CN108726541A - A kind of method that recycling coal chemical industry exhaust gas prepares niter cake with waste water - Google Patents
A kind of method that recycling coal chemical industry exhaust gas prepares niter cake with waste water Download PDFInfo
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- CN108726541A CN108726541A CN201810523555.2A CN201810523555A CN108726541A CN 108726541 A CN108726541 A CN 108726541A CN 201810523555 A CN201810523555 A CN 201810523555A CN 108726541 A CN108726541 A CN 108726541A
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- 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
- C01D5/02—Preparation of sulfates from alkali metal salts and sulfuric acid or bisulfates; Preparation of bisulfates
Abstract
A kind of method that recycling coal chemical industry exhaust gas prepares niter cake with waste water, it is related to waste water, exhaust gas and recycling field.The purpose of the present invention is to solve can be effectively treated and recycle to coal chemical industry exhaust gas and strong brine simultaneously currently without one kind.The present invention improves the resource rate of coal chemical industry water body and gas when handling coal chemical industry exhaust gas with strong brine.The present invention prepares the raw material of niter cake, i.e. sodium chloride in sulfur dioxide and strong brine in coal chemical industry exhaust gas results from coal chemical industry production process, has economic feasibility；The present invention directly utilizes the sulphur dioxide production sulfuric acid in exhaust gas, and recovery technology of sulfur when saving coal chemical industry processing exhaust gas saves energy consumption.
Description
Technical field
The present invention relates to waste water, exhaust gas and recycling field more particularly to a kind of utilization coal chemical industry exhaust gas and dense salt
The method that water prepares niter cake.
Background technology
China is coal resources big country, and coal resources reserves account for 75% or more of energy resources total amount.China in Recent Years coal
Chemical industry high speed development, while country strengthens to coal chemical industry environmental protection and supervision.National New Coal Chemical industry
Using high-energy source conversion ratio as direction, has the few feature of " waste water, exhaust gas, waste liquid " discharge capacity, while strengthening to production process
In by-product and resource recycling.
Coal chemical industry strong brine results from the grey water system of coal chemical industry water resource recycling, contains a large amount of hardly degraded organic substances
(COD 500-5,000mg/L) and salt (up to 100,000mg/L, with Na+、Cl-、SO4 2-、NO3 -Based on), therefore coal chemical industry is dense
Brine water quality complexity is difficult, is the principal element for restricting coal chemical industry development." film concentration+evaporative crystallization " is to be applied in fact
A kind of coal chemical industry strong brine treatment technology in the engineering of border, coal chemical industry strong brine are concentrated into one third or so by reverse osmosis membrane
Enter evaporative crystallization technique, conventional machinery falling film evaporation MVR evaporations, two-effect evaporation or multiple-effect evaporation technique, eventually by TVR afterwards
Crystallizing evaporator, desiccation crystallization and the crystallizers such as two effect crystallizers prepare crystal salt.
Major pollutants in coal chemical industry exhaust gas are hydrogen sulfide and sulfur dioxide, include additionally oxide, flue dust, dioxy
Change carbon.Hydro carbons and other organic matters etc..The different technical process such as burnt, coal liquifaction and coal gas for coal system, exhaust gas have at
Point and content difference.Sulfur dioxide application ammonia absorption process in coal chemical industry exhaust gas, alkali absorption method, milk of lime gypsum now
Method, limestone washing method, zinc oxide absorption process, citrate method etc. are handled, and are prepared by Crouse or Scott technique
At recyclable sulphur.
Harbin Institute of Technology proposes《A kind of method that coal chemical industry strong brine separation evaporative crystallization prepares Nacl》, patent
Number：105399262 A of CN, the invention pass through coagulating sedimentation, stripping, ultrafiltration, nanofiltration, activated carbon, ion exchange resin and evaporative crystallization
Technique money recycles technical grade crystal salt using coal chemical industry strong brine.《A kind of method of preparing sulfuric acid by using sulfur dioxide》, patent No. CN
102530888 A, the invention by by the sulfur dioxide gas in anhydrite cement production technology by two sections of catalytic oxidations and
Vanadium oxide or lithium sulfate catalyst preparation sulfuric acid.However above-mentioned first is invented the sodium chloride only related to and sodium nitrate preparation, the
Two are invented the preparation for only relating to the concentrated sulfuric acid in cement industry.Therefore a kind of recycling coal chemical industry exhaust gas is prepared with strong brine
The method of niter cake requires study.
