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CN105540762A - Wastewater treatment method, wastewater treatment system, molecular sieve preparation method and molecular sieve preparation system - Google Patents

Wastewater treatment method, wastewater treatment system, molecular sieve preparation method and molecular sieve preparation system Download PDF

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Publication number
CN105540762A
CN105540762A CN201510726216.0A CN201510726216A CN105540762A CN 105540762 A CN105540762 A CN 105540762A CN 201510726216 A CN201510726216 A CN 201510726216A CN 105540762 A CN105540762 A CN 105540762A
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waste water
water
quaternary ammonium
unit
electrodialysis
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周丽娜
刘中清
罗一斌
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN201510726216.0A priority Critical patent/CN105540762A/en
Publication of CN105540762A publication Critical patent/CN105540762A/en
Priority to JP2018522000A priority patent/JP6917369B2/en
Priority to PCT/CN2016/000593 priority patent/WO2017071116A1/en
Priority to SG11201803576SA priority patent/SG11201803576SA/en
Priority to RU2018119084A priority patent/RU2730338C2/en
Priority to SG10201911200UA priority patent/SG10201911200UA/en
Priority to EP16858567.7A priority patent/EP3369710B1/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/085—Group IVB- metallosilicates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Molecular Biology (AREA)
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  • Separation Using Semi-Permeable Membranes (AREA)
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Abstract

The invention discloses a molecular sieve preparation process wastewater treatment method, a wastewater treatment system, a molecular sieve preparation method and a molecular sieve preparation system. The wastewater treatment method comprises the following steps: allowing wastewater containing quaternary ammonium ions to optionally be in contact with a precipitating agent to make silicon form colloid, carrying out solid-liquid separation, and carrying out electrodialysis treatment to obtain desalinated water with reduced content of the quaternary ammonium ions, and a concentrate liquid containing the quaternary ammonium ions. The wastewater treatment method effectively reduces the content of the quaternary ammonium ions (especially tetrapropyl quaternary ammonium ions) in wastewater in order to reduce the COD value of the wastewater, and the desalinated water recovered by adopting the wastewater treatment method can be recycled.

Description

The preparation method of the treatment process of waste water and Waste Water Treatment and molecular sieve and molecular sieve system
Technical field
The present invention relates to a kind for the treatment of process of waste water and a kind of Waste Water Treatment, the invention still further relates to a kind of preparation method of molecular sieve and a kind of molecular sieve system.
Background technology
TS-1 molecular sieve is a kind of HTS with MFI structure.It has excellent selective oxidation performance and higher catalytic activity, demonstrates good catalytic activity, be thus widely used in the organic oxidizing reaction such as oxidation of the epoxidation of alkene, pimelinketone oximate and alcohol.
TS-1 molecular sieve adopts directed agents hydrothermal crystallization method to synthesize usually.
CN1167082A discloses a kind of preparation method with the HTS of MFI structure, the method is dissolved in the TPAOH aqueous solution by titanium source, and mix with solid silicone bead and obtain reaction mixture, by this reaction mixture in autoclave in 130-200 DEG C of hydrothermal crystallizing 1-6 days, then carry out filtering, wash, dry and roasting, thus obtain the HTS with MFI structure.
CN1239015A discloses a kind of preparation method with the titanium-silicon molecular sieve TS-1 of MFI structure, the method first prepares a kind of reaction mixture for the synthesis of TS-1 molecular sieve, by this reaction mixture in sealed reactor in 110-145 DEG C of pre-crystallization 0.1-5 hour, then raised temperature is little of 3 days to 150-200 DEG C of continuation crystallization 1, thus obtains product.
CN1239016A discloses a kind of preparation method with the titanium-silicon molecular sieve TS-1 of MFI structure, and the method comprises the following steps:
(1) silicon source, organic amine compound and water are hydrolyzed 10-300 minute in proportion at the temperature of 0-40 DEG C, obtain the hydrating solution of silicon, wherein, organic amine compound is fatty amines or alcamine compound;
(2) titanium source, Virahol, organic bases and water are mixed in proportion, 5-90 minute is hydrolyzed at the temperature of 0-40 DEG C, obtain the hydrating solution of titanium, described organic bases is TPAOH or the mixture that forms for TPAOH and alcamine compound;
(3) hydrating solution of the titanium of step (2) gained and the hydrating solution of the silicon of step (1) gained are proportionally mixed at the temperature of 50-100 DEG C also stirring reaction 0.5-6 hour, obtain titanium colloidal silica;
(4) by step (3) gained titanium colloidal silica hydrothermal crystallizing according to a conventional method in sealed reactor, then product is reclaimed.
Visible, in the building-up process of HTS (as titanium-silicon molecular sieve TS-1), usually use quaternary ammonium hydroxide (as TPAOH) as template.Template has structure-directing effect, has promoter action to the formation in the structural unit of molecular sieve, cage or duct, is the indispensable raw material of hydrothermal synthesis method synthesis of titanium silicon molecular sieve.
In actual production process, complete preparation technology's flow process (as shown in Figure 1) of molecular sieve is: in synthesis step, titanium source, silicon source, template and water are reacted, the reaction mixture obtained is carried out hydrothermal crystallizing, then crystallization mixture is carried out filtering and washing, and then obtain zeolite product.As shown in Figure 1, filtration and the washing process of molecular sieve all produce waste water, and the wastewater flow rate produced is high, and usual 1 ton of finished product molecular sieve produces 10-20 ton waste water.The COD value (potassium dichromate process) of these waste water is up to more than 50,000, and sometimes even up to more than 100,000, the source of its COD is mainly the template TPAOH used in process of producing molecular sieve.
Organic amine (ammonium) belongs to hazardous and noxious substances, and the waste water containing organic amine (ammonium) must purify, and could discharge after making water quality reaching standard (COD value is below 60mg/L).The existing treatment process containing organic amine (ammonium) waste water mainly comprises anaerobic oxidation method, advanced oxidation processes, membrane separation process, absorption method and burning method etc.
CN104098228A discloses a kind for the treatment of process of organic amine wastewater, comprises the following steps:
A, preoxidation
Organic amine wastewater Fenton or 03 is carried out preoxidation, decomposes hazardous and noxious substances, improve the biodegradability of waste water, waste water after preoxidation is adjusted to neutrality, enter settling tank precipitation 2-4 hour;
B, anaerobism
Waste water through precipitation is carried out anaerobic treatment, organics removal;
C, Anoxybiotic-aerobic biologic reactor
Anaerobic effluent is entered Anoxybiotic-aerobic biologic reactor, remove the COD in sewage and nitrogen;
D, enhanced coagulation
Enhanced coagulation is carried out to the water outlet of Anoxybiotic-aerobic biologic reactor, removes the hydrophobic organic compound matter of bio-chemical effluent;
E, advanced oxidation
Advanced oxidation is carried out to the water outlet after enhanced coagulation, produces the hydroxyl radical free radical with Strong oxdiative ability, make macromole hardly degraded organic substance be oxidized to low toxicity or nontoxic small-molecule substance;
F, biological process advanced treatment
Advanced oxidation water outlet enters BAF, controls the residence time, dissolved oxygen, removes COD further, make water outlet qualified discharge.
CN104211250A discloses a kind of method reclaiming organic amine from 3,4-Dihydro-6-methyl-1,2,3-oxathiazin-4-one 2,2-dioxide potassium salt trade effluent, comprises the following steps:
Adopt lime powder neutralized wastewater, the pH value of water quality is made to reach weakly acidic pH, lime powder gradation adds and vigorous stirring, calcium sulfate after suction filtration removing neutralization, pH is adjusted to about 8 with soda ash by filtrate in evaporating pot, and amine is disengaged, then collects the cut of organic amine with separation column fractionation, finally organic amine is dewatered by molecular sieve drying and resin absorption, obtain the organic amine that can reuse.
CN104230077A discloses a kind of organic amine wastewater treatment process of phosphorous aluminium silicon, and the method comprises the following steps:
(1) by the organic amine wastewater of phosphorous aluminium silicon through weight-removing column, discharge from tower reactor after the heavy constituent in waste water is concentrated, enter waste liquid spray drying system, the light constituent that weight-removing column tower top obtains enters lightness-removing column and purifies further;
(2) lightness-removing column tower reactor waste water is sent Crystallization of Zeolite unit back to and is recycled, and the water that lightness-removing column tower top obtains and organic amine are after Liquid liquid Separation, and aqueous phase returns lightness-removing column, and the organic amine obtained enters after treating tower purifies, and recycles.
