CN105314757A - Treatment method of mother liquid waste water in SAPO molecular sieve production - Google Patents
Treatment method of mother liquid waste water in SAPO molecular sieve production Download PDFInfo
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- CN105314757A CN105314757A CN201410314404.8A CN201410314404A CN105314757A CN 105314757 A CN105314757 A CN 105314757A CN 201410314404 A CN201410314404 A CN 201410314404A CN 105314757 A CN105314757 A CN 105314757A
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Abstract
The invention relates to a treatment method of mother liquid waste water in SAPO molecular sieve production and mainly solves the problems that large quantity of organic amine in mother liquid waste water in production of a SAPO molecular sieve cannot be recycled and directly causes environment pollution. In the method, by means of an inorganic high-molecular composite flocculant, aluminum ion, silicon ion and phosphorus ion are removed from the SAPO molecular sieve crystallization mother liquid waste water being high in ionic concentration. Alkali is added to the deionized waste water to regulate the pH value so that the organic amine grease is separated from the waste water, and then the waste water passes through an oil-water separator to separate the organic amine which is used for synthesizing the SAPO molecular sieve. The method has good flocculation effect, low cost and high treatment speed, can effectively solves the problems that the organic amine waste water in the SAPO molecular sieve production is high in COD and causes environment pollution when being discharged directly and the organic amine resource cannot be effectively recycled and reused. The method is used for treating the SAPO molecular sieve crystallization mother liquid waste water in industry.
Description
Technical field
The present invention relates to a kind of field of wastewater, relate to high organic amine, high phosphorus aluminium content crystallization mother liquor method of wastewater treatment, specifically a kind of mother liquor waste water of being produced by the SAPO molecular sieve containing high ion concentration salt, organic amine adds the first deionizing process of compound inorganic high molecular flocculant, rear recovery organic amine, and be back to the method for the synthesis of SAPO molecular sieve, make waste discharge reach state sewage emission standard.
Background technology
In the production process of SAPO molecular sieve, a large amount of waste water can be produced, wherein containing aluminium salt, phosphoric acid salt, silicon salt and organic amine.At least one of organic amine mainly in diethylamine, triethylamine, morpholine, di-n-propylamine, Isopropylamine, tetraethyl ammonium hydroxide and tetraethylammonium bromide.Organic amine toxicity is large and expensive, with direct discharging of waste water not only can cause environmental pollution and also factory effluent amount large especially, must be recycled, the employing burning disposal of factory effluent in the past, the relevant report not having other to process, annual wastewater treatment need increase a large amount of expense, add production cost, reclaim the organic amine in waste water through process, can be back to the synthesis of SAPO molecular sieve, the microcosmic salt of enriching and recovering directly can be used as the raw material of phosphate industry.The COD of waste discharge is less than 500, reaches wastewater discharge standard.
Flocculent precipitation because of its investment cost low, equipment is simple, the advantages such as the treatment time is short are used in the treatment of waste water comparatively widely, composite flocculation agent improves the usefulness of flocculation reaction greatly, current inorganic polymer flocculant by general inorganic aluminate and molysite to high molecular polymerization aluminium and polymeric iron future development, polymeric aluminum (iron) Main Morphology is to high electric charge polynuclear complex future development, polymeric aluminum (iron) counter anion is from a low price to high price future development, if inorganic polymer flocculant and inorganic polymer coagulant active silicic acid used in combination, namely polysilicon acid anionic composite flocculation agent is formed, the treatment effect of complicated ingredient waste water can be improved.
Chinese patent 201010577240 discloses a kind of secondary calcium phosphate method of wastewater treatment, is to be sent in premix steel basin by the waste water that production calcium hydrophosphate fodder produces, and adds medicament and the milk of lime adjusted to ph of ferrous sulfate pulvis simultaneously; The add-on of medicament is pressed in ferrous sulfate and waste water and is calculated with arsenic, and mass ratio is 5 ~ 20, and milk of lime adjusted to ph is 10 ~ 12; Then by the waste water outflow after premix to aeration tank Air Exposure 30 ~ 60 minutes; Waste water again after aeration sends into the process of settling pool supernatant; Clear water after supernatant is sent into pH value and is returned tune pond, adopts sulfuric acid to return and adjusts rear clear water pH value to be 6.5 ~ 7.5, namely obtain the clear water of system recoverable after adjusted to ph is qualified.The method can dephosphorization, but can form gel because aluminium salt exists with chalybeate, the acting in conjunction of calcium base, is not suitable for the complex system process of SAPO waste water.
