CN205473139U - Alkaline residue waste liquid treatment device - Google Patents
Alkaline residue waste liquid treatment device Download PDFInfo
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- CN205473139U CN205473139U CN201620017048.8U CN201620017048U CN205473139U CN 205473139 U CN205473139 U CN 205473139U CN 201620017048 U CN201620017048 U CN 201620017048U CN 205473139 U CN205473139 U CN 205473139U
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Abstract
The utility model discloses an alkaline residue waste liquid treatment device, subside unit, oil phase recovery unit, tail gas processing unit and cooling crystal separation unit including the acidizing, wherein (1) acidizing subside the unit and include material conveying equipment, line mixer, acidizing settling cask, (2 )The oil phase is retrieved the unit and is included the refined equipment of oil phase storage tank and oil phase, (3 )Tail gas processing unit includes organic amine scrubbing tower and diesel oil absorption tower, (4 )Adjust jar, cooling crystal system and centrifuge with water during cooling crystal separation unit includes, wherein cool off the crystal system and include precooler, forced circulation pump, cooling heat exchanger, crystallizer and refrigerating unit etc.. The device not only can be in to the alkaline residue when high concentration sulphide and COD carry out efficient handling of, retrieves useful material in the alkaline residue waste liquid, realizes acidizing tail gas discharge to reach standard, in addition greatly reduced in with the salt content of water, avoided containing the impact of salt sewage to sewage disposal field.
Description
Technical field
This utility model belongs to environment-protection wastewater processing technology field, is specifically related to a kind of alkali residue waste liquid processing means, is particularly well-suited to refinery alkaline residue, ethylene and petrochemical industry Containing Sulfur sodium alkali residue waste liquid, the integrated treatment of acylate alkali residue waste liquid.
Background technology
During Refinery Oil alkali refining, or in ethene cracking gas sodium hydroxide solution alkaline cleaning procedure, the alkaline waste liquor containing high density pollution thing can be produced, the discharge capacity of its COD, sulfide and phenol accounts for the biggest proportion of oil plant or this type of pollutant discharge amount of ethylene plant, is mainly made up of ordinary pressure diesel alkaline residue, FCC gasoline caustic sludge, catalytic diesel oil alkaline residue, liquid hydrocarbon alkali residue, ethylene alkaline residue etc..These alkali residue waste liquid, if directly discharged, can serious environment pollution；If being passed to sewage farm, it will have a strong impact on the normal operating in sewage farm, sewage is made to be difficult to qualified discharge, and severe corrosion equipment.Alkaline residue problem generally exists at oil plant.In the last few years, along with national environmental protection regulation, standard are the most complete and strict, and people were more and more higher to the cry improving environmental quality, and the process of alkaline residue increasingly comes into one's own.In these several alkaline residues, what sulfide content was the highest is coker gasoline and diesel alkaline residue, liquid hydrocarbon alkali residue and ethylene alkaline residue, commonly use wet oxidation at present to process, oxidation waste liquid sulphuric acid neutralizes, and reclaims phenol, petroleum acids, produces in alkaline residue and water, but COD is the highest, up to 30000-60000mg/L, and create substantial amounts of salt in oxidation and N-process, the sewage farm of Petrochemical Enterprises is impacted the biggest.Ordinary pressure diesel alkaline residue mainly contains petroleum acids, processes with recovery aphthenic acids, produce in diesel alkaline residue and water in commonly used sulphuric acid, and COD is relatively low, but salinity is the highest, just can enter sewage farm after needing Macrodilution.
For the process of high sulfur-bearing height COD alkali residue waste liquid, some patent proposes different processing meanss.
CN200720169916.5 discloses the processing means of a kind of alkaline sewage, and including biochemical treatment unit, and microelectrolysis processing unit is or/and coagulating kinetics unit；Microelectrolysis processing unit is made up of cloth pond and electrolyzer, and coagulating kinetics unit is made up of coagulating basin and sedimentation tank, and biochemical treatment unit is made up of intake pool and multi-stage aeration biological filter tank；BAF is separated into multiple space cell equipped with biologic packing material bed, the inside of this packed bed by filter, and each space cell is filled with Active biological filler, and the lower section of packed bed sets aerating pipelines.This device is applicable to the process of high-concentration wastewater containing alkaline mud, has COD, ammonia nitrogen, sulfide removal effective, to features such as the tolerance height of petroleum-type, shock resistances.This patent does not accounts for the recovery of the petroleum acids materials such as phenol, and economy is the highest.
