CN1623899A - Guiding agent for preparing 4A zeolite - Google Patents
Guiding agent for preparing 4A zeolite Download PDFInfo
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- CN1623899A CN1623899A CN 200410155445 CN200410155445A CN1623899A CN 1623899 A CN1623899 A CN 1623899A CN 200410155445 CN200410155445 CN 200410155445 CN 200410155445 A CN200410155445 A CN 200410155445A CN 1623899 A CN1623899 A CN 1623899A
- Authority
- CN
- China
- Prior art keywords
- sodium aluminate
- crystallization
- zeolite
- concentration
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010457 zeolite Substances 0.000 title claims abstract description 73
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 59
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 58
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 83
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 66
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 66
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 29
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000002360 preparation method Methods 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims 2
- 229910052593 corundum Inorganic materials 0.000 claims 2
- 229910052906 cristobalite Inorganic materials 0.000 claims 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 2
- 229910052682 stishovite Inorganic materials 0.000 claims 2
- 229910052905 tridymite Inorganic materials 0.000 claims 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 abstract description 62
- 239000011734 sodium Substances 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 81
- 238000002425 crystallisation Methods 0.000 description 75
- 230000008025 crystallization Effects 0.000 description 74
- 239000007788 liquid Substances 0.000 description 32
- 238000005245 sintering Methods 0.000 description 32
- 238000003756 stirring Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 25
- 238000001914 filtration Methods 0.000 description 22
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- 239000012467 final product Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 229910052791 calcium Inorganic materials 0.000 description 11
- 238000012805 post-processing Methods 0.000 description 8
- 239000003292 glue Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000035922 thirst Effects 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A guiding agent for preparing 4A zeolite from the solution of sodium aluminate generated in the production of alumina features that the solution of sodium aluminate, water glass and sodium hydroxide are proportionally mixed while the Si/Al ratio and Na/Al ratio are controlled to be 5-20 and 10-25. Its advantages are high productivity and high quality of 4A zeolite.
Description
Technical field
The present invention relates to a kind of 4A of preparation zeolite directed agents, be used for the crystalline of zeolite, be suitable for especially preparing zeolite product with the sodium aluminate solution in the alumina by sintering production.
Background technology
The 4A zeolite can be applied to wash industry and catalyst industry, and in the washing industry, the 4A zeolite that needs will possess thinner granularity, and requires epigranular to concentrate and as far as possible high calcium switching performance; In the catalyst industry, require 4A zeolite high-crystallinity and high water absorbing capacity.Instructions for use difference, preparation technology are also different.
Washing is adopted chemical synthesis mostly with the production of 4A zeolite, mainly is synthetic with industrial water glass and sodium aluminate solution, at first prepares sodium aluminate solution with sodium hydroxide, trouble, cost height.And sintering process is produced in the industrial process of aluminium oxide, sodium aluminate solution almost runs through whole production process all the time, (produce in the alumina technology in sintering process, the grog stripping obtains the high dense thick liquid of sodium aluminate by isolated by filtration to the high dense thick liquid of the sodium aluminate of never desiliconization, contains Al
2O
3150～300g/l, SiO
28～25g/l, Na
2O130～310g/l is for subsequent use after the smart filter of the high dense thick liquid of sodium aluminate.), to Al
2O
3The seed precipitation solution that content is less.How to make full use of the sodium aluminate solution in variant stage in the alumina by sintering production, neither influence the ordinary production of aluminum oxide, the effective constituent that can make full use of is wherein obtained by product again, is the problem that people pay close attention to always and thirst for solving.The sodium aluminate solution of different phase, the content of each active ingredient has very big difference, such as Al
2O
3The content size issue, SiO
2Content size issue etc., the content difference, active ingredient have an environment difference, directly affect the mode of utilizing of each composition, different compositions, different performances needs to determine that different process routes is or/and different technical parameters.Chinese patent 86106033 has been put down in writing a kind of method of utilizing seed precipitation solution to prepare the 4A zeolite, takes full advantage of the residual Al in the seed precipitation solution
2O
3, the Matter Transfer in reduce producing, employing be two-stage crystallization method, obtain the 4A zeolite product by the adjusting process situation, produce easily bulk in this method pulp process, and the production cycle is long, be generally 8～12 hours, the 4A zeolite crystallinity of output is lower, only has 70～75%, and granularity is disperseed, at 1～10 μ m, the calcium exchange is on the low side, is 280～295mg/g, Al in the mother liquor
2O
3Residual is 16～18g/L, still higher.Chinese patent 02118924.2 has been introduced a kind of levigated finished product zeolite that utilizes and has been done crystal seed, and the 4A zeolite is separated out in the silicon source crystallization of using in the sodium aluminate solution, at first need the finished product zeolite is carried out levigate processing, and complex process, the energy consumption height, and the crystalline product quality is undesirable.Await studying some novel crystalline seed at present, make full use of the sodium aluminate solution in the alumina by sintering production, promote the crystallization production of 4A zeolite, reduce production costs, enhance productivity, improve the quality of products.
