CN112850731A - Method and device for recovering boron trifluoride from wastewater containing boron trifluoride - Google Patents
Method and device for recovering boron trifluoride from wastewater containing boron trifluoride Download PDFInfo
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- CN112850731A CN112850731A CN202110133523.3A CN202110133523A CN112850731A CN 112850731 A CN112850731 A CN 112850731A CN 202110133523 A CN202110133523 A CN 202110133523A CN 112850731 A CN112850731 A CN 112850731A
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- boron trifluoride
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- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 229910015900 BF3 Inorganic materials 0.000 title claims abstract description 104
- 239000002351 wastewater Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 84
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004327 boric acid Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 238000006073 displacement reaction Methods 0.000 claims abstract description 27
- 238000011084 recovery Methods 0.000 claims abstract description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 6
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 39
- 238000001816 cooling Methods 0.000 claims description 32
- 230000000536 complexating effect Effects 0.000 claims description 22
- 238000004821 distillation Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- MEMUCXUKCBNISQ-UHFFFAOYSA-N acetonitrile;trifluoroborane Chemical compound CC#N.FB(F)F MEMUCXUKCBNISQ-UHFFFAOYSA-N 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000010668 complexation reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 40
- 239000002585 base Substances 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- 238000005119 centrifugation Methods 0.000 description 9
- -1 fluorine ions Chemical class 0.000 description 9
- 239000007787 solid Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical compound [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- MLYYVTUWGNIJIB-BXKDBHETSA-N cefazolin Chemical compound S1C(C)=NN=C1SCC1=C(C(O)=O)N2C(=O)[C@@H](NC(=O)CN3N=NN=C3)[C@H]2SC1 MLYYVTUWGNIJIB-BXKDBHETSA-N 0.000 description 2
- 229960001139 cefazolin Drugs 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229910004039 HBF4 Inorganic materials 0.000 description 1
- 125000003713 acetylimino group Chemical group [H]C([H])([H])C(=O)N=[*] 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- C01B35/06—Boron halogen compounds
- C01B35/061—Halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method and a device for recovering boron trifluoride in wastewater containing boron trifluoride. The recovery method provided by the invention comprises the following steps: mixing wastewater containing boron trifluoride with strong base to perform acid-base neutralization reaction to obtain a neutralization reaction product; hydrolyzing boron trifluoride contained in the wastewater into fluoroboric acid and boric acid; and mixing the neutralization reaction product with fuming sulfuric acid to perform a displacement reaction to obtain boron trifluoride gas. According to the method, strong base is added into the wastewater containing boron trifluoride to perform acid-base neutralization reaction with fluoboric acid in the wastewater, so that sodium fluoborate is obtained; reacting sodium fluoborate, boric acid and fuming sulfuric acid to obtain boron trifluoride gas; the invention utilizes simple chemical reaction to recover boron trifluoride in the wastewater. The recovery method provided by the invention is simple and feasible; the influence of boron trifluoride on the environment and the existing wastewater treatment system is reduced; the waste of resources is reduced.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method and a device for recovering boron trifluoride in wastewater containing boron trifluoride.
Background
Currently, in chemical industry, products using boron trifluoride as a polymerization/condensation catalyst are increasing, and in industries such as petroleum resin, medicine, perfume and the like, boron trifluoride is mostly used as a polymerization/condensation catalyst, and the amount of boron trifluoride is increasing rapidly in recent years. With the widespread use of boron trifluoride, the wastewater produced after the chemical reaction contains a high concentration of boron fluoride compounds. Because the boron-fluorine compound can pollute the environment, the content of fluorine and boron in the wastewater is strictly limited by the nation, and the content of fluorine ions in some local standard wastewater is required to be less than 30 ppm.
The existing sewage treatment system has no degradation and conversion effect on the boron fluoride; and the fluorine-boron compound in the wastewater has extremely strong toxicity to biochemical bacteria of the traditional sewage treatment, and the damage to a sewage treatment system can be caused by carelessness. At present, no method for recovering boron trifluoride in wastewater exists.
