure treatment is carried out to the spent lye after oil wash, makes it
Pressure reduces to 0.08MPaG~flare pressure (about 0.05MPaG).Pressure reduces, and hydro carbons is in spent lye
In solubility reduce, the gaseous hydrocarbons of dissolving can be removed, while annoying propose a small amount of organic oxygen
Compound.Deaerated by oil wash, the content of organics in spent lye can be reduced by about 6000-10000mg/l
To about 2000-4500mg/l.
In step (2), spent lye needs to stand in storage tank stops time enough, is layered profit
So as to remove free oils.The standing residence time except considering profit layering, it is also necessary to consider
The buffer time of operational load fluctuation and the waste alkali liquor treatment device maintenance of MTO agent sets.According to
Improvement handling process provided by the invention, it is preferable that in step (2), spent lye is in storage tank
It is 5-10 days to stop time of repose.
In order that oil particulates small in spent lye are fully gathered into compared with larger oil droplet, to ensure deoiling effect,
According to improvement handling process provided by the invention, it is preferable that in step (2), spent lye is in storage tank
Free oils is further removed by coalescer after middle water-oil separating.
In step (3), inorganic acid is added into the spent lye after stewing process；There is provided according to the present invention
Improvement handling process, it is preferable that in step (3), the inorganic acid be selected from sulfuric acid, hydrochloric acid and
One or more in nitric acid；More preferably sulfuric acid.
According to improvement handling process provided by the invention, it is preferable that in step (3), control PH
It is worth for 7-7.5.Need to take into full account the etching problem that acid-base neutralization is common in the step, reduce PH ripples
It is dynamic.Simultaneously in view of carrying out the possible high temperature of stripping step in next step, carbon steel can be used by reducing pH value
Material.
Step (4) is the core procedure of the present invention, is the key for ensureing spent lye COD removal effects.
By step (1) and (2), the oil content to dissociate in spent lye is down to 50-100mg/l, but molten
Organic matter of the solution in spent lye, including hydro carbons and organic oxygen compound, its content still exist
3000-4000mg/l。
After neutralisation treatment, close to neutrality, the corrosion to equipment reduces, entered the pH value of spent lye
And relax the process condition of subsequent treatment.By setting air lift Tower System, further removing is useless
Organic matter in alkali lye.According to improvement handling process provided by the invention, it is preferable that in step (4)
In, the operating pressure of air lift Tower System is 0.05-0.3MPaG, and operation temperature is 50-150 DEG C.The gas
Content of organics can be removed to below 300-500mg/l by stripper system；Particularly oxygen-containing organic closes
Thing, such as dimethyl ether, are removed to below 10mg/l, reach spent lye into the processing of full factory's sewage plant
Content requirement.While the air lift Tower System ensures organic matter, particularly oxygen-bearing organic matter removal effect,
Coking and the material corrosion problem of system are taken into full account.Work is handled according to provided by the invention improve
Skill, it is preferable that in step (4), the stripping medium in air lift Tower System is steam, methane or nitrogen
Gas；More preferably steam.
The beneficial effect that technical scheme is brought is：
1st, for MTO spent lyes the characteristics of, after present invention process is handled, COD clearances can
To reach more than 92%；The organic oxygen compound that sewage plant is difficult to degrade is removed to below 20mg/l, can be with
Meet traditional wastewater processing requirement；
2nd, subsidiary conditions used in the present invention are common washing oil, steam, nitrogen etc., and regular chemical plant holds
Be easy to get to；Spent lye need not be burned, effectively controls energy consumption；
3rd, in present invention process, neutralisation treatment is arranged on before gas stripping process, delays process condition
With equipment and materials is carbon steel, and cost is relatively low.
Brief description of the drawings
Fig. 1 shows the improvement processing technological flow figure of MTO alkali cleaning spent lyes.
Label is described as follows in figure：
1- oil washes deaerate；2- storage tanks are stood；3- is neutralized；4- air lift organic matters.
Embodiment
The preferred embodiment of the present invention is more fully described below with reference to accompanying drawings.Although show in accompanying drawing
The preferred embodiment of the present invention is shown, however, it is to be appreciated that may be realized in various forms the present invention
Without should be limited by embodiments set forth herein.
Embodiment 1
The spent lye of one MTO caustic wash towers bottom discharge, wherein：COD is 8000mg/l, Na2CO3
Concentration is 7.6wt%, NaOH concentration 1.6wt%, and free oils is 250mg/l, methanol concentration
0.03mol%, dimethyl ether con 0.01mol%.