Invention content
The purpose of the present invention is to solve can be handled with waste water coal chemical industry exhaust gas simultaneously currently without one kind
And the problem of recycling, and a kind of method that recycling coal chemical industry exhaust gas prepares niter cake with waste water is provided.
The method that a kind of recycling coal chemical industry exhaust gas of the present invention prepares niter cake with waste water, it is according to following
What step carried out：
One, regulating reservoir：Coal chemical industrial waste water is passed through regulating reservoir, adjusting water outlet water and stabilizing water quality；
Two, passivation technology：Calcium oxide, magnesia mixture, sodium carbonate, coagulant and flocculation aid are added in coal chemical industrial waste water, it is described
Calcium oxide dosage be 100~150mg/L；The sodium carbonate dosage is 60~70mg/L；The coagulant is thrown
Dosage is 50mg/L~100mg/L；The flocculation aid dosage is 0.5~1.0mg/L；The magnesia mixture and coal chemical industrial waste water
Middle SiO3 2-Mass ratio be 12：1；Wherein, go out the water hardness and be less than 50mg/L, silicon is less than 25mg/L；
Three, multi-medium filtering：By the water outlet of step 2 be passed through in more medium filter remove coal chemical industrial waste water in particle,
Colloid and suspended matter, step 3 delivery turbidity are less than 0.1NTU；
Four, ion exchange resin：The water outlet of step 3 is passed through in ion exchange resin switch, is obtained through ion exchange resin
Hardness is less than the water outlet of 2mg/L afterwards；
Five, nanofiltration separation：The water outlet of step 4 is passed through in nanofiltration system, is formed after nanofiltration is handled and with sodium chloride is
Main nanofiltration permeate liquid and with sodium sulphate be main nanofiltration concentrated water；
Six, exhaust gas washs：Coal chemical industry exhaust gas is removed into removing exhaust gas by cyclone separator, spray column, electrostatic precipitator, drying tower
In suspended impurity, acid mist, fluorine and moisture；To obtain dry purification gas；
Seven, sulfur dioxide absorbs：It will obtain dry purification gas to be passed through in the middle part of desulfurizing tower, enter at the top of desulfurizing tower
Desulfurizing agent counter current contacting, make desulfurizing agent absorbing sulfur dioxide in exhaust gas；Treated coal chemical industry exhaust gas is at the top of desulfurizing tower
The desulfurizing agent for having adsorbed sulfur dioxide is discharged from desulfurization tower bottom for discharge；
Eight, desulfurizing agent pyrolysis regeneration：In step 7 absorb rich solution be sent into regenerator, pure sulfur dioxide gas from
Discharge, the lean solution after regeneration return to desulfurizing tower top and recycle at the top of regenerator；The rich solution is the desulfurization of sulfur dioxide
Agent；
Nine, catalysis oxidation prepares sulfur trioxide：The sulfur dioxide gas of step 8 discharge is sent into contact chamber, at 450 DEG C
Under the catalytic action of temperature and vanadic anhydride, sulfur trioxide is made；
Ten, prepared by pyrosulfuric acid：Sulfur trioxide gas temperature prepared by step 9 is down to 150 DEG C by heat exchange, then
After its concentrated sulfuric acid for being 98.3% with volumn concentration in absorption tower is absorbed, pyrosulfuric acid is prepared；
11, prepared by sulfuric acid：Water is added to prepare the industrial concentrated sulfuric acid pyrosulfuric acid that step 10 obtains；
12, distilation：The industrial concentrated sulfuric acid that step 11 is prepared is purified by distillation technique；
13, the nanofiltration permeate liquid based on sodium chloride that step 5 generates is passed through in reaction kettle, while step is added
The concentrated sulfuric acid that 12 volumn concentrations prepared are 95%, carries out the preparation of sodium bisulfate in a kettle；
14：Niter cake evaporative crystallization technique：By step 13 prepare sodium bisulfate be passed through temperature be 90~
Niter cake is prepared in 120 DEG C of crystallizing evaporator, then prepares industrial sulphuric acid in the crystallizer that temperature is 130~195 DEG C
Hydrogen sodium；
15：Anhydrous sodium sulfate evaporative crystallization technique：Step 5 is pumped into evaporator with sodium sulphate for main nanofiltration concentrated water
In, the salt content in making step 5 be discharged is concentrated by evaporation to 180,000~200000mg/L, and concentration saline solution is then delivered to knot
In brilliant device, control crystallization temperature is 95 DEG C~105 DEG C, and industrial anhydrous sodium sulfate is prepared.
