CN115676868A - Method for recovering barium sulfate from solid waste barium-containing salt mud - Google Patents
Method for recovering barium sulfate from solid waste barium-containing salt mud Download PDFInfo
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- barium
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 167
- 150000003839 salts Chemical class 0.000 title claims abstract description 40
- 239000002910 solid waste Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 33
- 229910052788 barium Inorganic materials 0.000 title claims abstract description 31
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002244 precipitate Substances 0.000 claims abstract description 54
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001422 barium ion Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 20
- 239000011812 mixed powder Substances 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000010802 sludge Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 159000000009 barium salts Chemical class 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 150000001768 cations Chemical class 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 210000001035 gastrointestinal tract Anatomy 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 241000006351 Leucophyllum frutescens Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000009621 Solvay process Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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Abstract
The invention discloses a method for recovering barium sulfate from solid waste barium-containing salt mud. In the method, firstly, hydrochloric acid is used for dissolving and separating barium sulfate which is insoluble in hydrochloric acid and barium salt which is soluble in acid, and then the separated barium sulfate and barium salt which is soluble in acid are respectively treated: converting barium sulfate into barium salt capable of being dissolved in hydrochloric acid, and reacting barium ions dissolved in hydrochloric acid with a sulfuric acid solution to obtain barium sulfate precipitate, so that the barium sulfate is purified; and carrying out precipitation reaction on the acid solution containing barium ions and the sulfuric acid solution, then reacting the precipitate with the hydrochloric acid solution, and dissolving the sulfate except the barium sulfate by the hydrochloric acid to realize the separation of the barium ions and other cations. The method has high recovery rate of barium salt, and the recovered barium sulfate has high purity, small fineness and good dispersibility.
Description
Technical Field
The invention relates to the technical field of solid waste utilization, in particular to a method for recovering barium sulfate from solid waste barium-containing salt mud.
Background
Barium sulfate plays an important role in medical treatment, and barium sulfate is mainly used as a gastrointestinal contrast agent in radiological examination because barium sulfate is mainly used for developing the gastrointestinal tract by absorbing X-rays in the gastrointestinal tract. The product can be used in various industries such as paint, printing ink, plastic, rubber and raw material or filler of storage battery, surface coating agent of printing paper and copperplate paper, sizing agent for textile industry, etc.
Many solid wastes such as salt slurry generated in the process of producing soda ash by an ammonia-soda process in a soda ash plant and salt slurry generated in the process of refining salt in the process of producing soda ash by an electrolysis method all contain a large amount of barium salt. If the solid waste barium-containing salt mud is directly dumped, not only the waste of resources is caused, but also the environment is seriously polluted. Therefore, the method has very important significance for recovering barium salt from the solid waste barium salt-containing mud to prepare barium sulfate.
