CN104030499A - Comprehensive treatment method of special-type molecular sieve synthesis mother solution - Google Patents
Comprehensive treatment method of special-type molecular sieve synthesis mother solution Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 55
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 51
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 51
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000010413 mother solution Substances 0.000 title abstract 8
- 239000012528 membrane Substances 0.000 claims abstract description 80
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 56
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000909 electrodialysis Methods 0.000 claims abstract description 43
- 239000000706 filtrate Substances 0.000 claims abstract description 31
- 239000002351 wastewater Substances 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000919 ceramic Substances 0.000 claims abstract description 11
- 230000001105 regulatory effect Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 72
- 239000003513 alkali Substances 0.000 claims description 67
- 239000001117 sulphuric acid Substances 0.000 claims description 44
- 235000011149 sulphuric acid Nutrition 0.000 claims description 44
- 239000012452 mother liquor Substances 0.000 claims description 37
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 239000012065 filter cake Substances 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 12
- 125000002091 cationic group Chemical group 0.000 claims description 10
- 239000003011 anion exchange membrane Substances 0.000 claims description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 8
- 238000005189 flocculation Methods 0.000 claims description 7
- 230000016615 flocculation Effects 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000011045 prefiltration Methods 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims 11
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052710 silicon Inorganic materials 0.000 abstract description 10
- 239000010703 silicon Substances 0.000 abstract description 10
- 238000001914 filtration Methods 0.000 abstract description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000908 ammonium hydroxide Substances 0.000 abstract 4
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract 4
- 239000011148 porous material Substances 0.000 abstract 2
- 230000003311 flocculating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 150000004760 silicates Chemical class 0.000 abstract 1
- 150000001412 amines Chemical group 0.000 description 31
- 239000007789 gas Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- -1 polypropylene Polymers 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 108010040082 Junctional Adhesion Molecule A Proteins 0.000 description 1
- 102100022304 Junctional adhesion molecule A Human genes 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BHTYXHCGQDYPIO-UHFFFAOYSA-N [Si].O[Si](O)(O)O Chemical compound [Si].O[Si](O)(O)O BHTYXHCGQDYPIO-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ZACYQVZHFIYKMW-UHFFFAOYSA-N iridium titanium Chemical compound [Ti].[Ir] ZACYQVZHFIYKMW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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Abstract
The invention discloses a comprehensive treatment method of a special-type molecular sieve synthesis mother solution. The special-type molecular sieve synthesis mother solution is a mother solution containing silicates and a quaternary ammonium hydroxide template agent. The method comprises the following steps: prefiltering the special-type molecular sieve synthesis mother solution with a tubular ceramic membrane with the pore size of 0.1-1.2 mu m, adding acid to regulate the pH value to 7-8, carrying out primary filtration with a suspended-bag centrifugal machine, regulating the pH value of the filtrate to 5-6, stirring, flocculating, carrying out secondary filtration with the suspended-bag centrifugal machine, standing the filtrate, carrying out precision filtration by using a tubular ceramic membrane with the pore size of 10-50 nm, treating the filtrate with a bipolar membrane electrodialysis system to respectively obtain a quaternary ammonium hydroxide pure product water solution corresponding to the quaternary ammonium hydroxide template agent contained in the mother solution wastewater and a sulfuric acid solution. The method can effectively solve the problem of ammonia nitrogen pollution caused by discharge of the special-type molecular sieve synthesis mother solution, and can obtain the high-grade template agent of tetrapropyl ammonium hydroxide or any other quaternary ammonium hydroxide while recovering the available silicon source in the mother solution.
Description
Technical field
The present invention relates to the method for the extraordinary molecular sieve synthesis mother liquid of a kind of comprehensive treating process, more specifically to a kind ofly utilizing the comprehensive treating process of bipolar membrane electrodialysis integrated technology, utilize TS-1, beta-molecular sieve synthesis mother liquid and reclaim the method for the quaternary amine alkali template such as high-quality TPAOH.
