CN102923807A - Application of low-silicon micro-pore NaA type and NaX type molecular sieves in treatment of low-concentration heavy metal ions - Google Patents
Application of low-silicon micro-pore NaA type and NaX type molecular sieves in treatment of low-concentration heavy metal ions Download PDFInfo
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Abstract
The invention belongs to the technical field of sewage treatment, and in particular relates to application of low-silicon micro-pore NaA type and NaX type molecular sieves in treatment of low-concentration heavy metal ions. The invention solves the problem that the concentration of the low-concentration heavy metal ions is not up to standard in primary treatment of sewage through selecting proper conditions to carry out exchange separation under the trace concentration; the concentration of the low-concentration heavy metal ions in the sewage, which is subjected to secondary treatment through the technology, is far lower than the industrial standard; and the application has the advantages of easiness in operation of exchange steps and conditions, and low cost, and is very suitable for a sewage treatment process in industry. Through regeneration, after the molecular sieves are exchanged, most of the absorbed heavy metal ions are replaced to sodium ions, and the regenerated molecular sieves are recycled. The NaX and the NaY related by the invention are obtained by hydro-thermal synthesis, and a ratio of silicon to aluminum is 1: 1-1: 3.
Description
Technical field
The invention belongs to technical field of sewage, be specifically related to the application aspect the processing low-concentration heavy metal ions of a kind of low silicon micropore NaA type and NaX type molecular sieve.
Background technology
Along with increasingly sharpening of industrial rapidly development and Process of Urbanization Construction, the use range of heavy metal is more and more extensive, and the problem of consequent sternness is exactly the pollution that water body has been subject to heavy metal.The existing sewage disposal technology of China has a lot, for example adopt electrochemical method (CN201437512U, CN101088938A, CN201864610U, CN1459421A, CN2910910Y), biochemical method (CN101352672A, CN101992000A, CN101402491A, CN1900271A, CN101628756A, CN1958465A, CN101063096A), mud method (CN1194238A, CN1548382A, CN1702044A), organic matter removal method (CN101070205A, CN1803659A, CN101905148A, CN1676635A, CN101804330A, CN101947381A, CN101746843A, CN101560002A, CN101992064A, CN101757885A, CN101759270A), method of magnetic (CN87210733U, CN87105033A, CN86108101A) and additive method (CN101492197A, CN101613135A, CN101037287A, CN101186375A, CN101987765A, CN101774719A, CN101618892A, CN201439503U, CN101805052A, CN102030439A, CN101913921A, CN201020342Y, CN101041485A, CN1210503A).
Some equipment of these methods complicated (electrochemical method, method of magnetic), some cost higher (biochemical process), some poor effect.In recent years, adsorption separation technology is efficient with it, less energy-consumption and product purity high, has occupied consequence in the evolution of chemical separation technology, for example exchange resin method (CN101746906A, CN101037243A).But, these methods before all are exchange and the removals to the heavy metal ion of high density, and for the removal of the heavy metal ion of micro-solubility, not yet the someone studies.
Zeolite molecular sieve is a kind of important adsorption and separation material.Traditional zeolite is a kind of silico-aluminate of crystallization, has the three-dimensional framework structure in the even duct of molecular scale size.Because those are fit to its big or small molecules the meeting preferentially adsorbed of the duct in the zeolite, and the isolated too large molecule of those sizes, they are just as a kind of sieve with molecular scale size.Therefore, zeolite is the part of molecular sieve.They are comprised of hard crystallization silicon dioxide skeleton.In the skeleton, part Si
4+If by Al
3+Substitute, will make so skeleton carry a negative charge.So, contain can be loose in the hole of aluminium zeolite molecular sieve some positively charged ions of distribution, keep the electric neutrality of molecular sieve.Wherein partial cation can carry out cationic exchange, and the absorption polar molecule that zeolite molecular sieve can be reversible, and these character have promoted the success that zeolite molecular sieve is obtained in commercial applications significantly.These have the molecular sieve of three-dimensional framework structure, in many different field good application are arranged, such as: washing powder, petroleum refining and petrochemical industry, sorbent material, gas delivery, agricultural and gardening, dyestuff and jewelry etc.The aluminium atom and the Siliciumatom that in the skeleton of zeolite molecular sieve, contain equivalent, each Sauerstoffatom can connect an aluminium atom and a Siliciumatom simultaneously so, and such molecular sieve has just had the tradable positively charged ion of maximum density.At present, the ion-exchange market of zeolite molecular sieve maximum is the application in washing powder, and cation exchange capacity (CEC) has determined that zeolite molecular sieve can replace to sodium ion with the calcium in the washing water, magnesium ion in much degree ground.So just stoped the tensio-active agent in calcium, magnesium and the washing powder to generate water-fast salt, thereby the washing that has increased washing powder is renderd a service.
