CN103771608B - A kind for the treatment of process of refinery alkaline residue - Google Patents
A kind for the treatment of process of refinery alkaline residue Download PDFInfo
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- CN103771608B CN103771608B CN201210404040.3A CN201210404040A CN103771608B CN 103771608 B CN103771608 B CN 103771608B CN 201210404040 A CN201210404040 A CN 201210404040A CN 103771608 B CN103771608 B CN 103771608B
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- flue gas
- residue
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 230000008569 process Effects 0.000 title claims abstract description 39
- 238000011282 treatment Methods 0.000 title claims abstract description 16
- 239000002699 waste material Substances 0.000 claims abstract description 68
- 239000003513 alkali Substances 0.000 claims abstract description 63
- 239000007788 liquid Substances 0.000 claims abstract description 63
- 238000000605 extraction Methods 0.000 claims abstract description 39
- 230000020477 pH reduction Effects 0.000 claims abstract description 35
- 239000003546 flue gas Substances 0.000 claims abstract description 31
- 230000008929 regeneration Effects 0.000 claims abstract description 24
- 238000011069 regeneration method Methods 0.000 claims abstract description 24
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000002989 phenols Chemical class 0.000 claims abstract description 18
- 238000007730 finishing process Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000004571 lime Substances 0.000 claims abstract description 11
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 10
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004062 sedimentation Methods 0.000 claims abstract description 6
- 239000000284 extract Substances 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002283 diesel fuel Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000010802 sludge Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 235000012255 calcium oxide Nutrition 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003518 caustics Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000001301 oxygen 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
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 230000009719 regenerative response Effects 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 43
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 239000010865 sewage Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229910017053 inorganic salt Inorganic materials 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 4
- 235000010261 calcium sulphite Nutrition 0.000 description 4
- 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 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000009279 wet oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- -1 crude phenols Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Treating Waste Gases (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a kind for the treatment of process of refinery alkaline residue, comprising: (1) will containing SO
2and CO
2flue gas carry out deoxidation; (2) after adopting deoxidation, flue gas carries out acidification to alkali residue waste liquid, when waste liquid pH value reaches 2 ~ 7, and stopping acidification; (3) acidifying produce organic sulfide and H
2s acidifying tail gas, is sent to sour gas pipe network; (4) acid waste liquid after acidifying carries out sedimentation, reclaims oil phase; (5) after reclaiming oil phase, waste liquid extracts, and reduces COD further; (6) the partial neutral water after extraction adds lime and carries out causticization regeneration, and after isolating throw out, regeneration alkali lye is back to oil product soda finishing process.The present invention utilizes containing SO
2and CO
2flue gas acidification alkali residue waste liquid after deoxidation, the treatment of wastes with processes of wastes against one another, efficiently can remove the sulfide in alkali residue waste liquid, reclaim crude phenols, effectively reduce COD, then through causticization regeneration after, be back to oil product soda finishing process.The present invention makes high-risk unmanageable alkali residue waste liquid resource utilization, greatly reduces environmental pollution.
Description
Technical field
The present invention relates to the high sulfur-bearing height COD alkali residue waste liquid of a kind for the treatment of process of alkali residue waste liquid, particularly catalytic gasoline, the generation of catalytic diesel oil soda finishing process, or the mixing alkali residue waste liquid of FCC gasoline caustic sludge, catalytic diesel oil alkaline residue, liquid hydrocarbon alkali residue etc.
Background technology
In Refinery Oil soda finishing process, the alkaline waste liquor containing high density pollution thing can be produced, the quantity discharged of its COD, sulfide and phenol accounts for 40wt% ~ more than the 50wt% of this type of pollutant discharge amount of refinery, primarily of compositions such as ordinary pressure diesel alkaline residue, FCC gasoline caustic sludge, catalytic diesel oil alkaline residue, liquid hydrocarbon alkali residue.These alkali residue waste liquid, if directly discharged, meeting serious environment pollution; If delivered to sewage farm, the normal running in sewage farm will be had a strong impact on, make sewage be difficult to qualified discharge, and severe corrosion equipment.Alkaline residue problem is at refinery ubiquity.In the last few years, along with national environmental protection regulation, standard are increasingly complete and strict, and the cry of people to environmental protect quality was more and more higher, and the process of alkali residue waste liquid more and more comes into one's own.