CN103304430A discloses a kind of technique reclaiming organic amine from catalyst production waste water, comprising:
(1) catalyst recovery in waste water, reclaims after micro-strainer interception containing a small amount of particulate molecular sieve in waste water;
(2) organic amine absorbing process, becomes organic amine salt with acid regeneration by waste water after the absorption of organic amine resin cation (R.C.);
(3) organic amine salt is exchanged by resin anion(R.A) and is reduced into organic amine, and the organic amine of reduction is as raw materials for production reuse, and anionite-exchange resin NaOH regenerates.
CN102399032A discloses a kind of method for the treatment of organic amine industrial waste water by Fenton-like oxidation-flocculation, comprises the following steps:
(1) regulate wastewater pH to 3-5, adjust the temperature to 20-40 DEG C;
(2) add catalyzer, the catalyzer effective constituent of fenton-type reagent is: ferrous sulfate, anhydrous cupric sulfate and Manganous sulfate monohydrate, and the mass ratio of each component is (5-10): 1:(0-5);
(3) H that mass percentage concentration is 30% is added 2o 2, oxidation time 1-4 hour;
(4) oxidation terminate after hydro-oxidation sodium adjustment waste water pH to 8-10, add chemical coagulator and macromolecule organic flocculating agent, by the partial suspended solid in waste water, colloid, part organic amine together coagulation get off.
CN102079712A discloses a kind of method reclaiming anhydrous organic amine from organic amine salt, and the mixture that the method adopts calcium oxide or calcium oxide content to be greater than 50% is raw material, reclaims anhydrous organic amine with organic amine salt stirring reaction.
CN102151544A discloses a kind of organic wastewater modified bentonite adsorbent, wherein, this sorbent material is utilize organic amine in organic amine waste water as properties-correcting agent, to the sorbent material that the sodium base of having purified or calcium-base bentonite carry out modification and obtain, that the wilkinite powder of purification is joined stirring at normal temperature 10-120 minute in organic amine waste water, then filter, obtain organic wastewater modified bentonite filter cake, dry under 90-105 DEG C of condition, grind, obtain organic wastewater modified bentonite, then inserted roasting in retort furnace, obtained after being cooled to normal temperature.
CN103663609A discloses a kind of method of microwave catalysis oxidation process high COD organic wastewater.Microwave radiation is produced strong oxidizing property group and is used for oxide treatment high COD organic wastewater by the method on the surface of microwave catalyst, make the oxidation operations such as organic amine wherein be degraded to CO 2with water or inorganic acid radical ion.
CN104529034A discloses a kind of method reclaiming TPAOH in catalyst production waste water, nanofiltration membrane has higher decreasing ratio to divalence or polyvalent ion and the organism of molecular weight between 200-500, TPAOH molecule is separated effectively by nanofiltration, wastewater pH is regulated to be 5-7 with the hydrochloric acid that massfraction is 10%, nanofiltration device pressure is regulated to be 20kg, the waste water regulating pH is injected nanofiltration water-in, dense water and rare water is obtained after nanofiltration interception, dense water and rare water ratio are 1:5, dense water continues to inject nanofiltration device, by pressure increase to 25kg, concentrate the dense water obtaining second step and rare water further, dense water and rare water ratio are 1:2, repeat previous step and carry out third time operation, pressure-controlling is 30kg, the dense water obtained and rare water ratio are 1:1, the most all rare water mixing obtained, the dense water obtained is the water that former water concentrates after 36 times.
CN104773787A discloses a kind of method reducing the chemical oxygen demand of zeolite molecular sieve factory effluent, comprise and add hydrogen peroxide in zeolite molecular sieve factory effluent, by the nitrogen-containing organic compound oxidative degradation in zeolite molecular sieve factory effluent under UV-irradiation, described nitrogen-containing organic compound is one or more of quaternary ammonium salt, quaternary ammonium hydroxide and organic amine.
CN104773786A discloses a kind of method reducing the total content of organic carbon of zeolite molecular sieve waste water, comprise and add hydrogen peroxide in zeolite molecular sieve factory effluent, by the nitrogen-containing organic compound oxidative degradation in zeolite molecular sieve factory effluent under UV-irradiation, described nitrogen-containing organic compound is one or more in quaternary ammonium salt, quaternary ammonium hydroxide and organic amine.
But aforesaid method exists that facility investment is large, and working cost is high, and treatment effect is unstable, easily produces the shortcomings such as secondary pollution, therefore for the process of the higher waste water of organic amine content, rarely has the industrialization example of successful operation.
Summary of the invention
The object of the invention is to provide a kind of method of wastewater treatment, the method is adopted to process the molecular sieve spent process water containing quaternary ammonium radical ion, effectively can not only reduce the quaternary ammonium radical ion content in waste water, and quaternary ammonium radical ion can be enriched in electrodialysis dope.
According to a first aspect of the invention, the invention provides a kind for the treatment of process of molecular sieve spent process water, described waste water contains at least one quaternary ammonium radical ion, and the method comprises electrodialysis step and optional pre-treatment step:
In pre-treatment step, waste water is carried out solid-liquid separation, obtain solid phase and liquid phase, before waste water is carried out solid-liquid separation, alternatively waste water is contacted with at least one precipitation agent, form colloid to make the silicon in waste water;
In electrodialysis step, the liquid phase described waste water or pre-treatment step obtained carries out electrodialysis, obtains the desalination water that quaternary ammonium radical ion content reduces and the concentrated solution containing quaternary ammonium radical ion.
According to the present invention second aspect, the invention provides a kind of Waste Water Treatment, described waste water is the molecular sieve spent process water containing quaternary ammonium radical ion, comprises waste water storage unit, optional pretreatment unit and electrodialysis cell,
Described waste water storage unit is used for receiving and storing wastewater;
Described pretreatment unit is used for the waste water coming from waste water storage unit to contact with at least one precipitation agent alternatively, after forming colloid, carries out solid-liquid separation, to obtain liquid phase and solid phase to make the silicon in described waste water;
The liquid phase that described electrodialysis cell is used for described waste water or described pretreatment unit export carries out electrodialysis, obtains the desalination water that quaternary ammonium radical ion content reduces and the concentrated solution containing quaternary ammonium radical ion.
According to a third aspect of the present invention, the invention provides a kind of preparation method of molecular sieve, the method comprises synthesis step, crystallization steps, separating, washing step and waste water treatment step,
In described synthesis step, by raw material and water contact reacts, described raw material contains silicon source, quaternary ammonium hydroxide and optional titanium source;
In described crystallization steps, the reaction mixture obtained by synthesis step carries out crystallization;
In separating, washing step, mixture crystallization steps obtained carries out solid-liquid separation, obtains solid phase and crystallization mother liquor, and washs described solid phase, obtains molecular sieve and washes;
In waste water treatment step, waste water is carried out electrodialysis, obtain the desalination water that concentrated solution containing quaternary ammonium radical ion and quaternary ammonium radical ion content reduce, described waste water is the mixed solution of described crystallization mother liquor, described washes or described crystallization mother liquor and described washes, wherein, the method described in the present invention first aspect is adopted to process described waste water.
According to a fourth aspect of the present invention, the invention provides a kind of molecular sieve system, this system comprises synthesis unit, crystallization unit, separating, washing unit and treatment unit for waste water,
Described synthesis unit is used for raw material and water contact reacts, and described raw material contains silicon source, quaternary ammonium hydroxide and optional titanium source;
The reaction mixture that described crystallization unit is used for synthesis step to obtain carries out crystallization;
The mixture that described separating, washing unit is used for crystallization steps to obtain carries out solid-liquid separation, obtains solid phase and crystallization mother liquor, and washs described solid phase, obtain molecular sieve and washes;
Described treatment unit for waste water contains the system described in the present invention second aspect, for waste water is carried out electrodialysis, obtain the desalination water that concentrated solution containing quaternary ammonium radical ion and quaternary ammonium radical ion content reduce, described waste water is the mixed solution of described crystallization mother liquor, described washes or described crystallization mother liquor and described washes.
The present invention adopts electrodialysis to process the molecular sieve spent process water containing quaternary ammonium radical ion, effectively can reduce quaternary ammonium radical ion (the particularly tetrapropyl quaternary ammonium radical ion) content in waste water, and then reducing the COD value of waste water, purifying waste water of obtaining can be cycled to used in sieve synthesis procedure; Can also obtain the concentrated solution being enriched quaternary ammonium radical ion, this concentrated solution can be cycled to used in sieve synthesis procedure simultaneously.Adopt method of the present invention to process the process of producing molecular sieve waste water containing quaternary ammonium radical ion, achieve rationally effectively recycling of resource.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.
Fig. 1 is a kind of typical process flow of preparation HTS.
