CN107098361A - A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing - Google Patents
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing Download PDFInfo
- Publication number
- CN107098361A CN107098361A CN201710332771.4A CN201710332771A CN107098361A CN 107098361 A CN107098361 A CN 107098361A CN 201710332771 A CN201710332771 A CN 201710332771A CN 107098361 A CN107098361 A CN 107098361A
- Authority
- CN
- China
- Prior art keywords
- salt
- solution
- liquid
- mother liquor
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C01D3/06—Preparation by working up brines; seawater or spent lyes
-
- 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
- C01D3/14—Purification
- C01D3/145—Purification by solid ion-exchangers or solid chelating agents
-
- 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
Abstract
The invention discloses a kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, comprise the steps of:1) well mine salt bittern is clarified by former halogen, enters centrifuge after dosing reaction and smart halogen clarification and get rid of salt slurry progress thickening processing after liquid, centrifugation;2) stood after salt slurry thickening processing, supernatant liquor overflow enters mother liquor pond, and the salt slurry of deposited bottom is pumped into dissolving bucket, liquid after being filtered after being dissolved in water fully;3) liquid removes Ca by ion exchange resin after filtering2+、Mg2+With part of sulfuric acid radical ion, then solution is heated and is evaporated under reduced pressure, occur after crystal precipitation that keeping temperature and pressure are constant, the mixed solution that hydrogen peroxide and ethanol are added into solution carries out dissolved;4) solution is filtered after dissolved, it is brilliant that gained filtrate is pumped into evaporative crystallization forming salt in evaporator.The present invention saves cost, on the basis of 1,000,000 tons/year of sal prunella combined production device, and it is about 3,400,000 yuan that annual new units increased in production, which can increase benefit, while the salt crystalline substance reclaimed significantly eliminates Ca2+、Mg2+And SO4 2‑Deng foreign ion.
Description
Technical field
The present invention relates to salt industry technical field, more particularly to a kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing.
Background technology
Salt is as the necessity of human survival and one of the most basic raw material of chemical industry, in the daily life of national economy
In all occupy very important status.China is production salt one of most long country, and China's salt resource is very in history of the world
Abundant, Qinghai, Xinjiang, Tibet etc. are saved, autonomous region is dispersed with several thousands of salt lakes with spreading all over the place, Sichuan, Yunnan, Jiangsu,
Shandong, Henan etc. save subsurface storage and abundant rock salt, and Huai'an possesses the maximum salt mine in the whole world.
China's sulfate type salt mine contains Mg mostly through the bittern after hydromining2+、Ca2+、SO4 2-Deng foreign ion, with this
Bittern salt manufacturing, the separation problem and foreign ion for always be unableing to do without salt and nitre removes problem.The method that past is commonly used is freezing
Carry nitre and vacuum salt production, in a very long time, salt it is with low quality, the cost and energy consumption for carrying nitre and purification are also higher.
Last century, late nineteen eighties China introduced sal prunella co-production technology, the salt making technology level of China is generated a leap, also gives
The technological progress of well mine salt industry provides model.Sal prunella coproduction, is exactly by technique groups in same covering device as its name suggests
Close, salt and nitre can be pressed to the output of matter according to quantity respectively, such a technology has advanced reliable, product quality height, comprehensive energy
Consumption is low, be the breakthrough of salt producing craft technical field the characteristics of reduce investment outlay, first most of large-scale salt making enterprises at home gradually
Popularization and application.
Flow quantity is about 130m after 1000000 tons/year of sal prunella combined production device crude salt centrifugal drying3/ h, saliferous crystalline substance, which is measured, is about
0.53% (mass fraction), these salt crystalline substance is deposited on bottom of pond after entering smart halogen mother liquor pond, is discharged by the brine pump of bottom of pond, this is just
6000 tons of salt crystalline substances were there are about equivalent to 1 year and do not enter the smart halogen of progress next step in smart halogen barrel with liquid after centrifugal drying, but discharge is unrestrained
Take.The difficulty reclaimed in view of this part salt crystalline substance, and purification problem neither one good solution is reclaimed, adopt extensively at present
Joint production process of salt and salt-cake does not consider the brilliant recovery of these salt mostly, causes resource and the significant wastage of wealth.
The content of the invention
Based on above-mentioned technical problem, the invention provides a kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, following step is included
Suddenly:
1) well mine salt bittern is clarified by former halogen, gets rid of liquid into centrifuge after dosing reaction and smart halogen clarification, centrifugation
Liquid pump enters mother liquor pond afterwards, and inputs in smart halogen bucket and carry out follow-up sal prunella coproduction process, and salt slurry carries out thickening processing after centrifugation;
2) stood after salt slurry thickening processing, supernatant liquor overflow enters liquid after mother liquor pond and the centrifugation and mixed, defeated in the lump
Enter in smart halogen bucket, the salt slurry of deposited bottom is pumped into dissolving bucket, distilled water is added into dissolving bucket and make it that soluble fraction fills in salt slurry
The solution divided in dissolving, filtering dissolving bucket, liquid after being filtered;
3) Ca by liquid after the filtering after ion exchange resin removes filtering in liquid2+、Mg2+With part of sulfuric acid root
After ion, ion exchange, solution is heated to 50~90 DEG C and is evaporated under reduced pressure, keeping temperature and pressure after there is crystal precipitation
Constant, the mixed solution that hydrogen peroxide and ethanol are added into solution carries out dissolved;
4) solution is filtered after dissolved, it is brilliant that gained filtrate is pumped into evaporative crystallization forming salt in evaporator.
