CN108128954A - A kind for the treatment of process of highly concentrated organic spent lye - Google Patents
A kind for the treatment of process of highly concentrated organic spent lye Download PDFInfo
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- CN108128954A CN108128954A CN201711442066.6A CN201711442066A CN108128954A CN 108128954 A CN108128954 A CN 108128954A CN 201711442066 A CN201711442066 A CN 201711442066A CN 108128954 A CN108128954 A CN 108128954A
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- Prior art keywords
- spent lye
- effect
- organic
- evaporator
- steam
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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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
-
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/10—Liquid waste
- F23G2209/101—Waste liquor
Abstract
The present invention relates to organic waste Caustic Treating Technology fields, specifically disclose a kind for the treatment of process of highly concentrated organic spent lye.The treatment process includes at least following steps：By a concentration of 100,000~300,000 ppm of COD, organic spent lye that calorific value is 200~600Kcal/kg is pre-processed by concentrating, and the organic matter of more than 95wt% in organic spent lye and 100% component of inorganic salts are retained in concentrate, obtain concentrate and condensed water；Condensed water using Fenton oxidation and air-float technology is handled, concentrate is subjected to high temperature incineration processing.The present invention is pre-processed by concentrating, and realizes efficiently separating for highly concentrated useless organic liquor and moisture content, the condensed water content of organics being evaporated is few, and production link is back to after being handled by Fenton oxidation；Concentrate calorific value and COD value have been greatly improved, into incinerator compatibility incineration disposal, cost reduction 70 80%.
Description
Technical field
The present invention relates to organic waste Caustic Treating Technology field more particularly to a kind of processing works of highly concentrated organic spent lye
Skill.
Background technology
In petrochemical production process, H is absorbed frequently with NaOH solution2S, alkali cleaning oil product and cracking gas are generated containing big
Measure the spent lye of pollutant.The chemical oxygen demand of waste water (COD) is up to tens thousand of to hundreds thousand of mg/L, simultaneously the sulphur containing high concentration
The hazardous contaminants such as compound, phenols, petroleum-type, pH is more than 12.The conventional process side of current such organic spent lye
Method has neutralisation, burning method, wet air oxidation and biological treatment.
Neutralisation is to use to add acidic materials into spent lye, and the pH value of waste water is transferred to the range of requirement, is mainly adopted
With inorganic acid (common sulfuric acid) and sour gas (CO2、H2S), alkaline matter can only be directed to, the COD of waste liquid can not be reduced；It burns
Method is since waste liquid amount is big, while itself calorific value is not high needs to add in a large amount of fuel, and energy consumption is excessive；Wet air oxidation be
High temperature (150~350 DEG C) high pressure (0.5~20.0MPa) sulfide and will have in the liquid phase using the oxygen in air as oxidant
Machine object is oxidized to sulfate, CO2, water or small organic molecule chemical process, the drawback is that more demanding (the resistance to height to equipment
Temperature, high pressure and anti-corrosion), investment is larger, and energy consumption is larger；Biological treatment is the metabolism by microorganism, will be vulcanized
The pollutants such as object and phenols are converted into the process of innocuous substance.The drawback is that it can not ensure disposable up to standard, and salinity and pollution
Object concentration has larger impact to microorganism, needs a large amount of water that could be handled after being diluted.
Traditional multiple-effect evaporation concentration systems can effectively reduce evaporation energy consumption, but low separation efficiency itself.
Invention content
The problems such as handling big energy consumption, complex process for existing spent lye, the present invention provide a kind of highly concentrated organic spent lye
Treatment process.
To achieve the above object of the invention, the embodiment of the present invention employs following technical solution：
A kind for the treatment of process of highly concentrated organic spent lye, the treatment process include at least following steps：
Step 1, by a concentration of 100,000~300,000 ppm of COD, calorific value is that organic spent lye of 200~600Kcal/kg passes through
Concentration pretreatment, the organic matter of more than 95wt% in organic spent lye and 100% component of inorganic salts are retained in concentrate,
Obtain concentrate and condensed water；
Step 2 handles condensed water using Fenton oxidation and air-float technology, and concentrate is carried out at high temperature incineration
Reason.