Summary of the invention
The object of the present invention is to provide a kind of preparation 4A zeolite directed agents, the sodium aluminate solution in utilizing alumina by sintering production prepares in the process of 4A zeolite, can promote the crystallization of 4A zeolite, reduces production costs, and enhances productivity, and improves the quality of products.
Preparation 4A zeolite directed agents of the present invention is with Al
2O
3Concentration is sodium aluminate solution, the SiO of 30～120g/l
2Concentration is that the waterglass of 8～20% weight ratios and NaOH mix, and the control silica alumina ratio is 5～20, the sodium aluminum ratio is 10～25 to make.
Preferably adopt Al
2O
3Concentration is industrial sodium aluminate solution, the SiO of 50～60g/L
2Concentration is that waterglass and the NaOH of 10～15% weight ratios is prepared burden, and the control silica alumina ratio is 9～10, the sodium aluminum ratio is 12～16.
The used sodium aluminate solution of directed agents can be the solution of preparing separately, also can be the sodium aluminate solution of taking from the alumina by sintering production process; Sodium hydroxide can add with solid form, also can add with aqueous solution form, and solution is preferably with high density.
During application, the add-on of directed agents is 1 ‰～20% of total liquor capacity.
The crystallization of 4A zeolite prepares the pulp temperature and is generally 30～85 ℃, and the general time of pulp is 5～30 minutes; Crystallization temperature is generally 60～100 ℃, is preferably 70～95 ℃, and crystallization time was generally 1～4 hour, was preferably 2～2.5 hours.
Directed agents of the present invention forms simple, makes easily, and cost is low, and is easy to use, operates control easily, directly joins in the reaction mixture before the temperature raising crystallization to get final product after the raw material pulp.The directed agents wide adaptability both had been adapted to provide the sodium aluminate solution production in silicon source, also was adapted to provide the sodium aluminate production in aluminium source.Utilize directed agents of the present invention, can realize the step crystallization operation that the 4A zeolite is produced, with short production cycle, there are crystallization time in the past 8～12 hours to be reduced to 1～3 hour, significantly improved production capacity, the aluminum oxide that returns after the crystallization in the seed precipitation solution is reduced to 0.5～3g/L by the 16～18g/L in past, provide the sodium aluminate crystallization filtrate silicon content in silicon source to have only 1～4g/l, production cost is low, the production efficiency height, the 4A zeolite product quality that obtains is good, product degree of crystallinity brought up to 80～85% by 70～75% of the past, granularity becomes 1～4 μ m that evenly concentrates by dispersive 1～10 μ m, and the calcium exchange is brought up to more than the 300mg/g product (NaO by the 280～295mg/g in past
2Al
2O
32SiO
24.5H
2O) crystalline phase purity height.The adding of directed agents is not introduced any impurity to course of reaction, therefore need not removal of impurities, and the sodium aluminate solution during the alumina by sintering that was utilized is produced can directly turn back to the production of carrying out aluminium oxide in the normal alumina producing flow process.
Description of drawings
Fig. 1, one embodiment of the invention Production Flow Chart block diagram provide the silicon source to produce the 4A zeolite by the high dense thick liquid of the sodium aluminate of not desiliconization
Fig. 2, another embodiment of the present invention Production Flow Chart block diagram provide the aluminium source to produce the 4A zeolite by seed precipitation solution.
Embodiment
The present invention is further illustrated below in conjunction with embodiment.