Now, existing people is engaged in the research of zeolite molecular sieve being carried out the heavy metal ion exchange in the world, and also belongs to blank in this field of China.And the exchange of micro heavy ion is separated, there be not in the world successful technology to obtain announcing yet.Why important exchange isolation technique for the micro heavy ion is, is because the wastewater processing technology of existing industrial trade often can not disposablely obtain meeting disposing of sewage of state sewage emission standard.In the sewage after this primary treatment, the concentration of heavy metal ion is greatly diminished, but still has the concentration over-standard of one or more heavy metal ion.Common sewage disposal technology is the heavy metal ion of trace further can not be removed, if this below standard primary treatment sewage is discharged in the river, will inevitably to environment, affect people's domestic water safety.And the consideration cost of sewage disposal, the water technology that some are high-end, the treatment technology of tap water for example, also be not suitable for the sewage disposal in the common industrial production, any cost in sewage disposal, the capital increases the cost of industrial production product greatly, is unfavorable for the competition of enterprise product on market.So, a kind of efficient, practical, cheap sewage disposal technology is existing industrial enterprise in the urgent need to.
Summary of the invention
Based on the characteristics of above-mentioned zeolite molecular sieve and in the present situation of ion-exchange application facet, the present invention will hang down first silicon (silica alumina ratio is 1:1～1.3) micropore NaA(and contain Na
+) type molecular sieve (belonging to LTA type micro porous molecular sieve) and NaX(contain Na
+) the type molecular sieve is applied to (belonging to FAU type micro porous molecular sieve) adsorption treatment of several frequently seen low-concentration heavy metal ions in the sewage.
NaA and NaX all obtain by Hydrothermal Synthesis, and its step is as follows:
1. the preparation of silicon source solution
With 0.15～4.8 gram Na
2SiO
39H
2O joins in 10～15 ml deionized water, is stirred to dissolving evenly, obtains silicon source solution;
2. the preparation of aluminium source solution
(a) NaA type molecular sieve: with 0.15～1.5 gram NaAlO
2Join in 10～15 ml deionized water, be stirred to dissolving evenly, add again 0.188～1.875 gram NaOH and continue to stir 15～30 minutes, obtain aluminium source solution;
(b) NaX type molecular sieve: 0.3～1.2 gram NaOH is joined in 6.5～10 ml deionized water, be stirred to dissolving evenly, add again 0.13～0.52 gram NaAlO
2Continue to stir 15～30 minutes, obtain aluminium source solution;
3. crystallization
The aluminium source solution that then will leave standstill adds in the silicon source solution that is stirring slowly, continues to stir 30～50 minutes, and the reactor of then packing into, crystallization is 1 hour～48 hours under 100 ℃ of conditions;
4. sample obtains and processes
After crystallization is finished, cool off under the reactor room temperature, then the white depositions in the solution is carried out the suction filtration oven dry, the powder that obtains white is NaA or NaX type molecular sieve.
The present invention is by choosing suitable condition, and the exchange of carrying out under the micro-concentrations separates, and has solved primary treatment heavy metal ions in sewage concentration problem not up to standard; Use the concentration of the heavy metal ions in sewage after this technology secondary treatment, far below industry standard; Exchange step and condition operate easily, and cost is low, are fit to very much the sewage treatment process in the industry.
The invention provides a kind of application NaA(and contain Na
+) type, NaX(contain Na
+) the type molecular sieve removes the technology of the heavy metal ion of trace in the sewage, under the normal temperature common heavy metal ion (is exchanged 30 minutes, still can obviously reduce its concentration in that concentration is extremely low in 1～100ppm) the situation.