Technical background
In the production process of extraordinary molecular sieve (as TS-1, β), template is except a part is by molecular sieve adsorption with a small amount of decomposition, still some is present in waste water in mother liquor, efficiently do not utilized, yet template accounts for the 50-70% of molecule synthesis cost Raw cost.At present, such template mainly contains TPAOH (TPAOH), n-Butyl Amine 99, quadrol, tetraethyl ammonium hydroxide etc., wherein best with the result of use of TPAOH, it is the especially best template of TS-1 molecular sieve of synthetic extraordinary molecular sieve, but the use of this class template agent but causes molecular sieve synthesis mother liquid waste water to become alkalescence by force, easily becomes colloid, strong basicity high ammonia-nitrogen wastewater that quantity is large, becomes one of primary pollution source of Zeolite synthesis industry.For the extraordinary molecular sieve of part, with existing technical qualification, the template such as TPAOH are absolutely necessary.Therefore,, no matter from the utilization of resources or environment protection angle, reclaim, utilize template and silicon source in synthesis of molecular sieve mother liquor all significant.
At present, the mode that main employing is directly applied mechanically or indirectly applied mechanically is processed molecular sieve synthesis mother liquid, as Cao Houxu etc. is reported in paper " molecular sieve is administered the exploitation of technology in producing containing ammonia-nitrogen sewage " the template in ZSM-5 crystallization slurries is reclaimed, synthetic for ZSM-5 molecular sieve, successfully reduce the quantity discharged of mother liquor, improved raw material availability; Jihong ZHOU has been summarized composition and the treatment process of several conventional molecular sieve synthesis mother liquids in " synthesis of molecular sieve mother liquor and utilize research ", the main direct reuse of processing scheme of molecular sieve mother liquor in Zeolite synthesis of the same race be indirectly back to synthetic other molecular sieves or two kinds of methods of compound.Employing direct reuse or the indirectly method of reuse mother liquor have reduced the quantity discharged of mother liquor to a great extent, improve the utilization ratio of extraordinary Zeolite synthesis template, have reduced the pollution of mother liquor to environment, contribute to reduce synthetic cost.But for the synthesis mother liquid that uses the extraordinary molecular sieves such as TS-1 that the expensive quaternary amine bases such as TPAOH are template, due to the meeting of template in building-up process part pyrolytic decomposition, the template quality that causes reuse does not meet the requirement of preparing congeneric elements sieve, cannot direct reuse; Although the method that can adopt degradation to process, the part or all of mother liquor of reuse is to other sieve synthesis procedures, but the increase along with reuse number of times, degradation production and impurity can be by constantly enrichments, have a strong impact on molecular sieve quality, the method cannot thoroughly solve the processing problem of molecular sieve synthesis mother liquid.Visible exploitation can be able to reclaim in extraordinary molecular sieve (as TS-1) synthesis mother liquid to reclaim again the high-quality quaternary amine alkali template such as TPAOH significant to the clean synthetic technology of extraordinary molecular sieve (as TS-1, β) in siliceous source.
Summary of the invention
The object of the invention is to provide a kind of integrated conduct method of extraordinary molecular sieve synthesis mother liquid, specifically be to provide a kind of processing containing the extraordinary molecular sieve synthesis mother liquid of TS-1 of the quaternary amine alkali class template agent such as silicate, TPAOH, reclaim silicon source and utilize bipolar membrane electrodialysis technology to reclaim the method that obtains the quaternary amine alkali template such as high-quality TPAOH.The inventive method adopts specific recovery method, after silicon source is removed and reclaimed to the pretreatment process in method, enter again bipolar membrane electrodialysis system and reclaim the quaternary amine alkali template such as TPAOH in synthesis mother liquid, improved the purity in the silicon source of reclaiming, obtain meeting the synthetic quaternary amine alkali template such as TPAOH that require, for solving extraordinary molecular sieve synthesis mother liquid, process problem, make full use of wherein precious resources effective way is provided.
