CN115231596A - Industrial preparation method of bayer stone - Google Patents
Industrial preparation method of bayer stone Download PDFInfo
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- CN115231596A CN115231596A CN202210938596.4A CN202210938596A CN115231596A CN 115231596 A CN115231596 A CN 115231596A CN 202210938596 A CN202210938596 A CN 202210938596A CN 115231596 A CN115231596 A CN 115231596A
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- seed crystal
- sodium aluminate
- aluminate solution
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- 239000004575 stone Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 57
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000706 filtrate Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 20
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 18
- 239000012065 filter cake Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 26
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 13
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000006386 neutralization reaction Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 49
- 239000007789 gas Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 239000003518 caustics Substances 0.000 description 4
- 229910001679 gibbsite Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 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 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001647 dawsonite Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
- C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
- C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
- C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
A method for the industrial preparation of Bayer stones. NaHCO is used in the invention 3 And preparing a seed crystal 1 and a seed crystal 2 by a neutralization method, adding the seed crystal 1 into the sodium aluminate solution for seed decomposition, and then filtering, washing and drying the decomposition slurry to obtain the superfine aluminum hydroxide. Adding crystal seed 2 into sodium aluminate solution, and introducing CO 2 After a certain period of time of carbon decomposition, the slurry is filtered, and the filter cake is washed and dried to obtain the catalyst bayer stone. The filtrate is continuously introduced with CO 2 Until complete decomposition, filtering, delivering the filter cake to an aluminum hydroxide recovery system, and continuously introducing CO into the filtrate 2 Until the pH value reaches about 9.0, the solution enters a seed crystal 1 and seed crystal 2 preparation system to realize NaHCO 3 The recycling of (2).
Description
Technical Field
The invention relates to the field of inorganic material preparation, in particular to a deep processing method of an aluminum hydroxide production method.
Background
Bayer's stone (beta-Al (OH) 3)]Is an important aluminum hydroxide with higher surface energy than Gibbsite (Gibbsite), a variant of alumina fired with bayer alumina (. Eta. -Al) 2 O 3 ) Generally has higher specific surface area and relative active sites, and has important application as a catalyst in the field of petrochemical industry. Furthermore, the Bayer stones may also be used for the production of lithium-aluminium layered double hydroxides ([ LiAl2 (OH) 6 ] for ion exchange]ClxH 2O), and has a certain application prospect in the battery industry. No bayer stone with a specific particle size of 20-30 microns is currently available on the market. The Bayer stone with the grain diameter is used as a catalyst. . . . . And the like, are expected.
Furthermore, the preparation of bayer stones is usually carried out by using low-temperature natural decomposition, CO, of a sodium aluminate solution 2 Decomposition, neutralization, etc. The low-temperature decomposition method needs higher cold quantity, and has the disadvantages of slow decomposition speed, low yield and difficult industrial operation. The neutralization method needs a certain amount of acid or aluminum salt, the by-product is difficult to recover, and the operation cost is high. CO 2 2 The raw material adopted by the decomposition method is CO 2 Due to CO 2 Is a greenhouse gas, so the method can reduce the emission of the greenhouse gas while generating the Bayer stones, and has positive significance to the environment. But CO 2 The decomposition method produces a large amount of Na 2 CO 3 The Na being 2 CO 3 Can not be directly sold as industrial raw materials, thus the method is almost industrial waste for enterprises, and not only wastes materials, but also is an environmental burden.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a bayer stone having a particle size of 20 to 30 μm.
Another technical problem solved by the present invention is to achieve the recycling of sodium carbonate by-product in the industrial production process of bayer stone.
According to an aspect of the invention, naHCO is used 3 The seed crystal prepared by neutralization method is used for preparing beta-aluminum hydroxide (Bayer stone) by carbonation, and in the preferable aspect, superfine aluminum hydroxide is also simultaneously produced to realize NaHCO 3 The alkali balance of the system is achieved.