The technical solution used in the present invention is: choose plan sewage solution and the molecular sieve exchange material of suitable proportion under the normal temperature, continue to stir 30 minutes.The preparation of simulated sewage is to choose six kinds of common heavy metal ion Ni
2+, Co
2+, Mn
2+, Cu
2+, Zn
2+And Cd
2+, every kind of ion is joined respectively the aqueous solution of three kinds of different concns (100ppm, 10ppm, 1ppm).
The implementation step is with under the normal temperature, and NaA type molecular sieve is to containing the Ni of 100ppm
2+Solion is exchanged for example, describes.Take by weighing 0.316g NaA type micro porous molecular sieve in beaker, add the Ni that contains 100ppm of the required processing of 20ml
2+Solution continues under the normal temperature to stir 30 minutes, can finish the exchange of heavy metal ion and remove.For the exchange result is detected, be that the wetting ability cellulose acetate hybrid films of 0.22 μ is carried out suction filtration at film filter with stirring the mixing solutions that obtains after 30 minutes with the aperture, the complete rear collection filtrate of suction filtration is in reagent bottle, wait until and carry out constituent content ICP mensuration and analyze (the inductively coupled plasma emmission spectrum is called for short ICP).This collects solution process, is only limited to solution is as a result detected.In the actually operating, molecular sieve can be selected to leave standstill to separate with sewage solution.
In the ICP data, no matter be monometallic solion or hybrid metal solion, concentration of metal ions all has obvious reduction after exchange, this explanation NaA type and NaX type molecular sieve have stronger exchange capacity to the metal ion of micro-concentrations, and multiple hybrid metal solion is still had exchange capacity; The removal effect that GOLD FROM PLATING SOLUTION belongs to ion increases along with the increase of molecular sieve consumption.
Description of drawings
Fig. 1: the NaA type molecular sieve of different amounts is the removal result curve of the hybrid metal solion of 100ppm to six metal ion species concentration;
Fig. 2: the NaA type molecular sieve of different amounts is the removal result curve of the hybrid metal solion of 10ppm to six metal ion species concentration;
Fig. 3: the NaA type molecular sieve of different amounts is the removal result curve of the hybrid metal solion of 1ppm to six metal ion species concentration;
Fig. 4: the NaX type molecular sieve of different amounts is the removal result curve of the hybrid metal solion of 100ppm to six metal ion species concentration;
Fig. 5: the NaX type molecular sieve of different amounts is the removal result curve of the hybrid metal solion of 10ppm to six metal ion species concentration;
Fig. 6: the NaX type molecular sieve of different amounts is the removal result curve of the hybrid metal solion of 1ppm to six metal ion species concentration;
Fig. 7: the crystal particle diameter size is scanning electron microscope diagram sheet (a) and the powder x-ray diffraction spectrogram (b) of 0.7 micron NaA type molecular sieve;
Fig. 8: the crystal particle diameter size is scanning electron microscope diagram sheet (a) and the powder x-ray diffraction spectrogram (b) of 10 microns NaX type molecular sieve;
Fig. 9: the crystal particle diameter size is the scanning electron microscope diagram sheet of different amplification of 0.8 micron NaA type molecular sieve;
Figure 10: the crystal particle diameter size is the scanning electron microscope diagram sheet of different amplification of 2 microns NaA type molecular sieve;
Figure 11: the crystal particle diameter size is the scanning electron microscope diagram sheet of different amplification of 6.5 microns NaA type molecular sieve;
Figure 12: the crystal particle diameter size is the scanning electron microscope diagram sheet of different amplification of 11 microns NaA type molecular sieve;
Figure 13: the crystal particle diameter size is the scanning electron microscope diagram sheet of different amplification of 2 microns NaX type molecular sieve;
Figure 14: the crystal particle diameter size is the scanning electron microscope diagram sheet of different amplification of 6 microns NaX type molecular sieve.
As shown in Figure 1, 2, 3, be that NaA type molecular sieve is respectively to the exchange result of the mixing solutions of 100ppm, 10ppm, 1ppm.For the mixing solutions of each concentration, the molecular sieve of getting respectively five different masies (mole number) exchanges it, can see the increase along with the consumption of molecular sieve, and it is thorough that the removal effect of metal ion also is tending towards gradually.