Chinese patent CN107555462B discloses a method for comprehensively recycling soda waste residues, which comprises the specific steps of preparation of a treatment liquid; mixing and stirring the waste soda ash residue and the treatment solution for reaction; and solid-liquid separation and recovery of precipitated barium sulfate. During the process of recovering barium sulfate, the main components in the treatment solution are hydrochloric acid and barium salt capable of being dissolved in the hydrochloric acid, salt mud is dissolved through the hydrochloric acid, and an insoluble substance in the salt mud is barium sulfate; and the soluble barium salt in the treatment liquid is combined with the sulfate radical in the salt slurry to obtain barium sulfate precipitate. The barium sulfate and the sulfate radical in the salt mud are actually separated in the process, and the barium salt which can be dissolved in hydrochloric acid in the salt mud does not have a recycling function, so that the barium salt in the solid waste barium-containing salt mud cannot be recycled to the maximum extent, and the recycling rate of the barium salt is low.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for recovering barium sulfate from solid waste barium-containing salt mud, the recovery rate of barium salt is high, and the recovered barium sulfate has high purity and small fineness and can be used as an important raw material in products such as rubber, plastics, coatings and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the method for recovering barium sulfate from the solid waste barium-containing salt mud comprises the following steps:
mixing solid waste barium-containing salt mud with a hydrochloric acid solution, filtering to obtain filter residue and filtrate, washing the filter residue with pure water for 3-5 times to obtain filter residue containing barium sulfate and washing liquid, and mixing the washing liquid with the filtrate to obtain mixed liquid containing acid-soluble barium ions for later use;
drying the filter residue containing barium sulfate in the step (1) to obtain crude powdered barium sulfate, mixing the crude powdered barium sulfate with carbon powder to obtain mixed powder, and calcining the mixed powder at the temperature of 600-800 ℃ for 2-3h, wherein the reaction formula is as follows:
BaSO 4 +2C＝BaS+2CO 2 ↑…………………………………(1)；
placing the calcined mixed powder into a hydrochloric acid solution for reaction, wherein the reaction formula is as follows:
BaS+2HCl＝BaCl 2 +H 2 S↑…………………………………(2)；
after the reaction is finished, filtering, and taking filtrate;
adding ammonia water into the mixed liquid containing the acid-soluble barium ions obtained in the step (1) to generate a precipitate, stopping adding the ammonia water when the precipitate is not increased any more, and filtering to obtain a filtrate;
step (4), combining the filtrate obtained in the step (2) and the filtrate obtained in the step (3) to obtain a mixed filtrate, adding a sulfuric acid solution into the mixed filtrate under the stirring condition to generate a precipitate, stopping adding the sulfuric acid solution when the precipitate is not increased any more, adjusting the pH value to be neutral, filtering, taking the precipitate, and washing the precipitate with pure water for 3-5 times to obtain a washed precipitate;
and (5) drying the washed precipitate obtained in the step (4) to obtain barium sulfate.
Preferably, in the step (1), the concentration of the hydrochloric acid solution is 1-2mol/L, and the mass ratio of the solid waste barium-containing salt mud to the hydrochloric acid solution is 1.
Preferably, in the step (2), the drying conditions are as follows: drying at 80-100 deg.C for 1-2 hr.
Preferably, in the step (2), the mass ratio of the crude powdered barium sulfate to the carbon powder in the mixed powder is 233.
Preferably, in the step (2), the concentration of the hydrochloric acid solution is 1-2mol/L.
Preferably, in the step (2), the mass ratio of the calcined mixed powder to the hydrochloric acid solution is 1.
Preferably, in the step (3), the concentration of the ammonia water is 1-2mol/L.
Preferably, in the step (4), the stirring speed is 800-1200rpm, and the concentration of the sulfuric acid solution is 1-2mol/L.
Preferably, in the step (5), the drying is carried out by adopting a drying converter, the temperature is 150-220 ℃, and the drying time is 8-12 hours.
Preferably, in the step (4), before filtration, a dispersant is added into the reaction solution, and then filtration is performed, so as to obtain a precipitate, and the precipitate is washed with pure water, so as to obtain a washed precipitate;
and (5) drying the washed precipitate obtained in the step (4) to obtain the high-dispersity barium sulfate.
The dispersing agent is an inorganic dispersing agent and/or an organic dispersing agent, the inorganic dispersing agent is one or two of nano aluminum oxide and nano silicon oxide, and the organic dispersing agent is one or more of a silane coupling agent, a titanate coupling agent and sulfonate.
