CN117819490A - Treatment recovery method for waste sulfuric acid liquid in adamantanone production - Google Patents
Treatment recovery method for waste sulfuric acid liquid in adamantanone production Download PDFInfo
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- CN117819490A CN117819490A CN202311739841.XA CN202311739841A CN117819490A CN 117819490 A CN117819490 A CN 117819490A CN 202311739841 A CN202311739841 A CN 202311739841A CN 117819490 A CN117819490 A CN 117819490A
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- sulfuric acid
- acid liquid
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- adamantanone
- bentonite
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 282
- 239000007788 liquid Substances 0.000 title claims abstract description 71
- 239000002699 waste material Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000011084 recovery Methods 0.000 title abstract description 4
- IYKFYARMMIESOX-SPJNRGJMSA-N adamantanone Chemical compound C([C@H](C1)C2)[C@H]3C[C@@H]1C(=O)[C@@H]2C3 IYKFYARMMIESOX-SPJNRGJMSA-N 0.000 title description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000000440 bentonite Substances 0.000 claims abstract description 38
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 38
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000084 colloidal system Substances 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- IYKFYARMMIESOX-UHFFFAOYSA-N adamantanone Chemical compound C1C(C2)CC3CC1C(=O)C2C3 IYKFYARMMIESOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000011837 pasties Nutrition 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 13
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 32
- 238000001179 sorption measurement Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- 239000002344 surface layer Substances 0.000 claims description 8
- 239000011343 solid material Substances 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000000701 coagulant Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000007667 floating Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 239000011362 coarse particle Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000002002 slurry Substances 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 49
- 230000000694 effects Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 12
- 238000005345 coagulation Methods 0.000 description 8
- 230000015271 coagulation Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 239000002893 slag Substances 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 239000004927 clay Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- PTSXVDYGQRXTMI-UHFFFAOYSA-N 2-adamantyl hydrogen sulfate Chemical compound OS(=O)(=O)OC1C2CC3CC(C2)CC1C3 PTSXVDYGQRXTMI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- -1 2-substituted adamantane Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012840 feeding operation Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002522 swelling effect Effects 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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/905—Removal of organic impurities
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a treatment recovery method of waste sulfuric acid liquid in 2-adamantanone production, which comprises the steps of preparing pasty slurry composed of inorganic mineral bentonite, alkane organic solvent and dilute sulfuric acid liquid, mixing the pasty slurry into the waste sulfuric acid liquid, agglomerating the pasty slurry to remove suspension polymerization colloid in the waste sulfuric acid liquid, evaporating and concentrating the pasty slurry, and removing sulfur dioxide in the waste sulfuric acid liquid by adopting hydrogen peroxide oxidation treatment to obtain purer dilute sulfuric acid liquid capable of being directly utilized. The invention has simple operation and low treatment cost, and the recovered dilute sulfuric acid solution can be directly used as other materials.
Description
Technical Field
The invention relates to the technical field of chemical engineering, in particular to a method for treating and recycling waste sulfuric acid liquid generated in the production process of a 2-adamantanone product.
Background
2-adamantanone is used as a raw material for preparing various other 2-substituted adamantane derivative products, is an important intermediate for producing various medicines, and is prepared by taking adamantane or 1-adamantanol as a starting raw material and adopting a concentrated sulfuric acid direct oxidation method for reaction in the industrial production at home and abroad at present. And (3) carrying out an oxidation reaction on adamantane or 1-adamantanol and sulfuric acid to generate an intermediate product 2-adamantanol sulfate, and carrying out a hydrolysis reaction when meeting water after the reaction is ended to release a target product 2-adamantanone. Since polymerization side reaction of the reaction intermediate 2-adamantanol sulfate is inevitably generated under the condition of concentrated sulfuric acid and heating, polymerized colloid is generated. In the traditional oxidation production process, only 40% -50% of the initial raw materials are converted into target products, and the rest 50% -60% of the raw materials are changed into polymer colloid due to side reactions. Even with the improved oxidation process, typically not less than 20% to 30% of the raw materials are converted to polymeric gums by side reactions. The oxidation reaction process of 2-adamantanone needs to dilute the reaction materials with water when the reaction is terminated, so as to eliminate the oxidability of concentrated sulfuric acid, and simultaneously hydrolyze 2-adamantanol sulfate which is an intermediate substance in the reaction, so as to release the target product 2-adamantanone. The reaction mixture after water dilution mainly comprises dilute sulfuric acid solution, the sulfuric acid content is generally 30% -40%, the target product 2-adamantanone floats on the surface layer of the dilute sulfuric acid solution in a precipitated crystal state, a large amount of polymerized colloid generated by side reaction is dispersed in the dilute sulfuric acid solution in a stable suspended matter state, and more sulfur dioxide serving as an oxidation reaction product is mixed in the dilute sulfuric acid solution.
