CN105884106A - Benzene hydrogenation wastewater desulfurization and deamination treatment method aiming at improving deamination and treatment device applying same - Google Patents
Benzene hydrogenation wastewater desulfurization and deamination treatment method aiming at improving deamination and treatment device applying same Download PDFInfo
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- CN105884106A CN105884106A CN201610257461.6A CN201610257461A CN105884106A CN 105884106 A CN105884106 A CN 105884106A CN 201610257461 A CN201610257461 A CN 201610257461A CN 105884106 A CN105884106 A CN 105884106A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention relates to a benzene hydrogenation wastewater desulfurization and deamination treatment method and device. Alkaline liquid is added before deacidification tower kettle liquid enters a deamination tower to fix sulfur ions left in wastewater after desulfurization, so that influence on quality of ammonia water or liquid ammonia due to the fact that the sulfur ions left in the wastewater enters ammonia in a form of hydrogen sulfide in the process of ammonia distilling is avoided. On the basis of a petrochemical desulfurization and deamination process, the whole desulfurization and deamination process is simplified, operation difficulty is lowered, and equipment investment is saved.
Description
Technical field
The invention belongs to waste water and process field of Environment Protection, be specifically related to a kind of improve for deamination workshop section
Benzene hydrogenation waste water desulfurization deamination preprocess method and the processing means of application the method.
Background technology
The waste water of crude benzole hydrogenation technique has high ammonia nitrogen, high COD, high-sulfur compound, feature that flow is little.
This kind of waste water must carry out pretreatment, ammonia nitrogen and sulfide drop to finite concentration (ammonia nitrogen≤150mg/L,
Sulfide≤50mg/L), just can enter sewage plant biochemical system.Otherwise can make the micro-life in biochemical system
Thing is poisoned, and causes the collapse of whole biochemical system.
For the high ammonia nitrogen of benzene hydrogenation process this type of waste water, high COD, high-sulfur compound waste water, typically adopt
Pretreatment is carried out by double tower desulfurization deamination technique.This technique as its name suggests, is taken off by waste water desulfurization and waste water
Ammonia two parts form.Waste water desulfurization includes that waste water steams sulfur and hydrogen sulfide reclaims Liang Ge workshop section；Waste water deaminizing bag
Include waste water ammonia still process and Ammonia recovery Liang Ge workshop section.
Specifically, the technique of waste water deaminizing part is, waste water, after desulfurization processes, enters ammonia still
Deamination, the ammonia of abjection is made into ammonia or liquefied ammonia in Ammonia recovery workshop section.Due in the waste water after desulfurization
Still a small amount of sulphion having, a small amount of sulphion of residual can be during waste water deaminizing, with sulfuration
The form of hydrogen enters in ammonia vapour, and therefore the ammonia vapour of deammoniation tower needs the mode using multistage fractional condensation to remove
Hydrogen sulfide gas in ammonia vapour and steam.Removing hydrogen sulfide gas and the ammonia of steam, available water is inhaled
Receive and produce ammonia, to produce liquefied ammonia, in addition it is also necessary to a set of adsorpting desulfurization device so that the sulfur in ammonia
Change hydrogen less than 5ppm.
Double tower desulfurization deamination technique, particularly deamination some processes, it is not appropriate for this high ammonia of crude benzole hydrogenation
Nitrogen, high-sulfur compound, technique waste water that the water yield is little.Owing to the water yield is little, callable ammonia amount is the fewest, because of
If this selects to produce liquefied ammonia, investment is big, deficiency in economic performance.But, if selecting to produce ammonia, due to ammonia
Vapour is after three grades of fractional condensers, and in ammonia, the hydrogen sulfide gas of the most remaining trace, therefore, has in ammonia
The sulphion of trace, affects the quality of ammonia.Simultaneously as, three grades of fractional condensation process operations are complex,
Cause whole deamination technological operation unstable.
Summary of the invention
According to above the problems of the prior art, it is an object of the invention to improve traditional desulfurization deamination
The deamination part of technique so that it is be more suitable for processing this high ammonia nitrogen of crude benzole hydrogenation, high-sulfur compound, the water yield little
Technique waste water.
