CN109455789A - The purification method of coking distilled ammonia wastewater - Google Patents
The purification method of coking distilled ammonia wastewater Download PDFInfo
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- CN109455789A CN109455789A CN201811490467.3A CN201811490467A CN109455789A CN 109455789 A CN109455789 A CN 109455789A CN 201811490467 A CN201811490467 A CN 201811490467A CN 109455789 A CN109455789 A CN 109455789A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
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Abstract
The present invention relates to a kind of purification method of coking distilled ammonia wastewater, mainly solves ammon amount height in distilled ammonia wastewater, oil content is big, influences the technical issues of operation of subsequent biochemical device is discharged.The present invention passes through the following steps are included: the distilled ammonia wastewater of coke-oven plant is pre-processed by adsorbent A, remove the part tar ingredients in remained ammonia, distilled ammonia wastewater after tar removing is sent into the adsorption tower for being filled with crystallite adsorbent B, adsorb the ammonia and oil in remained ammonia, waste water after absorption is sent into wastewater biochemical pond, adsorbent B after adsorption saturation solves above-mentioned technical problem with the technical solution continued to use after 50 ~ 400 DEG C of nitrogen or steam regeneration.The processing method can be used for coking wastewater except in the industrial production of ammonia.
Description
Technical field
The invention belongs to the ammonia-removal methods of distilled ammonia wastewater in Treatment of Coking Effluent field, especially coking wastewater.
Background technique
Coking wastewater mostlys come from the subtractive process of coking, gas purification and chemical products, for high concentration containing phenol, cyanogen,
The waste water of oil, ammonia nitrogen and toxic organics, wherein using remained ammonia as main source.Remained ammonia passes through the steaming after ammonia still process
Ammonia waste water still contains the no small tar of concentration, solid ammonium-salt, phenol cyanogen class.Tar, phenol cyanogen class, ammonia nitrogen substances enter biochemical treatment
When device, bioactivity can be significantly inhibited, increases the load of biochemical treatment apparatus, influences final wastewater treatment efficiency.Ammonia still process
The current difficulty in treatment of waste water is how the total phenol of high concentration effectively to be removed from waste water, and solve the precondition of the difficult point
It is first to solve the oil removing problem before dephenolize.After pre-processing oil removing Resolving probiems, solvent dephenolize can be only achieved target, waste water
In COD be substantially reduced, the ammonia nitrogen and COD index into biochemical system waste water are effectively controlled, sewage treatment each unit
Stable operation.Therefore, it in order to mitigate biochemical system processing load, the effective qualified discharge of coking wastewater or recycling, needs pair
Distilled ammonia wastewater carries out oil removing advanced treating.
Absorption method is as a kind of common method for treating water, by the adsorptivity using porous solid, to handle in water
Pollutant has the advantages that applied widely, treatment effect is obvious, process is simple and recyclable utility, therefore
Water treatment field has obtained more and more concerns.Most common adsorbent is active carbon, and active carbon is since usage amount is big,
Regeneration is difficult, mostly as the supplementary means of other wastewater treatments, such as is combined etc. with membrane technology combination, with ozone.
Chinese patent CN201610611939.0 is related to a kind of wastewater treatment equipment, and the wastewater treatment equipment is by filtering
Pond, evaporation tank and active carbon water treating pond composition, filtering bottom of pond portion and evaporation tank top are connected, evaporation tank top surface and active carbon water
Processing pond top surface is connected, and coarse filtration film and refined filtration film are equipped in the filtering ponds, and the evaporation bottom of pond portion is equipped with heating device, evaporation
One lateral roof of pond is equipped with fan, is equipped with active carbon water process layer, active carbon water treating pond bottom in the active carbon water treating pond
Equipped with discharge outlet；Sufficiently, when COD is 600mg/L in waste water, the removal rate of COD is 80-90% for filtering；When COD is lower than in waste water
The removal rate of 500 mg/L, COD are 90-99%.This method does not mention the effect of the oil removing of active carbon energy and oil removing.
