CN103045289B - Comprehensive treatment method of liquid hydrocarbon alkali residue waste liquid - Google Patents

Comprehensive treatment method of liquid hydrocarbon alkali residue waste liquid Download PDF

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Publication number
CN103045289B
CN103045289B CN201110313313.9A CN201110313313A CN103045289B CN 103045289 B CN103045289 B CN 103045289B CN 201110313313 A CN201110313313 A CN 201110313313A CN 103045289 B CN103045289 B CN 103045289B
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waste liquid
liquid
alkali residue
alkali
accordance
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CN201110313313.9A
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Chinese (zh)
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CN103045289A (en
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刘忠生
赵磊
王有华
王新
周旗
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中国石油化工股份有限公司
中国石油化工股份有限公司抚顺石油化工研究院
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Abstract

The invention relates to a comprehensive treatment method of liquid hydrocarbon alkali residue waste liquid. The comprehensive treatment method comprises the steps of: (1) acidizing the liquid hydrocarbon alkali residue waste liquid by a N2/SO2 gas mixture, wherein sulfide in the waste liquid volatilizes in the form of H2S along with the continuous increase of the acidity of the waste liquid; and stopping acidizing when the pH value of the waste liquid reaches 2-6; (2) sending tail gases discharged in the acidizing process in the step (1) into a sulphur production device for preparing sulphur; (3) subsiding the waste liquid generated after the acidizing process in the step (1), and recovering an oil phase, wherein the oil phase mainly contains crude phenol which can be further recovered; and (4) regenerating the waste liquid without the oil phase by using lime, wherein the regenerated waste liquid can be recycled for refinement process of liquid hydrocarbon alkali after precipitates are separated out from the regenerated waste liquid. The comprehensive treatment method is low in investment; the process is simple and flexible; operation conditions are mild; due to the application of the comprehensive treatment method, the alkali residue waste liquid is recycled, the impact of high-concentration waste water on a sewage treatment plant is avoided, simultaneously the sulfide and crude phenol in the alkali residue waste liquid can be recycled, and certain economic benefit is achieved.

