CN114368763B - Comprehensive treatment method for industrial waste salt - Google Patents
Comprehensive treatment method for industrial waste salt Download PDFInfo
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- CN114368763B CN114368763B CN202111632635.XA CN202111632635A CN114368763B CN 114368763 B CN114368763 B CN 114368763B CN 202111632635 A CN202111632635 A CN 202111632635A CN 114368763 B CN114368763 B CN 114368763B
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- 150000003839 salts Chemical class 0.000 title claims abstract description 151
- 239000002440 industrial waste Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 126
- 239000002699 waste material Substances 0.000 claims abstract description 98
- 238000002425 crystallisation Methods 0.000 claims abstract description 62
- 230000008025 crystallization Effects 0.000 claims abstract description 61
- 238000001816 cooling Methods 0.000 claims abstract description 37
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 230000008020 evaporation Effects 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000000197 pyrolysis Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000004090 dissolution Methods 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 51
- 238000001223 reverse osmosis Methods 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 35
- 238000009292 forward osmosis Methods 0.000 claims description 30
- 238000001728 nano-filtration Methods 0.000 claims description 26
- 239000012266 salt solution Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 16
- 239000002826 coolant Substances 0.000 claims description 10
- 239000010802 sludge Substances 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- 238000000108 ultra-filtration Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 8
- 239000010865 sewage Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 150000003841 chloride salts Chemical group 0.000 claims description 4
- 150000001805 chlorine compounds Chemical group 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 239000002910 solid waste Substances 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 150000001804 chlorine Chemical class 0.000 claims description 3
- 239000002361 compost Substances 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 238000011110 re-filtration Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 description 132
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 19
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 18
- 239000007789 gas Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 10
- 238000005265 energy consumption Methods 0.000 description 9
- 239000001103 potassium chloride Substances 0.000 description 9
- 235000011164 potassium chloride Nutrition 0.000 description 9
- 239000002918 waste heat Substances 0.000 description 8
- 238000012432 intermediate storage Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000000112 cooling gas Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C01D3/08—Preparation by working up natural or industrial salt mixtures or siliceous minerals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to an industrial waste salt comprehensive treatment method, which comprises the following steps: s100: dissolving industrial waste salt, separating organic matters, recrystallizing, granulating, drying waste salt grains, and inputting into an incinerator; s200: the waste salt grains are pyrolyzed at high temperature in an incinerator to remove organic matters; cooling and crushing the waste salt after pyrolysis to obtain waste salt particles; s300: the waste salt particles are input into a dissolving and filtering tank for dissolving and filtering to realize carbon-salt separation; s400: inputting the solution dissolved in the filtering tank into a neutralization tank, and removing indissolvable hydroxide under the action of alkali liquor; s500: inputting the solution obtained in the step S400 into a membrane separation unit, and separating to obtain chloride concentrated water and sulfate concentrated water; s600: the chloride concentrated water is input into a first evaporation crystallization unit, and chloride is recovered through crystallization; and the concentrated sulfate water is input into a second evaporation crystallization unit, and sulfate is recovered by crystallization.
Description
Technical Field
The invention belongs to the technical field of industrial waste salt treatment and resource utilization, and particularly relates to an industrial waste salt comprehensive treatment method.
Background
The industrial waste salt has wide sources, relates to a plurality of industries such as pesticides, medicines, coal chemical industry, printing and dyeing, electroplating and the like, has complex components, contains a large amount of toxic and harmful substances such as organic matters, heavy metals and the like, has great toxicity and difficult degradation, and is accompanied by pungent odor. Industrial waste salt not only damages ecological environment and endangers human health, but also soluble salt and impurities in the waste salt easily cause salinization of soil, endanger survival and development of peripheral agriculture, forestry and animal husbandry, and even cause serious pollution to peripheral water sources and underground water, so that the hazard is extremely high. Particularly, with the rapid development of the fine chemical industry, the manyfold increase of salt-containing solid waste is still the biggest bottleneck of the next development of enterprises, and the effective and safe disposal of industrial waste salt has become an environmental problem to be solved.
Along with the improvement of the overall environmental protection concept of society, waste salt is subjected to quality and salt separation, high-purity inorganic salt with economic value is recovered from the waste salt, harmless and recycling utilization of the waste salt is realized, and the waste salt becomes a research hot spot in the current environmental protection field. The existing common salt separation modes comprise high-temperature incineration, membrane separation, salt washing method, recrystallization, extraction method and the like, and the industrial waste salt has complex components, so that a plurality of technologies are combined, and impurities in the waste salt are comprehensively removed to obtain purer industrial crystalline salt.
The high-temperature incineration method is used for high-temperature incineration of industrial waste salt to remove organic matters in the waste salt, is suitable for waste salt with higher organic matter content, is limited by various factors such as technology and the like, and is easy to melt or soften and agglomerate after the waste salt is incinerated, and is adhered in an incinerator to cause serious corrosion or obstruction of the incinerator, so that the incinerator cannot continuously operate.
