CN101143753A - Deep treatment method for waste salt water produced in MDI producing process - Google Patents
Deep treatment method for waste salt water produced in MDI producing process Download PDFInfo
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Abstract
A deep processing method for the waste salt water, which is produced in a MDI production process, comprises the following steps: (1) the waste salt water produced in the MDI production process with the total amount of the aniline and the methylene diphenylamine not greater than 10ppm and a chemical oxidant are transmitted to a oxidation reactor, and the aeration is processed by the inflation of the air; (2) the waste salt water processed by the step (1) is transmitted to an adsorption tower for the absorption. The invention also comprises a step of ultrasonic deep oxidation treatment. The method of the invention can be removed the amine organic compound in the waste salt water of MDI completely; the TOC of the processed waste salt water is less than 10ppm, the TN is less than 3ppm. Besides, the processed waste salt water can be used as the raw material during the production of the chloro-alkaline ionic membrane caustic soda, and the basic chemical material, which is required during the MDI production of the chlorine, the caustic soda, the hydrochloride and the hydrogen etc. The method regenerates the sodium chloride and the water resources in the waste salt water of the MDI production, which realizes the recycling use of the material in the industry chain.
Description
Technical field
The present invention relates to a kind of deep treatment method of industrial waste salt water, more particularly, is the deep treatment method of the effluent brine that produces in diphenylmethanediisocyanate (hereinafter to be referred as the MDI) production process.
Background technology
MDI is one of main raw material of urethane industry.Aniline and formaldehyde being carried out condensation reaction under the hydrochloric acid catalyst effect, obtain polymethylene polyphenyl polyamine, utilize the polymethylene polyphenyl polyamine phosgenation reaction to produce monomer MDI and polymeric MDI again, is well-known method in the urethane industry.
Aniline and formaldehyde carry out condensation reaction under the hydrochloric acid catalyst effect, obtain the polymethylene polyphenyl polyamine hydrochloride, neutralize with caustic soda then, obtain polyamines, are one of key links of MDI preparation method.Above-mentioned N-process can produce a large amount of effluent brines, and organism such as the aniline in the effluent brine, polyamines are handled through extraction, stripping, can discharge after detection of contamination content is up to standard.The MDI effluent brine contains 14%～18% sodium-chlor approximately, and the pH value is generally between 12～14, wherein contains the organism of trace, mainly is aniline, diamines, polyamines etc., and no colloid and suspended substance in the effluent brine.Because annual effluent brine quantity discharged is very big, causes the waste of great amount of water resources and salt, consider from sustainable development and recycling economy aspect, can will utilize again after a large amount of MDI effluent brine advanced treatment.
Summary of the invention
The purpose of this invention is to provide and a kind of the MDI effluent brine is carried out the method for advanced treatment, the salt solution after the processing can be utilized effectively.
The treatment process of MDI effluent brine provided by the present invention may further comprise the steps:
(1) effluent brine and the chemical oxidizing agent that the aniline that produces in the MDI production process and ditan diamines total amount are no more than 10ppm is delivered in the oxidation reactor;
(2) effluent brine after step (1) is handled is delivered to adsorption tower and is adsorbed.
In the method for the invention, generally speaking, be delivered to the aniline in the effluent brine of oxidation reactor and the total content of ditan diamines (hereinafter to be referred as DAM) and preferably be no more than 10ppm (liquid-phase chromatographic analysis).When their total content surpasses 10ppm, preferably effluent brine is turned back to that the MDI production equipment extracts, stripping,, be delivered to oxidation reactor of the present invention again and handle during up to the total content of aniline and ditan diamines less than 10ppm.
In the method for the invention, described oxidation reactor can be selected any reactor that is applicable to this reaction process for use, for example, and bubbling column reactor or have the still pot type oxidation reactor of aerating apparatus.