Fig. 2 is for illustration of a kind of embodiment of the electrodialysis related in method and system according to the present invention.
Fig. 3 is for illustration of a kind of preferred implementation of molecular sieve preparation method according to the present invention and molecular sieve system.
Fig. 4 is for illustration of the another kind of preferred implementation of molecular sieve preparation method according to the present invention and molecular sieve system.
Description of reference numerals
1: cationic exchange membrane 2: anion-exchange membrane
Embodiment
The invention provides a kind for the treatment of process of molecular sieve spent process water, described waste water contains quaternary ammonium radical ion.Described quaternary ammonium radical ion refers to NH 4 +in four hydrogen replaced by organic group and the ion formed.Usually, described quaternary ammonium radical ion can be the quaternary ammonium radical ion shown in formula I,
In formula I, R 1, R 2, R 3and R 4can be C separately 1-C 5alkyl or C 6-C 12aryl.Described C 1-C 5alkyl comprise C 1-C 5straight chained alkyl and C 3-C 5branched-chain alkyl, its specific examples comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.Described C 6-C 12the specific examples of aryl can include but not limited to: phenyl, naphthyl, 4-aminomethyl phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-ethylphenyl, 2-ethylphenyl and 3-ethylphenyl.
Preferably, described quaternary ammonium radical ion is tetramethyl ammonium, tetraethyl ammonium ion, tetrapropyl ammonium ion and TBuA ion.As a preferred embodiment, described quaternary ammonium radical ion is tetrapropyl ammonium ion.
Described waste water for adopting quaternary ammonium hydroxide as the molecular sieve spent process water of template, can prepare as adopted the hydrothermal crystallization method of directed agents the waste water produced in the process of molecular sieve.Particularly, described waste water can for adopting the crystallization mother liquor of the molecular sieve process of quaternary ammonium hydroxide, the washes of molecular sieve process adopting quaternary ammonium hydroxide or the mixed solution of described crystallization mother liquor and described washes.
Described quaternary ammonium hydroxide can for being suitable for the quaternary ammonium hydroxide of the structure directing agent as molecular sieve.Particularly, described quaternary ammonium hydroxide is selected from the compound shown in formula II,
In formula II, R 1, R 2, R 3and R 4can be C separately 1-C 5alkyl or C 6-C 12aryl.Described C 1-C 5alkyl comprise C 1-C 5straight chained alkyl and C 3-C 5branched-chain alkyl, its specific examples comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.Described C 6-C 12the specific examples of aryl can include but not limited to: phenyl, naphthyl, 4-aminomethyl phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-ethylphenyl, 2-ethylphenyl and 3-ethylphenyl.
Preferably, described quaternary ammonium hydroxide is Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH and TBAH.As a preferred embodiment, described quaternary ammonium hydroxide is TPAOH.
Described molecular sieve can for common various using quaternary ammonium hydroxide as template by molecular sieve prepared by hydrothermal synthesis method, as at least one in HTS, BETA molecular sieve, SSZ-13 molecular sieve and Silicate-1.Described HTS is the general name that titanium atom replaces a class zeolite of a part of Siliciumatom in lattice framework, it can be the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, one or more in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.
As a preferred embodiment, described molecular sieve is HTS, is preferably titanium-silicon molecular sieve TS-1 and/or hollow HTS.Described hollow HTS is the HTS of MFI structure, and the crystal grain of this HTS is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300 nanometer, and this HTS is at 25 DEG C, P/P 0=0.10, adsorption time is that the benzene adsorptive capacity recorded under the condition of 1 hour is at least 70 milligrams/grams, there is hysteresis loop between the adsorption isothermal line of the nitrogen absorption under low temperature of this HTS and desorption isotherm.Described hollow HTS can be commercially available (be such as purchased from the trade mark of Hunan Jianchang Petrochemical Co., Ltd be the molecular sieve of HTS), also method can prepare disclosed in CN1132699C.
In described waste water, the content of quaternary ammonium radical ion is not particularly limited, fixed with the source of waste water.Usually, in described waste water, the concentration of quaternary ammonium radical ion can, at more than 1000mg/L, as more than 2000mg/L, can be even more than 10000mg/L, as more than 15000mg/L.In described waste water, the most high-content of quaternary ammonium radical ion is not particularly limited.Usually, in described waste water, the concentration of quaternary ammonium radical ion can be below 35000mg/L usually, as below 30000mg/L.
According to method of wastewater treatment of the present invention, comprise optional pre-treatment step: in pre-treatment step, waste water is carried out solid-liquid separation, obtain solid phase and liquid phase, before waste water is carried out solid-liquid separation, waste water is contacted with at least one precipitation agent alternatively, form colloid to make the silicon in waste water.
In the present invention, term " alternatively " and " optionally " represent that the feature connected with it is inessential feature, can be understood as " contain or do not contain " or " comprise or do not comprise ".
According to method of the present invention, be the object that waste water contacts with precipitation agent to reduce the content of precipitable species (as silicon) in waste water, to avoid in electrodialysis process, these precipitable species form solid and are attached to ion-exchange membrane surface, affect electrodialytic effect, shorten the work-ing life of film; The object of waste water being carried out solid-liquid separation is to reduce the solid matter content in waste water.It will be appreciated by persons skilled in the art that and can select whether carry out pre-treatment step and pretreated mode according to the content of waste water whether containing precipitable species and/or solid matter and these two kinds of materials.
As described precipitation agent, AlCl can be listed 3, polymeric aluminum, bronsted lowry acids and bases bronsted lowry.Described alkali is preferably mineral alkali, is more preferably selected from alkali metal hydroxide and ammoniacal liquor, is preferably selected from sodium hydroxide, potassium hydroxide and ammoniacal liquor further, most preferably is sodium hydroxide.Described alkali preferably provides in form of an aqueous solutions, and the concentration of the aqueous solution of alkali is not particularly limited, and can be normal concentration according to the concrete kind of alkali.For improving strainability, flocculation agent and/or flocculating aids can also be added, thus improve the strainability of colloidal silica.
One of the present invention preferred embodiment in, in described waste water, add at least one acid, to make silicon in waste water form colloidal precipitation, and carry out solid-liquid separation, thus obtain solid phase and liquid phase.
Colloidal silica is a kind of material of more sad filter, when adopting plate and frame filter to filter, is easy to produce the phenomenon of wearing filter or blocking filter cloth, thus usually uses flocculation agent and/or flocculating aids.With employing AlCl 3compare with polymeric aluminum, adopt acid, the colloidal silica of formation can be made to have better strainability on the one hand, thus omit the demand for flocculation agent and flocculating aids; Higher silicon deposition rate can also be obtained on the other hand, thus obtain the higher silicon rate of recovery.
Described acid is preferably mineral acid, and its specific examples can include but not limited to hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.Preferably, described acid is sulfuric acid and/or hydrochloric acid.Described acid provides in form of an aqueous solutions, and the concentration of aqueous acid is not particularly limited, and can be normal concentration according to the concrete kind of acid.
The concrete consumption of described acid can be selected according to the character of the kind of acid and waste water, forms colloid be as the criterion can make the silicon in described waste water.Usually, the consumption of described acid makes the pH value of waste water in the scope of 5-8, preferably makes the pH value of waste water in the scope of 6-7.
The duration of contact of described waste water and at least one acid is as the criterion to be enough to the making most of silicon in waste water form colloid.Usually, duration of contact can be 0.5-24 hour.Described waste water can contact with at least one acid at the temperature of 10-95 DEG C, preferably at the temperature of 40-85 DEG C.In actual mechanical process, after waste water can being mixed with described acid, at the temperature of 0-95 DEG C, preferably, leave standstill 5-24 hour at the temperature of 40-85 DEG C, can better solid-liquid separation effect be obtained like this.
In pre-treatment step, the method for described solid-liquid separation can be conventional selection, as the combination of filtration, centrifugal or two or more separation method, preferably filters.When filtering, common various filtration mediums can be adopted, as the combination of one or more in fabric, porous material, solid particle layer and porous-film.Described porous-film can be the combination of organic membrane, mineral membrane or two or more porous-film.Described mineral membrane can be ceramic membrane and/or metallic membrane, and described organic membrane can be hollow-fibre membrane.Preferably, described filtration medium is porous-film.More preferably, described filtration medium is ultra-filtration membrane.
According to method of wastewater treatment of the present invention, comprise electrodialysis step: liquid phase waste water or pre-treatment step obtained carries out electrodialysis, obtain the desalination water that quaternary ammonium radical ion content reduces and the concentrated solution containing quaternary ammonium radical ion.