Disclosure of Invention
Aiming at the problems, the invention provides an industrial waste salt comprehensive treatment method, which adopts a combined technology of incineration pyrolysis and multistage filtration, has simple process and solves the problems that the existing industrial waste salt separation process has large energy consumption and the pyrolyzed salt is adhered to the surface of an incinerator to form scale.
The comprehensive treatment method of the industrial waste salt comprises the following steps:
S100: dissolving industrial waste salt, separating organic matters, recrystallizing, granulating, drying waste salt grains, and inputting into an incinerator;
S200: the waste salt grains are pyrolyzed at high temperature in an incinerator to remove organic matters; cooling and crushing the waste salt after pyrolysis to obtain waste salt particles;
s300: the waste salt particles are input into a dissolving and filtering tank for dissolving and filtering to realize carbon-salt separation;
s400: inputting the solution dissolved in the filtering tank into a neutralization tank, and removing indissolvable hydroxide under the action of alkali liquor;
s500: inputting the solution obtained in the step S400 into a membrane separation unit, and separating to obtain chloride concentrated water and sulfate concentrated water;
S600: the chloride concentrated water is input into a first evaporation crystallization unit, and chloride is recovered through crystallization; and the concentrated sulfate water is input into a second evaporation crystallization unit, and sulfate is recovered by crystallization.
Optionally, step S100 specifically includes the following steps:
(1) Dissolving industrial waste salt in a pretreatment tank, mechanically stirring at normal temperature to fully dissolve, and standing for layering;
(2) The upper oil phase of the pretreatment tank is a nonpolar organic matter, and the upper oil phase is discharged into a sewage treatment plant for treatment;
(3) Heating the lower water phase of the pretreatment tank, mechanically stirring until insoluble salt is fully dissolved, and then separating while the insoluble salt is hot to obtain a waste salt solution;
(4) Naturally cooling the waste salt solution under mechanical stirring, and when the waste salt solution is cooled to room temperature, continuing to cool by using a cooling medium until no solid is separated out, so as to obtain waste salt grains;
(5) And (3) inputting the waste salt grains into a dryer for drying, wherein the heat source of the dryer is the hot tail gas of the incinerator, and the tail gas of the dryer enters a tail gas treatment device for treatment.
In the step (2), the lower water phase of the pretreatment tank contains insoluble matters such as impurities and suspended matters of waste salt and indissolvable salt at normal temperature; in the step (3), impurities, suspended matters and the like of the waste salt are separated from the waste salt solution by hot separation; the step can also continuously release the nonpolar organic matters and discharge the nonpolar organic matters into a sewage treatment plant for treatment.
Optionally, in the step (4), the grain size of the waste salt grains is 5-15mm, and the waste salt grains with the grain size growing to 5-15mm are continuously filtered out of the solution system in the processes of natural cooling and cooling of the cooling medium.
Optionally, in the step (4), the residual water phase can be used as the next dissolved industrial waste salt, and when the polar organic matter content in the water phase is large, the water phase is discharged into a sewage treatment plant for treatment.
The pretreatment is carried out on the industrial waste salt aiming at the characteristics of easy caking and adhesion in the incinerator, the components of the industrial waste salt are complex, the waste salt is easy to adhere to form blocks due to the existence of organic matters, and the distribution of the organic matters in waste salt particles is very irregular, so that the organic matters are pyrolyzed by the waste salt particles in the incinerator, and the organic matters are embedded in the particles and are not pyrolyzed completely, so that the integral pyrolysis time is prolonged, and the energy consumption is increased.
According to the invention, most of the nonpolar organic matters are removed by virtue of the dissolution of the waste salt in a layered manner, and the nonpolar organic matters do not enter the incinerator but are treated by the sewage treatment plant, so that the energy consumption for pyrolyzing the nonpolar organic matters is saved. The lower water phase of the heating pretreatment tank has the functions of promoting the dissolution of insoluble salt to fully enter the subsequent crystallization process, promoting the dissolution of polar organic matters in waste salt in water and promoting the release of nonpolar organic matters, and preparing preconditions for the subsequent cooling crystallization. The dissolution of waste salt is also beneficial to the advanced removal of impurities, suspended matters and the like, and reduces the load of the ultrafiltration unit. The waste salt has higher crystal grain purity, uniform grain diameter and larger specific surface area. Because the polar organic matters are dissolved in the water phase, most of the polar organic matters are left in the water, so that the energy consumption of the incinerator for pyrolyzing the polar organic matters is further saved, and a small part of the polar organic matters are attached to the outer surfaces of the waste salt grains when the waste salt grains are discharged out of the pretreatment tank and are pyrolyzed preferentially after entering the incinerator, so that the time of the incinerator procedure is shortened.
