CN1286722C - Method for producing 4A zeolite for washing use from byproduct sodium silica slag generated in producing alumina - Google Patents
Method for producing 4A zeolite for washing use from byproduct sodium silica slag generated in producing alumina Download PDFInfo
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- CN1286722C CN1286722C CN 200410023916 CN200410023916A CN1286722C CN 1286722 C CN1286722 C CN 1286722C CN 200410023916 CN200410023916 CN 200410023916 CN 200410023916 A CN200410023916 A CN 200410023916A CN 1286722 C CN1286722 C CN 1286722C
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- Prior art keywords
- sodium
- zeolite
- stripping
- crystallization
- washing
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- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 44
- 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 44
- 239000010457 zeolite Substances 0.000 title claims abstract description 44
- 238000005406 washing Methods 0.000 title claims abstract description 38
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 239000006227 byproduct Substances 0.000 title claims abstract description 15
- 239000011734 sodium Substances 0.000 title claims description 59
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims description 41
- 229910052708 sodium Inorganic materials 0.000 title claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 20
- 239000000377 silicon dioxide Substances 0.000 title claims description 10
- 239000002893 slag Substances 0.000 title 1
- 238000002425 crystallisation Methods 0.000 claims abstract description 49
- 230000008025 crystallization Effects 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 238000004090 dissolution Methods 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 72
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 18
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000012530 fluid Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 235000019353 potassium silicate Nutrition 0.000 claims description 15
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 11
- 235000017550 sodium carbonate Nutrition 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 9
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 239000010436 fluorite Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims 1
- 235000011941 Tilia x europaea Nutrition 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical group [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 abstract 5
- HIGRAKVNKLCVCA-UHFFFAOYSA-N alumine Chemical compound C1=CC=[Al]C=C1 HIGRAKVNKLCVCA-UHFFFAOYSA-N 0.000 abstract 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 238000007781 pre-processing Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012257 stirred material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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Abstract
The present invention relates to a method for producing a washing 4A zeolite by using byproducts, namely sodium silicon residues obtained from the production of alumine. The washing 4A zeolite is formed by that the sodium silicon residues are processed by purification preprocessing, allocation, sintering, dissolution, crystallization, etc. In the present invention, the byproduct sodium silicon residues obtained from the production of alumine can be used and produced into the qualified washing 4A zeolite products; the sodium silicon residues are fully used, namely that wastes are changed into valuables; after the 4A zeolite is used in industrial production, the low efficiency circulation of the sodium silicon residues is avoided, and the equipment utilization rate of alumina production is improved; the alumina production flow path is optimized, and thus, the production cost is reduced, and the production cost of the washing 4A zeolite is also reduced; the 4A zeolite products of the present invention used as washing additives do not contain phosphorus, and the 4A zeolite is a green environmental protection product.
Description
Technical field
The present invention uses the 4A zeolite with sodium white residue production washing, is the waste residue treatment technology of silicates, also belongs to the production technology of washing with the 4A zeolite.
Background technology
According to the difference of 4A zeolite quality, it can be used for doing molecular sieve in chemical industry, also can be applied to wash industry, is used as the additive of cleaning product.
United States Patent (USP) 3310373, BE840315 and IT19617/79 introduce with the raw ore that is rich in aluminum oxide to come preparing washing auxiliary agent 4A zeolite (Na
2OAl
2O
32SiO
24.5H
2O), with the zeolite of bauxite preparation color and the purity at crystallization and final product, it is not enough to also have several aspects such as pollutent is residual to exist, and has directly influenced use.What the patent 86106033 of China was introduced is to produce washing 4A zeolite with sodium aluminate solution and water glass synthesis method, and the zeolite properties that this kind method generates is relatively good, and still, it will consume raw material---the sodium aluminate solution of producing aluminum oxide, cost height.On the other hand, produce in the production technique of aluminum oxide in sintering process, thick liquid contains a certain amount of silicon, and this part silicon is deleterious to alumina producing, need remove with the form of sodium white residue, has obtained a kind of byproduct sodium white residue (Na like this
2OAl
2O
31.7～1.8SiO
22.4H
2O).Because the sodium white residue also contains aluminium and sodium simultaneously, so be that the sodium white residue is returned batching as low-grade ore on producing now.Used ore grade is generally alumina silica ratio greater than 5.0 in sintering process, and the alumina silica ratio of sodium white residue has only 1.0, so returning with respect to using high-grade ore of it reduced usage ratio of equipment, this problem is particularly outstanding when the amount of sodium white residue is very big.