The present invention includes following advantageous effect：
One, the present invention improves coal when handling coal chemical industry exhaust gas with waste water (strong brine especially in waste water)
The resource rate of chemical industry water body and gas.
Two, the present invention prepares the raw material of niter cake, i.e. chlorination in sulfur dioxide and strong brine in coal chemical industry exhaust gas
Sodium results from coal chemical industry production process, has economic feasibility；
Three, the present invention directly utilizes the sulphur dioxide production sulfuric acid in exhaust gas, sulphur when saving coal chemical industry processing exhaust gas
Sulphur recovery process saves energy consumption.
The resource conversion rate of the present invention reaches 80% or more.
Description of the drawings
Fig. 1 is the flow chart that recycling coal chemical industry exhaust gas prepares niter cake with strong brine.
Specific implementation mode
Specific implementation mode one：A kind of recycling coal chemical industry exhaust gas of present embodiment prepares niter cake with waste water
Method, it is followed the steps below：
One, regulating reservoir：Coal chemical industrial waste water is passed through regulating reservoir, adjusting water outlet water and stabilizing water quality；
Two, passivation technology：Calcium oxide, magnesia mixture, sodium carbonate, coagulant and flocculation aid are added in coal chemical industrial waste water, it is described
Calcium oxide dosage be 100~150mg/L；The sodium carbonate dosage is 60~70mg/L；The coagulant is thrown
Dosage is 50mg/L~100mg/L；The flocculation aid dosage is 0.5~1.0mg/L；The magnesia mixture and coal chemical industrial waste water
Middle SiO3 2-Mass ratio be 12：1；Wherein, go out the water hardness and be less than 50mg/L, silicon is less than 25mg/L；
Three, multi-medium filtering：By the water outlet of step 2 be passed through in more medium filter remove coal chemical industrial waste water in particle,
Colloid and suspended matter, step 3 delivery turbidity are less than 0.1NTU；
Four, ion exchange resin：The water outlet of step 3 is passed through in ion exchange resin switch, is obtained through ion exchange resin
Hardness is less than the water outlet of 2mg/L afterwards；
Five, nanofiltration separation：The water outlet of step 4 is passed through in nanofiltration system, is formed after nanofiltration is handled and with sodium chloride is
Main nanofiltration permeate liquid and with sodium sulphate be main nanofiltration concentrated water；
Six, exhaust gas washs：Coal chemical industry exhaust gas is removed into removing exhaust gas by cyclone separator, spray column, electrostatic precipitator, drying tower
In suspended impurity, acid mist, fluorine and moisture；To obtain dry purification gas；
Seven, sulfur dioxide absorbs：It will obtain dry purification gas to be passed through in the middle part of desulfurizing tower, enter at the top of desulfurizing tower
Desulfurizing agent counter current contacting, make desulfurizing agent absorbing sulfur dioxide in exhaust gas；Treated coal chemical industry exhaust gas is at the top of desulfurizing tower
The desulfurizing agent for having adsorbed sulfur dioxide is discharged from desulfurization tower bottom for discharge；
Eight, desulfurizing agent pyrolysis regeneration：In step 7 absorb rich solution be sent into regenerator, pure sulfur dioxide gas from
Discharge, the lean solution after regeneration return to desulfurizing tower top and recycle at the top of regenerator；The rich solution is the desulfurization of sulfur dioxide
Agent；
Nine, catalysis oxidation prepares sulfur trioxide：The sulfur dioxide gas of step 8 discharge is sent into contact chamber, at 450 DEG C
Under the catalytic action of temperature and vanadic anhydride, sulfur trioxide is made；
Ten, prepared by pyrosulfuric acid：Sulfur trioxide gas temperature prepared by step 9 is down to 150 DEG C by heat exchange, then
After its concentrated sulfuric acid for being 98.3% with volumn concentration in absorption tower is absorbed, pyrosulfuric acid is prepared；
11, prepared by sulfuric acid：Water is added to prepare the industrial concentrated sulfuric acid pyrosulfuric acid that step 10 obtains；
12, distilation：The industrial concentrated sulfuric acid that step 11 is prepared is purified by distillation technique；