Compared with the prior art, the invention has the following beneficial effects:
the method comprises the following steps of firstly dissolving and separating hydrochloric-acid-insoluble barium sulfate and acid-soluble barium salt by hydrochloric acid to obtain a mixed solution containing barium sulfate-containing filter residue and acid-soluble barium ions, and then respectively treating the mixed solution containing the barium sulfate-containing filter residue and the acid-soluble barium ions:
mixing the filter residue containing barium sulfate with carbon powder, calcining to convert barium sulfate into barium sulfate salt which can be dissolved in hydrochloric acid, reacting the calcined mixed powder with a hydrochloric acid solution to dissolve barium sulfate in hydrochloric acid, and filtering to remove the filter residue containing impurities, so that solid impurities in the filter residue containing barium sulfate can be effectively removed;
adding ammonia water into the mixed solution containing acid-soluble barium ions to convert calcium ions and magnesium ions in the mixed solution containing the acid-soluble barium ions into hydroxide precipitates, and filtering to remove calcium hydroxide and magnesium hydroxide so as to effectively purify the barium ions in the mixed solution containing the acid-soluble barium ions;
mixing filtrates obtained by respectively processing mixed liquor of filter residues containing barium sulfate and acid-soluble barium ions, adding a sulfuric acid solution into the mixed filtrate under the stirring condition to convert all barium ions in the filtrate into barium sulfate precipitates, and finally drying the barium sulfate precipitates to prevent the mutual bonding of solid particles of the barium sulfate and the growth of crystal grains caused by high-temperature drying; the method has high recovery rate of barium salt, and the recovered barium sulfate has high purity, small fineness and good dispersibility.
Drawings
FIG. 1 is a process flow diagram of the present invention for recovering barium sulfate from solid waste barium-containing salt sludge;
FIG. 2 is a bar graph showing the results of measuring the content of barium sulfate obtained in examples 1 to 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person of ordinary skill in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
Example 1
The method for recovering barium sulfate from the solid waste barium-containing salt mud comprises the following steps:
mixing solid waste barium-containing salt mud and hydrochloric acid solution with the concentration of 1mol/L according to the mass ratio of 1;
drying the filter residue containing barium sulfate in the step (1) at the temperature of 80 ℃ for 2 hours to obtain crude powdered barium sulfate, mixing the crude powdered barium sulfate with carbon powder according to the mass ratio of 233; placing the calcined mixed powder into a hydrochloric acid solution with the concentration of 1mol/L for reaction, wherein the mass ratio of the calcined mixed powder to the hydrochloric acid solution is 1;
adding ammonia water with the concentration of 1mol/L into the mixed liquid containing the acid-soluble barium ions obtained in the step (1) to generate a precipitate, stopping adding the ammonia water when the precipitate is not increased any more, and filtering to obtain a filtrate;
step (4), combining the filtrate obtained in the step (2) and the filtrate obtained in the step (3) to obtain a mixed filtrate, adding a sulfuric acid solution with the concentration of 1mol/L into the mixed filtrate under the condition of stirring at the speed of 800rpm to generate a precipitate, stopping adding the sulfuric acid solution when the precipitate is not increased any more, adding ammonia water to adjust the pH value to be neutral, filtering, taking the precipitate, and washing the precipitate for 3 times by using pure water to obtain a washed precipitate;
and (5) drying the washed precipitate obtained in the step (4) for 8 hours at 220 ℃ in a drying converter to obtain barium sulfate.
Example 2
The method for recovering barium sulfate from the solid waste barium-containing salt mud comprises the following steps:
mixing solid waste barium-containing salt mud and hydrochloric acid solution with the concentration of 2mol/L according to the mass ratio of 1 to 30, filtering to obtain filter residue and filtrate, washing the filter residue for 5 times by using pure water to obtain filter residue containing barium sulfate and washing liquid, and combining the washing liquid and the filtrate to obtain mixed liquid containing acid-soluble barium ions for later use;
drying the filter residue containing barium sulfate in the step (1) at the temperature of 100 ℃ for 1h to obtain crude powdered barium sulfate, mixing the crude powdered barium sulfate with carbon powder according to the mass ratio of 233; placing the calcined mixed powder into a hydrochloric acid solution with the concentration of 2mol/L for reaction, wherein the mass ratio of the calcined mixed powder to the hydrochloric acid solution is 1;
step (3), adding ammonia water with the concentration of 2mol/L into the mixed liquid containing the acid-soluble barium ions obtained in the step (1) to generate a precipitate, stopping adding the ammonia water when the precipitate is not increased any more, and filtering to obtain filtrate;
step (4), combining the filtrate obtained in the step (2) and the filtrate obtained in the step (3) to obtain a mixed filtrate, adding a sulfuric acid solution with the concentration of 2mol/L into the mixed filtrate under the stirring condition of 1200rpm to generate a precipitate, stopping adding the sulfuric acid solution when the precipitate is not increased any more, adding hydrogen peroxide to adjust the pH value to be neutral, filtering, taking the precipitate, and washing the precipitate with pure water for 5 times to obtain a washed precipitate;
and (5) drying the washed precipitate obtained in the step (4) at the temperature of 150 ℃ in a drying converter for 12 hours to obtain barium sulfate.