In the method for the invention, the temperature of reaction of described oxidation reactor is controlled at 25～90 ℃, is preferably 30～80 ℃; Reaction times was controlled at 30～120 minutes, was preferably 60～120 minutes.The air capacity that is fed in the oxidation reactor is 10～60: 1 according to the ratio of air and effluent brine volumetric flow rate, and preferred 20～50: 1 controls.
In the method for the invention, chemical oxidizing agent is selected from hydrogen peroxide, ozone or contains the oxygenant of free chlorine.The described oxygenant that contains free chlorine can be liquid chlorine, chlorine or clorox etc.Oxygenant of the present invention both can be the general-purpose industrial product, also can be the recovery article of commercial run by-product.The add-on of described chemical oxidizing agent can be determined according to employed chemical oxidizing agent and concrete processing condition by those skilled in the art.Described oxygenant preferably contains the oxygenant of free chlorine, and is further preferred from the effusive light salt brine that contains free chlorine of chlor-alkali factory ion-exchange membrane electrolyzer; And the add-on that contains the light salt brine of free chlorine is controlled according to the standard that every liter of effluent brine adds 50～5000 milligrams of free chlorines, and preferred every liter of effluent brine adds 100～4000 milligrams of free chlorines.
In the method for the invention, the adsorption process of described effluent brine can be carried out in the various adsorption towers that are fit to this processing requirement, wherein, and preferred activated carbon adsorber.The present invention does not have particular requirement for the decoration form of adsorption tower, as long as can satisfy processing requirement.Adsorption tower can be provided with one, also can be provided with a plurality of; When a plurality of adsorption tower is set, it is arranged in parallel, the setting of also can connecting.Wherein, preferably adopt two placed in-line fixed-bed type activated carbon adsorbers.The cylindrical gac of the preferred ature of coal of gac in the described activated carbon adsorber, the particle diameter of gac is 1.5～5mm, is preferably 2～4mm.After charcoal absorption is saturated,, preferably gac is delivered to manufacturer and carried out the activating and regenerating processing for fear of secondary pollution.Gac can be reused 2～3 times generally speaking.Unrenewable gac can be used for thermal power generation, for example, can be used as the fuel of thermoelectric unit roasting kiln, its furnace temperature up to 1300～1400 ℃ about, organism is fully burnt, and recovered energy.
In adsorption process of the present invention, adsorption temp is controlled at 30～70 ℃, is preferably 30～65 ℃; The mean residence time of effluent brine in adsorption tower was controlled at 5～20 minutes, was preferably 7～15 minutes.
In addition, in the method for the invention, the effluent brine after chemical oxidation of gold is handled preferably carries out the ultrasonic wave deep oxidation earlier and handles, and then is introduced into adsorption tower.When the effluent brine system is in ultrasonic environment following time, ultrasonic wave can make effluent brine solution generation ultrasonic cavitation, and cavitation effect can make oxygenant mix with the homogeneous phase that aniline, DAM etc. reaches rapidly under the molecularity, improves oxidizing reaction rate; Simultaneously, the heat effect that cavitation produces can make a large amount of free hydroxyl of water generates, and it has high redox potential, and the various organism that can oxidation are difficult to degrade improve oxidation efficiency, and it is more thorough that aniline, DAM etc. are decomposed.Nonetheless, still can more remainingly not have the thoroughly organism of decomposition, therefore, need carry out charcoal absorption and handle.
In above-mentioned ultrasonic wave deep oxidation treating processes, can adopt tower or groove type ultrasonic ripple reactor, two kinds of pattern reactors all can be buied from ultrasonic equipment manufacturer.In ultrasound reactor, temperature of reaction is controlled at 30～80 ℃, is preferably 40～70 ℃; Reaction times was controlled at 15～90 minutes, was preferably 25～60 minutes; Frequency of ultrasonic is 20～40 kilo hertzs, and the ultrasonic wave sound intensity is 2～8 kilowatts/square metre.
