CN109956483A - A kind of innoxious and method of resource of chemical industry abraum salt - Google Patents
A kind of innoxious and method of resource of chemical industry abraum salt Download PDFInfo
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- CN109956483A CN109956483A CN201910297361.XA CN201910297361A CN109956483A CN 109956483 A CN109956483 A CN 109956483A CN 201910297361 A CN201910297361 A CN 201910297361A CN 109956483 A CN109956483 A CN 109956483A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention belongs to hazardous wastes to handle disposal field, specifically disclose a kind of innoxious and method of resource with sodium chloride chemical industry abraum salt as main component, specifically: take a certain amount of chemical industry abraum salt to be placed in water, it is sufficiently dissolved under the synergy of ultrasound and stirring, obtains the salting liquid A close to saturation；Salting liquid A is filtered, the insoluble impurities in salting liquid A is removed, obtains salting liquid B；Salting liquid B is subjected to catalytic oxidation treatment, by mineralization of organic material in salting liquid B or resolves into small organic molecule；Secondary filter is carried out to salting liquid B, obtains salting liquid C；Salting liquid C is subjected to spray drying treatment, so that salting liquid C small molecular organic matter is entered gas phase with vapor, and be discharged after purification, finally obtains dry sodium salt product.The method of the present invention can not only realize the innoxious of this hazardous waste of chemical industry abraum salt, additionally it is possible to the sodium salt byproduct for meeting industrial product quality requirement be prepared, to realize the innoxious and recycling of chemical industry abraum salt.
Description
Technical field
The invention belongs to hazardous waste processing disposition and recycling field, and in particular to one kind is using sodium chloride as main component
Chemical industry abraum salt innoxious and method of resource.
Background technique
It takes place frequently in recent years, hazardous waste illegally handles disposition case, causes the extensive concern of various circles of society.Wherein permitted
More cases are directed to the processing disposition of the hazardous waste of chemical industry, especially waste residue abraum salt.This kind of waste has source wide
The features such as general, many kinds of, complicated component, poisonous and harmful substance content is high, not only environmental hazard is big, but also in face of increasingly stringent
Processing disposition require and environmental management policies, processing disposition requires and cost is continuously improved, therefore processing difficulty is very big,
Through becoming one of main problem urgently to be resolved in current environmental protection industry (epi).On the other hand, salt is also a kind of important industrial chemicals,
If the abraum salt of chemical industry can be carried out innoxious and recycling treatment and as a by-product reuse make the raw material of industry or
Other purposes can not only eliminate its harm to environment, can also make full use of abraum salt resource, be advantageously implemented chemical industry
Waste resource recovery and circular economy.
The innoxious and recycling of chemical industry abraum salt mainly has following technological approaches at present:
1) purification technique is melted；
I.e. under the high temperature conditions, abraum salt is melted, organic matter therein volatilizees from melt due to low boiling point, then passes through
Organic toxic harmful substance in abraum salt is finally being removed, is being obtained after purification by the gas purification techniques such as burning by exhaust-gas treatment
Inorganic salts.This is that a kind of processing dangerous waste salt is more effective and a kind of feasible most common technology, such as publication number
CN104310434A " a kind of for handling the device and technique of abraum salt ", CN106152109A " gas fuel fused salt integration pot
The patent of invention of the device of furnace thermal release substance ", grant number be CN203928459U " a kind of fused salt cooling recovery system ",
The utility model patent of CN205659976U " fusion method industrial chlorinations sodium abraum salt processing equipment " all reports this technology.It is this
Although technology can remove the toxic organics in abraum salt, there is also some shortcomings, such as because of abraum salt ingredient, form, grain
The influence of the factors such as degree, uneven heating is even, and efficiency is low, and the coking that is carbonized can also occur for organic matter, influences the quality of salt；Abraum salt is molten
It is more serious to melt bonding phenomenon, corrosive equipment surface leads to equipment damage when serious；Only consider poisonous and harmful in removal abraum salt
Organic matter, treated, and dangerous waste salt impurity content is high, is still difficult to resource utilization, can only carry out landfill disposal, not only cause
The waste of resource, and it is also higher to fill expense.