Chinese patent 201210119762.4 discloses the renewable difficult biology of Powdered Activated Carbon processing that recycles of one kind and drops
Solve the PACT new process of waste water, comprising the following steps: 1) Powdered Activated Carbon to precipitate in secondary settling tank and biology is living
Property sludge extraction；2) Powdered Activated Carbon and biological activated sludge of step 1) extraction are carried out dehydrating；3) to step
2) the dewatered Powdered Activated Carbon and biological activated sludge obtained be successively dried, destructive distillation and activation processing, keeps powder living
Property charcoal absorption organic matter decompose volatilization, biological activated sludge pyrolysis be active carbon；4) product for obtaining step 3) is milled
It is used afterwards as regeneration Powdered Activated Carbon investment biochemistry pool.In the present invention, after Powdered Activated Carbon is dehydrated with biological activated sludge
It is regenerated through drying, destructive distillation and activation processing, while biological activated sludge pyrolysis is active carbon, and it is living to have reached recycling powder
The purpose of property charcoal and biological activated sludge, greatly reduces the operating cost of PACT technique.The process requirement will be inhaled with sludge pump
The Powdered Activated Carbon of attached saturation is extracted out from wing, and cesspool needs to drain water when extracting Powdered Activated Carbon, to regenerating active carbon, is returned
Could put into operation again after filling out, time-consuming, this will lead to the cesspool long period stop work and make sewage disposal system without
Method operates normally.It is unable to satisfy the demand of sewage disposal system continuous operation.
Chinese patent 201510548775.7 discloses a kind of ozone, organic in active carbon combination processing high slat-containing wastewater
The method of object, method includes the following steps: after raw wastewater is aoxidized by ozone bubbling form, according to residual in waste water
The amount of the organic matter stayed using the organic matter in appropriate excessive activated carbon adsorption waste water, when activated carbon adsorption carry out auxiliary plus
Heat.The method of the present invention can effectively remove the organic matter in high slat-containing wastewater, and the removal rate of COD can be tall and big by 99.6%, decolourize to water quality
Effect is obvious, and can significantly reduce the dosage of active carbon.This method does not mention the effect of the oil removing of active carbon energy and oil removing, and living
Property charcoal and ozone be combined, power consumption is big, the high requirements on the equipment, is easy to happen ozone leakage, causes secondary pollution.
In above-mentioned document, the report using tar in molecular sieve absorption distilled ammonia wastewater is not all disclosed.
Summary of the invention
The technical problem to be solved by the present invention is to the high technical problems of oil content in coking distilled ammonia wastewater, provide one kind
The purification method of coking distilled ammonia wastewater, the processing method have process short, and low equipment investment, regeneration is simple, and low energy consumption, industrialization
The strong advantage of implementation.
In order to solve the above technical problems, the present invention uses a kind of purification method of coking distilled ammonia wastewater, comprising the following steps:
A) distilled ammonia wastewater of coke-oven plant is pre-processed by adsorbent A, removes the part tar ingredients in distilled ammonia wastewater,
B) distilled ammonia wastewater after tar removing is sent into the adsorption tower for being filled with crystallite adsorbent B, adsorbs ammonia and oil in distilled ammonia wastewater,
C) waste water after adsorbing is sent into wastewater biochemical pond,
D) adsorbent B in step b) after adsorption saturation, with being continued to use after 50 ~ 400 DEG C of nitrogen or steam regeneration.
In the above-mentioned technical solutions, preferred technical solution is, the crystallite adsorbent B be selected from including X-type molecular sieve,
Y type molecular sieve, A type molecular sieve, TS-1, Ti-MWW, Ti-MOR, ZSM type molecular sieve, modenite, beta molecular sieve, SAPO type
Molecular sieve, MCM-22, MCM-49, MCM-56, ZSM-5/ modenite, ZSM-5/ β zeolite, the boiling of ZSM-5/Y, MCM-22/ mercerising
Stone, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite, ZSM-5/ β zeolite/Y zeolite or ZSM-5/Y zeolite/mercerising boiling
At least one of stone.
In the above-mentioned technical solutions, the silica alumina ratio of preferred technical solution, the molecular sieve is greater than 2.
In the above-mentioned technical solutions, preferred technical solution, also containing including element week in the adsorbent of molecular sieve
At least one of Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element element in phase table.