Shown in Fig. 4,5,6, be that NaX type molecular sieve is respectively to the exchange result of the mixing solutions of 100ppm, 10ppm, 1ppm.For the mixing solutions of each concentration, the molecular sieve of getting respectively too five different masies (mole number) exchanges it, can see the increase along with the molecular sieve consumption, and it is thorough that the removal effect of metal ion also is tending towards gradually.
As shown in Figure 7, scanned picture surface NaA type molecular sieve has good pattern and the particle diameter of homogeneous; Powder x-ray diffraction conforms to the standard spectrogram, shows that the crystal for preparing is the good NaA type molecular sieve of crystallization; The crystal grain size is about 0.7 micron;
As shown in Figure 8, scanned picture surface NaX type molecular sieve has good pattern and the particle diameter of homogeneous; Powder x-ray diffraction conforms to the standard spectrogram, shows that the crystal for preparing is the good NaX type molecular sieve of crystallization; Crystallographic dimension is about 10 microns;
As shown in Figure 9, can see that NaA type Molecular Sieve Morphology is better, crystallization complete, the size homogeneous, size is 0.8 micron;
As shown in figure 10, can see that NaA type Molecular Sieve Morphology is better, crystallization complete, the size homogeneous, size is 2 microns;
As shown in figure 11, can see that NaA type Molecular Sieve Morphology is better, crystallization complete, the size homogeneous, size is 6.5 microns;
As shown in figure 12, can see that NaA type Molecular Sieve Morphology is better, crystallization is complete, the size homogeneous, size is 11 microns;
As shown in figure 13, can see that NaX type Molecular Sieve Morphology is better, crystallization is complete, the size homogeneous, size is 2 microns;
As shown in figure 14, can see that NaX type Molecular Sieve Morphology is better, crystallization is complete, the size homogeneous, size is 6 microns.
Embodiment
Embodiment 1
1. compound concentration is the Ni of 1ppm, 10ppm, 100ppm
2+Solution.
2. NaA type molecular sieve (by embodiment 11 preparations) is to Ni
2+Exchange
ICP tests test result and shows, in the final solution, and Ni
2+Concentration is all less than 0.02ppm.
Embodiment 2
1. compound concentration is the Mn of 1ppm, 10ppm, 100ppm
2+Solution.
2. NaA type molecular sieve (by embodiment 11 preparations) is to Mn
2+Exchange
ICP test test result shows, works as Mn
2+Starting point concentration when being 1ppm and 10ppm, in the final solution, Mn
2+Concentration is less than 0.02ppm; Work as Mn
2+Starting point concentration when being 100ppm, in the final solution, Mn
2+Concentration is 0.09ppm;
3. NaX type molecular sieve (by embodiment 12 preparations) is to Mn
2+Exchange
ICP test test result shows, works as Mn
2+Starting point concentration when being 1ppm, 10ppm and 100ppm, in the final solution, Mn
2+Concentration is all less than 0.02ppm.
Embodiment 3
1. compound concentration is the Co of 1ppm, 10ppm, 100ppm
2+Solution.
2. NaA type molecular sieve (by embodiment 11 preparations) is to Co
2+Exchange
ICP test test result shows, works as Co
2+Starting point concentration when being 1ppm and 10ppm, in the final solution, Co
2+Concentration is less than 0.02ppm; Work as Co
2+Starting point concentration when being 100ppm, in the final solution, Co
2+Concentration is 0.03ppm;
3. NaX type molecular sieve (by embodiment 12 preparations) is to Co
2+Exchange
Embodiment 4
1. compound concentration is the Cu of 1ppm, 10ppm, 100ppm
2+Solution.
2. NaA type molecular sieve (by embodiment 11 preparations) is to Cu
2+Exchange
ICP test test result shows, works as Cu
2+Starting point concentration when being 1ppm, 10ppm and 100ppm 6, in the final solution, Cu
2+Concentration is all less than 0.02ppm.
3. NaX type molecular sieve (by embodiment 12 preparations) is to Cu
2+Exchange
ICP test test result shows, works as Cu
2+Starting point concentration when being 1ppm and 10ppm, in the final solution, Co
2+Concentration is less than 0.02ppm; Work as Co
2+Starting point concentration when being 100ppm, in the final solution, Co
2+Concentration is 0.15ppm.