Disclosure of Invention
In view of the above, the present invention provides a method and an apparatus for recovering boron trifluoride from wastewater containing boron trifluoride, which can recover boron trifluoride in wastewater well, reduce the influence of boron trifluoride on the environment and wastewater treatment system, and reduce the waste of resources.
In order to solve the technical problem, the invention provides a method for recovering boron trifluoride in wastewater containing boron trifluoride, which comprises the following steps:
mixing wastewater containing boron trifluoride with strong base to perform acid-base neutralization reaction to obtain a neutralization reaction product, wherein the wastewater contains fluoboric acid and boric acid, the fluoboric acid and the boric acid are obtained by hydrolyzing boron trifluoride, and the neutralization reaction product contains sodium fluoborate and boric acid;
and mixing the neutralization reaction product with fuming sulfuric acid to perform a displacement reaction to obtain boron trifluoride gas.
Preferably, the method further comprises the following steps after obtaining the boron trifluoride gas: mixing boron trifluoride gas and acetonitrile, and carrying out complex reaction to obtain a boron trifluoride acetonitrile complex.
Preferably, the mass ratio of the boron trifluoride gas to the acetonitrile is 1: 3-10;
the temperature of the complexation reaction is 120-160 ℃, and the pressure is 0.18-0.22 MPa.
Preferably, the mass percent of the fluoroboric acid in the wastewater containing boron trifluoride is 3-20%, and the mass percent of the boric acid in the wastewater containing boron trifluoride is 1-6%.
Preferably, the strong base comprises a soluble hydroxide;
and the pH value of the solution after the neutralization reaction is 4-5.
Preferably, the mass concentration of the oleum is 120%.
Preferably, the neutralization reaction further comprises:
dehydrating and concentrating the product of the neutralization reaction to obtain a concentrated solution;
crystallizing the concentrated solution to obtain a crystallized product, wherein the crystallized product comprises sodium fluoborate and boric acid.
Preferably, the dehydration concentration is reduced pressure distillation;
the vacuum degree of the reduced pressure distillation is-0.088 to-0.092 MPa, and the temperature is 78 to 82 ℃; the crystallization is cooling crystallization, and the temperature of the cooling crystallization is 28-32 ℃.
The invention also provides a recovery device of boron trifluoride in wastewater containing boron trifluoride, which comprises a neutralization reaction tank 1, wherein the bottom of the neutralization reaction tank is provided with a second outlet 1-9, and the top of the neutralization reaction tank is provided with a second inlet 1-7;
a third inlet 2-3 is communicated with a second outlet 1-9 of the neutralization reaction tank 1 to form a replacement reaction tank 2.
Preferably, the top of the replacement reaction tank 2 is provided with a third outlet 2-4;
also comprises a complexing tank with an inlet 3-3 communicated with a third outlet 2-4.
The invention provides a method for recovering boron trifluoride in wastewater containing boron trifluoride, which comprises the following steps: mixing wastewater containing boron trifluoride with strong base to perform acid-base neutralization reaction to obtain a neutralization reaction product; the wastewater contains fluoboric acid and boric acid, the fluoboric acid and the boric acid are obtained by hydrolyzing boron trifluoride, and the neutralization reaction product contains sodium fluoborate and boric acid; and mixing the neutralization reaction product with fuming sulfuric acid to perform a displacement reaction to obtain boron trifluoride gas. According to the method, strong base is added into the wastewater to perform acid-base neutralization reaction with the fluoboric acid in the wastewater, so that sodium fluoborate is obtained; reacting sodium fluoborate, boric acid and fuming sulfuric acid to obtain boron trifluoride gas; the invention utilizes simple chemical reaction to recover boron trifluoride in the wastewater. The recovery method provided by the invention is simple and feasible; the influence of boron trifluoride on the environment and the existing wastewater treatment system is reduced; the waste of resources is reduced.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for recovering boron and fluorine from wastewater in an embodiment; wherein 1 is a neutralization reaction tank, 1-1 is a cooling pipe inlet, 1-2 is a cooling pipe outlet, 1-3 is a heating pipe inlet, 1-4 is a heating pipe outlet, 1-5 is a stirrer, 1-6 is a first inlet, 1-7 is a second inlet, 1-8 is a first outlet, 1-9 is a second outlet, 2 is a displacement reaction tank, 2-1 is a heating pipe inlet, 2-2 is a heating pipe outlet, 2-3 is a third inlet, 2-4 is a third outlet, 2-5 is a stirrer, 3 is a complexing tank, 3-1 is a circulating water inlet, 3-2 is a circulating water outlet, 3-3 is a complexing tank inlet, 3-4 is a stirrer, 4 is a condenser, 4-1 is a cooling pipe inlet, 4-2 is a cooling pipe outlet, 4-3 is a condenser inlet, 4-4 is a condenser outlet, 5 is a water storage tank, 5-1 is a water storage tank inlet, 5-2 is a water storage tank outlet, 5-3 is a water outlet, 6 is a vacuum pump, 7 is a centrifuge, 7-1 is a centrifuge inlet, 7-2 is a liquid outlet, 7-3 is a solid outlet, 8 is a dryer, 8-1 is a dryer inlet, and 8-2 is a dryer outlet.