2) pyrolytic technique
I.e. high temperature and be lower than abraum salt melting temperature under conditions of, so that the organic matter in abraum salt volatilize, and by aoxidize or
The organic matter removal that will volatilize of the technologies such as burning realizes the detoxification of abraum salt and innoxious.Such as Publication No. CN106424112A " one
Multistage thermal desorption processes and equipment kind for abraum salt purification ", CN106824980A " a kind of coal chemical industry crystallization abraum salt it is innoxious
" one kind is handled for abraum salt by processing method ", CN107185948A " a kind of industrial waste salt system and method ", CN107062836A
Radiant type rotary drying device ", " organic matter is CN108408744A in a kind of hot fluid classification stripping process industrial waste salt
The patents of invention such as system and method " report this technology.This technology is preferable for the detoxification efficiency of abraum salt, has accomplished harmless
Change, but does not also limit its recycling in view of the inorganic and other impurity for being not easy vaporization at high temperature in abraum salt.
But there is also some problems in operation for this technology, because of the shadow of the factors such as abraum salt ingredient, form, granularity
It rings, uneven heating is even, and efficiency is low；Abraum salt bond vitrified phenomenon is more serious, and corrosive equipment surface causes equipment to be damaged when serious
It is bad；Only consider the toxic organics in removal abraum salt, treated, and dangerous waste salt impurity content is high, is still difficult to recycling benefit
With can only carry out landfill disposal, not only cause the waste of resource, but also it is also higher to fill expense.
3) water-soluble, salting liquid purification and resource technology
This technology is that abraum salt is dissolved with water, becomes liquid, then uses the means such as chemical subtraction or film of wastewater treatment
Equal solid-liquid separation techniques isolate and purify salt from liquid phase, obtain purer salting liquid, then further produce salt.Such as it discloses
Number be CN103693658A " waste salt comprehensive treatment device and its application method based on three-segment incinerator " patent of invention,
It is that inorganic impurity is removed by chemical treatment, is then done again after the industrial waste salt based on sodium chloride-containing is passed through dissolution
Dry, pyrolysis dehydration, organic matter volatilizees and enters gas phase in the process, then so that exhaust gas is met emission request through burning disposal,
Abraum salt is purified simultaneously, reaches chlorine industry salt requirement.A kind of " the abraum salt processing side Publication No. CN105883859A
The patent of invention of method " roasts abraum salt 0.5-4 hours at 300-600 DEG C, and the tail gas for roasting generation enters gas cleaning plant
It is discharged after being purified, product of roasting adds water to be beaten, and the treatment fluid that salinity is 15-25% is formed, by the treatment fluid through macropore
Discharge is after resin adsorption to get purer dense saline solution.Grant number is CN207933534U " a kind of purification devices of abraum salt "
NaCl waste salt dregs obtained in pesticide synthesis are dissolved in water by utility model patent；With being connected to salt dissolving groove nanofiltration membrane for salt dissolving
Salt water obtained in slot is filtered；Except cation impurity device, it is connected to the per-meate side of nanofiltration membrane, for obtaining nanofiltration membrane
Penetrating fluid in be removed cation impurity；Chelating resin column is connected to except cation impurity device, for except cation
The production water that impurity device obtains removes salt treatment using resin；Ion-exchange membrane electrolyzer is connected to chelating resin column, for setting chelating
The production water of rouge column carries out electrolysis processing, finally obtains caustic soda and chlorine.
Using this technology, available purer salt, it might even be possible to by obtained salt deep processing at other industrial chemicals,
It is a kind of method that abraum salt recycling is ideal, but the technical matters reported at present is complicated, processing cost is high, particularly with containing
The higher abraum salt of sodium chloride is dissolved in the salting liquid of water formation because that can make resin poison containing a large amount of chloride ions, causes to adsorb organic
Object it is ineffective, or even lose suction-operated, which also limits pass through resin adsorption to remove this technology of Organic substance in water
Industrial application.
In summary, it would be highly desirable to develop a kind of simple process, strong operability and processing cost it is low abraum salt is innoxious and money
Source processing technique.
Summary of the invention
Goal of the invention: technical problem to be solved by the invention is to provide a kind of innoxious and resources of chemical industry abraum salt
Change method, this method can not only realize the innoxious of this hazardous waste of chemical industry abraum salt, additionally it is possible to prepare satisfaction industry and produce
The sodium salt byproduct that quality requires, to realize the innoxious and recycling of chemical industry abraum salt.
Summary of the invention: in order to solve the above technical problems, the technical scheme adopted by the invention is as follows:
A kind of innoxious and method of resource of chemical industry abraum salt, specific operating procedure are as follows:
Step 1, it takes a certain amount of chemical industry abraum salt to be placed in water, sufficiently dissolves, obtain under the synergy of ultrasound and stirring
To the salting liquid A close to saturation；
Step 2, salting liquid A is filtered, removes the insoluble impurities in salting liquid A, obtains salting liquid B；
Step 3, salting liquid B is subjected to catalytic oxidation treatment, by mineralization of organic material in salting liquid B or resolves into small molecule and have
Machine object；
Step 4, secondary filter is carried out to the salting liquid B of step 3, obtains salting liquid C；
Step 5, salting liquid C is subjected to spray drying treatment, salting liquid C small molecular organic matter is made to enter gas with vapor
Phase, and the qualified discharge after purification, finally obtain dry sodium salt product.
