CN102874958A - Method for treating and reusing sodium sulfate containing organic waste water - Google Patents
Method for treating and reusing sodium sulfate containing organic waste water Download PDFInfo
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- CN102874958A CN102874958A CN2011101930930A CN201110193093A CN102874958A CN 102874958 A CN102874958 A CN 102874958A CN 2011101930930 A CN2011101930930 A CN 2011101930930A CN 201110193093 A CN201110193093 A CN 201110193093A CN 102874958 A CN102874958 A CN 102874958A
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Abstract
The invention discloses a method for treating and reusing sodium sulfate containing organic waste water. According to the method, sodium sulfate containing organic wastewater is processed through a system including a pretreatment apparatus, a filtering apparatus and a spray drying apparatus, so as to obtain a sodium sulfate industrial grade product. By the utilization of the method provided by the invention, this kind of wastewater is processed, and sodium sulfate in water is also recovered such that sodium sulfate is a qualified industrial grade sodium sulfate II product which reaches national standards. The method provided by the invention has advantages of short flow, high automation degree, simply-controlled operation, less land occupation and the like.
Description
Technical field
The present invention relates to a kind for the treatment of process of organic waste water, relate in particular to a kind of method of recycling of contains sodium sulfate organic waste water.
Background technology
In coking or Coal Chemical Industry industry, in the technique of the rectifying of coal tar and dephenolize, can adopt in a large number sulfuric acid and sodium hydroxide with purifying products, this process can produce the organic waste water of one high concentration sodium sulfate.Usually, in this type of organic waste water, sulfate concentration is between 12%～20%, and contain large amount of organic, its COD is at 20000～40000mg/L, and colourity has 60 times to 150 times, and sulfonium ion concentration is about 500 to 1000mg/L, chloride ion content is 2000 to 4000mg/L, and suspended solid is between 500 to 1500mg/L.
This type of organic waste water is because its high sodium sulfate and high organic characteristic, biochemical process can't be processed, and conventional materialization processing can not be with this wastewater treatment to qualified discharge, to process again after the dilution at present mostly, so to consume a large amount of water and also produce simultaneously a large amount of waste water, so seeking an effective treatment process in the industry, this type of waste water can processed, and preferably can reclaim the sodium sulfate in the waste water always.
CN101525189 discloses a kind of method that ammonia, vanadium, chromium and sodium sulfate wastewater are processed that contains.The method is that ammonia, vanadium and chromium are produced ammoniacal liquor by deamination, extract chromium hydroxide, with the operations such as resin column absorption process remove after, waste water after processing is transported in the triple-effect evaporator by pump, carry out evaporative crystallization with saturated steam, carry out solid-liquid separation by whizzer, will become the anhydrous sodium sulphate product after the gained crystal drying, thereby extract anhydrous sodium sulphate.In the waste water that the method is processed, organic content is not high, and adopts the method reclaim(ed) sulfuric acid sodium of evaporative crystallization, and facility investment is higher.
Not yet find at present the technology of the sodium sulfate organic waste water that the processing coal tar separates, as seen the processing of this type of waste water has suitable difficulty.
Therefore, those skilled in the art is devoted to develop a kind of sodium sulfate organic waste water that coal tar separates and technique of reclaim(ed) sulfuric acid sodium processed, and solving the problem of environmental pollution of this type of waste water, and reclaim(ed) sulfuric acid sodium is increased economic efficiency as Industrial products.
Summary of the invention
For achieving the above object, the invention provides the method for a kind of processing and reuse contains sodium sulfate organic waste water.
Particularly, the method for processing of the present invention and reuse contains sodium sulfate organic waste water is through comprising that the system of pretreatment unit, filtration unit and spray drying unit processes, and obtains the sodium sulfate technical grade product with described contains sodium sulfate organic waste water.That is, described organic waste water through pre-treatment, filtration and spray-dired processing, is obtained the sodium sulfate technical grade product.
By China national product standard GB/T6009-2003, technical grade sodium sulfate can be divided into 3 classes, wherein the requirement of the salable product of II class is: the massfraction of sodium sulfate＞97.0%, water-insoluble massfraction＜0.2%, calcium magnesium (in Mg) resultant massfraction＜0.4%, muriate (in Cl) massfraction＜0.9%, iron (in Fe) massfraction＜0.04%, and moisture content＜1.0%.
In better embodiment of the present invention, the method for processing of the present invention and reuse contains sodium sulfate organic waste water may further comprise the steps:
A, make described contains sodium sulfate organic waste water remove wherein suspended substance, sulfonium ion, organism through pretreatment unit, to the clearance of its colourity greater than 50%;
B, process filtration unit are to separate suspended solids and colloid wherein;
C, process spray drying unit are recycled into technical grade product with dried over sodium sulfate wherein.