Embodiment 5
1. compound concentration is the Zn of 1ppm, 10ppm, 100ppm
2+Solution.
2. NaA type molecular sieve (by embodiment 11 preparations) is to Zn
2+Exchange
3. NaX type molecular sieve (by embodiment 12 preparations) is to Zn
2+Exchange
ICP test test result shows, works as Zn
2+Starting point concentration when being 1ppm, 10ppm and 100ppm, in the final solution, Zn
2+Concentration is all less than 0.02ppm.
1. compound concentration is the Cd of 1ppm, 10ppm, 100ppm
2+Solution.
2. NaA type molecular sieve (by embodiment 11 preparations) is to Cd
2+Exchange
3. NaX type molecular sieve (by embodiment 12 preparations) is to Cd
2+Exchange
ICP test test result shows, works as Cd
2+Starting point concentration when being 1ppm, 10ppm and 100ppm, in the final solution, Cd
2+Concentration is all less than 0.02ppm.
The swap data of embodiment 1～6 shows that NaA and NaX molecular sieve all have obvious exchange effect to six kinds of different metal ions.
Embodiment 7
NaA type molecular sieve (by embodiment 11 preparations) is to the exchange of hybrid metal solion
(1) obtain solution
Preparation contains Ni
2+, Co
2+, Mn
2+, Zn
2+, Cu
2+, Cd
2+The mixing solutions of each 100ppm;
Preparation contains Ni
2+, Co
2+, Mn
2+, Zn
2+, Cu
2+, Cd
2+The mixing solutions of each 10ppm;
Preparation contains Ni
2+, Co
2+, Mn
2+, Zn
2+, Cu
2+, Cd
2+The mixing solutions of each 1ppm;
(2) ion-exchange
In described three kinds of mixing solutionss, the NaA type molecular sieve (0.05g, 0.1g, 0.3g, 0.5g and 0.8g) that adds respectively different amounts carries out ion-exchange in front.Its result is respectively shown in Fig. 1 (corresponding each concentration of metal ions is the mixing solutions of 100ppm), Fig. 2 (corresponding each concentration of metal ions is the mixing solutions of 10ppm), Fig. 3 (corresponding each concentration of metal ions is the mixing solutions of 1ppm).
NaX type molecular sieve (by embodiment 12 preparations) is to the exchange of hybrid metal solion
(1) obtain solution
Preparation contains Ni
2+, Co
2+, Mn
2+, Zn
2+, Cu
2+, Cd
2+The mixing solutions of each 100ppm;
Preparation contains Ni
2+, Co
2+, Mn
2+, Zn
2+, Cu
2+, Cd
2+The mixing solutions of each 10ppm;
Preparation contains Ni
2+, Co
2+, Mn
2+, Zn
2+, Cu
2+, Cd
2+The mixing solutions of each 1ppm;
(2) ion-exchange
In described three kinds of mixing solutionss, the NaX type molecular sieve (0.05g, 0.1g, 0.3g, 0.5g and 0.8g) that adds respectively different amounts carries out ion-exchange in front.Its result is respectively shown in Fig. 4 (corresponding each concentration of metal ions is the mixing solutions of 100ppm), Fig. 5 (corresponding each concentration of metal ions is the mixing solutions of 10ppm), Fig. 6 (corresponding each concentration of metal ions is the mixing solutions of 1ppm).
The regeneration of NaA type molecular sieve after the exchange (by embodiment 11 preparations)
Get concentration and be the NaA type molecular sieve 8g that the hybrid metal solion of 100ppm exchanged, be divided into two parts, a copy of it is 6g, with HF (massfraction 10%) with its dissolving, the solution that obtains carries out the ICP test, it is as shown in table 7 to obtain the result, other gets in the NaCl solution (1.7mol/L) that NaA type molecular sieve that portion (2g) exchanged joins high density and stirs, repeat 5 times, carry out the regeneration of molecular sieve, molecular sieve after regeneration HF(massfraction 10%) the ICP test is carried out in dissolving, the solution that obtains, and the result after its regeneration is as shown in table 1, by contrast, by regeneration, the heavy metal ion of absorption is replaced back sodium ion more after the molecular sieve exchange, and the molecular sieve of regeneration is reusable edible again.