Chinese patent 201110004976.2 discloses a kind of preparation method of wastewater treatment polymer composite flocculant, mainly solve oily substance in refinery water, but commute gel SAPO mother liquor waste water is not suitable for, waste water gel can be caused, hinder waste water to process further, the present invention is different with raw material from method prepared by its flocculation agent.
Chinese patent CN201210253447.0 discloses a kind of preparation method removing low temperature and low turbidity water phosphorus-containing wastewater flocculation agent, is elevated in the aluminium chlorhydrate solution of 65 DEG C adds Fe in temperature
3o
4powder, Al
2(SO
4)
3, MgCl
2, MnO
2, and continue stirring heating, when temperature is elevated to 85 DEG C, then add certain mass Al
2o
3the calcium aluminate powder of content, stirring reaction 2.5 hours at temperature 115 DEG C, in maintenance 115 DEG C of temperature, adds octadecyl trimethyl amine bromide, continues to stir, and stops stirring post curing.The polymer inorganic flocculating agent of the many metal core of a kind of poly-hydroxy that this method prepares, remarkable at low temperature, low turbidity water flocculating effect to Removal of Phosphorus in Wastewater, the power consumption of this method is different from the present invention.
Chinese patent CN201110004976.2 mono-kind, for the preparation method of the Composite Inorganic Polymer Flocculants of wastewater treatment, mainly comprises: the FeSO getting 1 weight part
47H
2o is dissolved in the deionized water of 7 weight parts, adds the KClO of 1 weight part
3, polymerization certain hour, obtains Polyferric Sulfate; Then the Na of residue 1 weight part is got
2siO
39H
2o is soluble in water, and instillation concentration is the H of 20%
2sO
4and adjust ph is about 5.0, stirs, control temperature is at 25 DEG C, and reactivate is polymerized, and obtains required active silicic acid solution; Obtained Polyferric Sulfate is joined in the active silicic acid solution obtained and reacts.This method solves the removal of grease thing and suspended substance in refinery water.
Summary of the invention
Technical problem to be solved by this invention can not get effectively recycling the problem causing production cost high to serious, the expensive organic formwork agent of existing SAPO molecular sieve mother liquor waste water process power consumption, provides a kind for the treatment of process of new SAPO molecular sieve mother liquor waste water.The method be used for the mother liquor waste water process of SAPO molecular sieve time, there is with low cost, that process is simple, energy consumption is low feature, can reuse purify after organic amine, decrease the pollution of organic amine discharging of waste liquid to environment.
For solve technique scheme, the present invention by the following technical solutions:
Containing a treatment process for SAPO molecular sieve mother liquor waste water, comprise the following steps:
(1) get in a SAPO molecular sieve mother liquor waste water and add iron(ic) chloride FeCl
36H
2o, hypochlorous acid or hypobromous acid, with the AlO in waste water
2 -waste water I is obtained after polymerization;
(2) separately get in a SAPO molecular sieve mother liquor waste water and add boric acid or borate, then drip magnesium chloride Mg Cl
2pH is regulated to be 2.5 ~ 6, with the SiO in waste water
3 2-after stirring at room temperature, add waste water I again form the waste water II containing anionic composite flocculation agent;
(3) in waste water II, add calcium lime powder, the pH value regulating waste water is 7 ~ 9.5, makes Al, Si, P ionic group in waste water be polymerized to particle;
(4) filtering above-mentioned particle obtains waste water III, within Al, Si, P total ion concentration drops to 1000ppm in waste water III excessively;
(5) adding alkaline solution after waste water III being moved into separator regulates pH to be 9 ~ 12.5, layering after leaving standstill, containing organic amine in upper oil phase, lower floor's aqueous phase carries out secondary filtration again, in filtrate, acid supplemented solution regulates pH to be 6 ~ 8, makes COD in waste water drop within 500, can be used as discharge of wastewater up to standard;
Total ion concentration containing Al, Si, P in described SAPO molecular sieve mother liquor waste water is 1 ~ 30 % by weight.