In the method for the invention, the standard of using pretreatment unit to remove is that other composition that other affects final sodium sulfate quality is not added again in the removal that reaches the impurity (such as organism, sulfonium ion, suspended substance and colourity etc.) of the best; Using filtration unit, mainly is to process rear remaining suspended solids and colloid in order to remove pretreatment unit, and its purpose also is to remove as much as possible impurity, to guarantee the quality of final sodium sulfate product.
In the method for the invention, it mainly is to remove impurity in this type of waste water such as organism, suspended particulate that organic waste water is carried out pre-treatment, and sulfonium ion etc., contain the device of electricity flocculation and electro-flotation for the organism in the waste water, the removal of sulfonium ion and suspended particulate has preferably effect, therefore, the preferred pretreatment device adopts electric flocculation plant and electric air floating device.Electricity flocculation plant and electric air floating device can be independently to install, and also can be integrated apparatus.Electricity flocculation and electro-flotation are linked in sequence, and namely electro-flotation is positioned at after the electricity flocculation.
Owing to electricity flocculation is to utilize electric current to make the ion stripping in the pole plate of electrode produce the effect of flocculation, the general pole plate that adopts is iron plate or aluminium sheet, preferably use in the method for the invention iron plate as battery lead plate, reach the purpose of removing sulfonium ion in the water because sulfonium ion and iron can form iron sulphide.And the electricity flocculation has better removal to the organism in this waste water than the traditional chemical flocculation, is better than especially the traditional chemical flocculation aspect decolouring, and its clearance can reach more than 50%.
In addition, in the flocculation process of electricity flocculation be with iron or aluminium atom direct ionization in water and can not increase other ion, add iron trichloride in the traditional chemical flocculation and can bring a large amount of chlorions into, therefore the electricity flocculation can not increase the impurity component of final sodium sulfate, can guarantee the returnability of product.
In addition, the hydrogen that negative electrode produces in the process of electricity flocculation can be used for air supporting, and this is after utilizing gas and impurity combination, to emerge, thereby reaches the effect of separation.Air supporting can be removed flco and organism, the especially hydrophobic organic compound in the water, such as oils or other high molecular polymer.In the method for the present invention, the operation that adopts electricity flocculation and electro-flotation to combine can be removed the impurity in this type of contains sodium sulfate organic waste water better.
There is no particular limitation for the operation of electricity flocculation, electro-flotation for method of the present invention, and those skilled in the art can easily determine operating parameters according to general knowledge.
In the method for the invention, described filtration unit is membrane filter plant, and the described filtration unit of waste water process that described step a is obtained is so that suspended solids wherein and colloid are removed to less than 1mg/L.
For waste water after pretreatment, although the pretreatment process of the flocculation of process electricity and electro-flotation still contains a small amount of suspended solids and colloid in its water, still need further to remove the purity with raising reclaim(ed) sulfuric acid sodium.Some is iron sulphide in this suspended solids, this particle is very tiny, general traditional strainer is not good to its removal effect, and the national standard of the II class salable product of technical grade sodium sulfate requires wherein iron content to want＜0.04%, therefore, preferably take in the method for the invention membrane filter plant, the aperture of film can be the scope of micro-filtration or ultrafiltration, be from 0.5 to 0.02 micron in aperture all can, mainly the suspended solids in the water is removed to less than 1mg/L.In the method for the invention, can adopt such as hollow-fibre membrane and carry out secondary filter.
Because it is little that the microfiltration membrane of immersion is taken up an area, level of automation is high, and the fluctuation of water resistant matter is high.More preferably, adopt the microfiltration membrane of immersion.
In the method for the invention, described spray drying unit adopts the high speed centrifugation atomizer.Through the waste water after pre-treatment and the membrane filtration processing, be sent to spray drying unit, preferably utilize the high speed centrifugation atomizer to convert waste water to vaporific water droplet, this water droplet is with during warm air contacts, its moisture content evaporates rapidly, sodium sulfate just becomes powder, takes out of with air, through becoming the finished product after cyclonic separation and the sack cleaner collection.This process is very of short duration; simple to operate, easily control, equipment is also very simple; to save manyly than the investment of adopting evaporative crystallization and boiling-bed drying, and not worry causing heat exchanger fouling in the vaporizer that energy consumption is risen and needing the problem such as stop cleaning because of the waste water complicated.Although spray-dired energy consumption is higher, utilizable waste heat source such as raw gas etc. are arranged in the factory usually, or flue gas, also be common in the production of these gas coking industries, therefore, adopt spraying drying can take full advantage of recovery heat energy, thus capable of reducing energy consumption.
There is no particular limitation for the operation of spray drying unit for method of the present invention, and those skilled in the art can easily determine operating parameters according to general knowledge.
The organic waste water of contains sodium sulfate described in the present invention is preferably the organic waste water that the coal tar separating technology produces.
