CN1331053A - Process for reclaiming ammonia-contained sewage - Google Patents
Process for reclaiming ammonia-contained sewage Download PDFInfo
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- CN1331053A CN1331053A CN 00110589 CN00110589A CN1331053A CN 1331053 A CN1331053 A CN 1331053A CN 00110589 CN00110589 CN 00110589 CN 00110589 A CN00110589 A CN 00110589A CN 1331053 A CN1331053 A CN 1331053A
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Abstract
A process for treating and recovering the ammonia/ammonium contained waste water generated in preparing catalyst includes reverse-osmosis concentration of the said waste with low ammonia content, direct use of the resultant liquid or partial use of it as the ammonia vapour absorbing liquid in stripping tower, mixing the concentrated liquid with the high-concentration the said waste water, adding alkali to regulate pH value, loading in stripping tower to recover ammonia from tower top and discharging the clean water. Its advantages include low energy and chemical consumption, and high recovery rate.
Description
The present invention relates to a kind of processing and recovery method that contains ammonia process waste water, contained the ammonia process wastewater treatment method especially for what produce in the catalyst preparation process, in the oil refining catalyst preparation process, the processing that contains ammonia process waste water and the recovery method that in exchange of catalyzer colloidal ammonium and washing, are discharged.
Oil refining catalyst is to be raw material with some chemicals that contain aluminium, silicon etc. mostly, as water glass, Tai-Ace S 150, aluminium hydroxide, pure aluminium silicate etc., through becoming synthetic NaY colloid or NaY type molecular sieves such as glue, crystallization, exchanges out Na through ammonium exchange or rare earth ammonium exchange process etc. again
+Ion, and wash out Na with chemical purification water (deionized water)
+Ion is at last by synthetic catalyst work in-process or catalyzer finished products such as drying, roasting, activation.In the above-mentioned preparation process of oil refining catalyst, need to consume that a large amount of chemical purification water is synthetic in order to the catalyzer colloid, ammonium exchange and washing etc., and in the efflux technology waste water of whole production, mainly be divided into three kinds according to different ammonia contents, first kind is the extremely low waste water of ammonia content, synthesize the water etc. that washes cloth that liquid filters the filter of draining, NaY colloid washing water, various filter plants, NH as the NaY colloid
3Generally below 100 μ g/g, the quantity discharged of this water accounts for 50% of total displacement to-N; Second kind is dense ammonia-containing water, as the exchange of catalyzer colloidal ammonium or rare earth ammonium exchange filtered liquid and first washing water, NH
3Generally in 4000 μ g/g-10000 μ g/g scopes, the quantity discharged of this water accounts for the 10%-15% of total displacement to-N; The third is rare ammonia-containing water, finishes ammonium exchange or rare earth ammonium exchange filtration and first washing water after washing, NH as the catalyzer colloidal
3Generally in 150-1500 μ g/g scope, the quantity discharged of this water accounts for the 35%-40% of total displacement to-N.The wastewater flow rate that is produced in the Catalyst Production process is very big, as produce the catalyst plant of 10000-20000t/a scale per year, the processing wastewater quantity discharged is about 300t/h, handle means owing to lack cost-effective ammonia-containing water at present, most of catalyst plants only adopt various catalyst process waste water are mixed, enter in the peripheral waters after removing suspended substance in the waste water by separation methods such as sedimentations, cause NH in the efflux wastewater
3-N reaches about 1000 μ g/g, causes severe contamination.