In technique scheme, step (1) is identical with the weight of the SAPO molecular sieve mother liquor waste water in (2), and step (1) and (2) can be carried out in same solution simultaneously; Ion containing Al in SAPO molecular sieve mother liquor waste water is AlO
2 -, the ion containing Si is SiO
3 2-, the ion containing P is PO
4 3-; Iron(ic) chloride FeCl
36H
2the preferable range of the ion weight ratio containing Al in O, hypochlorous acid or hypobromous acid and SAPO molecular sieve mother liquor waste water is (1 ~ 9): (1 ~ 4): (1 ~ 4); Preferable range containing the ion weight ratio of Si in boric acid or borate and waste water is (0.2 ~ 2.5): (0.1 ~ 3.5); Magnesium chloride Mg Cl
2be (0.1 ~ 2) with the preferable range of ion weight ratio containing Si in waste water: (3 ~ 20); Anionic composite flocculation agent in step (2) is poly-silicic-boric acid ferro-aluminum flocculation agent, i.e. poly-ferrosilicoaluminum boron (PSBFA), its Al
3+: Fe
3+: the preferable range of B:Si:P mol ratio is (0.3 ~ 0.8): (0.3 ~ 0.6): (0.3 ~ 0.8): (0.3 ~ 0.8): 1; More preferably scope is (0.4 ~ 0.6): (0.3 ~ 0.5): (0.4 ~ 0.6): (0.4 ~ 0.6): 1; The preferred version of organic amine is at least one in diethylamine, triethylamine, morpholine, di-n-propylamine, Isopropylamine, tetraethyl ammonium hydroxide and tetraethylammonium bromide; In step (1), the preferable range of polymerization time is 1 ~ 2 hour; In step (2), the preferable range of churning time is 1 ~ 2 hour; The preferred version of alkali is the one in sodium hydroxide and potassium hydroxide in step (5); In step (5), in waste water, COD drops within 500; Lower floor's aqueous phase secondary filtration in step (5), in filtrate, acid supplemented solution regulates the preferable range of pH to be 6 ~ 8, and the preferred version of acid solution used is hydrochloric acid soln or the sulphuric acid soln of 1 ~ 5 % by weight.
Invention is the deficiency for existing wastewater processing technology, can according to the composition of SAPO molecular sieve waste water, add inorganic salt by substep and form Composite Inorganic Polymer Flocculants, remove aluminium salt, phosphoric acid salt, the silicate in waste water, Deng salt, overcome SAPO waste water and cause gel owing to changing pH value, also overcome and because adding flocculation agent, waste water is solidified, waste water cannot be made to be processed further.The invention provides that a kind of flocculating effect is good, cheap, safety non-toxic, processing speed be fast, the method for the complicated waste water system of the applicable SAPO of good filtration effect, for the purification of organic amine provides possibility.
Use the inventive method, not only can ensure the purification reuse of organic amine in SAPO molecular sieve mother liquor, and making easy gel mother liqueur waste water after composite macromolecular flocculant process, the high salt ion in mother liquor is flocculated the object that precipitation reaches separation, makes discharge water reach sewage drainage standard, present method technique is simple, easy to operate, processing costs is lower, simultaneously the organic amine of unit take-back cost costliness and the raw material of phosphate fertilizer, be not only enterprise and create environmental benefit, and create larger economic benefit.
Below by embodiment, the invention will be further elaborated.
Accompanying drawing explanation
Treatment scheme of the present invention is shown in Fig. 1, and wherein 1 is the waste water containing composite flocculation agent, and 2 is filter cake, and 3 is filtrate, and 4 is alkaline solution, and 5 is organic amine, and 6 is waste water up to standard; I is stirrer, and II is whizzer, and III is separator.
Get in a SAPO molecular sieve mother liquor waste water and add iron(ic) chloride FeCl
36H
2o, hypochlorous acid or hypobromous acid, with the AlO in waste water
2 -, after polymerization, obtain first strand of waste water; Separately get in a SAPO molecular sieve mother liquor waste water and add boric acid or borate, then drip magnesium chloride Mg Cl
2regulate the SiO in pH and waste water
3 2-after stirring at room temperature, add first strand of waste water again form the waste water 1 containing composite flocculation agent; Waste water 1 containing composite flocculation agent is joined in stirrer I, then the pH value adding calcium lime powder adjustment waste water makes Al, Si, P ionic group in waste water be polymerized to particle; At whizzer II, filtering above-mentioned particle obtains filter cake 2 and filtrate 3 excessively, add alkaline solution 4 after filtrate 3 is moved into separator III and regulate pH, layering after leaving standstill, containing organic amine 5 in upper oil phase, lower floor's aqueous phase carries out secondary filtration again, in filtrate, acid supplemented solution regulates pH to lower the COD value of waste water, finally can be used as waste water 6 up to standard and discharges.