In the method for the invention, also of particular note, the effluent brine after adsorption treatment can be used in the ion film caustic soda production method, and as the ion film caustic soda raw materials for production, MDI produces required raw material with preparation.Above-mentionedly be collected in earlier usually in the finished product salt water pot through the salt solution after the adsorption treatment, its TCO (total organic carbon) less than 3ppm, is sent to the ion film caustic soda production equipment less than 10ppm and TN (total nitrogen) then.In this device, behind processization salt, the refining step, promptly can be used as the raw material of production of caustic soda, but electrolysis generates the raw materials for production that MDI devices such as caustic soda, chlorine and hydrogen need.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
1, the present invention can remove the amine organism in the MDI effluent brine totally, and the brinish TOC after the processing is less than 10ppm, and TN is less than 3ppm, thereby makes the MDI effluent brine realize zero release, fundamentally solves the problem of environmental pollution of effluent brine.
2, the salt solution after the method for the invention is handled can be used as chlor-alkali factory electrolysis with ion-exchange film raw material, generate the basic chemical industry raw material that MDI plant produced such as chlorine, caustic soda, hydrochloric acid and hydrogen need, and make resources such as sodium-chlor in the MDI effluent brine, water obtain regeneration, realized the utilization of MDI industrial chain internal recycle, reduce the consumption of crude salt and water, reduced production cost.
3, method provided by the invention can be combined closely MDI production equipment brine treatment technology and chlorine industry ionic membrane production equipment brine rectification process, and technology chain engages reason.The design closure of above-mentioned MDI effluent brine technical process the breach that be connected to exist of upstream and downstream industrial chain, thereby realized the recycling of industry intrachain resource.Chlorine industry is as the raw material supplier of polyurethane industrial MDI production equipment, and the liquid chlorine of conveying is byproduct HCl in the order-disorder transition of MDI device photoinitiator chemical, and the caustic soda of conveying produces effluent brine with the back in MDI device condensation operation and byproduct HCl; Effluent brine by above-mentioned treating processes after, sodium-chlor wherein and water change chlorine, hydrogen and caustic soda etc. into again as the raw material of chlor-alkali factory ion film caustic soda.
4, the present invention selects the effusive not dechlorination of ionic membrane ionization chamber light salt brine as oxygenant, on the one hand, useless chlorine in the light salt brine and the salkali waste in the effluent brine can be used, on the other hand, free chlorine in the light salt brine is used, can reduce dechlorinator load and follow-up S-WAT input amount, reduce alkali lye and absorb running costs such as tail chlorine.
5, be a green technology owing to what the present invention relates to, avoid the possibility of secondary pollution on the process design.After charcoal absorption is saturated, will delivers to manufacturer and carry out the activating and regenerating processing, can reuse 2～3 times.Unrenewable gac is delivered to the thermoelectric unit roasting kiln, is used for thermal power generation, furnace temperature up to 1300～1400 ℃ about, can make organism fully burn recovered energy.
Characteristics such as 6, the outstanding in design embodiment technology of technical process provided by the invention is succinct, easy to operate, reliable, the industrialization investment cost is low.
Embodiment
Further specify method provided by the present invention below, but therefore the present invention is not subjected to any restriction.
In preferred implementation of the present invention, at first the effluent brine that the MDI process is produced carries out chemical oxidation treatment, blasts air and carries out aeration, and add the oxygenant that contains free chlorine in the MDI effluent brine.Free chlorine can be with the amine organism complete oxidation in the effluent brine, and the partial organic substances of degrading.Bubbling air carries out aeration in the oxidation reaction process, and the one, utilize the oxygenizement of dissolved oxygen, the 2nd, the intermediate product of oxidation reaction process is taken out of by air stripping.Because the chemical oxidation treatment of the first step can't make intermidate oxide decompose fully, therefore, also need it is carried out follow-up processing, that is, adopt charcoal absorption to handle.Because acticarbon is to organic absorption property excellence, under the suitable situation of sorbent material consumption, the amine organism in the effluent brine can be removed fully totally, reach the purpose of TOC, TN in the removal effluent brine.
