CN1255329C - Method for treating high-sulphur-phenol waste alkali liquor under normal temperature and pressure conditions - Google Patents
Method for treating high-sulphur-phenol waste alkali liquor under normal temperature and pressure conditions Download PDFInfo
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- CN1255329C CN1255329C CN 03153325 CN03153325A CN1255329C CN 1255329 C CN1255329 C CN 1255329C CN 03153325 CN03153325 CN 03153325 CN 03153325 A CN03153325 A CN 03153325A CN 1255329 C CN1255329 C CN 1255329C
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- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002699 waste material Substances 0.000 title claims abstract description 16
- 239000003513 alkali Substances 0.000 title claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000002351 wastewater Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006477 desulfuration reaction Methods 0.000 claims description 36
- 230000023556 desulfurization Effects 0.000 claims description 36
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 239000006228 supernatant Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000007865 diluting Methods 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000007836 KH2PO4 Substances 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000011593 sulfur Substances 0.000 abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229910052700 potassium Inorganic materials 0.000 abstract description 4
- 239000007832 Na2SO4 Substances 0.000 abstract 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract 1
- 235000011152 sodium sulphate Nutrition 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 239000003518 caustics Substances 0.000 description 9
- 239000010802 sludge Substances 0.000 description 9
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004065 wastewater treatment Methods 0.000 description 6
- 102000005298 Iron-Sulfur Proteins Human genes 0.000 description 5
- 108010081409 Iron-Sulfur Proteins Proteins 0.000 description 5
- 238000005273 aeration Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003657 drainage water Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000001651 autotrophic effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
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Abstract
The present invention relates to a treating method for desulfurizing and dephenolizing waste alkali liquid with high content of sulfur and phenol. In the method, waste alkali liquid of high sulfur content is diluted until the sulfide concentration is approximately equal to or smaller than 20000 mg/L; the reaction temperature in a desulfurizing reactor is more than 55 DEG C, and the reaction time (or the hydraulic stay time) ranges from 15 to 20 hours; under the condition of the existence of a ferrous catalyst in the dosage which enables all the sulfide in water to exist in the intermediary of a compound of ferrum and sulfur, compressed air is used for stirring and reactions; the sulfide content is reduced from 20000 mg/L to less than 45 mg/L, and the removing rate of volatile phenol through oxidation can reach 15% to 25%. The waste alkali liquid of high sulfur content is appropriately diluted after being desulfurized so that the Na2SO4 content of biochemical water discharge is smaller than or equal to 44000 mg/L, and an appropriate amount of a compound of N, P and K is added to the waste water. Under the conditions that the reaction temperature ranges from 20 DEG C to 30 DEG C, and the hydraulic stay time ranges from 24 to 36 hours, the advanced treatment of the desulfurized waste water is realized by continuous flow biological contact oxidation technology; consequently, the final content of S<2-> from the water is smaller than 1 mg/L, the COD content is smaller than 150 mg/L, the volatile phenol content is smaller than 40 mg/L, and the pH value ranges from 6.0 to 9.0.
Description
Technical Field
The invention belongs to the field of environmental engineering, and particularly relates to desulfurization and dephenolization treatment of high-concentration sulfur-containing and phenol-containing waste alkali liquor generated in the production process of petrochemical enterprises.
Background
At present, the high-sulfur and phenol-containing waste alkali liquor produced in the petrochemical industry is generally subjected to wet oxidation treatment at high temperature and high pressure abroad. The method has high engineering investment and operation cost, and belongs to patents or proprietary technologies, so the method is rarely adopted in China. One of the traditional domestic treatment methods is an acidification method, which is more suitable for the desulfurization of alkaline residue containing high-concentration naphthenic acid and the recovery treatment of the naphthenic acid. Recently, there is a patented technology about "mild wet oxidation method" of alkaline residue in China. The reaction temperature adopted by the method is between 150 and 250 ℃, and the reaction pressure is 5kg/cm2～15kg/cm2In the meantime. Because the reaction temperature and pressure adopted by the method are both biased to be 'mild', the treatment effect cannot be ensured when the pollutant concentration of the waste alkali liquor is higher. In addition, the inventor has reported two inventions of 'a method for simultaneously desulfurizing and deaminating high-sulfur wastewater and high-sulfur alkali slag wastewater' and 'a method for comprehensively desulfurizing, deaminating and dephenolizing high-sulfur ammonia-containing and phenol-containing wastewater', but the two techniques are only suitable forThe method is used for comprehensive (mixed) treatment of acidic water and alkaline residue in the petrochemical industry, and is not suitable for independent desulfurization and dephenolization treatment of the alkaline residue.