CN200920199634.9 discloses the processing means of the alkaline residue that a kind of Light Oil Desulfurization produces, including light-end products input pipe, carbon dioxide tank, blender, fiber-film contact, settling tank, alkali liquor circulation pipe, alkali liquor input pipe, dilution water input pipe and waste liquid outlet tube, connect on alkali liquor input pipe and have alkali liquor oxidized tower, gas distributor and heater it is provided with in alkali liquor oxidized tower, the bottom of alkali liquor oxidized tower is provided with air inlet duct, the top of alkali liquor oxidized tower is provided with alkaline residue input pipe, and the top of alkali liquor oxidized tower is provided with offgas duct；Sodium mercaptides, oxidizing sodium sulphide are become sodium hydroxide, disulphide, sulfate etc. by alkaline residue in alkali liquor oxidized tower by so this device, sodium hydroxide is carbonized into sodium bicarbonate at fiber-film contact and separates with oil product, it is dissolved in refuse liquid, therefore this utility model is the environment-friendly processing unit of alkaline residue that a kind of Light Oil Desulfurization produces, and after making process, waste liquid reaches the quality of emission request that biological tank processes the light-end products that can improve extracting.The tail gas containing sulfide that this device produces, uses burning disposal, can produce containing SO2Waste gas, need to process further.Use the Organic substance of light-end products extracting acidization, but increasingly strict along with oil quality, the problem that oil quality is the most up to standard can be faced.
CN200520145126.4 discloses a kind of batch-type wastewater with high concentration of sulfide and alkali residue waste liquid processing means, in apparatus main body, order arranges the first desulfurization zone, second desulfurization zone, desalination district, deamination district and intermediate pool, deamination district and intermediate pool are placed in above desalination district, it is possible to arrange along length or width；Being respectively equipped with alkaline sewage water inlet pipe, adding of agent mouth, compressed air inlet, collection and confinement of gases mouth and water decanter on two desulfurization zones, intermediate pool is provided with water circulating pump, outlet；Desalination district is provided with device outlet and discharge pipeline；First desulfurization zone, the second desulfurization zone, desalination district and intermediate pool are respectively equipped with device evacuated tube；Deamination district is provided with gas feed, spray inlet and gas discharge outlet.This device is at iron content saline solution or other are containing by air oxidation, sulfides from wastewater being converted into sulfate under iron complexes effect, and add lime cream sulfate is precipitated out from water, achieve sulfides from wastewater removal more thoroughly, the ammonia in waste water is effectively treated simultaneously.This patent does not accounts for the recovery of the petroleum acids materials such as phenol yet, and economy is the highest.
CN02100855.8 discloses a kind of for petrochemical industry acid water with the desulfurization of alkaline residue, deamination, phenol removal device, this device includes desulfurizer and Gas feeding biological tower filter tank, wherein in desulfurizer, carry out desulfurization by addition iron salt and compressed air, it is passed through compressed air to Gas feeding biological tower filter tank, utilizes microorganism therein to carry out deamination and dephenolize.This invention does not accounts for the recovery of the petroleum acids materials such as phenol, and also without reference to producing the process problem of tail gas in processing procedure, environmental benefit and economic benefit are poor.
Utility model content
For the deficiencies in the prior art, this utility model provides a kind of alkali residue waste liquid processing means.This device includes being acidified sedimentation unit, oil phase recovery unit, tail gas treating unit and crystallisation by cooling separative element, can be while alkaline residue middle and high concentration sulfide and COD be efficiently treated through, reclaim utility in alkali residue waste liquid, realize acidifying tail gas qualified discharge, and greatly reduce the salt content neutralizing water, it is to avoid the saline sewage impact to sewage farm.