13, the nanofiltration permeate liquid based on sodium chloride that step 5 generates is passed through in reaction kettle, while step is added
The concentrated sulfuric acid that 12 volumn concentrations prepared are 95%, carries out the preparation of sodium bisulfate in a kettle；
14：Niter cake evaporative crystallization technique：By step 13 prepare sodium bisulfate be passed through temperature be 90~
Niter cake is prepared in 120 DEG C of crystallizing evaporator, then prepares industrial sulphuric acid in the crystallizer that temperature is 130~195 DEG C
Hydrogen sodium；
15：Anhydrous sodium sulfate evaporative crystallization technique：Step 5 is pumped into evaporator with sodium sulphate for main nanofiltration concentrated water
In, the salt content in making step 5 be discharged is concentrated by evaporation to 180,000~200000mg/L, and concentration saline solution is then delivered to knot
In brilliant device, control crystallization temperature is 95 DEG C~105 DEG C, and industrial anhydrous sodium sulfate is prepared.
The purpose that present embodiment step 2 adds medicament is to remove heavy metal in coal chemical industry strong brine, silicon and outstanding
Float.
In present embodiment step 3, the particle in coal chemical industry strong brine, colloid and suspended matter pass through more medium filter
Multilayer filtrate be retained in more medium filter, reach and remove particulate matter, colloid and the suspended matter in coal chemical industry strong brine
The purpose removed.
In present embodiment step 4, what the calcium ions and magnesium ions in coal chemical industry strong brine were formed with ion exchange resin functional group
Chemical bond energy is stronger, replaces the cation in ion exchange resin, effectively reduces the LSI indexes in strong brine.
Ion exchange resin described in present embodiment four has degree of cross linking height, and to processing haline water, high pH water quality
Characteristic.
NF membrane in present embodiment step 5 has that aperture is small and the strong feature of film surface elecrtonegativity, passes through and sieves effect
The hardly degraded organic substance in strong brine should be removed, retain multivalent ion by charge effect penetrates monovalention simultaneously.NF membrane
70% is more than to the rejection of organic matter, 60% is higher than to the rejection of polyvalent cation, multivalent anions rejection is more than
90%, it is 10% even negative rejection rate to the rejection of monovalent ion.
The material and configuration of NF membrane in present embodiment step 5 with to the contamination resistance phase of coal chemical industry strong brine
It closes, the contamination resistance of nanofiltration technique has an impact the Stability and dependability of technique.
Liquid dilute sulfuric acid in spray column in present embodiment step 6, dilute sulfuric acid a concentration of 10%；
The concentrated sulfuric acid a concentration of 93% to 95% in present embodiment step 6 in drying tower；
Gas componant of the present embodiment step 6 after exhaust gas washs is sulfur dioxide, oxygen, nitrogen.
The waste water of the present embodiment is strong brine.
The chemical reaction foundation that sulfur trioxide generates in contact chamber in present embodiment step 9
(reversible reaction) carries out；
Chemical reaction foundation in present embodiment step 10 absorption towerInto
Row；
Present embodiment step 11 pyrosulfuric acid is with water according to H2SO7+H2O=2H2SO4Generate sulfuric acid；
The concentrated sulfuric acid a concentration of 95% to 98% after 12 distilation of present embodiment；
The reaction equation for preparing niter cake in present embodiment 13 in reaction kettle is：
Specific implementation mode three：The present embodiment is different from the first embodiment in that：The structure of NF membrane includes volume
Formula NF membrane, dish tubular nanofiltration membrane or vibration membrane etc..It is other same as the specific embodiment one.
Specific implementation mode four：The present embodiment is different from the first embodiment in that：Coagulation described in step 2
Agent is poly-ferric chloride or ferrous sulfate, and flocculation aid is that polyacrylamide is other same as the specific embodiment one.