Described electrodialysis is carried out at least one electrodialyzer, and the membrane stack of described electrodialyzer has at least one film unit, and the film in described film unit and array mode thereof can be conventional selection.Preferably, as shown in Figure 2, the film in film unit is cationic exchange membrane 1 and anion-exchange membrane 2, and the internal space of described film unit is separated into feed liquid room and concentration compartments by anion-exchange membrane 2 and cationic exchange membrane 1.Also it should be noted that, Fig. 2 " ... " represent and be provided with multiple film unit between the positive pole and negative pole of electrodialyzer, these film units have the film unit structure identical with the structure shown in figure, are not thus illustrated.
When carrying out electrodialysis, the liquid phase that waste water or pre-treatment step obtain enters feed liquid room, water (desalination water that can obtain for deionized water and/or electrodialysis) enters in concentration compartments, under the effect of electric field, quaternary ammonium radical ion in the liquid phase that waste water or pre-treatment step obtain and other cation permeable cationic exchange membrane 1 enter in concentration compartments, anion-permeable anion-exchange membrane 2 in the liquid phase that waste water or pre-treatment step obtain enters in opposite side concentration compartments (not shown in Fig. 2), thus the desalination water of quaternary ammonium radical ion content reduction is obtained in feed liquid room, obtain in concentration compartments the concentrated solution being enriched quaternary ammonium radical ion simultaneously.
In electrodialysis step, the voltage applied to each film unit generally in the scope of 0.1-5V, preferably in the scope of 0.5-4V, more preferably in the scope of 1-3V, such as, in the scope of 1-2.5V.
In electrodialysis step, the quaternary ammonium radical ion content in the desalination water obtained by electrodialysis can be selected according to the desired use of desalination water.Particularly, when described desalination water is cycled to used in sieve synthesis procedure, in described desalination water, the mass content of quaternary ammonium radical ion is preferably below 2000mg/L, is preferably below 1700mg/L.According to method of wastewater treatment of the present invention, the desalination water with above-mentioned quaternary ammonium radical ion content can be obtained with the shorter electrodialysis time.
According to method of wastewater treatment of the present invention, in electrodialysis step, when carrying out electrodialysis, all use water at initial period, this part water can be pure water, as deionized water; The desalination water that also electrodialysis can be obtained is as the water of electrodialytic initial period, and the water that namely electrodialytic initial period uses comes from the desalination water in electrodialysis described in electrodialysis step at least partly; It can also be the mixing water of deionized water and desalination water.
According to method of wastewater treatment of the present invention, in electrodialysis described in electrodialysis step, described cationic exchange membrane is styrene type homogeneous phase cation exchange film.The present inventor finds in research process, when adopting homogeneous phase cation exchange film to carry out electrodialysis, with such as Na +mineral ion different, the travelling speed of quaternary ammonium radical ion and the material of homogeneous phase cation exchange film closely related, polyether-ether-ketone homogeneous phase cation exchange film, perfluoroethylene sulfonic acid homogeneous phase cation exchange film or polysulfones homogeneous phase cation exchange film is adopted to carry out electrodialysis, even if apply higher voltage to film unit, also cannot obtain good electrodialysis effect, in the desalination solution obtained, the content of quaternary ammonium radical ion is still higher; But adopt styrene type homogeneous phase cation exchange film, then can obtain good electrodialysis effect, quaternary ammonium radical ion is enriched in concentrated solution, and in the desalination water obtained, the content of quaternary ammonium radical ion obviously reduces.
Method according to the present invention is not particularly limited for the loading capacity of styrene type homogeneous phase cation exchange film, and can be conventional selection, such as, can be 1-3meq/g dry film, is preferably 1.5-3meq/g dry film, is more preferably 1.8-2.6meq/g dry film.According to method of the present invention, the membrane surface resistance of described styrene type cationic exchange membrane can be 1-15 Ω cm 2, be preferably 2-12 Ω cm 2.According to method of the present invention, from the angle improving electrodialysis effect further, the membrane surface resistance of described styrene type homogeneous phase cation exchange film is more preferably 4-9 Ω cm 2.
According to method of wastewater treatment of the present invention, in step (2) described electrodialysis, be generally conventional mineral ion by the negatively charged ion of anion-exchange membrane, the various anion-exchange membrane being enough to that negatively charged ion is passed through can be adopted.Particularly, described anion-exchange membrane can be heterogeneous anion-exchange membrane, also can be homogeneous-phase anion exchange film.From the further angle improving the work-ing life of anion-exchange membrane, described anion-exchange membrane is preferably homogeneous-phase anion exchange film.The material of described anion-exchange membrane is also not particularly limited, can be conventional selection, such as, can be one or more the combination in styrene type anion-exchange membrane, polysulfones type anion-exchange membrane, PEEK type anion-exchange membrane and perfluoroethylene sulfonic acid type anion-exchange membrane.According to method of the present invention, the design parameter for anion-exchange membrane is also not particularly limited, and can be conventional selection.Such as, the loading capacity of described anion-exchange membrane can be 0.5-5meq/g dry film, is preferably 1-4meq/g dry film, is more preferably 2-2.5meq/g dry film.The membrane surface resistance of described anion-exchange membrane can be 1-15 Ω cm 2, be preferably 2-12 Ω cm 2.
According to method of wastewater treatment of the present invention, when carrying out electrodialysis, the kind of the pole liquid that the anolyte compartment of electrodialyzer and cathode compartment use is not particularly limited, and can be conventional selection.Usually, described pole liquid can by obtaining at least one electrolyte dissolution in water.Described electrolytical concentration can be conventional selection, can be generally 0.1-50 % by weight, is preferably 0.1-40 % by weight, be more preferably 0.5-25 % by weight, more preferably 1-20 % by weight, is further preferably 2-10 % by weight, is particularly preferably 2.5-5 % by weight.The various ionogen that described ionogen can be commonly used for this area, as inorganic electrolyte and/or organic electrolyte.Particularly, described ionogen can be one or more in sodium sulfate, SODIUMNITRATE, sodium phosphate, sodium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC, saltpetre, potassiumphosphate, potassium hydrogen phosphate, potassium primary phosphate, sodium hydroxide, potassium hydroxide, formic acid, acetic acid, sodium formiate, potassium formiate and quaternary ammonium type ionogen.Described quaternary ammonium type ionogen can be various water soluble quaternary ammonium type ionogen, is preferably one or more in tetramethyl ammonium chloride, 4 bromide and Tetramethylammonium hydroxide.
According to method of wastewater treatment of the present invention, described electrodialysis can be carried out at conventional temperatures.Usually, described electrodialysis can be carried out at the temperature of 0-50 DEG C, preferably 5-40 DEG C, more preferably 10-35 DEG C.The described electrodialytic time length can be selected according to the composition of the desalination water of the character of waste water and expection, is not particularly limited.
Present invention also offers a kind of Waste Water Treatment, described waste water is the molecular sieve spent process water containing quaternary ammonium radical ion, comprises waste water storage unit, optional pretreatment unit and electrodialysis cell.
Described waste water storage unit is used for receiving and storing wastewater.Described waste water storage unit can adopt the hollow containers such as common tank to receive and storing wastewater.
Described pretreatment unit is selectable unit, for the waste water coming from waste water storage unit is contacted with at least one precipitation agent alternatively, colloid is formed to make the silicon in described waste water, obtain the mixture containing colloid, waste water or the mixture containing colloid are carried out solid-liquid separation, obtains liquid phase and solid phase.Kind and the consumption of described precipitation agent have been described in detail above, no longer describe in detail herein.
Described pretreatment unit can comprise precipitation reactor, for making waste water and precipitation agent contact reacts.
In described pretreatment unit, conventional equipment for separating liquid from solid can be comprised, as the combination of filtration unit, centrifugal device or two or more tripping device, preferably include filtration unit.Described filtration unit can adopt common various filtration mediums, as the combination of one or more in fabric, porous material, solid particle layer and porous-film.Described porous-film can be the combination of organic membrane, mineral membrane or two or more porous-film.Described mineral membrane can be ceramic membrane and/or metallic membrane, and described organic membrane can be hollow-fibre membrane.Preferably, using porous-film as filtration medium.More preferably, using ultra-filtration membrane as filtration medium.
According to Waste Water Treatment of the present invention, described pretreatment unit is for reducing the content of the species (as silicon) and/or solid matter that can form precipitation in waste water, to avoid these species to form fouling on ion-exchange membrane surface in electrodialysis process, thus affect electrodialysis effect and shorten work-ing life of ion-exchange membrane.It will be appreciated by persons skilled in the art that content and the solid matter of the species that can form precipitation in waste water are lower, when obviously can not affect electrodialysis generation, described pretreatment unit can not be set.