Wherein, in step 1, ultrasound working frequency is 15~60kHz.
Wherein, in step 2, in salting liquid B, the mass concentration of sodium chloride is 20~25%.
Wherein, in step 3, the catalytic oxidation treatment is catalytic wet oxidation or catalytic ozonation.
Wherein, the catalytic wet oxidation be at 120~200 DEG C of temperature, 1~5MPa of pressure, be passed through oxygen-enriched air or
Oxygen under the effect of the catalyst degrades catalytic organism.
Wherein, the ozone concentration of system is 1~5kg/m in the catalytic ozonation3。
Wherein, the catalyst that catalytic wet oxidation and catalytic ozonation use is therein for iron, manganese, cobalt, cerium, nickel, copper
Loaded catalyst composed by two or more composite oxide of metal.
Wherein, in step 5, the temperature of spray drying is 150~250 DEG C.
The present invention uses ultrasonic in combination stirring technique, and the stickiness containing organic matter and impurity is made by the cavitation effect of ultrasonic wave
High abraum salt can sufficiently dissolve；Cavitation effect is that a large amount of small gas can be constantly generated in liquid under the action of ultrasonic wave
Bubble, minute bubbles are grown into and increase with ultrasonic vibration, then rupture suddenly again, the bubble after division again continued growth and
It vanishes.These minute bubbles produce high temperature and pressure in bubble when rapidly rupturing, and because the liquid at high speed around bubble pours gas
It steeps and produces strong localised waving in the liquid near bubble, localized hyperthermia's high pressure is also formed, to produce super
The crushing of sound, emulsification, to accelerate and improve the dissolution efficiency of solable matter in abraum salt；Meanwhile the present invention utilizes
Organic matter is further processed in catalytic oxidation technique, and catalytic wet oxidation is under certain temperature and pressure, by solid
The catalytic action of body catalyst, using air or oxygen by water organic matter and ammonia nitrogen difference oxygenolysis at CO2、H2O and N2
Equal innocuous substances, to achieve the purpose that purification, catalytic ozonation is then in liquid-phase reaction system, due to depositing for ozone
Catalyst surface can generate the extremely strong hydroxyl radical free radical of oxidisability, to by mineralization of organic material or be decomposed into low-boiling small
Molecular substance achievees the purpose that purification.
The utility model has the advantages that processing method simple process of the present invention, on the one hand utilizes ultrasonic in combination stirring technique, abraum salt can be made to fill
It point is dissolved in the water, especially to those containing more than organic matter and impurity and abraum salt that stickiness is high, dissolution efficiency is higher, can be made
Close to the crude salt solution of saturation；On the other hand efficient degradation is carried out to the organic matter being dissolved in solution using catalytic oxidation technique,
Not degradable small organic molecule is removed using spray drying technology from salt finally, while realizing the de- of salting liquid again
Water；The organic matter that the method for the present invention both can have been removed efficiently in abraum salt keeps its innoxious, and does not introduce any foreign substance to system
(being not easily runed off in reaction process using loaded catalyst, can be with circulating and recovering) is finally obtained and meets product quality requirement
Sodium salt byproduct.
Detailed description of the invention
Fig. 1 is the process flow chart of the innoxious and method of resource of chemical industry abraum salt of the present invention.
Specific embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
It applies content described in example and is merely to illustrate the present invention, without sheet described in detail in claims should will not be limited
Invention.
As shown in Figure 1, the method for the present invention makes the dissolved constituent in abraum salt first with the synergy of ultrasonic wave and stirring
Efficiently dissolution, obtains the sodium chloride solution close to saturation；Then filter out insoluble impurities in solution, with catalytic wet oxidation or
Catalytic ozonation technology is by the mineralization of organic material in solution or resolves into small-molecule substance；Then by secondary filter obtain compared with
Solution, is finally spray-dried by clean sodium chloride solution, finally obtains the sodium chloride by-product for meeting product quality requirement
Product, while the small organic molecule of the not thorough mineralising after catalysis oxidation can enter gas phase with vapor, it is net through absorption tower
Qualified discharge after change.