Embodiment 1
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 55g/L
2Concentration is that waterglass and the NaOH of 10% weight ratio is prepared burden, and the control silica alumina ratio is 9, the sodium aluminum ratio is 12, mixes to get final product, and is for subsequent use.
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, at Al
2O
3Concentration adds SiO in the seed precipitation solution in the production of 30g/L alumina by sintering
2Concentration is the waterglass of 27% weight ratio, and two kinds of solution are heated to respectively 51 ± 1 ℃, then two solution is pressed [SiO
2]/[Al
2O
3]=1 joins respectively in the slurrying tank, and the speed of agitator of slurrying tank is 40 rev/mins, adds directed agents behind the stirring 5min, addition is 1 ‰ of total liquor capacity, then temperature raising to 93 ± 1 ℃, crystallization 1 hour, after filtration, wash, dry conventional post processing, get the 4A zeolite product.Index is as follows:
Calcium exchange granularity＜4um (%) whiteness (%) PH
301aco
3/g 96.2 98.1 10.96
Embodiment 2
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 40g/L
2Concentration is that waterglass and the NaOH of 12% weight ratio is prepared burden, and the control silica alumina ratio is 10, the sodium aluminum ratio is 13, mixes to get final product, and is for subsequent use.
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, at Al
2O
3Concentration adds SiO in the seed precipitation solution in the production of 40g/L alumina by sintering
2Concentration is the waterglass of 25% weight ratio, and two kinds of solution are heated to respectively 53 ± 1 ℃, then two solution is pressed [SiO
2]/[Al
2O
3]=1.9 are becoming glue to enter slurrying tank under the pulp synchronously continuously, the slurries that the one side of pulp on one side is good with pulp are then squeezed in the empty crystallization groove by pump, the speed of agitator of crystallization groove is 40 rev/mins, stir 10min and add directed agents, addition is 1 ‰ of total liquor capacity, again temperature raising to 85 ± 1 ℃, crystallization 1.5 hours, after filtration, wash, dry conventional post processing, get the 4A zeolite product.Index is as follows:
Calcium exchange granularity＜4um (%) whiteness (%) PH
303mgcaco
3/g 96.1 98.3 10.82
Embodiment 3
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 50g/L
2Concentration is that waterglass and the NaOH of 20% weight ratio is prepared burden, and the control silica alumina ratio is 9, the sodium aluminum ratio is 12, mixes to get final product, and is for subsequent use.
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, at Al
2O
3Concentration adds SiO in the seed precipitation solution in the production of 50g/L alumina by sintering
2Concentration is the waterglass of 20% weight ratio, and two kinds of solution are heated to respectively 55 ± 1 ℃, then two solution is pressed [SiO
2]/[Al
2O
3]=1 is becoming glue to enter slurrying tank under the pulp synchronously continuously, the slurries that the one side of pulp on one side is good with pulp are then squeezed in the empty crystallization groove by pump, the speed of agitator of crystallization groove is 40 rev/mins, stir 30min and add directed agents, addition is 5 ‰ of total liquor capacity, again temperature raising to 90 ± 1 ℃, crystallization 2.2 hours, after filtration, wash, dry conventional post processing, get the 4A zeolite product.Index is as follows:
Calcium exchange granularity＜4um (%) whiteness (%) PH
302mgcaco
3/g 96.8 98.2 10.84
Embodiment 4
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 60g/L
2Concentration is that waterglass and the NaOH of 15% weight ratio is prepared burden, and the control silica alumina ratio is 12, the sodium aluminum ratio is 20, mixes to get final product, and is for subsequent use.