The regeneration of NaX type molecular sieve after the exchange (by embodiment 12 preparations)
Get concentration and be the NaX type molecular sieve 8g that the hybrid metal solion of 100ppm exchanged, be divided into two parts, a copy of it is 6g, with HF (massfraction 10%) with its dissolving, the solution that obtains carries out the ICP test, it is as shown in table 7 to obtain the result, other gets in the NaCl solution (1.7mol/L) that NaX type molecular sieve that portion (2g) exchanged joins high density and stirs, repeat 5 times, carry out the regeneration of molecular sieve, molecular sieve after regeneration HF(massfraction 10%) the ICP test is carried out in dissolving, the solution that obtains, and the result after its regeneration is as shown in table 1, by contrast, by regeneration, the heavy metal ion of absorption is replaced back sodium ion more after the molecular sieve exchange, and the molecular sieve of regeneration is reusable edible again.
Before table 1 regenerating molecular sieve and the result after the regeneration:
Embodiment 11
The preparation of NaA type molecular sieve (0.7 micron):
With 1.5 gram NaAlO
2Join in 10 ml deionized water, after stirring makes its uniform dissolution, add 1.875 gram NaOH and continue to stir 30 minutes, leave standstill for a moment; Obtain aluminium source solution.
With 1.5 gram Na
2SiO
39H
2O joins in 10 ml deionized water, and stirring and dissolving is until evenly, obtain silicon source solution.
The aluminium source solution that then will leave standstill adds in the silicon source solution that is stirring slowly, continues to stir 30 minutes, and the teflon-lined stainless steel cauldron of packing into, crystallization is 5 hours under 100 ℃ of conditions, and the suction filtration oven dry obtains NaA type molecular sieve (0.7 micron).The gained sample size is even, crystallization good (accompanying drawing 1), and productive rate 70～75%, Si/Al=1:1, the aperture is 0.4nm.
The preparation of NaX type molecular sieve (10 microns):
0.3 gram NaOH is joined in 6.5 ml deionized water, after stirring, add 0.13 gram NaAlO
2Continue to stir 30 minutes, leave standstill a moment; Obtain aluminium source solution.
With 1.2 gram Na
2SiO
39H
2O joins in 15 ml deionized water, stirs until evenly, obtain silicon source solution.
Then in the silicon source solution that the aluminium source slow adding of solution that will leave standstill is being stirred, continue to stir 30 minutes, the teflon-lined stainless steel cauldron of packing into, crystallization is 3 days under 100 ℃ of conditions, the suction filtration oven dry obtains NaX type molecular sieve powder (10 microns) (accompanying drawing 2), productive rate 70～75%, Si/Al=1:1.3, the aperture is 1.0nm.
Embodiment 13
The preparation of NaA type molecular sieve (0.8 micron):
With 0.75 gram NaAlO
2Join in 10 ml deionized water, after stirring makes its uniform dissolution, add 0.94 gram NaOH and continue to stir 30 minutes, leave standstill for a moment; Obtain aluminium source solution.
With 0.75 gram Na
2SiO
39H
2O joins in 10 ml deionized water, and stirring and dissolving is until evenly, obtain silicon source solution.
The aluminium source solution that then will leave standstill adds in the silicon source solution that is stirring slowly, continues to stir 30 minutes, and the teflon-lined stainless steel cauldron of packing into, crystallization is 1 hour under 100 ℃ of conditions, and the suction filtration oven dry obtains NaA type molecular sieve (0.8 micron).The gained sample size is even, crystallization good (accompanying drawing 3), and productive rate 70～75%, Si/Al=1:1, the aperture is 0.4nm.
Embodiment 14
The preparation of NaA type molecular sieve (2 microns):
With 0.5 gram NaAlO
2Join in 10 ml deionized water, after stirring makes its uniform dissolution, add 0.63 gram NaOH and continue to stir 30 minutes, leave standstill for a moment; Obtain aluminium source solution.
With 0.5 gram Na
2SiO
39H
2O joins in 10 ml deionized water, and stirring and dissolving is until evenly, obtain silicon source solution.
