CN113460974A - Purification treatment process for high-concentration waste sulfuric acid - Google Patents
Purification treatment process for high-concentration waste sulfuric acid Download PDFInfo
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- CN113460974A CN113460974A CN202110933426.2A CN202110933426A CN113460974A CN 113460974 A CN113460974 A CN 113460974A CN 202110933426 A CN202110933426 A CN 202110933426A CN 113460974 A CN113460974 A CN 113460974A
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- sulfuric acid
- waste sulfuric
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- purification treatment
- oxidant
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 239000002699 waste material Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000746 purification Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 229920002678 cellulose Polymers 0.000 claims abstract description 9
- 239000001913 cellulose Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000007710 freezing Methods 0.000 claims abstract description 6
- 230000008014 freezing Effects 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 9
- 239000001923 methylcellulose Substances 0.000 claims description 9
- 235000010981 methylcellulose Nutrition 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 210000003298 dental enamel Anatomy 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 210000003454 tympanic membrane Anatomy 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 3
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 26
- 238000005804 alkylation reaction Methods 0.000 abstract description 10
- 238000005189 flocculation Methods 0.000 abstract description 7
- 230000016615 flocculation Effects 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000029936 alkylation Effects 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 4
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 201000008827 tuberculosis Diseases 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- RFRMMZAKBNXNHE-UHFFFAOYSA-N 6-[4,6-dihydroxy-5-(2-hydroxyethoxy)-2-(hydroxymethyl)oxan-3-yl]oxy-2-(hydroxymethyl)-5-(2-hydroxypropoxy)oxane-3,4-diol Chemical compound CC(O)COC1C(O)C(O)C(CO)OC1OC1C(O)C(OCCO)C(O)OC1CO RFRMMZAKBNXNHE-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- -1 alkyl sulfonic acid Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002912 waste gas Substances 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
- C01B17/92—Recovery from acid tar or the like, e.g. alkylation acids
Abstract
A purification treatment process of high-concentration waste sulfuric acid belongs to the technical field of concentrated sulfuric acid recovery treatment. The concentrated sulfuric acid after the alkylation reaction catalysis is finished generally contains 80-95% of H2SO4Besides, the water-based paint also contains 3-8% of organic matters and 2-8% of water. The invention utilizes: 1) adding waste sulfuric acid into water to dilute the waste sulfuric acid to 70% or below of mass concentration; 2) sequentially adding sulfate or bisulfate, cellulose adhesive, oxidant and silicon oxide, and stirring uniformly; 3) filtering the mixed liquid obtained in the step 2), cooling the liquid phase in a freezing separator to separate salt, heating the liquid phase to 90-120 ℃, adding an oxidant to react until the liquid phase is light brown, and finishing the treatment by an activated carbon adsorption tank. High temperature and a large amount of oxidant are not needed, organic impurities are removed by flocculation collection, the reaction process is mild, the removal is thorough, the cost is low, and the environmental protection effect is better.
Description
Technical Field
A purification treatment process of high-concentration waste sulfuric acid belongs to the technical field of concentrated sulfuric acid recovery treatment.
Background
In the gasoline production process, a large amount of high-concentration sulfuric acid with the mass concentration of more than 80% is generally needed as a catalyst, and the concentrated sulfuric acid after the alkylation reaction catalysis is finished generally contains 80-95% of H2SO4Besides, the catalyst also contains 3-8% of organic matters and 2-8% of water, the organic matters are mainly macromolecular olefin, dialkene, alkyl sulfonic acid, sulfate, mercaptan and the like, the impurities have great pollution to the environment, and the catalyzed concentrated sulfuric acid is difficult to repeatedly participate in alkylation reaction and can only be used in other industries, so that the waste and the pollution are serious and the treatment is difficult.
The existing method for treating the waste sulfuric acid comprises the following steps: the high-temperature cracking method is that sulfur dioxide generated by high-temperature cracking is catalyzed into sulfur trioxide, and then the sulfur trioxide is absorbed by dilute sulfuric acid to be concentrated sulfuric acid. The equipment cost is high, the treatment cost is high, the potential safety hazard is high, in addition, useful components in the waste combustion are burnt, resources are wasted, the cost of user enterprises is increased, the reaction conditions are harsh, the miniaturization is difficult, and the capital pressure of the user enterprises is large.