This utility model alkali residue waste liquid processing means, including acidifying sedimentation unit, oil phase recovery unit, tail gas treating unit and crystallisation by cooling separative element, wherein:
(1) acidifying sedimentation unit includes material transfer equipment, pipe-line mixer, acidifying settling tank, described material transfer equipment is for being delivered to alkali residue waste liquid, acidizing reagent and inert carrier gas be acidified in settling tank, pipe-line mixer for realizing being sufficiently mixed of alkali residue waste liquid and acidizing reagent, acidifying settling tank standing sedimentation after alkali residue waste liquid acidification reaction；
(2) petroleum acids such as oil phase recovery unit includes oil phase storage tank and oil phase purification apparatus, the phenol that oil phase storage tank is discharged for storing acidifying precipitation apparatus, oil phase purification apparatus is for discharging the refined recovery of oil phase；
(3) tail gas treating unit includes organic amine scrubbing tower and diesel oil absorption tower, and organic amine scrubbing tower is for removing the H in tail gas by organic amine absorbing liquid after tail gas counter current contacting2S, diesel oil absorption tower is for absorbing the organic sulfur compound in tail gas；
(4) crystallisation by cooling separative element includes neutralizing water regulation tank, crystallisation by cooling system and centrifugal separator, neutralize water regulation tank for being collected and regulate pH by the acid waste liquid of acidifying precipitation apparatus bottom and oil phase tank bottom, neutralization water after regulation is sent to after crystallisation by cooling system carries out crystallisation by cooling, solid-liquid separation is carried out with centrifugal separator, thus realizing the purpose of acid waste liquid desalination, the waste liquid after desalination is sent to biochemical treatment tank.
In this utility model, the material transfer equipment of acidifying sedimentation unit includes carrying the alkaline residue pump of alkali residue waste liquid, the sulfuric acid pump of conveying sulphuric acid, the compressor of conveying inert carrier gas or blower fan etc..Alkali residue waste liquid is through alkaline residue transport pump, and sulphuric acid carries through sulfuric acid pump, after the two is sufficiently mixed in pipe-line mixer, acidification reaction occurs, and enters acidifying settling tank and settles.Being provided with pH monitoring in acidifying settling tank, by regulating the amount of sulphuric acid, in control acidifying settling tank, the pH of alkali residue waste liquid is 2-7, preferably 2-4, the beneficially removing of the petroleum acids such as sulfide and phenol.Being provided with aerating system bottom acidifying settling tank, be passed through inert carrier gas such as nitrogen etc. at pot bottom, pneumatically supported effect is played in carrier gas, is on the one hand conducive to the petroleum acids such as phenol separated from the water, is on the other hand conducive to sulfide to remove the most thoroughly.Inert carrier gas transfer pipeline is provided with the anti-down flow tube of inverted U or one-way cock, prevents waste liquid from flowing backwards.Pipe-line mixer uses resistant material, such as carbon steel lining anti-corrosion material etc..The petroleum acids such as the phenol after acidifying sedimentation enter oil phase storage tank, and acid waste liquid enters and neutralizes water regulation tank.
In this utility model, it is provided with oil phase gravity line between acidifying settling tank and oil phase storage tank, oil phase can enter oil phase storage tank by liquid level difference gravity flow, reclaimed from pumping toward oil phase purification apparatus again, oil phase purification apparatus is mainly used in refining of crude phenol, improve the added value that alkali residue waste liquid processes, reduce processing cost.
In this utility model, acidifying settling tank, oil phase storage tank and neutralization water regulate the tank deck expellant gas such as tank, enter from organic amine wash tower bottoms, remove the H in tail gas after the organic amine absorbing liquid counter current contacting of top spray2S, organic amine absorbing liquid selects MDEA(N-methyl diethanolamine), rich absorbing liquid returns refinery's MDEA regenerative system.Organic amine scrubbing tower top is provided with froth breaking facility, prevents foam and liquid entrainment.Acidifying tail gas is through organic amine washing removing H2After S, entering diesel oil absorption tower, with qualified discharge after low temperature diesel oil absorption organic sulfur compound, diesel oil selection is treated that the raw oil of hydrotreating, rich diesel oil absorbent mix with Hydrogenation raw oil and is carried out hydrotreating.
In this utility model, being provided with inverted U gravity line between acidifying settling tank and neutralization water regulation tank, acid waste liquid is certainly flow to neutralize water and regulates tank by inverted U gravity line.It is provided with pH on-line monitoring in neutralizing water regulation tank, mends alkali pipeline, stirring facility and delivery pump etc., using sodium hydroxide lye regulation to neutralize water pH is 6-8, delivering to crystallisation by cooling separative element by delivery pump, water outlet meets the inflow requirement in petroleum chemical enterprise sewage farm.Inverted U gravity line top arranges exhaust line, is connected with acidifying exhaust pipe, it is to avoid air-resistance phenomenon occurs in inverted U gravity line.