In this several alkaline residue, what sulfide content was the highest is catalytic gasoline, catalytic diesel oil alkaline residue and liquid hydrocarbon alkali residue, generally use wet oxidation process at present, oxidation waste liquid sulfuric acid neutralizes, and reclaims phenol, petroleum acid, produces in alkaline residue and water, but COD is still very high, can 30000mg/L ~ 60000mg/L be reached, and create a large amount of salt in oxidation and N-process, impact very large to the sewage farm of Petrochemical Enterprises.Ordinary pressure diesel alkaline residue is mainly containing petroleum acid, and generally adopt in sulfuric acid and reclaim naphthenic acid process, produce in diesel alkaline residue and water, COD is relatively low, but salt concn is very high, just can enter sewage farm after needing Macrodilution.
For the process of high sulfur-bearing height COD alkali residue waste liquid, some patent proposes treatment technology, has hydrolysis method, oxidation style, biological process, extraction process, evaporation burning method etc.
CN98121081.3 discloses the treatment process of the waste lye that a kind of oil products in petroleum refining industry soda finishing system is discharged, and adopts wet oxidation+intermittent activated sludge process (SBR) combination treatment.But because COD concentration in the waste water after wet oxidation is still very high, and inorganic salt content also quite high (containing 200g/L ~ 300g/L in the waste liquid had).Inorganic salt have toxic action to microorganism, and the microorganism in SBR method generally can stand the inorganic salt content being less than 30g/L, and after exceeding this value, microorganism starts to disintegrate and floats, and finally cause active sludge to run off, reactor runs unsuccessfully.When therefore adopting SBR method process waste lye, the sewage in more fresh water or other source be adopted to dilute former water, be less than the requirement of 30g/L with inorganic salt content in satisfied water inlet.Like this, when the consumption of fresh water is generally more than 10 times of former water yields, just can enter sbr reactor pond, the surplus sludge volume of this technique is more in addition, needs regularly to discharge excess sludge, adds aftertreatment expense.
CN02130781.4 discloses a kind for the treatment of process of refinery basic sewage, comprise: the refinery basic sewage of evaporation containing evaporation accelerators at 101 ~ 115 DEG C, the gaseous condensate evaporated recycles, and the alkaline residue after concentrated enters incinerator and burn at 750 ~ 950 DEG C generation sodium carbonate and sodium sulfate.But in alkali residue waste liquid, volatile organism and Stenchy sulfides can evaporate in a large number in the process of evaporation, cause gaseous condensate Pollutant levels very high, and evaporation and to burn energy consumption very large.
CN00110702.X discloses the treatment process of alkaline sewage of a kind of high COD content, high inorganic salt content, adopt Membrane Bioreactor for Wastewater Treatment alkaline sewage, waste water is through activated sludge biochemical process, and after process, water outlet is discharged through membrane filtration, and the film used is microfiltration membrane or ultra-filtration membrane.This patent is only applicable to influent COD <12000mg/L, the alkaline sewage of inorganic salt content <50mg/L.For the COD of most of alkali residue waste liquid all far above this index, fresh water is still needed to dilute.
CN200810239660.X discloses the treatment process of a kind of waste lye or alkaline residue, utilize fluidized catalytic cracker regenerated flue gas to process, comprising: the alkaline residue of alkaline residue (abbreviation liquefied gas alkaline mud) and other devices that the alkaline residue (abbreviation gasoline alkaline residue) produce gasoline refining and liquefied gas refine generation is in harmonious proportion; Pass in alkaline residue after mediation fluidized catalytic cracker regenerated flue gas carry out in and; Isolate the oil in alkaline residue and phenol, naphthenic acid sulfide etc.But the method process alkaline residue, finally also can be formed in the alkaline residue of high salt and water, still can impact sewage farm.