Optionally, the pretreatment tank comprises a front part and a rear part, which are respectively a dissolution chamber and a crystallization chamber, a lifting control gate is arranged between the dissolution chamber and the crystallization chamber, when the gate is lifted, the two chambers are separated, and when the gate is lowered, the solution of the dissolution chamber and the crystallization chamber can be communicated, and the overflow gate enables impurities, suspended matters and other insoluble matters at the lower part of the dissolution chamber to remain in the dissolution chamber;
the dissolving chamber and the crystallization chamber are respectively provided with a first stirring part and a second stirring part, and the dissolving chamber is provided with a heating device;
The side wall of the dissolution chamber is provided with a lifting siphon, and the tail end of the siphon is connected with a waste water pipeline for discharging nonpolar organic matters; the head end of the siphon pipe is provided with a lifting device, so that the siphon pipe is convenient to adjust according to the height of the oil phase in the dissolution chamber.
Preferably, the second stirring part comprises a plurality of stirring paddles, the stirring paddles are uniformly distributed along the circumferential direction of the stirring shaft, the stirring paddles can move up and down along the stirring shaft, the stirring paddles are in a strainer shape, the aperture of a filter screen is 5mm, and waste salt grains with the grain diameter larger than 5mm are fished out while stirring; the stirring paddle can rotate, when the stirring paddle drags up waste salt grains and moves to the upper part of the stirring shaft and is above the liquid level, the stirring paddle rotates, the opening is downward, the grains are poured on the conveying belt, and the conveying belt is connected with the dryer.
The first stirring part is a common stirrer.
Preferably, an ultrasonic vibration plate is arranged in the dissolution chamber, and when the dissolution chamber is heated, the waste salt is ultrasonically promoted to be dissolved.
Optionally, the liquid outlet of crystallization room is connected the intermediate storage tank, and the liquid inlet of dissolution room is connected to the intermediate storage tank, makes dissolution room and the crystallization room of preliminary treatment pond realize continuous operation, and dissolution room is after dissolving useless salt and oil water separation, passes through the gate is discharged the feed liquid into the crystallization room, and dissolution room is the water of input intermediate storage tank again, continues to dissolve useless salt, and the feed liquid is discharged into the crystallization room and is carried out crystallization, after discharging useless salt grain, and the water of crystallization room is discharged into intermediate storage tank, and the crystallization room accepts the feed liquid of dissolution room again, in order to realize continuous production.
Optionally, in step S200, the waste salt grains are pyrolyzed at a high temperature in the upper part of the incinerator to remove organic matters; and (5) the waste salt after pyrolysis falls into the lower part of the incinerator to be pre-cooled and crushed, so as to obtain waste salt particles.
The incinerator comprises an incineration area, a pre-cooling area and a discharge area from top to bottom in sequence, a porous plate is arranged between the incineration area and the pre-cooling area and is used for placing the waste salt grains, and after organic matters on the surfaces of the waste salt grains are incinerated, the waste salt grains particles and part of melt flow down from the porous plate or flow down to the pre-cooling area;
the pre-cooling area is internally provided with a rotating part which is a hollow pipeline, and a cooling medium is introduced into the rotating part for cooling and crushing the burnt substances;
And a discharge hole is formed in the bottom of the discharge area and is connected with the dissolution filter tank.
Further optionally, the rotating member is a horizontally placed spiral pipe, two ends of the rotating member respectively penetrate through the side wall of the pre-cooling area, and mechanical seals are arranged at the penetrating positions and are respectively used for inputting and outputting cooling media; one end of the rotating member is connected with the driving device and is used for driving the rotating member to horizontally rotate, substances falling onto the rotating member are cooled and smashed, and then fall into the discharging area, so that the problems of easy agglomeration and blockage in discharging cooling of the traditional incinerator are solved.
The cooling medium is selected from cooling water or cooling gas.
Optionally, the hot tail gas of the incinerator can be input into a waste heat boiler, so that the waste heat of the incinerator is fully utilized, the waste heat boiler is connected with the tail gas treatment device to treat the tail gas generated by the waste heat boiler, and finally the tail gas can reach the emission standard.
Optionally, in step S300, the waste salt particles are input into a dissolution filter tank, wherein inorganic salt components are dissolved in water, and inorganic carbon components formed by pyrolysis of organic matters are filtered and separated; the solid waste outlet of the dissolving and filtering tank is connected with sludge dewatering equipment, sludge containing inorganic carbon is dewatered and reduced, and finally sludge is transported to compost, so that the recycling of organic matters in waste salt is realized.
Optionally, in step S400, the solute of the solution in the dissolution filter tank is an inorganic salt component of the waste salt, the inorganic salt solution is input into the neutralization tank, the feed inlet of the neutralization tank is connected with an alkali liquor storage tank in parallel, the alkali liquor storage tank provides alkali liquor for the neutralization tank, and calcium and magnesium ions in the inorganic salt solution are neutralized and precipitated.
Further optionally, the lye reservoir provides sodium hydroxide solution or potassium hydroxide solution.