In another preferred implementation of the present invention, the effluent brine after chemical oxidation of gold is handled preferably carries out the ultrasonic wave deep oxidation earlier and handles, and then is introduced into adsorption tower.When the effluent brine system is in ultrasonic environment following time, ultrasonic wave can make effluent brine solution generation ultrasonic cavitation, and cavitation effect can make oxygenant mix with the homogeneous phase that aniline, DAM etc. reaches rapidly under the molecularity, improves oxidizing reaction rate; Simultaneously, the heat effect that cavitation produces can make a large amount of free hydroxyl of water generates, and it has high redox potential, and the various organism that can oxidation are difficult to degrade improve oxidation efficiency, and it is more thorough that aniline, DAM etc. are decomposed.Nonetheless, still can more remainingly not have the thoroughly organism of decomposition, therefore, need carry out charcoal absorption and handle.
In another preferred implementation of the present invention, the oxygenant that contains free chlorine adopts from the effusive light salt brine that contains free chlorine of ion-exchange membrane electrolyzer.The effusive light salt brine of MDI effluent brine and ion-exchange membrane electrolyzer is taken from device separately, is transported to the effluent brine storage tank and the light salt brine storage tank at pilot scale scene respectively.Described light salt brine dissolves the chlorine of the 0.4g/L that has an appointment, sodium hydroxide reaction in this chlorine and the MDI effluent brine generates clorox, itself contains the clorox of hundreds of～2000ppm approximately this light salt brine, and its content can satisfy the needed clorox consumption of oxidizing reaction.
The following examples will further describe method provided by the present invention, but therefore the present invention is not subjected to any restriction.
Embodiment 1:
The effluent brine of taking from the MDI production equipment is delivered to storage tank, after the cooling, and sampling analysis.Wherein, the pH value is about 13, sodium chloride content 18%, the about 2.5ppm of aniline content, the about 0.8ppm of diamine contents, the about 26ppm of TOC, the about 3.8ppm of TN.
From the effluent brine storage tank, pipette 1200 milliliters of effluent brines, put into 2 liters of glass stills that have the insert aeration tube, add concentration 30% hydrogen peroxide (analytical pure, the Yantai chemical institute) 12 milliliter, carry out chemical oxidation reaction at normal temperatures, bubbling air, aeration rate 40 litres of air/hour, after 1 hour, the glass still is positioned in the KQ-400KDB type ultrasonic cleaner (Kunshan Ultrasonic Instruments Co., Ltd.'s manufacturing), open ultrasonic cleaner, ultrasonic wave operating frequency 40KHz, the ultrasonic wave sound intensity are about 5 kilowatts/square metre, and stop the bubbling air aeration, effluent brine in the glass still is carried out ultrasonication 45 minutes, and the temperature of effluent brine in the glass still is controlled at 30～40 ℃, close ultrasonic cleaner then.
To send into (diameter 30 mm in the glass adsorption column that has chuck according to 540 milliliters of/hour flows through the effluent brine after the ultrasonication in the glass still with volume pump, height 800mm), cylinder shape coal mass active carbon 100 grams that interior dress diameter is 4mm, 30～40 ℃ of effluent brine temperature, about 12 minutes of its residence time in the glass adsorption column, the collection salt solution behind the adsorption column of flowing through, and analyze.In the salt solution after the processing after testing less than aniline and diamines, the about 8.2ppm of TOC, the about 1.6ppm of TN, its organic content satisfies the processing requirement of ion film caustic soda.
Embodiment 2:
Adopt the MDI effluent brine identical to test with embodiment 1.