According to an embodiment of the invention, it provides a kind of benzene hydrogenation waste water desulfurization deamination process side
Method, it comprises the following steps:
A) waste water from crude benzole hydrogenation technique is entered after feed preheater 1, heat exchanger 2 deacidification
Tower 3, adds thermal release in extracting tower, and column bottom temperature is 148 to 168 DEG C, and tower top temperature is 50 to 85 DEG C,
Tower top obtains hydrogen sulfide, obtains deacidification still liquid at the bottom of tower；
B) by deacidification still liquid after heat exchanger 2, mix with the alkali liquor from lye tank (vat) 4, subsequently into
Deammoniation tower；
C) in deammoniation tower 5, thermal release is added, column bottom temperature 124.5 DEG C-144.5 DEG C, tower top dephlegmator 6
Front temperature is 119 to 139 DEG C, and overhead product is placed on the dephlegmator of deammoniation tower tower top and divides contracting by part
Rich ammonia vapour is cooled to liquid-phase reflux, and remaining part is expelled to condenser, and the waste water at the bottom of tower is discharged；
D) described remaining part warp being expelled to condenser 7 of dephlegmator will be passed through in step c)
Condenser is cooled to liquid-phase product；
E) the described liquid-phase product in step d) is imported ammonia dashpot 8, the ammonia that then will produce
Water imports Ammonia vessel 9；
Preferably, in step a), the column bottom temperature of described extracting tower be 153 DEG C to 163 DEG C, more excellent
Select 156 DEG C to 160 DEG C, most preferably 158 DEG C；
Described alkali liquor in step b) has no particular limits, as long as it can regulate deacidification still liquid
PH value and other will not be caused disadvantageous to react, it is preferable that in the described alkali liquor in step b)
Alkali be NaOH or NaHCO3, it is highly preferred that solid piece alkali NaOH or NaHCO3；
Preferably, the addition in the alkali liquor of step b) is so that desulfurization wastewater is from the deacidification of extracting tower
The pH value of still liquid is adjusted to 10-11；
Preferably, in step c), the column bottom temperature of described deammoniation tower is 129.5 DEG C to 139.5 DEG C,
More preferably 132.5 DEG C to 136.6 DEG C, most preferably 134.5 DEG C；Temperature before tower top dephlegmator 6 is 124 DEG C
To 134 DEG C, preferably 127 DEG C to 131 DEG C, most preferably 129 DEG C；
According to another implementation of the invention, it provides a kind of benzene hydrogenation waste water desulfurization deamination process
Device, described device includes:
Feed preheater 1, it includes feed preheater entrance 11 and feed preheater outlet 12；It is used for
Preheat the waste water from crude benzole hydrogenation technique；
Heat exchanger 2, it includes heat exchanger the first entrance 21, heat exchanger the second entrance 22, heat exchanger first
Outlet 23 and heat exchanger second export 24；Its for make preheated device 1 from crude benzole hydrogenation technique
Waste water further with the deacidification still liquid heat exchange bottom extracting tower 3；
Extracting tower 3, it includes extracting tower the first entrance 31, extracting tower the second entrance 32, extracting tower first
Outlet 33 and extracting tower second export 34, and wherein, described extracting tower the first entrance 31 is positioned at extracting tower side
Middle face, extracting tower the second entrance 32 are positioned at extracting tower top, extracting tower first exports 33 and is positioned at deacidification
Tower bottom and extracting tower second export 34 and are positioned at extracting tower top；It is used for will be through feed preheater 1
The waste water deacidification from crude benzole hydrogenation technique with heat exchanger 2 is to obtain deacidification still liquid and acid waste gas；
Lye tank (vat) 4, it includes lye tank (vat) outlet 41；Its for make from extracting tower 3 deacidification still liquid and
Alkali liquor mixes；
Deammoniation tower 5, it includes deammoniation tower entrance 51 and deammoniation tower outlet 52；It is used for making mixed taking off
Acid still liquid and alkali liquor rectification deamination；
Deammoniation tower dephlegmator 6, it is positioned at deamination tower top, exports 61 including dephlegmator；It is used for making from
The part richness ammonia vapour of deammoniation tower is cooled to liquid-phase reflux, and makes remaining rich ammonia vapour discharge；
Condenser 7, it includes condenser inlet 71 and condensator outlet 72；It will be for dividing from deammoniation tower
Remaining rich condensed device of ammonia vapour 7 that contracting device 6 is discharged is cooled to liquid-phase product；
Ammonia surge tank 8 and Ammonia vessel 9, it includes that ammonia surge tank entrance 81, ammonia surge tank go out
Mouth 82 and Ammonia vessel entrance 91；It is collected for liquid-phase product of in the future condenser 7, buffering and
Store；
Wherein, feed preheater entrance 11 receives the waste water from crude benzole hydrogenation technique, and feed preheater goes out
Mouth 12 is connected with heat exchanger the first entrance 21；
Heat exchanger first exports 23 and is connected with extracting tower the first entrance 31, and heat exchanger the second entrance 22 is with de-
Acid tower first exports 33 connections, and heat exchanger second exports 24 and enters with deammoniation tower together with lye tank (vat) outlet 41
Mouth 51 connects；
Extracting tower the second entrance 32 receives the waste water from crude benzole hydrogenation technique not preheated；
Deammoniation tower outlet 52 discharge waste water；
Dephlegmator outlet 61 is connected with condenser inlet 71；
Condensator outlet 72 is connected with ammonia surge tank entrance 81；
Ammonia surge tank outlet 82 is connected with Ammonia vessel entrance 91.