Detailed Description
The invention provides a method for recovering boron trifluoride in wastewater containing boron trifluoride, which comprises the following steps:
mixing wastewater containing boron trifluoride with strong base to perform acid-base neutralization reaction to obtain a neutralization reaction product; the wastewater contains fluoboric acid and boric acid, the fluoboric acid and the boric acid are obtained by hydrolyzing boron trifluoride, and the neutralization product contains sodium fluoborate and boric acid;
and mixing the neutralization reaction product with fuming sulfuric acid to perform a displacement reaction to obtain boron trifluoride gas.
In the present invention, all the raw materials are conventional commercially available products unless otherwise specified.
Mixing wastewater containing boron trifluoride with strong base to perform acid-base neutralization reaction to obtain a neutralization reaction product; the wastewater contains fluoboric acid and boric acid, the fluoboric acid and the boric acid are obtained by hydrolyzing boron trifluoride, and the neutralization product contains sodium fluoborate and boric acid. In the present invention, the wastewater containing boron trifluoride preferably includes wastewater produced in the process of preparing cefazolin.
In the present invention, the strong base preferably comprises a soluble hydroxide, preferably comprising sodium hydroxide or potassium hydroxide, more preferably sodium hydroxide. In the invention, the content of the fluoroboric acid in the wastewater containing boron trifluoride is preferably 3-20% by mass, and more preferably 10-15% by mass; the content of boric acid in the wastewater is preferably 1-6%, and more preferably 3-5%. In the invention, the pH value of the solution after the neutralization reaction is preferably 4-5. The invention has no special limitation on the quality of the strong base and the volume ratio of the wastewater containing boron trifluoride, as long as the pH value of the solution after the neutralization reaction can be ensured. In the present invention, the mixing of the wastewater containing boron trifluoride and the strong base is not particularly limited as long as the wastewater and the strong base can be uniformly mixed.
In the present invention, it is preferable to further include, after the neutralization reaction:
dehydrating and concentrating the product of the neutralization reaction to obtain a concentrated solution;
crystallizing the concentrated solution to obtain a crystallized product, wherein the crystallized product comprises sodium fluoborate and boric acid.
The invention carries out dehydration and concentration on the product of the neutralization reaction to obtain concentrated solution. In the present invention, the dehydration concentration is preferably distillation under reduced pressure; the vacuum degree of the reduced pressure distillation is preferably-0.088 to-0.092 MPa, and more preferably-0.09 MPa; the temperature is preferably 78 to 82 ℃, and more preferably 80 ℃. In the present invention, the water removed by the pressure distillation preferably accounts for 65 to 75% by mass, and more preferably 70% by mass of the solvent in the neutralized reaction product. In the present invention, the water removed by the distillation under reduced pressure may be directly discharged.