In this utility model, crystallisation by cooling system includes precooler, forced circulation pump, cooling heat exchanger, crystallizer and refrigeration unit etc., acid waste liquid regulates to suitable pH the precooler pre-cooling sending into crystallisation by cooling system in neutralizing water regulation tank, the low-temperature receiver of precooler is the cold mother liquor flowed out from crystallizer, neutralization water after pre-cooling enters crystallizer after again cooling down in forced circulation pump is sent to cooling heat exchanger, the low-temperature receiver of cooling heat exchanger is that refrigeration unit is circulated refrigeration to working media, neutralization water after cooling heat transferring enters in crystallizer, degree of supersaturation is produced in crystallizer tank body and crystal contact at liquid level, degree of supersaturation fades away, crystal is the most slowly grown up.The cold mother liquor produced enters in precooler as low-temperature receiver, through its change a thermogenetic hot mother liquor part by forced circulation pump be re-delivered in cooling heat exchanger continue crystallisation by cooling, thus adjusting the magma density in crystallizer, another part hot mother liquor is drained in biochemical treatment tank as waste water and carries out advanced treating.The satisfactory slurry that crystalliser feet produces enters centrifugal separator and separates, the salt based on sodium sulfate obtained after separation carries out burning or processing together as solid waste with sewage farm biochemical treatment tank activated sludge, and cold mother liquor produced by the liquid phase being centrifugally separating to obtain and above-mentioned crystallisation by cooling system mixes and is drained in precooler.
In this utility model, in alkaline residue with water after crystallisation by cooling separative element processes, its COD(chromium method, lower same) < 25000mg/L, and salinity < 7%, substantially meet entrance biochemical treatment tank index.And due to the removing of salt, the pending wastewater flow rate entering biochemical treatment tank also substantially reduces.
This utility model alkali residue waste liquid processing means is while being efficiently treated through alkaline residue middle and high concentration sulfide and COD, reclaim the utility in alkali residue waste liquid as far as possible, realize whole processing procedure and produce focusing on and qualified discharge of acidifying tail gas, and greatly reduce the salt content neutralizing water, it is directly entered biochemical treatment without dilution, decreases the saline sewage impact to sewage farm.This utility model makes the intractable alkali residue waste liquid of high harm be effectively addressed and reuse, it is to avoid its impact on sewage disposal system, has good environmental benefit and economic benefit.
Accompanying drawing explanation
Fig. 1 is the process chart of this utility model processing means；
Wherein: 1-alkaline residue pump, 2-sulfuric acid pump, 3-pipe-line mixer, the anti-down flow tube of 4-inverted U, 5-is acidified settling tank, 6-acidizing waste fluid pH monitors, 7-inverted U gravity line, 8-oil phase storage tank, 9-oil phase delivery pump, with water pH on-line monitoring in 10-, 11-regulates tank with water, 12-mixing plant, with water delivery pump in 13-, 14-organic amine scrubbing tower, 15-organic amine-rich delivery pump, 16-froth breaking facility, 17-oil phase purification apparatus, 18-diesel oil absorption tower, 19-biochemical treatment tank, 20-organic amine-rich regeneration of absorption solution system, 21-precooler, 22-forced circulation pump, 23-cooling heat exchanger, 24-refrigeration unit, 25-crystallizer, 26-centrifugal separator, 27-fixed-end forces system；
101-alkali residue waste liquid, 102-sulphuric acid, 103-acid waste liquid, the petroleum acids such as 104-phenol, 105-NaOH alkali liquor, in 106-alkaline residue and water, neutralize water after 107-pre-cooling, after 108-cooling, neutralize water, 109-slurry, the 110-salt based on sodium sulfate, the liquid phase that 111-is centrifugally separating to obtain, 112-cold mother liquor, 113-hot mother liquor, the cold working media of 114-, 115-thermodynamic medium；
201-inert carrier gas, 202-acidifying tail gas is (containing H2S and organic sulfur compound), 203-lean organic amine absorbing liquid, 204-organic amine-rich absorbing liquid, 205-removes H2Tail gas (containing organic sulfur compound) it is acidified after S.
Detailed description of the invention
With embodiment, this utility model is further described below in conjunction with the accompanying drawings.
This utility model alkali residue waste liquid processing means is as it is shown in figure 1, include being acidified sedimentation unit, oil phase recovery unit, tail gas treating unit and crystallisation by cooling separative element.