At present, the Technology that can be used for ammoniacal liquor separation and recovery mainly contains blow-off method and membrane separation process, and the former utilizes air or steam that ammonia is taken out of with gas form, and its technology is simple, reliability is high, the suitable treatment strong ammonia wastewater; Membrane separation process is to utilize ammonia to be easy to by dewatering microporous film, and water and other ion are difficult for by realizing that ammoniacal liquor separates.Blow-off method Ammonia-Containing Wastewater Treatment technology is very ripe, use single tower stripping to handle the refinery ammonia-containing water as ZL90107237.0, this technique means is to handling dense ammonia-containing water, particularly less when the water yield, water quality is under alkalescence or the neutrallty condition, and is comparatively suitable economically, because under this condition, ammonia in the waste water mainly is free state, do not consume or consume less alkali in the process, get final product a large amount of free ammonias in the stripping water outlet, reclaim strong aqua or ammonium.Yet the ammonia-containing water bigger for wastewater flow rate, that ammonia content is lower is particularly worked as water quality and is acid properties, employing steam/or the steam stripped processing mode of air, lot of energy and alkali will be consumed in the process, and the strong aqua that reclaims is less, economy is relatively poor, is not suitable for industrial application.CN1032465C has introduced a kind of novel process that ammonia/moisture film separates and reclaim ammonia that is used for, it replaces existing sour absorption process with the decompression method, it is characterized in that strong-hydrophobicity microporous membrane one side is a deposed ammonia in membrane separation unit, and the opposite side of film is established reliever, to reduce this side gas pressure, make its vacuum tightness remain on the 10-760mmHg scope, under film pressure at both sides gradient promotes, ammonia in the ammonia-containing water is constantly volatilized through porous-film, and can not see through the water and the discharging of other material of film; The ammonia that sees through film absorbs through condensation or with absorption agent, obtain to reclaim product, this technology is compared with general ammonia/moisture film separating technology, except that the deamination rate is relatively low (the deamination rate is about 93%), tangible advantage is arranged undoubtedly, as avoided ammonia/moisture film and separated the back and contact with the direct of film, make ammonia/water sepn and recovery ammonia become two processing steps that are independent of each other as the acid of ammonia absorption agent, widened the range of choice of ammonia/water sepn film greatly, reduced the acid proof requirement of microporous membrane; In the membrane sepn process, do not exist simultaneously soda acid chemical reaction, the temperature in the membrane separation unit to become and control easily, waste water is carried out under high slightly temperature.Yet the novel process that is proposed is the same with all ammonia/moisture film separating technology all is the ammonium in the waste water need be transformed ammonification, therefore consider from the economy of Technology, generally only is suitable for the processing of the dense ammonia-containing water of the little water yield.
The physics, the chemical process that also have some other Ammonia-Containing Wastewater Treatment, as: US4285830 has proposed to use HNO with the ammonium nitrate wastewater that contains that produces in the production of thermal degradation oxidative treatment nuclear industry
3And O
2Ammonia or ammonium in the oxidized waste water make it to generate NO
x, absorbing with nitric acid again, this treatment process limitation is very big, can only be used for the processing of specific ammonia-containing water, can not be used for the processing of catalyzer ammonia-containing water; US4292043 has proposed to use evaporation concentration, crystallization processes is handled sulfur acid ammonium waste water reclamation ammonium sulfate, but contain ammonia process waste water for catalyzer, this evaporation concentration, crystalline treatment process can only be useful in the relatively low dense ammonium that takes off that contains ammonia process waste water of wastewater flow rate and handle, and since the dense ammonia-containing water of catalyzer in except that containing the high density ammonium, also contain the Na of a great deal of
+Ion, also usually be the mixture of multiple ammonium in some waste water, as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate etc., if adopt evaporation concentration, crystalline treatment process, the ammonium salt that is obtained will contain a large amount of impurity and the mixture of ammonium, not reclaim and reuse value.
For the lower concentration ammonia-containing water that does not need to reclaim, can adopt biologic treating technique etc. to carry out purifying treatment, but can not reclaim wherein valuable ammonia components, and owing to contain salt in the water after handling and other impurity is difficult to recycle.
In sum, the technology of handling strong ammonia wastewater in the prior art is comparatively ripe, but the ammonia-containing water lower to concentration, particularly processing are the tart ammoniated wastewater in a large number, and energy consumption height, the chemical reagent consumption amount that has treatment technology now is big, the property recycled of purifying waste water is poor.