CN200510041778.8 discloses the method for a kind of Alkaline Residue complexometric extraction dephenolize, employ two kinds of mixed extractants I and II, successively mix with alkaline residue, complexometric extraction, obtain three phase extraction system, one is extracting phase mutually, by NaOH back extraction phase I, is extracted agent I and phenol, heating back extraction phase II, the sulfide in phase II can be removed, be extracted agent II, play the effect of desulfurization simultaneously and phenol.The sulfur method of the not mentioned alkali residue waste liquid of the method.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind for the treatment of process of refinery alkaline residue.The present invention utilizes containing SO
2and CO
2flue gas acidification alkali residue waste liquid after deoxidation, the treatment of wastes with processes of wastes against one another, can remove the sulfide in alkali residue waste liquid efficiently, reclaims crude phenols, reduces the COD of alkali residue waste liquid, then after causticization regeneration, is back to oil product soda finishing process.The present invention can make high-risk unmanageable alkali residue waste liquid resource utilization, greatly reduces environmental pollution.
The treatment process of refinery alkaline residue of the present invention, comprises the steps:
(1) will containing SO
2and CO
2flue gas carry out deoxidation;
(2) flue gas after adopting deoxidation carries out acidification to refinery alkaline residue, when the pH value of waste liquid reaches 2 ~ 7, and stopping acidification;
(3) step (2) acidification produce organic sulfide and H
2s acidifying tail gas, is sent to sour gas pipe network and focuses on;
(4) acid waste liquid after step (2) acidification carries out sedimentation, and reclaim oil phase, be mainly crude phenols in oil phase, crude phenols reclaim further;
(5) waste liquid after step (4) reclaims oil phase extracts, and reduces COD further;
(6) the partial neutral water obtained after step (5) extraction adds lime and carries out causticization regeneration, and after isolating throw out, the regeneration alkali lye obtained is back to oil product soda finishing process.
In the present invention, step (1) containing SO
2and CO
2flue gas derive from sulfur reclaimer tail gas incinerator, heating boiler, catalytic cracking catalyst revivifier or S-zorb revivifier, be preferably S-zorb revivifier produce flue gas, the temperature of flue gas is lower than 60 DEG C.Deoxidation adopts catalytic oxidation or sodium sulfite solution washing method, and after deoxidation, the oxygen level of flue gas is lower than 0.2v%.
In the present invention, in the acidification process of step (2), constantly strengthen along with waste liquid is acid, the sulfide in waste liquid is with organic sulfide and H
2s form evaporates, and the petroleum acids such as the phenol in alkaline residue and water stratification float over upper strata, when the pH value of waste liquid preferably reaches 3 ~ 6, and stopping acidification process.The acidification process of step (1), the sulfide clearance in alkali residue waste liquid is more than 99wt%.
In the present invention, except containing except nitrogen in the acidifying tail gas of step (3), also containing organic sulfide, hydrogen sulfide, a small amount of SO
2and CO
2, be sent to sour gas pipe network and focus on.
In the present invention, after step (4) reclaims crude phenols, the clearance of phenol can reach more than 75wt%, and COD clearance can reach more than 75wt%.
In the present invention, the mixture that the extraction agent that step (5) uses is petroleum fractions and organic amine, organic amine accounts for 5% ~ 40% of mixed extractant volume.The consumption of extraction agent and alkali residue waste liquid volume ratio are 1:2 ~ 1:8.Extraction employing 1 ~ 10 grade extraction, can adopt hybrid extraction equipment, cross current solvent extraction equipment or countercurrent extraction equipment.After extraction, the clearance of COD can reach more than 95wt%.