Example 3
The method for recovering barium sulfate from the solid waste barium-containing salt mud comprises the following steps:
mixing solid waste barium-containing salt mud and hydrochloric acid solution with the concentration of 1.5mol/L according to the mass ratio of 1 to 40, filtering to obtain filter residue and filtrate, washing the filter residue for 4 times by using pure water to obtain filter residue containing barium sulfate and washing liquid, and combining the washing liquid and the filtrate to obtain mixed liquid containing acid-soluble barium ions for later use;
drying the filter residue containing the barium sulfate in the step (1) at the temperature of 90 ℃ for 1.5 hours to obtain crude powdered barium sulfate, mixing the crude powdered barium sulfate with carbon powder according to the mass ratio of 233 to 28 to obtain mixed powder, and calcining the mixed powder at the temperature of 700 ℃ for 2.5 hours; placing the calcined mixed powder into a hydrochloric acid solution with the concentration of 1.5mol/L for reaction, wherein the mass ratio of the calcined mixed powder to the hydrochloric acid solution is 1;
adding ammonia water with the concentration of 1.5mol/L into the mixed liquid containing the acid-soluble barium ions obtained in the step (1) to generate a precipitate, stopping adding the ammonia water when the precipitate is not increased any more, and filtering to obtain a filtrate;
step (4), combining the filtrate obtained in the step (2) and the filtrate obtained in the step (3) to obtain a mixed filtrate, adding a sulfuric acid solution with the concentration of 1.5mol/L into the mixed filtrate under the condition of stirring at the speed of 100rpm to generate a precipitate, stopping adding the sulfuric acid solution when the precipitate is not increased any more, adding ammonia water to adjust the pH value to be neutral, adding a dispersing agent, filtering, taking the precipitate, and washing the precipitate for 4 times by using pure water to obtain a washed precipitate; wherein the dispersant is a mixture of nano silicon oxide and titanate coupling agent in a mass ratio of 1:1, and the dosage of the dispersant is 0.3 percent of the mass of the reaction liquid;
and (5) drying the washed precipitate obtained in the step (4) at 200 ℃ for 10 hours in a drying converter to obtain high-dispersity barium sulfate, wherein the activation rate is 99% through detection.
The solid waste barium-containing salt mud in the embodiment is salt mud generated in the process of preparing caustic soda by an ion membrane method by yellow Ye chlor-alkali Limited company of Dahua group of Hecang State.