Embodiment
[embodiment 1]
Total ion concentration containing Al, Si, P in SAPO molecular sieve mother liquor waste water is 2 % by weight.
Get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.16 kilogram of iron(ic) chloride FeCl
36H
2o, 0.028 kilogram of hypochlorous acid, with the AlO in waste water
2 -be polymerized and obtain waste water I after 1 hour;
Separately get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.04 kilogram of boric acid, then drip magnesium chloride Mg Cl
2pH is regulated to be 2.5, with the SiO in waste water
3 2-add waste water I after 1 hour again in stirring at room temperature and form the waste water II containing anionic composite flocculation agent; Its Al
3+: F
e 3+: the ratio of B:Si:P is 0.3:0.3:0.3:0.6:1; (wherein Al
3+mole number and waste water I in AlO
2 -mole number identical, the mole number of Si and SiO
3 2-mole number identical)
In waste water II, add 0.56 kilogram of calcium lime powder, the pH value regulating waste water is 9.5, makes Al, Si, P ionic group in waste water be polymerized to particle;
Cross and filter above-mentioned particle and obtain waste water III, in waste water III, Al, Si, P total ion concentration drops to 800ppm;
The sodium hydroxide solution adding 10 % by weight after waste water III is moved into separator regulates pH to be 10, layering after leaving standstill, containing the organic amine of triethylamine in upper oil phase, lower floor's aqueous phase carries out secondary filtration again, the hydrochloric acid soln adding 5 % by weight in filtrate regulates pH to be 6, make COD in waste water drop to 400, can be used as discharge of wastewater up to standard.
[embodiment 2]
Total ion concentration containing Al, Si, P in SAPO molecular sieve mother liquor waste water is 2 % by weight.
Get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.32 kilogram of iron(ic) chloride FeCl
36H
2o, 0.1 kilogram of hypochlorous acid, with the AlO in waste water
2 -be polymerized and obtain waste water I after 1 hour;
Separately get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.06 kilogram of boric acid, then drip magnesium chloride Mg Cl
2pH is regulated to be 2.5, with the SiO in waste water
3 2-add waste water I after 1 hour again in stirring at room temperature and form the waste water II containing anionic composite flocculation agent; Its Al
3+: Fe
3+: the ratio of B:Si:P is 0.6:0.6:0.5:0.3:1; (wherein Al
3+mole number and waste water I in AlO
2 -mole number identical, the mole number of Si and SiO
3 2-mole number identical)
In waste water II, add 0.56 kilogram of calcium lime powder, the pH value regulating waste water is 9.5, makes Al, Si, P ionic group in waste water be polymerized to particle;
Cross and filter above-mentioned particle and obtain waste water III, in waste water III, Al, Si, P total ion concentration drops to 800ppm;
The sodium hydroxide solution adding 10 % by weight after waste water III is moved into separator regulates pH to be 11, layering after leaving standstill, containing the organic amine of triethylamine in upper oil phase, lower floor's aqueous phase carries out secondary filtration again, the hydrochloric acid soln adding 5 % by weight in filtrate regulates pH to be 7, make COD in waste water drop to 450, can be used as discharge of wastewater up to standard.
[embodiment 3]
Total ion concentration containing Al, Si, P in SAPO molecular sieve mother liquor waste water is 10 % by weight.