In the present invention, the lime that step (6) uses can be unslaked lime or white lime, and the material worked when there is regenerative response is Ca (OH)
2.This step, while regeneration alkali lye, can precipitate the inferior sulfate radical and carbonate of removing more than 85wt%, obtain the regeneration alkali lye of 2wt% ~ 6wt%.Isolated throw out is mainly CaSO
3and CaCO
3, carry out the SO that Roasting Decomposition obtains
2and CO
2can be used for the acidification of step (2), CaO also can be used for the causticization regeneration of step (6).According to the requirement of oil product soda finishing, for oil product soda finishing process after regeneration alkali lye can mix with fresh alkali lye.
The high sulfur-bearing height COD alkali residue waste liquid that in the present invention, refinery alkaline residue is catalytic gasoline, catalytic diesel oil soda finishing process produces, or the mixing alkali residue waste liquid of FCC gasoline caustic sludge, catalytic diesel oil alkaline residue, liquid hydrocarbon alkali residue etc.
The treatment process tool of refinery alkaline residue of the present invention has the following advantages: (1) the inventive method thoroughly can remove sulfide, reclaim the petroleum acids such as crude phenols, reduce COD, after causticization regeneration, regeneration alkali lye is back to oil product soda finishing process, make alkali residue waste liquid resource utilization, there is good environmental benefit and economic benefit; (2) the present invention utilizes containing SO
2and CO
2flue gas acidification alkali residue waste liquid after deoxidation, can effectively in and alkaline residue alkali lye in OH
-, the treatment of wastes with processes of wastes against one another.Meanwhile, owing to being stripped of the oxygen in flue gas, the sulfite oxidation produced after avoiding acidifying becomes vitriol, causes carrying out causticization regeneration; (3) acidifying that the present invention relates to, causticization regenerative operation are simple, integral device investment and process cost low, without the need to large scale investment; Operational condition is gentle, does not relate to high-temperature high-pressure apparatus.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the inventive method.
Wherein: 101-device for deoxidizing, 102-acidification reactor, 103-slurry tank, 104-extraction equipment, 105-causticization regeneration reactor; 201-alkali residue waste liquid, 202-acid waste liquid, 203-oil phase, 204-reclaims the waste liquid after crude phenols, 205-extraction agent, the partial neutral water after 206-extraction, 207-lime, 208-throw out, and 209-regenerates alkali lye; 301-refinery flue gas, 302-deoxidation flue gas, 303-acidifying tail gas.
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described.In the present invention, wt% is massfraction, and v% is volume fraction.
As shown in Figure 1, will containing SO
2and CO
2refinery's flue gas 301 in device for deoxidizing 101, carry out deoxidation, deoxidation adopt catalysed oxidation processes, after deoxidation, the oxygen level of flue gas is lower than 0.2v%, and the temperature of flue gas is lower than 50 DEG C.Deoxidation flue gas 302 is adopted to carry out acidification to naphthenic acid alkali residue waste liquid 201 in acidification reactor 102, when the pH value of waste liquid reaches 2 ~ 7, stopping acidification; Sulfide clearance wherein can reach more than 99wt%.Acidifying tail gas 303 is discharged into sour gas pipe network and focuses on.Acid waste liquid 202 after acidification enters slurry tank 103 sedimentation, and reclaim oil phase 203, be mainly crude phenols in oil phase, crude phenols can reclaim further.After reclaiming crude phenols, the clearance of phenol can reach more than 75wt%, and COD clearance can reach more than 75wt%.Enter extraction plant 104, add extraction agent 205 and extract, reduce COD further.After extraction, the clearance of COD can reach more than 95wt%.Partial neutral water 206 after extraction enters causticization regeneration reactor 105, adds lime 207 and carries out causticization regeneration, can precipitate the inferior sulfate radical and carbonate of removing more than 85wt%.After isolating throw out 208, obtain regenerating alkali lye 209, for oil product soda finishing process after can mixing with fresh alkali lye.
The inventive method and effect is illustrated further below in conjunction with example.