The high-temperature carbonization method is characterized in that concentrated sulfuric acid and magnesium oxide react to prepare magnesium sulfate, impurities such as organic matters in the concentrated sulfuric acid are carbonized at high temperature, the carbide and the magnesium sulfate are dissolved and separated, and the solution is concentrated to obtain the magnesium sulfate. The carbides therein are of little use, causing waste to accumulate.
The high-temperature oxidation purification of the waste sulfuric acid requires a large amount of oxidant to oxidize and consume impurities in the waste sulfuric acid and then purify the impurities, the consumption of the oxidant is large, the energy consumption is high, the organic matter is not thoroughly treated, the treated waste sulfuric acid still cannot reach the purity of the return alkylation reaction, and the recovery and utilization expectation is difficult to achieve.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides a purification treatment process of high-concentration waste sulfuric acid, which has the advantages of simple treatment process, extremely low energy and material consumption and high recovery degree of the waste sulfuric acid.
The technical scheme adopted by the invention for solving the technical problems is as follows: a purification treatment process of high-concentration waste sulfuric acid is characterized by comprising the following steps: the method comprises the following steps:
1) adding waste sulfuric acid into water to dilute the waste sulfuric acid to 70% or below of mass concentration;
2) sequentially adding sulfate or bisulfate, cellulose adhesive, oxidant and silicon oxide, and stirring uniformly;
3) filtering the mixed liquid obtained in the step 2), cooling the liquid phase in a freezing separator to separate salt, heating the liquid phase to 90-120 ℃, adding an oxidant to react until the liquid phase is light brown, and performing treatment through an activated carbon adsorption tank after oxidation.
The applicant has found that the reason why high concentrations of spent sulfuric acid are difficult to handle is: two forms of oil and acid mixed systems exist in the high-concentration waste sulfuric acid, one is an acid-in-oil type of the alkylated waste sulfuric acid, and the other is an extremely fine dust type of dimethyl sulfate and other waste sulfuric acids; the organic impurities in the above two systems are repelled from the negative ions generated by sulfuric acid in a negative way in an acidic environment. On the basis of the above problems, the process of the present invention makes it possible to flocculate the organic impurities in the waste sulfuric acid by removing the negative electrons of the acid-in-oil or dust particles.
The sulfate or bisulfate added in the step 2) is equivalent to an oleic acid separating agent or a demulsifier, and can further separate the sulfuric acid and other macromolecular substances at the molecular level; then the added cellulose is equivalent to an adhesive, after the cellulose is dissolved in sulfuric acid, intermolecular acting force such as hydrogen bond force and van der waals force can be generated, and simultaneously positive electrons are generated to attract negative electrons in macromolecular organic matters, so that organic impurity molecules which are separated from an oil-in-acid form or an over-dispersed micro-dust form are gathered; the added oxidant is equivalent to an electron releasing agent, and attracts negative electrons on organic impurity molecules, so that the organic impurity molecules are mutually attracted; the added silicon oxide is used as a 'tuberculosis agent' to provide a positive charge center, so that organic impurities which are attracted and combined with each other in the waste sulfuric acid are further concentrated and fixed, and finally, the flocculation phenomenon is presented. After the flocculation impurities are filtered, the sulfuric acid is desalted, oxidized and adsorbed with trace residual oxidized micromolecular organic impurities, so that the purity of the obtained sulfuric acid can meet the reuse standard.
The flocculation mode is utilized to realize the treatment of organic impurities in the waste sulfuric acid, the whole process has no high temperature and no evaporation, and the mutual reaction between liquid phases is utilized, so that the organic impurities in the waste sulfuric acid are treated more cleanly, the energy consumption is low, the flow is short, the equipment is simple, the occupied area is small, and the method is suitable for various types of factories. And the filtered flocculated impurities can be completely used as organic fuel and other purposes, the calorific value is extremely high, the removed salts can be used as products or other purposes according to specific metal ions, the high-risk waste treatment is really realized without secondary pollution, the output value of a gasoline production plant is effectively improved, the hazardous waste treatment cost is reduced, and the environment protection effect is obvious.