Relative to the prior art, the treatment process of highly concentrated organic spent lye provided by the invention is pre-processed using concentration, real
Existing highly concentrated useless organic liquor and moisture content efficiently separate, and the condensed water content of organics being evaporated is few, gentle by Fenton oxidation
Production link is back to after floating process；Concentrate calorific value and COD value have been greatly improved, into incinerator incineration disposal,
Processing cost is substantially reduced than individually burning.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The embodiment of the present invention provides a kind for the treatment of process of highly concentrated organic spent lye, and the treatment process includes at least following
Step：
Step 1, by a concentration of 100,000~300,000 ppm of COD, calorific value is that organic spent lye of 200~600Kcal/kg passes through
Concentration pretreatment, the organic matter of more than 95wt% in organic spent lye and 100% component of inorganic salts are retained in concentrate,
Obtain concentrate and condensed water；
Step 2 handles condensed water using Fenton oxidation and air-float technology, and concentrate is carried out at high temperature incineration
Reason.
The treatment process of highly concentrated organic spent lye provided by the invention is pre-processed using concentration, realizes highly concentrated useless organic liquor
With efficiently separating for moisture content, the condensed water content of organics being evaporated is few, by being returned after Fenton oxidation and air supporting process
For production link；Concentrate calorific value and COD value have been greatly improved, and into incinerator incineration disposal, processing cost is than independent
Burning substantially reduces.
Preferably, the organic waste alkali liquor concentration pretreatment includes the following steps：Organic spent lye is preheated, temperature rises to
50-60 DEG C, heat exchange is carried out, organic waste alkali liquid temperature rises to 102-115 DEG C after heat exchange, becomes gas-liquid mixture, gas conduct
The heat source of heat exchange, liquid enter evaporator, after being concentrated by evaporation several times, obtain COD value as 500,000~2,000,000 ppm, calorific value
The condensate liquid that concentrate and COD value for 1000~3000Kcal/kg are 1000~5000ppm.
Preferably, in the evaporating concentration process several times, the steam that the evaporation of last waste water generates is as next time
The heat source of heat exchange.
The steam waste heat generated in evaporation process is fully recycled, and reduces cost.
Preferably, the organic waste alkali liquor concentration pretreatment carries out concentration pretreatment using multi-effect evaporator evaporation.It is described
Multi-effect evaporator is concentrated by evaporation pretreatment and includes the following steps：
Step A, by organic spent lye by preheating after, temperature rises to 50-60 DEG C, into one effect heat exchanger chuck in carry out
Countercurrent flow, organic waste alkali liquid temperature rises to 102-115 DEG C after heat exchange, becomes gas-liquid mixture, keeps in 1st effective evaporator absolutely
It is 0.01-0.045MPa to pressure, some vapor condensed after heat exchange enters an effect and balances in bucket, and it is pre- to enter back into an effect condensed water
In hot device；
Step B, the steam that 1st effective evaporator tower top comes out is as indirect steam, to entering being imitated from one in 2nd effect evaporator
The liquid of evaporator bottom of towe outflow is heated, and absolute pressure is in -0.024~-0.048MPa, saturation in holding 2nd effect evaporator
82-92 DEG C of steam, some vapor of the condensation after heat exchange enter two effects and balance in bucket；
Step C, the steam that 2nd effect evaporator tower top comes out, to entering the slave 2nd effect evaporator bottom of towe stream in triple effect evaporator
The liquid gone out is heated, and absolute pressure is in -0.072~-0.084MPa, saturated vapor pressure 55-65 in holding triple effect evaporator
DEG C, some vapor condensed after heat exchange enters in three-effect balance bucket, and three-effect balance bucket is connected with two effect balance buckets, the triple effect of mixing
It is squeezed into triple effect condensation water preheater with the condensed steam of two effects；
Step D, the condensed water evaporated is collected with concentrate in respective liquid-collecting barrel respectively.
Preferably, 1st effective evaporator heat exchange steam used is the steam generated by burning disposal, 2nd effect evaporator institute
It is the steam that waste water evaporation generates in 1st effective evaporator with heat exchange steam, heat exchange steam used is evaporated for two effects in triple effect evaporator
The steam that waste water evaporation generates in device.
Preferably, the triple effect evaporation leading portion is equipped with two-stage countercurrent preheater, first with triple effect steam condensate (SC) to having
Machine spent lye carries out first time preheating, and temperature rises to 30-40 DEG C by 15-25 DEG C, recycles an effect steam condensate (SC) to organic waste
Lye carries out second and preheats, and temperature rises to 50-60 DEG C by 30-40 DEG C.
Preferably, the multi-effect evaporator uses forced-circulation evaporator reactor；It is both provided with before the evaporator flat
Weigh bucket.