Optionally, in step S500, the following steps are included:
(6) Inputting the solution obtained in the step S400 into an ultrafiltration unit of a membrane separation unit to remove indissolvable hydroxides, impurities and suspended matters;
(7) The produced water of the ultrafiltration unit is a mixed salt solution and is input into the nanofiltration unit, the mixed salt solution is selectively separated, and chlorine salt and sodium sulfate are mainly separated;
(8) The produced water of the nanofiltration unit is chloride salt solution and is input into a first reverse osmosis unit for deep purification and separation; the produced water of the first reverse osmosis unit can be recycled as reclaimed water, and the concentrated water produced by the first reverse osmosis unit is chloride concentrated water;
(9) The concentrated water generated by the nanofiltration unit is input into a forward osmosis unit for further concentration, and the concentrated water generated by the forward osmosis unit is sulfate concentrated water;
(10) The produced water of the forward osmosis unit is input into a second reverse osmosis unit for separation and purification, and the concentrated water produced by the second reverse osmosis unit is input into the forward osmosis unit and is used as the drawing liquid of the forward osmosis unit; the produced water of the second reverse osmosis unit can be recycled as reclaimed water and is input into a recycling water tank.
Optionally, in step (7), the concentrated water generated by the ultrafiltration unit is fed into a dissolution filter tank, and the concentrated water containing insoluble hydroxide, impurities and suspended matters is returned to the dissolution filter tank for re-filtration.
Optionally, in the step (8), the produced water of the nanofiltration unit is firstly input into a nanofiltration produced water tank, and then enters the first reverse osmosis unit after standing, sedimentation and adjustment. Preferably, the nanofiltration water producing pool is connected with the nanofiltration unit and is used for taking the produced water of the nanofiltration unit as the cleaning water of the nanofiltration unit.
Optionally, in step (10), the concentrated water generated by the second reverse osmosis unit is Na 2SO4 solution, which returns to the forward osmosis unit and is used as the drawing liquid of the forward osmosis unit, the concentration of the concentrated water generated by the nanofiltration unit is lower than that of the drawing liquid, the nanofiltration concentrated water is drawn by the concentrated water of the second reverse osmosis unit and then concentrated to obtain forward osmosis concentrated liquid, the drawing liquid is diluted after forward osmosis, and the drawing liquid returns to the second reverse osmosis unit again as the produced water of the forward osmosis unit for purification.
Further optionally, in the step (10), the reuse water tank is connected in parallel with the first reverse osmosis unit, the second reverse osmosis unit and the dissolution filter tank through pipelines, and the second reverse osmosis unit is used for generating cleaning water of a reverse osmosis membrane or replenishing water of the dissolution filter tank or being used as reclaimed water for reuse.
In step S600, the concentrated chloride water mainly contains sodium chloride and potassium chloride, and is input into the first evaporation crystallization unit, and according to the difference of the influence of the solubility of NaCl and KCl along with the change of temperature, the solubility of NaCl increases slowly along with the increase of temperature, and the solubility of potassium chloride increases faster, so that pure NaCl crystals and KCl crystals are obtained by separation after evaporation drying through the first evaporation crystallization unit.
In step S600, the concentrated sulfate water mainly contains sodium sulfate, and is delivered to a second evaporation crystallization unit, and is evaporated at high temperature, cooled and crystallized to obtain Na 2SO4 crystals.
Optionally, the steam condensate of the first evaporation crystallization unit and the steam condensate of the second evaporation crystallization unit are returned to the dissolution filter tank to supplement water for the dissolution filter tank to dissolve molten salt.
Optionally, the first evaporative crystallization unit and the second evaporative crystallization unit are multi-effect evaporative crystallizers or MVR evaporators.
Drawings
FIG. 1 is a schematic diagram of a pretreatment tank;
FIG. 2 is a schematic structural view of the incinerator;
FIG. 3 is a flow chart of the comprehensive treatment method of the industrial waste salt.
In the drawing, a 1-dissolution chamber, a 2-crystallization chamber, a 3-gate, a 4-siphon, a 5-intermediate storage tank, a 6-incineration zone, a 7-pre-cooling zone, an 8-discharge zone, a 9-porous plate and a 10-rotating member are arranged.
Detailed Description
The industrial waste salt treated in the following examples and comparative examples is derived from industrial waste salt produced by a pharmaceutical processing company, and comprises the following components:
Example 1
The embodiment provides the comprehensive treatment method for the industrial waste salt, which comprises the following steps:
S100: heating and dissolving industrial waste salt in a common dissolving tank, separating nonpolar organic matters, recrystallizing and granulating to obtain waste salt grains with the particle size of 15-20mm, drying, and inputting into an incinerator;
The step S100 specifically includes:
(1) Dissolving industrial waste salt in a pretreatment tank, mechanically stirring at normal temperature to fully dissolve, and standing for layering;
(2) The upper oil phase of the pretreatment tank is a nonpolar organic matter, and the upper oil phase is discharged into a sewage treatment plant for treatment;
the lower water phase of the pretreatment tank contains insoluble matters such as impurities and suspended matters of waste salt and indissolvable salt at normal temperature;
(3) Heating the lower water phase of the pretreatment tank, mechanically stirring until insoluble salt is fully dissolved, then separating the insoluble salt while the insoluble salt is hot, and separating impurities, suspended matters and the like of the waste salt from the waste salt solution to obtain the waste salt solution;
the step can also continuously release nonpolar organic matters and discharge the nonpolar organic matters into a sewage treatment plant for treatment;
(4) Naturally cooling the waste salt solution under mechanical stirring, and when the waste salt solution is cooled to room temperature, continuing to cool by using a cooling medium until no solid is separated out, so as to obtain waste salt grains;
Mechanically stirring at 60-80 rpm, wherein the grain size of the waste salt grains is 15-20mm;
The rest water phase can be used as the next dissolved industrial waste salt, and is discharged into a sewage treatment plant for treatment when the polar organic matter content is large;
(5) And (3) inputting the waste salt grains into a dryer for drying, wherein the heat source of the dryer is the hot tail gas of the incinerator, and the tail gas of the dryer enters a tail gas treatment device for treatment.