Further, step is more specifically expressed as:
1) well mine salt bittern is clarified by former halogen, gets rid of liquid into centrifuge after dosing reaction and smart halogen clarification, centrifugation
Liquid pump enters mother liquor pond afterwards, and inputs in smart halogen bucket and carry out follow-up sal prunella coproduction process, and salt slurry is pumped into thickening with brine pump after centrifugation
Thickening processing is carried out in device, solid, liquid mass ratio is more than 1 after thickening:2.5;
2) stood after salt slurry thickening processing, time of repose >=2h, the supernatant liquor overflow of salt slurry enters mother liquor pond after standing
Mix, input in the lump in smart halogen bucket, the salt slurry of deposited bottom is pumped into dissolving bucket, and two are added into dissolving bucket with liquid after the centrifugation
Secondary distilled water make it that soluble fraction fully dissolves in salt slurry, and the solution in dissolving bucket, liquid after being filtered are filtered using suction filtration machine;
3) liquid after the filtering is removed into the Ca after filtering in liquid by ion exchange column2+、Mg2+、Ba2+And part of sulfuric acid
Be filled with ion exchange resin in radical ion, the ion exchange column, the ion exchange resin using it is preceding by sodium chloride and
Hydrochloric acid mixed solution is activated, and soak time is 10~40min, is cleaned and loaded in ion exchange column with redistilled water after activation,
After ion exchange, solution is imported in vacuum decompression evaporator, 75~85 DEG C is heated to and is evaporated under reduced pressure, the evaporation pressure is low
In 0.01 standard atmospheric pressure, keeping temperature and pressure are constant after there is crystal precipitation, and hydrogen peroxide and second are added into solution
The mixed solution of alcohol carries out dissolved;
4) solution is filtered after dissolved, gained filtrate is pumped into evaporative crystallization forming salt crystalline substance in evaporator, after the completion of crystallization, will
Salt crystalline substance is incubated 1~5h more than 160 DEG C, removes hydrogen peroxide, ethanol and the moisture of residual.
Further, the sodium chloride and hydrochloric acid mixed solution for mass fraction 5~7% HCl and mass fraction 3.5~
10% NaCl is mixed to form.
Further, agitating device and/or resistive heater are provided with the dissolving bucket so that salt slurry dissolution velocity increases
Plus.
Further, the hydrogen peroxide and ethanol are the H of mass fraction 30%2O2Mixed with ethanol, the quality point
The H of number 30%2O2Volume ratio with ethanol is 1~2:1, the addition volume of hydrogen peroxide and alcohol mixed solution is treats that dissolved is molten
The 10~20% of liquid product.
Further, the hydrogen peroxide is edible hydrogen peroxide.
Further, the ion exchange resin is food-grade sodium form cationic ion-exchange resin, is while removing Ca2+、Mg2 +、Ba2+With part of sulfuric acid radical ion, and improve removal ability, the sodium form cationic ion-exchange resin passes through modification, described
Modification procedure is:
1) sodium form cationic ion-exchange resin is fully leached in the ethanol water that volume fraction is 30%~70%, it is molten
Ultrasonic oscillation is carried out to solution during dissipating;
2) Na is added into the alcohol for leach ion exchange resin2SO4With the mixed aqueous solution of polyethylene glycol, by solution
60~80 DEG C of 2~4h of insulation are warming up to, insulation is filtered after terminating, isolate ion-exchange resin particles, and steamed with secondary
Distilled water is rinsed well;
3) ion-exchange resin particles rinsed well are incubated 100~120 DEG C under vacuum conditions, soaking time is at least
For 5h, vacuum is 0.05~0.1 standard atmospheric pressure, and resin particle is placed in distilled water after insulation and is cleaned by ultrasonic, filtering
Separation resin particle, and drying for standby.
Further, the sodium form cationic ion-exchange resin is 732 type cationic ion-exchange resins.
Further, the Na2SO4In the mixed aqueous solution of polyethylene glycol, Na2SO4Mass fraction for 11%~
20%, the volumetric concentration of polyethylene glycol is 30~60mL/L.
It is used as further preferred scheme, the Na2SO4In the mixed aqueous solution of polyethylene glycol, Na2SO4Mass fraction
For 18.5%, the volumetric concentration of polyethylene glycol is 46mL/L.
As can be seen from the above technical solutions, it is an advantage of the invention that:
1. the present invention is entered by designing the brilliant recovery process of salt, the salt slurry that liquid after sal prunella combined production device crude salt centrifugal drying is deposited
Row working process, removes the ion that is mingled with salt slurry, and allows salt slurry crystal to be grown up in evaporator production certified products product salt, passes through
Improve, on the basis of 1,000,000 tons/year of sal prunella combined production device, it is about 3,400,000 yuan that annual new units increased in production, which can increase benefit,.
2. the present invention is by designing deionization technique and dissolved technique, the salt slurry to recovery carries out deionization processing.In life
Deionization process is continued to optimize in production real process, the problem of ion remaval in the prior art is single and insufficient, this hair is abandoned
The bright activation sodium form cationic ion-exchange resin and hydrogen peroxide proposed suitable for well ore deposit salt manufacturing and ethanol system dissolved agent, a side
Face, compared to conventional sodium form cationic ion-exchange resin of the prior art, the present invention goes the species of deionization more, removal ability
It is stronger;On the other hand, there is the open method for using methanol dissolved or deionization being gone using ethanol dissolved merely in the prior art, but
It is applicants experimentally found that methanol is in NaCl-Na2SO4Removal effect is not obvious in system, and methanol toxicity is very strong, no
Suitable for the production of salt;Ethanol is used alone and extracts sulfate radical purity well, it is feasible for reclaiming sulfate, but for going
Except the scarce capacity of the sulfate ion in solution, it is impossible to meet the requirement of industrial salt manufacturing, hydrogen peroxide is have developed to this present invention
And ethanol system, take off SO4 2-Effect is notable, and nonhazardous.
3. present invention process effect stability, required apparatus and method are simply common, easy popularization and application, with huge reality
With prospect, there is facilitation to sal prunella coproduction industrial expansion.
Brief description of the drawings
Fig. 1 is flow chart of the invention.
