CN115571893A - Method for extracting and recovering boric acid from low-concentration hydrochloric acid waste liquid - Google Patents
Method for extracting and recovering boric acid from low-concentration hydrochloric acid waste liquid Download PDFInfo
- Publication number
- CN115571893A CN115571893A CN202211143590.4A CN202211143590A CN115571893A CN 115571893 A CN115571893 A CN 115571893A CN 202211143590 A CN202211143590 A CN 202211143590A CN 115571893 A CN115571893 A CN 115571893A
- Authority
- CN
- China
- Prior art keywords
- acid
- boric acid
- hydrochloric acid
- boron
- waste
- 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.)
- Pending
Links
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 123
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000004327 boric acid Substances 0.000 title claims abstract description 121
- 239000002699 waste material Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000007788 liquid Substances 0.000 title claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 75
- 229910052796 boron Inorganic materials 0.000 claims abstract description 63
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 62
- 230000008569 process Effects 0.000 claims abstract description 18
- 238000009833 condensation Methods 0.000 claims abstract description 14
- 230000005494 condensation Effects 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 230000008016 vaporization Effects 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 238000009834 vaporization Methods 0.000 claims description 11
- 238000005086 pumping Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000000498 cooling water Substances 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000001704 evaporation Methods 0.000 abstract description 8
- 230000008020 evaporation Effects 0.000 abstract description 8
- 238000002386 leaching Methods 0.000 abstract description 8
- 238000006386 neutralization reaction Methods 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 6
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 description 9
- 239000003365 glass fiber Substances 0.000 description 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 239000006028 limestone Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000006121 base glass Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- -1 boron ions Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
- C01B35/1054—Orthoboric acid
- C01B35/109—Purification; Separation; Concentration
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
- C01B7/0712—Purification ; Separation of hydrogen chloride by distillation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
A method for extracting and recovering boric acid from low-concentration hydrochloric acid waste liquid adopts the processes of negative pressure evaporation, condensation, crystallization, cleaning and microwave drying to effectively recover boric acid and hydrochloric acid in boron-containing waste hydrochloric acid solution after acid leaching in the production process of high silica fiber, thereby realizing the recovery and cyclic utilization of the boric acid-containing waste hydrochloric acid. The invention effectively separates impurities in the purification process, improves the extraction amount of boric acid in waste acid, reduces the content of boric acid and HCL in the waste acid, can reach the discharge standard after a small amount of neutralization treatment, reduces the consumption of alkali discharged by neutralization, avoids the consumption of a large amount of pure water and the generation of a large amount of waste water, has scientific and reasonable process steps, and provides a novel method for concentrating and extracting the boric acid from low-concentration hydrochloric acid waste liquid.
Description
Technical Field
The invention relates to the technical field of recovery of boric acid-containing waste hydrochloric acid, in particular to a method for extracting and recovering waste liquid boric acid in low-concentration hydrochloric acid through concentration.
Background
The ternary high silica glass fiber is a special glass fiber, has excellent characteristics of high temperature resistance, ablation resistance, good insulating property and the like, and is widely applied to the fields of aerospace, environmental protection, fire fighting, high temperature filtration, heat preservation, energy conservation and the like. The acid leaching process is an extremely important process in the production of high silica glass fibers.
In the production process of high silica glass fiber, acid leaching treatment is required to be carried out on base glass, and non-Si 0 in the fiber component is separated by utilizing the principle of micro-glass structure phase separation of the base glass 2 The components are leached out and dissolved in hydrochloric acid solution, and the acid leaching waste liquid after reaction mainly comprises hydrogen chloride, boric acid, sodium chloride and a small amount of organic impurities. In actual production, boric acid (H) is continuously available in the acid leaching process 3 BO 3 ) And the concentration gradually increases. When the concentration of boric acid reaches 40mg/L, the efficiency of acid leaching is affected and the quality of the product is obviously reduced. In order to ensure the quality of the high silica glass fiber product and the acid leaching efficiency, the boric acid-containing waste acid solution needs to be discharged periodically and a new hydrochloric acid solution needs to be supplemented.