Description

The integrated conduct method of liquid hydrocarbon alkali residue waste liquid
Technical field
The present invention relates to a kind for the treatment of process of alkali residue waste liquid, the integrated conduct method of the alkali residue waste liquid of particularly liquid alkali cleaning treating process generation.
Background technology
In Refinery Oil alkali cleaning treating process, produce the alkaline waste liquor containing high density pollution thing, the quantity discharged of its COD, sulfide and phenol accounts for more than 40% ~ 50% of this type of pollutant discharge amount of refinery, primarily of compositions such as ordinary pressure diesel alkaline residue, FCC gasoline caustic sludge, liquid hydrocarbon alkali residue.These alkali residue waste liquid, as direct discharge, meeting serious environment pollution, if delivered to sewage farm, will have a strong impact on the normal running in sewage farm, 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 alkaline residue process more and more comes into one's own.
In this several alkaline residue, what sulfide content was the highest is FCC gasoline caustic sludge 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.
Along with the development of oil refining process for refining, diesel oil and gasoline gradually adopt hydrofining technology, can avoid like this producing alkali residue waste liquid.But liquid hydrocarbon is still based on alkali cleaning process for refining, the alkali residue waste liquid of corresponding high sulfur content height COD can be produced.
For the process of the alkali residue waste liquid of high sulfur content height COD, some patent proposes treatment technology, has hydrolysis method, oxidation style, biological process, extraction process, evaporation burning method etc.CN98121081.3 discloses a kind for the treatment of process of salkali waste waste liquid, adopts the method for wet oxidation+intermittent activated sludge process (SBR) combination treatment alkaline residue.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 alkaline residue had).Inorganic salt have toxic action to microorganism, and the microorganism in SBR method generally can stand the inorganic salt content being less than 30 g/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 alkali residue waste liquid, the sewage in more fresh water or other source be adopted to dilute former water, be less than the requirement of 30 g/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 proposes 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 be able to send 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 proposes a kind of purifying method of alkali residue waste liquid, and under being included in active sludge existence, alkali residue waste liquid contacts with oxygen-containing gas, and after purification, water outlet is discharged by membrane filtration, and the film used is microfiltration membrane or ultra-filtration membrane.This patent is only applicable to influent COD <12000mg/L, inorganic salt content < 50mg/L.For in most of alkaline residue and the COD of water all far above this index, still need fresh water to dilute.
CN200510041778.8 describes 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.But can alkaline waste liquor be produced in the method process alkaline residue stripping process.
Summary of the invention
The invention provides a kind of integrated conduct method of high sulfur content height COD liquid hydrocarbon alkali residue waste liquid, the sulfide in alkali residue waste liquid can be removed efficiently, reduce the COD of waste water, reclaim crude phenols, after causticization regeneration, treating oil by alkali washing is carried out in reuse, can make high-risk unmanageable alkaline residue resource utilization, greatly reduce environmental pollution.
The integrated conduct method of liquid hydrocarbon alkali residue waste liquid of the present invention comprises following content:
(1) with N 2/ SO 2gas mixture liquid towards hydrocarbon alkali residue waste liquid carries out acidifying, and constantly strengthen along with waste liquid is acid, the sulfide in waste liquid is with H 2s form evaporates, when the pH value of waste liquid reaches 2 ~ 6, when being preferably 3 ~ 4, and stopping acidification process;
(2) tail gas discharged in acidification process in step (1), is sent to sulphur production installation for producing sulphur;
(3) waste liquid after step (1) acidification carries out sedimentation, and reclaim oil phase, be mainly crude phenols in oil phase, crude phenols can reclaim further;
(4) the waste liquid lime after being separated oil phase in step (3) regenerates, and after isolating throw out, is cycled to used in liquid hydrocarbon soda finishing process.
In the inventive method, step (1) N 2/ SO 2in gas mixture, N 2/ SO 2mol ratio be 50:1 ~ 100:1, SO 2can be any source, be preferably isolated throw out in step (4) and (be mainly CaSO 3) carry out the SO that Roasting Decomposition obtains 2.The acidification process of step (1), can by the sulfide clearance 99%(quality in alkali residue waste liquid) more than.
In the inventive method, except N in the tail gas obtained in step (2) 2outward, mainly hydrogen sulfide, also has a small amount of organic sulfide and sulfurous gas, as the raw material of sulphur production installation, or can be re-used as the raw material of sulphur production installation after removing organic sulfide wherein.
In the inventive method, after being separated crude phenols operation in step (3), the clearance of phenol can reach 80%(quality) more than, COD can reach more than 60% by clearance.
In the inventive method, the lime used in step (4) can be white lime or unslaked lime, and the material worked when there is regenerative response is Ca (OH) 2.This step is while regeneration alkali lye, and can precipitate the inferior sulfate radical of removal 85%, basicity can return to more than 40% of former alkali residue waste liquid, refines alkali lye after can supplementing fresh soda as treating oil by alkali washing.
In the inventive method, liquid hydrocarbon alkali residue waste liquid is the alkali residue waste liquid that liquid hydrocarbon soda finishing process produces.
The method of comprehensive utilization of high sulfur content height COD liquid hydrocarbon alkali residue waste liquid of the present invention has following features:
(1) sulfide and phenol can be reclaimed, reduce COD, after causticization regeneration, make alkali residue waste liquid resource utilization.
The inventive method technique contains and reclaims sulfide and phenol, after causticization regeneration and desalination, can add the alkali lye that fresh alkali lye refines as treating oil by alkali washing by certain proportion.Reclaim the principal pollutant matter of alkali residue waste liquid, make alkali residue waste liquid resource utilization, there is good economic benefit.
(2) concise in technology, flexible operation, investment operation expense is low.
The SO related in the present invention 2acidifying and causticization regenerative operation are simple, without the need to large scale investment.Operational condition is gentle, does not relate to high-temperature high-pressure apparatus.Integral device investment and process cost all lower.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the inventive method.
Wherein: 1-slag waste liquid, 2-nitrogen, 3-sulfur dioxide gas, 4-acidification reactor, 5-acidifying tail gas is sent to sulphur workshop, 6-dephenolize tank, and 7-reclaims crude phenols, 8-regeneration reactor, 9-lime/white lime, 10-reaction precipitation thing, and 11-regenerates water outlet.
Embodiment
The comprehensive treatment utilization method of high sulfur content height COD liquid hydrocarbon alkali residue waste liquid of the present invention mainly comprises the SO of alkaline residue 2acidifying and causticization regenerate two portions.
In the inventive method, as shown in Figure 1, first with N 2as carrier gas, carry under one's arms SO 2carry out acidifying to alkali residue waste liquid, reclaim the sulfide in waste water and phenol, sulfide clearance wherein can reach more than 99%, and volatile phenol clearance can reach more than 80%.Use Ca (OH) subsequently 2causticization regeneration is carried out to the alkaline residue water after acidifying, the sulfite ion that clearance can reach more than 85% can be precipitated simultaneously.Alkali lye after regeneration can add fresh alkali lye and refines alkali lye as treating oil by alkali washing by certain proportion.
Illustrate the inventive method and effect further below in conjunction with example, wherein percentage composition take quality as benchmark.
Embodiment 1
Certain enterprise's alkali cleaning liquid hydrocarbon alkali residue waste liquid, wherein COD is 1.27 × 10 5mg/L, sulfide is 1.08 × 10 4mg/L, volatile phenol 1.99 × 10 4mg/L.Use the inventive method process, first with N 2as carrier gas, carry under one's arms SO 2acidifying is carried out to alkali residue waste liquid, N 2/ SO 2=100(mol ratio), until the pH of alkali residue waste liquid is down to 3-4.Be sent to sulphur workshop Cross unit sulphur after using the organic sulfide in desulfuration adsorbent absorption tail gas, sweetening agent can be used by reprocessing cycle.Aqueous phase after acidifying, leaves standstill the phenol reclaimed with water stratification.Acidified process, removes sulfide more than 99.5%, removes phenol more than 80%, reduces COD more than 60%.
Use Ca (OH) 2carry out precipitation regeneration to the sour water after reclaiming phenol, produce calcium sulfite precipitation, inferior sulfate radical clearance can reach more than 85%, and basicity returns to 50% of former alkali residue waste liquid.Calcium sulfite roasting can obtain sulfurous gas and recycles.
Alkali residue waste liquid after the inventive method process, can add certain fresh alkali lye in proportion and refine alkali lye reuse as treating oil by alkali washing.
Embodiment 2
Certain enterprise's liquid hydrocarbon alkali residue waste liquid, wherein COD is 1.25 × 10 5mg/L, sulfide is 1.78 × 10 4mg/L, volatile phenol 7.17 × 10 4mg/L.Use the inventive method process, first with N 2as carrier gas, carry under one's arms SO 2acidifying is carried out to alkali residue waste liquid, N 2/ SO 2=50(mol ratio), until the pH of alkali residue waste liquid is down to 3-4.Be sent to sulphur workshop Cross unit sulphur after using the organic sulfide in desulfuration adsorbent absorption tail gas, sweetening agent can be used by reprocessing cycle.Aqueous phase after acidifying, leaves standstill the crude phenols reclaimed with water stratification.Acidified process, phase sulfur compound clearance can reach more than 99.7%, and phenol clearance can reach more than 80%, COD can reduce by more than 60%.
Use Ca (OH) 2carry out precipitation regeneration to the sour water after reclaiming phenol, produce calcium sulfite precipitation, inferior sulfate radical clearance can reach more than 85%, and basicity returns to 50% of former alkali residue waste liquid.
Alkali residue waste liquid after the inventive method process, can add certain fresh alkali lye in proportion and refine alkali lye reuse as treating oil by alkali washing.