Embodiment
Fig. 1 is flow chart of the invention, as illustrated, a kind of brilliant recovery method of salt manufacturing essence halogen mother liquor salt, includes following step
Suddenly:
1) well mine salt bittern is clarified by former halogen, gets rid of liquid into centrifuge after dosing reaction and smart halogen clarification, centrifugation
Liquid pump enters mother liquor pond afterwards, and inputs in smart halogen bucket and carry out follow-up sal prunella coproduction process, and salt slurry carries out thickening processing after centrifugation;
2) stood after salt slurry thickening processing, supernatant liquor overflow enters liquid after mother liquor pond and the centrifugation and mixed, defeated in the lump
Enter in smart halogen bucket, the salt slurry of deposited bottom is pumped into dissolving bucket, distilled water is added into dissolving bucket and make it that soluble fraction fills in salt slurry
The solution divided in dissolving, filtering dissolving bucket, liquid after being filtered;
3) Ca by liquid after the filtering after modified ion-exchange resin removes filtering in liquid2+、Mg2+With part sulphur
Acid ion.Modified resin is to Ca2+、Mg2+Adsorptivity is stronger, easily with the Ca in solution2+、Mg2+Generation ion exchange,
Deviate from the impurity in solution.After ion exchange, solution is heated to 50~90 DEG C and is evaporated under reduced pressure, protected after there is crystal precipitation
Hold that temperature and pressure is constant, the mixed solution that hydrogen peroxide and ethanol are added into solution carries out dissolved;
4) solution is filtered after dissolved, it is brilliant that gained filtrate is pumped into evaporative crystallization forming salt in evaporator.
Salt crystalline substance after crystallization is using the atomic absorption spectroscopy determination Ca described in GB/T13025.6-20122+、Mg2+
Content;Sulfate ion in salt crystalline substance is determined using conventional titration method, concrete operation step is shown in GB/T13025.8-2012 appearance
Amount method.
Embodiment 1
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, its step is:
1) well mine salt bittern is clarified by former halogen, gets rid of liquid into centrifuge after dosing reaction and smart halogen clarification, centrifugation
Liquid pump enters mother liquor pond afterwards, and inputs in smart halogen bucket and carry out follow-up sal prunella coproduction process, and salt slurry is pumped into thickening with brine pump after centrifugation
Thickening processing is carried out in device, solid, liquid mass ratio is 1 after thickening:2.5;
2) stood after salt slurry thickening processing, time of repose >=2h, the supernatant liquor overflow of salt slurry enters mother liquor pond after standing
Mix, input in the lump in smart halogen bucket, the salt slurry of deposited bottom is pumped into dissolving bucket, and two are added into dissolving bucket with liquid after the centrifugation
Secondary distilled water make it that soluble fraction fully dissolves in salt slurry, in order to improve dissolution velocity, in dissolving bucket provided with agitating device and/or
Resistive heater.The solution in dissolving bucket, liquid after being filtered are filtered using suction filtration machine;
3) liquid after the filtering is removed into the Ca after filtering in liquid by ion exchange column2+、Mg2+、Ba2+And part of sulfuric acid
Be filled with ion exchange resin in radical ion, the ion exchange column, the ion exchange resin using it is preceding by sodium chloride and
Hydrochloric acid mixed solution activate, soak time be 10min, wherein sodium chloride and hydrochloric acid mixed solution be mass fraction 5% HCl and
The NaCl of mass fraction 3.5% is mixed to form.Cleaned and loaded in ion exchange column with redistilled water after activation, ion exchange
Afterwards, solution is imported in vacuum decompression evaporator, is heated to 75~85 DEG C and is evaporated under reduced pressure, the evaporation pressure is 0.01 mark
Quasi- atmospheric pressure, keeping temperature and pressure are constant after there is crystal precipitation, and edible hydrogen peroxide and ethanol are added into solution
Mixed solution carries out dissolved, edible hydrogen peroxide and the H that alcohol mixed solution is mass fraction 30%2O2Mixed with ethanol,
The H of the mass fraction 30%2O2Volume ratio with ethanol is 1:1, the addition volume of hydrogen peroxide and alcohol mixed solution is treats
The 10% of dissolved liquor capacity.
4) solution is filtered after dissolved, gained filtrate is pumped into evaporative crystallization forming salt crystalline substance in evaporator, after the completion of crystallization, will
Salt crystalline substance is incubated 1h more than 160 DEG C, removes hydrogen peroxide, ethanol and the moisture of residual.
Ion exchange resin used in the above method is modified food 732 type cationic ion-exchange resins of level, and modification procedure is:
1) sodium form cationic ion-exchange resin is fully leached in the ethanol water that volume fraction is 30%, leaches process
In to solution carry out ultrasonic oscillation;
2) Na is added into the alcohol for leach ion exchange resin2SO4With the mixed aqueous solution of polyethylene glycol.
Na2SO4In the mixed aqueous solution of polyethylene glycol, Na2SO4Mass fraction be 11%, the volumetric concentration of polyethylene glycol is
30mL/L.Solution is warming up to 60 DEG C of 2~4h of insulation, insulation is filtered after terminating, and isolates ion-exchange resin particles, and
Rinsed well with redistilled water;
3) ion-exchange resin particles rinsed well are incubated 100~120 DEG C under vacuum conditions, soaking time is
5h, vacuum is 0.05 standard atmospheric pressure, and resin particle is placed in distilled water after insulation and is cleaned by ultrasonic, resin is separated by filtration
Particle, and drying for standby.
Gained salt crystalline substance determines Ca respectively in aforementioned manners2+、Mg2+And SO4 2-Content results are as shown in table 1.