The liquid phase that described electrodialysis cell is used for waste water or pretreatment unit to obtain carries out electrodialysis, obtains the desalination water that quaternary ammonium radical ion content reduces and the concentrated solution containing quaternary ammonium radical ion.
The liquid phase that waste water or pretreatment unit obtain by the electrodialyzer that described electrodialysis cell adopts carries out electrodialysis, is specifically as follows the electrodialyzer above described in composition graphs 2, no longer describes in detail herein.
In electrodialysis cell, the quantity of electrodialyzer can be one or more, can select according to the index of the desalination water of the treatment capacity of system and expection.When the quantity of electrodialyzer is multiple, can, for being connected in series, can, for being connected in parallel, can also be also the combination of parallel connection and serial connection between multiple electrodialyzer.In the present invention, be connected in series and refer to that multiple electrodialyzer links together in end to end mode and formed the glide path of fluid, the desalination water that the electrodialyzer being arranged in upstream exports then enters the electrodialyzer that downstream directly connects and proceeds electrodialysis, thus realizes multistage electrodialysis.In the present invention, be connected in parallel and refer to that the water inlet of multiple electrodialyzer is originated identical, form and do not have logistics to contact each other but there is the form in the tributary in identical source, thus realize multiprocessor Parallel Processing, improve the treatment capacity of device.In the present invention, series and parallel connections combinationally uses, refer to when multiple electrodialyzer is combinationally used, parallel connection and serial connection is used with, as the example that series and parallel connections combinationally uses, can arrange and organize electrodialyzer more, often between group for being connected in parallel, often group is interior for being connected in series, and can realize multistage electrodialysis like this, can obtain higher treatment capacity again.
According to Waste Water Treatment of the present invention, the cationic exchange membrane used in described electrodialysis cell is styrene type homogeneous phase cation exchange film.The parameter (as degree of crosslinking and loading capacity) of described styrene type homogeneous phase cation exchange film has been described in detail above, no longer describes in detail herein.
Invention further provides a kind of preparation method of molecular sieve, the method comprises synthesis step, crystallization steps, separating, washing step and waste water treatment step.
In described synthesis step, by raw material and water contact reacts, described raw material contains silicon source, quaternary ammonium hydroxide and optional titanium source.
The present invention is not particularly limited for the kind in silicon source, and can be conventional selection, such as, can be silicon sol and/or silicoorganic compound.Described silicoorganic compound can be the various silicon-containing compound that can form silicon-dioxide under hydrolysis-condensation reaction condition.Particularly, described organosilicon source can one or more for being selected from the silicon-containing compound shown in formula III,
In formula III, R 5, R 6, R 7and R 8can be C separately 1-C 4alkyl, comprise C 1-C 4straight chained alkyl and C 3-C 4branched-chain alkyl, such as: R 5, R 6, R 7and R 8can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-or the tertiary butyl separately.
Particularly, described organosilicon source can be one or more in positive quanmethyl silicate, tetraethyl orthosilicate, positive silicic acid four n-propyl and the positive butyl ester of positive silicic acid four.
According to the kind of the molecular sieve of preparation, described raw material can also contain other material, as titanium source.Described titanium source can be conventional selection, is not particularly limited.Such as, described titanium source can be inorganic titanium salt and/or organic titanate, is preferably organic titanate.Described inorganic titanium salt can be TiCl 4, Ti (SO 4) 2and TiOCl 2in one or more; Described organic titanate can be general formula R 9 4tiO 4the compound represented, wherein, R 9for C 1-C 6alkyl, be preferably C 2-C 4alkyl.
Described quaternary ammonium hydroxide can for being suitable for the quaternary ammonium hydroxide of the structure directing agent as molecular sieve.Particularly, described quaternary ammonium hydroxide is selected from the compound shown in formula II,
In formula II, R 1, R 2, R 3and R 4can be C separately 1-C 5alkyl or C 6-C 12aryl.Described C 1-C 5alkyl comprise C 1-C 5straight chained alkyl and C 3-C 5branched-chain alkyl, its specific examples comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.Described C 6-C 12the specific examples of aryl can include but not limited to: phenyl, naphthyl, 4-aminomethyl phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-ethylphenyl, 2-ethylphenyl and 3-ethylphenyl.
Preferably, described quaternary ammonium hydroxide is Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH and TBAH.More preferably, described quaternary ammonium hydroxide is TPAOH.
Ratio between described silicon source, quaternary ammonium hydroxide, alternatively titanium source and water is determined according to the concrete kind of molecular sieve, can be conventional selection, no longer describe in detail herein.
In described crystallization steps, the reaction mixture obtained by synthesis step carries out crystallization.
Described crystallization can be carried out under normal conditions.Usually, described Crystallizing treatment can carry out in closed environment.The temperature of described Crystallizing treatment can be 110-180 DEG C.The time of described Crystallizing treatment can be 6-72 hour.
According to the preparation method of molecular sieve of the present invention, also molecular sieve can be prepared with reference to condition known in the art, such as, as long as this molecular sieve adopts quaternary ammonium compound (being generally quaternary ammonium hydroxide) in preparation process, molecular sieve preparation method disclosed in CN1167082A, CN1239015A and CN1239016A.
In separating, washing step, mixture crystallization steps obtained carries out solid-liquid separation, obtains solid phase and crystallization mother liquor, and washs described solid phase, obtains molecular sieve and washes.
The method of described solid-liquid separation can be conventional selection, and as the combination of filtration, centrifugal or two or more separation method, the mixture preferably adopting the method for filtering crystallization steps to be obtained is separated.When filtering, common various filtration mediums can be adopted, as the combination of one or more in fabric, porous material, solid particle layer and porous-film.Described porous-film can be the combination of organic membrane, mineral membrane or two or more porous-film.Described mineral membrane can be ceramic membrane and/or metallic membrane, and described organic membrane can be hollow-fibre membrane.Preferred employing fabric is as filtration medium.Described filtration can be carried out in common filter plant, as plate and frame filter, band filter.
In waste water treatment step, waste water is carried out electrodialysis, obtain the desalination water that concentrated solution containing quaternary ammonium radical ion and quaternary ammonium radical ion content reduce, described waste water is the mixed solution of described crystallization mother liquor, described washes or described crystallization mother liquor and described washes, wherein, the described method of the present invention first aspect is adopted to process described waste water.
Preferably, according to molecular sieve preparation method of the present invention, also comprise desalination water circulation step, in desalination water circulation step, described desalination water is cycled to used in the one in following steps, both and three: described synthesis step, as synthesis water; Described crystallization steps, for stopping crystallization; Described separating, washing step, as washing water.
According to a fourth aspect of the present invention, the invention provides a kind of molecular sieve system, this system comprises synthesis unit, crystallization unit, separating, washing unit and treatment unit for waste water.
Described synthesis unit is used for raw material and water contact reacts, and described raw material contains silicon source, quaternary ammonium hydroxide and optional titanium source.The various synthesis reactor that described synthesis unit can adopt this area conventional, are not particularly limited.
The reaction mixture that described crystallization unit is used for synthesis step to obtain carries out crystallization.Crystallization unit can be conventional be enough to the reactor bearing heat and interior pressure, as high pressure crystallizing kettle.
The mixture that described separating, washing unit is used for crystallization steps to obtain carries out solid-liquid separation, obtains solid phase and crystallization mother liquor, and washs described solid phase, obtain molecular sieve and washes.In described separating, washing unit, filtration medium can adopt common various filtration mediums, as the combination of one or more in fabric, porous material, solid particle layer and porous-film.Described porous-film can be the combination of organic membrane, mineral membrane or two or more porous-film.Described mineral membrane can be ceramic membrane and/or metallic membrane, and described organic membrane can be hollow-fibre membrane.Preferred employing fabric is as filtration medium.Described separating, washing unit can adopt conventional equipment for separating liquid from solid, as plate and frame filter, band filter.
Described treatment unit for waste water is used for waste water to carry out electrodialysis, and obtain the concentrated solution containing quaternary ammonium radical ion and desalination water, wherein, described treatment unit for waste water adopts the described system of the present invention second aspect to process waste water.
Preferably, according to Waste Water Treatment of the present invention, also comprise desalination water transport pipe, the desalination water that described desalination water transport pipe is used for described treatment unit for waste water to reclaim is sent into the one in lower unit, both or three: described synthesis unit, as synthesis water; Described crystallization unit, for stopping crystallization; Described separating, washing unit, as washing water.