In the above-mentioned technical solutions, preferred technical solution, the IIth element A is selected from magnesium and calcium in the periodic table of elements
At least one of；Ith B race element is selected from least one of copper, silver；IIIth B race element in lanthanum, cerium, yttrium at least
It is a kind of.
In the above-mentioned technical solutions, preferred technical solution, ZSM type molecular sieve is selected from packet in the adsorbent of molecular sieve
At least one of ZSM-5, ZSM-23, ZSM-11, ZSM-48 are included, wherein the silica alumina ratio of the molecular sieve is greater than 20.
In the above-mentioned technical solutions, preferred technical solution, in treated waste water, the content of BaP is less than 0.03
Ug/L, ammonia-nitrogen content are less than 30mg/L, and COD is less than 400mg/L and is existed after the adsorbent of molecular sieve adsorption saturation with nitrogen
80 ~ 200 DEG C regeneration 3 ~ 60 hours after continue to use.
In the above-mentioned technical solutions, preferred technical solution, adsorbent bed operation temperature are 10 ~ 80 DEG C, and operating pressure is normal
Pressure.
In the above-mentioned technical solutions, preferred technical solution is, the pretreatment adsorbent A in step a) using active carbon,
At least one of activated coke, dedusting ash of nut coke, coke powder or dry coke quenching are used as adsorbent.
In the above-mentioned technical solutions, preferred technical solution is, after the pretreatment adsorbent A adsorption saturation in step a),
Coking Coal Blending System is returned to use.
In the above-mentioned technical solutions, preferred technical solution, before waste water feeding is filled with the adsorbent bed of adsorbent, through making a living
Property charcoal pretreatment.
In the above-mentioned technical solutions, preferred technical solution, after the adsorbent of molecular sieve adsorption saturation, again with nitrogen
After life, then with 60-200 DEG C of hot water injection.
In the above-mentioned technical solutions, preferred technical solution, in treated waste water, the content of tar is less than 10mg/L；
After the adsorbent of molecular sieve tar adsorption saturation, continued to use after being regenerated 3 ~ 20 hours with nitrogen at 100 ~ 200 DEG C.
In the above-mentioned technical solutions, preferred technical solution, adsorption tower operation temperature are 10 ~ 60 DEG C, and operating pressure is normal
Pressure.
In the above-mentioned technical solutions, preferred technical solution, be passed through in adsorption tower air, ozone, in double water oxygen water extremely
Few one kind.
In the above-mentioned technical solutions, preferred technical solution is that the exhaust gas after regeneration enters in the pre-cooling tower before desulfurizing tower,
Or before entering coal gas primary cooler.
In the above-mentioned technical solutions, preferred technical solution is that the exhaust gas after regeneration enters the pre-cooling tower before desulfurizing tower
Before, or before entrance coal gas primary cooler, first pass through cooling.
In the above-mentioned technical solutions, preferred technical solution, before distilled ammonia wastewater feeding is filled with the adsorption tower of adsorbent, warp
Cross Activated Carbon Pretreatment.
Using the technical program, oil-containing distilled ammonia wastewater is directly adsorbed with adsorbent, solves oil-containing in distilled ammonia wastewater, ammonia
The technical issues of nitrogen is high, influences the operation of subsequent biochemical device.When distilled ammonia wastewater solid ammonium-salt is 300mg/L(ammonium sulfate, chlorination
Ammonium), COD(COD) it is 3000 ± 1000 mg/L, and containing phenols, cyanide, oil slick (mainly based on aromatic hydrocarbon
Tar light oil) etc. substances, temperature be 70 DEG C~90 DEG C, after adsorption cleaning, (the NH containing ammonia nitrogen3- N) it is less than 10mg/L,
COD is less than 400mg/L.Entire treatment process process is short, and low equipment investment, regenerative operation is simple and reliable, and low energy consumption, achieve compared with
Good technical effect.
Detailed description of the invention
Fig. 1 is the flow diagram of distilled ammonia wastewater deoiling method of the invention.
I is activated carbon pretreatment system in Fig. 1, and II is adsorption tower, and III is wastewater biochemical pond, and IV is coal gas primary cooler.