In order to realize foregoing invention object, the technical solution used in the present invention is as follows:
An integrated conduct method for extraordinary molecular sieve synthesis mother liquid, described extraordinary molecular sieve synthesis mother liquid is the mother liquor containing silicate and the agent of quaternary amine alkali class template, it is characterized in that said method comprising the steps of:
(1) for extraordinary molecular sieve synthesis mother liquid, the tubular ceramic membrane of aperture 0.1-1.2 μ m (preferably 0.45 μ m) is carried out prefiltration, gained filtrate A adds dilute sulphuric acid adjust pH to be 7～8 (preferably 7.0) under agitation condition, flocculation, standing 1～10 hour, then with hanging bag type centrifugal machine, filter for the first time, obtain filter cake B and liquor B;
(2) liquor B adds dilute sulphuric acid adjust pH to be 5～6 (preferably 5.8) under agitation condition, then stirs after 1-3 hour, and then flocculation, standing 1～10 hour filters for the second time with hanging bag type centrifugal machine, obtains filter cake C and liquor C;
(3) liquor C, after standing 1～10 hour, is carried out secondary filter by the tubular ceramic membrane that aperture is 10-50nm (preferably 30nm), obtains filtrate D;
(4) filtrate D processes by bipolar membrane electrodialysis system, makes respectively the aqueous solution and the sulphuric acid soln of the quaternary amine alkali sterling corresponding with the quaternary amine alkali class template agent containing in mother liquor waste water.
Described molecular sieve synthesis mother liquid is the synthesis mother liquid containing quaternary amine alkali class template agent such as silicate, TPAOH that the extraordinary sieve synthesis procedure such as TS-1 molecular sieve, beta-molecular sieve produces.The agent of described quaternary amine alkali class template is generally TPAOH (TPAOH) or tetraethyl ammonium hydroxide.
In described molecular sieve synthesis mother liquid, silicate content is (with SiO conventionally
2meter) be 0-50g/L, quaternary amine alkali content is 0.5-50g/L, pH value 7-14.
Preferably, described molecular sieve synthesis mother liquid is the synthesis mother liquid of TS-1 molecular sieve, in described mother liquor, containing silicate and containing TPAOH template, after step (4) bipolar membrane electrodialysis is processed, make respectively the TPAOH aqueous solution and sulphuric acid soln.
Further, the dilute sulphuric acid in step of the present invention (1) or step (2) refers to the sulfuric acid of massfraction 1～10%, the sulfuric acid of preferred mass mark 10%.
In described method, the hanging bag type centrifugal machine in described step (1) or step (2) can, for 3-foot hanging bag centrifuge and flat hanging bag centrifuge, not limit to its concrete structure.Described gallus-type whizzer material is corrosion resistant material, conventionally can be 316L, titanium steel etc.
In described step (1), when hanging bag type centrifugal machine filters for the first time, filter bag used is preferably 100-400 object filter bag;
In described step (2), when hanging bag type centrifugal machine filters for the second time, filter bag used is preferably 500-1000 object filter bag.
The material of filter bag used is generally the materials such as terylene, polypropylene fibre or polyvinyl, is conventional material.
In the inventive method, step (1) is filtered and is obtained filter cake B for the first time, step (2) is filtered and is obtained filter cake C for the second time, filter cake B or filter cake C are white gluey orthosilicic acid precipitation, main component is orthosilicic acid, preferably the filter cake C of the filter cake B of step (1) and step (2) is collected and is merged, after acidified, dewater, be dried etc. processed, silicic acid can be obtained, silicon source can be further used as for the synthesis of molecular sieve.
Tubular ceramic membrane of the present invention can be single passage or hyperchannel tubular type film, and working pressure is 0.1-0.5MPa.
Step of the present invention (1) is used ceramic membrane prefiltration, be mainly used in removing large granular impurity in mother liquor, the main separated mother liquor of filtration and the silicon gel of step (1) and twice hanging bag type centrifugal machine of step (2), step is carried out secondary filter by tubular ceramic membrane in (3), and object is to guarantee to filter in rear mother liquor without easily producing the impurity that precipitates or affect follow-up bipolar membrane electrodialysis process.In described step (4), filtrate D is used bipolar membrane electrodialysis system to process, described bipolar membrane electrodialysis system can adopt conventional bipolar membrane electrodialysis system, and use therein Bipolar Membrane, cationic exchange membrane, anion-exchange membrane and negative electrode, anode etc. all can adopt conventional commercially available prod.Further, preferably Bipolar Membrane is monolithic method Bipolar Membrane, and it is prepared by same base material, and Catalytic Layer in the middle of band; Preferred described anion-exchange membrane, cationic exchange membrane are a kind of in heterogeneous membrane, half homogeneous membrane, homogeneous membrane, and more preferably described anion-exchange membrane, cationic exchange membrane are homogeneous ion-exchange membrane.