Preferably, the amount of the sulfate or bisulfate in the step 2) is 10-70% of the weight of the waste sulfuric acid; the cellulose consumption is 0.05-2% of the weight of the waste sulfuric acid; the using amount of the oxidant is 0.15-5% of the weight of the waste sulfuric acid; the amount of the silicon oxide is 0.3-1% of the weight of the waste sulfuric acid.
The dosage of the common sulfate or bisulfate is positively correlated with the content of organic impurities in the waste sulfuric acid, and when the dosage is 50 percent of the weight of the original waste sulfuric acid, the organic macromolecular substances in most of different alkylated waste sulfuric acids can be effectively separated, which is equivalent to complete demulsification.
The optimized dosage can avoid introducing excessive impurity ions into the waste sulfuric acid and can ensure that the macromolecular organic impurities are fully dissociated and then are subjected to tuberculosis flocculation.
Preferably, the oxidant in step 2) is one or a mixture of several of potassium permanganate, sodium sulfite, nitric acid and sodium chlorate in any proportion.
Since organic macromolecular impurities are oxidized in concentrated sulfuric acid, strong oxidants are preferred, with preferred oxidants being particularly suitable for concentrated sulfuric acid systems.
Preferably, the cellulose binder in step 2) is methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose or carboxymethyl cellulose.
Preferably, the silica in step 2) is diatomite or powdered silica.
The optimized silicon oxide can adapt to a concentrated sulfuric acid system, has good effect of attracting organic macromolecular substances and is low in price.
Preferably, the sulfate or bisulfate is added in the step 2), and then the next component is added after stirring at 1000-2000 rpm for 0.5-1.5 h.
The first step is the process of separating macromolecular substances from acids, especially for the acid-in-oil form, the membrane composed of organic substances needs to be broken sufficiently, so that sufficient stirring reaction needs to be ensured, and the removal effect is ensured.
Preferably, the oxidant in the step 3) is one or a mixture of several of ozone, hydrogen peroxide, nitric acid and potassium permanganate in any proportion, and the total dosage is 0.2-0.5% of the total weight of the liquid phase.
The oxidation mainly has the function of oxidizing and decomposing the residual trace macromolecular organic matters without flocculation precipitation into micromolecular organic matters, so that the back adsorption and removal in the activated carbon or the adsorption resin are facilitated in the next step. Preferred oxidizing agents are effective in oxidatively decomposing macromolecular organic impurities.
Preferably, the step 1) and the step 2) are both carried out in an enamel stirred tank, and the filtration in the step 3) adopts a corrosion-resistant tympanic membrane filter press.
The preferable equipment has low cost and strong corrosion resistance.
Compared with the prior art, the invention has the beneficial effects that: the waste sulfuric acid is treated by a flocculation mode, so that high temperature and evaporation are avoided, organic impurity molecules are thoroughly treated, the energy consumption is low, the flow is short, the application is wide, other wastes are not generated in the treatment process, and the burden of gasoline manufacturers is reduced and even income is brought.
Detailed Description
The present invention is further illustrated by the following examples, example 1 being the best mode of carrying out the invention.
The initial alkylation waste sulfuric acid used in the following examples and comparative examples was obtained from a refinery and had a sulfuric acid concentration of 90% by mass.