The 1 oil-containing distilled ammonia wastewater come for coke-oven plant, 2 be the waste water after Activated Carbon Pretreatment, and 3 be tar adsorption and organic
Waste water after object, ammonia nitrogen, 4 be 50 ~ 400 DEG C of nitrogen, and 5 be 60-200 DEG C of hot water, and 6 be to regenerate the gas come.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
[embodiment 1]
Specific embodiment device process as shown in Figure 1,60mg/L containing tar-concentration are 3g/L(sulphur containing fixed ammonia content
Sour ammonium, ammonium chloride), COD(COD) the pretreatment absorption of dedusting ash is filled with for the remained ammonia feeding of 3000 mg/L
The adsorption tower of agent, the remained ammonia after absorption enter deamination adsorption tower, wherein attached dose loaded is adsorbent of molecular sieve, absorption
Agent uses hydrophobic type ZSM 5 molecular sieve；Waste water after absorption is sent into tank；Tar content is 1.2 in treated waste water
Mg/L, ammonia-nitrogen content 40mg/L, COD content are 300mg/L.
After pretreatment adsorbent adsorption saturation, dedusting ash after filtering, is sent to coaling-base's coal blending.Suction in deamination adsorption tower
After attached dose of adsorption saturation, with nitrogen regeneration 5 hours of 150 DEG C, the exhaust gas after regeneration entered the pre-cooling tower before desulfurizing tower, and nitrogen is again
After life, then with 90 DEG C of hot water adsorbent is cleaned, adsorbent continues to use after cleaning.
[embodiment 2]
The remained ammonia feeding of specific embodiment device process as shown in Figure 1, the 68mg/L containing tar-concentration is filled with suction
Attached dose of adsorption tower, wherein the adsorbent is adsorbent of molecular sieve, adsorbent uses TS-1 type molecular sieve；It is surplus after absorption
Remaining ammonium hydroxide is sent into tank；A part of waste water in tank is as cooling water reuse, a part discharge.Remaining ammonia before processing
Water 680mg/L containing tar-concentration is 300mg/L containing fixed ammonia content, and COD is 3200 mg/L, in treated distilled ammonia wastewater,
Tar content is 1.3 mg/L, and ammonia-nitrogen content 4mg/L, COD content is 325 mg/L.
[embodiment 3]
The distilled ammonia wastewater feeding of specific embodiment device process as shown in Figure 1, the 50mg/L containing tar-concentration is filled with suction
Attached dose of adsorption tower, wherein the adsorbent is adsorbent of molecular sieve, adsorbent uses Ti-MOR molecular sieve；Steaming after absorption
Ammonia waste water is sent into tank；A part of waste water in tank is as cooling water reuse, a part discharge.
Distilled ammonia wastewater 50mg/L containing tar-concentration before processing, is 280mg/L containing fixed ammonia content, and COD is 3200 mg/
L, in treated distilled ammonia wastewater, tar content is 0.8 mg/L, and ammonia-nitrogen content 4mg/L, COD content is 328 mg/L.
[embodiment 4]
The distilled ammonia wastewater feeding of specific embodiment device process as shown in Figure 1, the 85mg/L containing tar-concentration is filled with suction
Attached dose of adsorption tower, wherein the adsorbent is adsorbent of molecular sieve, adsorbent uses hydrophobic Ti-MWW type molecular sieve；It inhales
Attached distilled ammonia wastewater is sent into biochemistry pool.
Distilled ammonia wastewater 75mg/L containing tar-concentration before processing, is 350mg/L containing fixed ammonia content, and COD is 3500 mg/
L, in treated distilled ammonia wastewater, tar content is 0.25 mg/L, and ammonia-nitrogen content 6mg/L, COD content is 330 mg/L.
After adsorbent saturation, with nitrogen regeneration 5 hours of 150 DEG C, the exhaust gas after regeneration entered the first cold tower before desulfurizing tower,
Adsorbent continues to use after regeneration, the distilled ammonia wastewater 60mg/L containing tar-concentration before processing, is 380mg/L containing fixed ammonia content,
COD is 3600 mg/L, and in treated distilled ammonia wastewater, tar content is 0.2 mg/L, ammonia-nitrogen content 5mg/L, COD content
For 320 mg/ L, adsorbent activity can be restored.