After the concentrated solution is obtained, the concentrated solution is crystallized to obtain a crystallized product, wherein the crystallized product comprises sodium fluoborate and boric acid. In the invention, the crystallization is preferably a temperature-reducing crystallization, and the temperature of the temperature-reducing crystallization is preferably 20-30 ℃, and more preferably 25 ℃.
In the present invention, the crystallization preferably further comprises: centrifuging the crystallized product; and drying the solid obtained by centrifugation to obtain sodium fluoborate and boric acid. In the invention, the rotation speed of the centrifugation is preferably 800-1000 r/min, and more preferably 850-900 r/min; the time is preferably 10 to 20min, and more preferably 15 to 18 min.
In the present invention, the supernatant obtained by the centrifugation contains a part of sodium fluoroborate and boric acid, and it is preferable to mix the supernatant obtained by the centrifugation with waste water and recycle the mixture. The invention preferably dries the solid obtained by centrifugation to obtain sodium fluoborate and boric acid. In the present invention, the drying is preferably vacuum drying, and the degree of vacuum of the vacuum drying is preferably-0.09 to-0.1 MPa, more preferably-0.093 to-0.095 MPa; the temperature is preferably 70-80 ℃, and more preferably 75-78 ℃; the time is preferably 2.8-3.2 h, and more preferably 3 h. In the present invention, the water content of the sodium fluoroborate and boric acid obtained after vacuum drying is preferably 3% or less.
After the neutralization reaction product is obtained, the neutralization reaction product and fuming sulfuric acid are mixed for replacement reaction to obtain boron trifluoride gas. In the present invention, the oleum is preferably 120% sulfuric acid. In the present invention, the free SO in oleum3Absorbing water generated in the reaction, ensuring the concentration of sulfuric acid to be kept above 95% after the reaction is finished, and reducing BF3Residual in sulfuric acid, the higher the sulfuric acid solution concentration, BF3The smaller the solubility. The amount of the fuming sulfuric acid used is not particularly limited, as long as the concentration of the sulfuric acid is kept to be more than 95% after the reaction is completed. In the examples of the present invention, the mass ratio of the total mass of sodium fluoroborate and boric acid to 120% sulfuric acid was 1: 3.5.
The present invention is not particularly limited as long as the neutralization reaction product and fuming sulfuric acid can be uniformly mixed. In the invention, the temperature of the replacement reaction is preferably 120-160 ℃, and more preferably 130-140 ℃. The time of the displacement reaction is not particularly limited, and the completion of the displacement reaction is indicated when the gas is not generated any more.
The boron trifluoride gas obtained preferably further comprises: mixing boron trifluoride gas and acetonitrile, and carrying out complex reaction to obtain a boron trifluoride acetonitrile complex.
In the present invention, the mass ratio of the boron trifluoride gas to the acetonitrile is preferably 1:3 to 10, and more preferably 1:5 to 7. In the present invention, the pressure of the complexation reaction is preferably 0.18 to 0.22MPa, and more preferably 0.2 MPa. In the present invention, the time of the complexing reaction is not particularly limited, and it is sufficient to complete the reaction of boron trifluoride. In the present invention, the complexing reaction is preferably accompanied by stirring, since the reaction of boron trifluoride and acetonitrile is an exothermic reaction, and the reaction is favorably carried out by lowering the temperature with stirring.
In the invention, the boron trifluoride gas is not easy to store and transport, and the boron trifluoride gas and acetonitrile are subjected to a complex reaction to fix the boron trifluoride in a complex, so that the storage of the boron trifluoride is facilitated; meanwhile, the boron trifluoride acetonitrile complex is also a complex commonly used in the pharmaceutical industry, and can be directly sold.
Taking strong base as sodium hydroxide as an example, the reaction equation in the recovery method of the invention is as follows:
hydrolysis reaction of boron trifluoride: 4BF3+3H2O＝3HBF4+H3BO3；
Acid-base neutralization reaction: HBF4+NaOH＝NaBF4+H2O；
And (3) replacement reaction: 3NaBF4+H3BO3+3H2SO4＝4BF3↑+3NaHSO4+3H2O；
And (3) complexing reaction: c2H3N+BF3＝C2H3N·BF3。
The method thoroughly solves the problem of boron trifluoride discharge in the wastewater, and the wastewater removed by reduced pressure distillation does not contain boron fluoride ions and can be directly discharged; the supernatant after centrifugation can be recycled; the recovery method provided by the invention realizes the cyclic utilization of the fluorine and boron resources, saves natural resources and has higher environmental protection benefit and social comprehensive benefit.