Preferably, the pH value of the condensed water is transferred to 3-4, adds in ferrous sulfate and hydrogen peroxide, reacted 1-4h, then adjust
Section pH value is 7-8, adds in flocculant, and by air-float technology, precipitation is detached with clear liquid.
Preferably, in the condensed water, the addition of ferrous sulfate is 0.19-0.65wt%；In the condensed water, use
Mass fraction is the hydrogen peroxide of 30-35%, and addition is per ton for 20-100L/, and the flocculant is polyacrylamide or alkali formula chlorine
Change at least one of aluminium.
The condensed water COD being evaporated is between 1000~5000ppm, and for pH 7 or so, content of organics is few, passes through sweet smell
Pause and aoxidize, after adding in flocculant, by air-float technology, oversaturated air is released, forms micro-bubble, it is rapid attached
It on suspended matter, it is promoted to the surface of flotation tank, so as to form the sludge floating layer of removal is easy to, by precipitation and clearly
Liquid detaches, and production link is back to after clear liquid processing.
Air-float technology：Using the characteristic of water different solubility at various pressures, to treated, condensed water pressurizes
And aerating, increase the Underwater sound field of waste liquid, be passed through in the water for adding in coagulant, discharged in normal pressure, shape is precipitated in air
Into minute bubbles, it is adhered on impurity wadding grain, wadding grain global density is caused to be less than water and rise, so as to make separation of solid and liquid.
It is provided in an embodiment of the present invention in order to better illustrate, it is illustrated below by embodiment is further.
Embodiment 1
The present embodiment provides a kind for the treatment of process of highly concentrated organic spent lye, the treatment process includes the following steps：
Step 1, COD is a concentration of up to 299500mg/L, calorific value is that organic spent lye of 588Kcal/kg contains organic matter
4.8wt%, wherein be mainly concentrated by evaporation and pre-processed by multi-effect evaporator containing organic matters such as thiophenol, thioether, phenols, it will be organic
The organic matter of more than 95wt% and 100% component of inorganic salts are retained in concentrate in spent lye, obtain concentrate and condensation
Water；
Step 2 handles condensed water using Fenton oxidation and air-float technology, and concentrate is carried out at high temperature incineration
Reason.
Multi-effect evaporator is concentrated by evaporation pretreatment and includes the following steps：
Step A, by organic spent lye by preheating after, temperature rises to 50-60 DEG C, into one effect heat exchanger chuck in carry out
Countercurrent flow, organic waste alkali liquid temperature rises to 102-115 DEG C after heat exchange, becomes gas-liquid mixture, keeps in 1st effective evaporator absolutely
It is 0.01-0.045MPa to pressure, some vapor condensed after heat exchange enters an effect and balances in bucket, and it is pre- to enter back into an effect condensed water
In hot device；
Step B, the steam that 1st effective evaporator tower top comes out is as indirect steam, to entering being imitated from one in 2nd effect evaporator
The liquid of evaporator bottom of towe outflow is heated, and absolute pressure is in -0.024~-0.048MPa, saturation in holding 2nd effect evaporator
82-92 DEG C of steam, some vapor of the condensation after heat exchange enter two effects and balance in bucket；
Step C, the steam that 2nd effect evaporator tower top comes out, to entering the slave 2nd effect evaporator bottom of towe stream in triple effect evaporator
The liquid gone out is heated, and absolute pressure is in -0.072~-0.084MPa, saturated vapor pressure 55-65 in holding triple effect evaporator
DEG C, some vapor condensed after heat exchange enters in three-effect balance bucket, and three-effect balance bucket is connected with two effect balance buckets, the triple effect of mixing
It is squeezed into triple effect condensation water preheater with the condensed steam of two effects；
Step D, the condensed water evaporated is collected with concentrate in respective liquid-collecting barrel respectively.
After multiple-effect evaporation, 100 parts of organic wastewater can with to 20 parts of concentrate, remaining 80 parts for distilled water and
Low-boiling organic matter such as thioether etc., and content of organics is low, COD is about in 3000mg/L.In the subsequent processing, need to enter high temperature
The concentrate of burning has been reduced 80%, the calorific value about 3000Kcal/kg of concentrate.
Concentrate and diesel oil are subjected to compatibility and carry out burning disposal, compatibility and cost calculation are as shown in table 1.