The object of the invention is to propose to contain in a kind of energy consumption is low, the chemical reagent consumption the is few Catalyst Production process comprehensive treating process and the recovery method of ammonia/ammonium processing wastewater, what make in the catalyst preparation process to be produced contains the ammonia process discharged wastewater met the national standard, and in waste water ammonia-removal, pay attention to consider the recovery of ammonia and the reuse of water, to keep whole waste water treatment process economy, effectively and reasonably.
Processing and recovery method process that Catalyst Production technology of the present invention contains ammonia/ammonium waste water may further comprise the steps:
1, rare ammonia/ammonium waste water that contains concentrates through reverse osmosis membrane, and membrane permeation liquid is as the absorption liquid of steam stripped tower ammonia steam or directly recycling;
2, membrane concentration liquid mixes and adds alkali adjusting pH value with the dense ammonia/ammonium waste water that contains;
3, the ammonia-containing water after the alkalization enters the steam stripped tower, reclaims wherein ammonia or ammonium, and stripping is purified waste water and reached
The mark discharging.
Rare in the step 1 contains ammonia/ammonium waste water and comes from that the catalyzer colloid is finished the ammonium exchange or the exchange of rare earth ammonium is filtered and first washing water after washing, its NH
4-N is generally at 150~1500 μ g/g scopes, Na
+Generally at 100~3000 μ g/g, its pH value is generally 3~7 for content.Selected reverse osmosis membrane is selected from cellulose acetate membrane, polysulfone membrane, polyimide film etc., and the permeability rate of film is 90~120l/m
2H, saturating salt rate is 95~99%.The working pressure of reverse osmosis is controlled at 1.5~4.5MPa.For this rare ammonia-containing water, under the situation that does not add any chemical agent, carry out 1~3 grade reverse osmosis concentration and handle, concentrated solution is concentrated to the into 10%-20% of water weight, NH
4-N is concentrated to 1500 μ g/g-15000 μ g/g.Because the NH in rare ammoniated wastewater
4 +With Na
+Content is about the same, and its osmotic pressure is basic identical, under the condition that keeps 95% above film ratio of desalinization, through 1 grade or the processing of multistage reverse osmosis concentration, the NH in the membrane permeation liquid
4 +With Na
+All can reach below the 5 μ g/g, the make up water of the chemical water that can be used as in the catalyst preparation process to be added and in order to the absorption liquid of the evaporation ammonia that absorbs the stripping tower cat head that dense ammonia-containing water steam stripped handles is recycled water and ammonia.
The membrane concentration liquid that step 1 obtains mixes with the dense ammonia/ammonium waste water that contains, and mixed solution adds alkali and regulates pH, with soda ash and other alkali lye or waste lye the dense ammonia/ammonium waste water that contains that is produced in the Catalyst Production process is alkalized and is adjusted to pH and reaches more than 10.5.The described dense ammonia/ammonium waste water that contains is from the exchange of catalyzer colloidal ammonium or rare earth ammonium exchange filtered liquid and first washing water, NH
4Generally in 4000 μ g/g-10000 μ g/g scopes, salts contg is also very high for-N, usually Na
+Can reach 500~3000 μ g/g.