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, at Al
2O
3Concentration adds SiO in the seed precipitation solution in the production of 60g/L alumina by sintering
2Concentration is the waterglass of 15% weight ratio, and two kinds of solution are heated to respectively 56 ± 1 ℃, then two solution is pressed [SiO
2]/[Al
2O
3]=2 are becoming glue to enter slurrying tank under the pulp synchronously continuously, the speed of agitator that the slurries that the one side of pulp on one side is good with pulp are then squeezed into slurrying tank in the empty crystallization groove by pump is 40 rev/mins, stir 30min and add directed agents, addition is 5 ‰ of total liquor capacity, again temperature raising to 83 ± 1 ℃, crystallization 2 hours after filtration, wash, dry conventional post processing, gets the 4A zeolite product.Index is as follows:
Calcium exchange granularity＜4um (%) whiteness (%) PH
302mgcaco
3/g 95.0 98.3 10.85
Embodiment 5
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 100g/L
2Concentration is that the waterglass of 20% weight ratio and the sodium hydroxide solution of 40% weight ratio are prepared burden, and the control silica alumina ratio is 7, the sodium aluminum ratio is 10, mixes to get final product, and is for subsequent use
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, at Al
2O
3Concentration adds SiO in the seed precipitation solution in the production of 78g/L alumina by sintering
2Concentration is the waterglass of 10% weight ratio, and two kinds of solution are heated to respectively 65 ± 1 ℃, and two kinds of solution enter slurrying tank by flowmeter respectively then, and the speed of agitator of slurrying tank is 50 rev/mins, and two solution are by [SiO
2]/[Al
2O
3]=2 are becoming glue to enter slurrying tank under the pulp synchronously continuously, the slurries that the one side of pulp on one side is good with pulp are then squeezed in the empty crystallization groove by pump, the speed of agitator of crystallization groove is 40 rev/mins, stir 30min and add directed agents, addition is 10 ‰ of total liquor capacity, again temperature raising to 96 ± 1 ℃, crystallization 2.5 hours, after filtration, wash, dry conventional post processing, get the 4A zeolite product.Index is as follows:
Calcium exchange granularity＜4um (%) whiteness (%) PH
301mgcaco
3/g 95.4 98.0 10.89
Embodiment 6
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 45g/L
2Concentration is that waterglass and the NaOH of 15% weight ratio is prepared burden, and the control silica alumina ratio is 10, the sodium aluminum ratio is 14, mixes to get final product, and is for subsequent use.
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, at Al
2O
3Concentration adds SiO in the seed precipitation solution in the production of 45g/L alumina by sintering
2Concentration is the waterglass of 25% weight ratio, and two kinds of solution are heated to respectively 52 ± 1 ℃, then two solution is pressed [SiO
2]/[Al
2O
3]=1.8 are becoming glue to enter slurrying tank under the pulp synchronously continuously, the slurries that the one side of pulp on one side is good with pulp are then squeezed in the empty crystallization groove by pump, the speed of agitator of crystallization groove is 40 rev/mins, stir 20min and add directed agents, addition is 8 ‰ of total liquor capacity, more than again temperature raising to 90 ± 1 ℃, and crystallization 1.5 hours, after filtration, wash, dry conventional post processing, get the 4A zeolite product.Index is as follows:
Calcium exchange granularity＜4um (%) whiteness (%) PH
302mgcaco
3/g 96.2 98.3 10.84
Embodiment 7
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 40g/L
2Concentration is that waterglass and the NaOH of 12% weight ratio is prepared burden, and the control silica alumina ratio is 14, the sodium aluminum ratio is 15, mixes to get final product, and is for subsequent use.
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, at Al
2O
3Concentration adds SiO in the seed precipitation solution in the production of 55g/L alumina by sintering
2Concentration is the waterglass of 24% weight ratio, and two kinds of solution are heated to respectively 70 ± 1 ℃, then two solution is pressed [SiO
2]/[Al
2O
3]=1.3 are becoming glue to enter slurrying tank under the pulp synchronously continuously, the slurries that the one side of pulp on one side is good with pulp are then squeezed in the empty crystallization groove by pump, the speed of agitator of crystallization groove is 40 rev/mins, stir 15min and add directed agents, addition is 8 ‰ of total liquor capacity, again temperature raising to 88 ± 1 ℃, crystallization 2.5 hours, after filtration, wash, dry conventional post processing, get the 4A zeolite product.Index is as follows:
Calcium exchange granularity＜4um (%) whiteness (%) PH
303mgcaco
3/g 96.3 98.1 10.80
Embodiment 8
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 30g/L
2Concentration is that the waterglass of 14% weight ratio and the sodium hydroxide solution of 60% weight ratio are prepared burden, and the control silica alumina ratio is 10, the sodium aluminum ratio is 16, mixes to get final product, and is for subsequent use
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, at Al
2O