[embodiment 5]
55mg/L containing tar-concentration is 300mg/L(ammonium sulfate, ammonium chloride containing fixed ammonia content), COD(COD) be
The distilled ammonia wastewater of 3000 mg/L is sent into the adsorption tower for being filled with the pretreatment adsorbent of coke powder, and the remained ammonia after absorption enters
Deamination adsorption tower, wherein attached dose loaded is adsorbent of molecular sieve, adsorbent uses hydrophobic Y type molecular sieve；After absorption
Waste water is sent into tank；Tar content is 0.6 mg/L in treated waste water, and ammonia-nitrogen content 7mg/L, COD content is
280mg/L。
After pretreatment adsorbent adsorption saturation, coke powder after filtering, is sent to coaling-base's coal blending.Absorption in deamination adsorption tower
After agent adsorption saturation, with nitrogen regeneration 3 hours of 180 DEG C, the exhaust gas after regeneration entered the pre-cooling tower before desulfurizing tower, nitrogen regeneration
Afterwards, then with 95 DEG C of hot water adsorbent is cleaned, adsorbent continues to use after cleaning.
[embodiment 6]
The distilled ammonia wastewater feeding of specific embodiment device process as shown in Figure 1, the 84mg/L containing tar-concentration is filled with suction
Attached dose of adsorption tower, wherein the adsorbent is adsorbent of molecular sieve, adsorbent uses the ZSM-5 zeolite molecule of copper zinc modification
The silica alumina ratio of sieve, molecular sieve is greater than 600；Remained ammonia after absorption is sent into tank；A part of waste water in tank
As cooling water reuse, a part discharge.Tar content is 1.2mg/L in treated waste water.
[embodiment 7]
The distilled ammonia wastewater feeding of specific embodiment device process as shown in Figure 1, the 79mg/L containing tar-concentration is filled with suction
Attached dose of adsorption tower, wherein the adsorbent is adsorbent of molecular sieve, adsorbent uses the ZSM-5 zeolite molecule of copper zinc modification
The silica alumina ratio of sieve, molecular sieve is greater than 600；Air is passed through in adsorption process in adsorption tower, the distilled ammonia wastewater after absorption is sent into
Tank；A part of waste water in tank is as cooling water reuse, a part discharge.BaP content in treated waste water
For 1.1mg/L.
[embodiment 8]
90mg/L containing tar-concentration is 300mg/L(ammonium sulfate, ammonium chloride containing fixed ammonia content), COD(COD) be
The distilled ammonia wastewater of 4000 mg/L is sent into the adsorption tower for being filled with the pretreatment adsorbent of nut coke, and the distilled ammonia wastewater after absorption enters
Deamination adsorption tower, wherein attached dose loaded is adsorbent of molecular sieve, adsorbent uses Y type molecular sieve；Waste water after absorption is sent
Enter tank；Tar content is 1.0 mg/L in treated waste water, and ammonia-nitrogen content 8mg/L, COD content is 375mg/L.
After pretreatment adsorbent adsorption saturation, coke powder after filtering, is sent to coaling-base's coal blending.Absorption in deamination adsorption tower
After agent adsorption saturation, with steam regeneration 3 hours of 150 DEG C, the exhaust gas after regeneration entered the pre-cooling tower before desulfurizing tower, and nitrogen is again
After life, then with 80 DEG C of hot water adsorbent is cleaned, adsorbent continues to use after cleaning.
[embodiment 9]
The distilled ammonia wastewater of the 85mg/L containing tar-concentration is sent into the adsorption tower for being filled with adsorbent, wherein the adsorbent is molecule
Sieve adsorbant, adsorbent use hydrophobic Ti-MWW type molecular sieve；Distilled ammonia wastewater after absorption is sent into biochemistry pool.