Embodiment 1
The abraum salt residue that certain fine chemistry industry company triple-effect evaporation plant is precipitated, which is in faint yellow powder agglomates shape, through detecting
Sodium chloride-containing 86.5%, moisture 4.6%, organic matter 1.2g and other impurity in the abraum salt, the abraum salt is currently as hazardous waste
Commission factory carries out processing disposition.
Above-mentioned abraum salt is handled by following steps of the present invention:
Step 1, water will be added in dissolving tank, sets ultrasound working frequency as 30kHz, opens ultrasonic wave driving power,
And constantly Xiang Shuizhong adds abraum salt, until the salt added does not dissolve, the dosage of salt is regarded as close to chlorine at this time
Change the saturation dosage of sodium, stops stirring, obtain thick strong brine；
Step 2, thick strong brine step 1 obtained is sent into filter device and carries out primary filtration, removes insoluble in strong brine
Property substance, through in salt water obtained by Preliminary detection, the mass concentration of sodium chloride is 23.1%, TOC2140mg/L；
Step 3, the filtered strong brine of step 2 is passed through the fixed bed ozone equipped with Fe-Co-MnOx loaded catalyst
In catalyst oxidation reactor, control system ozone dosage is 5kg/m3, strong brine is discharged after reacting 0.5h, carries out micro-filtration, obtains
To cleaner strong brine；
Step 4, it is sent into spray drying tower by pumping the strong brine for obtaining step 3, by strong brine at a temperature of 180 DEG C
Drop is dried, and the gas (the low boiling point small organic molecule obtained after organic matter degradation is with vapor) of generation is from tower
Top imports after absorption tower is purified and discharges, and the granular salt fines that droplet drying is formed are deposited to tower bottom, obtains final sodium chloride
Product.
The ingredient of sampled detection, sodium chloride product obtained is as follows: sodium chloride > 98.5%, the total content of magnesium and calcium < 0.5%,
Sulfate radical < 0.5%, moisture < 0.2%, insoluble matter < 0.2% reach second level work in " Nacl " (GB/T 5462-2015)
The quality criteria requirements of the dry salt of industry.
Embodiment 2
Certain chemical company's abraum salt in light gray, is consolidated into blocky and somewhat viscous based on sodium chloride, sampled analysis,
Each ingredient is as follows: sodium chloride 90.1%, moisture 7.6%, organic matter 1.05% and other impurity.
Above-mentioned abraum salt is handled by following steps of the present invention:
Step 1, water will be added in dissolving tank, sets ultrasound working frequency as 20kHz, opens ultrasonic wave driving power,
And constantly Xiang Shuizhong adds abraum salt, until the salt added does not dissolve, the dosage of salt is regarded as close to chlorine at this time
Change the saturation dosage of sodium, stops stirring, obtain thick strong brine；
Step 2, thick strong brine step 1 obtained is sent into filter device and carries out primary filtration, removes insoluble in strong brine
Property substance, through in salt water obtained by Preliminary detection, the mass concentration of sodium chloride is 24%, TOC6190mg/L；
Step 3, the filtered strong brine of step 2 is added and copper, nickel, manganese metal composite oxide loaded catalyst is housed
Fixing bed wet oxidation reactor in, control system temperature be 200 DEG C, oxygen partial pressure be 2.4MPa under, react 1h after be discharged
Strong brine carries out micro porous filtration, obtains cleaner strong brine；
Step 4, clean strong brine step 3 obtained is sent into spray drying tower, by strong brine drop at a temperature of 250 DEG C
It is dried, the gas (the low boiling point small organic molecule obtained after organic matter degradation is with vapor) of generation is led from tower top
Enter after absorption tower is purified and discharge, the granular salt fines that droplet drying is formed are deposited to tower bottom, obtain final sodium chloride product.
Sampled detection, the ingredient of sodium chloride product obtained are as follows: sodium chloride > 98.9%, sulfate radical < 0.4%, calcium and magnesium
< 0.4%, moisture 0.2%, insoluble matter < 0.1% reach the dry salt of level-one industry in " Nacl " (GB/T 5462-2015)
Quality criteria requirements.
Compared with the dissolution of traditional abraum salt mechanical stirring, using ultrasonic in combination stirring and dissolving technology, abraum salt can be made sufficiently to dissolve
Yu Shuizhong, especially to those containing more than organic matter and impurity and abraum salt that stickiness is high, dissolution efficiency is higher, can be made close to full
The crude salt solution of sum.
Catalytic wet oxidation and catalytic ozonation, can by the thorough mineralising of organic matter or part mineralising in salting liquid,
Generate carbon dioxide or other low boiling point small molecule compounds；In conjunction with spray drying technology, make the hydrone and oxygen in salting liquid
The low boiling point small molecule compound that change process generates is volatized into gas phase, while carrying out the purification of gas, and final recycling is accorded with
Close the salt that product quality requires.