3Concentration adds SiO in the seed precipitation solution in the production of 65g/L alumina by sintering
2Concentration is the waterglass of 23% weight ratio, and two kinds of solution are heated to respectively 53 ± 1 ℃, then two solution is pressed [SiO
2]/[Al
2O
3]=1.6 are becoming glue to enter slurrying tank under the pulp synchronously continuously, the slurries that the one side of pulp on one side is good with pulp are then squeezed in the empty crystallization groove by pump, the speed of agitator of crystallization groove is 40 rev/mins, stir 13min and add directed agents, addition is 11 ‰ of total liquor capacity, again temperature raising to 75 ± 1 ℃, crystallization 3.5 hours, after filtration, wash, dry conventional post processing, get the 4A zeolite product.Index is as follows:
Calcium exchange granularity＜4um (%) whiteness (%) PH
301mgcaco
3/g 96.2 98.3 10.81
Embodiment 9
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, utilize the directed agents of following preparation, join the high dense thick liquid (Al of sodium aluminate of the not desiliconization in the alumina by sintering production
2O
3180g/l, SiO
218g/l, Na
2O250g/l is for subsequent use after the smart filter of the high dense thick liquid of sodium aluminate) in, directly obtain washing and use 4A crystallization of zeolites, wherein being formulated as follows of directed agents:
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 55g/L
2Concentration is that waterglass and the NaOH of 10% weight ratio is prepared burden, and the control silica alumina ratio is 9, the sodium aluminum ratio is 12, mixes to get final product, and is for subsequent use.
Concrete operations control is as follows:
At first the high dense thick liquid of sodium aluminate is warming up to 50 ± 1 ℃, under powerful stirring action, the above-mentioned non-crystalline state directed agents that adds the high dense thick liquid long-pending 4% of sodium aluminate is carried out pulp mixing, pulp time 25min; Slow down stirring velocity then,, be warmed up to 77 ± 1 ℃ again and carry out crystallization to the middling speed stirring, crystallization time 40min, after crystallization finished, filtering separation was obtained the 4A crystallization of zeolites, must wash after the crystallization filter cake is washed, dries with distilled water or softening water and use the 4A zeolite product.
Embodiment 10
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, utilize the directed agents of following preparation, join the high dense thick liquid (Al of sodium aluminate of the not desiliconization in the alumina producing
2O
3250g/l, SiO
215g/l, Na
2O160g/l is for subsequent use after the smart filter of the high dense thick liquid of sodium aluminate) in, directly obtain washing and use 4A crystallization of zeolites, wherein being formulated as follows of directed agents:
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 60g/L
2Concentration is that waterglass and the NaOH of 15% weight ratio is prepared burden, and the control silica alumina ratio is 10, the sodium aluminum ratio is 13, mixes to get final product, and is for subsequent use.
Concrete operations control is as follows:
At first the high dense thick liquid of sodium aluminate is warming up to 50 ± 1 ℃, under powerful stirring action, the above-mentioned directed agents that adds the high dense thick liquid long-pending 9% of sodium aluminate is carried out pulp mixing, pulp time 100min; Slow down stirring velocity then, stir to middling speed, be warmed up to 70 ± 1 ℃ again and carry out crystallization, crystallization time 120min, after crystallization finished, filtering separation was obtained the 4A crystallization of zeolites, with crystallization after filtration, washing, oven dry aftertreatment must wash and use the 4A zeolite product.
Embodiment 11
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, utilize the directed agents of following preparation, join the high dense thick liquid (Al of sodium aluminate of the not desiliconization in the alumina producing
2O
3200g/l, SiO
220g/l, Na
2O190g/l is for subsequent use after the smart filter of the high dense thick liquid of sodium aluminate) in, directly obtain washing and use 4A crystallization of zeolites, wherein being formulated as follows of directed agents:
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 55g/L
2Concentration is that waterglass and the NaOH of 16% weight ratio is prepared burden, and the control silica alumina ratio is 9, the sodium aluminum ratio is 15, mixes to get final product, and is for subsequent use.
Concrete operations control is as follows:
At first the high dense thick liquid of sodium aluminate is warming up to 45 ± 1 ℃, under powerful stirring action, the above-mentioned directed agents that adds the high dense thick liquid long-pending 6% of sodium aluminate is carried out pulp mixing, pulp time 80min; Slow down stirring velocity then, stir to middling speed, be warmed up to 85 ± 1 ℃ again and carry out crystallization, crystallization time 150min, after crystallization finished, filtering separation was obtained the 4A crystallization of zeolites, with crystallization after filtration, washing, oven dry aftertreatment must wash and use the 4A zeolite product.