Fig. 3 show adopt the present invention to process molecular sieve spent process water one preferred embodiment.In embodiment described in Fig. 3, Waste Water Treatment comprises salt cellar, electrodialyzer and concentration tank and desalination tank.Film in the film unit of described electrodialyzer is cationic exchange membrane and anion-exchange membrane, thus the internal space of described film unit is separated into feed liquid room and concentration compartments.
Described salt cellar is for receiving waste water, and be communicated with the feed liquid room of the electrodialyzer in described electrodialysis cell, there is provided into water for described feed liquid room and in electrodialytic process, receive the water outlet of described feed liquid room, namely, in electrodialytic process, described salt cellar and described feed liquid room form a liquid circulation passage.
Described concentration tank is communicated with the concentration compartments of described electrodialyzer, there is provided into water for described concentration compartments and in electrodialytic process, receive the water outlet of described concentration compartments, namely, in electrodialytic process, described concentration tank and described concentration compartments form another liquid circulation passage.Described desalination tank is communicated with the feed liquid room of described electrodialyzer, for receiving the desalination water met the demands that described feed liquid room exports.
Preferably, as shown in Figure 3, this system also comprises concentrated solution storage tank and desalination water withdrawing can, the concentrated solution of described concentrated solution storage tank for receiving concentration tank to export; Described desalination water withdrawing can is for receiving the desalination water met the demands exported from desalination tank.Preferably, as shown in Figure 3, described desalination water withdrawing can is also communicated with concentration tank simultaneously, and then provides the initial water of electrodialysis and for concentration compartments supplements electrodialysis water in electrodialytic process for concentration compartments.Preferably, as shown in Figure 3, desalination water withdrawing can is communicated with the one in separating, washing unit, both or three with synthesis unit, crystallization unit, send in synthesis unit with the desalination water that electrodialysis is obtained and be used as sieve synthesis procedure water, send in crystallization unit and be used as to stop crystallization water, send in separating, washing unit and be used as bath water.Preferably, as shown in Figure 3, concentrated solution storage tank is communicated with synthesis unit, is used as alkali source to be sent in synthesis unit by concentrated solution.
When adopting the embodiment shown in Fig. 3 to process waste water, following flow process can be adopted to carry out.
The waste water collected by waste liquid tank is sent in salt cellar, sends into water (desalination water that can obtain for deionized water and/or a front electrodialysis) in concentration tank.Open the water inlet of electrodialyzer, and be adjusted to predetermined amount of flow, then the power supply of electrodialyzer is connected, carry out electrodialysis, the composition of the water in salt cellar is monitored, when composition meets the demands, stop electrodialysis and discharging, during discharging, desalination water is sent in desalination tank, and then introducing desalination water withdrawing can carries out reuse; Concentrated solution in concentration tank is sent in concentrated solution storage tank.After discharging completes, in salt cellar, send into the pending waste water of next batch, and process by aforesaid operations.
Fig. 4 shows the another preferred embodiment adopting the present invention to process molecular sieve spent process water.The difference of the embodiment shown in the embodiment shown in Fig. 4 and Fig. 3 is: in electrodialysis process, desalination tank and feed liquid room form a fluid path, the feed liquid room that salt cellar is only used to electrodialyzer provide electrodialysis initially to intake and in electrodialytic process make up water.In the embodiment shown in Fig. 4, the multiple electrodialyzer of preferred employing, and link together to major general's part electrodialyzer with the form of series connection, carry out multistage electrodialysis like this, thus obtain the desalination water that quaternary ammonium radical ion content meets the demands, namely multiple electrodialyzer be connected in series is connected with desalination tank, forms the fluid path that can be carried out multistage electrodialysis.
According to molecular sieve preparation method of the present invention and molecular sieve system, can effectively process the waste water produced in molecular sieve process.
Describe the present invention in detail below in conjunction with embodiment, but therefore do not limit the scope of the invention.
In following examples and comparative example, adopt the content of the quaternary ammonium radical ion in the method wastewater measurement of titration and desalination water, adopt potassium dichromate process to measure the COD value of water.Adopt the content of all the other ions in inductively coupled plasma method (ICP) method wastewater measurement and desalination water.Adopt the strength of current in reometer method mensuration electrodialysis process.
Test case 1-8 is for illustration of the cationic exchange membrane used in electrodialysis and anion-exchange membrane.
Test case 1
The washes of this test case to titanium-silicon molecular sieve TS-1 production process processes, COD value and the composition of this waste water are listed in Table 1, waste water adopts following methods to carry out pre-treatment before carrying out electrodialysis: waste water is sent in the pre-treatment tank of 20L, under envrionment temperature (25 DEG C), the HCl (for the acid solution that a front bipolar membrane electrodialysis obtains) that concentration is 3 % by weight is added, so that the pH value of waste water is adjusted to 6.6 with stirring.Then, the temperature of waste water is increased to 55 DEG C, stops stirring, and leave standstill 12 hours at such a temperature.Then filter with the ultra-filtration membrane that aperture is 50nm, obtain solid phase and liquid phase, liquid phase is carried out electrodialysis as waste water.
This test case adopts the method shown in Fig. 3 to carry out electrodialysis, the cationic exchange membrane adopted is that (loading capacity is 2.51meq/g dry film purchased from the styrene type homogeneous phase cation exchange film of Hebei Guang Ya company, membrane surface resistance (25 DEG C, the 0.1mol/LNaCl aqueous solution, lower same) be 4.59 Ω cm 2); The anion-exchange membrane adopted is that (loading capacity is 2.45meq/g dry film, and membrane surface resistance is 9.46 Ω cm purchased from the homogeneous phase styrene type anion-exchange membrane of Hebei Guang Ya company 2).Electrodialyzer (membrane stack is of a size of 200 × 400mm) has 12 film units.The pole liquid used is the Na of 3 % by weight 2sO 4the aqueous solution.
The present embodiment adopts following technical process to process molecular sieve spent process water, as shown in Figure 3.Waste water is sent in salt cellar, in concentration tank, send into water (desalination water that a front electrodialysis obtains), send into pole liquid to pole flow container (not shown in Fig. 3).Opening the fill cycle pump of each room of electrodialyzer, and be 70L/h by the feed liquid room of electrodialyzer and the Flow-rate adjustment of concentration compartments, is 70L/h by the Flow-rate adjustment of the pole liquid chamber of electrodialyzer.After stability of flow, open direct supply, carry out electrodialysis, the voltage being applied to each film unit is 2V, opens refrigerator and keeps the temperature of each film unit of electrodialysis to be not higher than 35 DEG C.Carry out the electrodialysis of 200 minutes altogether, obtain the desalination water exported from feed liquid room, the concentrated solution containing tetrapropyl ammonium ion exported from dope room.Measure the composition of desalination water, result is listed in Table 1.
Test case 2
The method identical with test case 1 is adopted to carry out electrodialysis to the waste water of equivalent, unlike, the cationic exchange membrane used is that (loading capacity is 0.9meq/g dry film, and membrane surface resistance is 1.77 Ω cm purchased from the homogeneous phase cation exchange film of German FuMA-Tech company 2).Experimental result is listed in Table 1.
Test case 3
The method waste water to equivalent identical with test case 1 is adopted to process, unlike, the cationic exchange membrane used is that (loading capacity is 2.3meq/g dry film, and membrane surface resistance is 3.35 Ω cm purchased from the homogeneous phase cation exchange film of Japanese Tokuyama company 2).Experimental result is listed in Table 1.
Test case 4
Adopt the method waste water to equivalent identical with test case 1 to process, (loading capacity is 0.89meq/g dry film to the homogeneous phase cation exchange film that the cationic exchange membrane unlike, use is purchased from American E.I.Du Pont Company, and membrane surface resistance is 0.52 Ω cm 2).Experimental result is listed in Table 1.
Test case 5
The method waste water to equivalent identical with test case 4 is adopted to process, unlike, the voltage being applied to each film unit is 2.8V.Experimental result is listed in Table 1.
Test case 6
The method waste water to equivalent identical with test case 1 is adopted to process; unlike the use of cationic exchange membrane be the heterogeneous cationic exchange membrane of 3361-BW purchased from the model of Shanghai Chemical Plant; the heterogeneous anion-exchange membrane that the anion-exchange membrane used is is 3362-BW purchased from the model of Shanghai Chemical Plant, the voltage being applied to each film unit is 3V.Experimental result is listed in Table 1.
Test case 7
The method waste water to equivalent identical with test case 1 is adopted to process, unlike, the anion-exchange membrane used is that (loading capacity is 2.1meq/g dry film, and membrane surface resistance is 5.9 Ω cm purchased from the homogeneous-phase anion exchange film of Japanese Tokuyam company 2).Experimental result is listed in Table 1.