From the effluent brine storage tank, pipette 1200 milliliters of effluent brines, put into 2 liters of glass stills that have the insert aeration tube, (reagent is pure to add concentration 10% clorox, Yantai three and chemical reagent factory) 6 milliliters, under 40 ℃, carry out chemical oxidation reaction, bubbling air, 40 liters/hour of aeration rates, after 1 hour, the glass still is positioned in the KQ-400KDB type ultrasonic cleaner, open ultrasonic cleaner, ultrasonic wave operating frequency 40KHz, the ultrasonic wave sound intensity are about 5 kilowatts/square metre, and stop the bubbling air aeration, the temperature of effluent brine in the glass still is controlled at 30～40 ℃, the effluent brine in the glass still was carried out ultrasonication 45 minutes, close ultrasonic cleaner then.
To send in the glass adsorption column that has chuck according to 540 milliliters of/hour flows through the effluent brine after the ultrasonication in the glass still with volume pump, the adsorption column that is adopted is identical with embodiment 1,30～40 ℃ of effluent brine temperature, about 12 minutes of the residence time of effluent brine in the glass adsorption column.In the salt solution after the processing after testing less than aniline and diamines, the about 7.5ppm of TOC, the about 1.3ppm of TN, its organic content satisfies the processing requirement of ion film caustic soda.
Embodiment 3:
Adopt the MDI effluent brine identical to test with embodiment 1.
Fetch not dechlorination light salt brine from chlor-alkali ion film caustic soda production equipment, after the cooling, sampling analysis, the about 1500ppm of free chlorine (hypochlorite) content, the about 5ppm of TOC, the about 2.5ppm of TN.Adopt this not the dechlorination light salt brine as chemical oxidizing agent.
From the effluent brine storage tank, pipette 1200 milliliters of effluent brines, put into 2 liters of glass stills that have the insert aeration tube, add 600 milliliters of above-mentioned not dechlorination light salt brines, at room temperature carry out chemical oxidation reaction, bubbling air, 60 liters/hour of aeration rates, after 1 hour, the glass still is positioned in the KQ-400KDB type ultrasonic cleaner, opens ultrasonic cleaner, ultrasonic wave operating frequency 40KHz, the ultrasonic wave sound intensity is about 5 kilowatts/square metre, and stops the bubbling air aeration, and the temperature of effluent brine in the glass still is controlled at 30～40 ℃, effluent brine in the glass still is carried out ultrasonication 20 minutes, close ultrasonic cleaner then.
To send in the glass adsorption column that has chuck according to 540 milliliters of/hour flows through the effluent brine after the ultrasonication in the glass still with volume pump, the adsorption column that is adopted is identical with embodiment 1.30～40 ℃ of the adsorption temps of effluent brine, about 12 minutes of the residence time in the glass adsorption column.In the salt solution after the processing after testing less than aniline and diamines, the about 6.8ppm of TOC, the about 1.2ppm of TN, its organic content satisfies the processing requirement of ion film caustic soda.
Embodiment 4:
Adopt the MDI effluent brine identical to test with embodiment 1.The chemical oxidizing agent that is adopted is identical with embodiment 3.
From the effluent brine storage tank, pipette 1200 milliliters of effluent brines, put into 2 liters of glass stills that have the insert aeration tube, add not 600 milliliters of dechlorination light salt brines, under 50～60 ℃, carry out chemical oxidation reaction, bubbling air, 60 liters/hour of aeration rates, after 1 hour, the glass still is positioned in the KQ-400KDB type ultrasonic cleaner, opens ultrasonic cleaner, ultrasonic wave operating frequency 40KHz, the ultrasonic wave sound intensity is about 5 kilowatts/square metre, and stops the bubbling air aeration, and the temperature of effluent brine in the glass still is controlled at 65～70 ℃, effluent brine in the glass still is carried out ultrasonication 45 minutes, close ultrasonic cleaner then.
To send in the glass adsorption column that has chuck according to 540 milliliters of/hour flows through the effluent brine after the ultrasonication in the glass still with volume pump, the adsorption column that is adopted is identical with embodiment 1.The adsorption temp of effluent brine is 60～65 ℃, about 12 minutes of the residence time of effluent brine in the glass adsorption column.In the salt solution after the processing after testing less than aniline and diamines, the about 7.1ppm of TOC, the about 1.3ppm of TN, its organic content satisfies the processing requirement of ion film caustic soda.