Distilled ammonia wastewater 75mg/L containing tar-concentration before processing, is 350mg/L containing fixed ammonia content, and COD is 3250 mg/
L, in treated distilled ammonia wastewater, tar content is 0.25 mg/L, and ammonia-nitrogen content 7.5mg/L, COD content is 270 mg/
L。
After adsorbent saturation, with nitrogen regeneration 5 hours of 150 DEG C, the exhaust gas after regeneration entered the pre-cooling tower before desulfurizing tower,
After nitrogen regeneration, then with 90 DEG C of hot water adsorbent is cleaned, adsorbent continues to use after cleaning, and the distilled ammonia wastewater before processing is containing coke
Oil concentration 75mg/L is 360g/L containing fixed ammonia content, and COD is 3200 mg/L, in treated distilled ammonia wastewater, tar content
For 0.3 mg/L, ammonia-nitrogen content 7mg/L, COD content is 285 mg/ L, and adsorbent activity can be restored.
[embodiment 10]
The distilled ammonia wastewater of the 75mg/L containing tar-concentration is sent into the adsorption tower for being filled with adsorbent, wherein the adsorbent is molecule
Sieve adsorbant, adsorbent use hydrophobic Ti-MWW type molecular sieve；Distilled ammonia wastewater after absorption is sent into biochemistry pool.
Distilled ammonia wastewater 75mg/L containing tar-concentration before processing is 350g/L, COD 3250mg/L containing fixed ammonia content,
In treated distilled ammonia wastewater, tar content is 0.25 mg/L, and ammonia-nitrogen content 6mg/L, COD content is 300mg/L.
After adsorbent saturation, with nitrogen regeneration 5 hours of 150 DEG C, before the exhaust gas after regeneration enters coal gas primary cooler, nitrogen
After regeneration, then with 90 DEG C of hot water adsorbent is cleaned, adsorbent continues to use after cleaning, and the distilled ammonia wastewater before processing is dense containing tar
75mg/L is spent, is 360mg/L containing fixed ammonia content, COD is 3200 mg/L, and in treated distilled ammonia wastewater, tar content is
0.27mg/L, ammonia-nitrogen content 9mg/L, COD content are 310 mg/ L, and adsorbent activity can be restored.
[embodiment 11]
The distilled ammonia wastewater of the 85mg/L containing tar-concentration is sent into the pretreatment adsorption tower that active carbon is housed, pretreated distilled ammonia wastewater
Into the adsorption tower for being filled with adsorbent, wherein the adsorbent is adsorbent of molecular sieve, adsorbent uses hydrophobic MOR type
Molecular sieve；Distilled ammonia wastewater after absorption is sent into biochemistry pool.
Distilled ammonia wastewater 75mg/L containing tar-concentration before processing, is 350mg/L containing fixed ammonia content, and COD is 3250 mg/
L, in treated distilled ammonia wastewater, tar content is 0.1mg/L, and ammonia-nitrogen content 5mg/L, COD content is 300 mg/L.
After adsorbent saturation, with nitrogen regeneration 5 hours of 150 DEG C, before the exhaust gas after regeneration enters coal gas primary cooler, nitrogen
After regeneration, then with 90 DEG C of hot water adsorbent is cleaned, adsorbent continues to use after cleaning, and the distilled ammonia wastewater before processing is dense containing tar
750mg/L is spent, is 350mg/L containing fixed ammonia content, COD is 3250 mg/L, and in treated distilled ammonia wastewater, tar content is
0.2 mg/L, ammonia-nitrogen content 6mg/L, COD content are 286 mg/ L, and adsorbent activity can be restored.
Claims (10)
1. a kind of purification method of coking distilled ammonia wastewater, comprising the following steps:
A) distilled ammonia wastewater of coke-oven plant is pre-processed by adsorbent A, removes the part tar ingredients in remained ammonia,
B) distilled ammonia wastewater after tar removing is sent into the adsorption tower for being filled with crystallite adsorbent B, adsorb ammonia in remained ammonia and
Oil,
C) waste water after adsorbing is sent into wastewater biochemical pond,
D) adsorbent B in step b) after adsorption saturation, with being continued to use after 50 ~ 400 DEG C of nitrogen or steam regeneration.