Embodiment 12
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, utilize the directed agents of following preparation, join the high dense thick liquid (Al of sodium aluminate of the not desiliconization in the alumina producing
2O
3160g/l, SiO
218g/l, Na
2O230g/l is for subsequent use after the smart filter of the high dense thick liquid of sodium aluminate) in, directly obtain washing and use 4A crystallization of zeolites, wherein being formulated as follows of directed agents:
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 30g/L
2Concentration is that the waterglass of 10% weight ratio and 60% sodium hydroxide solution are prepared burden, and the control silica alumina ratio is 7, the sodium aluminum ratio is 10, mixes to get final product, and is for subsequent use.
Concrete operations control is as follows:
At first the high dense thick liquid of sodium aluminate is warming up to 60 ± 1 ℃, under powerful stirring action, the above-mentioned directed agents that adds the high dense thick liquid long-pending 11% of sodium aluminate is carried out pulp mixing, pulp time 60min; Slow down stirring velocity then, stir to middling speed, be warmed up to 75 ± 1 ℃ again and carry out crystallization, crystallization time 140min, after crystallization finished, filtering separation was obtained the 4A crystallization of zeolites, with crystallization after filtration, washing, oven dry aftertreatment must wash and use the 4A zeolite product.
Embodiment 13
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, utilize the directed agents of following preparation, join the high dense thick liquid (Al of sodium aluminate of the not desiliconization in the alumina producing
2O
3190g/l, SiO
220g/l, Na
2O260g/l is for subsequent use after the smart filter of the high dense thick liquid of sodium aluminate) in, directly obtain washing and use 4A crystallization of zeolites, wherein being formulated as follows of directed agents:
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 80g/L
2Concentration is that waterglass and the NaOH of 18% weight ratio is prepared burden, and the control silica alumina ratio is 9, the sodium aluminum ratio is 17, mixes to get final product, and is for subsequent use.
Concrete operations control is as follows:
At first the high dense thick liquid of sodium aluminate is warming up to 50 ± 1 ℃, under powerful stirring action, the above-mentioned directed agents that adds the high dense thick liquid long-pending 6% of sodium aluminate is carried out the pulp mixing, slow down stirring velocity then,, be warmed up to 78 ± 1 ℃ again and carry out crystallization to the middling speed stirring, crystallization time 150min, after crystallization finished, filtering separation was obtained the 4A crystallization of zeolites, with crystallization after filtration, washing, oven dry aftertreatment must wash and use the 4A zeolite product.
Embodiment 14
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, utilize the directed agents of following preparation, join the high dense thick liquid (Al of sodium aluminate of the not desiliconization in the alumina producing
2O
3210g/l, SiO
219g/l, Na
2O180g/l is for subsequent use after the smart filter of the high dense thick liquid of sodium aluminate) in, directly obtain washing and use 4A crystallization of zeolites, wherein being formulated as follows of directed agents:
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 100g/L
2Concentration is that the waterglass of 11% weight ratio and 45% sodium hydroxide solution are prepared burden, and the control silica alumina ratio is 9, the sodium aluminum ratio is 15, mixes to get final product, and is for subsequent use.
Concrete operations control is as follows:
At first the high dense thick liquid of sodium aluminate is warming up to 52 ± 1 ℃, under powerful stirring action, the above-mentioned directed agents that adds the high dense thick liquid long-pending 7% of sodium aluminate is carried out pulp mixing, pulp time 60min; Slow down stirring velocity then, stir to middling speed, be warmed up to 82 ± 1 ℃ again and carry out crystallization, crystallization time 85min, after crystallization finished, filtering separation was obtained the 4A crystallization of zeolites, with crystallization after filtration, washing, oven dry aftertreatment must wash and use the 4A zeolite product.