It is as follows using the processing technological flow figure shown in Fig. 1, the treatment process steps：
(1) oil wash deaerates：Using the difference of solubility, MTO spent lyes are washed using washing oil
Wash, by stratification, washing oil and spent lye are separated, it is preliminary to remove entrained oil in spent lye
Class；Reduced pressure treatment is carried out to the spent lye after oil wash, its pressure is reduced to by 1.4MPaG
0.05MPaG；Deaerated by oil wash, the content of organics of oil content and dissolving in spent lye reduces
To about 4000mg/l；
(2) storage tank is stood：By the spent lye after preliminary removing oils and reduced pressure treatment, enter in storage tank
Row, which stops, to be stood, and stop time of repose of the spent lye in storage tank is 6 days；After profit layering, lead to
Cross oil skimming and further remove oil slick；
(3) neutralize：Sulfuric acid is added into the spent lye after stewing process, it is 7-8 to control pH value；
(4) air lift organic matter：By the spent lye after neutralisation treatment, carried out in air lift Tower System
Steam air lift, the operating pressure for controlling air lift Tower System are 0.19MPaG, and operation temperature is 133 DEG C and removed
Remove to be dissolved in the organic matter in spent lye, content of organics is removed to below 500mg/l, wherein dimethyl ether
Below 10mg/l is removed to, COD is below 400mg/l.
Embodiment 2
The spent lye of one MTO caustic wash towers bottom discharge, wherein：COD is 15000mg/l, Na2CO3
Concentration is 6.7wt%, NaOH concentration 1.5wt%, free oil 1000mg/l, methanol concentration
0.04mol%, dimethyl ether con 0.02mol%.
It is as follows using the processing technological flow figure shown in Fig. 1, the treatment process steps：
(1) oil wash deaerates：Using the difference of solubility, MTO spent lyes are washed using washing oil
Wash, by stratification, washing oil and spent lye are separated, it is preliminary to remove entrained oil in spent lye
Class；Reduced pressure treatment is carried out to the spent lye after oil wash, its pressure is reduced to by 1.3MPaG
0.05MPaG；Deaerated by oil wash, the content of organics of oil content and dissolving in spent lye reduces
To about 4000mg/l；
(2) storage tank is stood：By the spent lye after preliminary removing oils and reduced pressure treatment, enter in storage tank
Row, which stops, to be stood, and stop time of repose of the spent lye in storage tank is 8 days；After profit layering, lead to
Cross oil skimming and further remove oil slick；
(3) neutralize：Sulfuric acid is added into the spent lye after stewing process, it is 7-7.5 to control pH value；
(4) air lift organic matter：By the spent lye after neutralisation treatment, carried out in air lift Tower System
Steam air lift, the operating pressure for controlling air lift Tower System are 0.15MPaG, and operation temperature is 130 DEG C and removed
Remove to be dissolved in the organic matter in spent lye, content of organics is removed to below 500mg/l, wherein dimethyl ether
Below 10mg/l is removed to, COD is below 450mg/l.
Embodiment 3
The spent lye of one MTO caustic wash towers bottom discharge, wherein：COD is 8000mg/l, Na2CO3
Concentration is 7.6wt%, NaOH concentration 1.6wt%, and free oils is 250mg/l, methanol concentration
0.03mol%, dimethyl ether con 0.01mol%.
It is as follows using the processing technological flow figure shown in Fig. 1, the treatment process steps：
(1) oil wash deaerates：Using the difference of solubility, MTO spent lyes are washed using washing oil
Wash, by stratification, washing oil and spent lye are separated, it is preliminary to remove entrained oil in spent lye
Class；Reduced pressure treatment is carried out to the spent lye after oil wash, its pressure is reduced to by 1.4MPaG
0.15MPaG；Deaerated by oil wash, the content of organics of oil content and dissolving in spent lye reduces
To about 6100mg/l；
(2) storage tank is stood：By the spent lye after preliminary removing oils and reduced pressure treatment, enter in storage tank
Row, which stops, to be stood, and stop time of repose of the spent lye in storage tank is 6 days；After profit layering, lead to
Cross oil skimming and further remove oil slick；
(3) neutralize：Sulfuric acid is added into the spent lye after stewing process, it is 8-9 to control pH value；
(4) air lift organic matter：By the spent lye after neutralisation treatment, carried out in air lift Tower System
Steam air lift, the operating pressure for controlling air lift Tower System are 0.06MPaG, and operation temperature is 120 DEG C and removed
Remove to be dissolved in the organic matter in spent lye, content of organics is removed to below 550mg/l, wherein dimethyl ether
Below 10mg/l is removed to, COD is below 450mg/l.
Comparative example 1
The spent lye of one MTO caustic wash towers bottom discharge, wherein：COD is 8000mg/l, Na2CO3
Concentration is 7.6wt%, NaOH concentration 1.6wt%, and free oils is 250mg/l, methanol concentration
0.03mol%, dimethyl ether con 0.01mol%.
It is as follows using the processing technological flow figure shown in Fig. 1, the treatment process steps：
(1) oil wash deaerates：Using the difference of solubility, MTO spent lyes are washed using washing oil
Wash, by stratification, washing oil and spent lye are separated, it is preliminary to remove entrained oil in spent lye
Class；Reduced pressure treatment is carried out to the spent lye after oil wash, its pressure is reduced to by 1.4MPaG
0.05MPaG；Deaerated by oil wash, the content of organics of oil content and dissolving in spent lye reduces
To about 4000mg/l；
(2) storage tank is stood：By the spent lye after preliminary removing oils and reduced pressure treatment, enter in storage tank
Row, which stops, to be stood, and stop time of repose of the spent lye in storage tank is 6 days；After profit layering, lead to
Cross oil skimming and remove oil slick；
(3) neutralize：Sulfuric acid is added into the spent lye after stewing process, it is 7-8 to control pH value；
The spent lye of comparative example 1 is handled according to the handling process of embodiment 1, unlike, it is not provided with
Stripping step, after processing, content of organics is only removed to 4000mg/l, and diformazan ether content does not reduce.
Various embodiments of the present invention are described above, described above is exemplary, and exhaustive
Property, and it is also not necessarily limited to disclosed each embodiment.In the model without departing from illustrated each embodiment
Enclose and spirit in the case of, many modifications and changes for those skilled in the art
It will be apparent from.
Claims (10)
1. a kind of improvement handling process of MTO alkali cleanings spent lye, it is characterised in that the improvement is handled
Technique comprises the following steps：
(1) oil wash deaerates：MTO spent lyes are washed using washing oil, tentatively remove spent lye
Middle entrained oil class；Reduced pressure treatment is carried out to the spent lye after oil wash, reduces to its pressure
0.15MPaG~flare pressure；
(2) storage tank is stood：By the spent lye after preliminary removing oils and reduced pressure treatment, enter in storage tank
Row, which stops, to be stood, and oil slick is further removed after profit layering；
(3) neutralize：Inorganic acid is added into the spent lye after stewing process, it is 7-9 to control pH value；
(4) air lift organic matter：By the spent lye after neutralization, enter promoting the circulation of qi in air lift Tower System
Carry, remove the organic matter being dissolved in spent lye.
2. the improvement handling process of MTO alkali cleanings spent lye according to claim 1, wherein,
In step (4), the operating pressure of air lift Tower System is 0.05-0.3MPaG, and operation temperature is
50-150℃。
3. the improvement handling process of MTO alkali cleanings spent lye according to claim 1, wherein,
In step (4), the stripping medium in air lift Tower System is steam, methane or nitrogen；Preferably steam
Vapour.
4. the improvement handling process of MTO alkali cleanings spent lye according to claim 1, wherein,
In step (2), spent lye is further removed by coalescer free in storage tank after water-oil separating
Oils.
5. the improvement handling process of MTO alkali cleanings spent lye according to claim 1, wherein,
In step (2), stop time of repose of the spent lye in storage tank is 5-10 days.
6. the improvement processing work of the MTO alkali cleaning spent lyes according to any one of claim 1-5
Skill, wherein, in step (1), reduced pressure treatment is carried out to the spent lye after oil wash, subtracts its pressure
To 0.08MPaG~flare pressure.
7. the improvement processing work of the MTO alkali cleaning spent lyes according to any one of claim 1-5
Skill, wherein, in step (1), the washing oil is the gasoline containing benzene.
8. the improvement processing work of the MTO alkali cleaning spent lyes according to any one of claim 1-5
Skill, wherein, in step (3), one kind in sulfuric acid, hydrochloric acid and nitric acid of the inorganic acid or
It is a variety of.
9. the improvement handling process of MTO alkali cleanings spent lye according to claim 8, wherein,
In step (3), the inorganic acid is sulfuric acid.
10. the improvement processing work of the MTO alkali cleaning spent lyes according to any one of claim 1-5
Skill, wherein, in step (3), it is 7-7.5 to control pH value.
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| CN201610377879.0A CN107445374B (en) | 2016-05-31 | 2016-05-31 | Improved treatment process of MTO alkaline washing waste alkali liquor |
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| CN201610377879.0A CN107445374B (en) | 2016-05-31 | 2016-05-31 | Improved treatment process of MTO alkaline washing waste alkali liquor |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730894A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Method for treating waste alkaline liquor produced in butanol and octanol production device |
| CN202497742U (en) * | 2012-03-02 | 2012-10-24 | 江苏克莱斯克能源装备有限公司 | Waste alkali oil-water separating coalescer |
| CN105217830A (en) * | 2014-06-25 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of method for oxidation of methanol-to-olefins waste lye |
-
2016
- 2016-05-31 CN CN201610377879.0A patent/CN107445374B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730894A (en) * | 2011-04-15 | 2012-10-17 | 中国石油化工股份有限公司 | Method for treating waste alkaline liquor produced in butanol and octanol production device |
| CN202497742U (en) * | 2012-03-02 | 2012-10-24 | 江苏克莱斯克能源装备有限公司 | Waste alkali oil-water separating coalescer |
| CN105217830A (en) * | 2014-06-25 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of method for oxidation of methanol-to-olefins waste lye |
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