Test case 8
The method waste water to equivalent identical with test case 1 is adopted to process, unlike, the anion-exchange membrane used is that (loading capacity is 2.5meq/g dry film, and membrane surface resistance is 2.36 Ω cm purchased from the homogeneous phase styrene type anion-exchange membrane of Beijing Tingrun Membrane Technology Development Co., Ltd. 2).Experimental result is listed in Table 1.
Table 1
Project COD value (mg/L) Tetrapropyl ammonium ion (mg/L)
Waste water 65409 20520.4
Test case 1 2123 486.5
Test case 2 62375 19370.55
Test case 3 58117 18105
Test case 4 61729 19282.1
Test case 5 60117 18928
Test case 6 56018 17513.1
Test case 7 1998 451.1
Test case 8 2035 459.9
As indicated in the result of test case in table 11,7 and 8, adopt styrene type homogeneous phase cation exchange film, can obtain good electrodialysis effect, in the desalination solution of acquisition, the content of quaternary ammonium radical ion is low, and more quaternary ammonium radical ion can be made to be enriched in concentrated solution.
Embodiment 1-5 is for illustration of the present invention.
Embodiment 1
The washes of the present embodiment to titanium-silicon molecular sieve TS-1 production process processes, COD value and the composition of this waste water are listed in table 2, waste water adopts following methods to carry out pre-treatment before carrying out electrodialysis: waste water is sent in the pre-treatment tank of 20L, under envrionment temperature (25 DEG C), the HCl (for the acid solution that a front bipolar membrane electrodialysis obtains) that concentration is 3 % by weight is added, so that the pH value of waste water is adjusted to 6.8 with stirring.Then, the temperature of waste water is increased to 50 DEG C, stops stirring, and leave standstill 18 hours at such a temperature.Then filter with the ultra-filtration membrane that aperture is 50nm, obtain solid phase and liquid phase, liquid phase is carried out electrodialysis as waste water.
In the present embodiment, the cationic exchange membrane of employing is the styrene type homogeneous phase cation exchange film (with test case 1) purchased from Hebei Guang Ya company; The anion-exchange membrane adopted is the homogeneous phase styrene type anion-exchange membrane (with test case 1) purchased from Hebei Guang Ya company.Electrodialyzer (membrane stack is of a size of 200 × 400mm) has 12 film units.The pole liquid used is the Na of 3 % by weight 2sO 4the aqueous solution.
The present embodiment adopts following technical process to process molecular sieve spent process water.
(1) as shown in Figure 4, waste water is sent in salt cellar, in concentration tank, send into water (desalination water that a front electrodialysis obtains), send into pole liquid to pole flow container (not shown in Fig. 4).
Opening the fill cycle pump of each room of electrodialyzer, and be 70L/h by the feed liquid room of electrodialyzer and the Flow-rate adjustment of concentration compartments, is 70L/h by the Flow-rate adjustment of the pole liquid chamber of electrodialyzer.
Opening the direct supply of electrodialyzer, wherein, is 25V by the voltage-regulation of electrodialyzer.Carry out the electrodialysis of 40 minutes altogether.Experimental result is listed in table 2.
Embodiment 2
The method identical with embodiment 4 is adopted to process waste water, unlike, in step (2), be 33V by the voltage-regulation of electrodialyzer.Run 30 minutes.Experimental result is listed in table 2.
Table 2
Project COD value (mg/L) Tetrapropyl ammonium ion (mg/L)
Waste water 65409 20520.4
Embodiment 1 2029 451.1
Embodiment 2 1257 265.4
Embodiment 3
The washes of the present embodiment to titanium-silicon molecular sieve TS-1 production process processes, COD value and the composition of this waste water are listed in table 3, waste water adopts following methods to carry out pre-treatment before carrying out electrodialysis: waste water is sent in the pre-treatment tank of 20L, under envrionment temperature (25 DEG C), the HCl (for the acid solution that a front bipolar membrane electrodialysis obtains) that concentration is 5 % by weight is added, so that the pH value of waste water is adjusted to 6.5 with stirring.Then, the temperature of waste water is increased to 50 DEG C, stops stirring, and leave standstill 24 hours at such a temperature.Then filter with the ultra-filtration membrane that aperture is 50nm, obtain solid phase and liquid phase, liquid phase is carried out electrodialysis as waste water.
In the present embodiment, the cationic exchange membrane of employing is that (loading capacity is 2.5meq/g dry film, and membrane surface resistance is 8 Ω cm purchased from the styrene type homogeneous phase cation exchange film of Beijing Tingrun Membrane Technology Development Co., Ltd. 2); The anion-exchange membrane adopted is that (loading capacity is 2.5meq/g dry film, and membrane surface resistance is 2.36 Ω cm purchased from the homogeneous phase styrene type anion-exchange membrane of Beijing Tingrun Membrane Technology Development Co., Ltd. 2); Electrodialyzer (membrane stack is of a size of 200 × 400mm) has 20 film units.
The pole liquid used in the present embodiment is the Na of 5 % by weight 2sO 4the aqueous solution.
The present embodiment adopts following technical process to process molecular sieve spent process water.
(1) as shown in Figure 3, waste water being sent in salt cellar, respectively to sending into water (desalination water that a front electrodialysis obtains) in concentration tank, sending into pole liquid to pole flow container (not shown in Fig. 3).
Opening the fill cycle pump of each room of electrodialyzer, and be 120L/h by the feed liquid room of electrodialyzer and the Flow-rate adjustment of concentration compartments, is 120L/h by the Flow-rate adjustment of the pole liquid chamber of electrodialyzer.Opening the direct supply of electrodialyzer, wherein, is 40V by the voltage-regulation of electrodialyzer.Carry out the electrodialysis of 60 minutes altogether.
Wherein, the composition of desalination water that exports of electrodialyzer and COD value are listed in table 3.
Embodiment 4
The method identical with embodiment 3 is adopted to process waste water, unlike, in step (2), be 55V by the voltage-regulation of electrodialyzer.Run 40 minutes.Wherein, the composition of desalination water that exports of electrodialyzer and COD value are listed in table 3.
Table 3
Project COD value (mg/L) Tetrapropyl ammonium ion (mg/L)
Waste water 65409 20520.4
Embodiment 3 2651 707.6
Embodiment 4 1532 344.9
Embodiment 5
The present embodiment processes the washes of HTS HTS production process and the mixed solution of crystallization mother liquor, COD value and the composition of this waste water are listed in table 4, waste water adopts following methods to carry out pre-treatment before carrying out electrodialysis: waste water is sent in the pre-treatment tank of 20L, under envrionment temperature (25 DEG C), the HCl (for the acid solution that a front bipolar membrane electrodialysis obtains) that concentration is 3 % by weight is added, so that the pH value of waste water is adjusted to 6.4 with stirring.Then, the temperature of waste water is increased to 50 DEG C, stops stirring, and leave standstill 12 hours at such a temperature.Then filter with the ultra-filtration membrane that aperture is 50nm, obtain solid phase and liquid phase, liquid phase is carried out electrodialysis as waste water.
In the present embodiment, the cationic exchange membrane of employing is with embodiment 3; The anion-exchange membrane adopted is same embodiment 3; Electrodialyzer (membrane stack is of a size of 200 × 400mm) has 20 film units.The pole liquid used is the Na of 4 % by weight 2sO 4the aqueous solution.
The present embodiment adopts following technical process to process molecular sieve spent process water.
(1) as shown in Figure 4, waste water being sent in salt cellar, respectively to sending into water (desalination water that a front electrodialysis obtains) in concentration tank, sending into pole liquid to pole flow container (not shown in Fig. 4).Opening the fill cycle pump of each room of electrodialyzer, and be 120L/h by the Flow-rate adjustment of the feed liquid room of electrodialyzer, alkali room and sour room, is 120L/h by the Flow-rate adjustment of the pole liquid chamber of electrodialyzer.Opening the direct supply of electrodialyzer, wherein, is 40V by the voltage-regulation of electrodialyzer.Carry out the electrodialysis of 60 minutes altogether.Wherein, the composition of desalination water that exports of electrodialyzer and COD value are listed in table 4.
Table 4
Project COD value (mg/L) Tetrapropyl ammonium ion (mg/L)
Waste water 63258 19635.9
Embodiment 5 2437 619.1
The result of embodiment 1-5 confirms, adopts method of the present invention to process the waste water containing quaternary ammonium radical ion, effectively can reduce the quaternary ammonium radical ion content in water, can also reclaim simultaneously and obtain quaternary ammonium hydroxide.

