CN1948191A - Reuse technology of oil refining, chemical catalyst production waste water - Google Patents
Reuse technology of oil refining, chemical catalyst production waste water Download PDFInfo
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- CN1948191A CN1948191A CN 200610100912 CN200610100912A CN1948191A CN 1948191 A CN1948191 A CN 1948191A CN 200610100912 CN200610100912 CN 200610100912 CN 200610100912 A CN200610100912 A CN 200610100912A CN 1948191 A CN1948191 A CN 1948191A
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Abstract
The present invention relates to a waste water treatment, recovery and reutilization process, in particular it relates to a recovery and reutilization process of waste water produced by oil-refining and chemical catalyst production. Said method is characterized by including the following several main steps: firstly, removing silica gel or silicon oxide, sodium salt and suspension which are harmful to production from the waste water, recovering valuable ammonia and clean water from the waste water and reutilizing them in the production process. Besides, said invention also provides the concrete measures of the above-mentioned every step.
Description
Technical field
The present invention relates to a kind of wastewater treatment and reuse technology, refer in particular to a kind of oil refining, chemical catalyst production waste water reuse technology of being used for.
Background technology
Oil refining, chemical catalyst mostly are silicon, aluminum compound, in preparation process, with water glass, Tai-Ace S 150, aluminum oxide, pure aluminium silicate etc. is raw material, after chemical reaction becomes glue, crystallization synthesis of molecular sieve, again through ammonium exchange or rare earth exchanged, wash out sodium ion with chemical water then, at last by synthetic catalyst finished product or work in-process such as drying, roasting, activation.In the exchange of production process and washing process, produce a large amount of ammonia nitrogen waste water and high-salt wastewater.Catalyst production waste water is divided into three kinds, and first kind is to hang down to contain ammonia or do not contain ammonia sewage, comprises the synthetic water that washes cloth, microballoon alumino silica gel waste water and the platinum agent dry glue powder waste water that filters draining, NaY colloid washing water, filter of NaY colloid; Second kind is low ammonia-containing water, comprises the washing water after the exchange; The third is high ammonia-containing water, comprises exchange filtrate and first washing water.
The processing of ammonia nitrogen waste water is a big technical barrier of petrochemical catalyst production industry always.In the production process of catalyzer, need to use ammoniations such as a large amount of ammonium chloride, ammonium sulfate, liquefied ammonia, and they only are used in the technological process, do not appear in the finished product, all these ammonia nitrogens all will enter in waste water and the atmosphere, so ammonia-nitrogen content height in the waste water, the ammonia-nitrogen content of efflux wastewater is at 1000-4000mg/L, and considerably beyond the discharging standards of 15mg/L, management task is very urgent.The characteristics of this kind waste water are saltiness height, ammonia nitrogen concentration height, and contain higher suspended substance, and the biodegradability of waste water is poor.Excessive ammonia nitrogen enters water body will cause body eutrophication, destroy physical environment, and the nitrate of oxidized generation and nitrite also can influence hydrobiont even human beings'health, and therefore, this denitrogenation of waste water is handled and got more and more people's extensive concerning.China improves day by day to requirement on environmental protection along with this year, and the processing of this waste water is the key of Business survival.
At present, main denitrogenation method has biological nitration denitrification, break point chlorination, stripping stripping and ion exchange method etc., and the treatment process of high-concentration ammonia nitrogenous wastewater can be divided into physico-chemical process, biochemical integrated process and new bio denitrogenation.Traditional ammonia nitrogen improvement method comprises blow-off method, vaporizing extract process, the energy consumption height, and the alkaline consumption height, the running cost height, enterprise can't bear.And biochemical process owing to do not have carbon source in the waste water, also is difficult to realize.