Acidifying sedimentation unit includes alkaline residue pump 1, sulfuric acid pump 2, pipe-line mixer 3, acidifying settling tank 5, alkali residue waste liquid 101 carries through alkaline residue pump 1, sulphuric acid 102 carries through sulfuric acid pump 2, after the two is sufficiently mixed in pipe-line mixer 3, enters acidifying settling tank 5 and settles.PH monitoring 6 it is provided with in acidifying settling tank, by regulating the amount of sulphuric acid, the removing that pH is 2-7, preferably 2-4, beneficially sulfide and petroleum acids of alkali residue waste liquid in control acidifying settling tank.It is provided with aerating system bottom acidifying settling tank, is passed through inert carrier gas 201 such as nitrogen at pot bottom, play pneumatically supported effect, be on the one hand conducive to the petroleum acids such as phenol separated from the water, be on the other hand conducive to sulfide to remove the most thoroughly.Inert carrier gas transfer pipeline is provided with the anti-down flow tube of inverted U 4, prevents waste liquid from flowing backwards.By in sulphuric acid and alkali residue waste liquid, can efficiently remove the sulfide in alkali residue waste liquid and crude phenols, reduce the COD of waste liquid.
Oil phase recovery unit includes oil phase storage tank 8 and oil phase purification apparatus 17, and the upper oil phase after acidifying sedimentation enters in oil phase storage tank, then uses oil phase purification apparatus to carry out refinement treatment, reclaims the petroleum acids 104 such as phenol.It is provided with oil phase gravity line between acidifying settling tank 5 and oil phase storage tank 8, oil phase can flow automatically and enter oil phase storage tank 8, being sent to oil phase purification apparatus by oil phase delivery pump 9 again reclaim, oil phase purification apparatus is mainly used in refining of crude phenol, improves the added value that alkali residue waste liquid processes.
Tail gas treating unit includes organic amine scrubbing tower 14 and diesel oil absorption tower 18, the acidifying tail gas 202 that acidifying settling tank 5, oil phase storage tank 8 and neutralization water regulation tank 11 tank deck are discharged, enter bottom organic amine scrubbing tower 14, remove the H in tail gas after lean organic amine absorbing liquid 203 counter current contacting of top spray2S.Organic amine scrubbing tower top is provided with froth breaking facility 16, and organic amine-rich absorbing liquid 204 is sent to refinery's organic amine-rich regeneration of absorption solution system 20 by organic amine-rich delivery pump 15.Acidifying tail gas is through organic amine washing removing H2The acidifying tail gas 205 containing organic sulfur compound after S, enters diesel oil absorption tower 18, and with qualified discharge after low temperature diesel oil absorption organic sulfur compound, diesel oil selection is treated that the raw oil of hydrotreating, rich diesel oil absorbent mix with Hydrogenation raw oil and carried out hydrotreating.
Being provided with inverted U gravity line 7 between acidifying settling tank 5 and neutralization water regulation tank 11, acid waste liquid 103 certainly flow to neutralize water by inverted U gravity line 7 and regulates tank 11.It is provided with neutralization water pH on-line monitoring 10, stirring facility 12 in neutralizing water regulation tank, neutralizes water delivery pump 13 etc., using sodium hydroxide lye 105 regulation to neutralize water pH is 6-8, delivers to Crystallization Separation unit by neutralization water delivery pump 13 process with water 106 in alkaline residue.
Crystallisation by cooling separative element includes neutralizing water regulation tank 11, crystallisation by cooling system and centrifugal separator 26, neutralize the water regulation tank 11 acid waste liquid 103 bottom by acidifying settling tank 5 bottom and oil phase storage tank 8 collect and regulate pH, in alkaline residue after regulation and water 106 is sent into after crystallisation by cooling system carries out crystallisation by cooling, solid-liquid separation is carried out with centrifugal separator 26, thus realizing the purpose of acid waste liquid desalination, the waste liquid after desalination is sent to biochemical treatment tank 19.