Disclosure of Invention
The invention aims to find a new technology for carrying out desulfurization and dephenolization treatment on waste alkali liquor with high sulfur content and phenol content under the conditions of normal temperature and normal pressure, and the technology is required to have the characteristics of investment saving, low operation cost, good treatment effect, simple and reliable system and no secondary pollution.
Accordingly, it is an object of thepresent invention to provide a method for treating a high sulfur-containing, phenol-containing lye change at ambient temperature and pressure conditions comprising diluting the high sulfur-containing, phenol-containing lye change to a sulfide concentration of about 20000mg/L or less (e.g., with water, such as the effluent from a wastewater treatment plant), placing in a desulfurization reactor, under the condition of the dosage of the iron-containing catalyst which enables more than 90 percent of sulfide in the inlet water to exist in the form of an iron-sulfur compound intermediate, the reaction temperature is more than 55 ℃, usually 55-85 ℃, the reaction is carried out for 12-30 hours by stirring with compressed air, preferably 15-20 hours, the reactants are subjected to solid-liquid separation, the discharged supernatant is subjected to biological contact oxidation, the remainder is supplemented with an alkali liquor diluted to the sulfide concentration of 20000mg/L or less and an iron-containing catalyst in the desulfurization reactor, and the above process is repeated.
The iron-containing catalyst is any catalyst capable of producing Fe2+Or Fe3+The iron-containing catalyst comprises ferric sulfate, ferrous sulfate, ferric hydroxide, ferric nitrate and the like.
The above process may be carried out in a batch or continuous manner.
In a batch mode, as shown in FIG. 1, the method comprises diluting the high-sulfur and phenol-containing waste lye to a sulfide concentration of about 20000mg/L or less (for example, with water such as the wastewater from a wastewater treatment plant), reacting the high-sulfur and phenol-containing waste lye in a desulfurization reactor at a reaction temperature of 55 ℃ or higher, usually 55-85 ℃, with compressed air under stirring for 12-30 hours, preferably 15-20 hours, in the presence of an iron-containing catalyst in an amount such that all or 90% ormore of the sulfides in the feed water are present as an iron-sulfur complex intermediate, subjecting the reaction product to solid-liquid separation, diluting the discharged supernatant in an intermediate preparation tank with water, adding complex trace elements and nutrient salts, subjecting the mixture to biological oxidation in a biological contact oxidation tank, supplementing the remainder with the lye diluted to a sulfide concentration of 20000mg/L or less and the iron-containing catalyst in the desulfurization reactor, the above process is repeated.
In the continuous process, as shown in FIG. 2, the high sulfur and phenol-containing waste lye is diluted to a sulfide concentration of 20000mg/L or less (for example, with water such as the drainage water of a wastewater treatment plant), the reaction temperature is set to 55 ℃ or higher, usually 55-85 ℃, in a desulfurization reactor, under the condition of an iron-containing catalyst in an amount such that 90% or more of the sulfide in the feed water is present as an iron-sulfur complex intermediate, the reaction is stirred with compressed air, the hydraulic retention time of the feed is 12-30 hours, preferably 15-20 hours, the desulfurized reactant is subjected to solid-liquid separation in a sedimentation tank, the iron-containing catalyst (desulfurizing agent) is recovered and returned to the desulfurization reactor, the desulfurization reactor is continuously supplemented with the lye diluted to a sulfide concentration of 20000mg/L or less and the iron-containing catalyst, the supernatant after the desulfurizing agent is diluted with water, adding composite nutrient salt, and performing biological oxidation in a biological contact oxidation pond.
Diluting the supernatant discharged from the desulfurization device by 0.5-2 times with water (such as the wastewater of a wastewater treatment plant), adding N, P, K-containing compound into the supernatant, and performing reverse desulfurization by using a continuous flow biological contact oxidation process under the conditions that the reaction temperature is 20-30 ℃ and the hydraulic retention time is 24-36 hoursThe discharged water of the reactor is subjected to advanced treatment, and the advanced treated discharged water enters a wastewater treatment field. N, P is added in such an amount that the COD of the waste water to be treated is 100: 2.5-3.5, preferably about 3, and the COD of the waste water to be treated is 100: 0.3-0.9, preferably about 0.6, where the K-containing compound is K3PO4、K2HPO4、KH2PO4Or 1 of them (i.e. the P and K sources are the same source), and the dosage satisfying P is taken as the standard. If other kinds of K salts are selected, then K isThe dosage of the additive is 20-30 mg/L.