Example 1
A purification treatment process of high-concentration waste sulfuric acid comprises the following steps:
1) slowly adding the coarse-filtered alkylated waste sulfuric acid into water, and diluting the mixture in an enamel stirring kettle to obtain a mixed solution with the sulfuric acid mass concentration of 70%;
2) adding sodium bisulfate accounting for 40 percent of the weight of the mixed solution obtained in the step 1) into an enamel stirring kettle at normal temperature, and stirring at the rotating speed of 1500rpm for 1 h; adding methyl cellulose accounting for 1 percent of the weight of the initial alkylation waste sulfuric acid, and continuously stirring for 0.5 h; adding potassium permanganate accounting for 0.2 percent of the weight of the initial alkylation waste sulfuric acid, and continuing stirring for 0.5 h; adding diatomite accounting for 1 percent of the weight of the initial alkylation waste sulfuric acid and uniformly stirring;
3) and (3) pumping the mixed solution obtained in the step 2) into a corrosion-resistant tympanic membrane filter press for solid-liquid separation, pumping the liquid phase (red sulfuric acid) into a freezing separator for cooling and separating salt and acid, feeding the acid into a corrosion-resistant oxidation tank, heating to 100 ℃, adding potassium permanganate with the weight of 0.1% of the acid and hydrogen peroxide with the weight of 0.2% of the acid, reacting to light brown, and finishing the treatment by using an activated carbon adsorption tank.
Wherein, the flocculate solid obtained by filtering in the step 2) is directly used for combustion to obtain steam, and the salt solid obtained in the step 3) is sold as mixed sulfate in a freezing separator.
Example 2
A high-concentration waste sulfuric acid purification treatment process is characterized in that on the basis of example 1, sodium bisulfate in step 2) is replaced by magnesium sulfate, and other conditions are the same as those in example 1.
Example 3
A high-concentration waste sulfuric acid purification treatment process is based on example 1, and step 2) of methyl cellulose is replaced by hydroxypropyl methyl cellulose, the amount of the methyl cellulose is set to be 27% by weight of the initial alkylation waste sulfuric acid, and other conditions are the same as example 1.
Example 4
A purification treatment process of high-concentration waste sulfuric acid is based on example 1, potassium permanganate in step 2) is replaced by sodium chlorate, the dosage is set to be 0.25 percent of the weight of the initial alkylated waste sulfuric acid, and other conditions are the same as those in example 1.
Example 5
A process for purifying high-concentration waste sulfuric acid, based on example 1, wherein diatomaceous earth in step 2) is replaced with powdered silica in an amount of 0.5 wt% of the original alkylated waste sulfuric acid, and the other conditions are the same as in example 1.
Example 6
A high-concentration waste sulfuric acid purification treatment process is based on example 1, wherein step 2) methyl cellulose is replaced by carboxymethyl cellulose, the amount of the methyl cellulose is set to 35% by weight of the initial alkylation waste sulfuric acid, and other conditions are the same as example 1.
Comparative example 1
A high-concentration waste sulfuric acid purification treatment process is based on example 1, and comprises the step 1) of diluting a mixed solution with the mass concentration of 80%, and other conditions are the same as those of example 1.
Comparative example 2
A high-concentration waste sulfuric acid purification treatment process is characterized in that on the basis of example 1, sodium bisulfate in step 2) is replaced by sodium nitrate, and other conditions are the same as those in example 1.
Comparative example 3
A high-concentration waste sulfuric acid purification treatment process is based on example 1, and sodium bisulfate and methylcellulose in step 2) are added into an enamel stirring kettle at the same time and stirred for 1 hour at the rotating speed of 1500rpm, and other conditions are the same as those in example 1.
Comparative example 4
A high-concentration waste sulfuric acid purification treatment process is based on example 1, no methyl cellulose is added in step 2), and other conditions are the same as example 1.
Comparative example 5
A high-concentration waste sulfuric acid purification treatment process is based on example 1, potassium permanganate is not added in step 2), and other conditions are the same as those in example 1.
Comparative example 6
The purification treatment process of high-concentration waste sulfuric acid is based on the example 1, diatomite is not added in the step 2), and other conditions are the same as the example 1.
Performance testing
And (3) observing the color depth of the treated waste sulfuric acid by naked eyes, wherein the darker the color is, the more organic impurity molecules in the waste sulfuric acid are represented, and the lighter the waste sulfuric acid is, the more thorough the treatment is.
The content of organic impurities in the treated waste sulfuric acid was characterized by detecting the carbon content in the treated waste sulfuric acid using an organic carbon analyzer, and the initial state of the alkylated waste sulfuric acid used in the above examples and comparative examples was obtained from a refinery, wherein the organic carbon content was 51000 mg/L.