The invention also provides a recovery device of boron trifluoride in wastewater containing boron trifluoride, which comprises a neutralization reaction tank 1, wherein the bottom of the neutralization reaction tank is provided with a second outlet (1-9), and the top of the neutralization reaction tank is provided with a second inlet (1-7);
a third inlet 2-3 is communicated with a second outlet 1-9 arranged at the bottom of the neutralization reaction tank 1, and the third inlet 2-3 is communicated with the replacement reaction tank 2.
In the present invention, the second inlets 1 to 7 are preferably inlets of wastewater containing boron trifluoride and strong alkali.
In one embodiment of the invention, cooling pipes and heating pipes which are alternately coiled are arranged on the outer surface of the neutralization reaction tank 1, a cooling pipe inlet 1-1 is arranged at the upper part of the neutralization reaction tank 1, a cooling pipe outlet 1-2 is arranged at the upper part of the neutralization reaction tank 1, and the cooling pipe inlet 1-1 is connected with cooling water; and cooling water is introduced into the cooling pipe to play a role in cooling. A heating pipe inlet 1-3 is arranged at the lower part of the neutralization reaction tank, a heating pipe outlet 1-4 is arranged at the lower part of the neutralization reaction tank, and the heating pipe inlet 1-3 is connected with steam; and steam is introduced into the heating pipe to heat the reaction liquid in the neutralization reaction tank.
In one embodiment of the present invention, a stirrer 1-5 is disposed in the neutralization reaction tank 1.
In one embodiment of the present invention, the top of the neutralization reaction tank 1 is provided with a first outlet 1-8, and the first outlet 1-8 is used for performing reduced pressure distillation.
In one embodiment of the invention, the recovery device further comprises a condenser 4 with an inlet 4-3 communicated with the first outlet 1-8, and the bottom of the condenser 4 is provided with an outlet 4-4; the condenser 4 is used for condensing water distilled out under reduced pressure and condensing gaseous water into liquid water. In one scheme of the invention, a cooling pipe is coiled on the outer surface of the condenser 4, an inlet 4-1 of the cooling pipe is arranged at the lower part of the condenser 4, an outlet 4-2 of the cooling pipe is arranged at the upper part of the condenser 4, and the inlet 4-1 of the cooling pipe is connected with cooling circulating water.
In one embodiment of the invention, the recovery device further comprises a water storage tank 5 with an inlet 5-1 communicated with an outlet 4-4 of the condenser; an outlet 5-2 is formed in the top of the water storage tank 5, and a water outlet 5-3 is formed in the bottom of the water storage tank 5; the water storage tank 5 is used for storing water condensed by the condenser 4, and the water outlet 5-3 is used for discharging water in the water storage tank 5.
In one embodiment of the invention, the recycling device further comprises a vacuum pump 6 with an inlet communicated with the outlet 5-2 of the water storage tank, the vacuum pump 6 is used for pumping vacuum in the neutralization reaction tank 1,
in one embodiment of the present invention, a centrifuge 7 and a dryer 8 are further connected between the neutralization reaction tank 1 and the displacement reaction tank 2 in sequence. In the present invention, the second outlet 1-9 is communicated with the centrifuge inlet 7-1, and the liquid outlet 7-2 of the centrifuge 7 is communicated with the first inlet 1-6 provided at the top of the neutralization reaction tank 1, for transferring the centrifuged supernatant to the neutralization reaction tank 1. The solid outlet 7-3 of the centrifuge 7 is communicated with the dryer inlet 8-1, and the dryer outlet 8-2 is communicated with a third inlet 2-3 arranged at the top of the displacement reaction tank 2.