Summary of the invention
The object of the present invention is to provide a kind ofly to make full use of the sodium white residue, turn waste into wealth, reduced the production cost of washing again with the 4A zeolite with the method for the washing of the byproduct sodium white residue production in the alumina producing with the 4A zeolite.
Of the present invention with the method for the washing of the byproduct sodium white residue production in the alumina producing with the 4A zeolite, at first the sodium white residue is purified pre-treatment, handle getting final product according to conventional purifying treatment mode, generally comprise filtration, washing and oven dry etc., the preparation directed agents is standby, the preparation of directed agents:
The preparation alumina content is that sodium aluminate solution and the silica content of 30～60g/l is that 160～200g/l, sodium oxide content are the water glass of 50～80g/l, presses Na
2O and Al
2O
3Mol ratio (10～18): 1, SiO
2And Al
2O
3Mol ratio be (8～14): 1, H
2O and Al
2O
3Mol ratio be (280～350): 1 ratio has been calculated the consumption of sodium aluminate solution, water glass, sodium hydroxide and water, attemperation is 40～60 ℃, under brute force stirs, four kinds of raw materials are mixed, continue to stir after 10～60 minutes and left standstill 45～100 hours, promptly get directed agents;
Carry out according to following steps successively then:
(1) batching: in the sodium white residue, allocate yellow soda ash or sodium hydroxide into, press alkali number and sodium white residue proportioning respectively with wherein Na
2O and SiO
2+ Al
2O
3Mol ratio be (0.9～1.30): 1 ratio batching mixing.
(2) sintering: the batching that will mix gets grog at 800 ℃～1050 ℃ roasting temperature sintering.It is too high that sintering temperature is difficult for, in order to avoid hygroscopic effect is serious when grog is levigate in the back.Sintering time is difficult for too short, and it is fully reacted completely, and decides on inventory, generally is difficult for being lower than 1 hour, is advisable in 1.5～3 hours.
(3) stripping: the grog behind the sintering is pulverized, placed sodium hydroxide solution, and add directed agents, heat stripping and handle.
(4) crystallization: dissolution fluid is carried out the degree of crystallinity that the temperature raising crystallization is improved the 4A fluorite, must wash crystallization through aftertreatment and use the 4A zeolite product.
Among the present invention:
During stripping was handled, the chamotte powder behind the sintering was broken to and lacked 120 mesh sieves and be advisable, and is thin more good more naturally, is beneficial to stripping.
During stripping was handled, the add-on of directed agents was 1～6% of a dissolution fluid volume.
The control Heating temperature is 60～80 ℃, under agitation carries out, and dissolution time is 1～3 hour.Stirring is a principle to have stirred material, and making material can not be deposited in container bottom is minimum stirring intensity, and the highest stirring intensity is difficult for greater than 300 rev/mins.
It is suitable that the addition of stripping grog is expressed as 50～150g/l with solid content.
Stripping is suitable with 23～40g/l with the sodium oxide equivalent concentration of sodium hydroxide solution.
Crystallization temperature is controlled to be 85～98 ℃, and crystallization time is 1～3 hour.
The sodium aluminate solution that uses in the directed agents of the present invention can be Al (OH)
3Stripping product in NaOH solution also can be that alkali-lime sinter process is produced the intermediate product in the alumina process, preferably will handle through purifying, can meet service requirements fully, is convenient to utilize, and has further reduced production cost again.
Crystallization of the present invention gets product after filtering, drying, if granularity does not reach specification of quality, the mode of available mechanical disintegration is carried out further thinning processing and got final product.The washing that the present invention makes reaches the QB-1768-93 of Ministry of Light Industry standard with the 4A zeolite product, and calcium exchanges more than 285mg/g.
The present invention can utilize the byproduct sodium white residue in the alumina producing to produce qualified washing 4A zeolite product, make full use of the sodium white residue, turn waste into wealth, after being applied to industrial production, can avoid the poor efficiency circulation on stream of sodium white residue, improve the plant factor of alumina producing, optimize the alumina producing flow process, and then reduction manufacturing cost of aluminum oxide, also reduced the production cost of washing with the 4A zeolite, and product 4A zeolite of the present invention as the washing use additive, not phosphorous, be a kind of Green Product.