Get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.43 kilogram of iron(ic) chloride FeCl
36H
2o, 0.15 kilogram of hypochlorous acid, with the AlO in waste water
2 -be polymerized and obtain waste water I after 1 hour;
Separately get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.12 kilogram of boric acid, then drip magnesium chloride Mg Cl
2pH is regulated to be 2.5, with the SiO in waste water
3 2-add waste water I after 1 hour again in stirring at room temperature and form the waste water II containing anionic composite flocculation agent; Its Al
3+: F
e 3+: the ratio of B:Si:P is 0.32:0.3:0.4:0.6:1; (wherein Al
3+mole number and waste water I in AlO
2 -mole number identical, the mole number of Si and SiO
3 2-mole number identical)
In waste water II, add 1.1 kilograms of calcium lime powders, the pH value regulating waste water is 9.5, makes Al, Si, P ionic group in waste water be polymerized to particle;
Cross and filter above-mentioned particle and obtain waste water III, in waste water III, Al, Si, P total ion concentration drops to 800ppm;
The sodium hydroxide solution adding 10 % by weight after waste water III is moved into separator regulates pH to be 11, layering after leaving standstill, containing the organic amine of triethylamine in upper oil phase, lower floor's aqueous phase carries out secondary filtration again, the hydrochloric acid soln adding 5 % by weight in filtrate regulates pH to be 8, make COD in waste water drop to 400, can be used as discharge of wastewater up to standard.
[embodiment 4]
Total ion concentration containing Al, Si, P in SAPO molecular sieve mother liquor waste water is 25 % by weight.
Get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 1.3 kilograms of iron(ic) chloride FeCl
36H
2o, 0.78 kilogram of hypochlorous acid, with the AlO in waste water
2 -be polymerized and obtain waste water I after 1 hour;
Separately get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.4 kilogram of boric acid, then drip magnesium chloride Mg Cl
2pH is regulated to be 2.5, with the SiO in waste water
3 2-add waste water I after 1 hour again in stirring at room temperature and form the waste water II containing anionic composite flocculation agent; Its Al
3+: Fe
3+: the ratio of B:Si:P is 0.8:0.6:0.8:0.4:1; (wherein Al
3+mole number and waste water I in AlO
2 -mole number identical, the mole number of Si and SiO
3 2-mole number identical)
In waste water II, add 0.96 kilogram of calcium lime powder, the pH value regulating waste water is 7.0, makes Al, Si, P ionic group in waste water be polymerized to particle;
Cross and filter above-mentioned particle and obtain waste water III, in waste water III, Al, Si, P total ion concentration drops to 900ppm;
The sodium hydroxide solution adding 10 % by weight after waste water III is moved into separator regulates pH to be 10, layering after leaving standstill, containing the organic amine of triethylamine in upper oil phase, lower floor's aqueous phase carries out secondary filtration again, the hydrochloric acid soln adding 5 % by weight in filtrate regulates pH to be 6, make COD in waste water drop to 480, can be used as discharge of wastewater up to standard.
[embodiment 5]
Total ion concentration containing Al, Si, P in SAPO molecular sieve mother liquor waste water is 30 % by weight.
Get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 1.35 kilograms of iron(ic) chloride FeCl
36H
2o, 1.5 kilograms of hypochlorous acid, with the AlO in waste water
2 -be polymerized and obtain waste water I after 1 hour;
Separately get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.5 kilogram of boric acid, then drip magnesium chloride Mg Cl
2pH is regulated to be 2.5, with the SiO in waste water
3 2-add waste water I after 1 hour again in stirring at room temperature and form the waste water II containing anionic composite flocculation agent; Its Al
3+: Fe
3+: the ratio of B:Si:P is 0.4:0.5:0.6:0.8:1; (wherein Al
3+mole number and waste water I in AlO
2 -mole number identical, the mole number of Si and SiO
3 2-mole number identical)
In waste water II, add 1.0 kilograms of calcium lime powders, the pH value regulating waste water is 8.5, makes Al, Si, P ionic group in waste water be polymerized to particle;
Cross and filter above-mentioned particle and obtain waste water III, in waste water III, Al, Si, P total ion concentration drops to 1000ppm;
The sodium hydroxide solution adding 10 % by weight after waste water III is moved into separator regulates pH to be 10, layering after leaving standstill, containing the organic amine of triethylamine in upper oil phase, lower floor's aqueous phase carries out secondary filtration again, the hydrochloric acid soln adding 5 % by weight in filtrate regulates pH to be 7, make COD in waste water drop to 500, can be used as discharge of wastewater up to standard.
[embodiment 6]
Total ion concentration containing Al, Si, P in SAPO molecular sieve mother liquor waste water is 1 % by weight.