Claims (9)

1. an integrated conduct method for liquid hydrocarbon alkali residue waste liquid, is characterized in that comprising following content:
(1) with N 2/ SO 2gas mixture liquid towards hydrocarbon alkali residue waste liquid carries out acidifying, and constantly strengthen along with waste liquid is acid, the sulfide in waste liquid is with H 2s form evaporates, when the pH value of waste liquid reaches 3 ~ 4, and stopping acidification process;
(2) tail gas discharged in acidification process in step (1), is sent to sulphur production installation for producing sulphur;
(3) waste liquid after step (1) acidification carries out sedimentation, and reclaim oil phase, be mainly crude phenols in oil phase, crude phenols reclaim further;
(4) the waste liquid lime after being separated oil phase in step (3) regenerates, and after isolating throw out, is cycled to used in liquid hydrocarbon soda finishing process.
2. in accordance with the method for claim 1, it is characterized in that: step (1) N 2/ SO 2in gas mixture, N 2/ SO 2mol ratio be 50:1 ~ 100:1.
3. in accordance with the method for claim 1, it is characterized in that: the acidification process of step (1), the sulfide clearance in alkali residue waste liquid is more than 99% in mass.
4. in accordance with the method for claim 1, it is characterized in that: the tail gas that step (2) obtains is re-used as the raw material of sulphur production installation after adopting the method organic sulfide removal compound of absorption.
5. in accordance with the method for claim 1, it is characterized in that: after being separated crude phenols operation in step (3), the clearance of phenol is more than 80%, COD in mass can clearance be more than 60%.
6. in accordance with the method for claim 1, it is characterized in that: the lime used in step (4) is white lime or unslaked lime, the material worked when there is regenerative response is Ca (OH) 2.
7. in accordance with the method for claim 1, it is characterized in that: step (4) is while regeneration alkali lye, and precipitation removes inferior sulfate radical, and basicity can return to more than 40% of former alkali residue waste liquid.
8. in accordance with the method for claim 7, it is characterized in that: precipitation is removed the throw out of inferior sulfate radical and carried out the SO that Roasting Decomposition obtains 2, and be cycled to used in the acidification step of step (1).
9. in accordance with the method for claim 1, it is characterized in that: liquid hydrocarbon alkali residue waste liquid is the alkali residue waste liquid that liquid hydrocarbon soda finishing process produces.
CN201110313313.9A 2011-10-17 2011-10-17 Comprehensive treatment method of liquid hydrocarbon alkali residue waste liquid CN103045289B (en)

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Publication number Priority date Publication date Assignee Title
CN104611003B (en) * 2013-11-05 2017-01-04 中国石油化工股份有限公司 The processing method of refinery alkaline residue
CN104607435B (en) * 2013-11-05 2017-01-04 中国石油化工股份有限公司 A kind of comprehensive processing method of sulfur-bearing alkaline residue
CN105712457B (en) * 2014-12-05 2018-07-20 中国石油化工股份有限公司 A kind of refinery basic sewage acidification reactor and debubbling method with defoaming function
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
CN105712456B (en) * 2014-12-05 2018-04-10 中国石油化工股份有限公司 A kind of processing method of alkali residue waste liquid
CN104984652A (en) * 2015-07-11 2015-10-21 河北新启元能源技术开发股份有限公司 Treating device for tail gas in acidifying refinement of alkaline residues and treating process thereof

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