Embodiment 5:
Adopt the MDI effluent brine identical to test with embodiment 1.The chemical oxidizing agent that is adopted is identical with embodiment 3.Concrete chemical oxidation step is identical with embodiment 4 with ultrasonic wave deep oxidation step.To send in the glass adsorption column that has chuck according to 540 milliliters of/hour flows through the effluent brine after the ultrasonication in the glass still with volume pump, the specification of the adsorption column that is adopted is identical with embodiment 1, cylinder shape coal mass active carbon 120 grams that interior dress diameter is 4mm, the adsorption temp of effluent brine is 55～60 ℃, about 16 minutes of the residence time of effluent brine in the glass adsorption column.In the salt solution after the processing after testing less than aniline and diamines, the about 7.6ppm of TOC, the about 1.4ppm of TN, its organic content satisfies the processing requirement of ion film caustic soda.
Embodiment 6:
Adopt the MDI effluent brine identical to test with embodiment 1.The chemical oxidizing agent that is adopted is identical with embodiment 3.
With volume pump from the effluent brine storage tank with 360 milliliters/hour flow, carry effluent brine to the 1 liter of glass still that has the insert aeration tube, simultaneously, add not dechlorination light salt brine with volume pump with 180 milliliters of/hour flows, at room temperature carry out chemical oxidation reaction, continuous bubbling air, 20 liters/hour of aeration rates, about 1 hour of the mean residence time of effluent brine in the glass still.Be transported in the glass still in the KQ-400KDB type ultrasonic cleaner (1 liter) with the effluent brine of 540 milliliters/hour flows after above-mentioned oxidation, open ultrasonic cleaner, ultrasonic wave operating frequency 40KHz, the ultrasonic wave sound intensity is about 5 kilowatts/square metre, the supersound process process is aeration not, about 45 minutes of mean residence time in the glass still of effluent brine in ultra-sonic generator is controlled at 30～40 ℃ with the temperature of effluent brine in the glass still.
To send in the glass adsorption column that has chuck according to 540 milliliters/hour flow through the effluent brine after the ultrasonication in the glass still with volume pump, the specification of the adsorption column that is adopted is identical with embodiment 1.The adsorption temp of effluent brine is 30～40 ℃, about 12 minutes of the residence time of effluent brine in the glass adsorption column.In the salt solution after the processing after testing less than aniline and diamines, the about 6.5ppm of TOC, the about 1.3ppm of TN, its organic content satisfies the processing requirement of ion film caustic soda.
Embodiment 7:
The effluent brine that is adopted, chemical oxidizing agent and oxidation and adsorption step are substantially the same manner as Example 6, close ultrasonic generator in process of the test.After opening each volume pump, effluent brine through placing second glass still in the ultrasonic cleaner, proceeds chemical oxidation reaction, the active carbon adsorption column of flowing through then through first glass still generation chemical oxidation reaction.In the salt solution after the processing after testing less than aniline and diamines, the about 7.5ppm of TOC, the about 1.4ppm of TN, its organic content satisfies the processing requirement of ion film caustic soda.
Embodiment 8:
Take from the effluent brine of MDI production equipment and put into 12 cubic metres of effluent brine storage tanks, after the cooling, sampling analysis.Wherein, the pH value is about 13, sodium chloride content 18%, the about 3.8ppm of aniline content, the about 0.6ppm of diamine contents, the about 28ppm of TOC, the about 3.9ppm of TN.Fetch not the dechlorination light salt brine from chlor-alkali ion film caustic soda production equipment and put into 10 cubic metres of light salt brine storage tanks, after the cooling, sampling analysis, the about 1500ppm of free chlorine content, the about 5ppm of TOC, the about 2.5ppm of TN.