The results of the measurements are shown in Table 1 below.
Table 1 results of performance testing
Meanwhile, in the implementation process of the embodiment 1, 0.8 ton of steam can be obtained by burning the organic impurities extracted from each ton of concentrated sulfuric acid, meanwhile, the downstream process refines to obtain more than 0.85 ton of 98% sulfuric acid, the steam value is recovered to be more than 120 yuan, the sulfuric acid value is more than 425 yuan, the total treatment of each ton of the refinery waste sulfuric acid obtains 545 yuan, and in the process of the embodiment 1, the total cost of materials, energy and working hours except for equipment is less than 500 yuan, and the profit of each ton of the waste sulfuric acid in the embodiment can be 45 yuan.
In the traditional natural gas cracking treatment process for alkylated waste sulfuric acid, each ton of waste sulfuric acid has more than 600 yuan of treatment energy, working hours and raw material cost, the treatment cost of generated cracking waste gas and high acid-containing waste materials is nearly 100 yuan, the recovered acid only can be sold as low-purity sulfuric acid due to higher organic impurities, and the value is less than 450 yuan, namely, each ton of waste sulfuric acid needs to be treated by 150 yuan.
The total cost of the enamel stirring kettle, the tympanic membrane filter press, the freezing separator, the oxidation reaction tank and the adsorption tank is less than 300 ten thousand yuan, and the cracking core device needs 700-1300 ten thousand yuan.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (8)
1. A purification treatment process of high-concentration waste sulfuric acid is characterized by comprising the following steps: the method comprises the following steps:
1) adding waste sulfuric acid into water to dilute the waste sulfuric acid to 70% or below of mass concentration;
2) sequentially adding sulfate or bisulfate, cellulose adhesive, oxidant and silicon oxide, and stirring uniformly;
3) filtering the mixed liquid obtained in the step 2), cooling the liquid phase in a freezing separator to separate salt, heating the liquid phase to 90-120 ℃, adding an oxidant to react until the liquid phase is light brown, and finishing the treatment by an activated carbon adsorption tank.
2. The purification treatment process of high-concentration waste sulfuric acid according to claim 1, characterized in that: the using amount of the sulfate in the step 2) is 10-70% of the weight of the waste sulfuric acid; the cellulose consumption is 0.05-2% of the weight of the waste sulfuric acid; the using amount of the oxidant is 0.15-5% of the weight of the waste sulfuric acid; the amount of the silicon oxide is 0.3-1% of the weight of the waste sulfuric acid.
3. The purification treatment process of high-concentration waste sulfuric acid according to claim 1, characterized in that: the oxidant in the step 2) is one or a mixture of more of potassium permanganate, sodium sulfite, nitric acid and sodium chlorate in any proportion.
4. The purification treatment process of high-concentration waste sulfuric acid according to claim 1, characterized in that: the cellulose adhesive in the step 2) is methyl cellulose adhesive, hydroxypropyl methyl cellulose adhesive, hydroxyethyl cellulose adhesive or carboxymethyl cellulose adhesive.
5. The purification treatment process of high-concentration waste sulfuric acid according to claim 1, characterized in that: the silicon oxide in the step 2) is diatomite or powder silicon dioxide.
6. The purification treatment process of high-concentration waste sulfuric acid according to claim 1, characterized in that: and 2) adding sulfate or bisulfate, stirring at 1000-2000 rpm for 0.5-1.5 h, and adding the next component.
7. The purification treatment process of high-concentration waste sulfuric acid according to claim 1, characterized in that: the oxidant in the step 3) is one or a mixture of more of ozone, hydrogen peroxide, nitric acid and potassium permanganate in any proportion; the total dosage is 0.2-0.5% of the total weight of the liquid phase.
8. The purification treatment process of high-concentration waste sulfuric acid according to claim 1, characterized in that: the step 1) and the step 2) are carried out in an enamel stirred tank, and the filtration in the step 3) adopts a corrosion-resistant tympanic membrane filter press.
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