Crystallisation by cooling system includes precooler 21, forced circulation pump 22, cooling heat exchanger 23, refrigeration unit 24 and crystallizer 25, alkaline residue is delivered to precooler 21 pre-cooling with water 106 neutralized water delivery pump 13, the low-temperature receiver of precooler 21 is the cold mother liquor 112 flowed out from crystallizer, neutralization water 107 after pre-cooling enters crystallizer 25 after again cooling down during forced circulation pump 22 is sent to cooling heat exchanger 23, the low-temperature receiver of cooling heat exchanger 23 is refrigeration unit 24 working media cold to working media 114(), 115(thermodynamic medium) it is circulated refrigeration, neutralize water 108 after cooling and enter in crystallizer 25, degree of supersaturation is produced in crystallizer 25 tank body and crystal contact at liquid level, degree of supersaturation fades away, crystal is the most slowly grown up.The cold mother liquor 112 produced enters in precooler 21 as low-temperature receiver, change thermogenetic hot mother liquor 113 part through it to be re-delivered in cooling heat exchanger 23 continue crystallisation by cooling by forced circulation pump 22, thus adjusting the magma density in crystallizer, another part hot mother liquor is drained in biochemical treatment tank 19 as waste water and carries out advanced treating.The satisfactory slurry 109 produced bottom crystallizer 25 enters centrifugal separator 26 and separates, and the salt 110 based on sodium sulfate obtained after separation can carry out burning or entering together with the biochemical treatment tank activated sludge of sewage farm in fixed-end forces system 27 processing.Cold mother liquor 112 produced by the liquid phase 111 being centrifugally separating to obtain and above-mentioned crystallisation by cooling system mixes and is drained in precooler 21.
After above-mentioned process, the efficient process of alkali residue waste liquid middle and high concentration sulfide and COD can be realized, utility in Recycling of waste liquid, realize processing procedure produces the qualified discharge of tail gas, and greatly reduce the salt content neutralizing water, it is directly entered biochemical treatment tank without Macrodilution, decreases the saline sewage impact to sewage farm.
Embodiment 1
The FCC gasoline caustic sludge of certain enterprise and the alkali residue waste liquid of liquid hydrocarbon alkali residue mixing, wherein COD is 3.21 × 105Mg/L, sulfide is 1.99 × 104Mg/L, volatile phenol is 1.07 × 105mg/L.Using the device shown in this utility model Fig. 1 to process, set pH monitoring in acidifying settling tank, in control acidifying settling tank, the pH of alkali residue waste liquid is 3, employs nitrogen as carrier gas.By in sulphuric acid and alkali residue waste liquid, can efficiently remove the sulfide in alkali residue waste liquid and crude phenols, reduce the COD of waste liquid.Upper oil phase after acidifying sedimentation enters in oil phase storage tank, then uses oil phase purification apparatus to carry out refinement treatment, reclaims the petroleum acids such as crude phenols.The acidifying tail gas that acidifying settling tank, oil phase storage tank and neutralization water regulation tank tank deck are discharged, enters from organic amine wash tower bottoms, removes the H in tail gas after the lean organic amine absorbing liquid counter current contacting of top spray2S.Organic amine scrubbing tower top is provided with froth breaking facility, and organic amine-rich absorbing liquid is sent to refinery's organic amine regeneration of absorption solution system by organic amine-rich delivery pump.Acidifying tail gas is through organic amine washing removing H2After S containing organic sulfur compound gas, enter diesel oil absorption tower, absorb qualified discharge after organic sulfur compound with low temperature diesel oil, diesel oil is selected the gas-oil treating hydrotreating, rich diesel oil absorbent to mix with Hydrogenation raw oil to carry out hydrotreating.Neutralize water regulation tank for collecting acidifying settling tank bottom and the acid waste liquid of oil phase tank bottom, and regulate pH, using sodium hydroxide lye regulation to neutralize water pH is 6-8, neutralize salinity in water and reach 15%-25%, predominantly sodium sulfate salt, crystallisation by cooling system is delivered to by delivery pump, neutralization water is down to 0 DEG C, through centrifugation, processed waste water salinity is 4%-6%, sodium sulfate crystal carries moisture content, after crystallization treatment, the water yield reduces about 50%, again through a small amount of dilution heel row toward biochemical treatment tank, water outlet meets the inflow requirement in petroleum chemical enterprise sewage farm.The salt based on sodium sulfate obtained after separation can carry out burning or processing together as solid waste with sewage farm biochemical treatment tank activated sludge.After above-mentioned process, organic sulfur compound and H2S removes the most completely, and volatile phenol clearance is more than 99.5%, and alkali residue waste liquid COD clearance after biochemical treatment is more than 99.0%.