The sodium chloride recycled by this method, product quality meet the quality standard of " Nacl " (GB/T 5462-2015)
It is required that.This method not only may be implemented using sodium chloride as the innoxious place of this kind of hazardous waste of chemical industry abraum salt of principal component
Reason, while the sodium chloride product for meeting target level of product quality requirement can also be made, efficiently solve this danger of chemical industry abraum salt
Useless processing problem, present invention process process is simple, strong operability, has significant environmental benefit, economic benefit and practical valence
Value.
Claims (8)
1. a kind of innoxious and method of resource of chemical industry abraum salt, it is characterised in that: specific operating procedure are as follows:
Step 1, it takes a certain amount of chemical industry abraum salt to be placed in water, sufficiently dissolves, connect under the synergy of ultrasound and stirring
The salting liquid A being closely saturated；
Step 2, salting liquid A is filtered, removes the insoluble impurities in salting liquid A, obtains salting liquid B；
Step 3, salting liquid B is subjected to catalytic oxidation treatment, by mineralization of organic material in salting liquid B or to resolve into small molecule organic
Object；
Step 4, secondary filter is carried out to the salting liquid B of step 3, obtains salting liquid C；
Step 5, salting liquid C is subjected to spray drying treatment, salting liquid C small molecular organic matter is made to enter gas phase with vapor,
And be discharged after purification, finally obtain dry sodium salt product.
2. the innoxious and method of resource of chemical industry abraum salt according to claim 1, it is characterised in that: in step 1,
Ultrasound working frequency is 15~60kHz.
3. the innoxious and method of resource of chemical industry abraum salt according to claim 1, it is characterised in that: in step 2,
In salting liquid B, the mass concentration of sodium chloride is 20~25%.
4. the innoxious and method of resource of chemical industry abraum salt according to claim 1, it is characterised in that: in step 3,
The catalytic oxidation treatment is catalytic wet oxidation or catalytic ozonation.
5. the innoxious and method of resource of chemical industry abraum salt according to claim 4, it is characterised in that: the catalysis
Wet oxidation is to be passed through oxygen-enriched air or oxygen, under the effect of the catalyst at 120~200 DEG C of temperature, 1~5MPa of pressure
Catalytic organism is degraded.
6. the innoxious and method of resource of chemical industry abraum salt according to claim 4, it is characterised in that: the ozone
The ozone concentration of system is 1~5kg/m in catalysis oxidation3。
7. the innoxious and method of resource of chemical industry abraum salt according to claim 5 or 6, it is characterised in that: catalysis
The catalyst that wet oxidation and catalytic ozonation use is iron, manganese, cobalt, cerium, nickel, copper two or more metal composite therein
Loaded catalyst composed by oxide.
8. the innoxious and method of resource of chemical industry abraum salt according to claim 1, it is characterised in that: in step 5,
The temperature of spray drying is 150~250 DEG C.
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Cited By (4)
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| CN111087005A (en) * | 2019-12-25 | 2020-05-01 | 洛阳森蓝化工材料科技有限公司 | Method for preventing fluorine gas purifying agent from sintering and discoloring |
| CN112978767A (en) * | 2021-02-26 | 2021-06-18 | 鄂尔多斯市永胜污水处理有限公司 | Treatment process for recycling and reusing industrial mixed salt in caustic soda plant |
| CN113023753A (en) * | 2021-02-26 | 2021-06-25 | 鄂尔多斯市永胜污水处理有限公司 | Treatment process for producing high-purity industrial salt and anhydrous sodium sulphate by using industrial miscellaneous salt |
| CN114249336A (en) * | 2021-12-30 | 2022-03-29 | 盐城市国投环境技术股份有限公司 | Process for preparing industrial sodium carbonate by using chemical tail gas waste salt |
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| CN112978767A (en) * | 2021-02-26 | 2021-06-18 | 鄂尔多斯市永胜污水处理有限公司 | Treatment process for recycling and reusing industrial mixed salt in caustic soda plant |
| CN113023753A (en) * | 2021-02-26 | 2021-06-25 | 鄂尔多斯市永胜污水处理有限公司 | Treatment process for producing high-purity industrial salt and anhydrous sodium sulphate by using industrial miscellaneous salt |
| CN114249336A (en) * | 2021-12-30 | 2022-03-29 | 盐城市国投环境技术股份有限公司 | Process for preparing industrial sodium carbonate by using chemical tail gas waste salt |
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Application publication date: 20190702 |