Embodiment 15
Utilize the sodium aluminate solution production in the alumina by sintering production process to wash the method for using the 4A zeolite, utilize the directed agents of following preparation, join the high dense thick liquid (Al of sodium aluminate of the not desiliconization in the alumina producing
2O
3120g/l, SiO
219g/l, Na
2O190g/l is for subsequent use after the smart filter of the high dense thick liquid of sodium aluminate) in, directly obtain washing and use 4A crystallization of zeolites, wherein being formulated as follows of directed agents:
Al is adopted in the directed agents preparation
2O
3Concentration is industrial sodium aluminate solution, the SiO of 110g/L
2Concentration is that waterglass and the NaOH of 13% weight ratio is prepared burden, and the control silica alumina ratio is 10, the sodium aluminum ratio is 13, mixes to get final product, and is for subsequent use.
Concrete operations control is as follows:
At first the high dense thick liquid of sodium aluminate is warming up to 56 ± 1 ℃, under powerful stirring action, the above-mentioned directed agents that adds the high dense thick liquid long-pending 8% of sodium aluminate is carried out pulp mixing, pulp time 40min; Slow down stirring velocity then, stir to middling speed, be warmed up to 82 ± 1 ℃ again and carry out crystallization, crystallization time 90min, after crystallization finished, filtering separation was obtained the 4A crystallization of zeolites, with crystallization after filtration, washing, oven dry aftertreatment must wash and use the 4A zeolite product.
Claims (2)
1. one kind prepares 4A zeolite directed agents, it is characterized in that with Al2O3 concentration being that the sodium aluminate solution of 30～120g/l, water glass that SiO2 concentration is 8～20% weight ratios and sodium hydroxide mix, and the control silica alumina ratio is 5～20, the sodium aluminum ratio is 10～25 to make.
2. preparation 4A zeolite directed agents according to claim 1, it is characterized in that adopting Al2O3 concentration is that the industrial sodium aluminate solution of 50～60g/L, water glass and the sodium hydroxide that SiO2 concentration is 10～15% weight ratios carry out batch mixes, and the control silica alumina ratio is 9～10, the sodium aluminum ratio is 12～16 to make.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004101554453A CN100348487C (en) | 2004-11-12 | 2004-11-12 | Guiding agent for preparing 4A zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101554453A CN100348487C (en) | 2004-11-12 | 2004-11-12 | Guiding agent for preparing 4A zeolite |
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| CN1623899A true CN1623899A (en) | 2005-06-08 |
| CN100348487C CN100348487C (en) | 2007-11-14 |
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ID=34766927
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009127104A1 (en) * | 2008-04-18 | 2009-10-22 | 中国铝业股份有限公司 | A method for producing 4a zeolite used in detergent |
| CN100577565C (en) * | 2007-08-03 | 2010-01-06 | 中国铝业股份有限公司 | Method for producing 4A zeolite |
| CN107673368A (en) * | 2017-10-25 | 2018-02-09 | 常州大学盱眙凹土研发中心 | A kind of method for synthesizing 5A molecular sieves using directed agents for raw material with recessed soil |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032803C (en) * | 1992-07-18 | 1996-09-18 | 中国石油化工总公司石油化工科学研究院 | Method for prepn. of small crystal grain NaY molecular sieve |
| CN1289398C (en) * | 2002-04-30 | 2006-12-13 | 上海信渊实业有限公司 | 4A zeolite, manufacture method and use thereof |
-
2004
- 2004-11-12 CN CNB2004101554453A patent/CN100348487C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100577565C (en) * | 2007-08-03 | 2010-01-06 | 中国铝业股份有限公司 | Method for producing 4A zeolite |
| WO2009127104A1 (en) * | 2008-04-18 | 2009-10-22 | 中国铝业股份有限公司 | A method for producing 4a zeolite used in detergent |
| CN107673368A (en) * | 2017-10-25 | 2018-02-09 | 常州大学盱眙凹土研发中心 | A kind of method for synthesizing 5A molecular sieves using directed agents for raw material with recessed soil |
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Owner name: CHINESE ALUMINIUM CO., LTD. Free format text: FORMER OWNER: SHANDONG ALUMINIUM INDUSTRY CO., LTD. Effective date: 20071026 |
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Effective date of registration: 20071026 Address after: 100082 No. 62 North Main Street, Beijing, Xizhimen Patentee after: Aluminum Corporation of China Limited Address before: 255052 No. 1, five km road, Zhangdian District, Shandong, Zibo Patentee before: Shandong Aluminium Industry Co., Ltd. |