Description of drawings
Fig. 1, embodiment of the invention Production Flow Chart block diagram.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
The preparation of directed agents: the preparation alumina content is that sodium aluminate solution and the silica content of 45g/l is that 180g/l, sodium oxide content are the water glass (ortho-water glass gets final product, and general modulus is 3.0～3.3) of 65g/l, presses Na
2O and Al
2O
3Mol ratio 15: 1, SiO
2And Al
2O
3Mol ratio be 10: 1, H
2O and Al
2O
3Mol ratio be the consumption that 300: 1 ratio has been calculated sodium aluminate solution, water glass, sodium hydroxide and water, attemperation is 45 ℃, under brute force stirs four kinds of raw materials is mixed, and continues to stir to leave standstill after 48 hours after 30 minutes promptly to get directed agents.
Of the present invention with the method for the washing of the byproduct sodium white residue production in the alumina producing with the 4A zeolite, follow these steps to successively carry out:
Sodium white residue (Na
2OAl
2O
31.7～1.8SiO
22.4H
2O) filter, prepare burden after the washing, oven dry, promptly join alkali, institute join alkali with yellow soda ash for well, be yellow soda ash and sodium white residue 1.2 to prepare burden by the alkali ratio.Because be solid reaction, should mix fully after the batching.
Mixed material abundant sintering under 1000 ℃～1030 ℃ temperature, it is reacted completely, sintering time 1.5 hours.
The levigate back stripping of grog that sintering is crossed, the granularity of the grog that grinds should be fully thin, crosses 120 mesh sieves.The addition of stripping grog is expressed as 100g/l with solid content, Na in the used sodium hydroxide solution of stripping
2The equivalent concentration of O is N
K=30g/l, the stripping temperature is 65 ℃, carries out dissolution time 1.5 hours under agitation condition.The directed agents that adds dissolution fluid volume 4% during stripping guides the crystallisation process of zeolite.
After the stripping, do not carry out liquid-solid separation, directly dissolution fluid temperature raising crystallization, 95 ℃ of crystallization temperatures, crystallization time 2 hours.
Crystallization finishes, with crystallization filter, dry washing 4A zeolite product.
Embodiment 2
The preparation of directed agents: the preparation alumina content is that sodium aluminate solution and the silica content of 48g/l is that 178g/l, sodium oxide content are the water glass of 66g/l, presses Na
2O and Al
2O
3Mol ratio 16: 1, SiO
2And Al
2O
3Mol ratio be 9: 1, H
2O and Al
2O
3Mol ratio be the consumption that 280: 1 ratio has been calculated sodium aluminate solution, water glass, sodium hydroxide and water, attemperation is 47 ℃, under brute force stirs four kinds of raw materials is mixed, and continues to stir after 25 minutes and leaves standstill 49 hours, promptly gets directed agents.
Of the present invention with the method for the washing of the byproduct sodium white residue production in the alumina producing with the 4A zeolite, follow these steps to successively carry out:
The sodium white residue is filtered, prepares burden after the washing, oven dry, promptly with addition of yellow soda ash, is yellow soda ash and sodium white residue 1.15 to prepare burden by the alkali ratio.
Mixed material abundant sintering under 960 ℃～1000 ℃ temperature, sintering 2.5 hours.
Stripping behind levigate mistake 150 mesh sieves of grog that sintering is crossed, the addition of stripping grog is expressed as 105g/l with solid content, Na in the used sodium hydroxide solution of stripping
2The equivalent concentration of O is N
K=28g/l, the stripping temperature is 60 ℃, under agitation carries out, dissolution time 2.2 hours, the directed agents that adds dissolution fluid volume 5% during stripping guides the crystallisation process of zeolite.
After the stripping, do not carry out liquid-solid separation, directly dissolution fluid temperature raising crystallization, 93 ℃ of crystallization temperatures, crystallization time 1.2 hours.
Crystallization finishes, with crystallization filter, dry washing 4A zeolite product.
Embodiment 3
The preparation of directed agents: the preparation alumina content is that sodium aluminate solution and the silica content of 43g/l is that 185g/l, sodium oxide content are the water glass of 63g/l, presses Na
2O and Al
2O
3Mol ratio 11: 1, SiO
2And Al
2O
3Mol ratio be 12: 1, H
2O and Al
2O
3Mol ratio be the consumption that 330: 1 ratio has been calculated sodium aluminate solution, water glass, sodium hydroxide and water, attemperation is 44 ℃, under brute force stirs four kinds of raw materials is mixed, and continues to stir after 27 minutes and leaves standstill 50 hours, promptly gets directed agents;
Of the present invention with the method for the washing of the byproduct sodium white residue production in the alumina producing with the 4A zeolite, follow these steps to successively carry out:
The sodium white residue is filtered, prepares burden after the washing, oven dry, promptly with addition of sodium hydroxide, is sodium hydroxide and sodium white residue 1.22 to prepare burden by the alkali ratio.