In Japan, the amount of boric acid used is 35000 tons/year, and most of the boric acid is discharged without being recovered. Along with the increasing environmental protection situation, the pollution and disordered discharge of boric acid to water sources arouse great attention and wide attention of people. Under such circumstances, japan modified the water pollution prevention law in 2001 and started to restrict the discharge of wastewater containing boron. The standard for discharging the wastewater containing boron to the ocean is set to 230ppm or less, and the standard for discharging the wastewater containing boron to the river is set to 10ppm or less. There are various methods for removing boron from ordinary industrial wastewater, such as a coprecipitation removal method using magnesium salts, an ion exchange resin, a boron adsorbent removal method, or a combined separation method using boron.
At present, many manufacturers remove boron in wastewater by adopting an ion exchange boron extraction method, and the mechanism of the ion exchange method is to utilize functional groups on ion exchange resin to perform exchange reaction with target ions, so as to achieve the purpose of separation and concentration. The chemical structure of the ion exchange resin generates complex anions between the hydroxyl groups in the functional groups and boron, and the amine groups of the ion exchange resin are used as anion exchange groups to capture the generated complex anions, so that the boron ions are selectively adsorbed. The method is mainly used for removing boron from low-concentration boron solution, and is combined with other boron removal methods for integral purification and boron removal.
The combined boron separating method is to use other methods (such as adsorption method) as pretreatment to remove most of boron in the solution, and then use ion exchange method to remove the rest of a small amount of boron, so that the method reduces the workload and cost of the resin, and simultaneously utilizes the high efficiency of ion exchange to separate boron. However, when boron is removed at a high concentration, the amount of adsorbent added and the amount of resin consumed are large, and thus the economic efficiency is poor.
If the hydrochloric acid waste liquid containing boron is treated by adopting an acid-base neutralization method, the neutralized waste acid liquid containing boron is directly discharged into the environment, and three problems are brought, namely the problem of environmental protection treatment. Through actual measurement, the boric acid content in the neutralized waste acid solution is far greater than the discharge standard, the boric acid solution cannot be directly discharged, the boric acid solution can reach the discharge standard after being diluted by a large amount of water, and the waste of water resources is large, the discharge capacity is large, and the discharge cost is high. Secondly, the problem of resource waste. Boric acid and hydrochloric acid in the boron-containing waste acid solution have recycling value, and after neutralization, direct discharge cannot effectively utilize resources, and a large amount of alkaline substances are consumed for neutralization, so that great waste is caused. Third, it is a problem in the discharge process. The solubility of the boric acid is 3.6g at 10 ℃, the solubility of the boric acid is 2.7g at 0 ℃, the solubility of the boric acid is low at low temperature, the crystallization is easy, and the phenomenon of pipeline blockage is easy to cause in the discharge process in winter (the solubility of the boric acid is shown in table 1).
TABLE 1 boric acid solubility Table
| Temperature of | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 | 100 |
| Solubility g/100g | 2.7 | 3.6 | 4.8 | 6.6 | 8.7 | 11.5 | 14.5 | 16.7 | 23.7 | 30.3 | 40.2 |
In view of the foregoing, the disposal of boric acid-containing acid leach liquors has been a significant problem in the production of high silica glass fibers. The direct discharge of such waste liquid not only seriously pollutes the environment, but also causes great waste. According to the national requirements for building an environment-friendly and resource-saving society, the development of an advanced waste acid liquid treatment process and device is imperative, the environmental protection pressure of enterprises is relieved, the effective utilization of resources is improved, and the implementation of green circular economy has great significance.
The prior art only discloses a preparation process for extracting boric acid from waste acid in the journal of glass fiber in 2 months 1972, namely a technical process measure for extracting boric acid from waste acid published by the first glass fiber factory in Shaanxi. The preparation process for extracting boric acid from the waste acid comprises the following steps: a. firstly, pumping waste acid with the temperature of 90-95 ℃ into an acid storage tank through an acid-resistant pump, and cooling for 48 hours to reduce the temperature of a waste acid solution to room temperature; b. redissolving the crystallized boric acid, filtering and concentrating; c. packaging the boric acid crystallized twice; d. and neutralizing and discharging the waste liquid containing a small amount of boric acid in a neutralization pond by using limestone.