The aluminium source solution that then will leave standstill adds in the silicon source solution that is stirring slowly, continues to stir 50 minutes, and the teflon-lined stainless steel cauldron of packing into, crystallization is 1 hour under 100 ℃ of conditions, and the suction filtration oven dry obtains NaA type molecular sieve (2 microns).The gained sample size is even, crystallization good (accompanying drawing 4), and productive rate 70～75%, Si/Al=1:1, the aperture is 0.4nm.
Embodiment 15
The preparation of NaA type molecular sieve (6.5 microns):
With 0.3 gram NaAlO
2Join in 10 ml deionized water, after stirring makes its uniform dissolution, add 0.37 gram NaOH and continue to stir 30 minutes, leave standstill for a moment; Obtain aluminium source solution.
With 0.3 gram Na
2SiO
39H
2O joins in 10 ml deionized water, and stirring and dissolving is until evenly, obtain silicon source solution.
The aluminium source solution that then will leave standstill adds in the silicon source solution that is stirring slowly, continues to stir 30 minutes, and the teflon-lined stainless steel cauldron of packing into, crystallization is 3 hours under 100 ℃ of conditions, and the suction filtration oven dry obtains NaA type molecular sieve (6.5 microns).The gained sample size is even, crystallization good (accompanying drawing 5), and productive rate 70～75%, Si/Al=1:1, the aperture is 0.4nm.
Embodiment 16
The preparation of NaA type molecular sieve (11 microns):
With 0.15 gram NaAlO
2Join in 10 ml deionized water, after stirring makes its uniform dissolution, add 0.188 gram NaOH and continue to stir 30 minutes, leave standstill for a moment; Obtain aluminium source solution.
With 0.15 gram Na
2SiO
39H
2O joins in 10 ml deionized water, and stirring and dissolving is until evenly, obtain silicon source solution.
The aluminium source solution that then will leave standstill adds in the silicon source solution that is stirring slowly, continues to stir 30 minutes, and the teflon-lined stainless steel cauldron of packing into, crystallization is 3 hours under 100 ℃ of conditions, and the suction filtration oven dry obtains NaA type molecular sieve (11 microns).The gained sample size is even, crystallization good (accompanying drawing 6), and productive rate 70～75%, Si/Al=1:1, the aperture is 0.4nm.
Embodiment 17
The preparation of NaX type molecular sieve (6 microns):
0.6 gram NaOH is joined in 6.5 ml deionized water, after stirring makes its uniform dissolution, add 0.26 gram NaAlO
2Continue to stir 30 minutes, leave standstill a moment; Obtain aluminium source solution.
With 2.4 gram Na
2SiO
39H
2O joins in 15 ml deionized water, stirs until evenly, obtain silicon source solution.
Then in the silicon source solution that the aluminium source slow adding of solution that will leave standstill is being stirred, continue to stir 30 minutes, the teflon-lined stainless steel cauldron of packing into, crystallization is 2 days under 100 ℃ of conditions, the suction filtration oven dry obtains NaX type molecular sieve powder (6 microns) (accompanying drawing 7), productive rate 70～75%, Si/Al=1:1.3, the aperture is 1.0nm.
Embodiment 18
The preparation of NaX type molecular sieve (2 microns):
With 1.2 gram NaOH join stir in 6.5 ml deionized water after, add 0.52 gram NaAlO
2Continue to stir 30 minutes, leave standstill a moment; Obtain aluminium source solution.
With 4.8 gram Na
2SiO
39H
2O joins and stirs in 15 ml deionized water until evenly, obtain silicon source solution.
Then in the silicon source solution that the aluminium source slow adding of solution that will leave standstill is being stirred, continue to stir 50 minutes, the teflon-lined stainless steel cauldron of packing into, crystallization is 1 day under 100 ℃ of conditions, the suction filtration oven dry obtains NaX type molecular sieve powder (2 microns) (accompanying drawing 8), productive rate 70～75%, Si/Al=1:1.3, the aperture is 1.0nm.
Claims (4)
1. low silicon micropore NaA type molecular sieve or the NaX type molecular sieve application aspect the processing low-concentration heavy metal ions.