Mixed material abundant sintering under 980 ℃～1020 ℃ temperature, sintering 2 hours.
Stripping behind levigate mistake 180 mesh sieves of grog that sintering is crossed, the addition of stripping grog is expressed as 98g/l with solid content, Na in the used sodium hydroxide solution of stripping
2The equivalent concentration of O is N
K=32g/l, the stripping temperature is 65 ℃, under agitation carries out, dissolution time 1.8 hours, the directed agents that adds dissolution fluid volume 3% during stripping guides the crystallisation process of zeolite.
After the stripping, do not carry out liquid-solid separation, directly dissolution fluid temperature raising crystallization, 96 ℃ of crystallization temperatures, crystallization time 2 hours.
Crystallization finishes, with crystallization filter, dry washing 4A zeolite product.
Embodiment 4
Of the present invention with the method for the washing of the byproduct sodium white residue production in the alumina producing with the 4A zeolite, follow these steps to successively carry out:
The sodium white residue is filtered, prepares burden after the washing, oven dry, promptly with addition of yellow soda ash, is yellow soda ash and sodium white residue 1.13 to prepare burden by the alkali ratio.
Mixed material abundant sintering under 1010 ℃～1040 ℃ temperature, sintering 1.8 hours.
Stripping behind levigate mistake 130 mesh sieves of grog that sintering is crossed, the addition of stripping grog is expressed as 104g/l with solid content, Na in the used sodium hydroxide solution of stripping
2The equivalent concentration of O is N
K=36g/l, the stripping temperature is 65 ℃, under agitation carries out, dissolution time 2 hours, the directed agents that adds dissolution fluid volume 2% during stripping guides the crystallisation process of zeolite.After the stripping, do not carry out liquid-solid separation, directly dissolution fluid temperature raising crystallization, 92 ℃ of crystallization temperatures, crystallization time 2 hours.
Crystallization finishes, with crystallization filter, dry washing 4A zeolite product.
Other is with embodiment 1.
Embodiment 5
The preparation of directed agents: the preparation alumina content is that sodium aluminate solution and the silica content of 55g/l is that 200g/l, sodium oxide content are the water glass of 65g/l, presses Na
2O and Al
2O
3Mol ratio 13: 1, SiO
2And Al
2O
3Mol ratio be 13: 1, H
2O and Al
2O
3Mol ratio be the consumption that 310: 1 ratio has been calculated sodium aluminate solution, water glass, sodium hydroxide and water, attemperation is 52 ℃, under brute force stirs four kinds of raw materials is mixed, and continues to stir after 25 minutes and leaves standstill 60 hours, promptly gets directed agents.
Of the present invention with the method for the washing of the byproduct sodium white residue production in the alumina producing with the 4A zeolite, follow these steps to successively carry out:
The sodium white residue is filtered, prepares burden after the washing, oven dry, promptly with addition of yellow soda ash, is yellow soda ash and sodium white residue 0.9 to prepare burden by the alkali ratio.
Mixed material abundant sintering under 860 ℃～900 ℃ temperature, sintering 2.5 hours.
Stripping behind levigate mistake 130 mesh sieves of grog that sintering is crossed, the addition of stripping grog is expressed as 75g/l with solid content, Na in the used sodium hydroxide solution of stripping
2The equivalent concentration of O is N
K=32g/l, the stripping temperature is 75 ℃, under agitation carries out, dissolution time 2 hours, the directed agents that adds dissolution fluid volume 4.5% during stripping guides the crystallisation process of zeolite.
After the stripping, do not carry out liquid-solid separation, directly dissolution fluid temperature raising crystallization, 88 ℃ of crystallization temperatures, crystallization time 1.5 hours.
Crystallization finishes, with crystallization filter, dry washing 4A zeolite product.
Embodiment 6
The preparation of directed agents: the preparation alumina content is that sodium aluminate solution and the silica content of 43g/l is that 190g/l, sodium oxide content are the water glass of 76g/l, presses Na
2O and Al
2O
3Mol ratio 12: 1, SiO
2And Al
2O
3Mol ratio be 12: 1, H
2O and Al
2O
3Mol ratio be the consumption that 310: 1 ratio has been calculated sodium aluminate solution, water glass, sodium hydroxide and water, attemperation is 48 ℃, under brute force stirs four kinds of raw materials is mixed, and continues to stir after 50 minutes and leaves standstill 80 hours, promptly gets directed agents;
Of the present invention with the method for the washing of the byproduct sodium white residue production in the alumina producing with the 4A zeolite, follow these steps to successively carry out:
The sodium white residue is filtered, prepares burden after the washing, oven dry, promptly with addition of sodium hydroxide, is sodium hydroxide and sodium white residue 1.12 to prepare burden by the alkali ratio.