Get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.16 kilogram of iron(ic) chloride FeCl
36H
2o, 0.028 kilogram of hypochlorous acid, with the AlO in waste water
2 -be polymerized and obtain waste water I after 1 hour;
Separately get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.04 kilogram of boric acid, then drip magnesium chloride Mg Cl
2pH is regulated to be 6, with the SiO in waste water
3 2-add waste water I after 1.5 hours again in stirring at room temperature and form the waste water II containing anionic composite flocculation agent; Its Al
3+: Fe
3+: the ratio of B:Si:P is 0.3:0.3:0.3:0.6:1; (wherein Al
3+mole number and waste water I in AlO
2 -mole number identical, the mole number of Si and SiO
3 2-mole number identical)
In waste water II, add 0.56 kilogram of calcium lime powder, the pH value regulating waste water is 8, makes Al, Si, P ionic group in waste water be polymerized to particle;
Cross and filter above-mentioned particle and obtain waste water III, in waste water III, Al, Si, P total ion concentration drops to 800ppm;
The sodium hydroxide solution adding 10 % by weight after waste water III is moved into separator regulates pH to be 12.5, layering after leaving standstill, containing the organic amine of triethylamine in upper oil phase, lower floor's aqueous phase carries out secondary filtration again, the hydrochloric acid soln adding 5 % by weight in filtrate regulates pH to be 6, make COD in waste water drop to 400, can be used as discharge of wastewater up to standard.
[embodiment 7]
Total ion concentration containing Al, Si, P in SAPO molecular sieve mother liquor waste water is 20 % by weight.
Get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.16 kilogram of iron(ic) chloride FeCl
36H
2o, 0.028 kilogram of hypochlorous acid, with the AlO in waste water
2 -be polymerized and obtain waste water I after 1 hour;
Separately get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.04 kilogram of boric acid, then drip magnesium chloride Mg Cl
2pH is regulated to be 4, with the SiO in waste water
3 2-add waste water I after 2 hours again in stirring at room temperature and form the waste water II containing anionic composite flocculation agent; Its Al
3+: F
e 3+: the ratio of B:Si:P is 0.3:0.3:0.3:0.6:1; (wherein Al
3+mole number and waste water I in AlO
2 -mole number identical, the mole number of Si and SiO
3 2-mole number identical)
In waste water II, add 0.56 kilogram of calcium lime powder, the pH value regulating waste water is 8, makes Al, Si, P ionic group in waste water be polymerized to particle;
Cross and filter above-mentioned particle and obtain waste water III, in waste water III, Al, Si, P total ion concentration drops to 900ppm;
The sodium hydroxide solution adding 5 % by weight after waste water III is moved into separator regulates pH to be 9, layering after leaving standstill, containing the organic amine of triethylamine in upper oil phase, lower floor's aqueous phase carries out secondary filtration again, the hydrochloric acid soln adding 5 % by weight in filtrate regulates pH to be 6, make COD in waste water drop to 400, can be used as discharge of wastewater up to standard.
[comparative example 1]
Total ion concentration containing Al, Si, P in SAPO molecular sieve mother liquor waste water is 2 % by weight.
Get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.08 kilogram of iron(ic) chloride FeCl
36H
2o, 0.028 kilogram of hypochlorous acid, with the AlO in waste water
2 -be polymerized and obtain waste water I after 1 hour;
Separately get in 10 kilograms of SAPO molecular sieve mother liquor waste waters and add 0.04 kilogram of boric acid, then drip magnesium chloride Mg Cl
2pH is regulated to be 2.5, with the SiO in waste water
3 2-add waste water I after 1 hour again in stirring at room temperature and form the waste water II containing anionic composite flocculation agent; Its Al
3+: F
e 3+: the ratio of B:Si:P is 0.3:0.15:0.3:0.6:1; (wherein Al
3+mole number and waste water I in AlO
2 -mole number identical, the mole number of Si and SiO
3 2-mole number identical)
In waste water II, add 0.56 kilogram of calcium lime powder, the pH value regulating waste water is 9.5, makes Al, Si, P ionic group in waste water be polymerized to particle;
Cross and filter above-mentioned particle and obtain waste water III, in waste water III, Al, Si, P total ion concentration drops to 1200ppm;
The sodium hydroxide solution adding 10 % by weight after waste water III is moved into separator regulates pH to be 10, layering after leaving standstill, containing the organic amine of triethylamine in upper oil phase, lower floor's aqueous phase carries out secondary filtration again, the hydrochloric acid soln adding 5 % by weight in filtrate regulates pH to be 5.5, makes COD in waste water drop to 600.