After method processing of the present invention, the sodium sulfate product that reclaims meets national standard, has following composition: the massfraction of sodium sulfate＞97.0%, water-insoluble massfraction＜0.2%, calcium magnesium (in Mg) resultant massfraction＜0.4%, muriate (in Cl) massfraction＜0.9%, iron (in Fe) massfraction＜0.04%, and moisture content＜1.0%.
In the method for the invention, the device of processing contains sodium sulfate organic waste water can also comprise the utility appliance that some are commonly used, such as after-treatment device such as the chimney of exhaust gas emission and the foam dedusting of processing waste gas to the gas after the spraying drying, charcoal absorption and biological bed absorption etc. are processed a small amount of volatile organic matter in the what emission gases.
The method of processing of the present invention and reuse contains sodium sulfate organic waste water has not only been processed this type of waste water, and has reclaimed the salable product that the sodium sulfate in the water makes its technical grade sodium sulfate II series products that is up to state standards.The pre-treatment that method of the present invention adopts, membrane filtration and spray-dired combination have flow process short, and level of automation is high, and operation control is simple, takes up an area the advantages such as little.
Embodiment
Embodiment 1
The organic waste water of the contains sodium sulfate that the coke-oven plant, Shanxi Province produces, indices is as follows:
Sulfate radical in waste water concentration and contains large amount of organic about 18%, its COD is 39500mg/L, and colourity is 64 times, and sulfonium ion concentration is about 580mg/L, and chlorine ion concentration is 1895mg/L, and the concentration of suspended solid is 545mg/L.
The below adopts method of the present invention to process above-mentioned organic waste water, and the water yield of processing is 2 cubes m/hs.
Pretreatment unit adopts electric flocculation plant, two covers that be arranged in parallel, and every cover 10 plate electrode plates, battery lead plate is iron plate, is of a size of 600mm*1200mm*3mm, rearmounted electro-flotation settling bowl is designed to the high circular pond of 1m diameter 4m.After pretreatment unit was processed, colourity was reduced to 30 times.
Membrane filter plant adopts submerged ultrafiltration, 9 groups of the PVDF hollow fiber film assemblies (KRIM-1520R-IMF) of employing Kaimo Filteration Tech (Shanghai) Co., Ltd., every contains 20 square metres of filtration areas, the long 1600mm of assembly, wide 700mm, membrane pore size is 0.08 micron.After membrane filter plant was processed, the concentration of suspended solid was 0.8mg/L
Above-mentioned organic waste water is sent into the spray dried tower behind pre-treatment and membrane filtration, diameter 5500mm, and high 5500mm, the tail gas after the raw gas burning in the employing factory carries out drying.
The electric current of electricity flocculation plant adopts 32A, and voltage is 3V; Submerged ultrafiltration adopts negative pressure-pumping, and its vacuum pressure is at 20～30Kpa, 2 cubic meters/hours of water production rates.
After using method of the present invention to move continuously, in the product of its dry gained, the massfraction of sodium sulfate is 97.5%,, water-insoluble is 0.15%, and calcium magnesium (take magnesium) is 0.13%, and muriate is 0.8%, and iron is 0.03%, water ratio is 0.7%.The yield of sodium sulfate can reach more than 98%.From these indexs, the sodium sulfate that uses method of the present invention to obtain meets the requirement of the II class salable product of industrial sulphuric acid sodium in the national standard fully.Wherein still there is a small amount of other impurity to be mainly sodium sulphite, and a small amount of organism, so its color with any yellowish brown, but does not affect its industrial application.
Embodiment 2
The sodium sulfate organic waste water of processing among the embodiment 1 is processed without above-mentioned pretreatment unit and filtration unit, carry out drying and directly enter spray drying unit, obtain auburn sodium sulfate pressed powder, detect by analysis, wherein, the massfraction of sodium sulfate is 82.5%, water-insoluble is 1.4%, calcium magnesium (take magnesium) is 0.56%, and muriate is 1.16%, and iron is 0.03%, water ratio is 0.38%, do not reach the reuse standard of sodium sulfate, wherein sodium sulphite impurity has accounted for greatly, if not reuse of sodium sulfate, the economic worth of this type of wastewater treatment is just very low, this shows that method of the present invention carries out pretreated necessity before drying.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area need not creative work and just can design according to the present invention make many modifications and variations.Therefore, all in the art technician all should be in the determined protection domain by claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (9)
1. the method for a processing and reuse contains sodium sulfate organic waste water is characterized in that, with described contains sodium sulfate organic waste water through comprising that the system of pretreatment unit, filtration unit and spray drying unit processes, and obtains the sodium sulfate technical grade product.