2. the purification method of coking distilled ammonia wastewater according to claim 1, it is characterised in that the exhaust gas after regeneration enters de-
In pre-cooling tower before sulphur tower, or before entrance coal gas primary cooler.
3. the purification method of coking distilled ammonia wastewater according to claim 1, it is characterised in that the crystallite adsorbent B is
Adsorbent of molecular sieve, molecular sieve be selected from including X-type molecular sieve, Y type molecular sieve, A type molecular sieve, TS-1, Ti-MWW, Ti-MOR,
ZSM type molecular sieve, modenite, beta molecular sieve, SAPO type molecular sieve, the boiling of MCM-22, MCM-49, MCM-56, ZSM-5/ mercerising
Stone, ZSM-5/ β zeolite, ZSM-5/Y, MCM-22/ modenite, ZSM-5/Magadiite, ZSM-5/ β zeolite/modenite,
ZSM-5/ β zeolite/at least one of Y zeolite or ZSM-5/Y zeolite/modenite, the silica alumina ratio of the molecular sieve
Greater than 2.
4. the purification method of coking distilled ammonia wastewater according to claim 3, it is characterised in that the adsorbent of molecular sieve
In also containing including in the periodic table of elements in the Ith A, II A, V A, I B, II B, III B, IV B, V B, VI B, VII B or the VIIIth race's element
At least one element.
5. the purification method of coking distilled ammonia wastewater according to claim 4, it is characterised in that in the periodic table of elements
IIth element A is selected from least one of magnesium and calcium；Ith B race element is selected from least one of copper, silver；The choosing of IIIth B race element
From at least one of lanthanum, cerium, yttrium；In the adsorbent of molecular sieve ZSM type molecular sieve be selected from including ZSM-5, ZSM-23,
At least one of ZSM-11, ZSM-48, ZSM-22, wherein the silica alumina ratio of the molecular sieve is greater than 20.
6. the purification method of coking distilled ammonia wastewater according to claim 1, it is characterised in that adsorption tower operation temperature be 10 ~
80 DEG C, operating pressure is normal pressure；Pretreatment adsorbent A in step a) using active carbon, activated coke, nut coke, coke powder or is done
At least one of dedusting ash of quenching is used as adsorbent.
7. the purification method of coking distilled ammonia wastewater according to claim 6, it is characterised in that the pretreatment in step a) is inhaled
After attached dose of A adsorption saturation, returns to Coking Coal Blending System and use.
8. the purification method of coking distilled ammonia wastewater according to claim 1, it is characterised in that in treated waste water, benzo
For the content of pyrene less than 0.03 ug/L, ammonia-nitrogen content is less than 10mg/L, and COD is less than 400mg/L, and the adsorbent of molecular sieve is inhaled
After attached saturation, continued to use after being regenerated 3 ~ 60 hours with nitrogen at 80 ~ 200 DEG C.
9. the purification method of coking distilled ammonia wastewater according to claim 2, it is characterised in that the exhaust gas after regeneration enters de-
Before pre-cooling tower before sulphur tower, or before entrance coal gas primary cooler, first pass through cooling.
10. the purification method of coking distilled ammonia wastewater according to claim 1, it is characterised in that the adsorbent of molecular sieve
After adsorption saturation, after nitrogen regeneration, then with 60 ~ 200 DEG C of hot water injection.
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|---|---|---|---|---|
| CN111348663A (en) * | 2020-03-16 | 2020-06-30 | 山东洲蓝环保科技有限公司 | Method for purifying coking strong ammonia water |
| CN115430398A (en) * | 2022-08-10 | 2022-12-06 | 中国石油化工股份有限公司 | High-performance adsorbent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111348663A (en) * | 2020-03-16 | 2020-06-30 | 山东洲蓝环保科技有限公司 | Method for purifying coking strong ammonia water |
| CN115430398A (en) * | 2022-08-10 | 2022-12-06 | 中国石油化工股份有限公司 | High-performance adsorbent and preparation method and application thereof |
| CN115430398B (en) * | 2022-08-10 | 2024-02-09 | 中国石油化工股份有限公司 | High-performance adsorbent and preparation method and application thereof |
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Application publication date: 20190312 |