S200: the waste salt grains are pyrolyzed at high temperature in a common incinerator to remove organic matters; cooling and crushing the waste salt after pyrolysis to obtain waste salt particles;
S300: the waste salt particles are input into a dissolving and filtering tank for dissolving and filtering, inorganic salt components in the waste salt particles are dissolved in water, and inorganic carbon components formed by pyrolysis of organic matters are filtered and separated out, so that carbon-salt separation is realized;
s400: feeding the solution in the dissolving and filtering tank into a neutralization tank, and removing calcium hydroxide and magnesium hydroxide under the action of sodium hydroxide solution;
S500: inputting the solution obtained in the step S400 into a nanofiltration unit of a membrane separation unit, and separating to obtain concentrated chloride water and concentrated sulfate water;
The water produced by the nanofiltration unit is chloride concentrated water, and the concentrated water produced by the nanofiltration unit is sulfate concentrated water;
s600: the chloride concentrated water is input into a first evaporation crystallization unit, and chloride is recovered through crystallization; the concentrated sulfate water is input into a second evaporation crystallization unit, and sulfate is recovered through crystallization;
The concentrated chloride water mainly contains sodium chloride and potassium chloride, and is input into a first evaporation crystallization unit, according to the difference of the influence of the solubility of NaCl and KCl along with the change of temperature, the solubility of NaCl increases slowly along with the increase of temperature, and the solubility of potassium chloride increases faster, so that pure NaCl crystals and KCl crystals are obtained by separation of the first evaporation crystallization unit after evaporation and drying;
The concentrated sulfate water mainly contains sodium sulfate, is conveyed to a second evaporation crystallization unit, is evaporated at high temperature, and is cooled and crystallized to obtain Na 2SO4 crystals;
The first evaporative crystallization unit and the second evaporative crystallization unit are multi-effect evaporative crystallizers.
As shown in fig. 1, the pretreatment tank comprises a front part and a rear part, which are respectively a dissolution chamber 1 and a crystallization chamber 2, a lifting control gate 3 is arranged between the dissolution chamber 1 and the crystallization chamber 2, when the gate 3 is lifted, the two chambers are separated by liquid, when the gate 3 is lowered, the solution of the dissolution chamber 1 and the crystallization chamber 2 can be communicated, and the overflow gate 3 enables impurities, suspended matters and other insoluble matters at the lower part of the dissolution chamber 1 to remain in the dissolution chamber 1;
The dissolving chamber 1 and the crystallization chamber 2 are internally provided with a first stirring part and a second stirring part respectively, and the dissolving chamber 1 is provided with a heating device; the first stirring part and the second stirring part are common stirring devices;
the side wall of the dissolution chamber 1 is provided with a lifting siphon pipe 4, and the tail end of the siphon pipe 4 is connected with a waste water pipeline for discharging nonpolar organic matters; the head end of the siphon pipe 4 is provided with a lifting device, so that the height of the siphon pipe 4 can be conveniently adjusted according to the height of the oil phase in the dissolution chamber 1; the lifting device is a supporting seat driven by a hydraulic cylinder;
the liquid outlet of crystallization room 2 is connected middle storage tank 5, and the liquid inlet of dissolution room 1 is connected to middle storage tank 5 for dissolution room 1 and crystallization room 2 of pretreatment tank can realize continuous operation, and dissolution room 1 is after normal atmospheric temperature dissolves useless salt and oil water separation, passes through gate 3 is got rid of the feed liquid into crystallization room 2, and dissolution room 1 imports the water of middle storage tank 5 again, continues to dissolve useless salt, and the feed liquid is got rid of crystallization room 2 and is heated and dissolved and crystallization, after the discharge waste liquid granule, the water of crystallization room 2 is got rid of middle storage tank 5, and crystallization room 2 accepts the feed liquid of dissolution room 1 again, so that realize continuous production.
Comparative example 1
This comparative example provides the above-mentioned industrial waste salt comprehensive treatment method, which is the same as that of example 1, except that step S100 is specifically: the industrial waste salt is input into a dryer through a feeder for drying, the dried waste salt is input into a waste salt conditioning tank for granulating, and waste salt particles with the particle size of 15-20mm are obtained and then input into an incinerator.