In one scheme of the invention, a stirrer 2-5 is arranged in the displacement reaction tank 2; the outer surface of the replacement reaction tank 2 is coiled with a heating pipe, an inlet 2-1 of the heating pipe is arranged on the upper part of the replacement reaction tank, an outlet 2-2 of the heating pipe is arranged on the lower part of the replacement reaction tank, and the inlet 2-1 of the heating pipe is connected with steam for heating feed liquid in the replacement reaction tank 2.
In one embodiment of the invention, the top of the replacement reaction tank 2 is provided with a third outlet 2-4, and the third outlet 2-4 is communicated with a complexing tank inlet 3-3 arranged at the top of a complexing tank 3. In one embodiment of the invention, a circulating water pipe is coiled on the outer surface of the complexing tank 3, a circulating water inlet 3-1 of the circulating water pipe is arranged at the lower part of the complexing tank, a circulating water outlet 3-2 is arranged at the upper part of the complexing tank, and the circulating water inlet 3-1 is connected with circulating water to neutralize heat released by the complexing reaction and promote the complexing reaction to proceed towards the positive reaction direction. In one scheme of the invention, a stirrer 3-4 is also arranged in the complexing tank 3.
In a specific embodiment of the present invention, the method provided by the present invention comprises the steps of:
putting the waste water containing boron trifluoride and strong base into a neutralization reaction tank 1 through a second inlet 1-7, and starting a stirrer 1-5 to perform acid-base neutralization reaction;
introducing steam into an inlet 1-3 of a heating pipe arranged on the outer surface of a neutralization reaction tank 1 to ensure that the temperature of the feed liquid in the neutralization reaction tank 1 reaches the reduced pressure distillation temperature, closing a first inlet 1-6, a second inlet 1-7 and a second outlet 1-9, introducing cooling circulating water into an inlet 4-1 of a cooling pipe on the outer surface of a condenser 4, starting a vacuum pump 6 to ensure that the vacuum degree in the neutralization reaction tank reaches the reduced pressure distillation vacuum degree, carrying out reduced pressure distillation, and stopping the reduced pressure distillation when the mass of the feed liquid in the neutralization reaction tank 1 with water removed accounts for 65-75% of the mass of the solvent before the reduced pressure distillation;
closing steam at an inlet 1-3 of a heating pipe, introducing cooling water into an inlet 1-1 of a cooling pipe arranged on the outer surface of a neutralization reaction tank 1 to reduce the temperature of feed liquid in the neutralization reaction tank 1 to the temperature of cooling crystallization, and starting a stirrer 1-5 to carry out cooling crystallization;
after cooling and crystallization, transferring the feed liquid in the neutralization reaction tank 1 to a centrifuge 7 for centrifugation; transferring the supernatant obtained by centrifugation to a neutralization reaction tank 1, transferring the solid obtained by centrifugation to a dryer 8, and drying to obtain sodium fluoborate and boric acid;
transferring sodium fluoborate and boric acid into a displacement reaction tank 2, adding 120% sulfuric acid into the displacement reaction tank, introducing steam into a heating pipe inlet 2-1 arranged on the outer surface of the displacement reaction tank 2, ensuring the temperature of a material liquid in the displacement reaction tank to be the temperature of displacement reaction, and carrying out displacement reaction to obtain boron trifluoride gas;
acetonitrile is pumped in through an inlet 3-3 of the complexing tank, when the pressure in the displacement reaction tank 2 is the pressure required by the complexing reaction, a third outlet 2-4 is communicated with the inlet 3-3 of the complexing tank, a stirrer 3-4 is started to carry out the complexing reaction to obtain a boron trifluoride acetonitrile complex, meanwhile, the circulating water is pumped into a circulating water inlet arranged on the outer surface of the complexing tank to neutralize the heat released by the complexing reaction, and when the pressure in the displacement reaction tank 2 is 0, the complexing reaction is stopped.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