Embodiment 2
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, its step is:
1) well mine salt bittern is clarified by former halogen, gets rid of liquid into centrifuge after dosing reaction and smart halogen clarification, centrifugation
Liquid pump enters mother liquor pond afterwards, and inputs in smart halogen bucket and carry out follow-up sal prunella coproduction process, and salt slurry is pumped into thickening with brine pump after centrifugation
Thickening processing is carried out in device, solid, liquid mass ratio is 1 after thickening:2;
2) stood after salt slurry thickening processing, time of repose >=2h, the supernatant liquor overflow of salt slurry enters mother liquor pond after standing
Mix, input in the lump in smart halogen bucket, the salt slurry of deposited bottom is pumped into dissolving bucket, and two are added into dissolving bucket with liquid after the centrifugation
Secondary distilled water make it that soluble fraction fully dissolves in salt slurry, in order to improve dissolution velocity, in dissolving bucket provided with agitating device and/or
Resistive heater.The solution in dissolving bucket, liquid after being filtered are filtered using suction filtration machine;
3) liquid after the filtering is removed into the Ca after filtering in liquid by ion exchange column2+、Mg2+、Ba2+And part of sulfuric acid
Be filled with ion exchange resin in radical ion, the ion exchange column, the ion exchange resin using it is preceding by sodium chloride and
Hydrochloric acid mixed solution activate, soak time be 20min, wherein sodium chloride and hydrochloric acid mixed solution be mass fraction 5% HCl and
The NaCl of mass fraction 5% is mixed to form.Cleaned and loaded in ion exchange column with redistilled water after activation, after ion exchange,
Solution is imported in vacuum decompression evaporator, 75~85 DEG C is heated to and is evaporated under reduced pressure, less than 0.01 mark of the evaporation pressure
Quasi- atmospheric pressure, keeping temperature and pressure are constant after there is crystal precipitation, and edible hydrogen peroxide and ethanol are added into solution
Mixed solution carries out dissolved, edible hydrogen peroxide and the H that alcohol mixed solution is mass fraction 30%2O2Mixed with ethanol,
The H of the mass fraction 30%2O2Volume ratio with ethanol is 2:1, the addition volume of hydrogen peroxide and alcohol mixed solution is treats
The 15% of dissolved liquor capacity.
4) solution is filtered after dissolved, gained filtrate is pumped into evaporative crystallization forming salt crystalline substance in evaporator, after the completion of crystallization, will
Salt crystalline substance is incubated 3h more than 160 DEG C, removes hydrogen peroxide, ethanol and the moisture of residual.
Ion exchange resin used in the above method is modified food 732 type cationic ion-exchange resins of level, and modification procedure is:
1) sodium form cationic ion-exchange resin is fully leached in the ethanol water that volume fraction is 40%, leaches process
In to solution carry out ultrasonic oscillation;
2) Na is added into the alcohol for leach ion exchange resin2SO4With the mixed aqueous solution of polyethylene glycol.
Na2SO4In the mixed aqueous solution of polyethylene glycol, Na2SO4Mass fraction be 15%, the volumetric concentration of polyethylene glycol is
40mL/L.Solution is warming up to 60~80 DEG C of 2~4h of insulation, insulation is filtered after terminating, and isolates ion exchange resin
Grain, and rinsed well with redistilled water;
3) ion-exchange resin particles rinsed well are incubated 100~120 DEG C under vacuum conditions, soaking time is
5h, vacuum is 0.07 standard atmospheric pressure, and resin particle is placed in distilled water after insulation and is cleaned by ultrasonic, resin is separated by filtration
Particle, and drying for standby.
Gained salt crystalline substance determines Ca respectively in aforementioned manners2+、Mg2+And SO4 2-Content results are as shown in table 1.
Embodiment 3
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, its step is:
1) well mine salt bittern is clarified by former halogen, gets rid of liquid into centrifuge after dosing reaction and smart halogen clarification, centrifugation
Liquid pump enters mother liquor pond afterwards, and inputs in smart halogen bucket and carry out follow-up sal prunella coproduction process, and salt slurry is pumped into thickening with brine pump after centrifugation
Thickening processing is carried out in device, solid, liquid mass ratio is more than 1 after thickening:1.5;
2) stood after salt slurry thickening processing, time of repose >=2h, the supernatant liquor overflow of salt slurry enters mother liquor pond after standing
Mix, input in the lump in smart halogen bucket, the salt slurry of deposited bottom is pumped into dissolving bucket, and two are added into dissolving bucket with liquid after the centrifugation
Secondary distilled water make it that soluble fraction fully dissolves in salt slurry, in order to improve dissolution velocity, in dissolving bucket provided with agitating device and/or
Resistive heater.The solution in dissolving bucket, liquid after being filtered are filtered using suction filtration machine;
3) liquid after the filtering is removed into the Ca after filtering in liquid by ion exchange column2+、Mg2+、Ba2+And part of sulfuric acid
Be filled with ion exchange resin in radical ion, the ion exchange column, the ion exchange resin using it is preceding by sodium chloride and
Hydrochloric acid mixed solution is activated, and soak time is the HCl that 35min, wherein sodium chloride and hydrochloric acid mixed solution are mass fraction 6.3%
It is mixed to form with the NaCl of mass fraction 7.5%.Cleaned and loaded in ion exchange column with redistilled water after activation, ion exchange
Afterwards, solution is imported in vacuum decompression evaporator, is heated to 75~85 DEG C and is evaporated under reduced pressure, the evaporation pressure is 0.01 mark
Quasi- atmospheric pressure, keeping temperature and pressure are constant after there is crystal precipitation, and edible hydrogen peroxide and ethanol are added into solution
Mixed solution carries out dissolved, edible hydrogen peroxide and the H that alcohol mixed solution is mass fraction 30%2O2Mixed with ethanol,
The H of the mass fraction 30%2O2Volume ratio with ethanol is 1.8:1, the addition volume of hydrogen peroxide and alcohol mixed solution is
Treat the 18% of dissolved liquor capacity.
4) solution is filtered after dissolved, gained filtrate is pumped into evaporative crystallization forming salt crystalline substance in evaporator, after the completion of crystallization, will
Salt crystalline substance is incubated 3h more than 160 DEG C, removes hydrogen peroxide, ethanol and the moisture of residual.
Ion exchange resin used in the above method is modified food 732 type cationic ion-exchange resins of level, and modification procedure is:
1) sodium form cationic ion-exchange resin is fully leached in the ethanol water that volume fraction is 60%, leaches process
In to solution carry out ultrasonic oscillation;
2) Na is added into the alcohol for leach ion exchange resin2SO4With the mixed aqueous solution of polyethylene glycol.