The concentrated sulfuric acid used in the production and preparation of 2-adamantanone is usually large in amount, and after the target product 2-adamantanone is hydrolyzed, diluted, separated and extracted, more waste dilute sulfuric acid liquid is left, and 30-50 tons of waste dilute sulfuric acid liquid is generated in each 1 ton of 2-adamantanone production. The waste sulfuric acid liquid contains a large amount of suspended polymeric colloid and a large amount of sulfur dioxide, so that the waste sulfuric acid liquid is in a dark gray thin paste state, and the environment is polluted by the odor of the sulfur dioxide which emits malodor. In order to treat these waste sulfuric acid solutions, the common method is to neutralize them with an inorganic strong base (sodium hydroxide, etc.), in neutral or weakly alkaline aqueous solution, the polymeric colloid is easily agglomerated and separated, and the sulfate and sulfite aqueous solutions after removal of the polymeric colloid are subjected to re-evaporation and concentration treatment.
It is also recognized that if the waste sulfuric acid solution is directly treated and recycled in an optimal way, a great amount of suspension polymerized colloid exists in the waste sulfuric acid solution, and the polymerized colloid is in a fine suspension particle state in the dilute sulfuric acid solution, so that the suspension stability is good, the polymer colloid cannot be removed through filtration, and is difficult to effectively adsorb and agglomerate by using a flocculating agent, activated carbon and the like, and the difficulty of preparing pure dilute sulfuric acid by treating the waste sulfuric acid solution is high, so that the technology is also an urgent technical problem to be solved.
Disclosure of Invention
The invention aims to provide a treatment and recovery method for waste sulfuric acid liquid in adamantanone production, which aims to effectively remove suspension polymerization colloid and sulfur dioxide in the waste sulfuric acid liquid in 2-adamantanone production, and prepare pure dilute sulfuric acid for recycling.
The invention adopts the following solution for treating and recycling the waste sulfuric acid liquid containing suspension polymerization colloid and sulfur dioxide generated in the production of 2-adamantanone:
1. preparing special adsorption coagulant paste:
firstly, bentonite is mixed and infiltrated with an organic solvent, and after the bentonite swells, the bentonite is strongly mixed with dilute sulfuric acid solution to prepare paste.
The bentonite used in the method is inorganic mineral bentonite which is insoluble in water but swells a plurality of times when meeting water, and can be well infiltrated and swelled with an organic solvent, and is not suitable for activated clay and natural bleaching clay which are poor in infiltration and swelling in water and the organic solvent, and is not suitable for organic bentonite which is too strong in expansibility in water and the organic solvent to form gel.
The organic solvent used herein is an alkane solvent, preferably petroleum ether (60-120deg.C distillation range), mineral spirits (60-120deg.C distillation range), n-hexane, n-heptane and n-octane.
The content of the dilute sulfuric acid used in the method is 55% -65%, and the dilute sulfuric acid prepared by the method can be directly used in actual operation.
Bentonite, organic solvent, dilute sulfuric acid=2 (1-2): 15 (mass ratio)
The operation temperature is normal temperature (20-40 ℃ all right).
2. Adsorbing the suspension polymerization colloid in the condensed waste sulfuric acid liquid:
adding the paste prepared in the step 1 into waste sulfuric acid liquid to be treated, strongly stirring for 20-30 minutes at 40-50 ℃, stopping stirring, standing for more than 6 hours, and naturally cooling to normal temperature (15-30 ℃). And the solid materials in the waste sulfuric acid liquid fully float to the surface layer and are condensed into coarse particles.
Here, the specific addition amount of the waste sulfuric acid liquid to the paste material=100:2 to 8 (mass ratio) depends on the content of the suspension polymerized colloid in the waste sulfuric acid liquid, so that the suspension polymerized colloid in the waste sulfuric acid liquid can be sufficiently adsorbed and aggregated.
3. Separating and removing condensed solid materials:
and fishing out the coagulated solid materials on the surface layer of the waste sulfuric acid liquid, and further disposing the fished-out solid slag.