Specific implementation mode five：The present embodiment is different from the first embodiment in that：Magnesia mixture described in step 2
For magnesia.It is other same as the specific embodiment one.Magnesia mixture includes magnesia, and what front was said is magnesia mixture, this specific implementation
Say that magnesia mixture is that magnesia has a hunch that range reference is upper problematic in example the inside.
Specific implementation mode six：The present embodiment is different from the first embodiment in that：More Jie described in step 3
Mass filter filtrate is activated carbon-quartz sand-magnetic iron ore etc..It is other same as the specific embodiment one.
Specific implementation mode eight：The present embodiment is different from the first embodiment in that：Desulfurizing agent described in step 7
For reproducible organic solvent tetraethyleneglycol dimethyl ether, volumn concentration 98%.It is other same as the specific embodiment one.
Specific implementation mode nine：The present embodiment is different from the first embodiment in that：In step 13 in reaction kettle
The concentrated sulfuric acid is 1~1.2 in molar ratio with sodium chloride：1.It is other same as the specific embodiment one.
Specific implementation mode ten：The present embodiment is different from the first embodiment in that：Kettle temperature is reacted in step 13
Degree is 120 DEG C, reaction time 20min.It is other same as the specific embodiment one.
Specific implementation mode 11：The present embodiment is different from the first embodiment in that：The desulfurizing agent is
24wt% phosphate solutions.It is other same as the specific embodiment one.
Specific implementation mode 12：The present embodiment is different from the first embodiment in that：The desulfurizing agent is
28wt%TMHEED amine, i.e. N, mono- trimethyl of N, N, N mono- (2 ethoxy) ethylenediamine.It is other same as the specific embodiment one.
Specific implementation mode 13：The present embodiment is different from the first embodiment in that：In step 14 and 15
The crystallizing evaporator device is mechanical falling film evaporation MVR evaporators, forced-circulation evaporation crystallizer, continuous evaporating crystallizer and
Multi-effect evaporation crystallizer.It is other same as the specific embodiment one.
Beneficial effects of the present invention are verified by following embodiment：
Embodiment 1
The method that a kind of recycling coal chemical industry exhaust gas of the present embodiment prepares niter cake with strong brine, it be according to
What following steps carried out：
One, regulating reservoir：Coal chemical industry strong brine raw water is passed through regulating reservoir, adjusting water outlet water quality and water；
Two, passivation technology：Coal chemical industry strong brine in step 1 is passed through in passivation technology, and add calcium oxide, magnesia mixture,
Sodium carbonate, coagulant and flocculation aid, the Process for Effluent hardness are less than 50mg/L, and silicon is less than 25mg/L；The throwing of the calcium oxide
Dosage is 2000mg/L；The sodium carbonate dosage is 2500mg/L；The coagulant charging quantity be 50mg/L~
100mg/L；The flocculation aid dosage is 0.5mg/L；The magnesia mixture and SiO in coal chemical industry strong brine3 2-Mass ratio be
12：1；
Three, multi-medium filtering：The water outlet of step 2 is passed through in more medium filter and removes particle, suspended matter with colloid,
Step 3 delivery turbidity is less than 0.1NTU；
Four, ion exchange resin；Step 3 water outlet is passed through in ion exchange resin device, by by coal chemical industry strong brine
In calcium ions and magnesium ions and ion exchange resin functional group the hardness in displacement removal strong brine occurs, step 4 goes out the water hardness and is less than
2mg/L；
Five, nanofiltration separation：The water outlet of step 4 is passed through in nanofiltration system, it will be in coal chemical industry strong brine by NF membrane
Organic matter multivalent salts retain, and are formed after nanofiltration is handled and are main nanofiltration permeate liquid with sodium chloride and are that main nanofiltration is dense with sodium sulphate
Water；
Six, exhaust gas washs：Coal chemical industry exhaust gas is removed into removing exhaust gas by cyclone separator, spray column, electrostatic precipitator, drying tower
In suspended impurity, acid mist, fluorine and moisture.It is detached in sedimentation exhaust gas by using mechanical force in the cyclone separator
Suspended impurity；Exhaust gas is sprayed into exhaust gas by spray column liquid level or with the liquid in spray column, further removes removing exhaust gas
In impurity；The effect of the electrostatic precipitator is by the acid mist removal in exhaust gas；Exhaust gas is passed through drying tower and concentrated sulfuric acid adverse current
Contact, to obtain dry purification gas；
Seven, sulfur dioxide absorbs：Exhaust gas in step 6 by washing will be passed through in the middle part of desulfurizing tower, and at the top of desulfurizing tower
The desulfurizing agent counter current contacting of entrance, makes desulfurizing agent absorbing sulfur dioxide in exhaust gas.Treated coal chemical industry exhaust gas is from desulfurizing tower
Top is discharged, and the desulfurizing agent for having adsorbed sulfur dioxide is discharged from desulfurization tower bottom；
Eight, desulfurizing agent pyrolysis regeneration：Rich solution (desulfurizing agent for absorbing sulfur dioxide) in step 7 is sent into regenerator,
Rich solution is heated in regenerator is decomposited sulfur dioxide while being regenerated in the form of lean solution.Wherein pure sulfur dioxide gas
It is discharged at the top of from regenerator, the lean solution after regeneration returns to desulfurizing tower top and recycles.