The amount of desulfurizing agent (i.e., iron-containing catalyst) added or supplemented is only required to form 30% of the influent sulfur compounds (FeS or Fe) into iron-sulfur complexes (FeS or Fe) in terms of desulfurization efficiency in a given reaction time2S3) The processing requirements can be met. In order to avoid air pollution caused by the stripping of hydrogen sulfide from the reaction mixture, the iron-containing catalyst is preferably supplemented or added so that the sulfide in the influent is preferably present in an amount of 90% or more, or more preferably in the form of an iron-sulfur complex intermediate.
The pH value of the high-sulfur and phenol-containing waste alkali liquor of petrochemical enterprises is generally 10-14, the concentration of sulfide is 50000-100000 mg/L, the concentration of volatile phenol is 1000-5000 mg/L, and the COD is 100000-300000 mg/L. If the technique is carried out by the intermittent flow treatment, the caustic sludge can be diluted to a sulfide concentration of about 20000mg/L or less by the wastewater from the sewage treatment plant when the sulfide concentration of the caustic sludge is more than 20000 mg/L. Before the treatment system is started, firstly adding a solution of iron-containing salts or other iron-containing compounds into a dealkalization reactor, and then adding caustic soda into the reactor. Stirring and reacting by using compressed air, and enabling the possible Fe to exist in the range of the pH value of the mixed solution to be about 8.0-9.02+Is totally oxidized into Fe3+. The volume of the mixed liquor was adjusted to the capacity of the desulfurization reactor working volume 1/2. In this case, Fe is contained in the iron hydroxide3+The concentration of (B) is preferably about 20000X 2 Fe/3S-23542 mg/L (about equal to or higher than 21188mg/L in the case where the sulfide concentration is about 20000mg/L and 90% or more exists in the form of an iron-sulfur complex intermediate).
And lifting the diluted alkaline residue into the desulfurization reactor by using a chemical pump until the effective volume of the reactor is reached. In this case, the sulfur content of the reaction mixture is about 8000-12000, more approximately 10000mg/L, and the iron content is about 10000-12000, more approximately 11771mg/L, both being Fe2S3The morphology exists. Stirring the mixture with compressed air for reaction, and heating the mixture by using water vapor to adjust the reaction temperature to be between 55 and 75 ℃. After 12 to 20 hours of reaction, preferably about 16 hours, heating and aeration are stopped,the concentration of sulphide in the mixture may be less than 40mg/L, with about 65% to 70% of the sulphide being oxidised to sulphate and about 30% to 35% of the sulphide being oxidised to thiosulphate. Meanwhile, the oxidation removal rate of the phenolic substances is about 15-25%. The reaction mixture is allowed to settle by standing for about 3 to 10 hours, preferably about 4 hours,fe (OH) is used as iron3The morphology is deposited at the bottom of the reactor. The supernatant in the desulfurization reactor was then drained in less than 2.5 hours until an effective level of 1/2 was reached. After that, the aeration and heating device is quickly started, and the iron-containing salt solution is supplemented into the desulfurization reactor as a desulfurizing agent according to 0.8-2%, preferably about 1% of the first dosage, and the agent supplementing time is controlled within 0.5 hour. And finally, adding alkaline residue into the desulfurization reactor for 1 hour until the effective liquid level of the reactor is reached. The 1 operating cycle was controlled to be exactly 24 hours. The relevant equation for the desulfurization reaction is:
the above reaction formula shows that: the iron plays a role of a desulfurization catalyst, and in addition, the pH value of the mixed solution is reduced along with the removal of sulfides.
The alkaline residue desulfurization wastewater discharged from the desulfurization reactor contains about 6000 to 7000mg/L of inorganic COD generated by thiosulfate. In general, it is not suitable for direct discharge into a waste water treatment plant, but for further pretreatment. For the reason of intermittent desulfurization treatment, the effluent of the desulfurization reactor should be firstly discharged into a wastewater adjusting tank, and COD and phenolic substances in the wastewater are further removed by adopting a biological contact oxidation process. For biochemical feeding of waterControlling the temperature below 35 deg.C, and treating Na in the mixed solution2SO4The content is controlled below 44000mg/L, and biochemical inhibition effect of high salt content is eliminated so that the biochemical treatment system can normally operate, and therefore, the discharged water of the caustic sludge desulfurization reactor is diluted by 0.6-2 times, preferably about 1 time. When the wastewater enters the biochemical reactor, necessary nutrient elements are added into the wastewater, and the elements comprise N, P, K and the like.