4. Further adsorbing and removing fine aggregate particles which are still suspended in the waste sulfuric acid liquid:
adding activated carbon powder into the waste sulfuric acid solution from which the floating slag is removed, stirring for about 1 hour at 50-60 ℃, cooling to 20-30 ℃, and then carrying out suction filtration on the material to remove solid materials.
Here, the waste sulfuric acid liquid is composed of active carbon powder=100:0.2-0.5 (mass ratio)
5. Evaporating and concentrating, and removing most of sulfur dioxide:
evaporating the waste sulfuric acid liquid from which the active carbon solid materials are removed under reduced pressure, distilling most sulfur dioxide in the waste sulfuric acid liquid along with water vapor, and collecting and further disposing. And stopping evaporating and concentrating when the sulfuric acid content reaches about 60 percent. Cooling to 40-50 ℃.
6. Removing residual sulfur dioxide:
and (3) dropwise adding a proper amount of hydrogen peroxide into the evaporated and concentrated dilute sulfuric acid solution, and oxidizing and removing residual sulfur dioxide. The hydrogen peroxide is added in an amount to completely oxidize the residual sulfur dioxide.
The reaction operation temperature is 40-50 ℃.
After the reaction is completed, the diluted sulfuric acid solution is cooled to normal temperature and is packaged for other use.
The researchers of the application observe through multiple experiments that when bentonite or an organic solvent is added into waste sulfuric acid liquid for mixing, or bentonite and the organic solvent are added into the waste sulfuric acid liquid for mixing, respectively, suspension polymerization colloid in the waste sulfuric acid liquid can not be effectively adsorbed and condensed. If only the swelling pasty materials of the bentonite and the organic solvent are prepared, the dispersion effect is not good after the waste sulfuric acid liquid is added, and the limited adsorption, condensation and polymerization colloid effect can be achieved only by using more pasty materials. However, if only the swelling paste of both bentonite and dilute sulfuric acid is prepared, the adsorption coagulation of the adsorption polymer gum is hardly effective. Only after the bentonite, the organic solvent and the dilute sulfuric acid solution are prepared into the expanded pasty material in sequence according to the method of the application, the expanded pasty material is added into the waste sulfuric acid solution for mixing, so that the pasty material is less, and the suspension polymerization colloid in the waste sulfuric acid solution has good adsorption and coagulation effects. And even if these three materials are used, but the order of feeding operations of bentonite, an organic solvent and dilute sulfuric acid is changed, a paste having a good adsorption coagulation effect cannot be prepared.
The researchers of the application also observe through experiments that the paste material prepared by using inorganic mineral bentonite which is insoluble in water but swells a plurality of times when meeting water and can well infiltrate and swell with an organic solvent has good dispersion effect after adding waste sulfuric acid liquid, has good adsorption and coagulation effect on suspension polymerization colloid, and is convenient for dragging and separating the coagulation slag floating on the surface of the acid liquid. On the other hand, when activated clay and natural bleaching clay having poor swelling properties in water and in an organic solvent are used, it is difficult to prepare a good paste, and the dispersion effect after the addition of waste sulfuric acid solution is poor, and the adsorption/coagulation effect on the suspension polymerization gum is also poor. If organic bentonite with strong expansibility in water and organic solvent is used, gel materials (rather than pasty materials) are easy to prepare, and the gel materials are well dispersed after the waste sulfuric acid liquid is added, and the adsorption and agglomeration effects on suspension polymerization colloid are good, but the agglomeration particle solids which are easy to scoop and separate are difficult to form, and film materials which form viscosity float on the surface layer of the acid liquid and adhere to the periphery of a container, and are easy to adhere to an operation tool during scooping, so that inconvenience is brought to the separation operation of agglomeration residues.
The researchers of the application used various organic solvents as paste preparation experiments, and compared and screened from the angles of the least using amount and the best adsorption and condensation effects on the suspension polymerization colloid, the best effect of using alkane organic solvents is observed. From the viewpoint of raw material sources and material costs, petroleum ether having a distillation range of 60 to 120 ℃, solvent oil having a distillation range of 60 to 120 ℃, n-hexane, n-heptane and n-octane are preferable.
Researchers in the application judge according to a plurality of experimental phenomena, the special paste prepared by the method can be better dispersed and contacted with suspension polymerization colloid after being added with waste sulfuric acid liquid, and the suspension polymerization colloid synthesized by adamantane oxidation polymerization has stronger oleophylic hydrophobicity, so that adsorption coalescence is easy to occur with bentonite immersed and expanded by an organic solvent.