Nine, catalysis oxidation prepares sulfur trioxide：The sulfur dioxide gas of step 8 discharge is sent into contact chamber, passes through 450
The catalytic action of DEG C high temperature and vanadic anhydride prepares sulfur trioxide.The chemical reaction foundation that sulfur trioxide generates in contact chamber(reversible reaction) carries out；
Ten, prepared by pyrosulfuric acid：Sulfur trioxide gas temperature prepared by step 9 is reduced to 150 DEG C by heat exchange, is being inhaled
It receives and prepares pyrosulfuric acid (H after being absorbed with 98.3% concentrated sulfuric acid in tower2S2O7).Chemical reaction foundation in absorption towerIt carries out；
11, prepared by sulfuric acid：Water is added to prepare sulfuric acid the pyrosulfuric acid that step 10 obtains.Pyrosulfuric acid is with water according to H2SO7+H2O
=2H2SO4Generate sulfuric acid；
12, distilation：The industrial concentrated sulfuric acid that step 11 is prepared is purified by distillation technique；
13, the nanofiltration permeate liquid based on sodium chloride that step 5 generates is passed through in reaction kettle, while step is added
12 95% concentrated sulfuric acids prepared, carry out the preparation of sodium bisulfate in a kettle；
14：Niter cake evaporative crystallization technique：It is 90- that sodium bisulfate prepared by step 13, which is passed through temperature,
Niter cake is prepared in 120 DEG C of crystallizing evaporator, then prepares industrial sulphuric acid hydrogen in the crystallizer that temperature is 130-195 DEG C
Sodium.
15：Anhydrous sodium sulfate evaporative crystallization technique：The nanofiltration concentrated water of step 5 is pumped into evaporator, step 5 is made to go out
Salt content in water is concentrated by evaporation to 200,000mg/L, and then concentration saline solution is delivered in crystallizer, and control crystallization temperature is
Between 95 DEG C~105 DEG C, industrial anhydrous sodium sulfate is prepared.
The waste water of the present embodiment is strong brine.
The purpose that the present embodiment step 2 adds medicament is to remove heavy metal, silicon and the suspension in coal chemical industry strong brine
Object.
In the present embodiment step 3, the particle in coal chemical industry strong brine, colloid and suspended matter pass through more medium filter
Multilayer filtrate is retained in more medium filter, is reached particulate matter, colloid and the suspended matter removal in coal chemical industry strong brine
Purpose.
In the present embodiment step 4, the change of calcium ions and magnesium ions and the formation of ion exchange resin functional group in coal chemical industry strong brine
Key bond energy is stronger, replaces the cation in ion exchange resin, effectively reduces the LSI indexes in strong brine.
Ion exchange resin described in the present embodiment four has degree of cross linking height, and the spy to processing haline water, high pH water
Property.
NF membrane in the present embodiment step 5 has that aperture is small and the strong feature of film surface elecrtonegativity, passes through sieve effect
The hardly degraded organic substance in strong brine is removed, retain multivalent ion by charge effect penetrates monovalention simultaneously.NF membrane pair
The rejection of organic matter is more than 70%, is higher than 60% to the rejection of polyvalent cation, is more than to multivalent anions rejection
90%, it is 10% even negative rejection rate to the rejection of monovalent ion.