The arrangement mode of film in bipolar membrane electrodialysis system,, the array mode of membrane stack is not all critical, can adopt the means of well known to a person skilled in the art.
Further, three cell structure that bipolar membrane electrodialysis system preferably adopts Bipolar Membrane+anion-exchange membrane+cationic exchange membrane to form, bipolar membrane electrodialysis system both sides are utmost point liquid chamber, described utmost point liquid chamber is divided into anolyte compartment and cathode compartment, in the middle of two side pole liquid chambers, be electrodialysis compartment, in electrodialysis compartment, Bipolar Membrane, anion-exchange membrane, cationic exchange membrane are spaced and form sour chamber, feed liquid chamber, alkali chamber.When bipolar membrane electrodialysis is processed, respectively to sour chamber, alkali chamber adds pure water, the filtrate D that adds same volume in feed liquid chamber, the sulphuric acid soln that adds mass concentration 1-3% at utmost point liquid chamber (anolyte compartment and cathode compartment), by the anode of bipolar membrane electrodialysis system, negative electrode is connected with D.C. regulated power supply positive and negative electrode respectively, then according to conventional bipolar membrane electrodialysis working method, operate, after electrodialysis process, acid chamber obtains sulphuric acid soln, alkali chamber obtains the aqueous solution of the quaternary amine alkali sterling corresponding with the quaternary amine alkali class template agent containing in mother liquor, mother liquor waste water after feed liquid chamber is processed.
More specifically, in the embodiment of the present invention, during bipolar membrane electrodialysis, control utmost point liquid chamber flow 200～300L/h, control the flow 400～500L/h of feed liquid chamber, alkali chamber, sour chamber, guarantee that each compartment intake pressure is all no more than 0.02MPa, in control bipolar membrane electrodialysis system, the current density of Bipolar Membrane and yin, yang ion-exchange membrane is 30-50mA/cm
2(preferred 40mA/cm
2), the temperature of controlling feed liquid, acid solution, alkali lye is 30 ℃, adopt cyclical operation technique, when feed liquid specific conductivity is reduced to 1.00ms/cm when following, close down equipment, acid chamber obtains sulphuric acid soln, and alkali chamber obtains the aqueous solution of the quaternary amine alkali sterling corresponding with the quaternary amine alkali class template agent containing in mother liquor, the mother liquor waste water after feed liquid chamber is processed.
Step of the present invention (4) makes respectively the certain density quaternary amine alkali aqueous solution and sulphuric acid soln.Concrete, the mass concentration of the quaternary amine alkali aqueous solution is the controlled 4-25% that is made as conventionally, and the mass concentration of sulphuric acid soln is the controlled 2-12% that is made as conventionally.
The resulting sulphuric acid soln of step (4) can directly overlap for step (1) or step (2), is used for regulating the pH value of filtrate A or liquor B as dilute sulphuric acid.
In described step (4), can adopt the mode of multiple batches of circular treatment filtrate D to improve the concentration of sulphuric acid soln, the quaternary amine alkali aqueous solution, directly to meet reuse concentration requirement without enrichment process, concrete, described step (4) can operate according to the following steps:
(i) filtrate D, as feed liquid, processes by bipolar membrane electrodialysis system;
(ii) when feed liquid specific conductivity is reduced to 1.00ms/cm when following, waste water after processing in feed liquid chamber is discharged to 80～90% of its cumulative volume, add and the isopyknic untreated filtrate D of waste water discharging, in sour chamber, alkali chamber, solution is not replaced, and remains unchanged;
(iii) cyclical operation step (i)～(ii), until the quaternary amine alkali aqueous solution mass concentration that in sour chamber, sulphuric acid soln mass concentration reaches more than 10% or in alkali chamber reaches 20-25%, with the sulphuric acid soln of pure water displacement 80～90% volumes or with the quaternary amine alkali aqueous solution of pure water displacement 80～90% volumes, other remains unchanged;
(iv) cyclical operation step (i)～(iii), make respectively more than 10% sulphuric acid soln of mass concentration and the quaternary amine alkali aqueous solution of mass concentration 20-25%.