The invention is realized by the following technical scheme:
a process for the industrial preparation of bayer stone, comprising the steps of:
1) Introducing CO into the sodium aluminate solution 2 in the presence of a seed crystal 2 2 Carrying out carbon decomposition to obtain slurry 1;
2) Filtering the slurry 1 to obtain a filter cake 1 and a filtrate 1, washing the filter cake 1, and drying and dispersing to obtain a bayer stone powder;
3) Introducing CO into the filtrate 1 2 Obtaining slurry 2, and filtering the slurry 2 to obtain filtrate 2 and a filter cake 2;
4) Introducing CO into the filtrate 2 2 Obtaining sodium bicarbonate solution;
5) Mixing the sodium bicarbonate solution with a sodium aluminate solution 1 to prepare a seed crystal, wherein the seed crystal at least comprises the seed crystal 2 in the step 1).
In the present invention, naHCO is used 3 Neutralizing the aqueous solution with the sodium aluminate fine solution to prepare seed crystals, and optionally adding a part of the seed crystals into the sodium aluminate solution to prepare superfine aluminum hydroxide; adding another part of seed crystal into the sodium aluminate solution, and adding CO 2 Introducing sodium aluminate solution to separate out beta-aluminum hydroxide, washing, filtering to obtain product, introducing CO into the filtrate 2 Separating out residual Al component, recovering the residual Al component for preparing sodium aluminate solution, and continuously introducing CO into the filtrate 2 To saturation, naHCO is obtained 3 The solution was used to prepare seeds. The method realizes the recycling of sodium carbonate without waste discharge, and can obtain the Bayer stone with the single crystal grain diameter range of 20-35 mu m and the uniform grain size.
Drawings
FIG. 1 is a specific flow chart of the production method according to the present invention;
FIG. 2 is an XRD diffractogram of the Bayer pattern prepared in example 1;
FIG. 3 is an XRD diffractogram of the Bayer pattern prepared in example 2;
FIG. 4 is an XRD diffractogram of the Bayer stone morphology prepared in example 3;
FIG. 5 is an XRD diffractogram of the Bayer pattern prepared in comparative example 1;
FIG. 6 is an XRD diffractogram of the Bayer stone morphology prepared in comparative example 2;
FIG. 7 is a Scanning Electron Microscope (SEM) image of the Bayer stone prepared in example 1;
FIG. 8 is a Scanning Electron Microscope (SEM) image of the Bayer stone prepared in example 2;
FIG. 9 is a Scanning Electron Microscope (SEM) image of the Bayer stone prepared in example 3;
FIG. 10 is a Scanning Electron Microscope (SEM) image of the Bayer stone morphology prepared in comparative example 1;
FIG. 11 is a Scanning Electron Microscope (SEM) image of the Bayer stone morphology prepared in comparative example 2.
Detailed Description
Alpha mentioned in the present disclosure k And N k Have the ordinary meaning in the art. In particular, na of sodium aluminate solution 2 O content, including Na, which reacts with alumina to form sodium aluminate 2 O and free Na in the form of NaOH 2 O, which are caustic alkalis and are designated as Nk, is the content of Na in the sodium aluminate solution 2 The concentration of NaOH expressed as O. Caustic Na in sodium aluminate solution 2 O and Al 2 O 3 Is recorded as alpha k 。
Preparation of seed crystals
The aluminum hydroxide seed crystals were prepared by reacting sodium bicarbonate solution with sodium aluminate solution 1. In the present invention, the aluminum hydroxide seed crystals include a seed crystal 1 for preparing ultra-fine aluminum hydroxide from a sodium aluminate solution and a seed crystal 2 for preparing bayer stone, and the sodium aluminate solution 1 for preparing both seed crystals may be the same material, for example, have the same α k The value is obtained. The sodium aluminate solution 1 may be obtained by dissolving industrial aluminum hydroxide in caustic alkali, or may be a filtrate obtained by leaching aluminum from bauxite with caustic alkali and separating red mud, and the main component thereof is sodium aluminate containing a certain amount of impurities such as oxalate converted from organic matter during bauxite leaching. Alpha of sodium aluminate solution 1 suitable for the invention k The value is between 1.3 and 1.8, preferably between 1.4 and 1.6. Al (Al) 2 O 3 The concentration is suitably from 80g/L to 160g/L, preferably from 100g/L to 120g/L, more preferably from 140g/L to 160g/L.