Pipeline well known in the art, pump, effusion meter, heater etc. are also included in the device of the application,
Their 26S Proteasome Structure and Function is identical with its 26S Proteasome Structure and Function of the prior art, does not repeats them here.
The method according to the invention, before deacidification tower bottoms enters deammoniation tower, with the alkali from lye tank (vat)
Liquid mixes, thus the sulphion of remaining in waste water after fixing desulfurization, it is to avoid in waste water the sulphion of remaining with
The form of hydrogen sulfide enters into the quality affecting product ammonia in ammonia；It is simultaneously introduced alkali liquor and can also improve de-
The pH value of acid tower bottoms so that deacidification tower bottoms is more easy to ammonia to steam in the basic conditions.
Additionally, set dephlegmator at deamination tower top, cooling segment richness ammonia vapour becomes liquid phase, as backflow.Point
The rich the most condensed cooler of ammonia vapour separated out is cooled to liquid phase and enters ammonia dashpot as product, then produces
Raw strong aqua ammonia enters Ammonia vessel.
Compared with the technique of traditional desulfurization deamination liquid ammonia recovery, the deamination part of the application is by recovered liquid
Ammonia changes into reclaiming ammonia, eliminates three grades of fractional condensation systems, absorption desulphurization system and ammonia liquefied ammonia system；
And, the deamination part of the application not only eliminates three grades of fractional condensation systems and ammonia absorption tower, also by adding
Enter alkali liquor with fixing sulphion, improve the quality of ammonia.
Therefore, compared with traditional desulfurization deamination technique, the application simplifies technological process, decreases and set
Standby investment, reduce technological operation difficulty and energy resource consumption, be more suitable for processing this high ammonia nitrogen of crude benzole hydrogenation,
The little technique waste water of high-sulfur compound, the water yield.
Accompanying drawing explanation
Fig. 1 be a diagram that the schematic diagram of the technique of the present invention.
Reference
1-feed preheater；2-heat exchanger；3-extracting tower；4-lye tank (vat)；5-deammoniation tower；6-deammoniation tower divides
Contracting device；7-condenser；8-ammonia surge tank；9-Ammonia vessel；11-feed preheater entrance；12-raw material
Preheater exports；21-heat exchanger the first entrance；22-heat exchanger the second entrance；23-heat exchanger first exports；
24-heat exchanger second exports；31-extracting tower the first entrance；32-extracting tower the second entrance；33-extracting tower
One outlet；34-extracting tower second exports；41-lye tank (vat) exports；51-deammoniation tower entrance；52-deammoniation tower goes out
Mouthful；61-dephlegmator exports；71-condenser inlet；72-condensator outlet；81-ammonia surge tank entrance；
82-ammonia surge tank exports；91-Ammonia vessel entrance.
Detailed description of the invention
Hereinafter accompanying drawing be will combine according to embodiment and presently filed embodiment, but the reality of the application described in detail
The mode of executing is not limited only to following example.