CN1123543C has introduced comprehensive treating process and the recovery method that a kind of catalyzer contains ammonia/ammonium processing wastewater, it mainly may further comprise the steps: 1) rare ammonia/ammonium waste water of containing concentrates through reverse osmosis membrane, and membrane permeation liquid is directly recycled or as the absorption liquid of steam stripped tower ammonia steam; 2) membrane concentration liquid mixes and adds alkali adjusting pH value with the dense ammonia/ammonium waste water that contains; 3) ammonia-containing water after the alkalization enters stripping tower, reclaims ammonia/ammonium wherein, the stripping qualified discharge of purifying waste water.This method is lower a little than the working cost that adopts blow-off method, vaporizing extract process etc. separately, but it has still adopted vaporizing extract process, and the working cost enterprise of vaporizing extract process still can't bear; Still contain certain ammonia/ammonium in the discharge water of stripping tower in addition, can not reach the environment protection emission requirement, salts contg is higher in the waste water, can not carry out biological chemistry and handle, so this method finally can not be applied.
CN1032465C has introduced the novel process that a kind of ammonia/moisture film separates and reclaim ammonia, 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 gaseous tension, 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, obtains to reclaim product.Since this method to ammonia-N removal rate about 93%, if the ammonia nitrogen in the sewage reaches at 1000-4000mg/l, ammonia-nitrogen content is still at 100-400mg/l in the water behind the embrane method ammonia nitrogen removal, and the ammonia nitrogen of this moment still far surpasses environmental emission standard, and working cost is higher.
Have multiplely though handle the treatment process of high-concentration ammonia nitrogenous wastewater, also do not have a kind ofly can to take into account that flow process is simple at present, reduced investment, technology maturation, control makes things convenient for and all respects such as non-secondary pollution.According to catalyst plant factory effluent saltiness height, characteristics that ammonia nitrogen concentration is high, adopt any single technology all can not reach the double requirements of technical and economic requirements.There is the working cost height in prior art or can not reaches the emission request of environmental protection.
Summary of the invention
The objective of the invention is to be improved and innovate, provide that a kind of working cost is low, the effective a kind of oil refining of treatment effect, chemical catalyst production waste water handles and reuse technology at the shortcoming that exists in the background technology and problem.
The present invention includes following steps:
A, at first ammonia nitrogen waste water is imported retort, and in retort, add poly-aluminium and polyacrylamide, be used for adsorption aqueous solution silicon, aluminum compound and suspended substance and form the macrobead flco;
B, again the liquid after formation reaction input is come unstuck except that the suspended substance device, the silicon in the liquid, aluminum compound, suspended substance are separated with clear water, the waste residue outward transport landfill that colloid after wherein separating and suspended substance form or do deep processing and handle;
C, the water that comes unstuck except that suspended substance that flocculates enter the two-pass reverse osmosis system, be used for removing water ammonia nitrogen and sodium salt, wherein the clear water after the part process first-stage reverse osmosis system enters the two-pass reverse osmosis system again, can reach reuse standard, and the dense water of another part is recycled to feed-water end to be continued to handle;
D, the dense water that is retained down in the first-stage reverse osmosis system is carried out pH value regulate, pH value 10.5-11.5 wherein adds lime, is used for further precipitation and filter cleaner;
E, the waste water after will removing the gred carry out the embrane method ammonia nitrogen removal to be handled, and is used for obtaining to reclaim product ammonia;
Sewage behind f, the embrane method ammonia nitrogen removal enters except that the sodium salt system again, adds the alpha-cylodextrin sodium removing agent in sewage, makes Na in Solution salt generation chelatropic reaction, forms the solid chemical compound precipitation;
G, remove the water inlet that water behind the sodium salt turns back to the one-level permeator, realized the zero release that ammonia-nitrogen sewage is handled;
H or remove sodium salt after water be delivered to sanitary sewage and mix, enter sewage work together and reach comprehensive utilization.
The present invention is the characteristics according to Catalyst Production technology, from the angle of recycling economy, pays attention to ammonia useful in the waste water being reclaimed and water being carried out recycle.The present invention be with in the waste water to producing deleterious silica gel or silicon oxide, sodium salt and suspended substance removal, ammonia that recovery value is arranged in the waste water and clean water are back to use in the production technique.Reached and promptly protected environment, reclaimed the useful matter in the waste water again, water and ammonia nitrogen have been back to use in the production, greatly reduced working cost, solved a big technical barrier of puzzlement catalyst plant.