Mixed material abundant sintering under 990 ℃～1020 ℃ temperature, sintering 2 hours.
Stripping behind levigate mistake 160 mesh sieves of grog that sintering is crossed, the addition of stripping grog is expressed as 95g/l with solid content, Na in the used sodium hydroxide solution of stripping
2The equivalent concentration of O is N
K=30g/l, the stripping temperature is 65 ℃, under agitation carries out, dissolution time 1.8 hours, the directed agents that adds dissolution fluid volume 3.5% during stripping guides the crystallisation process of zeolite.
After the stripping, do not carry out liquid-solid separation, directly dissolution fluid temperature raising crystallization, 96 ℃ of crystallization temperatures, crystallization time 2 hours.
Crystallization finishes, with crystallization filter, dry washing 4A zeolite product.
Claims (3)
1, the byproduct sodium white residue production washing in a kind of usefulness alumina producing is characterized in that at first the sodium white residue being purified pre-treatment with the method for 4A zeolite, and it is standby to prepare directed agents, the preparation of directed agents:
The preparation alumina content is that sodium aluminate solution and the silica content of 30～60g/l is that 160～200g/l, sodium oxide content are the water glass of 50～80g/l, presses Na
2O and Al
2O
3Mol ratio (10～18): 1, SiO
2And Al
2O
3Mol ratio be (8～13): 1, H
2O and Al
2O
3Mol ratio be (280～350): 1 ratio has been calculated the consumption of sodium aluminate solution, water glass, sodium hydroxide and water, attemperation is 40～60 ℃, under brute force stirs, four kinds of raw materials are mixed, continue to stir after 10～60 minutes and left standstill 45～100 hours, promptly get directed agents;
Carry out according to following steps successively then:
(1) batching: in the sodium white residue, allocate yellow soda ash or sodium hydroxide into, press alkali number and sodium white residue proportioning respectively with wherein Na
2O and SiO
2+ Al
2O
3Mol ratio be (0.9～1.30): 1 ratio batching mixing;
(2) sintering: the batching that will mix gets grog at 860 ℃～1050 ℃ roasting temperature sintering;
(3) stripping: the grog behind the sintering is pulverized, place sodium hydroxide solution, and adding directed agents, the add-on of directed agents is 1～6% of a dissolution fluid volume, heats stripping and handles, and Heating temperature was 60～80 ℃ during stripping was handled, under agitation carry out, dissolution time 1～3 hour, the addition of stripping grog is expressed as 50～150g/l with solid content, and stripping is 23～40g/l with the sodium oxide concentration of sodium hydroxide solution;
(4) crystallization: dissolution fluid is carried out the degree of crystallinity that the temperature raising crystallization is improved the 4A fluorite, and crystallization temperature is 85～98 ℃, and crystallization time is 1～3 hour, must wash crystallization through aftertreatment and use the 4A zeolite product.
2, method according to claim 1 is characterized in that the chamotte powder behind the sintering is broken to and lacked 120 mesh sieves in the stripping processing.
3, method according to claim 1 is characterized in that the sodium aluminate solution that uses in the directed agents is that alkali one lime sinter process is produced the intermediate product in the alumina process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410023916 CN1286722C (en) | 2004-04-14 | 2004-04-14 | Method for producing 4A zeolite for washing use from byproduct sodium silica slag generated in producing alumina |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410023916 CN1286722C (en) | 2004-04-14 | 2004-04-14 | Method for producing 4A zeolite for washing use from byproduct sodium silica slag generated in producing alumina |
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| Publication Number | Publication Date |
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| CN1562748A CN1562748A (en) | 2005-01-12 |
| CN1286722C true CN1286722C (en) | 2006-11-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200410023916 Expired - Lifetime CN1286722C (en) | 2004-04-14 | 2004-04-14 | Method for producing 4A zeolite for washing use from byproduct sodium silica slag generated in producing alumina |
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| CN (1) | CN1286722C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139099B (en) * | 2007-05-22 | 2010-05-19 | 中国铝业股份有限公司 | Technique for producing 4A zeolite by using sodium white slime |
| CN102976353A (en) * | 2012-12-05 | 2013-03-20 | 北京科技大学 | Method for preparing 4A molecular sieve from bauxite tailings |
| CN104291354B (en) * | 2013-07-20 | 2017-02-08 | 东北大学 | Method for preparation of zeolite 4A and vanadium-titanium catalyst from vanadium slag |
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