The quaternary amine alkali aqueous solution such as prepared TPAOH can be concentrated into after satisfactory concentration, building-up process as template reuse to extraordinary molecular sieves such as TS-1, beta-molecular sieves, thereby improve the utilization ratio of the expensive quaternary amine alkali template such as TPAOH, when solving molecular sieve synthesis mother liquid processing problem, improve raw material availability, save Zeolite synthesis cost, produce good social and economic benefits.After the quaternary amine alkali solution such as TPAOH that are generally 4-25% by amount concentration are concentrated into mass concentration 25% aqua, its content of halide ions is lower than 500ppm, alkali metal ion content measured, lower than 20ppm, meets the requirements of extraordinary sieve synthesis procedure to quaternary amine alkali template purity such as TPAOH such as TS-1, beta-molecular sieve.
The mother liquor waste water of step (3) after bipolar membrane electrodialysis is processed can enter routine biochemistry system and carry out biochemical treatment.
A, B in the filtrate A occurring in each step of the present invention, filter cake B, liquor B, filter cake C, liquor C, filtrate D, C, D only refer to for distinguishing filter cake or the filtrate that different step processing obtains, and do not represent chemical sense.
Useful technique effect of the present invention is:
The invention solves existing direct reuse or indirectly reuse mode process defect and the problem existing in molecular sieve synthesis mother liquid process, the method of bipolar membrane electrodialysis after employing control pH value, multiple times of filtration, in reclaiming mother liquor, in useful silicon source, obtain the required quaternary amine alkali template such as TPAOH of extraordinary Zeolite synthesis such as the high-quality TS-1 of can be used for, β.
The present invention can reclaim silicon source in mother liquor waste water well by secondary acid adding flocculation sediment, by post-processed, obtains meeting the synthetic silicic acid silicon source requiring, and realizes efficient recovery, the utilization in silicon source in mother liquor waste water.
The quaternary amine alkali aqueous solution mass concentrations such as TPAOH that the present invention reclaims are controlled at 4-25%, and sulphuric acid soln concentration is controlled at 2-12%, can realize well the high-quality TPAOH of online recycling and recycled sulphuric acid soln.
The present invention can effectively solve the ammonia and nitrogen pollution problem that extraordinary molecular sieve synthesis mother liquid discharge brings, but also fully reclaim wherein available stock, from waste water, obtain high-quality synthesis material, realize synthesis material value maximization, improve to greatest extent raw material availability, not only there is good economic benefit, also there is good social benefit.
Accompanying drawing explanation
The process flow diagram of the integrated conduct method of the extraordinary molecular sieve mother liquor of Fig. 1 the present invention.
The synthetic TPAOH gas chromatogram of using of Fig. 2 TS-1.
Fig. 3 embodiment 1 gained TPAOH gas chromatogram.
Fig. 4 embodiment 2 gained TPAOH gas chromatograms.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.Protection scope of the present invention is not limited to this.
Take TS-1 molecular sieve synthesis mother liquid waste water as processing object, and the contained template of this mother liquor waste water is TPAOH (TPAOH), and mother liquor pH value is 10-13, and silicate content is (with SiO
2meter) be 2-10g/L, TPAOH is 1.5-5g/L.