From the effluent brine storage tank with 300 kilograms/hour flow volume delivery MDI effluent brine at the bottom of the bubble tower (in 500 * 3300mm) the liquid phase feeding pipes, simultaneously, add not the dechlorination light salt brine to feed-pipe with 150 kilograms of/hour flows, from the continuous bubbling air of tower spirit phase feed-pipe, 13 cubic metres/hour of aeration rates, after effluent brine flows out from bubble tower top discharge nozzle, from ultrasonic wave tower reactor (600 * 3700mm, be provided with 8 ultrasonic vibration plates altogether, 0.9KW/ piece, ultrasonic frequency 27KHz, about 4 kilowatts/square metre of the ultrasonic wave sound intensity, make by Jining Jin Baite company) the bottom feed mouth enters, and in ultrasound reactor, the temperature of effluent brine is controlled at 30～40 ℃.After effluent brine flows out from ultrasonic wave tower reactor top, from activated carbon adsorber (600 * 3550mm, the ature of coal cylinder shape gac that to load 400 kilograms of diameters altogether be 4mm) the liquid phase feeding pipeline at the bottom of the tower enters, flow through behind the active carbon bed, flow out from the adsorption tower top, enter 20 cubic metres of finished product salt water pots.The finished product salt water pot is the salt solution after handling, by analysis, after testing less than aniline and diamines, the average 6.8ppm of TOC, the average 1.5ppm of TN, its organic content satisfies the processing requirement of ion film caustic soda.
Above-mentioned MDI effluent brine is handled pilot plant and is moved 1200 hours continuously, about 540 tons of salt solution after the processing, its analysis indexes all satisfies the ion film caustic soda manufacturing technique requirent, send into ionic membrane production equipment brine treatment system after, the every processing parameter of production equipment is all normal.
Embodiment 9:
The effluent brine that this embodiment adopted, chemical oxidizing agent and main operational condition are substantially the same manner as Example 8, but have closed the power supply of 8 vibration plates of ultrasound reactor.Get the sample of finished product salt water pot and analyze, in the salt solution after the processing after testing less than aniline and diamines, the average 7.0ppm of TOC, the average 1.5ppm of TN, its organic content satisfies the processing requirement of ion film caustic soda.
Under the above-mentioned processing condition, the MDI effluent brine is handled pilot plant and is moved 2400 hours continuously, about 1080 tons of the salt solution after the processing, and its analysis indexes all satisfies the ion film caustic soda manufacturing technique requirent, after sending into ionic membrane production equipment brine treatment system, the every processing parameter of production equipment is all normal.
Embodiment 10:
The effluent brine that this embodiment adopted, chemical oxidizing agent and main operational condition are substantially the same manner as Example 9, but the flow of MDI effluent brine is 338 kilograms/hour, and the feed rate of light salt brine is 113 kilograms/hour.Get the sample of finished product salt water pot and analyze, in the salt solution after the processing after testing less than aniline and diamines, the average 7.5ppm of TOC, the average 1.7ppm of TN, its organic content satisfies the processing requirement of ion film caustic soda.
Under the above-mentioned processing condition, the MDI effluent brine is handled pilot plant and is moved 1000 hours continuously, about about 450 tons of the salt solution after the processing, and its analysis indexes all satisfies the ion film caustic soda manufacturing technique requirent, after sending into ionic membrane production equipment brine treatment system, the every processing parameter of production equipment is all normal.
The comparative example
MDI production equipment condensation reaction operation produce in and effluent brine, mainly contain the sodium-chlor about 18%, about 1.1% aniline, about 0.1% ditan diamines etc.This salt solution need be handled in the brine treatment operation, make organic content such as aniline and ditan diamines up to standard after, could discharge.The technology that production equipment brine treatment operation is taked be one's own profession those skilled in the art be familiar with: effluent brine extracts earlier, and then it is carried out stripping, and the effluent brine after the processing is delivered to surge tank.Detect the effluent brine index in the surge tank, total amine content is less than 5ppm (liquid-phase chromatographic analysis), just can deliver to sewage plant, when total amine content is higher than 5ppm, the salt solution of surge tank can be turned back to the front operation, extract again, stripping handles, and adjusts processing parameters such as extraction agent and steam consumption, makes total amine content less than 5ppm.Generally speaking, the TOC that handles the back effluent brine is about 30ppm, and TN is about 3.5ppm.