The process for extracting boric acid from waste acid mainly utilizes the principle that the solubility of boric acid is reduced along with the reduction of the solution temperature, and the boric acid is saturated in the solution to precipitate crystals to extract the boric acid. The process has the following problems: 1. the waste acid at 90-95 ℃ stored in the acid storage tank is naturally cooled to room temperature, the time for cooling and crystallizing the waste acid liquid is longer, and the boron extraction efficiency is very low. 2. The waste acid solution after condensation and crystallization still dissolves a large amount of boric acid, which far exceeds the discharge standard of environmental protection. 3. With the continuous increase of the discharge amount of the waste acid liquid, a large number of glass fiber reinforced plastic acid storage tanks are required, so that the equipment investment is large, the occupied area is large, and the economical efficiency is poor. 4. When the boric acid content can reach more than 90 percent, the boric acid can be directly used as a raw material, and the boric acid content in the boric acid extract obtained by secondary crystallization is 40 to 50 percent, so that the boric acid extract cannot be directly used. 5. The waste hydrochloric acid solution needs to be neutralized with limestone, the limestone reacts violently with acid when being put in, a large amount of dust and smoke are generated, a large amount of precipitates are accumulated at the bottom of a neutralization tank, and the waste hydrochloric acid solution needs to be cleaned regularly to generate solid waste. Meanwhile, the discharge contains a large amount of calcium ions, which easily causes secondary pollution.
Disclosure of Invention
In order to overcome the defects of low content of extracted boric acid, low extraction efficiency, large volume of extraction equipment, difficult standard environmental-friendly discharge of waste liquid after extracting boric acid, secondary pollution generated by using limestone for neutralization and the like in the prior art, the invention provides a method for extracting and recovering boric acid from low-concentration hydrochloric acid waste liquid.
The specific process of the invention is as follows:
step 1, vaporization separation:
pumping the boron-containing waste acid into a graphite evaporator from an acid storage tank by a permanent magnet variable frequency vacuum pump under the atmospheric pressure of-0.08 MP. Heating the boron-containing waste acid to a boiling point through steam at 110-120 ℃, and carrying out vaporization separation on the boron-containing waste acid in a graphite evaporator for 18-24 hours to finish the vaporization separation of the boron-containing waste acid.
And after the vaporization separation is finished, pumping the residual boron-containing waste acid to a condensation stirring tank by an acid-proof pump.
Step 2, recovering hydrochloric acid:
pumping the evaporated hydrochloric acid-containing water vapor into the graphite condenser through a permanent magnet variable frequency vacuum pump under the atmospheric pressure of-0.08 MP, and condensing for 1-2 hours under the action of circulating cooling water at the temperature of 5-10 ℃ to obtain the recovered hydrochloric acid. The concentration of the recovered hydrochloric acid is 1-3%.
Step 3, preparation of crude boric acid:
and cooling and crystallizing the boron-containing waste acid in the condensation stirring tank.
Stirring the boron-containing waste acid, and simultaneously introducing circulating cooling water to cool and crystallize the boron-containing waste acid.
During stirring, the power of a stirring motor is 4kw, and the rotating speed is 20r/min; stirring for 2-4 h, and cooling the crystals of the boron-containing waste acid to 5-15 ℃ to obtain crystallized crude boric acid.
The temperature of the cooling water is 0-5 ℃.
And 4, cleaning:
putting the crystallized crude boric acid into a spray drying machine for cleaning; and (3) starting to spray tap water during cleaning, and cleaning the crude boric acid to remove residual hydrochloric acid and sodium chloride on the surface of the boric acid. The rotating speed of the spray drying machine is 150-300 r/min, and the spraying time is 10-30 min. And after spraying is finished, spin-drying and dehydrating the cleaned crude boric acid for 30-60 min to obtain the crystallized boric acid with the boric acid content of 80-85%.
Step 5, microwave heating:
the obtained crystalline boric acid is placed in a microwave oven, and the obtained crystalline boric acid is heated by the microwave oven. The heating temperature is 90-105 ℃, the heating time is 10-30 mim, so as to remove the redundant water and the residual hydrochloric acid contained in the boric acid, and obtain the solid boric acid with the boric acid content of 90-95%.
Step 6, grinding:
and (3) grinding the obtained solid boric acid with the content of 90-95% in a grinding mill until the granularity of the solid boric acid reaches 2000-3000 meshes, and packaging for later use.