Mixing after the alkalization contains the ammonia waste liquid and enters the steam stripped tower, and the design of stripping tower is the general designer's in this area a general knowledge.For example, use the general operational requirement(GOR) of turret to be: quantity of steam is 3~10w% of flooding quantity, preferred 5~8w%, and the deamination rate is generally 95~99.5%.Cat head lays the vapor condensation cooling apparatus and ammonia absorbs facility, reclaims high density ammoniacal liquor or ammonium salt.The absorbing medium of cat head ammonia can be selected the acid solution of chemical water purification or lower concentration for use, and example hydrochloric acid, sulfuric acid etc., this acid solution are preferably selected for use and more purifiedly (contained Na
+Ion is extremely low) contain ammoniacal liquor and prepare, as adopting the membrane permeation liquid of the rare ammonia-containing water of step 1 after reverse osmosis desalination is handled, to save the consumption of chemical purification water in the whole process.Absorb that dense behind the ammonia contains ammoniacal liquor or ammonium salt-containing water can be directly as colloid ammonium exchange liquid and washings in the Catalyst Production process, the chemical water and fresh ammonium salt or the ammoniacal liquor that are added in the part replacement process.The stripping tower stripping is purified waste water, because salts contg is higher, not easy to be recycled, but ammonia-nitrogen content satisfies emission request, can directly discharge.The stripping NH in the water that purifies waste water
3-N reaches below the 100 μ g/g.
Fig. 1 is that catalyzer of the present invention contains ammonia/ammonium waste water treatment and reclamation schematic flow sheet.Further specify the solution of the present invention and effect below in conjunction with accompanying drawing.
A kind of Catalyst Production provided by the present invention contains processing and the recovery method of ammonia process waste water, mainly be applicable to above-mentioned second production technology waste water and the third production technology waste water to mentioning in the Catalyst Production process, namely be used for the ammonium exchange of catalyst colloid or the dense ammonia-containing water (NH of rare earth ammonium exchange filtered fluid and first washings4-N is generally in 4000 μ g/g-10000 μ g/g scopes) and be used for that the catalyst colloid is finished the ammonium exchange or the exchange of rare earth ammonium is filtered and first washing after rare ammonia-containing water (NH of washings3-N one As in 150 μ g/g~1500 μ g/g scopes).
Dense ammonia-containing water is because NH4-N concentration is higher, and discharge capacity is lower, adopts to add the steam stripped processing of alkali PROCESS FOR TREATMENT is namely with soda ash and other alkali lye or dense the contain ammonia of spent lye to producing in the Catalyst Production process Waste water alkalizes and is adjusted to pH and reaches more than 10.5. Keeping vapor flow of stripper is the 3%w~10 of inflow %w makes stripping deamination rate reach 95%~99.5%, uses purer (to contain Na+Ion is extremely low) chemistry Water or pickle absorb the ammonia of stripper cat head, and rare ammonia-containing water of mentioning such as the back is through reverse osmosis deaslination Film penetrating fluid after the processing or with the pickle of this water preparation, to contain ammoniacal liquor direct for dense behind institute's absorbing ammonia like this As colloid ammonium exchange liquid and cleaning solution in the Catalyst Production process, Partial Replacement in the catalyst preparation process The chemical water that adds and fresh ammonium salt and ammoniacal liquor.
Rare ammonia-containing water that the Catalyst Production process produces is because NH4-N concentration is generally at 150~1500 μ About g/g, discharge capacity is bigger, if adopt the stripping deamination processing mode identical with dense ammonia-containing water, meeting Consume a large amount of alkali, make stripper equipment huge, energy consumption increases, and it is relatively poor to process economy. The present invention proposes The method that adopts reverse osmosis process that rare ammonia-containing water is concentrated because waste water is acid properties, except containing The NH that certain content is arranged4Outside-the N, also contain certain density Na+And Cl-Deng, therefore select by operating condition and the film of control counter-infiltration, make reverse osmosis process reach higher film salt rejection rate, guarantee to contain in the reverse osmosis membrane penetrating fluid Na of trace+And Cl-Deng, can be directly as the cat head ammonia absorption liquid of dense ammonia-containing water steam stripping processing in the aforementioned process with as colloid ammonium exchange liquid or cleaning solution in the Catalyst Production process, after 1~3 grade of reverse osmosis membrane processing, reverse osmosis membrane trapped fluid (concentrate of rare ammonia-containing water) reaches 10 %-20% for the treatment of fluid, makes NH in the concentrate4-N reaches 1500 μ g/g-15000 μ g/g, with Catalyst Production The dense ammonia-containing water that produces in the process mixes and carries out the stripping processing. Like this, both having reclaimed in the waste water has The ammonia components that is worth, reclaimed most of water again, purifying waste water of reclaiming accounts for rare ammonia-containing water amount of processing 80~90%, and reduced the consumption of chemical reagent, reduced equipment investment and the operating cost of stripper.