Claims (10)
1., containing a treatment process for SAPO molecular sieve mother liquor waste water, comprise the following steps:
(1) get in a SAPO molecular sieve mother liquor waste water and add iron(ic) chloride FeCl
36H
2o, hypochlorous acid or hypobromous acid, with the AlO in waste water
2 -, after polymerization, obtain waste water I;
(2) separately get in a SAPO molecular sieve mother liquor waste water and add boric acid or borate, then drip magnesium chloride Mg Cl
2pH is regulated to be 2.5 ~ 6, with the SiO in waste water
3 2-after stirring at room temperature, add waste water I again form the waste water II containing anionic composite flocculation agent;
(3) in waste water II, add calcium lime powder, the pH value regulating waste water is 7 ~ 9.5, makes Al, Si, P ionic group in waste water be polymerized to particle;
(4) filtering above-mentioned particle obtains waste water III, within Al, Si, P total ion concentration drops to 1000ppm in waste water III excessively;
(5) adding alkaline solution after waste water III being moved into separator regulates pH to be 9 ~ 12.5, layering after leaving standstill, containing organic amine in upper oil phase, lower floor's aqueous phase carries out secondary filtration again, in filtrate, acid supplemented solution regulates pH to be 6 ~ 8, makes waste water COD drop within 500, can be used as discharge of wastewater up to standard;
Total ion concentration containing Al, Si, P in described SAPO molecular sieve mother liquor waste water is 1 ~ 30 % by weight.
2. the treatment process of SAPO molecular sieve mother liquor waste water according to claim 1, is characterized in that step (1) and (2) can be carried out in same solution simultaneously.
3. the treatment process of SAPO molecular sieve mother liquor waste water according to claim 1, is characterized in that the ion containing Al in SAPO molecular sieve mother liquor waste water is AlO
2 -, the ion containing Si is SiO
3 2-, the ion containing P is PO
4 3-.
4. the treatment process of SAPO molecular sieve mother liquor waste water according to claim 1, is characterized in that iron(ic) chloride FeCl
36H
2the weight ratio of the ion containing Al in O, hypochlorous acid or hypobromous acid and SAPO molecular sieve mother liquor waste water is (1 ~ 9): (1 ~ 4): (1 ~ 4).
5. the treatment process of SAPO molecular sieve mother liquor waste water according to claim 1, to is characterized in that in boric acid or borate and waste water containing the weight ratio of the ion of Si being (0.2 ~ 2.5): (0.1 ~ 3.5).
6. the treatment process of SAPO molecular sieve mother liquor waste water according to claim 1, is characterized in that magnesium chloride Mg Cl
2be (0.1 ~ 2) with the weight ratio of ion containing Si in waste water: (3 ~ 20).
7. the treatment process of SAPO molecular sieve mother liquor waste water according to claim 1, is characterized in that the anionic composite flocculation agent in step (2) is poly-silicic-boric acid ferro-aluminum flocculation agent, i.e. poly-ferrosilicoaluminum boron (PSBFA), its Al
3+: Fe
3+: the mol ratio (0.3 ~ 0.8) of B:Si:P: (0.3 ~ 0.6): (0.3 ~ 0.8): (0.3 ~ 0.8): 1.
8. the treatment process of SAPO molecular sieve mother liquor waste water according to claim 1, is characterized in that described organic amine is at least one in diethylamine, triethylamine, morpholine, di-n-propylamine, Isopropylamine, tetraethyl ammonium hydroxide and tetraethylammonium bromide.
9. the treatment process of SAPO molecular sieve mother liquor waste water according to claim 1, the alkali that it is characterized in that in step (5) is the one in sodium hydroxide and potassium hydroxide, within the ionic concn in step (5) in waste water drops to 1000ppm.
10. the treatment process of SAPO molecular sieve mother liquor waste water according to claim 1, it is characterized in that the lower floor's aqueous phase secondary filtration in step (5), in filtrate, acid supplemented solution regulates pH to be 6 ~ 8, and acid solution used is hydrochloric acid soln or the sulphuric acid soln of 1 ~ 5 % by weight.
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| CN107129398A (en) * | 2017-07-06 | 2017-09-05 | 清华大学 | The discarded object produced based on production molecular sieve prepares method and the composite fertilizer of composite fertilizer |
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