To prepare forAnd (2) seed crystal, namely, putting the sodium bicarbonate solution into the sodium aluminate solution 1, and reacting at the temperature of not higher than 30 ℃. The sodium bicarbonate solution can be prepared by using commercial industrial products, and can also be the sodium bicarbonate aqueous solution obtained in the process step of the invention. NaHCO in sodium bicarbonate solution 3 Mole number and OH in sodium aluminate solution 1 - At a molar ratio of 2-4: 1. The seed crystals 2 thus obtained are substantially pseudoboehmite and bayer, substantially free of other constituents, and have a particle size in the range of 1-2 μm. By using the seed crystal 2 having such a particle diameter, a bayer having a particle diameter of 20 to 30 μm can be obtained. The crystallization time does not exceed 30 minutes and is too long, otherwise the purity of the bayer stone is deteriorated and the bayer stone is gradually converted into gibbsite.
For the preparation of the seed crystal 1, the same sodium bicarbonate solution as described above can be used to react with the sodium aluminate solution 1 at a temperature of not higher than 40 ℃. The grain size of the crystal grains 1 obtained under this condition is in the range of 0.1 to 0.7 μm.
Preparation of Bayer stone by carbonation
In the present invention, the seed crystal 2 is charged into the sodium aluminate solution 2 in proportion, and the temperature of the solution is maintained between 20 and 50 ℃, preferably not more than 40 ℃, more preferably not more than 30 ℃. At lower temperatures, better purity can be achieved. Introducing CO at a set speed at the temperature 2 。
Sodium aluminate solution 2 is preferably alpha k A value of 1.4 to 1.8 k Solutions with values of 45-150g/L, more preferably alpha k A value of 1.4 to 1.6 k Solutions with values of 80-150g/L. The seed crystal 2 is introduced in an amount of 0.3 to 2.0%, preferably 0.3 to 1.0% by mass of the sodium aluminate solution 2. The mass of the precipitated bayer stone gradually increases as the decomposition proceeds. N of sodium aluminate solution k The value decreases gradually, when the Nk value decreases to the interval of 10-25g/L, 85-92% of aluminum in the sodium aluminate solution is precipitated in the form of Bayer stones, and the reaction is stopped at this time.
CO for use in the invention 2 The purity of the gas is not particularly critical, CO 2 May be provided in the form of a gas mixture, CO 2 The content therein is preferably not less than 20%. The preferred source is the energy released after the plant consumes natural gas or coalReleased gas containing CO 2 Of the exhaust gas of (1). It is understood that the mixed gas must not contain other reactive gases.
The obtained slurry 1 was filtered to obtain a filtrate 1 and a cake 1. And washing, dispersing and drying the filter cake 1 to obtain the target product of the Bayer stone. The particle size of the bayer stone obtained according to the present invention is in the range of 20 to 30 microns, which is particularly desirable for use in the manufacture of eta-alumina catalysts for alkyl dehydrogenation, or other alumina catalysts. The coarse particle size is beneficial to washing and pore distribution and forming of downstream catalysts. CO 2 2 Excessive introduction can mix impurities into the product, insufficient introduction can separate out insufficient product, and the yield is reduced.
Removing aluminum from filtrate 1
Continuously introducing CO into the filtrate 1 2 When solid is precipitated, the aim of the step is to remove the aluminum in the filtrate as much as possible, judge the reaction end point by detecting the aluminum content (calculated by aluminum hydroxide) in the solution, for example, when the aluminum content is less than or equal to 1 percent, stop introducing CO 2 . In the case of other process parameter determinations, it is also possible to set the CO feed 2 The endpoint is controlled.
The obtained slurry 2 was filtered to obtain a cake 2 and a filtrate 2. The filter cake 2 is essentially a mixture of aluminium hydroxide and dawsonite which can all be formulated into a sodium aluminate solution to be returned to the process.
Preparation of sodium bicarbonate solution
The filtrate 2 is essentially a mixture of sodium hydroxide and sodium carbonate, with an aluminium content of less than 1% calculated as aluminium hydroxide. Continuously introducing CO into the reactor 2 At a pH of 9.0, almost all of the sodium carbonate is converted to sodium bicarbonate, and a pure aqueous sodium bicarbonate solution is obtained.
Preparation of superfine aluminium hydroxide
The process for seeding the sodium aluminate solution 3 with the seed crystals 1 can adopt the mature process in the prior art. The crystal seeds 1 prepared by the applicant company in the invention have the particle size of 0.1-0.7 micron, and are used for dissolving sodium aluminateAnd (3) obtaining the superfine aluminum hydroxide with the D50 of 1-2 microns. In a typical embodiment, α of the sodium aluminate solution 3 k The value is 1.50,N k The value was 140g/L. . The amount of the seed crystal 1 to be introduced is about 1 to 10% by mass based on the sodium aluminate solution.