The material of NF membrane in the present embodiment step 5 is the composite film material of semi-aromatic piperazines polyamide.
NF membrane configuration in the present embodiment step 5 includes rolling NF membrane.
The material and configuration of NF membrane in the present embodiment step 5 are related to the contamination resistance to coal chemical industry strong brine,
The contamination resistance of nanofiltration technique has an impact the Stability and dependability of technique.
Liquid dilute sulfuric acid in spray column in the present embodiment step 6, dilute sulfuric acid a concentration of 10%；
The concentrated sulfuric acid a concentration of 93% to 95% in the present embodiment step 6 in drying tower；
Gas componant of the present embodiment step 6 after exhaust gas washs is sulfur dioxide, oxygen, nitrogen.
Desulfurizing agent described in the present embodiment step 7 is reproducible organic solvent tetraethyleneglycol dimethyl ether, a concentration of
98%；
The concentrated sulfuric acid a concentration of 95% to 98% after 12 distilation of the present embodiment；
The concentrated sulfuric acid and sodium chloride in molar ratio are 1 in reaction kettle in the present embodiment 13：1.
Temperature is 120 DEG C in reaction kettle in the present embodiment 13, and the reaction time is 20 minutes.
The reaction equation for preparing niter cake in the present embodiment 13 in reaction kettle is：
The correlated results of the present embodiment is as shown in table 1 to table 4.
1 influent quality table of table
2 coal chemical industry strong brine of table handles Inlet and outlet water water quality table
As shown in Table 2, coal chemical industry strong brine can effectively obtain the strong brine based on sodium chloride after the technical finesse.
3 exhaust-gas treatment of table is tested
As shown in Table 3,90% pyrosulfuric acid can be obtained by the above technical finesse, then by being obtained by the reaction with water
The concentrated sulfuric acid of 90% son 98%.
It is prepared by 4 niter cake liquid of table
Remarks：Solution NaCl concentration is 64071mg/L.
As shown in Table 4, the sodium chloride and sodium sulphate obtained by the above technology can efficiently generate niter cake.With sulphur
Acid concentration is increased to 98% from 90%, and the conversion ratio that sodium chloride solution generates niter cake with sulfuric acid reaction is increased to by 91.34
93.94%.
Claims (9)
1. a kind of method that recycling coal chemical industry exhaust gas prepares niter cake with waste water, it is characterised in that it is according to following
What step carried out：
One, regulating reservoir：Coal chemical industrial waste water is passed through regulating reservoir, adjusting water outlet water and stabilizing water quality；
Two, passivation technology：Calcium oxide, magnesia mixture, sodium carbonate, coagulant and flocculation aid, the oxygen are added in coal chemical industrial waste water
The dosage for changing calcium is 100~150mg/L；The sodium carbonate dosage is 60~70mg/L；The coagulant charging quantity
For 50mg/L~100mg/L；The flocculation aid dosage is 0.5~1.0mg/L；In the magnesia mixture and coal chemical industrial waste water
SiO3 2-Mass ratio be 12：1；Wherein, go out the water hardness and be less than 50mg/L, silicon is less than 25mg/L；
Three, multi-medium filtering：The water outlet of step 2 is passed through to particle, the colloid removed in more medium filter in coal chemical industrial waste water
And suspended matter, step 3 delivery turbidity are less than 0.1NTU；
Four, ion exchange resin：The water outlet of step 3 is passed through in ion exchange resin switch, is obtained hard after ion exchange resin
Water outlet of the degree less than 2mg/L；
Five, nanofiltration separation：The water outlet of step 4 is passed through in nanofiltration system, is formed after nanofiltration is handled and is received based on sodium chloride
Filter permeate and with sodium sulphate for main nanofiltration concentrated water；
Six, exhaust gas washs：Coal chemical industry exhaust gas is gone by cyclone separator, spray column, electrostatic precipitator, drying tower in removing exhaust gas
Suspended impurity, acid mist, fluorine and moisture；To obtain dry purification gas；
Seven, sulfur dioxide absorbs：Dry purification gas will be obtained to be passed through in the middle part of desulfurizing tower, it is de- with entering at the top of desulfurizing tower