Examples of the experiments
The content of barium sulfate obtained in examples 1 to 3 was measured according to the specifications in the industrial precipitated barium sulfate of standard GB/T2899-2017, and the measurement results are shown in table 1:
TABLE 1
As can be seen from Table 1, the content (i.e., purity) of the barium sulfate recovered from the solid waste barium-containing salt slurry is high, and the barium sulfate meets the requirements of qualified barium sulfate products in national standards, and can be directly used for industrial production.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The method for recovering barium sulfate from the solid waste barium-containing salt mud is characterized by comprising the following steps:
mixing solid waste barium-containing salt mud with a hydrochloric acid solution, filtering to obtain filter residue and filtrate, washing the filter residue with pure water to obtain filter residue containing barium sulfate and washing liquid, and combining the washing liquid with the filtrate to obtain mixed liquid containing acid-soluble barium ions for later use;
drying the filter residue containing barium sulfate in the step (1) to obtain crude powdered barium sulfate, mixing the crude powdered barium sulfate with carbon powder to obtain mixed powder, and calcining the mixed powder at the temperature of 600-800 ℃ for 2-3h, wherein the reaction formula is as follows:
BaSO 4 +2C＝BaS+2CO 2 ↑…………………………………(1)；
placing the calcined mixed powder into a hydrochloric acid solution for reaction, wherein the reaction formula is as follows:
BaS+2HCl＝BaCl 2 +H 2 S↑…………………………………(2)；
after the reaction is finished, filtering, and taking filtrate;
adding ammonia water into the mixed liquid containing the acid-soluble barium ions obtained in the step (1) to generate a precipitate, stopping adding the ammonia water when the precipitate is not increased any more, and filtering to obtain a filtrate;
step (4), combining the filtrate obtained in the step (2) and the filtrate obtained in the step (3) to obtain a mixed filtrate, adding a sulfuric acid solution into the mixed filtrate under the stirring condition to generate a precipitate, stopping adding the sulfuric acid solution when the precipitate is not increased any more, adjusting the pH value to be neutral, filtering, taking the precipitate, and washing the precipitate with pure water to obtain a washed precipitate;
and (5) drying the washed precipitate obtained in the step (4) to obtain barium sulfate.
2. The method for recovering barium sulfate from the solid waste barium-containing salt sludge as claimed in claim 1, wherein in the step (1), the concentration of the hydrochloric acid solution is 1-2mol/L, and the mass ratio of the solid waste barium-containing salt sludge to the hydrochloric acid solution is 1.
3. The method for recovering barium sulfate from the solid waste barium-containing salt slurry as claimed in claim 1, wherein in the step (2), the drying conditions are as follows: drying at 80-100 deg.C for 1-2 hr.
4. The method for recovering barium sulfate from the solid waste barium-containing salt slurry as claimed in claim 1, wherein in the step (2), the mass ratio of the crude powdered barium sulfate to the carbon powder in the mixed powder is 233.
5. The method for recovering barium sulfate from the solid waste barium-containing salt sludge as claimed in claim 1, wherein in the step (2), the concentration of the hydrochloric acid solution is 1-2mol/L.
6. The method for recovering barium sulfate from solid waste barium-containing salt slurry according to claim 1, wherein in the step (2), the mass ratio of the calcined mixed powder to the hydrochloric acid solution is 1.
7. The method for recovering barium sulfate from the solid waste barium-containing salt sludge as claimed in claim 1, wherein in the step (3), the concentration of ammonia water is 1-2mol/L.
8. The method for recovering barium sulfate from the solid waste barium-containing salt slurry as claimed in claim 1, wherein in the step (4), the stirring speed is 800-1200rpm, and the concentration of the sulfuric acid solution is 1-2mol/L.
9. The method for recovering barium sulfate from the solid waste barium-containing salt sludge as claimed in claim 1, wherein in the step (5), the drying is performed by using a drying converter, the temperature is 150-220 ℃, and the drying time is 8-12 hours.
10. The method for recovering barium sulfate from the solid waste barium-containing salt sludge as claimed in claim 1, wherein in the step (4), the dispersing agent is added to the reaction solution before filtration, and then filtration is carried out to obtain the precipitate, and the precipitate is washed with pure water to obtain the washed precipitate;
and (5) drying the washed precipitate obtained in the step (4) to obtain the high-dispersity barium sulfate.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2236791A1 (en) * | 1973-06-29 | 1975-02-07 | Inst Francais Du Petrole | Dilute sulphuric acid effluent treatment - by neutralisation with barium sulphide and high temp reduction of the sulphate with carbon |
| CN1569618A (en) * | 2004-05-12 | 2005-01-26 | 唐培堃 | Process for preparing hydrogen sulfide |
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