Thus, the recovery of boric acid in the hydrochloric acid waste liquid is completed.
The invention adopts the processes of negative pressure evaporation, condensation, crystallization, cleaning, microwave drying and the like, effectively recovers boric acid and hydrochloric acid in the boron-containing waste hydrochloric acid solution after acid leaching in the production process of the high silica fiber, and realizes the recovery and recycling of the boric acid-containing waste hydrochloric acid; solves the problem that the waste acid containing boron is difficult to discharge after reaching the standard, reduces the pressure of waste acid treatment by environmental protection equipment, and is beneficial to environmental protection.
The method can quickly evaporate and purify the waste hydrochloric acid solution, recycle the hydrochloric acid, effectively separate impurities in the purification process, extract the boric acid serving as a byproduct contained in the waste hydrochloric acid solution, solve the problem that the emission of the waste acid containing boron is difficult to reach the standard in conventional treatment, realize the recycling of the waste hydrochloric acid containing the boric acid, reduce the consumption of new hydrochloric acid, reduce the pressure of environment-friendly equipment on treating the waste acid, and be beneficial to environmental protection.
The practical production proves that the invention solves the problems of low efficiency, low boron extraction rate, more residual waste liquid, incapability of directly using extracted boric acid for production, secondary pollution of neutralized products and the like of the original direct cooling boron extraction process, greatly improves the extraction amount of boric acid in waste acid, reduces the content of boric acid and HCL in waste acid, can reach the discharge standard after being neutralized by a small amount, reduces the consumption of neutralizing discharged alkali, avoids the consumption of a large amount of pure water and the generation of a large amount of waste water, has scientific and reasonable process steps, and provides a novel method for concentrating and extracting boric acid from low-concentration hydrochloric acid waste liquid.
Compared with the prior art, the invention has the following beneficial effects:
1. with the continuous improvement of the environmental protection emission standard, the original boron extraction process can not meet the emission requirement, and compared with the original direct cooling boron extraction process, the new negative pressure distillation boron extraction process has the advantages that the boric acid recovery rate is improved to more than 40%, the hydrochloric acid recovery rate can reach more than 90%, and the boron extraction efficiency is improved by 8-10 times. The values of the boric acid content extracted by the new and old processes are shown in the table 1:
TABLE 1 comparison of boric acid content values extracted by the prior art and the present invention
2. The invention has remarkable economic benefit. Experiments prove that the invention carries out evaporation extraction and recovery on the boron-containing waste acid to obtain boric acid with the content of more than 90 percent and dilute hydrochloric acid with the concentration of 2 to 3 percent. The boric acid with the content of more than 90 percent is recovered and used as a boric acid raw material to be directly used for the production of company glass balls; the recovered dilute hydrochloric acid with the concentration of 2-3 percent is mixed with new acid solution to prepare the acid cleaning agent which can be continuously used for acid cleaning products such as high silica cloth/yarn and the like. Based on the emission amount of boron-containing waste acid of the applicant at present, 350 tons of boric acid can be extracted every year, and the purchasing cost of the boric acid is saved by 330 ten thousand yuan per ton according to the current price of 0.95 ten thousand yuan per ton. Meanwhile, 1500 tons of concentrated hydrochloric acid are used less per year, and the cost can be saved by more than 54 ten thousand yuan per year according to 360 yuan per ton.
3. The invention has remarkable social benefit. The boric acid is prepared by adopting the negative pressure evaporation and crystallization process, when the negative pressure of 0.08Mpa is formed by using the permanent magnet variable frequency vacuum pump, the boiling point of water is only 60.1 ℃, compared with the normal pressure evaporation process, the consumption of steam can be reduced by more than 40 percent for each ton of waste acid, the operation cost of the boron extraction process is reduced, and the energy-saving effect is obvious. Meanwhile, due to the characteristic of easy volatilization of the hydrochloric acid, the problem of acid gas overflow in the boron extraction process can be well controlled by adopting the negative pressure evaporation and crystallization processes, and environmental pollution caused by diffusion of a large amount of acid gas due to violent reaction in the evaporation of the waste acid is avoided. The table of the relationship between the boiling point and the vacuum degree of the negative pressure evaporation water is shown in table 2.