Example 2
The embodiment provides the comprehensive treatment method for industrial waste salt, which is the same as that of embodiment 1, and is different in that in the step (4), mechanical stirring is carried out at 90-100 rpm, and the grain size of waste salt grains is 5-15mm. In the natural cooling and cooling medium cooling processes, continuously filtering out waste salt grains with the grain size of 5-15mm from a solution system;
The second stirring part comprises a plurality of stirring paddles which are uniformly distributed along the circumferential direction of the stirring shaft, the stirring paddles can move up and down along the stirring shaft, the stirring paddles are in a strainer shape, the aperture of a filter screen is 5mm, and crystal particles with the particle size larger than 5mm are fished out while stirring; the stirring paddle can rotate, when the stirring paddle drags up waste salt crystallization grains and moves to the upper part of the stirring shaft and is above the liquid level, the stirring paddle rotates, the opening is downward, the grains are poured on the conveying belt, and the conveying belt is connected with the homogenizing mixer.
An ultrasonic vibration plate is arranged in the dissolution chamber 1, and when the dissolution chamber is heated, waste salt is promoted to be dissolved by ultrasonic.
Example 3
The embodiment provides the method for comprehensive treatment of industrial waste salt, which is the same as embodiment 2, except that in step S200, as shown in fig. 2, the waste salt grains are pyrolyzed at high temperature in the upper part of the incinerator to remove organic matters; and (5) the waste salt after pyrolysis falls into the lower part of the incinerator to be pre-cooled and crushed, so as to obtain waste salt particles.
The incinerator comprises an incineration zone 6, a pre-cooling zone 7 and a discharge zone 8 from top to bottom in sequence, a porous plate 9 is arranged between the incineration zone 6 and the pre-cooling zone 7 and is used for separating the two zones, and substances incinerated in the incineration zone are allowed to enter the pre-cooling zone 7 through the porous plate 9;
A rotating member 10 is arranged in the pre-cooling area, the rotating member 10 is a hollow pipeline, and a cooling medium is introduced into the rotating member 10 for cooling and crushing the burnt material;
And a discharge hole is formed in the bottom of the discharge area and is connected with the dissolution filter tank.
The perforated plate 9 is also used for receiving the waste salt grains, and after the organic matters on the surface and inside of the waste salt grains are burnt, the particles of the waste salt grains and part of melt leak down or flow down from the perforated plate to a pre-cooling area.
The rotary part is a horizontally placed spiral pipe fitting, two ends of the rotary part respectively penetrate through the side wall of the pre-cooling area, and mechanical seals are arranged at the penetrating parts and are respectively used for inputting and outputting cooling media; one end of the rotating member is connected with the driving device and is used for driving the rotating member to horizontally rotate, so that substances on the rotating member are cooled and smashed and then fall into the discharging area.
Because the porous plate 9 is positioned in the incinerator, the temperature is basically the same as that of the incineration area, and therefore, the melt of the waste salt grains is basically not hardened on the porous plate 9, and is cooled and crushed by the rotary piece 10 after leaking from the porous plate 9, so that the problems of easy caking and blockage in discharging cooling of the traditional incinerator are solved.
The cooling medium is selected from cooling water or cooling gas.
Example 4
The present embodiment provides the method for comprehensive treatment of industrial waste salt, which is the same as embodiment 3, except that in step S500, the method includes the following steps:
(6) Inputting the solution obtained in the step S400 into an ultrafiltration unit of a membrane separation unit to remove indissolvable hydroxides, impurities and suspended matters;
(7) The produced water of the ultrafiltration unit is a mixed salt solution and is input into the nanofiltration unit, the mixed salt solution is selectively separated, and chlorine salt and sodium sulfate are mainly separated;
The concentrated water generated by the ultrafiltration unit is input into a dissolution filter tank, and the concentrated water containing indissolvable hydroxides, impurities and suspended matters is returned to the dissolution filter tank for re-filtration;
(8) The produced water of the nanofiltration unit is chloride salt solution and is input into a first reverse osmosis unit for deep purification and separation; the produced water of the first reverse osmosis unit can be recycled as reclaimed water, and the concentrated water produced by the first reverse osmosis unit is chloride concentrated water;
(9) The concentrated water generated by the nanofiltration unit is input into a forward osmosis unit for further concentration, and the concentrated water generated by the forward osmosis unit is sulfate concentrated water;
(10) The produced water of the forward osmosis unit is input into a second reverse osmosis unit for separation and purification, and the concentrated water produced by the second reverse osmosis unit is input into the forward osmosis unit and is used as the drawing liquid of the forward osmosis unit; the produced water of the second reverse osmosis unit can be recycled as reclaimed water and is input into a recycling water tank;
The concentrated water generated by the second reverse osmosis unit is Na 2SO4 solution, the Na 2SO4 solution returns to the forward osmosis unit and is used as the drawing liquid of the forward osmosis unit, the concentration of the concentrated water generated by the nanofiltration unit is lower than that of the drawing liquid, the nanofiltration concentrated water is drawn by the concentrated water of the second reverse osmosis unit and then concentrated to obtain forward osmosis concentrated liquid, the drawing liquid is diluted after forward osmosis, and the drawing liquid is used as the produced water of the forward osmosis unit to return to the second reverse osmosis unit again for purification.