A kind of catalyst proposed by the invention contains the processing of ammonia process waste water and reclaims technology, is applicable to oil refining In the processing that contains ammonia process waste water that produces in the catalyst preparation process, especially for oil refining catalyst system In the standby process, in the processing that contains ammonia process waste water of in the ammonium of catalyst colloid exchanges and washs, discharging.
A kind of Catalyst Production proposed by the invention contains the processing of ammonia process waste water and reclaims technology, is to urge Change agent efflux technology waste water and carry out the water system division according to different ammonia contents, comprehensive recycling. Contain with existing The ammonia waste water treatment technology is compared: not only solved the dense ammonia process waste water that contains that produces in the catalyst preparation process Handle problems, and solved the rare ammonia process waste water handling problem that contains that produces, particularly processing Considered recovery and the water reuse of ammonia in the journey, made whole ammonia-containing water treatment process economy, effectively and reasonably. The inventive method chemical reagent consumption amount is few, equipment investment and operating cost is low, the rate of recovery of purifying waste water height, vapour Carrying rear waste water can qualified discharge.
Specify the scheme and the effect of the inventive method below by specific embodiment.
Embodiment 1
By flow process shown in Figure 1, reverse osmosis unit adopts cellulose acetate membrane, and rare ammonia-containing water adopts the two-pass reverse osmosis concentration, and 1 grade of penetrating fluid is as the water inlet of 2 grades of reverse osmosiss, the water inlet of concentrated solution adverse current to the 1 grade reverse osmosis of 2 grades of reverse osmosiss, 1, the average permeability rate of 2 grades of reverse osmosiss is respectively 95l/m
2H, 110l/m
2H, average saturating salt rate is respectively 95%, 98%.Stripper plant is that theoretical plate number is 13 sieve-tray tower, and the stripping medium is selected atmospheric steam for use.
Rare ammonia-containing water: ammonia-containing water (consists of NH
4Cl:0.48%, Na
+: 1086 μ g/g, pH 6.0) pump into reverse osmosis unit, 35 ℃ of service temperatures, film inlet pressure 3.7MPa, film top hole pressure 3.3MPa.Obtain concentrated solution: concentration ratio 18.5%, NH
4Cl 2.50%, Na
+5640 μ g/g; Membrane permeation liquid: NH
4 +3 μ g/g, Na
+5 μ g/g, membrane permeation liquid reclaims as chemical purification water, and the water rate of recovery is 82.5%.
Dense ammonia-containing water: the mixed solution (NH of the reverse osmosis concentrated liquid of the dense ammonia-containing water of catalyzer and rare ammonia-containing water
3-N:4120 μ g/g) add 20% alkali lye and regulate pH to 11.0, carry out the atmospheric steam stripping, quantity of steam is 5% of the weight of water inlet, and the deamination rate is 98%.Be mixed with 10% hydrochloric acid soln with the membrane permeation liquid of the rare ammonia-containing water two-pass reverse osmosis of part concentration and absorb the cat head ammonia, obtain the ammonium chloride solution of cat head 11.5%, the low NH that purifies waste water of tower
3-N:90.3 μ g/g, directly discharging.
Embodiment 2
By flow process shown in Figure 1, reverse osmosis unit adopts polysulfone membrane, rare ammonia-containing water adopts three grades of reverse osmosis concentration to handle, 1 grade of penetrating fluid is as the water inlet of 2 grades of reverse osmosiss, 2 grades of penetrating fluids are as the water inlet of 3 grades of reverse osmosiss, the concentrated solution of 3 grades, 2 grades reverse osmosiss is the water inlet of adverse current to 2 grade and 1 grade of reverse osmosis respectively, and 1, the average permeability rate of 2,3 grades of reverse osmosiss is respectively 92l/m
2H, 104l/m
2H, 114l/m
2H, average saturating salt rate is respectively 95%, 97%, 99%.Stripper plant is that theoretical plate number is 13 sieve-tray tower, and the stripping medium is selected steam for use.