Description of drawings
Accompanying drawing is a process flow sheet of the present invention
Embodiment
Processing step of the present invention and effect:
1, flocculation is come unstuck except that suspended substance: add medicament A and medicament B in ammonia nitrogen waste water, medicament adsorbs silicon, aluminum compound and suspended substance in the aqueous solution, forms the macrobead flco.In aforesaid lab scale, flocculation come unstuck except that the suspended substance effect obvious, can reach more than 97% the removal of silicon, can reach more than 99% the removal of aluminium, after flocculation, the content of silicon, aluminium is all less than 10ppm in the water.Water after the process flocculation is come unstuck can satisfy the water inlet requirement of reverse osmosis fully.(feed water by reverse osmosis is to the requirement of silicon: at neutrallty condition, 25 ℃ operation condition allows silicone content＜100ppm; PH value is high more, allows silicone content high more; Temperature is high more, allows silicone content high more.) if flocculation comes unstuck badly except that the suspended substance effect, silicon, aluminum compound and indicator of suspended solids are too high, all can influence the operation of reverse osmosis system, therefore flocculation come unstuck except that suspended substance be very crucial operation.
2, reverse osmosis desalination: flocculation is come unstuck and is entered the twin-stage reverse osmosis system except that the water behind the suspended substance, the twin-stage reverse osmosis to the clearance of sodium (salt) in each water sample more than 99%, the water outlet salts contg is below 1ppm, the twin-stage reverse osmosis to ammonia-N removal rate in each water sample more than 99%, ammonia nitrogen is 0 in the water outlet of twin-stage reverse osmosis, it is 0 that reverse osmosis goes out water turbidity, can reach the purpose of desalination fully.The water outlet of twin-stage reverse osmosis can direct reuse, but salt in the sewage and ammonia nitrogen all have been trapped in the dense water of first-stage reverse osmosis, ammonia nitrogen in the dense water reaches 2000-4000mg/l, salts contg reaches about 20000mg/l, reach and administer the final purpose of polluting, the advanced treatment that also must carry out ammonia nitrogen removal and desalination to the dense water of first-stage reverse osmosis.
3, embrane method ammonia nitrogen removal: the dense water of first-stage reverse osmosis enters embrane method ammonia nitrogen removal system, 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 gaseous tension, make its vacuum tightness remain on 10～760mmHg scope, under film pressure at both sides gradient promotes, the 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, obtains to reclaim product.It to ammonia-N removal rate more than 90%, if the ammonia nitrogen in the dense water of reverse osmosis reaches 2000-4000mg/l, ammonia-nitrogen content is still at 100-400mg/l in the water behind the embrane method ammonia nitrogen removal, salts contg is still about 20000mg/l, the ammonia nitrogen of this moment still far surpasses environmental emission standard, so sewage must further desalting treatment.
4, dosing removes sodium salt: the sewage behind the embrane method ammonia nitrogen removal enters except that the sodium salt system, medicament in the aqueous solution with sodium salt generation chelatropic reaction, form the solid chemical compound precipitation.Dosing removes sodium salt following feature:
The water sample that clearance is the highest is a molecular sieve NaY waste water, and its highest clearance is 72%, secondly is microballoon alumino silica gel 58%, and super steady one hands over 55%;
In the experiment water sample in the stoste the minimum concentration of sodium (salt) content be 700mg/l, remove the sodium DeGrain;
To with a kind of waste water, additive amount of medicament is big more, and it is good more to remove sodium (salt) effect;
For the waste water of sodium (salt) content more than 3000mg/l, behind the adding sodium removing agent tangible clearance is arranged;
For the waste water of sodium (salt) content below 3000mg/l, no tangible clearance behind the adding sodium removing agent;
Salts contg still about 20000mg/l, through except that after the operation behind the sodium salt, is estimated salts contg at 3000mg/l-6000mg/l in the water behind the embrane method ammonia nitrogen removal, and water can loop back reverse osmosis system, perhaps is mixed into sewage work with sanitary sewage.