Example 5
The embodiment provides the method for comprehensively treating industrial waste salt, which is the same as that of embodiment 4, as shown in fig. 3, and is different in that in step S100, hot tail gas of the incinerator is input into a waste heat boiler for fully utilizing waste heat of the incinerator, the waste heat boiler is connected with the tail gas treatment device to treat tail gas generated by the waste heat boiler, and finally the tail gas can reach the emission standard;
In step S300, a solid waste outlet of the dissolution filter tank is connected with a sludge dewatering device, sludge containing inorganic carbon is dewatered and reduced, and finally, the sludge is transported to compost, so that the recycling of organic matters in waste salt is realized;
In the step S400, a feed inlet of the neutralization tank is connected with an alkali liquor storage tank in parallel, the alkali liquor storage tank provides sodium hydroxide solution for the neutralization tank, and calcium and magnesium ions in the inorganic salt solution are neutralized and precipitated;
In the step S500 (10), the reuse water tank is connected with the first reverse osmosis unit, the second reverse osmosis unit and the dissolution filter tank in parallel through pipelines, and the generated second reverse osmosis unit is used as cleaning water of a reverse osmosis membrane and the dissolution filter tank is used as water replenishing water for reuse of reclaimed water.
In step S600, the vapor condensate of the first evaporative crystallization unit and the vapor condensate of the second evaporative crystallization unit are returned to the dissolution filter tank, and the water used for the dissolution filter tank is supplemented to dissolve the molten salt.
Table 1 incinerator energy consumption comparison table
| Incinerator energy consumption a | |
| Example 1 | 25 |
| Example 2 | 21 |
| Comparative example 1 | 38 |
A is the energy consumption of the incinerator for treating 1 ton of industrial waste salt, and the unit is kJ.
As can be seen from the table, the comprehensive treatment method for industrial waste salt provided by the invention can obviously reduce the energy consumption of the incinerator by removing organic matters from the industrial waste salt and recrystallizing and granulating, has good heating performance, further reduces the energy consumption of the incinerator and improves the treatment efficiency.
Example 3 improved incinerator, improved the phenomenon of serious caking and blockage of common incinerator, and matched with the method for re-crystallizing and granulating after removing organic matters from industrial waste salt, reduced impurities, shortened incineration treatment time, cooperated with the innovative structure of incinerator, and relieved the conditions of caking, blockage and corrosion.
The scheme of the embodiment 4 provides a more detailed membrane separation scheme, the waste salt is deeply purified and separated, the purity of the obtained chloride salt and sulfate is higher, the recovery rates of the sodium chloride, the potassium chloride and the sodium sulfate respectively reach 96%, 95% and 94%, the produced water and the concentrated water generated by each part of the membrane separation unit can be fully utilized, the recycled water is generated, and the zero discharge of the wastewater of the membrane separation unit is realized.
The scheme of example 5 was optimized to better recover the thermal energy, inorganic carbon sludge, reuse water and steam condensate of the evaporative crystallization unit of the whole system.
Claims (4)
1. The comprehensive treatment method of the industrial waste salt is characterized by comprising the following steps of:
S100: dissolving industrial waste salt, separating organic matters, recrystallizing, granulating, drying waste salt grains, and inputting into an incinerator;
S200: the waste salt grains are pyrolyzed at high temperature in an incinerator to remove organic matters; cooling and crushing the waste salt after pyrolysis to obtain waste salt particles;
s300: the waste salt particles are input into a dissolving and filtering tank for dissolving and filtering to realize carbon-salt separation;
s400: inputting the solution dissolved in the filtering tank into a neutralization tank, and removing indissolvable hydroxide under the action of alkali liquor;
s500: inputting the solution obtained in the step S400 into a membrane separation unit, and separating to obtain chloride concentrated water and sulfate concentrated water;
s600: the chloride concentrated water is input into a first evaporation crystallization unit, and chloride is recovered through crystallization; the concentrated sulfate water is input into a second evaporation crystallization unit, and sulfate is recovered through crystallization;
The step S100 specifically includes the following steps:
(1) Dissolving industrial waste salt in a pretreatment tank, mechanically stirring at normal temperature to fully dissolve, and standing for layering;
(2) The upper oil phase of the pretreatment tank is a nonpolar organic matter, and the upper oil phase is discharged into a sewage treatment plant for treatment;
(3) Heating the lower water phase of the pretreatment tank, mechanically stirring until insoluble salt is fully dissolved, and then separating while the insoluble salt is hot to obtain a waste salt solution;
(4) Naturally cooling the waste salt solution under mechanical stirring, and when the waste salt solution is cooled to room temperature, continuing to cool by using a cooling medium until no solid is separated out, so as to obtain waste salt grains;
(5) The waste salt grains are input into a dryer for drying, the heat source of the dryer is the hot tail gas of the incinerator, and the tail gas of the dryer enters a tail gas treatment device for treatment;
the pretreatment tank comprises a front part and a rear part, which are respectively a dissolution chamber and a crystallization chamber, and a lifting control gate is arranged between the dissolution chamber and the crystallization chamber;