Embodiment 1
(1) mother liquor carries out prefiltration by the tubular ceramic membrane of aperture 0.45 μ m, working pressure 0.25MPa, it is 7.0 that gained filtrate A adds the sulphuric acid soln adjust pH of massfraction 10% under agitation condition, flocculation, standing 3 hours, then with hanging bag type centrifugal machine, filter for the first time, filter bag used is 300 object polypropylene fibre filter bags, obtains filter cake B and liquor B;
(2) under agitation condition, to add the sulphuric acid soln adjust pH of massfraction 10% be 5.8 to liquor B, stir again after 1 hour, flocculation, standing 3 hours, then with hanging bag type centrifugal machine, filter for the second time, filter bag used is 800 object terylene filter bags, obtains filter cake C and liquor C;
(3) liquor C is after standing 3 hours, and the tubular ceramic membrane that is 30nm with aperture is carried out secondary filter, working pressure 0.25MPa, and the pH value of gained filtrate D is 6.0, specific conductivity is 15.28ms/cm,
(4) filtrate D is processed with bipolar membrane electrodialysis, parameter is as follows:
Bipolar membrane electrodialysis system is provided by Zhejiang Saite membrane technique company limited, model is CT-BM-2, the membrane stack that three compartments that adopt 20 groups of films to be of a size of Bipolar Membrane+anion-exchange membrane+cationic exchange membrane of 200*400mm combine, Bipolar Membrane is BPM-1 model (Beijing Ting Run membrane technique development corporation, Ltd.), anion-exchange membrane is JAM-1 model (Beijing Ting Run membrane technique development corporation, Ltd.), and cationic exchange membrane is JCM-1 model (Beijing Ting Run membrane technique development corporation, Ltd.).Negative electrode adopts ruthenium to be coated with iridium titanium combined electrode, anode adopts titanium to be coated with platinum electrode, 3 layers of dividing plate employings are anticreep, the elastic baffle leaking outside in anti-, in sour chamber, alkali chamber adds respectively 10L pure water, the filtrate D that adds 10L in feed liquid chamber, as feed liquid, the sulphuric acid soln 10L that adds mass concentration 1% at utmost point liquid chamber (anolyte compartment and cathode compartment), by the anode of bipolar membrane electrodialysis membrane stack, negative electrode is connected with D.C. regulated power supply positive and negative electrode respectively, opening device, control utmost point liquid chamber flow 200L/h, control feed liquid chamber, alkali chamber, acid chamber flow 400L/h, guarantee that each compartment intake pressure is no more than 0.02MPa, control Bipolar Membrane and the moon in bipolar membrane electrodialysis system, the current density of cationic exchange membrane is 40mA/cm
2control feed liquid, acid solution, alkali liquid temperature are 30 ℃, adopt cyclical operation technique, when feed liquid specific conductivity is reduced to 1.00ms/cm when following, close down equipment, acid chamber obtains the sulphuric acid soln of mass concentration 2.5%, and alkali chamber obtains the TPAOH aqueous solution of mass concentration 4.2%, and feed liquid chamber is mother liquor waste water after processing,
The TPAOH solution making is carried out to gas chromatographic analysis, gas chromatogram as shown in Figure 3, the gas chromatographic analysis spectrogram of the fresh TPAOH solution of TS-1 Zeolite synthesis use template as shown in Figure 2, Fig. 2, Fig. 3 compare, visible both appearance times are identical, illustrate that gained quaternary amine alkali is TPAOH; Through instrumental analysis such as chromatography of ions, through underpressure distillation, being concentrated into content of halide ions in the TPAOH solution of 25% mass concentration is 96.7ppm, alkalimetal ion total content 8.76ppm, meets the requirement of high-quality TPAOH aqua, can be used as the synthetic template of TS-1 and uses;
The gained TPAOH aqueous solution, after being concentrated into 25% mass concentration, meets the purity requirement of TS-1, beta-molecular sieve building-up process template; Gained 2.5% sulphuric acid soln purity reaches chemically pure reagent requirement, can be directly used in step (1), (2) for regulating pH value; After gained processing, mother liquor waste water reaches and enters biochemical treatment system requirement, can carry out biochemical treatment, reaches discharging standards;
Gained sulphuric acid soln, TPAOH solution can adopt the mode of multiple batches of circular treatment filtrate D to improve concentration, without enrichment process, directly meet reuse requirement, when feed liquid specific conductivity is reduced to 1.00ms/cm when following, with untreated filtrate D, replaced 90% volume, acid chamber, in alkali chamber, solution is not replaced, remain unchanged, continue circular treatment, until sulphuric acid soln concentration reaches more than 10% in sour chamber, with pure water, replace the sulphuric acid soln of 90% volume, or the TPAOH strength of solution in alkali chamber is while reaching 20-25%, with pure water, replace the TPAOH solution of 90% volume, continuing cyclical operation requires to close down equipment after treatment capacity requirement to completing.
Through multiple batches of circular treatment filtrate D, can obtain mass concentration and be 25% the TPAOH aqueous solution, the sulphuric acid soln that mass concentration is 12%.