TABLE 2 corresponding relationship table of boiling point and vacuum degree of water
| Serial number | Vacuum degree Mpa | Boiling point of |
| 1 | 0.000 | 99.6 |
| 2 | -0.010 | 96.7 |
| 3 | -0.020 | 93.5 |
| 4 | -0.030 | 89.9 |
| 5 | -0.040 | 85.9 |
| 6 | -0.050 | 81.3 |
| 7 | -0.060 | 75.9 |
| 8 | -0.070 | 69.1 |
| 9 | -0.080 | 60.1 |
| 10 | -0.090 | 45.8 |
4. The condenser, the evaporator and the condensing and stirring tank in the boron extracting equipment are all changed into graphite materials from the past enamel type, the average service life of the equipment is changed from the original 6-12 months to the present 2-3 years, the equipment investment is saved by 50%, and the maintenance and operation cost is greatly reduced.
Detailed Description
The invention relates to a method for extracting boric acid by concentrating low-concentration hydrochloric acid waste liquid by using a negative pressure distillation system in the prior art. The recovery system comprises a permanent magnet variable frequency vacuum pump, an acid storage tank, a graphite evaporator, a condensation stirring tank, a graphite condenser, a condensation stirring tank, a drying machine, a microwave oven and a grinding mill.
The invention describes the technical scheme in detail through 5 embodiments.
The specific process of the invention is as follows:
step 1, vaporization separation:
pumping the boron-containing waste acid into a graphite evaporator from an acid storage tank by a permanent magnet variable frequency vacuum pump under the atmospheric pressure of-0.08 MP. Heating the boron-containing waste acid to a boiling point at 110-120 ℃, and carrying out vaporization separation on the boron-containing waste acid in a graphite evaporator for 18-24 hours to finish the vaporization separation of the boron-containing waste acid.
And after the vaporization separation is finished, pumping the residual boron-containing waste acid to a condensation stirring tank by an acid-proof pump.
TABLE 3 technical parameters of the examples in step 1
Step 2, recovering hydrochloric acid:
pumping the evaporated hydrochloric acid-containing water vapor into the graphite condenser through a permanent magnet variable frequency vacuum pump under the atmospheric pressure condition of-0.08 MP, and condensing for 1-2 h through circulating cooling water at the temperature of 5-15 ℃ to obtain recovered hydrochloric acid; the recovered hydrochloric acid can be reused. The concentration of the recovered hydrochloric acid is 1-3%. The recovery of hydrochloric acid is completed.
TABLE 4 technical parameters of the examples in step 2
Step 3, preparation of crude boric acid:
and (3) stirring the residual boron-containing waste acid entering the condensation stirring tank in the step (1), and simultaneously introducing circulating cooling water at 0-5 ℃ to cool and crystallize the boron-containing waste acid.
During stirring, the power of a stirring motor is 4kw, and the rotating speed is 20r/min; stirring for 2-4 h, and obtaining crystallized crude boric acid when the crystallization of the boron-containing waste acid is cooled to 5-15 ℃.
TABLE 5 technical parameters of the examples in step 3
And 4, cleaning:
putting the crystallized crude boric acid into a spray drier for cleaning; and starting to spray tap water during cleaning to clean the crude boric acid so as to remove residual hydrochloric acid and sodium chloride on the surface of the boric acid. The rotating speed of the spray drying machine is 150-300 r/min, and the spraying time is 10-30 min. And after spraying is finished, spin-drying and dehydrating the cleaned crude boric acid for 30-60 min to obtain the crystallized boric acid with the boric acid content of 80-85%.
TABLE 6 technical parameters of the examples in step 4
Step 5, microwave heating:
the obtained crystalline boric acid is placed in a microwave oven, and the obtained crystalline boric acid is heated by the microwave oven. The heating temperature is 90-105 ℃, the heating time is 10-30 mim, so as to remove the redundant water and residual hydrochloric acid contained in the boric acid, and obtain the solid boric acid with the boric acid content of 90-95%.
TABLE 7 technical parameters of the examples in step 5
Step 6, grinding:
and (3) putting the obtained solid boric acid with the content of 90-95% into a grinding mill for grinding until the granularity of the solid boric acid reaches 2000-3000 meshes, and packaging for later use.