The pH value of discharged water after the alkaline residue is subjected to desulfurization treatment is 9.5-10.5, in the acclimatization culture stage of microorganisms of a biochemical treatment system, besides a proper amount of nutrient elements and trace elements, acid is added to adjust the pH value of the wastewater to be about 9.0, the pH value of biochemical effluent is gradually reduced along with the continuous proliferation of autotrophic sulfur bacteria of the biochemical system, the water inflow is gradually increased, the acid addition is gradually reduced to improve the pH value of the inlet water, and the pH value of the outlet water is maintained at 6.0-9.0. When the microbial acclimation culture of the biochemical system is finished, raw water can be directly fed instead of adding acid to adjust the pH.
When the biochemical system normally operates, if the COD of the inlet water is about 3000mg/L and the phenolic substances are about 50mg/L, the COD of the outlet water is less than 100mg/L and the phenolic substances are less than 0.5mg/L after 36 hours of biochemical treatment. If the COD of the biochemical inlet water is about 4000mg/L and the phenolic substances are about 400mg/L, the COD of the outlet water is about 160mg/L and the phenolic substances are about 35mg/L after 36 hours of biochemical treatment. Under the treatment effect, the effluent is discharged into the oily wastewater biochemical system, and the treatment effect of the total discharge biochemistry is not influenced. The biochemical reaction of the desulfurization alkaline residue biochemical treatment system is as follows:
drawings
FIG. 1 is a flow chart of the batch process of the present invention, ① is used in the caustic sludge blending tank when the sulfide concentration S of the raw lye is0When the flow rate is less than or equal to 20000mg/L, it is not necessary to add water for dilution ②, such as the average flow rate of caustic sludge is Q1The alkaline residue is desulfurized and then added with dilution water flow ofQ2Then Q is2＝(S0-10000)Q1/10000. When S is0When the concentration is less than or equal to 10000mg/L, no dilution water is needed.
FIG. 2 is a flow chart ① of the continuous process of the present invention in the caustic sludge blending tank when the sulfide concentration S of the raw lye is0When the flow rate is less than or equal to 20000mg/L, it is not necessary to add water for dilution ②, such as the average flow rate of caustic sludge is Q1The alkaline residue is desulfurized and then added with dilution water with the flow rate of Q2Then Q is2＝(S0-10000)Q1/10000. When S is0When the concentration is less than or equal to 10000mg/L, no dilution water is needed.
Detailed Description
The present invention is further illustrated by the following examples, which are provided for purposes of illustration only and are not to be construed as limiting the scope of the invention in any way.
With an effective volume of 2m3The desulfurization reactor adopts an intermittent flow treatment process to carry out desulfurization and dephenolization treatment on the high-sulfur waste alkali liquor of a certain petrochemical plant. FeSO is added into the reactor4·7H2O116.04kg, the effluent of the sewage treatment plant was added to the reactor as dilution water, the reaction was stirred with compressed air, and caustic soda was added to adjust the pH of the mixture to 8.0. Adjusting the volume of the mixed liquid to the effective volume of the reactor1/2 (i.e., V1 m)3). The reaction temperature was adjusted to about 50 ℃ with steam, and after 16 hours of reaction, the mixture turned from grayish green to reddish brown, indicating Fe2+Has been totally oxidized into Fe3+. Then the caustic sludge diluted to the sulfide concentration of 20000mg/L and the volatile phenol of 815mg/L is lifted to a desulfurization reactor by a chemical pump until an effective liquid level is reached (V is 2 m)3). Stirring and reacting with compressed air (the blast volume is 0.6-0.7 nm)3Min), controlling the reaction temperature to about 65 ℃ by using water vapor, stopping heating and aeration after 16 hours of reaction, standing the reaction mixed solution for 4 hours, discharging supernatant liquid which is half of the effective volume within 2.5 hours, and taking supernatant liquid to be dividedAnd (4) separating out sulfide, volatile phenol and COD value of the discharged water. After the water drainage is finished, the aeration and heating facilities are quickly started, and FeSO is added into the desulfurization reactor4·7H2O1.16 kg to replenish the lost desulfurizing agent. Under the condition of aeration and stirring, FeSO is added in the form of solution4·7H2O, so as to prevent the side reaction caused by local low pH value. The operation time for supplementing the desulfurizer is controlled within 0.5 hour. And finally, adding the caustic sludge into the desulfurization reactor for 1 hour to reach an effective liquid level (due to evaporation, the volume of the reaction mixed liquid is gradually reduced, and dilution water is supplemented at regular time according to the evaporation amount condition during the experiment). The desulfurization treatment experiment was continuously carried out for 10 cycles in the above manner, and the effluent had an average concentration of sulfide of 32.6mg/L, an average concentration of volatile phenol of 631.5mg/L, and an average concentration of COD of 7235 mg/L. Wherein the concentration of the drained water in the last 1 operating cycle is: s2-36.1mg/L, volatile phenol 639.2mg/L, and COD 7356 mg/L.