Embodiment 2
The FCC gasoline caustic sludge of certain enterprise, catalytic diesel oil and the alkali residue waste liquid of liquid hydrocarbon alkali residue mixing, wherein COD is 2.35 × 105Mg/L, sulfide is 3.68 × 104Mg/L, volatile phenol is 5.89 × 104mg/L.Using the method shown in this utility model Fig. 1 to process, set pH monitoring in acidifying settling tank, in control acidifying settling tank, the pH of alkali residue waste liquid is 5, employs nitrogen as carrier gas.By in sulphuric acid and alkali residue waste liquid, can efficiently remove the sulfide in alkali residue waste liquid and crude phenols, reduce the COD of waste liquid.Upper oil phase after acidifying sedimentation enters in oil phase storage tank, then uses oil phase purification apparatus to carry out refinement treatment, reclaims the petroleum acids such as crude phenols.The acidifying tail gas that acidifying settling tank, oil phase storage tank and neutralization water regulation tank tank deck are discharged, enters from organic amine wash tower bottoms, removes the H in tail gas after the lean organic amine absorbing liquid counter current contacting of top spray2S.Organic amine scrubbing tower top is provided with froth breaking facility, and organic amine-rich absorbing liquid is sent to refinery's organic amine regeneration of absorption solution system by organic amine-rich delivery pump.Acidifying tail gas is through organic amine washing removing H2After S containing organic sulfur compound gas, enter diesel oil absorption tower, absorb qualified discharge after organic sulfur compound with low temperature diesel oil, diesel oil is selected the gas-oil treating hydrotreating, rich diesel oil absorbent to mix with Hydrogenation raw oil to carry out hydrotreating.Neutralize water regulation tank for collecting acidifying settling tank bottom and the acid waste liquid of oil phase tank bottom, and regulate pH, using sodium hydroxide lye regulation to neutralize water pH is 6-8, neutralize salinity in water and reach 10%-20%, predominantly sodium sulfate salt, crystallisation by cooling system is delivered to by delivery pump, neutralization water is down to-5 DEG C, through centrifugation, processed waste water salinity is 3%-5%, sodium sulfate crystal carries moisture content, after crystallization treatment, the water yield reduces about 50%, again through a small amount of dilution heel row toward biochemical treatment tank, water outlet meets the inflow requirement in petroleum chemical enterprise sewage farm.The salt based on sodium sulfate obtained after separation can carry out burning or processing together as solid waste with sewage farm biochemical treatment tank activated sludge.After above-mentioned process, organic sulfur compound and H2S clearance is 99.9%, and volatile phenol clearance is more than 98.8%, and alkali residue waste liquid COD clearance after biochemical treatment is more than 98.5%.
Claims (10)
1. an alkali residue waste liquid processing means, it is characterised in that include being acidified sedimentation unit, oil phase recovery unit, tail gas treating unit and crystallisation by cooling separative element, wherein:
(1) acidifying sedimentation unit includes material transfer equipment, pipe-line mixer, acidifying settling tank, described material transfer equipment is for being delivered to alkali residue waste liquid, acidizing reagent and inert carrier gas be acidified in settling tank, pipe-line mixer for realizing being sufficiently mixed of alkali residue waste liquid and acidizing reagent, acidifying settling tank standing sedimentation after alkali residue waste liquid acidification reaction；
(2) oil phase recovery unit includes oil phase storage tank and oil phase purification apparatus, and oil phase storage tank is for storing the phenols petroleum acids that acidifying precipitation apparatus is discharged, and oil phase purification apparatus is for discharging the refined recovery of oil phase；
(3) tail gas treating unit includes organic amine scrubbing tower and diesel oil absorption tower, and organic amine scrubbing tower is for removing the H in tail gas by organic amine absorbing liquid after tail gas counter current contacting2S, diesel oil absorption tower is for absorbing the organic sulfur compound in tail gas；
(4) crystallisation by cooling separative element includes neutralizing water regulation tank, crystallisation by cooling system and centrifugal separator, neutralize water regulation tank for being collected and regulate pH by the acid waste liquid of acidifying precipitation apparatus bottom and oil phase tank bottom, neutralization water after regulation is sent to after crystallisation by cooling system carries out crystallisation by cooling, solid-liquid separation is carried out with centrifugal separator, thus realizing the purpose of acid waste liquid desalination, the waste liquid after desalination is sent to biochemical treatment tank.
Device the most according to claim 1, it is characterised in that: the material transfer equipment of described acidifying sedimentation unit includes carrying the alkaline residue pump of alkali residue waste liquid, the sulfuric acid pump of conveying sulphuric acid, the compressor of conveying inert carrier gas or blower fan.