Claims (8)
1. A method for extracting and recovering boric acid from low-concentration hydrochloric acid waste liquid is characterized in that a negative pressure distillation system is used for recovering boric acid, and the negative pressure distillation system comprises a permanent magnet variable frequency vacuum pump, an acid storage tank, a graphite evaporator, a condensation stirring tank, a graphite condenser, a condensation stirring tank, a drying machine, a microwave oven and a grinding mill; the method is characterized by comprising the following specific processes:
step 1, vaporization separation:
pumping boron-containing waste acid into a graphite evaporator from an acid storage tank through a permanent magnet variable frequency vacuum pump, heating the boron-containing waste acid to a boiling point through steam, and carrying out vaporization separation on the boron-containing waste acid in the graphite evaporator;
pumping the residual boron-containing waste acid to a condensation stirring tank by an acid-proof pump after the vaporization separation is finished;
step 2, recovering hydrochloric acid:
pumping the evaporated hydrochloric acid-containing water vapor into a graphite condenser through a permanent magnet variable frequency vacuum pump, and condensing through circulating cooling water to obtain recovered hydrochloric acid;
step 3, preparation of crude boric acid:
stirring the residual boron-containing waste acid entering the condensation stirring tank in the step 1, and simultaneously introducing circulating cooling water at 0-5 ℃ to cool and crystallize the boron-containing waste acid; cooling the crystallization of the boron-containing waste acid to 5-15 ℃ to obtain crude boric acid;
and 4, cleaning:
putting the obtained crude boric acid into a spray drier, starting spray tap water to clean the crude boric acid so as to remove residual hydrochloric acid and sodium chloride on the surface of the boric acid and obtain crystallized boric acid;
step 5, microwave heating:
placing the obtained crystallized boric acid in a microwave oven, and heating the obtained crystallized boric acid by the microwave oven to remove redundant moisture and residual hydrochloric acid contained in the boric acid and obtain solid boric acid with boric acid content of 90-95%;
step 6, grinding:
putting the obtained solid boric acid into a grinding mill, grinding until the granularity of the solid boric acid reaches 2000-3000 meshes, and packaging for later use; thus, the recovery of boric acid in the hydrochloric acid waste liquid is completed.
2. The method for extracting and recovering the boric acid from the low-concentration hydrochloric acid waste liquid as claimed in claim 1, wherein the pressure of the permanent magnet variable frequency vacuum pump is-0.08 MP and is kept; the temperature of the steam is 110-120 ℃; the time for vaporizing and separating the boron-containing waste acid is 18-24 h.
3. The method for extracting and recovering boric acid from the low-concentration hydrochloric acid waste liquid as claimed in claim 1, wherein the temperature of the circulating cooling water is 5-10 ℃ and the condensation time is 1-2 h when the hydrochloric acid is recovered.
4. The method for extracting and recovering boric acid from low-concentration hydrochloric acid waste liquid according to claim 1, wherein the concentration of the recovered hydrochloric acid is 1 to 3 percent.
5. The method for extracting and recovering boric acid from the low-concentration hydrochloric acid waste liquid as claimed in claim 1, wherein the stirring motor power is 4kw and the rotation speed is 20r/min when the crude boric acid is prepared; stirring for 2-4 h.
6. The method for extracting and recovering the boric acid from the low-concentration hydrochloric acid waste liquid as claimed in claim 1, wherein the rotation speed of a spray drier is 150-300 r/min, the spraying time is 10-30 min, and the spin-drying dehydration is 30-60 min.
7. The method for extracting and recovering boric acid from the low-concentration hydrochloric acid waste liquid as claimed in claim 1, wherein the boric acid content in the obtained crystallized boric acid is 80-85%.