Na2SO4In the mixed aqueous solution of polyethylene glycol, Na2SO4Mass fraction be 18.5%, the volumetric concentration of polyethylene glycol is
46mL/L.Solution is warming up to 60~80 DEG C of 2~4h of insulation, insulation is filtered after terminating, and isolates ion exchange resin
Grain, and rinsed well with redistilled water;
3) ion-exchange resin particles rinsed well are incubated 100~120 DEG C under vacuum conditions, soaking time is
5h, vacuum is 0.05 standard atmospheric pressure, and resin particle is placed in distilled water after insulation and is cleaned by ultrasonic, resin is separated by filtration
Particle, and drying for standby.
Gained salt crystalline substance determines Ca respectively in aforementioned manners2+、Mg2+And SO4 2-Content results are as shown in table 1.
Embodiment 4
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, its step is:
1) well mine salt bittern is clarified by former halogen, gets rid of liquid into centrifuge after dosing reaction and smart halogen clarification, centrifugation
Liquid pump enters mother liquor pond afterwards, and inputs in smart halogen bucket and carry out follow-up sal prunella coproduction process, and salt slurry is pumped into thickening with brine pump after centrifugation
Thickening processing is carried out in device, solid, liquid mass ratio is 1 after thickening:2.5;
2) stood after salt slurry thickening processing, time of repose >=2h, the supernatant liquor overflow of salt slurry enters mother liquor pond after standing
Mix, input in the lump in smart halogen bucket, the salt slurry of deposited bottom is pumped into dissolving bucket, and two are added into dissolving bucket with liquid after the centrifugation
Secondary distilled water make it that soluble fraction fully dissolves in salt slurry, in order to improve dissolution velocity, in dissolving bucket provided with agitating device and/or
Resistive heater.The solution in dissolving bucket, liquid after being filtered are filtered using suction filtration machine;
3) liquid after the filtering is removed into the Ca after filtering in liquid by ion exchange column2+、Mg2+、Ba2+And part of sulfuric acid
Be filled with ion exchange resin in radical ion, the ion exchange column, the ion exchange resin using it is preceding by sodium chloride and
Hydrochloric acid mixed solution activate, soak time be 10min, wherein sodium chloride and hydrochloric acid mixed solution be mass fraction 7% HCl and
The NaCl of mass fraction 3.5% is mixed to form.Cleaned and loaded in ion exchange column with redistilled water after activation, ion exchange
Afterwards, solution is imported in vacuum decompression evaporator, is heated to 75~85 DEG C and is evaporated under reduced pressure, the evaporation pressure is less than 0.01
Standard atmospheric pressure, keeping temperature and pressure are constant after there is crystal precipitation, and edible hydrogen peroxide and ethanol are added into solution
Mixed solution carry out dissolved, edible hydrogen peroxide and alcohol mixed solution are the H of mass fraction 30%2O2With ethanol mixing and
Into the H of the mass fraction 30%2O2Volume ratio with ethanol is 2:1, the addition volume of hydrogen peroxide and alcohol mixed solution
To treat the 10% of dissolved liquor capacity.
4) solution is filtered after dissolved, gained filtrate is pumped into evaporative crystallization forming salt crystalline substance in evaporator, after the completion of crystallization, will
Salt crystalline substance is incubated 5h more than 160 DEG C, removes hydrogen peroxide, ethanol and the moisture of residual.
Ion exchange resin used in the above method is modified food 732 type cationic ion-exchange resins of level, and modification procedure is:
1) sodium form cationic ion-exchange resin is fully leached in the ethanol water that volume fraction is 70%, leaches process
In to solution carry out ultrasonic oscillation;
2) Na is added into the alcohol for leach ion exchange resin2SO4With the mixed aqueous solution of polyethylene glycol.
Na2SO4In the mixed aqueous solution of polyethylene glycol, Na2SO4Mass fraction be 20%, the volumetric concentration of polyethylene glycol is
40mL/L.Solution is warming up to 60~80 DEG C of 2~4h of insulation, insulation is filtered after terminating, and isolates ion exchange resin
Grain, and rinsed well with redistilled water;
3) ion-exchange resin particles rinsed well are incubated 100~120 DEG C under vacuum conditions, soaking time is at least
For 5h, vacuum is 0.05~0.1 standard atmospheric pressure, and resin particle is placed in distilled water after insulation and is cleaned by ultrasonic, filtering
Separation resin particle, and drying for standby.
Gained salt crystalline substance determines Ca respectively in aforementioned manners2+、Mg2+And SO4 2-Content results are as shown in table 1.
Embodiment 5
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, its step is:
1) well mine salt bittern is clarified by former halogen, gets rid of liquid into centrifuge after dosing reaction and smart halogen clarification, centrifugation
Liquid pump enters mother liquor pond afterwards, and inputs in smart halogen bucket and carry out follow-up sal prunella coproduction process, and salt slurry is pumped into thickening with brine pump after centrifugation
Thickening processing is carried out in device, solid, liquid mass ratio is 1 after thickening:1;
2) stood after salt slurry thickening processing, time of repose >=2h, the supernatant liquor overflow of salt slurry enters mother liquor pond after standing
Mix, input in the lump in smart halogen bucket, the salt slurry of deposited bottom is pumped into dissolving bucket, and two are added into dissolving bucket with liquid after the centrifugation
Secondary distilled water make it that soluble fraction fully dissolves in salt slurry, in order to improve dissolution velocity, in dissolving bucket provided with agitating device and/or
Resistive heater.The solution in dissolving bucket, liquid after being filtered are filtered using suction filtration machine;
3) liquid after the filtering is removed into the Ca after filtering in liquid by ion exchange column2+、Mg2+、Ba2+And part of sulfuric acid
Be filled with ion exchange resin in radical ion, the ion exchange column, the ion exchange resin using it is preceding by sodium chloride and
Hydrochloric acid mixed solution activate, soak time be 40min, wherein sodium chloride and hydrochloric acid mixed solution be mass fraction 7% HCl and
The NaCl of mass fraction 6.5% is mixed to form.Cleaned and loaded in ion exchange column with redistilled water after activation, ion exchange
Afterwards, solution is imported in vacuum decompression evaporator, is heated to 75~85 DEG C and is evaporated under reduced pressure, the evaporation pressure is less than 0.01
Standard atmospheric pressure, keeping temperature and pressure are constant after there is crystal precipitation, and edible hydrogen peroxide and ethanol are added into solution
Mixed solution carry out dissolved, edible hydrogen peroxide and alcohol mixed solution are the H of mass fraction 30%2O2With ethanol mixing and
Into the H of the mass fraction 30%2O2Volume ratio with ethanol is 2:1, the addition volume of hydrogen peroxide and alcohol mixed solution
To treat the 20% of dissolved liquor capacity.