100kg of wastewater containing boron trifluoride (wastewater generated in the process of preparing cefazolin) and 8.2kg of sodium hydroxide are put into a neutralization reaction tank 1 through a second inlet 1-7, and a stirrer 1-5 is started to perform acid-base neutralization reaction for 30 min;
introducing steam into an inlet 1-3 of a heating pipe arranged on the outer surface of a neutralization reaction tank 1 to ensure that the temperature of feed liquid in the neutralization reaction tank 1 reaches 80 ℃, closing a first inlet 1-6, a second inlet 1-7 and a second outlet 1-9, introducing cooling circulating water into an inlet 4-1 of a cooling pipe on the outer surface of a condenser 4, and starting a vacuum pump 6 to ensure that the vacuum degree in the neutralization reaction tank is-0.09 MPa; performing reduced pressure distillation, and stopping the reduced pressure distillation when the mass of the feed liquid in the neutralization reaction tank 1, which is removed water, accounts for 70 percent of the mass of the solvent before the reduced pressure distillation;
closing steam at an inlet 1-3 of a heating pipe, introducing cooling water into an inlet 1-1 of a cooling pipe arranged on the outer surface of a neutralization reaction tank 1, reducing the temperature of feed liquid in the neutralization reaction tank 1 to 25 ℃, and starting a stirrer 1-5 for cooling and crystallizing for 30 min;
after cooling and crystallization, transferring the feed liquid in the neutralization reaction tank 1 to a centrifuge 7, centrifuging (800r/min, 20min), transferring the supernatant obtained by centrifuging to the neutralization reaction tank 1, transferring the solid obtained by centrifuging to a dryer 8, and drying for 3 hours at the temperature of 75 ℃ and under the vacuum degree of-0.093 MPa to obtain sodium fluoborate and boric acid;
transferring sodium fluoborate and boric acid into a displacement reaction tank 2, adding 120% sulfuric acid into the displacement reaction tank (the mass ratio of the total mass of the sodium fluoborate and the boric acid to the 120% sulfuric acid is 1:3.5), introducing steam into a heating pipe inlet 2-1 arranged on the outer surface of the displacement reaction tank 2, ensuring the temperature of a feed liquid in the displacement reaction tank to be 140 ℃, and carrying out displacement reaction to obtain boron trifluoride gas;
adding acetonitrile (the mass ratio of boron trifluoride gas to acetonitrile is 1:10) through an inlet 3-3 of a complex tank, communicating a third outlet 2-4 with the inlet 3-3 of the complex tank when the pressure in a displacement reaction tank 2 is 0.2MPa, starting a stirrer 3-4 to perform complex reaction to obtain a boron trifluoride acetonitrile complex, simultaneously introducing circulating water into a circulating water inlet arranged on the outer surface of the complex tank to neutralize the heat released by the complex reaction, and stopping the complex reaction when the pressure in the displacement reaction tank 2 is 0.
Example 2
Boron trifluoride in the boron trifluoride-containing wastewater was recovered by the method of example 1, except that the mass ratio of boron trifluoride gas to acetonitrile was 1: 6.8; the temperature for cooling and crystallizing is 25 ℃; the temperature of the metathesis reaction was 140 ℃.
Example 3
Boron trifluoride in the boron trifluoride-containing wastewater was recovered by the method of example 1, except that the mass ratio of boron trifluoride gas to acetonitrile was 1: 6.2; the temperature for cooling and crystallizing is 20 ℃; the temperature of the metathesis reaction was 160 ℃.
Weighing the total mass of the sodium fluoroborate prepared in the examples 1 to 3 and boric acid, and the results are listed in table 1; the yields of sodium fluoroborate and boric acid obtained in examples 1 to 3 were calculated, and the results are shown in table 1; the water contents of the sodium fluoroborate and the boric acid obtained in examples 1 to 3 were measured by the karl fischer moisture detection method, and the results are shown in table 1; the mass percentage content of the sodium fluoroborate and the boric acid obtained in examples 1 to 3 was measured according to GB/T22667-2008 and GB/T538-2006, and the results are shown in Table 1.