The desulfurization deamination of embodiment 1 benzene hydrogenation waste water processes
With reference to Fig. 1, according to the benzene hydrogenation waste water desulfurization deamination processing method of the present invention, will add from crude benzol
The waste water of hydrogen technique is through feed preheater 1, and heat exchanger 2 post-heating, to 85 to 92 DEG C, enters extracting tower
Adding thermal release in 3, column bottom temperature is 158 DEG C, and tower top temperature is 60 to 75 DEG C, and tower top obtains hydrogen sulfide
Discharge, at the bottom of tower, obtain deacidification still liquid；By described deacidification still liquid through heat exchanger 2 with aforesaid from crude benzol
After the wastewater heat exchange of hydrogenation technique, mix with the NaOH that concentration is 20%～40% from lye tank (vat) 4,
Subsequently into deammoniation tower 5, wherein, described alkali liquor is stored in lye tank (vat), lye pump (do not show in figure
Go out) extraction, mix with the desulfurization wastewater at the bottom of extracting tower in pipe-line mixer (not shown), make
The pH obtaining desulfurization wastewater rises to 10～11；Thermal release is added in deammoniation tower 5, column bottom temperature 134.5 DEG C,
Before tower top dephlegmator, temperature is 129 DEG C, and overhead product is placed on the deammoniation tower dephlegmator 6 of deammoniation tower tower top
Point contracting, is cooled to liquid-phase reflux to deammoniation tower 5 by rich for part ammonia vapour, and remaining part is expelled to condenser 7,
The waste water obtained at the bottom of tower is discharged；By by remaining the part warp being expelled to condenser described in dephlegmator
Condenser 7 is cooled to ammonia, and the ammonia temperature of dephlegmator outlet is 50 DEG C；Described liquid-phase product is imported
Ammonia dashpot 8, then imports the ammonia of generation in Ammonia vessel 9 and obtains final ammonia product.
The detection of the ammonia of the detection of embodiment 2 energy consumption and preparation
It is 10000～30000mg/l that the processing method of the present invention can process sulfide content, NH3-N contains
Amount is the waste water of 6000～20000mg/l, and treating capacity is 6-11m3/ h, after process (at the bottom of deammoniation tower tower)
Waste water ammon amount≤150mg/l, sulfide≤50mg/l, can additionally obtain the ammonia of 18%-20% concentration
Water, can be directly as other raw materials of industry after concentrating further and be refined；
Described method processes one ton of waste water needs steam 0.33-0.35 ton, compared with conventional method, Ke Yijie
About mass energy；And in the method for the present invention, extracting tower tower top acid gas ammonia≤2%, steam≤2%,
The three wastes i.e. discharged greatly reduce, the CODcr≤2000mg/l of deammoniation tower tower reactor waste water, can directly use
Process in activated sludge systems.
Therefore, according to method described herein, before deacidification tower bottoms enters deammoniation tower, add alkali liquor,
In making deammoniation tower, ammonia is more easy to steam in the basic conditions.Deamination tower top sets dephlegmator simultaneously, effectively
Make ammonia concentrate condensation, simplify technological process, saved equipment investment.Additionally, due to waste water ammonia still process
Energy consumption is big, in the present invention, takes full advantage of middle heat and carries out heat exchange, decrease the steam of this step
Consume.
Claims (10)
1. a benzene hydrogenation waste water desulfurization deamination processing method, it comprises the following steps:
A) waste water from crude benzole hydrogenation technique is entered after feed preheater, heat exchanger extracting tower,
Adding thermal release in extracting tower, column bottom temperature is 148 to 168 DEG C, and tower top temperature is 50 to 85 DEG C, tower
Top obtains hydrogen sulfide, obtains deacidification still liquid at the bottom of tower；
B) by deacidification still liquid after heat exchanger, mix with the alkali liquor from lye tank (vat), subsequently into deamination
Tower；
C) in deammoniation tower, thermal release is added, column bottom temperature 124.5 DEG C-144.5 DEG C, temperature before tower top dephlegmator
Degree is 119 to 139 DEG C, and overhead product is placed on the dephlegmator of deammoniation tower tower top and divides contracting by rich for part ammonia
Vapour is cooled to liquid-phase reflux, and remaining part is expelled to condenser, and the waste water at the bottom of tower is discharged；
D) described remaining part being expelled to condenser of dephlegmator will be passed through in step c) through cold
Condenser is cooled to liquid-phase product；
E) the described liquid-phase product in step d) is imported ammonia dashpot, the ammonia that then will produce
Import Ammonia vessel.
Method the most according to claim 1, wherein,
In step a), the column bottom temperature of described extracting tower is 153 DEG C to 163 DEG C.
Method the most according to claim 1, wherein,
In step a), the column bottom temperature of described extracting tower is 156 DEG C to 160 DEG C.
Method the most according to claim 1, wherein,
The alkali in described alkali liquor in step b) is NaOH or NaHCO3。
Method the most according to claim 1, wherein,
Addition in the alkali liquor of step b) is so that desulfurization wastewater is from the pH of the deacidification still liquid of extracting tower
Value is adjusted to 10-11.
Method the most according to claim 1, wherein,
In step c), the column bottom temperature of described deammoniation tower is 129.5 DEG C to 139.5 DEG C.