Rare ammonia-containing water: ammonia-containing water (consists of NH
4NO
3: 0.43%, Na
+: 986 μ g/g, pH 4) pump into reverse osmosis unit, 45 ℃ of service temperatures, film inlet pressure 3.7MPa, film top hole pressure 3.4MPa.Obtain concentrated solution: concentration ratio 15.4%, NH
4NO
32.7%, Na
+6083 μ g/g; Membrane permeation liquid: NH
4 +3.6 μ g/g, Na
+4.3 μ g/g, membrane permeation liquid reclaims as chemical purification water, and the water rate of recovery is 84.9%.。
Dense ammonia-containing water: the mixed solution (NH of the reverse osmosis concentrated liquid of the dense ammonia-containing water of catalyzer and rare ammonia-containing water
3-N:4500 μ g/g) add 20% alkali lye and regulate pH to 11.0, carry out the atmospheric steam stripping, quantity of steam is 8% of the weight of water inlet, and the deamination rate is 99.5%, the membrane permeation liquid absorption cat head ammonia of handling with rare ammonia-containing water reverse osmosis concentration.Obtain cat head strong aqua: NH
3-N:69222 μ g/g, the low NH that purifies waste water of tower
3-N:20.3 μ g/g, directly discharging.
Claims (6)
1, a kind of Catalyst Production technology contains the processing and the recovery method of ammonia/ammonium waste water, and process may further comprise the steps:
(1) NH
4-N is that the ammonia/ammonium waste water that contains of 150~1500 μ g/g concentrates through reverse osmosis membrane, and membrane permeation liquid is as the absorption liquid of stripping tower ammonia steam or directly recycling;
(2) membrane concentration liquid and NH
4-N mixes and adds alkali adjusting pH value at the ammonia/ammonium waste water that contains of 4000 μ g/g-10000 μ g/g;
(3) ammonia-containing water after the alkalization enters stripping tower, reclaims ammonia wherein, the stripping discharging of purifying waste water.
2, in accordance with the method for claim 1, the permeability rate that it is characterized in that the employed reverse osmosis membrane of described step (1) is 90~120l/m
2H, ratio of desalinization is 95~99%.
3,, it is characterized in that the working pressure of described step (1) reverse osmosis is controlled at 1.5~4.5MPa according to claim 1 or 2 described methods.
4,, it is characterized in that the reverse osmosis concentrated 10%-20% that is reduced to flooding quantity of described step (1) according to claim 1 or 2 described methods.
5, in accordance with the method for claim 1, it is characterized in that the pH value in the described step (2) is more than 10.5.
6, in accordance with the method for claim 1, it is characterized in that described step (3) stripping tower adopts steam stripped, quantity of steam is 3~10w% of flooding quantity.
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CN101172622B (en) * | 2006-11-01 | 2011-08-31 | 三菱瓦斯化学株式会社 | Method of recovering ammonia |
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CN105198140A (en) * | 2015-11-03 | 2015-12-30 | 安徽洋森环保节能科技有限公司 | Ammonia water permo-treatment method for high-salinity wastewater |
CN109748290A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | The ammonium of modenite exchanges method of modifying |
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CN114605012A (en) * | 2022-03-30 | 2022-06-10 | 光大环境科技(中国)有限公司 | Forward osmosis zero-emission system with ammonium bicarbonate as drawing liquid and operation process thereof |
CN114605012B (en) * | 2022-03-30 | 2023-05-02 | 光大环境科技(中国)有限公司 | Forward osmosis zero-emission system taking ammonium bicarbonate as drawing liquid and operation process thereof |
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