If the water behind the dosing desalination directly loops back reverse osmosis system, then can reach zero release substantially; If the water behind the dosing desalination carries out biochemical treatment, then must mix with sanitary sewage, because the nutritive substance that does not have microorganism to need in this sewage, when mixing with sanitary sewage, sanitary sewage: residue ammonia-nitrogen sewage＞4, adopt anaerobism-anoxic-aerobic process, the sewage ratio is easier to realize qualified discharge.
Embodiment:
Ammonia nitrogen waste water pumps into retort, adding medicine A and B in retort, silicon, aluminium and suspended substance are formed the macrobead flco, enter then and come unstuck except that the suspended substance device, the content of silicon, aluminium is all less than 10ppm in the water outlet, suspended substance is lower than the 50ppm clear water and enters the first-stage reverse osmosis system, and the waste residue that colloid and suspended substance form is transported outward landfill, removed cement mill or brick field; The clear water of process first-stage reverse osmosis system handles is as the water inlet of two-pass reverse osmosis system, the clear water salts contg of two-pass reverse osmosis system below 1ppm, ammonia nitrogen is 0, turbidity is 0, clear water can direct reuse or discharging, and the dense water of two-pass reverse osmosis system turns back to the inlet chest of first-stage reverse osmosis system; The dense water of first-stage reverse osmosis system is recycled to inlet chest, and when the ammonia nitrogen concentration of ammonia nitrogen on-line detector detection reached a certain value, the dense water of first-stage reverse osmosis system entered the pH value blend tank; Dense water is regulated pH value postprecipitation, filter cleaner, enters embrane method ammonia nitrogen removal device again, and ammonia is separated by sulfuric acid absorption and formed sulphur ammonia, and sulphur ammonia is as raw materials for production, and ammonia-nitrogen content is still at 100-400mg/l in the water behind the embrane method ammonia nitrogen removal; Handle except that the water behind the ammonia removes sodium salt through dosing, turn back to the water inlet of first-stage reverse osmosis device except that the water behind the sodium salt.Perhaps go to mix, enter sewage work then together, make sewage both reach comprehensive utilization, reach the emission request of environmental protection again with sanitary sewage except that the water behind the sodium salt.So a whole set of technology has realized the zero release that ammonia-nitrogen sewage is handled substantially.
According to removing the water inlet operational path working cost that water behind the sodium salt turns back to the first-stage reverse osmosis device: be 5.933 yuan of/ton water, 1.7 yuan of/ton water of sulphur ammonia recovery value, can be used as chemical water or water of productive use reuse, its recovery value through the water after this art breading: 3.5 yuan of/ton water
Actual motion expense: 5.933-1.7-3.5=0.733 unit/ton water (not comprising facility investment and labor wage).
According to going and sanitary sewage hybrid technique route working cost except that the water behind the sodium salt: be 5.4 yuan of/ton water, 1.7 yuan of/ton water of sulphur ammonia recovery value can be used as chemical water or water of productive use reuse, its recovery value through the water after this art breading: 2.6 yuan of/ton water
Actual motion expense: 5.4-1.7-2.6=1.1 unit/ton water (not comprising facility investment and labor wage).
Claims (1)
1, a kind of oil refining, chemical catalyst production waste water reuse technology is characterized in that may further comprise the steps:
A, at first ammonia nitrogen waste water is imported retort, and in retort, add poly-aluminium and polyacrylamide, be used for adsorption aqueous solution silicon, aluminum compound and suspended substance and form the macrobead flco;
B, again the liquid after formation reaction input is come unstuck except that the suspended substance device, the silicon in the liquid, aluminum compound, suspended substance are separated with clear water, the waste residue outward transport landfill that colloid after wherein separating and suspended substance form or do deep processing and handle;
C, the water that comes unstuck except that suspended substance that flocculates enter the two-pass reverse osmosis system, be used for removing water ammonia nitrogen and sodium salt, wherein the clear water after the part process first-stage reverse osmosis system enters the two-pass reverse osmosis system again, can reach reuse standard, and the dense water of another part is recycled to feed-water end to be continued to handle;
D, the dense water that is retained down in the first-stage reverse osmosis system is carried out pH value regulate, pH value 10.5-11.5 wherein adds lime, is used for further precipitation and filter cleaner;
E, the waste water after will removing the gred carry out the embrane method ammonia nitrogen removal to be handled, and is used for obtaining to reclaim product ammonia;
Sewage behind f, the embrane method ammonia nitrogen removal enters except that the sodium salt system again, adds the alpha-cylodextrin sodium removing agent in sewage, makes Na in Solution salt generation chelatropic reaction, forms the solid chemical compound precipitation;
G, remove the water inlet that water behind the sodium salt turns back to the one-level permeator, realized the zero release that ammonia-nitrogen sewage is handled;
H or remove sodium salt after water be delivered to sanitary sewage and mix, enter sewage work together and reach comprehensive utilization.