Method the most according to claim 1, wherein,
In step c), the column bottom temperature of described deammoniation tower is 132.5 DEG C to 136.6 DEG C.
Method the most according to claim 1, wherein,
In step c), the temperature before tower top dephlegmator is 124 DEG C to 134 DEG C.
Method the most according to claim 1, wherein,
In step c), the temperature before tower top dephlegmator is 127 DEG C to 131 DEG C.
10. a benzene hydrogenation waste water desulfurization deamination processing means, described device includes:
Feed preheater 1, it includes feed preheater entrance 11 and feed preheater outlet 12；It is used for
Preheat the waste water from crude benzole hydrogenation technique；
Heat exchanger 2, it includes heat exchanger the first entrance 21, heat exchanger the second entrance 22, heat exchanger first
Outlet 23 and heat exchanger second export 24；Its for make preheated device 1 from crude benzole hydrogenation technique
Waste water further with bottom extracting tower 3 discharge deacidification still liquid heat exchange；
Extracting tower 3, it includes extracting tower the first entrance 31, extracting tower the second entrance 32, extracting tower first
Outlet 33 and extracting tower second export 34, and wherein, described extracting tower the first entrance 31 is positioned at extracting tower side
Middle face, extracting tower the second entrance 32 are positioned at extracting tower top, extracting tower first exports 33 and is positioned at deacidification
Tower bottom and extracting tower second export 34 and are positioned at extracting tower top；It is used for will be through feed preheater 1
The waste water deacidification from crude benzole hydrogenation technique with heat exchanger 2 is to obtain deacidification still liquid and acid waste gas；
Lye tank (vat) 4, it includes lye tank (vat) outlet 41；Its for make from extracting tower 3 deacidification still liquid and
Alkali liquor mixes；
Deammoniation tower 5, it includes deammoniation tower entrance 51 and deammoniation tower outlet 52；It is used for making mixed taking off
Acid still liquid and alkali liquor rectification deamination；
Deammoniation tower dephlegmator 6, it is positioned at deamination tower top, exports 61 including dephlegmator；It is used for making from
The part richness ammonia vapour of deammoniation tower is cooled to liquid-phase reflux, and makes remaining rich ammonia vapour discharge；
Condenser 7, it includes condenser inlet 71 and condensator outlet 72；It will be for dividing from deammoniation tower
Remaining rich condensed device of ammonia vapour 7 that contracting device 6 is discharged is cooled to liquid-phase product；
Ammonia surge tank 8 and Ammonia vessel 9, it includes that ammonia surge tank entrance 81, ammonia surge tank go out
Mouth 82 and Ammonia vessel entrance 91；It is collected for liquid-phase product of in the future condenser 7, buffering and
Store；
Wherein, feed preheater entrance 11 receives the waste water from crude benzole hydrogenation technique, and feed preheater goes out
Mouth 12 is connected with heat exchanger the first entrance 21；
Heat exchanger first exports 23 and is connected with extracting tower the first entrance 31, and heat exchanger the second entrance 22 is with de-
Acid tower first exports 33 connections, and heat exchanger second exports 24 and enters with deammoniation tower together with lye tank (vat) outlet 41
Mouth 51 connects；
Extracting tower the second entrance 32 receives the waste water from crude benzole hydrogenation technique not preheated；
Deammoniation tower outlet 52 discharge waste water；
Dephlegmator outlet 61 is connected with condenser inlet 71；
Condensator outlet 72 is connected with ammonia surge tank entrance 81；
Ammonia surge tank outlet 82 is connected with Ammonia vessel entrance 91.
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| CN110065986A (en) * | 2019-05-23 | 2019-07-30 | 金猛 | A kind of system recycling ammonium sulfate from ammonia-containing water |
| CN111252839A (en) * | 2020-01-18 | 2020-06-09 | 河北荣特化工股份有限公司 | Novel process for treating hydrogenation type waste water and waste gas |
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| CN106277529A (en) * | 2016-08-31 | 2017-01-04 | 中科合成油工程股份有限公司 | H in a kind of recovery acid water2s and NH3and the method purifying acid water |
| CN110065986A (en) * | 2019-05-23 | 2019-07-30 | 金猛 | A kind of system recycling ammonium sulfate from ammonia-containing water |
| CN111252839A (en) * | 2020-01-18 | 2020-06-09 | 河北荣特化工股份有限公司 | Novel process for treating hydrogenation type waste water and waste gas |
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