Embodiment 1
The refinery alkaline residue of certain enterprise, wherein COD is 2.53 × 10
5mg/L, sulfide is 2.93 × 10
4mg/L, volatile phenol is 7.39 × 10
4mg/L.Use the technical process process shown in the inventive method Fig. 1.Flue gas is S-zorb regenerator flue gas, wherein SO
2content is 0.9v% ~ 5.4v%, O
2content is 0.1v% ~ 0.5v%, CO
2content is 1.6v% ~ 2.3v%, after adopting catalytic oxidation deoxidation, and O
2content is down to below 0.1v%.
Adopt the flue gas after deoxidation to carry out acidification to alkali residue waste liquid, until the pH of alkali residue waste liquid is down to 3 ~ 4, stopping acidification, the sulfide in alkali residue waste liquid removes more than 99.7wt%.The acidifying tail gas produced in acidification process enters oil-extraction plant acidic gas pipe network and focuses on.Acid waste liquid after acidification carries out sedimentation, and be separated upper oil phase, be mainly crude phenols in this oil phase, crude phenols can reclaim further.After reclaiming crude phenols, the clearance of phenol can reach more than 75wt%, and COD clearance can reach more than 75wt%.
After acidification, COD is still higher, carries out extracting reducing COD further.Extraction uses organic amine and diesel oil mixed extractant, and wherein organic amine accounts for 20% of mixed extractant volume.The consumption of extraction agent and the volume ratio of alkali residue waste liquid are 1:4.After single-stage extraction, COD clearance can reach more than 95wt%.
Use white lime to carry out causticization regeneration to the partial neutral water after extraction, produce calcium sulfite and precipitation of calcium carbonate, inferior sulfate radical and carbonate clearance can reach more than 85wt%, and the NaOH obtaining 4wt% regenerates alkali lye.Calcium sulfite and calcium carbonate roasting obtain SO
2and CO
2can be cycled to used in acidification step, the CaO of generation also may be used for causticization regenerative process.
Alkali residue waste liquid after the inventive method process, can add fresh alkali lye in proportion for oil product soda finishing process.
Embodiment 2
Certain enterprise's refinery alkaline residue, wherein COD is 2.33 × 10
5mg/L, sulfide is 3.58 × 10
4mg/L, volatile phenol is 5.79 × 10
4mg/L.The technical process of the inventive method Fig. 1 is used to process.Flue gas is FCC catalyst regeneration flue gas, wherein SO
2content is 0.1v% ~ 0.5v%, O
2content is 1.5v% ~ 3.0v%, CO
2content is 16v% ~ 19v%, after adopting catalytic oxidation deoxidation, and O
2content is down to below 0.2v%.
Adopt the flue gas after deoxidation to carry out acidification to alkali residue waste liquid, until the pH of alkali residue waste liquid is down to 3 ~ 4, stopping acidification, the sulfide in alkali residue waste liquid removes more than 99.8wt%.The acidifying tail gas produced in acidification process enters oil-extraction plant acidic gas pipe network and focuses on.Acid waste liquid after acidification carries out sedimentation, and be separated upper oil phase, be mainly crude phenols in this oil phase, crude phenols can reclaim further.After reclaiming crude phenols, the clearance of phenol can reach more than 75wt%, and COD clearance can reach more than 75wt%.
After acidification, COD is still higher, carries out extracting reducing COD further.Extraction uses organic amine and diesel oil mixed extractant, and wherein organic amine accounts for 25% of mixed extractant volume.The consumption of extraction agent and the volume ratio of alkali residue waste liquid are 1:4.After single-stage extraction, COD clearance can reach more than 95wt%.
Use white lime to carry out causticization regeneration to the partial neutral water after extraction, produce calcium sulfite and precipitation of calcium carbonate, inferior sulfate radical and carbonate clearance can reach more than 85wt%, and the NaOH obtaining 5wt% regenerates alkali lye.Calcium sulfite and calcium carbonate roasting obtain SO
2and CO
2can be cycled to used in acidification step, the CaO of generation also may be used for causticization regenerative process.
Alkali residue waste liquid after the inventive method process, can add fresh alkali lye in proportion for oil product soda finishing process.