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| CN 200610100912 CN1948191A (en) | 2006-07-27 | 2006-07-27 | Reuse technology of oil refining, chemical catalyst production waste water |
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| CN 200610100912 CN1948191A (en) | 2006-07-27 | 2006-07-27 | Reuse technology of oil refining, chemical catalyst production waste water |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781048A (en) * | 2009-10-20 | 2010-07-21 | 北京林业大学 | Low ammonia nitrogen waste water treatment and recycling method |
| CN102689995A (en) * | 2012-06-01 | 2012-09-26 | 北京联众华禹环保科技有限公司 | Method for treating and recycling oil-gas field produced water |
| CN103047725A (en) * | 2013-01-14 | 2013-04-17 | 浙江理工大学 | Two-stage reverse osmosis regenerative heat source tower heat pump system |
| CN103043859A (en) * | 2012-12-24 | 2013-04-17 | 中国市政工程华北设计研究总院 | Method for treating landfill leachate |
| CN105417826A (en) * | 2015-12-30 | 2016-03-23 | 北京清大国华环境股份有限公司 | Catalyst waste water zero discharge method and device |
| CN109179756A (en) * | 2018-09-26 | 2019-01-11 | 衢州华友钴新材料有限公司 | A kind for the treatment of process purifying SS from hydrometallurgy cobalt copper solution |
-
2006
- 2006-07-27 CN CN 200610100912 patent/CN1948191A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781048A (en) * | 2009-10-20 | 2010-07-21 | 北京林业大学 | Low ammonia nitrogen waste water treatment and recycling method |
| CN101781048B (en) * | 2009-10-20 | 2012-08-22 | 北京林业大学 | Low ammonia nitrogen waste water treatment and recycling method |
| CN102689995A (en) * | 2012-06-01 | 2012-09-26 | 北京联众华禹环保科技有限公司 | Method for treating and recycling oil-gas field produced water |
| CN103043859A (en) * | 2012-12-24 | 2013-04-17 | 中国市政工程华北设计研究总院 | Method for treating landfill leachate |
| CN103047725A (en) * | 2013-01-14 | 2013-04-17 | 浙江理工大学 | Two-stage reverse osmosis regenerative heat source tower heat pump system |
| CN103047725B (en) * | 2013-01-14 | 2015-09-09 | 浙江理工大学 | The heat source tower heat pump system of double-stage reverse osmosis regeneration |
| CN105417826A (en) * | 2015-12-30 | 2016-03-23 | 北京清大国华环境股份有限公司 | Catalyst waste water zero discharge method and device |
| CN109179756A (en) * | 2018-09-26 | 2019-01-11 | 衢州华友钴新材料有限公司 | A kind for the treatment of process purifying SS from hydrometallurgy cobalt copper solution |
| CN109179756B (en) * | 2018-09-26 | 2022-02-11 | 衢州华友钴新材料有限公司 | Treatment process for purifying SS from hydrometallurgical cobalt-copper solution |
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Effective date of registration: 20070413 Address after: Room 58, No. 309, Fucheng Road, Beijing, Haidian District Applicant after: Beijing Zhongtianyuan Environmental Engineering Co., Ltd. Address before: Yueyang City, Hunan Province eight door Yueyang City Xinke environmental protection equipment Engineering Co., Ltd. Applicant before: Xinke Environment Protection Equipment Engineering Co., Ltd., Yueyang City |
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