Device the most according to claim 1, it is characterised in that: being provided with pH monitoring in described acidifying settling tank, by regulating the amount of sulphuric acid, in control acidifying settling tank, the pH of alkali residue waste liquid is 2-7；It is provided with aerating system, for being passed through inert carrier gas at pot bottom bottom described acidifying settling tank.
Device the most according to claim 1, it is characterised in that: on inert carrier gas transfer pipeline, it is provided with the anti-down flow tube of inverted U or one-way cock, prevents waste liquid from flowing backwards；Being provided with oil phase gravity line between acidifying settling tank and oil phase storage tank, oil phase can enter oil phase storage tank by liquid level difference gravity flow, then is reclaimed from pumping toward oil phase purification apparatus.
Device the most according to claim 1, it is characterised in that: acidifying settling tank, oil phase storage tank and neutralization water regulation tank tank deck expellant gas, enter from organic amine wash tower bottoms, remove the H in tail gas after the organic amine absorbing liquid counter current contacting of top spray2S, organic amine absorbing liquid selects MDEA(N-methyl diethanolamine), rich absorbing liquid returns refinery's MDEA regenerative system.
Device the most according to claim 1 or 5, it is characterised in that: organic amine scrubbing tower top is provided with froth breaking facility, prevents foam and liquid entrainment.
Device the most according to claim 1, it is characterized in that: be provided with pH on-line monitoring in neutralizing water regulation tank, mend alkali pipeline, stirring facility and delivery pump, using sodium hydroxide lye regulation to neutralize water pH is 6-8, delivering to crystallisation by cooling separative element by delivery pump, water outlet meets the inflow requirement in petroleum chemical enterprise sewage farm.
Device the most according to claim 1, it is characterised in that: being provided with inverted U gravity line between acidifying settling tank and neutralization water regulation tank, acid waste liquid is certainly flow to neutralize water and regulates tank by inverted U gravity line.
Device the most according to claim 8, it is characterised in that: inverted U gravity line top arranges exhaust line, is connected with acidifying exhaust pipe, it is to avoid air-resistance phenomenon occurs in inverted U gravity line.
Device the most according to claim 1, it is characterized in that: crystallisation by cooling system includes precooler, forced circulation pump, cooling heat exchanger, crystallizer and refrigeration unit, acid waste liquid regulates to suitable pH the precooler pre-cooling sending into crystallisation by cooling system in neutralizing water regulation tank, the low-temperature receiver of precooler is the cold mother liquor flowed out from crystallizer, neutralization water after pre-cooling enters crystallizer after again cooling down in forced circulation pump is sent to cooling heat exchanger, the low-temperature receiver of cooling heat exchanger is that refrigeration unit is circulated refrigeration to working media, neutralization water after cooling heat transferring enters in crystallizer, degree of supersaturation is produced in crystallizer tank body and crystal contact at liquid level, degree of supersaturation fades away, crystal is the most slowly grown up；The cold mother liquor produced enters in precooler as low-temperature receiver, through its change a thermogenetic hot mother liquor part by forced circulation pump be re-delivered in cooling heat exchanger continue crystallisation by cooling, thus adjusting the magma density in crystallizer, another part hot mother liquor is drained in biochemical treatment tank as waste water and carries out advanced treating.
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| CN201620017048.8U CN205473139U (en) | 2016-01-11 | 2016-01-11 | Alkaline residue waste liquid treatment device |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117208A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | The processing method and processing unit of a kind of alkali residue waste liquid |
| CN109019955A (en) * | 2018-08-06 | 2018-12-18 | 陈式好 | A kind of petroleum liquid waste treatment system |
| CN109292860A (en) * | 2018-06-12 | 2019-02-01 | 华北水利水电大学 | Falling film evaporation couples absorption refrigeration high-salt sewage processing equipment and high-salt sewage processing method |
-
2016
- 2016-01-11 CN CN201620017048.8U patent/CN205473139U/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117208A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | The processing method and processing unit of a kind of alkali residue waste liquid |
| CN108117208B (en) * | 2016-11-29 | 2020-09-11 | 中国石油化工股份有限公司 | Treatment method and treatment device for alkaline residue waste liquid |
| CN109292860A (en) * | 2018-06-12 | 2019-02-01 | 华北水利水电大学 | Falling film evaporation couples absorption refrigeration high-salt sewage processing equipment and high-salt sewage processing method |
| CN109019955A (en) * | 2018-08-06 | 2018-12-18 | 陈式好 | A kind of petroleum liquid waste treatment system |
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