Sulphur agent counter current contacting, makes desulfurizing agent absorbing sulfur dioxide in exhaust gas；Treated coal chemical industry exhaust gas is discharged at the top of desulfurizing tower,
The desulfurizing agent for having adsorbed sulfur dioxide is discharged from desulfurization tower bottom；
Eight, desulfurizing agent pyrolysis regeneration：The rich solution that absorbs in step 7 is sent into regenerator, and pure sulfur dioxide gas is from regeneration
Top of tower is discharged, and the lean solution after regeneration returns to desulfurizing tower top and recycles；The rich solution is the desulfurizing agent of sulfur dioxide；
Nine, catalysis oxidation prepares sulfur trioxide：The sulfur dioxide gas of step 8 discharge is sent into contact chamber, in 450 DEG C of temperature,
And under the catalytic action of vanadic anhydride, sulfur trioxide is made；
Ten, prepared by pyrosulfuric acid：Sulfur trioxide gas temperature prepared by step 9 is down to 150 DEG C by heat exchange, then by it
After the concentrated sulfuric acid for being 98.3% with volumn concentration in absorption tower absorbs, pyrosulfuric acid is prepared；
11, prepared by sulfuric acid：Water is added to prepare the industrial concentrated sulfuric acid pyrosulfuric acid that step 10 obtains；
12, distilation：The industrial concentrated sulfuric acid that step 11 is prepared is purified by distillation technique；
13, the nanofiltration permeate liquid based on sodium chloride that step 5 generates is passed through in reaction kettle, while step 12 is added
The concentrated sulfuric acid that the volumn concentration of preparation is 95% carries out the preparation of sodium bisulfate in a kettle；
14：Niter cake evaporative crystallization technique：It is 90~120 DEG C that sodium bisulfate prepared by step 13, which is passed through temperature,
Crystallizing evaporator in prepare niter cake, then prepare industrial sulphuric acid hydrogen sodium in temperature is 130~195 DEG C of crystallizer；
15：Anhydrous sodium sulfate evaporative crystallization technique：Step 5 is pumped into for main nanofiltration concentrated water in evaporator with sodium sulphate, is made
Salt content in step 5 water outlet is concentrated by evaporation to 180,000~200000mg/L, and concentration saline solution is then delivered to crystallizer
In, control crystallization temperature is 95 DEG C~105 DEG C, and industrial anhydrous sodium sulfate is prepared.
2. the method that a kind of recycling coal chemical industry exhaust gas according to claim 1 prepares niter cake with waste water,
It is characterized in that the coagulant described in step 2 is poly-ferric chloride or ferrous sulfate.
3. the method that a kind of recycling coal chemical industry exhaust gas according to claim 1 prepares niter cake with waste water,
It is characterized in that the flocculation aid described in step 2 is polyacrylamide.
4. the method that a kind of recycling coal chemical industry exhaust gas according to claim 1 prepares niter cake with waste water,
It is characterized in that the magnesia mixture described in step 2 is magnesia.
5. the method that a kind of recycling coal chemical industry exhaust gas according to claim 1 prepares niter cake with waste water,
It is characterized in that the more medium filter filtrate described in step 3 is activated carbon-quartz sand-magnetic iron ore.
6. the method that a kind of recycling coal chemical industry exhaust gas according to claim 1 prepares niter cake with waste water,
It is characterized in that the desulfurizing agent described in step 7 is reproducible organic solvent tetraethyleneglycol dimethyl ether, volumn concentration is
98%.
7. the method that a kind of recycling coal chemical industry exhaust gas according to claim 1 prepares niter cake with waste water,
It is characterized in that in step 13 in reaction kettle that the concentrated sulfuric acid and sodium chloride in molar ratio are 1~1.2：1.
8. the method that a kind of recycling coal chemical industry exhaust gas according to claim 1 prepares niter cake with waste water,
It is characterized in that in step 13 that temperature of reaction kettle is 120 DEG C, reaction time 20min.
9. the method that a kind of recycling coal chemical industry exhaust gas according to claim 1 prepares niter cake with waste water,
It is characterized in that the waste water is strong brine.
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| CN110028085A (en) * | 2019-04-23 | 2019-07-19 | 鞍钢集团工程技术有限公司 | A kind of technique and system for producing anhydrous sodium sulphate using Desulphurization |
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