4) solution is filtered after dissolved, gained filtrate is pumped into evaporative crystallization forming salt crystalline substance in evaporator, after the completion of crystallization, will
Salt crystalline substance is incubated 4h more than 160 DEG C, removes hydrogen peroxide, ethanol and the moisture of residual.
Ion exchange resin used in the above method is modified food 732 type cationic ion-exchange resins of level, and modification procedure is:
1) sodium form cationic ion-exchange resin is fully leached in the ethanol water that volume fraction is 70%, leaches process
In to solution carry out ultrasonic oscillation;
2) Na is added into the alcohol for leach ion exchange resin2SO4With the mixed aqueous solution of polyethylene glycol.
Na2SO4In the mixed aqueous solution of polyethylene glycol, Na2SO4Mass fraction be 18%, the volumetric concentration of polyethylene glycol is
60mL/L.Solution is warming up to 60~80 DEG C of 2~4h of insulation, insulation is filtered after terminating, and isolates ion exchange resin
Grain, and rinsed well with redistilled water;
3) ion-exchange resin particles rinsed well are incubated 100~120 DEG C under vacuum conditions, soaking time is at least
For 5h, vacuum is 0.05~0.1 standard atmospheric pressure, and resin particle is placed in distilled water after insulation and is cleaned by ultrasonic, filtering
Separation resin particle, and drying for standby.
Gained salt crystalline substance determines Ca respectively in aforementioned manners2+、Mg2+And SO4 2-Content results are as shown in table 1.
Comparative example 1
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, as described in Example 3, it is distinguished for its operating procedure and technological parameter
It is only that:The Na2SO4In the mixed aqueous solution of polyethylene glycol, Na2SO4Mass fraction be 30%, the body of polyethylene glycol
Product concentration is 100mL/L.Other step methods are identical with embodiment 3 with parameter.
Gained salt crystalline substance determines Ca respectively in aforementioned manners2+、Mg2+And SO4 2-Content results are as shown in table 1.
Comparative example 2
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, as described in Example 3, it is distinguished for its operating procedure and technological parameter
It is only that:Ion exchange resin used is used in step without after modification direct activation.Other step methods and ginseng
Number is identical with embodiment 3.
Gained salt crystalline substance determines Ca respectively in aforementioned manners2+、Mg2+And SO4 2-Content results are as shown in table 1.
Comparative example 3
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, as described in Example 3, it is distinguished for its operating procedure and technological parameter
It is only that:Ion exchange resin used is modified to be directly used in step without activation process.Other step methods and ginseng
Number is identical with embodiment 3.
Gained salt crystalline substance determines Ca respectively in aforementioned manners2+、Mg2+And SO4 2-Content results are as shown in table 1.
Comparative example 4
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, as described in Example 3, it is distinguished for its operating procedure and technological parameter
It is only that:Do not include dissolved part in step, i.e., edible hydrogen peroxide is added not into solution and the mixed solution of ethanol enters
Row dissolved.Other step methods are identical with embodiment 3 with parameter.
Gained salt crystalline substance determines Ca respectively in aforementioned manners2+、Mg2+And SO4 2-Content results are as shown in table 1.
Comparative example 5
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, as described in Example 3, it is distinguished for its operating procedure and technological parameter
It is only that:Dissolved uses merely ethanol solution, the amount ethanol equivalent substitution of corresponding hydrogen peroxide in step.Other step methods and
Parameter is identical with embodiment 3.
Gained salt crystalline substance determines Ca respectively in aforementioned manners2+、Mg2+And SO4 2-Content results are as shown in table 1.
Comparative example 6
A kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing, as described in Example 3, it is distinguished for its operating procedure and technological parameter
It is only that:Do not include dissolved part in step, i.e., edible hydrogen peroxide is added not into solution and the mixed solution of ethanol enters
Row dissolved;Ion-exchange step is not included, ie in solution, which is introduced directly into after being dissolved in dissolving bucket in vacuum decompression evaporator, to be subtracted yet
Pressure evaporation.Other step methods are identical with embodiment 3 with parameter.
Gained salt crystalline substance determines Ca respectively in aforementioned manners2+、Mg2+And SO4 2-Content results are as shown in table 1.
Table 1
Ca2+Content (mg/kg) | Mg2+Content (mg/kg) | SO4 2-Content (mass percent) | |
Embodiment 1 | 28.689 | 4.575 | 0.07% |
Embodiment 2 | 21.774 | 4.284 | 0.04% |
Embodiment 3 | 18.683 | 3.519 | 0.04% |
Embodiment 4 | 26.335 | 3.731 | 0.08% |
Embodiment 5 | 23.998 | 4.936 | 0.05% |
Comparative example 1 | 97.538 | 6.667 | 0.08% |
Comparative example 2 | 166.852 | 10.939 | 0.10% |
Comparative example 3 | 105.441 | 10.154 | 0.11% |
Comparative example 4 | 19.434 | 3.682 | 0.53% |
Comparative example 5 | 18.637 | 3.669 | 0.29% |
Comparative example 6 | 333.875 | 13.265 | 0.66% |
Comparative example 1~5 and comparative example 6 understand that the method for the invention can preferably be gone within parameter area
Except Ca contained in salt2+、Mg2+And SO4 2-, wherein the Ca2+Maximum material removal rate be 94.4%, Mg2+Maximum material removal rate
For 73.5%, SO4 2-Maximum material removal rate be 93.9%, effect is very notable.