And taking the drainage water of the last 1 period, diluting the drainage water by 1 time, and performing advanced treatment by using a biological contact oxidation process. The water inlet index is S2-The concentration of volatile phenol is 319.6mg/L, COD is 3678mg/L, and the pH value is 10.2. Inorganic nitrogen with the COD concentration of 1-5 percent, preferably about 3 percent, inorganic phosphorus with the COD concentration of 0.2-1.0 percent, preferably about 0.6 percent, and proper amount of salt containing K are added into the water sample. In 1 biological contact oxidation reactor with effective volume of 12L, the hydraulic retention time is 36 hours, the reaction temperature is 20-25 ℃, and the pH value of inlet water is 9.0 (by H) from the initial stage of acclimatization2SO4Acidification) to normal operation, raw water is directly fed without acidification, and after biological culture and domestication for about 25 days, the indexes of a discharged clear solution are as follows: s2-Less than 1mg/L, COD less than 150mg/L, volatile phenol less than 35mg/L and pH of 6.5-8.0.
Claims (7)
1. A process for treating the waste alkali liquid containing high content of S and phenol at ordinary temp and pressure includes diluting the waste alkali liquid containing high content of S and phenol to obtain the sulfide concentration equal to or less than 20000mg/L, stirring in desulfurizing reactor at 55 deg.C or more under the condition of iron-contained catalyst to make the sulfide existing in the water be more than 90% in the form of intermediate of Fe-S compound, solid-liquid separation, biological contact oxidizing, adding the diluted liquid supernatant to obtain the mixture of S and Fe, repeating said steps, adding N, P, K-contained compound to the diluted liquid supernatant, reacting at 20-30 deg.C, and under the condition that the hydraulic retention time is 24-36 hours, performing advanced treatment on the discharged water of the desulfurization reactor by adopting a continuous flow biological contact oxidation method.
2. The method as set forth in claim 1, wherein the reaction temperature is 55-85 ℃ and the reaction is carried out for 15-20 hours with stirring with compressed air.
3. The method of claim 1, wherein the iron-containing catalyst is any catalyst capable of producing Fe2+Or Fe3+Or a mixture thereof.
4. The process as claimed in claim 1, wherein the reaction temperature is from 55 ℃ to 85 ℃.
5. The method as set forth in claim 1, wherein the supernatant after the desulfurization treatment is diluted to Na in the biochemical treatment liquid2SO4The concentration is not more than 44000 mg/L.
6. The method of claim 1, wherein the make-up amount of iron-containing catalyst is 0.8-2% of the first addition.
7. The process according to claim 1, wherein N and P are added in such an amount that the wastewater to be treated has a COD: N of 100: 3; the COD of the waste water to be treated is 100: 0.6; wherein the K-containing compound is K3PO4、K2HPO4、KH2PO4The mixture of (1) or the mixture of (1) in the amount satisfying the P addition; if other K salts are selected, the dosage of K is between 20 and 30 mg/L.
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| CN101798068B (en) * | 2010-03-29 | 2011-10-26 | 罗德春 | Sulfide or thiosulfate catalytic air complete oxidation at normal temperature and pressure |
| CN102773049B (en) * | 2012-07-19 | 2015-03-04 | 辽宁正渤辽西环保产业园开发有限公司 | Wet oxidation treating method for sulfur-containing waste alkaline liquor in petrochemical industry |
| CN104817211B (en) * | 2015-05-20 | 2017-10-24 | 南京大学 | A kind of method of vulcanized sodium waste water desulfurization |
| CN115124212B (en) * | 2022-06-24 | 2023-03-21 | 西安德兴环保科技有限公司 | Method for treating high-sulfur high-asphaltene oil sludge |
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