Claims (23)

1. a treatment process for molecular sieve spent process water, described waste water contains at least one quaternary ammonium radical ion, and the method comprises electrodialysis step and optional pre-treatment step:
In pre-treatment step, waste water is carried out solid-liquid separation, obtain solid phase and liquid phase, before waste water is carried out solid-liquid separation, alternatively waste water is contacted with at least one precipitation agent, form colloid to make the silicon in waste water;
In electrodialysis step, the liquid phase described waste water or pre-treatment step obtained carries out electrodialysis, obtains the desalination water that quaternary ammonium radical ion content reduces and the concentrated solution containing quaternary ammonium radical ion.
2. method according to claim 1, wherein, described precipitation agent is selected from acid, is preferably selected from hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, is more preferably sulfuric acid and/or hydrochloric acid.
3. method according to claim 1 and 2, wherein, the consumption of described precipitation agent makes the pH value of described waste water in the scope of 5-8, preferably makes the pH value of described waste water in the scope of 6-7.
4. according to the method in claim 1-3 described in any one, wherein, described electrodialysis is carried out at least one electrodialyzer, the membrane stack of described electrodialyzer has at least one film unit, film in described film unit is cationic exchange membrane and anion-exchange membrane, and the internal space of described film unit is separated into feed liquid room and concentration compartments by described anion-exchange membrane and cationic exchange membrane;
The liquid phase that described waste water or pre-treatment step obtain enters described feed liquid room, water enters described concentration compartments, in electrodialysis process, obtained the desalination water of quaternary ammonium radical ion content reduction by described feed liquid room, obtain the concentrated solution containing quaternary ammonium radical ion by described concentration compartments.
5., according to the method in claim 1-4 described in any one, wherein, in described electrodialytic process, be applied to the voltage of each film unit in the scope of 0.1-5V, preferably in the scope of 0.5-4V, more preferably in the scope of 1-3V.
6. according to the method in claim 1-5 described in any one, wherein, the film unit in the electrodialyzer that described electrodialysis uses comprises cationic exchange membrane, and described cationic exchange membrane is styrene type homogeneous phase cation exchange film.
7. method according to claim 6, wherein, the membrane surface resistance of described styrene type homogeneous phase cation exchange film is 1-15 Ω cm 2, be preferably 3-12 Ω cm 2, be more preferably 4-9 Ω cm 2.
8. the method according to claim 6 or 7, wherein, the loading capacity of described styrene type homogeneous phase cation exchange film is 1-5meq/g dry film, is preferably 1.5-3meq/g dry film, is more preferably 1.8-2.6meq/g dry film.
9. according to the method in claim 1-8 described in any one, wherein, described electrodialytic condition makes the mass content of quaternary ammonium radical ion in the desalination water obtained be below 2000ppm, is preferably below 1700ppm.
10. according to the method in claim 1-9 described in any one, wherein, in described waste water, the concentration of quaternary ammonium radical ion is 1000-35000mg/L.
11. according to the method in claim 1-10 described in any one, and wherein, described quaternary ammonium radical ion is the quaternary ammonium radical ion shown in formula I,
In formula I, R 1, R 2, R 3and R 4be C separately 1-C 5alkyl or C 6-C 12aryl;
Preferably, described quaternary ammonium radical ion is tetrapropyl ammonium ion.
12. according to the method in claim 1-11 described in any one, wherein, described waste water is adopt the molecular sieve spent process water of quaternary ammonium hydroxide, is preferably the crystallization mother liquor in the crystallization steps of the molecular sieve process adopting quaternary ammonium hydroxide, adopts the mixed solution of washes in the washing step of the molecular sieve process of quaternary ammonium hydroxide or described crystallization mother liquor and described washes.
13. methods according to claim 12, wherein, described quaternary ammonium hydroxide is selected from the compound shown in formula II,
In formula II, R 1, R 2, R 3and R 4be C separately 1-C 5alkyl or C 6-C 12aryl;
Preferably, described quaternary ammonium hydroxide is TPAOH.
14. 1 kinds of Waste Water Treatments, described waste water is the molecular sieve spent process water containing quaternary ammonium radical ion, comprises waste water storage unit, optional pretreatment unit and electrodialysis cell,
Described waste water storage unit is used for receiving and storing wastewater;
Described pretreatment unit is used for the waste water coming from waste water storage unit to contact with at least one precipitation agent alternatively, after forming colloid, carries out solid-liquid separation, obtains liquid phase and solid phase to make the silicon in described waste water;
The liquid phase that described electrodialysis cell is used for described waste water or described pretreatment unit export carries out electrodialysis, obtains the desalination water that quaternary ammonium radical ion content reduces and the concentrated solution containing quaternary ammonium radical ion.
15. systems according to claim 14, wherein, described electrodialysis cell comprises electrodialyzer, the membrane stack of described electrodialyzer has at least one film unit, film in described film unit is cationic exchange membrane and anion-exchange membrane, the internal space of described film unit is separated into feed liquid room and concentration compartments by described anion-exchange membrane and cationic exchange membrane, the liquid phase that described feed liquid room receives described waste water or described pretreatment unit to export, the concentrated solution containing quaternary ammonium radical ion is formed at described concentration compartments.
16. systems according to claims 14 or 15, wherein, the film unit in described electrodialysis cell comprises cationic exchange membrane, and described cationic exchange membrane is styrene type homogeneous phase cation exchange film.
17. systems according to claim 16, wherein, the membrane surface resistance of described styrene type homogeneous phase cation exchange film is 1-15 Ω cm 2, be preferably 3-12 Ω cm 2, be more preferably 4-9 Ω cm 2.
18. systems according to claim 16 or 17, wherein, the loading capacity of described styrene type homogeneous phase cation exchange film is 1-5meq/g dry film, is preferably 1.5-3meq/g dry film, is more preferably 1.8-2.6meq/g dry film.
19. according to system described in any one in claim 14-18, and wherein, this system also comprises the first cycling element, and described first cycling element is used for sending in electrodialysis cell by desalination water, as electrodialysis water.
The preparation method of 20. 1 kinds of molecular sieves, the method comprises synthesis step, crystallization steps, separating, washing step and waste water treatment step,
In described synthesis step, by raw material and water contact reacts, described raw material contains silicon source, quaternary ammonium hydroxide and optional titanium source;
In described crystallization steps, the reaction mixture obtained by synthesis step carries out crystallization;
In separating, washing step, mixture crystallization steps obtained carries out solid-liquid separation, obtains solid phase and crystallization mother liquor, and washs described solid phase, obtains molecular sieve and washes;
In waste water treatment step, waste water is carried out electrodialysis, obtain the desalination water that concentrated solution containing quaternary ammonium radical ion and quaternary ammonium radical ion content reduce, described waste water is the mixed solution of described crystallization mother liquor, described washes or described crystallization mother liquor and described washes, wherein, the method in claim 1-9 described in any one is adopted to process described waste water.
21. methods according to claim 20, wherein, the method also comprises desalination water circulation step, in desalination water circulation step, described desalination water is cycled to used at least one in following steps: described synthesis step, as synthesis water; Described crystallization steps, for stopping crystallization; Described separating, washing step, as washing water.
22. 1 kinds of molecular sieve systems, this system comprises synthesis unit, crystallization unit, separating, washing unit and treatment unit for waste water,
Described synthesis unit is used for raw material and water contact reacts, and described raw material contains silicon source, quaternary ammonium hydroxide and optional titanium source;
The reaction mixture that described crystallization unit is used for synthesis step to obtain carries out crystallization;
The mixture that described separating, washing unit is used for crystallization steps to obtain carries out solid-liquid separation, obtains solid phase and crystallization mother liquor, and washs described solid phase, obtain molecular sieve and washes;
Described treatment unit for waste water contains the system in claim 14-19 described in any one, for waste water is carried out electrodialysis, obtain the desalination water that concentrated solution containing quaternary ammonium radical ion and quaternary ammonium radical ion content reduce, described waste water is the mixed solution of described crystallization mother liquor, described washes or described crystallization mother liquor and described washes.
23. systems according to claim 22, wherein, described treatment unit for waste water also comprises desalination water transport pipe, the desalination water that described desalination water transport pipe is used for described treatment unit for waste water to reclaim is sent into at least one in lower unit: described synthesis unit, as at least part of synthesis water; Described crystallization unit, as stopping crystallization water at least partly; Described separating, washing unit, as bath water.
CN201510726216.0A 2015-10-30 2015-10-30 Wastewater treatment method, wastewater treatment system, molecular sieve preparation method and molecular sieve preparation system Pending CN105540762A (en)

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RU2018119084A RU2730338C2 (en) 2015-10-30 2016-10-28 Method of treating waste water and a system for treatment thereof, as well as a method of producing a molecular sieve and a system for producing it
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