The mass of boron trifluoride obtained in examples 1 to 3 was weighed, and the yield of boron trifluoride was calculated, and the results are shown in table 1; the boron trifluoride acetonitrile complexes prepared in examples 1 to 3 were measured for the content of boron trifluoride according to HG/T5788-2020, and the results are shown in Table 1.
TABLE 1 summary of the recovery conditions of examples 1 to 3
As is clear from the data in Table 1, according to the recovery method provided by the present invention, the boron-fluorine compounds in the wastewater can be recovered well.
The recovery method provided by the invention has higher economic benefits: the raw material of the mixture of the sodium fluoborate and the boric acid obtained by recycling is only NaOH, the consumption is about 0.3kg/kg, the cost is about 2.0 yuan, the fuming sulfuric acid is required to be added when the obtained mixture of the sodium fluoborate and the boric acid is used for preparing boron trifluoride gas, the cost of the fuming sulfuric acid is 1.0 yuan/kg, and the total cost of power and labor cost in the recycling process does not exceed 5.0 yuan/kg. The total cost of the recovery method provided by the invention is 8.0 yuan/kg. The selling price of the mixture of the sodium borate and the boric acid is 6.0 yuan/kg, BF3The selling price of the raw materials is 7.0 yuan/kg. According to the calculation, the recovery method provided by the invention has higher economic benefit.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and the embodiments are within the scope of the present invention.
Claims (10)
1. A method for recovering boron trifluoride from wastewater containing boron trifluoride comprises the following steps:
mixing wastewater containing boron trifluoride with strong base to perform acid-base neutralization reaction to obtain a neutralization reaction product, wherein the wastewater contains fluoboric acid and boric acid, the fluoboric acid and the boric acid are obtained by hydrolyzing boron trifluoride, and the neutralization reaction product contains sodium fluoborate and boric acid;
and mixing the neutralization reaction product with fuming sulfuric acid to perform a displacement reaction to obtain boron trifluoride gas.
2. The recovery method according to claim 1, further comprising, after obtaining the boron trifluoride gas: mixing boron trifluoride gas and acetonitrile, and carrying out complex reaction to obtain a boron trifluoride acetonitrile complex.
3. The recovery method according to claim 2, wherein the mass ratio of the boron trifluoride gas to the acetonitrile is 1:3 to 10;
the temperature of the complexation reaction is 120-160 ℃, and the pressure is 0.18-0.22 MPa.
4. The recovery method according to claim 1, wherein the content by mass of the fluoroboric acid in the wastewater containing boron trifluoride is 3 to 20%, and the content by mass of the boric acid in the wastewater containing boron trifluoride is 1 to 6%.
5. The recovery process of claim 4, wherein the strong base comprises a soluble hydroxide;
and the pH value of the solution after the neutralization reaction is 4-5.
6. The recovery method according to claim 4, wherein the concentration by mass of oleum is 120%.
7. The recovery method according to claim 1, further comprising, after the neutralization reaction:
dehydrating and concentrating the product of the neutralization reaction to obtain a concentrated solution;
crystallizing the concentrated solution to obtain a crystallized product, wherein the crystallized product comprises sodium fluoborate and boric acid.
8. The recovery method according to claim 7, wherein the dehydration concentration is a distillation under reduced pressure;
the vacuum degree of the reduced pressure distillation is-0.088 to-0.092 MPa, and the temperature is 78 to 82 ℃; the crystallization is cooling crystallization, and the temperature of the cooling crystallization is 28-32 ℃.
9. A recovery device of boron trifluoride in waste water containing boron trifluoride comprises a neutralization reaction tank (1), wherein a second outlet (1-9) is formed in the bottom of the neutralization reaction tank, and a second inlet (1-7) is formed in the top of the neutralization reaction tank;
a third inlet (2-3) is communicated with a second outlet (1-9) of the neutralization reaction tank (1) to form a replacement reaction tank (2).
10. A recovery device according to claim 9, characterized in that the top of the displacement reaction tank (2) is provided with a third outlet (2-4);
also comprises a complexing tank with an inlet (3-3) communicated with a third outlet (2-4).
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