Claims (13)
1. a treatment process for refinery alkaline residue, is characterized in that comprising the steps:
(1) will containing SO
2and CO
2flue gas carry out deoxidation;
(2) flue gas after adopting deoxidation carries out acidification to refinery alkaline residue, when the pH value of waste liquid reaches 2 ~ 7, and stopping acidification;
(3) step (2) acidification produce organic sulfide and H
2s acidifying tail gas, is sent to sour gas pipe network and focuses on;
(4) acid waste liquid after step (2) acidification carries out sedimentation, and reclaim oil phase, be mainly crude phenols in oil phase, crude phenols reclaim further;
(5) waste liquid after step (4) reclaims oil phase extracts, and reduces COD further;
(6) the partial neutral water obtained after step (5) extraction adds lime and carries out causticization regeneration, and after isolating throw out, the regeneration alkali lye obtained is back to oil product soda finishing process.
2. in accordance with the method for claim 1, it is characterized in that: step (1) containing SO
2and CO
2flue gas derive from sulfur reclaimer tail gas incinerator, heating boiler, catalytic cracking catalyst revivifier or S-zorb revivifier.
3. in accordance with the method for claim 1, it is characterized in that: step (1) containing SO
2and CO
2flue gas derive from S-zorb revivifier.
4. in accordance with the method for claim 1, it is characterized in that: the deoxidation of step (1) adopts catalytic oxidation or sodium sulfite solution washing method, and after deoxidation, the oxygen level of flue gas is lower than 0.2v%.
5. in accordance with the method for claim 1, it is characterized in that: when the acidifying pH value of step (2) reaches 3 ~ 6, stopping acidification.
6. in accordance with the method for claim 1, it is characterized in that: the mixture that the extraction agent that step (5) uses is petroleum fractions and organic amine, organic amine accounts for 5% ~ 40% of mixed extractant volume.
7. according to the method described in claim 1 or 6, it is characterized in that: the consumption of extraction agent and the volume ratio of alkali residue waste liquid are 1:2 ~ 1:8.
8. according to the method described in claim 1 or 6, it is characterized in that: extraction employing 1 ~ 10 grade extraction, adopts hybrid extraction equipment, cross current solvent extraction equipment or countercurrent extraction equipment.
9. in accordance with the method for claim 1, it is characterized in that: the lime that step (6) uses is unslaked lime or white lime, the material worked when there is regenerative response is Ca (OH)
2.
10. in accordance with the method for claim 1, it is characterized in that: step (6) is while regeneration alkali lye, and precipitation removes inferior sulfate radical and the carbonate of more than 85wt%, obtains the regeneration alkali lye of 2wt% ~ 6wt%.
11. according to the method described in claim 1 or 10, it is characterized in that: throw out is CaSO
3and CaCO
3, carry out the SO that Roasting Decomposition obtains
2and CO
2for the acidification of step (2), CaO regenerates for the causticization of step (6).
12. in accordance with the method for claim 1, it is characterized in that: according to the requirement of oil product soda finishing, for oil product soda finishing process after regeneration alkali lye mixes with fresh alkali lye.
13. in accordance with the method for claim 1, it is characterized in that: the high sulfur-bearing height COD alkali residue waste liquid that refinery alkaline residue is catalytic gasoline, catalytic diesel oil soda finishing process produces, or the mixing alkali residue waste liquid of FCC gasoline caustic sludge, catalytic diesel oil alkaline residue, liquid hydrocarbon alkali residue etc.
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| CN105712521B (en) * | 2014-12-05 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of processing method of refinery alkaline residue |
| CN105712522B (en) * | 2014-12-05 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of acidization tool of refinery basic sewage |
| CN105712556B (en) * | 2014-12-05 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of processing method of refinery basic sewage |
| KR101926481B1 (en) * | 2016-10-31 | 2018-12-10 | 에스케이이노베이션 주식회사 | Layer-separation method of spent caustic |
| CN113998727A (en) * | 2021-02-24 | 2022-02-01 | 福建农林大学 | Method for recovering alkali from lignocellulose alkaline reaction solution |
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