2. the method for processing as claimed in claim 1 and reuse contains sodium sulfate organic waste water may further comprise the steps:
A, make described contains sodium sulfate organic waste water remove wherein suspended substance, sulfonium ion and organism through described pretreatment unit, to the clearance of the colourity of described contains sodium sulfate organic waste water greater than 50%;
B, the described filtration unit of process are to separate suspended solids and colloid wherein;
C, the described spray drying unit of process are recycled into technical grade product with dried over sodium sulfate wherein.
3. the method for processing as claimed in claim 1 and reuse contains sodium sulfate organic waste water, wherein said pretreatment unit adopts electric flocculation plant and electric air floating device.
4. the method for processing as claimed in claim 3 and reuse contains sodium sulfate organic waste water, the battery lead plate in the wherein said electric flocculation plant uses iron plate.
5. the method for processing as claimed in claim 2 and reuse contains sodium sulfate organic waste water, wherein said filtration unit is membrane filter plant, the described filtration unit of waste water process that described step a is obtained is so that suspended solids wherein and colloid are removed to less than 1mg/L.
6. the method for processing as claimed in claim 5 and reuse contains sodium sulfate organic waste water, the filtering membrane that wherein said membrane filter plant adopts is microfiltration membrane or ultra-filtration membrane, the aperture is 0.5 to 0.02 micron.
7. the method for processing as claimed in claim 5 and reuse contains sodium sulfate organic waste water, the filtering membrane that wherein said membrane filter plant adopts is the microfiltration membrane of immersion.
8. the method for processing as claimed in claim 1 and reuse contains sodium sulfate organic waste water, wherein said spray drying unit adopts the high speed centrifugation atomizer.
9. such as the method for the described processing of one of claim 1-8 and reuse contains sodium sulfate organic waste water, wherein said contains sodium sulfate organic waste water is the organic waste water that the coal tar processing process produces.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361769A (en) * | 2013-07-24 | 2013-10-23 | 宜宾海翔化工有限责任公司 | Method for recovering acid and base from viscose fiber sodium sulfate waste liquid by use of bipolar membrane electrodialysis method |
| CN104402156A (en) * | 2014-09-30 | 2015-03-11 | 深圳能源资源综合开发有限公司 | Coal chemical high brine purification, evaporative crystallization and recovery technology and special-purpose equipment |
| CN104609641A (en) * | 2013-11-05 | 2015-05-13 | 中蓝连海设计研究院 | Sebacic acid wastewater evaporative desalination pretreatment method |
| CN109956483A (en) * | 2019-04-12 | 2019-07-02 | 河海大学 | A kind of innoxious and method of resource of chemical industry abraum salt |
| CN110054203A (en) * | 2019-04-12 | 2019-07-26 | 河海大学 | A kind of method of resource of industrial waste salt |
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| RU2205795C2 (en) * | 2001-05-21 | 2003-06-10 | Открытое акционерное общество ВНИИ галургии | Potassium sulfate production process |
| CN101323458A (en) * | 2008-06-03 | 2008-12-17 | 南京师范大学 | Method for comprehensively processing petroleum acid slag and alkaline residue |
| CN102115286A (en) * | 2009-12-30 | 2011-07-06 | 凯膜特种分离技术(上海)有限公司 | Treatment method for recycling coking wastewater and assembled treatment system |
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Patent Citations (3)
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| RU2205795C2 (en) * | 2001-05-21 | 2003-06-10 | Открытое акционерное общество ВНИИ галургии | Potassium sulfate production process |
| CN101323458A (en) * | 2008-06-03 | 2008-12-17 | 南京师范大学 | Method for comprehensively processing petroleum acid slag and alkaline residue |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103361769A (en) * | 2013-07-24 | 2013-10-23 | 宜宾海翔化工有限责任公司 | Method for recovering acid and base from viscose fiber sodium sulfate waste liquid by use of bipolar membrane electrodialysis method |
| CN103361769B (en) * | 2013-07-24 | 2016-02-10 | 宜宾海翔化工有限责任公司 | Viscose sodium sulfate waste liquor reclaims the method for soda acid through bipolar membrane electrodialysis method |
| CN104609641A (en) * | 2013-11-05 | 2015-05-13 | 中蓝连海设计研究院 | Sebacic acid wastewater evaporative desalination pretreatment method |
| CN104609641B (en) * | 2013-11-05 | 2017-02-15 | 中蓝连海设计研究院 | Sebacic acid wastewater evaporative desalination pretreatment method |
| CN104402156A (en) * | 2014-09-30 | 2015-03-11 | 深圳能源资源综合开发有限公司 | Coal chemical high brine purification, evaporative crystallization and recovery technology and special-purpose equipment |
| CN109956483A (en) * | 2019-04-12 | 2019-07-02 | 河海大学 | A kind of innoxious and method of resource of chemical industry abraum salt |
| CN110054203A (en) * | 2019-04-12 | 2019-07-26 | 河海大学 | A kind of method of resource of industrial waste salt |
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Application publication date: 20130116 |