Knowable to comparative example 3 and comparative example 1, Na2SO4With Na in polyethylene glycol mixed aqueous solution2SO4And polyethylene glycol
Modification of the concentration to exchanger resin it is most important, this depends mainly in resin (- SO3Na) the generation effect of group.When
Na2SO4During concentration incorrect (higher or relatively low) with polyethylene glycol, the activity of ion exchange resin is influenceed, and then in processing salt
Ca in crystalline substance2+And Mg2+When inefficiency, remove it is insufficient.But to SO4 2-Influence is smaller.
Comparative example 3 and comparative example 1 or comparative example 2 are understood, Ca is removed in salt ion exchange2+And Mg2+During,
Exchanger resin needs process modification+activation process, could maximize the removal effect of foreign ion, before unmodified or use not
The ion exchange resin of activation effect when exchanging impurity element is less desirable.
Comparative example 3 and comparative example 4 are understood, molten using edible hydrogen peroxide and alcohol mixed solution dissolved saturated salt crystalline substance
Liquid, to Ca2+And Mg2+Removal almost without influence, but can significantly remove the sulfate ion in salt.
Knowable to the comparative example 5 of comparative example 3, SO in embodiment 34 2-Clearance be 93.9%, and without hydrogen peroxide
In the case of, simple ethanol is in NaCl-Na2SO4SO in system4 2-Clearance be 56.1%, illustrate be used alone ethanol removal
The scarce capacity of sulfate ion in salt manufacturing solution, it is impossible to meet the requirement of industrial salt manufacturing.
Contrast comparative example 4 and comparative example 6 understands that ion exchange process can also remove the SO of part4 2-Ion, but remove
Amount is extremely limited.
Technical scheme provided by the present invention is described in detail above, for those of ordinary skill in the art,
According to the thought of the embodiment of the present invention, it will change in specific embodiments and applications, in summary, this theory
Bright book content should not be construed as limiting the invention.
Claims (10)
1. the brilliant recovery method of the smart halogen mother liquor salt of a kind of salt manufacturing, it is characterised in that comprise the steps of:
1) well mine salt bittern is clarified by former halogen, gets rid of liquid after liquid, centrifugation into centrifuge after dosing reaction and smart halogen clarification
It is pumped into mother liquor pond, and inputs in smart halogen bucket and carry out follow-up sal prunella coproduction process, salt slurry carries out thickening processing after centrifugation;
2) stood after salt slurry thickening processing, supernatant liquor overflow enters liquid after mother liquor pond and the centrifugation and mixed, and essence is inputted in the lump
In halogen bucket, the salt slurry of deposited bottom is pumped into dissolving bucket, and distilled water is added into dissolving bucket and make it that soluble fraction is fully molten in salt slurry
Solution in solution, filtering dissolving bucket, liquid after being filtered;
3) Ca by liquid after the filtering after ion exchange resin removes filtering in liquid2+、Mg2+With part of sulfuric acid radical ion,
After ion exchange, solution is heated to 50~90 DEG C and is evaporated under reduced pressure, keeping temperature and pressure are constant after there is crystal precipitation,
The mixed solution that hydrogen peroxide and ethanol are added into solution carries out dissolved;
4) solution is filtered after dissolved, it is brilliant that gained filtrate is pumped into evaporative crystallization forming salt in evaporator.
2. the brilliant recovery method of the smart halogen mother liquor salt of a kind of salt manufacturing according to claim 1, it is characterised in that the step has more
Body is expressed as:
1) well mine salt bittern is clarified by former halogen, gets rid of liquid after liquid, centrifugation into centrifuge after dosing reaction and smart halogen clarification
It is pumped into mother liquor pond, and inputs in smart halogen bucket and carry out follow-up sal prunella coproduction process, salt slurry is pumped into thickener with brine pump after centrifugation
Thickening processing is carried out, solid, liquid mass ratio is more than 1 after thickening:2.5;
2) stood after salt slurry thickening processing, time of repose >=2h, the supernatant liquor overflow of salt slurry enters mother liquor pond and institute after standing
State liquid after centrifugation to mix, input in the lump in smart halogen bucket, the salt slurry of deposited bottom is pumped into dissolving bucket, and secondary steaming is added into dissolving bucket
Distilled water make it that soluble fraction fully dissolves in salt slurry, and the solution in dissolving bucket, liquid after being filtered are filtered using suction filtration machine;
3) liquid after the filtering is removed into the Ca after filtering in liquid by ion exchange column2+、Mg2+、Ba2+With part of sulfuric acid root from
Ion exchange resin is filled with son, the ion exchange column, the ion exchange resin passes through sodium chloride and hydrochloric acid using preceding
Mixed solution is activated, and soak time is 10~40min, is cleaned and loaded in ion exchange column with redistilled water after activation, ion
After exchange, solution is imported in vacuum decompression evaporator, 75~85 DEG C is heated to and is evaporated under reduced pressure, the evaporation pressure is less than
0.01 standard atmospheric pressure, keeping temperature and pressure are constant after there is crystal precipitation, and hydrogen peroxide and ethanol are added into solution
Mixed solution carry out dissolved;
4) solution is filtered after dissolved, gained filtrate is pumped into evaporative crystallization forming salt crystalline substance in evaporator, after the completion of crystallization, and salt is brilliant
1~5h is incubated more than 160 DEG C, hydrogen peroxide, ethanol and the moisture of residual is removed.
3. a kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing according to claim 1 or 2, it is characterised in that the chlorination
Sodium and hydrochloric acid mixed solution are that the HCl of mass fraction 5~7% and the NaCl of mass fraction 3.5~10% are mixed to form.
4. a kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing according to claim 1 or 2, it is characterised in that the dissolving
Agitating device and/or resistive heater are provided with bucket so that the increase of salt slurry dissolution velocity.
5. a kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing according to claim 1 or 2, it is characterised in that the dioxygen
Water and the H that ethanol is mass fraction 30%2O2Mixed with ethanol, the H of the mass fraction 30%2O2With the volume of ethanol
Than for 1~2:1, the addition volume of hydrogen peroxide and alcohol mixed solution is treat dissolved liquor capacity 10~20%.
6. a kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing according to claim 5, it is characterised in that the hydrogen peroxide is
Edible hydrogen peroxide.