Experiments also show that the special paste prepared by the method has good adsorption and coagulation effects on suspended colloid in the waste sulfuric acid liquid and also has a certain adsorption and removal effect on sulfur dioxide in the waste sulfuric acid liquid.
Through the adsorption and coagulation of the special pasty material, a small amount of fine coagulated particles remained in the acid liquor after the floating coagulated slag is removed are adsorbed and separated by the activated carbon powder, so that the suspension polymerized colloid in the waste sulfuric acid liquor can be fully removed, and the dilute sulfuric acid liquor without the suspension polymerized colloid is obtained.
The effects of concentrating sulfuric acid liquid and volatilizing most residual sulfur dioxide in the acid liquid are achieved through reduced pressure evaporation.
And finally, adding a proper amount of hydrogen peroxide to oxidize a small amount of sulfur dioxide remained in the acid liquor into sulfur trioxide (the sulfur trioxide and water are combined into sulfuric acid), so as to obtain purer dilute sulfuric acid liquor.
The method has good treatment effect on the waste sulfuric acid liquid produced by 2-adamantanone, is relatively simple and convenient to operate, and is put into production and implementation in enterprises where researchers are currently located.
The technical effects are as follows:
the technical scheme of the invention can achieve the following effects:
1. can effectively remove suspension polymerization colloid and sulfur dioxide in the waste sulfuric acid liquid produced by 2-adamantanone, and obtain purer dilute sulfuric acid liquid which can be recycled.
2. The treatment operation is simpler and more convenient, the treatment cost is lower, and the treated dilute sulfuric acid solution can bring certain economic benefit for other purposes.
Detailed Description
Example 1:
the example data were taken from the production examples of the treatment of waste sulfuric acid liquid produced in the mass production of 2-adamantanone by the enterprises of the researchers of the present application, where the sulfuric acid content of the waste sulfuric acid liquid to be treated was about 35% to 37%, the appearance was gray black and thin paste due to the high content of the suspension polymerized colloid, and the obvious malodor was emitted.
The processing operation is as follows:
1. preparing special adsorption coagulant paste:
the bentonite material is inorganic mineral bentonite powder, the organic solvent is petroleum ether (60-90 ℃ or 90-120 ℃ distillation range) or normal hexane, and the dilute sulfuric acid solution is directly used for recycling the dilute sulfuric acid solution with the content of about 60% after the pretreatment.
The bentonite and organic solvent are metered in such a way that the diluted sulfuric acid liquid=2:1.5:15 (mass ratio).
Firstly, adding an organic solvent into a glass lining reaction kettle, starting stirring, then adding bentonite in batches, stirring for 5-10 minutes, and stopping stirring. Standing for 1-2 hours to enable the bentonite and the organic solvent to mutually swell and wrap.
Adding dilute sulfuric acid solution into a reaction kettle, firstly, stirring for several times, and starting the stirrer after the swelled bentonite material floats upwards, and stirring for about 0.5 hour to obtain the thin pasty slurry.
The operation process usually does not need manual temperature control, so that the materials are naturally kept at the temperature of 20-40 ℃.
The paste prepared in one step according to the method is stored in the reaction kettle without discharging, and is produced and used (stirring for a plurality of minutes before use and discharging).
2. Treatment of spent sulfuric acid solution
(1) About 1000Kg of waste sulfuric acid solution to be treated is added into glass lining treatment kettle equipment, stirring (stirring speed is 120 r/min) is started, and heating is carried out to 40-50 ℃ for maintenance. Adding about 47Kg of the pasty material prepared in the previous step into a kettle, continuously stirring for about 30 minutes, taking a clean acid liquid sample in the material, detecting and confirming that the polymerized colloid in the material is completely coagulated and removed, stopping stirring, discharging the material in the reaction kettle into a coagulating tank, and standing for 6-8 hours under a natural cooling state.
(2) After the condensed slag on the surface layer of the material in the condensing tank is fully fished out by a tool (further treated), pumping the acid solution into a glass lining kettle, stirring and heating to 50-60 ℃ for maintaining, adding about 3Kg of active carbon powder, continuously stirring for about 1 hour, then cooling to 20-30 ℃ and stopping stirring. Discharging the materials in the kettle and filtering out the active carbon solid slag through a filter screen.