the dissolving chamber and the crystallization chamber are respectively provided with a first stirring part and a second stirring part, and the dissolving chamber is provided with a heating device;
The side wall of the dissolution chamber is provided with a lifting siphon, and the tail end of the siphon is connected with a waste water pipeline for discharging nonpolar organic matters;
The second stirring part comprises a plurality of stirring paddles which are uniformly distributed along the circumferential direction of the stirring shaft, the stirring paddles can move up and down along the stirring shaft, the stirring paddles are in a strainer shape, the aperture of a filter screen is 5mm, and waste salt crystal grains with the grain diameter larger than 5mm are fished out while stirring;
The stirring paddle can rotate, when the stirring paddle drags up waste salt grains and moves to the upper part of the stirring shaft and is above the liquid level, the stirring paddle rotates, the opening is downward, the grains are poured on a conveyor belt, and the conveyor belt is connected with the dryer;
the liquid outlet of the crystallization chamber is connected with the middle storage tank, and the middle storage tank is connected with the liquid inlet of the dissolution chamber, so that the dissolution chamber and the crystallization chamber of the pretreatment tank realize continuous operation;
The incinerator comprises an incineration area, a pre-cooling area and a discharge area from top to bottom in sequence, a porous plate is arranged between the incineration area and the pre-cooling area and is used for placing the waste salt grains, and after organic matters on the surfaces of the waste salt grains are incinerated, the waste salt grains particles and part of melt flow down from the porous plate or flow down to the pre-cooling area;
the pre-cooling area is internally provided with a rotating part which is a hollow pipeline, and a cooling medium is introduced into the rotating part for cooling and crushing the burnt substances;
a discharge hole is formed in the bottom of the discharge area and is connected with the dissolution filter tank;
The rotary part is a horizontally placed spiral pipe fitting, two ends of the rotary part respectively penetrate through the side wall of the pre-cooling area, and mechanical seals are arranged at the penetrating parts and are respectively used for inputting and outputting cooling media; one end of the rotating member is connected with a driving device for driving the rotating member to horizontally rotate and cool and break up substances falling onto the rotating member.
2. The method for integrated treatment of industrial waste salt according to claim 1, wherein in step S300, the waste salt particles are fed into a dissolution filter tank, wherein inorganic salt components are dissolved in water, and inorganic carbon components formed by pyrolysis of organic matters are filtered and separated;
and a solid waste outlet of the dissolving and filtering tank is connected with sludge dewatering equipment, so that sludge containing inorganic carbon is dewatered and reduced, and finally the sludge is transported to compost.
3. The method for comprehensive treatment of industrial waste salt according to claim 1, wherein in step S500, the steps of:
(6) Inputting the solution obtained in the step S300 into an ultrafiltration unit of a membrane separation unit to remove indissolvable hydroxides, impurities and suspended matters;
(7) The produced water of the ultrafiltration unit is a mixed salt solution and is input into the nanofiltration unit, the mixed salt solution is selectively separated, and chlorine salt and sodium sulfate are mainly separated;
(8) The produced water of the nanofiltration unit is chloride salt solution and is input into a first reverse osmosis unit for deep purification and separation; the produced water of the first reverse osmosis unit can be recycled as reclaimed water, and the concentrated water produced by the first reverse osmosis unit is chloride concentrated water;
(9) The concentrated water generated by the nanofiltration unit is input into a forward osmosis unit for further concentration, and the concentrated water generated by the forward osmosis unit is sulfate concentrated water;
(10) The produced water of the forward osmosis unit is input into a second reverse osmosis unit for separation and purification, and the concentrated water produced by the second reverse osmosis unit is input into the forward osmosis unit and is used as the drawing liquid of the forward osmosis unit; the produced water of the second reverse osmosis unit can be recycled as reclaimed water and is input into a recycling water tank.
4. The method for the integrated treatment of industrial waste salt according to claim 3, wherein in the step (7), the concentrated water generated by the ultrafiltration unit is fed into a dissolution filter tank, and the concentrated water containing insoluble hydroxide, impurities and suspended matters is returned to the dissolution filter tank for re-filtration;
In the step (8), the produced water of the nanofiltration unit is firstly input into a nanofiltration produced water tank, and then enters a first reverse osmosis unit after standing, sedimentation and adjustment;
In the step (10), the concentrated water generated by the second reverse osmosis unit is Na 2SO4 solution, which returns to the forward osmosis unit and is used as the drawing liquid of the forward osmosis unit, the concentration of the concentrated water generated by the nanofiltration unit is lower than that of the drawing liquid, the nanofiltration concentrated water is drawn by the concentrated water of the second reverse osmosis unit and then concentrated to obtain forward osmosis concentrated liquid, the drawing liquid is diluted after forward osmosis, and the drawing liquid returns to the second reverse osmosis unit again as the produced water of the forward osmosis unit for purification.
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