8. The method for extracting and recovering boric acid from low-concentration hydrochloric acid waste liquid as claimed in claim 1, wherein the heating temperature is 90-105 ℃ and the heating time is 10-30 mm during microwave heating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2022105099164 | 2022-05-11 | ||
| CN202210509916 | 2022-05-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115571893A true CN115571893A (en) | 2023-01-06 |
Family
ID=84580685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211143590.4A Pending CN115571893A (en) | 2022-05-11 | 2022-09-20 | Method for extracting and recovering boric acid from low-concentration hydrochloric acid waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115571893A (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394364A (en) * | 1977-11-16 | 1983-07-19 | Sandoz Ltd. | Separation of boric acid from mixtures thereof with sulphuric acid |
| JPH10310421A (en) * | 1997-05-01 | 1998-11-24 | Nittetsu Mining Co Ltd | Treatment of waste dilute hydrochloric acid used in glass cleaning |
| JP2001247305A (en) * | 2000-03-02 | 2001-09-11 | Nippon Rensui Co Ltd | Method for recovering boron |
| CN101786606A (en) * | 2009-12-11 | 2010-07-28 | 北京天泰兴工程科技有限公司 | Process for recycling iron/steel acid-washing waste hydrochloric acid through evaporation burning and coupling process |
| JP2012056803A (en) * | 2010-09-09 | 2012-03-22 | Sasakura Engineering Co Ltd | Method for recovering boron |
| CN102774908A (en) * | 2012-08-21 | 2012-11-14 | 昆明理工大学 | Method for regenerating hydrochloric acid by microwave heating hydrochloric acid-containing waste liquid |
| CN102863036A (en) * | 2012-09-24 | 2013-01-09 | 蒙自矿冶有限责任公司 | Method for regeneration of hydrochloric acid containing waste liquid by means of microwave heating |
| CN204111344U (en) * | 2014-10-16 | 2015-01-21 | 青岛瀚新石墨设备科技有限公司 | Full graphite equipment acid regeneration utilizes and reclaims iron protochloride crystal treatment system |
| CN204251334U (en) * | 2014-11-15 | 2015-04-08 | 湖南新紫继换热科技有限公司 | A kind of waste hydrochloric acid evaporation concentration treatment system |
| CN107311239A (en) * | 2017-04-13 | 2017-11-03 | 北京浦仁美华环保科技股份有限公司 | The MVR of hydrochloric spent acid is concentrated by evaporation recovery process |
| CN207046880U (en) * | 2017-08-05 | 2018-02-27 | 贵州申申环保科技有限公司 | Hydrochloric acid pickling waste liquor recovery and processing system |
| CN108622912A (en) * | 2018-07-11 | 2018-10-09 | 广东先导先进材料股份有限公司 | The production method of high temperature covering agent grade boric oxide |
| CN109678167A (en) * | 2019-03-05 | 2019-04-26 | 李洪岭 | A method of boric acid is produced from lithium borate waste solution is mentioned |
| CN113860257A (en) * | 2021-11-04 | 2021-12-31 | 浙江容跃环保科技有限公司 | Method and system for regenerating and recycling glass thinning waste acid liquor |
-
2022
- 2022-09-20 CN CN202211143590.4A patent/CN115571893A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4394364A (en) * | 1977-11-16 | 1983-07-19 | Sandoz Ltd. | Separation of boric acid from mixtures thereof with sulphuric acid |
| JPH10310421A (en) * | 1997-05-01 | 1998-11-24 | Nittetsu Mining Co Ltd | Treatment of waste dilute hydrochloric acid used in glass cleaning |
| JP2001247305A (en) * | 2000-03-02 | 2001-09-11 | Nippon Rensui Co Ltd | Method for recovering boron |
| CN101786606A (en) * | 2009-12-11 | 2010-07-28 | 北京天泰兴工程科技有限公司 | Process for recycling iron/steel acid-washing waste hydrochloric acid through evaporation burning and coupling process |
| JP2012056803A (en) * | 2010-09-09 | 2012-03-22 | Sasakura Engineering Co Ltd | Method for recovering boron |
| CN102774908A (en) * | 2012-08-21 | 2012-11-14 | 昆明理工大学 | Method for regenerating hydrochloric acid by microwave heating hydrochloric acid-containing waste liquid |
| CN102863036A (en) * | 2012-09-24 | 2013-01-09 | 蒙自矿冶有限责任公司 | Method for regeneration of hydrochloric acid containing waste liquid by means of microwave heating |
| CN204111344U (en) * | 2014-10-16 | 2015-01-21 | 青岛瀚新石墨设备科技有限公司 | Full graphite equipment acid regeneration utilizes and reclaims iron protochloride crystal treatment system |