1 concentrate of table and diesel oil compatibility tables of data
| Concentrate | Diesel oil | Liquid after compatibility | |
| Independent calorific value (Kcal/kg) | 3000 | 10200 | 3500 |
| Burn compatibility weight (t) | 0.931 | 0.069 | 1 |
Thus often one ton of organic waste alkali liquor concentration liquid of burning is calculated, needs to consume 0.074 ton of diesel oil, diesel-fuel price is 6500
Yuan/ton, then one ton of organic lye diesel oil cost of giving up is burned at about 481 yuan, is concentrated by evaporation steam and is about handled one ton of waste liquid consumption
0.25~0.5 ton of raw steam, one ton of steam price according to 180 yuan/ton calculating, steam consumption generate expense for 45~90 yuan/
Ton, the condensate liquid distilled out are handled using Fenton oxidation, and processing water outlet reaches《Integrated wastewater discharge standard》(GB18918-
2002) recycle water standard, COD<50mg/L is computed processing cost within about 50 yuan/ton using Fenton oxidation dosage.
One ton of organic spent lye is often handled using burning process after being concentrated by evaporation, processing cost is within 620 yuan/ton.
One ton of organic spent lye is burned in the prior art, it is as shown in table 2 below.
2 organic spent lye of table and diesel oil compatibility tables of data
As shown in Table 2, one ton of organic spent lye is burned, needs to consume 0.435 ton of diesel oil.Diesel-fuel price at 6500 yuan/ton,
One ton of organic lye diesel oil cost of giving up then is burned at about 2800 yuan.
By calculating it is found that the treatment process of the highly concentrated organic spent lye of present invention offer, is evaporated dense using multi-effect evaporator
Contracting pretreatment, the highly concentrated useless organic liquor of realization and moisture content efficiently separate, and the condensed water content of organics being evaporated is few, passes through sweet smell
Production link is back to after oxidation processes of pausing；Concentrate calorific value and COD value have been greatly improved, at incinerator compatibility burning
It puts, it is simple for process, substantially reduce cost, cost reduction 70-80%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modification, equivalent replacement or improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind for the treatment of process of highly concentrated organic spent lye, it is characterised in that：The treatment process includes at least following steps：
Step 1, by a concentration of 100,000~300,000 ppm of COD, calorific value is that organic spent lye of 200~600Kcal/kg passes through concentration
Pretreatment, the organic matter of more than 95wt% in organic spent lye and 100% component of inorganic salts are retained in concentrate, obtained
Concentrate and condensed water；
Step 2 handles condensed water using Fenton oxidation and air-float technology, and concentrate is carried out high temperature incineration processing.
2. the treatment process of highly concentrated organic spent lye as described in claim 1, it is characterised in that：The organic waste alkali liquor concentration
Pretreatment includes the following steps：Organic spent lye is preheated, temperature rises to 50-60 DEG C, carries out heat exchange, organic salkali waste after heat exchange
Liquid temperature rises to 102-115 DEG C, becomes gas-liquid mixture, heat source of the gas as heat exchange, and liquid enters evaporator, and process is several
After secondary evaporation and concentration, COD value is obtained as 500,000~2,000,000 ppm, and calorific value is the concentrate and COD value of 1000~3000Kcal/kg
Condensate liquid for 1000~5000ppm.
3. the treatment process of highly concentrated organic spent lye as described in claim 1, it is characterised in that：It is described to be concentrated by evaporation several times
In the process, the steam that the evaporation of last waste water generates is as the heat source to exchange heat next time.
4. such as the treatment process of the highly concentrated organic spent lye of claim 1-3 any one of them, it is characterised in that：The organic waste
Alkali liquor concentration pretreatment carries out concentration pretreatment using multi-effect evaporator evaporation.