7. a kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing according to claim 1 or 2, it is characterised in that the ion
Exchanger resin is food-grade sodium form cationic ion-exchange resin, is while removing Ca2+、Mg2+、Ba2+With part of sulfuric acid radical ion, and
Removal ability is improved, the sodium form cationic ion-exchange resin passes through modification, and the modification procedure is:
1) sodium form cationic ion-exchange resin is fully leached in the ethanol water that volume fraction is 30%~70%, leached
Ultrasonic oscillation is carried out to solution in journey;
2) Na is added into the alcohol for leach ion exchange resin2SO4With the mixed aqueous solution of polyethylene glycol, solution is heated up
To 60~80 DEG C of 2~4h of insulation, insulation is filtered after terminating, and isolates ion-exchange resin particles, and use redistilled water
Rinse well;
3) ion-exchange resin particles rinsed well are incubated 100~120 DEG C under vacuum conditions, soaking time is at least
5h, vacuum is 0.05~0.1 standard atmospheric pressure, and resin particle is placed in distilled water after insulation and is cleaned by ultrasonic, filtering point
From resin particle, and drying for standby.
8. a kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing according to claim 7, it is characterised in that the sodium form sun from
Sub-exchange resin is 732 type cationic ion-exchange resins.
9. a kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing according to claim 7, it is characterised in that the Na2SO4With
In the mixed aqueous solution of polyethylene glycol, Na2SO4Mass fraction be 11%~20%, the volumetric concentration of polyethylene glycol for 30~
60mL/L。
10. a kind of brilliant recovery method of the smart halogen mother liquor salt of salt manufacturing according to claim 9, it is characterised in that the Na2SO4With
In the mixed aqueous solution of polyethylene glycol, Na2SO4Mass fraction be 18.5%, the volumetric concentration of polyethylene glycol is 46mL/L.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710332771.4A CN107098361B (en) | 2017-05-12 | 2017-05-12 | A kind of salt manufacturing essence halogen mother liquor salt crystalline substance recovery method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710332771.4A CN107098361B (en) | 2017-05-12 | 2017-05-12 | A kind of salt manufacturing essence halogen mother liquor salt crystalline substance recovery method |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107098361A true CN107098361A (en) | 2017-08-29 |
CN107098361B CN107098361B (en) | 2017-12-08 |
Family
ID=59670100
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710332771.4A Active CN107098361B (en) | 2017-05-12 | 2017-05-12 | A kind of salt manufacturing essence halogen mother liquor salt crystalline substance recovery method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107098361B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111807385A (en) * | 2020-07-22 | 2020-10-23 | 湖南省湘衡盐化有限责任公司 | Method for improving purity of finished salt in evaporation method co-production salt-nitrate process |
CN112897670A (en) * | 2021-01-29 | 2021-06-04 | 江西晶昊盐化有限公司 | Salt production condensate water deamination method and equipment |
-
2017
- 2017-05-12 CN CN201710332771.4A patent/CN107098361B/en active Active
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111807385A (en) * | 2020-07-22 | 2020-10-23 | 湖南省湘衡盐化有限责任公司 | Method for improving purity of finished salt in evaporation method co-production salt-nitrate process |
CN111807385B (en) * | 2020-07-22 | 2024-02-23 | 湖南省湘衡盐化有限责任公司 | Method for improving purity of finished product salt of evaporation method co-production salt-nitrate process |
CN112897670A (en) * | 2021-01-29 | 2021-06-04 | 江西晶昊盐化有限公司 | Salt production condensate water deamination method and equipment |
Also Published As
Publication number | Publication date |
---|---|
CN107098361B (en) | 2017-12-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103572071B (en) | A kind of method of refining lithium from salt lake brine with high magnesium-lithium ratio | |
CN108004391B (en) | A method of processing lepidolite extracts metallic element | |
CN102531002A (en) | Method for purifying lithium carbonate | |
CN101973871B (en) | Electronic grade citric acid and production method thereof | |
CN104368316A (en) | Sulfydryl cellulose type straw adsorbent and preparation method thereof as well as recycling of noble metal silver | |
CN106744721A (en) | The recovery separation method and application of sulfuric acid and dissolubility titanium in titanium white waste acid | |
CN107098361B (en) | A kind of salt manufacturing essence halogen mother liquor salt crystalline substance recovery method | |
CN101070168B (en) | Method for producing sodium nitrate | |
CN103539165A (en) | Method for producing potassium sulfate by utilizing insoluble rocks containing potassium | |
CN107758705B (en) | Zinnwaldite extracts lithium carbonate technique | |
CN102701263A (en) | Method for preparing copper sulfate in mode that stanniferous copper slag is leached in selective mode and free of evaporation | |
CN109019636A (en) | A method of food-grade potassium chloride is produced using the salt of tail containing potassium | |
CN105177305B (en) | A kind of platinum wet-process purification method | |
CN109097584A (en) | The technique of platinum rhenium aluminium is recycled in a kind of platinum rhenium dead catalyst from alumina supporter | |
CN102605109A (en) | Method for producing xylose by sugarcane leaves | |
CN104150519B (en) | A kind of method utilizing sodium sulfate waste liquid to prepare barium sulfate and sodium carbonate | |
CN112593016A (en) | Process for preparing high-quality white granulated sugar and fulvic acid dry powder from beet | |
CN102633293B (en) | Method for refining multistage circulation evaporation-free copper sulfate | |
CN107739828B (en) | A method of with cobalt and manganese in ammonia-ammonium carbonate separation and recovery high manganese waste material of low cobalt | |
CN104528716A (en) | Hydrochloric acid steel pickling waste liquor resource application technology | |
CN106380233A (en) | Process for preparing potassic-magnesian fertilizer by using polyhalite | |
CN114409157A (en) | Resource method for preparing chlor-alkali by electrolyzing waste brine | |
CN106379917A (en) | Method for preparing potassium sulfate by using polyhalite | |
CN104447529B (en) | Method for extracting and purifying 3,6-matrigon | |
CN101973564A (en) | Potassium nitrate for fireworks and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |