CN106277428A - Freezing and crystallizing is utilized to remove and the method for sulfate in Propylene recovery nitrile waste water - Google Patents
Freezing and crystallizing is utilized to remove and the method for sulfate in Propylene recovery nitrile waste water Download PDFInfo
- Publication number
- CN106277428A CN106277428A CN201610640286.9A CN201610640286A CN106277428A CN 106277428 A CN106277428 A CN 106277428A CN 201610640286 A CN201610640286 A CN 201610640286A CN 106277428 A CN106277428 A CN 106277428A
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- Prior art keywords
- waste water
- sulfate
- freezing
- hollow fiber
- remove
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Classifications
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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
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/22—Treatment of water, waste water, or sewage by freezing
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
Abstract
Freezing and crystallizing is utilized to remove and the method for sulfate in Propylene recovery nitrile waste water, it is a feature of the present invention that, first in waste water, add NaOH, particle in waste water is removed in sand filtration, microfiltration and ultrafiltration and the molecular weight oligoacrylonitrile more than 30000, then delivered into the tube side of hydrophobic hollow fiber film by noncorrosive pump.In tube side during flowing, volatility NH3 in waste water occurs to neutralize reaction with H2SO4 absorbing liquid in the interface of film, generate nonvolatile (NH4) 2SO4 and be recovered, then waste water is rapidly frozen, make the high concentration sulfate crystallization in waste water, utilize high speed centrifuge to be separated.Mother solution returns or burning disposal, the crude sulphate of recovery through washing, the operation such as be dried and obtain refined salt.The method have easy and simple to handle, energy consumption is low, non-secondary pollution, recyclable with there being the advantages such as inorganic salt, be a kind of New Wastewater Treatment Technique efficient, economic, environment amenable.
Description
Technical field
The invention belongs to technical field of water pollution control, be related specifically to one and utilize freezing and crystallizing to remove acrylic nitrile waste water
The method of middle and high concentration sulfate.The method can change the high cost of current acrylic nitrile waste water to a certain extent and administer shape
Condition.
Background technology
Acrylonitrile (acrylonitrile is called for short AN), structural formula CH2=CH-CN, is that a kind of important organic chemical industry is former
Material, is widely used in many industrial circles such as synthetic fibers, synthesis chemistry and synthetic rubber.In recent years, along with under expoxy propane
The development of the aspects such as trip product acrylic fiber, ABS/AS, acrylamide, worldwide acrylonitrile demand is continuously increased.
The production technology of acrylonitrile is mainly propylene ammmoxidation process (Sohio method), and the method, with propylene, ammonia and air as raw material, is passed through
Fluidized-bed reaction, absorption, rectification etc. obtain product acrylonitrile.Owing in propylene ammmoxidation process, raw material is cheap and easy to get, technological process
Fairly simple, energy consumption is low, thus occupies leading position in the present age in process for production of acrylonitrile.
But, can discharge a large amount of containing high concentration cyanide, acrylonitrile, acetonitrile, acetone cyanogen in Acrylonitrile Production
The industrial wastewater of the poisonous and harmful substance such as alcohol, ammonium sulfate.At present, the processing method of acrylic nitrile waste water mainly includes burning method, adds
Setting-out solution-biochemical process, wet oxidation-biochemical process etc..Burning method needs to consume substantial amounts of auxiliary fuel oil, to the limited energy is
Waste greatly, and easily cause secondary pollution；Pressurizing hydrolysis is low to the removal efficiency of oligoacrylonitrile, and alkaline hydrolysis
After waste water need a large amount of acid to neutralize and waste water treatment plant could be entered after clear water dilution；Equipment material is wanted by wet oxidation process
Ask high, one-time investment is big, and needs the device of supporting heavy-metal ion removal (such as Cu2+ catalyst).At present, both at home and abroad
Each manufacturer the most all selects to add the mode that auxiliary fuel burns, the processing cost of waste water per ton 200～300 yuan it
Between, there is many drawbacks such as equipment investment is big, operating cost is high, secondary pollution.Therefore, seek efficient, economical, eco-friendly
Method, the research direction always received much concern.
The applicant in JIUYUE, 2008 propose to utilize film absorb remove and Propylene recovery nitrile Coal Gas Washing Cycling Water cyanide and
The method (publication number CN101381127) of ammonia nitrogen, it is to utilize height in hydrophobic hollow fiber membrance separation, Propylene recovery nitrile waste water
The volatile contaminant material (such as HCN and NH3) of concentration, has the advantages such as easy and simple to handle, energy consumption is low, recyclable utility.But
It is, after acrylic nitrile waste water removes cyanide and ammonia nitrogen substances, waste water still to retain the Sulfates (mass concentration 10 of high concentration
～20%).If this waste water sends to burning disposal, can expend the substantial amounts of energy equally, processing cost remains high；If carried out
Conventional biological treatment, then cause the microorganism cannot metabolism normally owing to salinity is the highest.
Summary of the invention
The present invention is directed to above-mentioned prior art and process problem and the defect that high-concentration acrylonitrile wastewater exists, it is proposed that be a kind of
Freezing and crystallizing is utilized to remove and the method for Propylene recovery nitrile Coal Gas Washing Cycling Water sulfate so that it is can be in Propylene recovery nitrile waste water
High concentration sulfate, creates certain economic worth, can reduce again the intractability of current high-concentration acrylonitrile wastewater.
Technical scheme is as follows:
A kind of freezing and crystallizing is utilized to remove and the method for sulfate in Propylene recovery nitrile waste water.It is characterized in that, use such as
Under processing step:
1) first adding the mass concentration 10～NaOH of 15% in acrylic nitrile waste water, wastewater temperature controls 30～55
℃；
2) particle and molecular weight during waste water sequentially passes through sand filtration, microfiltration and ultrafiltration removal waste water are more than 30000
Oligoacrylonitrile, subsequently into the tube side of hydrophobic hollow fiber film；
3) use mass concentration 10～15% H2SO4 solution enter hydrophobic hollow fiber as absorbing liquid, absorbing liquid
The shell side of film；
4) in the interface of hydrophobic hollow fiber film Yu absorbing liquid, H2SO4 sends out with volatility NH3 in acrylic nitrile waste water
Raw neutralization is reacted, and generates (NH4) 2SO4 and is recovered；
5) by the acrylic nitrile waste water quick freeze after removal ammonia nitrogen, the high concentration sulfate in waste water is made to crystallize out；
6) utilize high speed centrifuge to step 5) in waste water separate, mother solution return or send to burning disposal, reclaim
Crude sulphate through washing, obtain refined salt after drying process.
Hydrophobic hollow fiber film used in technique scheme is polypropylene or polyvinylidene fluoride material.
Compared with prior art, the present invention has the following advantages and salience effect: 1. the present invention is suitable for processing acrylonitrile
High concentration sulfate in waste water.Compared with the waste water desalination process such as electrodialysis, reverse osmosis, Membrane Materials, no membrane fouling of the present invention
Blocking with film, production efficiency is higher, operates simpler；Compared with traditional evaporative crystallization method, the present invention have energy consumption low, separate
The advantages such as efficiency is high, easy and simple to handle.
Accompanying drawing explanation
Fig. 1 is to use membrane absorption method to remove and the process chart of Propylene recovery nitrile high-concentration ammonia nitrogen in waste water.
Fig. 2 is to use freezing and crystallizing to remove and the process chart of sulfate in Propylene recovery nitrile waste water.
Detailed description of the invention
The a kind of of present invention offer utilizes freezing and crystallizing to remove and the method for sulfate in Propylene recovery nitrile waste water, and it is concrete
Processing step is as follows:
1) first adding the mass concentration 10～NaOH of 15% in acrylic nitrile waste water, wastewater temperature controls 30～55
℃；
2) particle and molecular weight during waste water sequentially passes through sand filtration, microfiltration and ultrafiltration removal waste water are more than 30000
Oligoacrylonitrile, subsequently into the tube side (as shown in Figure 1) of hydrophobic hollow fiber film；
3) use mass concentration 10～15% H2SO4 solution enter hydrophobic hollow fiber as absorbing liquid, absorbing liquid
The shell side of film；
4) in the interface of hydrophobic hollow fiber film Yu absorbing liquid, H2SO4 sends out with volatility NH3 in acrylic nitrile waste water
Raw neutralization is reacted, and generates (NH4) 2SO4 and is recovered；
5) by the acrylic nitrile waste water quick freeze after removal ammonia nitrogen, cryogenic temperature typically at 0 DEG C or less than 0 DEG C, makes waste water
In high concentration sulfate crystallize out (as shown in Figure 2)；
6) utilize high speed centrifuge to step 5) in waste water after freezing separate, mother solution returns or sends at burning
Reason, the crude sulphate of recovery obtains refined salt after washing, drying process.
Below by several specific embodiments, the technique of the present invention is further described.
Embodiment 1
Acrylic nitrile waste water used by test derives from the composite waste that certain acrylonitrile installation being currently running domestic produces, useless
Containing materials such as the acrylonitrile of high concentration, cyanide, acetonitrile .alpha.-hydroxyisobutyronitrile. and ammonium sulfate in water.Wherein, concentration of cyanide is
824.8～4517mg/L, ammonia nitrogen concentration is 23674～36708mg/L.The hydrophobicity Kynoar that certain is domestic selected by membrane module
Hollow-fibre membrane (PVDF).First adding the NaOH of mass concentration 10% in acrylic nitrile waste water, regulation wastewater temperature is at 30 DEG C.
Waste water sequentially passes through sand filtration, microfiltration (MF) and ultrafiltration and removes the particle in waste water and the molecular weight acrylonitrile more than 30000
Oligomer.When the waste water tube side flow at hollow-fibre membrane, the volatility NH3 gas in waste water is in hollow-fibre membrane interface
Occur to neutralize reaction with 10%H2SO4 absorbing liquid, generate nonvolatile (NH4) 2SO4 and be recovered.Reaction through 60min
Between, the clearance of ammonia nitrogen reaches more than 93.3%.After membrane absorption method removes ammonia nitrogen in high density, by acrylic nitrile waste water quick freeze extremely
0 DEG C, now the high concentration sulfate in waste water crystallizes out.Utilizing high speed centrifuge to separate waste water, mother solution is sent to and is burnt
Burning processes, the crude sulphate of recovery through washing, the operation such as be dried and obtain refined salt.After above-mentioned process, sulfate in waste water
Mass concentration successfully drop to 5.1% from 18%.
Embodiment 2
Acrylic nitrile waste water used by test derives from the composite waste that certain acrylonitrile installation being currently running domestic produces, useless
Containing materials such as the acrylonitrile of high concentration, cyanide, acetonitrile .alpha.-hydroxyisobutyronitrile. and ammonium sulfate in water.Wherein, concentration of cyanide is
824.8～4517mg/L, ammonia nitrogen concentration is 23674～36708mg/L.The hydrophobic polypropylene hollow that certain is domestic selected by membrane module
Fibrous membrane (PP).First adding the NaOH of mass concentration 15% in acrylic nitrile waste water, regulation wastewater temperature is at 55 DEG C.Waste water depends on
Secondary remove the particle in waste water and the molecular weight oligoacrylonitrile more than 30000 through sand filtration, microfiltration (MF) and ultrafiltration.
When the waste water tube side flow at hollow-fibre membrane, the volatility NH3 gas in waste water is in hollow-fibre membrane interface and 15%
H2SO4 absorbing liquid occurs to neutralize reaction, generates nonvolatile (NH4) 2SO4 and is recovered.Through the response time of 120min, ammonia
The clearance of nitrogen reaches more than 95%.After membrane absorption method removes ammonia nitrogen in high density, by acrylic nitrile waste water quick freeze to 0 DEG C, this
Time waste water in high concentration sulfate crystallize out.Utilizing high speed centrifuge to separate waste water, mother solution returns, recovery thick
Sulfate through washing, be dried etc. operation obtain refined salt.After above-mentioned process, in waste water, the mass concentration of sulfate is from 22%
Successfully drop to 5.9%.