Claims (10)
1. the deep treatment method of the effluent brine that produces in the MDI production process may further comprise the steps:
(1) effluent brine and the chemical oxidizing agent that the aniline that produces in the MDI production process and ditan diamines total amount are no more than 10ppm is delivered in the oxidation reactor, and bubbling air carries out aeration;
(2) effluent brine after step (1) is handled is delivered to adsorption tower and is adsorbed.
2. method according to claim 1 is characterized in that, the temperature of reaction of described effluent brine in oxidation reactor is controlled at 25～90 ℃, is preferably 30～80 ℃; Reaction times was controlled at 30～120 minutes, was preferably 60～120 minutes; The air capacity that is fed is 10～60: 1 according to the ratio of air and effluent brine volumetric flow rate, and preferred 20～50: 1 controls.
3. method according to claim 2 is characterized in that, described chemical oxidizing agent is selected from hydrogen peroxide, ozone or contains in the oxygenant of free chlorine any; Described oxidation reactor is bubbling column reactor or the still tank reactor that has aerating apparatus.
4. method according to claim 3, it is characterized in that, described chemical oxidizing agent is for from the effusive light salt brine that contains free chlorine of chlor-alkali factory ion-exchange membrane electrolyzer, and the add-on that contains the light salt brine of free chlorine is controlled according to the standard that every liter of effluent brine adds 50～5000 milligrams of free chlorines.
5. according to claim 1 or 4 described methods, it is characterized in that the effluent brine after step (1) is handled is delivered to activated carbon adsorber and adsorbed, adsorption temp is controlled at 30～70 ℃, is preferably 30～65 ℃; The mean residence time of effluent brine in adsorption tower was controlled at 5～20 minutes, was preferably 7～15 minutes.
6. method according to claim 5, it is characterized in that, effluent brine after step (1) is handled is introduced tower or groove type ultrasonic ripple reactor earlier, carrying out the ultrasonic wave deep oxidation handles, and then adsorb, and frequency of ultrasonic is 20～40 kilo hertzs, and the ultrasonic wave sound intensity is 2～8 kilowatts/square metre.
7. method according to claim 6 is characterized in that, in ultrasound reactor, the temperature of reaction of effluent brine is controlled at 30～80 ℃, is preferably 40～70 ℃; Reaction times was controlled at 15～90 minutes, was preferably 25～60 minutes.
8. method according to claim 7 is characterized in that, two the placed in-line fixed-bed type activated carbon adsorbers of flowing through of the effluent brine after step (1) is handled.
9. method according to claim 8 is characterized in that, the gac in the described activated carbon adsorber is the cylindrical gac of ature of coal, and particle diameter is 1.5～5mm, is preferably 2～4mm.
10. according to claim 1 or 9 described methods, it is characterized in that salt solution after treatment is delivered to chlor-alkali factory ion film caustic soda production equipment, as raw materials for production, MDI produces required caustic soda, chlorine, hydrochloric acid and hydrogen with preparation.
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| CNB2007101380652A CN100534931C (en) | 2007-08-08 | 2007-08-08 | Deep treatment method for waste salt water produced in MDI producing process |
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| CNB2007101380652A CN100534931C (en) | 2007-08-08 | 2007-08-08 | Deep treatment method for waste salt water produced in MDI producing process |
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| CN102046588A (en) * | 2008-05-26 | 2011-05-04 | 巴斯夫欧洲公司 | Method for producing diphenylmethane diamine |
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| CN112978766A (en) * | 2021-01-28 | 2021-06-18 | 上海市机电设计研究院有限公司 | Advanced treatment method for industrial waste salt |
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