| CN204251334U (en) * | 2014-11-15 | 2015-04-08 | 湖南新紫继换热科技有限公司 | A kind of waste hydrochloric acid evaporation concentration treatment system |
| CN107311239A (en) * | 2017-04-13 | 2017-11-03 | 北京浦仁美华环保科技股份有限公司 | The MVR of hydrochloric spent acid is concentrated by evaporation recovery process |
| CN207046880U (en) * | 2017-08-05 | 2018-02-27 | 贵州申申环保科技有限公司 | Hydrochloric acid pickling waste liquor recovery and processing system |
| CN108622912A (en) * | 2018-07-11 | 2018-10-09 | 广东先导先进材料股份有限公司 | The production method of high temperature covering agent grade boric oxide |
| CN109678167A (en) * | 2019-03-05 | 2019-04-26 | 李洪岭 | A method of boric acid is produced from lithium borate waste solution is mentioned |
| CN113860257A (en) * | 2021-11-04 | 2021-12-31 | 浙江容跃环保科技有限公司 | Method and system for regenerating and recycling glass thinning waste acid liquor |
Non-Patent Citations (2)
| Title |
|---|
| 蔡博等: "高硅氧酸沥滤废液环保处理的应用", 玻璃纤维, no. 3, 26 June 2022 (2022-06-26), pages 38 - 41 * |
| 陕西第一玻璃纤维厂: "从废酸中提取硼酸的技术工艺措施", 玻璃纤维, 31 December 1972 (1972-12-31), pages 22 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101307456B (en) | Pickling waste acid regeneration process | |
| CN104973726A (en) | Recovery processing method of high salinity wastewater containing sodium chloride and sodium sulfate | |
| CN104326612A (en) | Method and system for recovering salt from waste water treatment system | |
| CN105293772A (en) | Method for recovering of rare earth and resource utilization of ammonia nitrogen from rare earth processing and smelting wastewater | |
| CN103819041B (en) | A kind of method of cryoconcentration high-salt wastewater | |
| CN105461138B (en) | A kind of method that sulfuric acid and hydrochloric acid and fluorine open circuit are reclaimed from smelting wastewater | |
| CN103553138A (en) | Comprehensive utilization method for separating, concentrating and purifying manganese sulfate, magnesium sulfate and calcium sulfate in high-salt waste water | |
| CN101787537B (en) | Method for recovering waste nitric-hydrofluoric acid from stainless steel annealing-pickling by micro- and negative-pressure evaporation and crystallization processes | |
| CN102688607A (en) | Ammonia tail gas recycling method and system | |
| CN108862348B (en) | Method for recycling waste sulfuric acid generated by electrode foil corrosion | |
| CN102267717B (en) | Process for preparing zinc sulfate by evaporation and crystallization | |
| CN113336247A (en) | Method for recycling waste aluminum etching liquid | |
| CN107792869A (en) | A kind of method and technique that high-purity sodium metaaluminate is produced by mould alkali-washing waste liquid | |
| CN115571893A (en) | Method for extracting and recovering boric acid from low-concentration hydrochloric acid waste liquid | |
| CN103819042B (en) | A kind of hydrochloride waste purifying treatment method | |
| CN108658353B (en) | Calcium chloride wastewater treatment process | |
| CN102616743A (en) | Treatment recycling process of hydrochloric acid liquid waste produced in rare metals extraction process | |
| CN104711617A (en) | Regeneration method of acid washing waste acids | |
| CN113121060B (en) | Method and device for treating high-salinity wastewater generated in PAO production | |
| CN208649420U (en) | A kind of chlorination mentions the recovery and processing system of germanium and hydrochloric acid in germanium spent acid | |
| CN104524797B (en) | Energy-conservation concentration and evaporation method in zirconium oxychloride production process | |
| CN109369339B (en) | Method for treating waste p-toluenesulfonic acid iron n-butanol solution | |
| CN104986907A (en) | Method for low-temperature concentration of high-salinity wastewater | |
| CN101560032A (en) | Method for treating high density wastewater during phenolic resin production | |
| CN111498884A (en) | Treatment process and device for fluorine-containing waste hydrochloric acid |
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 |