Described bipolar membrane electrodialysis system current efficiency 85.67%, the TPAOH rate of recovery is more than 95.28%.
Embodiment 2
Step (1)～(3) are with embodiment 1, and difference is that step (4) adopts cyclical operation technique, as follows operation:
(i) filtrate D, as feed liquid, processes with bipolar membrane electrodialysis, and Parameter Conditions is with embodiment 1;
(ii) when feed liquid specific conductivity is reduced to 1.00ms/cm when following, the waste water after the processing in feed liquid chamber is discharged 90% of cumulative volume, the isopyknic untreated filtrate D of waste water that adds and discharge, and in sour chamber, alkali chamber, solution is not replaced, and remains unchanged;
(iii) cyclical operation step (i)～(ii), until the TPAOH aqueous solution mass concentration that in sour chamber, sulphuric acid soln mass concentration reaches more than 10% or in alkali chamber reaches 20-25%, now with pure water, replace the sulphuric acid soln of 90% volume or with pure water, replace the TPAOH aqueous solution of 90% volume, other remains unchanged;
(iv) cyclical operation step (i)～(iii), continuation cyclical operation requires to close down equipment after treatment capacity requirement to completing; Prepare the sulphuric acid soln of mass concentration 10%, alkali chamber obtains the TPAOH aqueous solution of mass concentration 20-25%.
The TPAOH solution making is carried out to gas chromatographic analysis, gas chromatogram as shown in Figure 4, the gas chromatographic analysis spectrogram of the fresh TPAOH solution of TS-1 Zeolite synthesis use template as shown in Figure 2, Fig. 2, Fig. 4 compare, visible both appearance times are identical, illustrate that gained quaternary amine alkali is TPAOH; Through chemical acid alkali analyzing purity, TPAOH mass concentration is 24.82%; Through instrumental analysis such as chromatography of ions, in TPAOH solution, content of halide ions is 83.6ppm, and alkalimetal ion total content 8.21ppm, meets the requirement of high-quality TPAOH aqua, can be used as the synthetic template of TS-1 and uses;
The gained TPAOH aqueous solution meets the purity requirement of TS-1, beta-molecular sieve building-up process template; Gained sulphuric acid soln meets acid adding and adjusts pH process required, also can make other raw materials; After gained processing, mother liquor waste water reaches and enters biochemical treatment system requirement, can carry out biochemical treatment, reaches discharging standards;
Described bipolar membrane electrodialysis system current efficiency is more than 93.61%, and the TPAOH rate of recovery is more than 96.37%.
Claims (10)
1. an integrated conduct method for extraordinary molecular sieve synthesis mother liquid, described extraordinary molecular sieve synthesis mother liquid is the mother liquor containing silicate and the agent of quaternary amine alkali class template, it is characterized in that said method comprising the steps of:
(1) extraordinary molecular sieve synthesis mother liquid carries out prefiltration by the tubular ceramic membrane of aperture 0.1-1.2 μ m, it is 7～8 that gained filtrate A adds dilute sulphuric acid adjust pH under agitation condition, flocculation, standing 1～10 hour, then with hanging bag type centrifugal machine, filter for the first time, obtain filter cake B and liquor B;
(2) under agitation condition, to add dilute sulphuric acid adjust pH be 5～6 to liquor B, then stir after 1-3 hour, and then flocculation, standing 1～10 hour filters for the second time with hanging bag type centrifugal machine, obtains filter cake C and liquor C;
(3) liquor C is after standing 1～10 hour, and the tubular ceramic membrane that is 10-50nm with aperture is carried out secondary filter, obtains filtrate D;
(4) filtrate D processes by bipolar membrane electrodialysis system, makes respectively the aqueous solution and the sulphuric acid soln of the quaternary amine alkali sterling corresponding with the quaternary amine alkali class template agent containing in mother liquor waste water.
2. the method for claim 1, is characterized in that the agent of described quaternary amine alkali class template is TPAOH or tetraethyl ammonium hydroxide.
3. the method for claim 1, it is characterized in that described molecular sieve synthesis mother liquid is the synthesis mother liquid of TS-1 molecular sieve, in described mother liquor, contain silicate and contain TPAOH template, after step (4) bipolar membrane electrodialysis is processed, make respectively the TPAOH aqueous solution and sulphuric acid soln.