(3) Pumping the filtered acid solution into a glass lining evaporation concentration kettle, starting stirring and vacuum pumping equipment, forming negative pressure in the kettle, heating and evaporating, concentrating until the concentration of sulfuric acid solution reaches 61-62% (at the moment, the water evaporation speed is slow), recovering normal pressure in the kettle, and cooling to 40-50 ℃.
(4) And (3) keeping the temperature of the materials in the kettle within the range of 40-50 ℃, dropwise adding hydrogen peroxide into the acid liquid in the kettle in batches from a high-level tank, sampling and detecting the residual quantity of sulfur dioxide in each batch after the completion of dropwise adding, and detecting that the residual sulfur dioxide content is lower than 0.2% when the total quantity of the added hydrogen peroxide reaches 8.3Kg, and stopping adding the hydrogen peroxide. Cooling the sulfuric acid liquid in the kettle to 30-35 ℃, transferring the sulfuric acid liquid into a transfer storage tank, and storing the sulfuric acid liquid in a barrel.
The pure sulfuric acid solution with pale yellow appearance is obtained by metering about 593Kg, and the content of the detected sulfuric acid is 60.7 percent.
Example 2:
the sulfuric acid content of the waste sulfuric acid solution to be treated is detected to be about 35.7%, and the appearance of the waste sulfuric acid solution is gray black and thin paste due to the fact that the waste sulfuric acid solution contains more suspension polymerization colloid, and the waste sulfuric acid solution emits obvious malodorous smell.
The processing operation is as follows:
1. preparing special adsorption coagulant paste:
the bentonite material is inorganic mineral bentonite powder, the organic solvent is petroleum ether (60-90 ℃ distillation range), and the dilute sulfuric acid solution is directly used for recovering the dilute sulfuric acid solution with 59.4% of the content treated before.
The bentonite and organic solvent are metered in such a way that the diluted sulfuric acid liquid=2:1.5:15 (mass ratio).
At normal temperature, firstly adding an organic solvent into a glass lining reaction kettle, starting stirring, then adding bentonite in batches, stirring for 10 minutes, and stopping stirring. Standing for 1.5 hours, and swelling and wrapping the bentonite and the organic solvent.
Adding dilute sulfuric acid solution into a reaction kettle, firstly, stirring for several times, and starting the stirrer after the swelled bentonite material floats upwards, and stirring for about 0.5 hour to obtain the thin pasty slurry.
The paste prepared in one step according to the method is stored in the reaction kettle without discharging, and is produced and used (stirring for a plurality of minutes before use and discharging).
2. Treatment of spent sulfuric acid solution
(1) About 1000Kg of waste sulfuric acid solution to be treated is added into glass lining treatment kettle equipment, stirring (stirring speed is 120 r/min) is started, and heating is carried out to 45+/-1 ℃ for maintenance. The pasty material prepared above is added into a kettle in batches, sampling and detection are carried out after 5 minutes of adding and stirring each time, after 52Kg of adding, the detection of the clean acid liquid sample in the material is taken to confirm that the polymeric colloid in the material is completely coagulated and removed, stirring is continued for about 30 minutes, stirring is stopped, the material in the reaction kettle is discharged into a coagulating tank, and standing is carried out for 7-8 hours under the state of natural cooling.
(2) After the condensed slag on the surface layer of the material in the condensing tank is fully fished out by a tool (further treated), the rest dilute sulfuric acid is pumped into a glass lining kettle, stirred and heated to 55+/-1 ℃ for maintenance, activated carbon powder is added for about 3Kg, stirring is continued for about 1 hour, then the temperature is reduced to 30+/-2 ℃, and stirring is stopped. Discharging the materials in the kettle and filtering out the active carbon solid slag through a filter screen.
(3) Pumping the filtered acid solution into a glass lining evaporation concentration kettle, starting stirring and vacuum pumping equipment, forming negative pressure in the kettle, heating and evaporating, concentrating until the concentration of sulfuric acid solution reaches 61% -62% (the water evaporation speed is slow), recovering normal pressure in the kettle, and cooling to 45+/-1 ℃.
(4) And (3) keeping the temperature of the materials in the kettle within the range of 45+/-1 ℃, dropwise adding hydrogen peroxide into the acid liquid in the kettle in batches from the overhead tank, sampling and detecting the residual quantity of sulfur dioxide in each batch after the completion of dropwise adding, and detecting that the residual sulfur dioxide content is lower than 0.2% when the total quantity of the added hydrogen peroxide reaches 7.1Kg, and stopping adding the hydrogen peroxide. Cooling the sulfuric acid liquid in the kettle to 30-35 ℃, transferring the sulfuric acid liquid into a transfer storage tank, and storing the sulfuric acid liquid in a barrel.