Embodiment 3:
Acrylic nitrile waste water used by test derives from the composite waste that certain acrylonitrile installation being currently running domestic produces, useless
Containing materials such as the acrylonitrile of high concentration, cyanide, acetonitrile .alpha.-hydroxyisobutyronitrile. and ammonium sulfate in water.Wherein, concentration of cyanide is
824.8～4517mg/L, ammonia nitrogen concentration is 23674～36708mg/L.The hydrophobic polypropylene hollow that certain is domestic selected by membrane module
Fibrous membrane (PP).First adding the NaOH of mass concentration 15% in acrylic nitrile waste water, regulation wastewater temperature is at 55 DEG C.Waste water depends on
Secondary remove the particle in waste water and the molecular weight oligoacrylonitrile more than 30000 through sand filtration, microfiltration (MF) and ultrafiltration.
When the waste water tube side flow at hollow-fibre membrane, the volatility NH3 gas in waste water is in hollow-fibre membrane interface and 15%
H2SO4 absorbing liquid occurs to neutralize reaction, generates nonvolatile (NH4) 2SO4 and is recovered.Through the response time of 120min, ammonia
The clearance of nitrogen reaches more than 95%.After membrane absorption method removes ammonia nitrogen in high density, by acrylic nitrile waste water quick freeze to-10 DEG C,
Now the high concentration sulfate in waste water crystallizes out.Utilizing high speed centrifuge to separate waste water, mother solution returns, recovery
Crude sulphate through washing, be dried etc. operation obtain refined salt.After above-mentioned process, in waste water the mass concentration of sulfate from
22% successfully drops to 3.2%.
Claims (2)
1. one kind utilizes freezing and crystallizing to remove and the method for sulfate in Propylene recovery nitrile waste water, it is characterised in that the method is adopted
Use following processing step:
1) first adding the mass concentration 10～NaOH of 15% in acrylic nitrile waste water, wastewater temperature controls at 30～55 DEG C；
2) waste water sequentially passes through sand filtration, microfiltration and ultrafiltration and removes the particle in waste water and the molecular weight propylene more than 30000
Nitrile oligomer, subsequently into the tube side of hydrophobic hollow fiber film；
3) the mass concentration 10～H of 15% is used2SO4Solution enters the shell of hydrophobic hollow fiber film as absorbing liquid, absorbing liquid
Journey；
4) at the interface of hydrophobic hollow fiber film Yu absorbing liquid, H2SO4With volatility NH in acrylic nitrile waste water3In generation
And reaction, generate (NH4)2SO4And be recovered；
5) by the acrylic nitrile waste water quick freeze after removal ammonia nitrogen, the sulphate crystal in waste water is made out；
6) utilize high speed centrifuge to step 5) in waste water after freezing separate, mother solution returns or sends to burning disposal, returns
The crude sulphate received obtains refined salt after washing, drying process.
The most according to claim 1 a kind of freezing and crystallizing is utilized to remove and the method for sulfate in Propylene recovery nitrile waste water,
It is characterized in that, the hydrophobic hollow fiber film used is polypropylene or polyvinylidene fluoride material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610640286.9A CN106277428A (en) | 2016-08-04 | 2016-08-04 | Freezing and crystallizing is utilized to remove and the method for sulfate in Propylene recovery nitrile waste water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610640286.9A CN106277428A (en) | 2016-08-04 | 2016-08-04 | Freezing and crystallizing is utilized to remove and the method for sulfate in Propylene recovery nitrile waste water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106277428A true CN106277428A (en) | 2017-01-04 |
Family
ID=57666103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610640286.9A Pending CN106277428A (en) | 2016-08-04 | 2016-08-04 | Freezing and crystallizing is utilized to remove and the method for sulfate in Propylene recovery nitrile waste water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106277428A (en) |
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2016
- 2016-08-04 CN CN201610640286.9A patent/CN106277428A/en active Pending
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| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170104 |
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| WD01 | Invention patent application deemed withdrawn after publication |