4. the method for claim 1, it is characterized in that in described step (4), three cell structure that bipolar membrane electrodialysis system adopts Bipolar Membrane, anion-exchange membrane and cationic exchange membrane to form, bipolar membrane electrodialysis system both sides are utmost point liquid chamber, described utmost point liquid chamber is divided into anolyte compartment and cathode compartment, in the middle of two side pole liquid chambers, be electrodialysis compartment, in electrodialysis compartment, Bipolar Membrane, anion-exchange membrane, cationic exchange membrane are spaced and form sour chamber, feed liquid chamber, alkali chamber; When bipolar membrane electrodialysis is processed, respectively to sour chamber, alkali chamber adds pure water, in feed liquid chamber, add filtrate D, the sulphuric acid soln that adds mass concentration 1-3% at utmost point liquid chamber, the anode of bipolar membrane electrodialysis system, negative electrode are connected with D.C. regulated power supply positive and negative electrode respectively, carry out electrodialysis process, when feed liquid specific conductivity is reduced to 1.00ms/cm when following, acid chamber obtains sulphuric acid soln, alkali chamber obtains the quaternary amine alkali aqueous solution corresponding with the quaternary amine alkali class template agent containing in mother liquor, the mother liquor waste water after feed liquid chamber is processed.
5. method as claimed in claim 4, while it is characterized in that bipolar membrane electrodialysis, control utmost point liquid chamber flow 200～300L/h, control the flow 400～500L/h of feed liquid chamber, alkali chamber, sour chamber, guarantee that each compartment intake pressure is all no more than 0.02MPa, in control bipolar membrane electrodialysis system, the current density of Bipolar Membrane and yin, yang ion-exchange membrane is 30-50mA/cm
2the temperature of controlling feed liquid, acid solution, alkali lye is 30 ℃, adopt cyclical operation technique, when feed liquid specific conductivity is reduced to 1.00ms/cm when following, close down equipment, acid chamber obtains sulphuric acid soln, and alkali chamber obtains the quaternary amine alkali aqueous solution corresponding with the quaternary amine alkali class template agent containing in mother liquor, the mother liquor waste water after feed liquid chamber is processed.
6. the method as described in claim 1, one of 4 or 5, is characterized in that described step (4) operates according to the following steps:
(i) filtrate D, as feed liquid, processes by bipolar membrane electrodialysis system;
(ii) when feed liquid specific conductivity is reduced to 1.00ms/cm when following, waste water after processing in feed liquid chamber is discharged to 80～90% of its cumulative volume, add and the isopyknic untreated filtrate D of waste water discharging, in sour chamber, alkali chamber, solution is not replaced, and remains unchanged;
(iii) cyclical operation step (i)～(ii), until the quaternary amine alkali aqueous solution mass concentration that in sour chamber, sulphuric acid soln mass concentration reaches more than 10% or in alkali chamber reaches 20-25%, with the sulphuric acid soln of pure water displacement 80～90% volumes or with the quaternary amine alkali aqueous solution of pure water displacement 80～90% volumes, other remains unchanged;
(iv) cyclical operation step (i)～(iii), make respectively more than 10% sulphuric acid soln of mass concentration and the quaternary amine alkali aqueous solution of mass concentration 20-25%.
7. the method for claim 1, is characterized in that the dilute sulphuric acid in described step (1) or step (2) is the sulfuric acid of massfraction 1～10%.
8. the method for claim 1, is characterized in that the sulphuric acid soln that step (4) obtains directly overlaps for step (1) or step (2), is used for regulating the pH value of filtrate A or liquor B as dilute sulphuric acid.
9. the method for claim 1, is characterized in that in described step (1), and when hanging bag type centrifugal machine filters for the first time, filter bag used is 100-400 object filter bag;
In described step (2), when hanging bag type centrifugal machine filters for the second time, filter bag used is 500-1000 object filter bag.
10. the method for claim 1, is characterized in that the filter cake B of described step (1) and the filter cake C of step (2) collect to merge, and after acidified, dehydration, drying treatment, obtains silicic acid.
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