5. the treatment process of highly concentrated organic spent lye as claimed in claim 4, it is characterised in that：The multi-effect evaporator evaporation
Concentration pretreatment includes the following steps：
Step A, by organic spent lye by preheating after, temperature rises to 50-60 DEG C, into one effect heat exchanger chuck in carry out adverse current
Heat exchange, organic waste alkali liquid temperature rises to 102-115 DEG C after heat exchange, becomes gas-liquid mixture, keeps absolute pressure in 1st effective evaporator
It is by force 0.01-0.045MPa, some vapor condensed after heat exchange enters an effect and balances in bucket, enters back into effect condensation water preheater
In；
Step B, the steam that 1st effective evaporator tower top comes out is as indirect steam, to entering being evaporated from an effect in 2nd effect evaporator
The liquid of device bottom of towe outflow is heated, and absolute pressure is in -0.024~-0.048MPa, saturated vapor in holding 2nd effect evaporator
82-92 DEG C, some vapor of the condensation after heat exchange enters two effects and balances in bucket；
Step C, the steam that 2nd effect evaporator tower top comes out flows out the slave 2nd effect evaporator bottom of towe entered in triple effect evaporator
Liquid is heated, and absolute pressure in triple effect evaporator is kept to be changed in -0.072~-0.084MPa, 55-65 DEG C of saturated vapor pressure
The some vapor condensed after heat enters in three-effect balance bucket, and three-effect balance bucket is connected with two effect balance buckets, the triple effect of mixing and two
The condensed steam of effect is squeezed into triple effect condensation water preheater；
Step D, the condensed water evaporated is collected with concentrate in respective liquid-collecting barrel respectively.
6. the treatment process of highly concentrated organic spent lye as claimed in claim 5, it is characterised in that：Used in the 1st effective evaporator
Heat exchange steam is the steam generated by burning disposal, and 2nd effect evaporator heat exchange steam used is waste water evaporation production in 1st effective evaporator
Raw steam, heat exchange steam used is waste water evaporation generates in 2nd effect evaporator steam in triple effect evaporator.
7. the treatment process of highly concentrated organic spent lye as claimed in claim 5, it is characterised in that：The triple effect evaporation leading portion is set
There is two-stage countercurrent preheater, first time preheating is carried out to organic spent lye first with triple effect steam condensate (SC), temperature is by 15-25
30-40 DEG C DEG C is risen to, an effect steam condensate (SC) is recycled to carry out second to organic spent lye and is preheated, temperature is risen by 30-40 DEG C
To 50-60 DEG C.
8. the treatment process of highly concentrated organic spent lye as claimed in claim 5, it is characterised in that：The multi-effect evaporator uses
Forced-circulation evaporator reactor；And/or
Balance bucket is both provided with before the evaporator.
9. the treatment process of highly concentrated organic spent lye as described in claim 1, it is characterised in that：By the pH value of the condensed water
3-4 is transferred to, adds in ferrous sulfate and hydrogen peroxide, reacts 1-4h, it is 7-8 then to adjust pH value, flocculant is added in, by air supporting work
Skill detaches precipitation with clear liquid.
10. the treatment process of highly concentrated organic spent lye as claimed in claim 9, it is characterised in that：In the condensed water, sulfuric acid
Ferrous addition is 0.19-0.65wt%；And/or
In the condensed water, hydrogen peroxide of the mass fraction for 30-35% is used, addition is per ton for 20-100L/；And/or
The flocculant is at least one of polyacrylamide or aluminium chloride.
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| CN106495384A (en) * | 2016-11-03 | 2017-03-15 | 南京格洛特环境工程股份有限公司 | The technique that a kind of utilization organic contamination high-salt wastewater prepares industrial purified salt |
| CN110902745A (en) * | 2019-12-12 | 2020-03-24 | 江苏新河农用化工有限公司 | System and method for treating m-phthalodinitrile production wastewater |
| CN112694209A (en) * | 2020-12-25 | 2021-04-23 | 山东东顺环保科技有限公司 | Method for treating refined/distilled residual liquid based on triple-effect distillation-Fenton oxidation process |
| CN114057338A (en) * | 2020-08-05 | 2022-02-18 | 苏州希图环保科技有限公司 | Pretreatment process for high-concentration oil-containing wastewater |
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| CN106495384A (en) * | 2016-11-03 | 2017-03-15 | 南京格洛特环境工程股份有限公司 | The technique that a kind of utilization organic contamination high-salt wastewater prepares industrial purified salt |
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| CN110902745A (en) * | 2019-12-12 | 2020-03-24 | 江苏新河农用化工有限公司 | System and method for treating m-phthalodinitrile production wastewater |
| CN110902745B (en) * | 2019-12-12 | 2022-03-22 | 江苏新河农用化工有限公司 | System and method for treating m-phthalodinitrile production wastewater |
| CN114057338A (en) * | 2020-08-05 | 2022-02-18 | 苏州希图环保科技有限公司 | Pretreatment process for high-concentration oil-containing wastewater |
| CN112694209A (en) * | 2020-12-25 | 2021-04-23 | 山东东顺环保科技有限公司 | Method for treating refined/distilled residual liquid based on triple-effect distillation-Fenton oxidation process |
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Application publication date: 20180608 |