2. low silicon micropore NaA type molecular sieve as claimed in claim 1 or the NaX type molecular sieve application aspect the processing low-concentration heavy metal ions, it is characterized in that: heavy metal ion is Ni
2+, Co
2+, Mn
2+, Cu
2+, Zn
2+Or Cd
2+
3. low silicon micropore NaA type molecular sieve as claimed in claim 1 or the NaX type molecular sieve application aspect the processing low-concentration heavy metal ions, it is characterized in that: the concentration of heavy metal ion is 1～100ppm.
4. low silicon micropore NaA type molecular sieve as claimed in claim 1 or the NaX type molecular sieve application aspect the processing low-concentration heavy metal ions, it is characterized in that: NaA type molecular sieve or NaX type molecular sieve obtain by Hydrothermal Synthesis, and its step is as follows:
1) preparation of silicon source solution
With 0.15～4.8 gram Na
2SiO
39H
2O joins in 10～15 ml deionized water, is stirred to dissolving evenly, obtains silicon source solution;
2) preparation of aluminium source solution
(a) NaA type molecular sieve: with 0.15～1.5 gram NaAlO
2Join in 10～15 ml deionized water, be stirred to dissolving evenly, add again 0.188～1.875 gram NaOH and continue to stir 15～30 minutes, obtain aluminium source solution;
(b) NaX type molecular sieve: 0.3～1.2 gram NaOH is joined in 6.5～10 ml deionized water, be stirred to dissolving evenly, add again 0.13～0.52 gram NaAlO
2Continue to stir 15～30 minutes, obtain aluminium source solution;
3) crystallization
The aluminium source solution that then will leave standstill adds in the silicon source solution that is stirring slowly, continues to stir 30～50 minutes, and the reactor of then packing into, crystallization is 1 hour～48 hours under 100 ℃ of conditions;
4) sample obtains and processes
After crystallization is finished, cool off under the reactor room temperature, then the white depositions in the solution is carried out the suction filtration oven dry, the powder that obtains white is NaA or NaX type molecular sieve.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107442092A (en) * | 2017-08-31 | 2017-12-08 | 长沙埃比林环保科技有限公司 | A kind of method that hydro-thermal prepares heavy metals sorbing material |
| CN108120630A (en) * | 2017-12-29 | 2018-06-05 | 大工（青岛）新能源材料技术研究院有限公司 | A kind of detection method of copper ion |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113480A (en) * | 1995-06-20 | 1995-12-20 | 北京新奇材料研究所 | Zeolite molecular sieve water purifying material and its manufacture |
| US20090031897A1 (en) * | 2005-12-15 | 2009-02-05 | Chunqing Liu | Cross-Linkable and Cross-Linked Mixed Matrix Membranes and Methods of Making the Same |
| CN102671553A (en) * | 2012-05-02 | 2012-09-19 | 珠海市吉林大学无机合成与制备化学重点实验室 | Method for growing inorganic microporous membranes by adopting electrostatic spinning technology |
-
2012
- 2012-09-28 CN CN 201210372180 patent/CN102923807B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1113480A (en) * | 1995-06-20 | 1995-12-20 | 北京新奇材料研究所 | Zeolite molecular sieve water purifying material and its manufacture |
| US20090031897A1 (en) * | 2005-12-15 | 2009-02-05 | Chunqing Liu | Cross-Linkable and Cross-Linked Mixed Matrix Membranes and Methods of Making the Same |
| CN102671553A (en) * | 2012-05-02 | 2012-09-19 | 珠海市吉林大学无机合成与制备化学重点实验室 | Method for growing inorganic microporous membranes by adopting electrostatic spinning technology |
Non-Patent Citations (1)
| Title |
|---|
| 孙霞等: "粉煤灰制备单相态分子筛及对溶液中Cu2+的吸附", 《化工环保》, vol. 30, no. 6, 15 December 2010 (2010-12-15) * |
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| CN108120630A (en) * | 2017-12-29 | 2018-06-05 | 大工（青岛）新能源材料技术研究院有限公司 | A kind of detection method of copper ion |
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| CN109012225B (en) * | 2018-07-27 | 2021-03-16 | 西安建筑科技大学 | Application of self-supporting Li-ABW molecular sieve membrane in separation of calcium ions in hard water |
| CN109081460A (en) * | 2018-09-03 | 2018-12-25 | 福州大学 | Dissolubility AOCs and Co (II)/Mn (II) method in a kind of adsorption treatment PTA waste water |
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