The pure dilute sulfuric acid solution with pale yellow appearance is obtained by measuring about 587Kg, and the content of the detected sulfuric acid is 60.2 percent.
Example 3:
the sulfuric acid content of the waste sulfuric acid solution to be treated is detected to be about 36.3%, and the appearance of the waste sulfuric acid solution is gray black and thin paste due to the fact that the waste sulfuric acid solution contains more suspension polymerization colloid, and the waste sulfuric acid solution emits obvious malodorous smell.
The processing operation is as follows:
1. preparing special adsorption coagulant paste:
the bentonite material is inorganic mineral bentonite powder, the organic solvent is n-hexane (industrial grade), and the dilute sulfuric acid solution is directly used for recycling the dilute sulfuric acid solution with the content of 60.4% after the pretreatment.
The bentonite and organic solvent are metered in such a way that the diluted sulfuric acid liquid=2:1.5:15 (mass ratio).
The preparation procedure was as in example 2.
2. Treatment of spent sulfuric acid solution
The operation method for treating the waste sulfuric acid liquid was the same as in example 2, wherein,
in the operation step (1), about 1000Kg of waste sulfuric acid solution to be treated is added, and 45Kg of the paste prepared above is added.
And (3) adding about 3Kg of activated carbon powder in the operation step (2).
In operation (4), 6.4Kg of hydrogen peroxide was added.
After the treatment is completed, about 591Kg of pure dilute sulfuric acid solution with pale yellow appearance is obtained by metering, and the content of the detected sulfuric acid is 60.7 percent.
Claims (6)
1. The method for treating and recycling the waste sulfuric acid liquid in the production of the 2-adamantanone is characterized by comprising the following steps of:
(1) Preparing special adsorption coagulant paste:
firstly, bentonite is mixed and infiltrated with an organic solvent, and after the bentonite swells, the bentonite is strongly mixed with dilute sulfuric acid solution to prepare pasty material;
(2) Adding the pasty material prepared in the step (1) into waste sulfuric acid liquid to be treated, stirring strongly at 40-50 ℃ to fully mix and disperse, standing and naturally cooling to normal temperature, and fully floating the solid material in the waste sulfuric acid liquid to the surface layer and agglomerating into coarse particles;
(3) Coarse solid particles on the surface layer of the material are separated and removed, and then the active carbon powder is stirred and adsorbed at 50-60 ℃ to remove fine coagulated particles remained in the dilute sulfuric acid solution;
(4) Evaporating the dilute sulfuric acid solution with the solid materials of the active carbon filtered out under reduced pressure, concentrating until the sulfuric acid content reaches about 60%, then adding hydrogen peroxide into the dilute sulfuric acid solution, reacting at 40-50 ℃, and oxidizing to remove residual sulfur dioxide to obtain purer dilute sulfuric acid solution.
2. The method for treating and recovering a waste sulfuric acid liquid from 2-adamantanone production according to claim 1, wherein the bentonite used in (1) is an inorganic mineral bentonite; the organic solvent is petroleum ether (60-120 deg.C distillation range), solvent oil (60-120 deg.C distillation range), n-hexane, n-heptane or n-octane; the concentration of the dilute sulfuric acid solution is 55-65%.
3. The method for treating and recovering a waste sulfuric acid liquid from 2-adamantanone production according to claim 1, wherein in (1), bentonite is organic solvent is diluted sulfuric acid=2, (1-2) 15 mass ratio, and the operation temperature is normal temperature.
4. The method for treating and recovering waste sulfuric acid liquid produced by 2-adamantanone according to claim 1, wherein in (2), the mass ratio of the waste sulfuric acid liquid to the pasty material is 100:2-8, and the specific adding amount of the pasty material depends on the content of the suspension polymerized colloid in the waste sulfuric acid liquid, so that the suspension polymerized colloid in the waste sulfuric acid liquid can be fully adsorbed and aggregated.
5. The method for treating and recovering waste sulfuric acid liquid produced by 2-adamantanone as claimed in claim 1, wherein in (3), the mass ratio of waste sulfuric acid liquid to active carbon powder is 100:0.2-0.5.
6. The method for treating and recovering a waste sulfuric acid liquid from 2-adamantanone production as claimed in claim 1, wherein in (4), hydrogen peroxide is added in an amount sufficient to oxidize residual sulfur dioxide completely.
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