The present invention will be further described with reference to the following examples.
Example 1:
(1) 50g/L NaHCO 3 The aqueous solution is slowly added to 30 ℃ sodium aluminate concentrate (alpha) k Is 1.45,N k 150 g/L), aging for 30 minutes after the addition is finished to obtain seed crystals, and measuring the solid content to be 65g/L;
(2) According to the seed crystal ratio of 0.5%, al (OH) prepared by the step (1) 3 Seed crystal, slowly adding into 40 deg.C sodium aluminate concentrate (alpha) k Is 1.45,N k 150 g/L), followed by passing CO with a purity of 99.5% at 1.2L/min 2 Gas is used for 60min, and N in the sodium aluminate solution is measured k Is 15g/L;
(3) And (3) filtering the slurry finally obtained in the step (2), filtering, washing and drying a filter cake to obtain beta-aluminum hydroxide for the catalyst, wherein the granularity is basically in the range of 20-30 mu m, the XRD of the product is shown in figure 1, and the crystal morphology is shown in figure 7. Calcining the obtained beta-aluminum hydroxide at 400 ℃ for 60min, and measuring the specific surface area of the alumina to be 260m 3 /g；
(4) And (3) mixing the filtrate obtained in step (3) according to the proportion of 1:1 adding deionized water, continuing to introduce CO with a purity of 99.5% at 1.2L/min 2 Gas up to Al in the slurry 2 O 3 The amount was 3g/L, the slurry was filtered and the filter cake was sent to Al (OH) 3 A dissolving system for preparing sodium aluminate solution;
(5) Filtering the filtrate of (4) with purity of 99.5% CO 2 Gas, until the pH value of the solution does not change, the obtained NaHCO is used 3 And (2) feeding the aqueous solution to the seed crystal preparation process in the step (1).
Example 2:
(6) 60g/L NaHCO 3 The aqueous solution is slowly added to 30 ℃ sodium aluminate concentrate (alpha) k Is 1.45,N k 150 g/L), aging for 25 minutes after the addition is finished to obtain seed crystals, and measuring the solid content to be 55g/L;
(7) Al (OH) prepared from (6) at a seed crystal ratio of 0.8% 3 Seed crystal, slowly adding into 30 deg.C sodium aluminate concentrate (alpha) k Is 1.45,N k 80 g/L), followed by passing in purity 80% CO at 1.5L/min 2 Gas is used for 45min, and the N in the sodium aluminate solution is measured k Is 12g/L;
(8) And (3) filtering the slurry finally obtained in the step (7), filtering, washing and drying a filter cake to obtain beta-aluminum hydroxide for the catalyst, wherein the granularity is basically in the range of 20-30 mu m, the XRD of the product is shown in figure 3, and the crystal morphology is shown in figure 8. Calcining the obtained beta-aluminum hydroxide at 400 ℃ for 60min, and measuring the specific surface area of the alumina to be 310m 3 (iv) g; example 3:
(9) Al (OH) prepared from (6) at a seed crystal ratio of 0.8% 3 Seed crystal, slowly adding into 45 deg.C sodium aluminate concentrate (alpha) k Is 1.8,N k 45 g/L), followed by passing through 80% CO at 1.0L/min purity 2 Gas is used for 65min, and the N in the sodium aluminate solution is measured k Is 18g/L;
(8) Filtering the slurry finally obtained in the step (7), filtering, washing and drying a filter cake to obtain the beta-aluminum hydroxide used for the catalyst, wherein the granularity is basically in the range of 20-30 mu m, the XRD of the product is shown in figure 4, and the crystal morphology is shown in figure 9. Calcining the obtained beta-aluminum hydroxide at 400 ℃ for 60min to obtain the alumina with the specific surface area of 230m 3 (ii)/g; comparative example 1:
(9) N of the slurry of sodium aluminate solution described in (2) in example 1 k The value is controlled to be 3g/L, other conditions are not changed, the obtained slurry is filtered, the obtained filter cake is washed and dried, the obtained product contains amorphous aluminum hydroxide, XRD is shown in figure 5, and crystal morphology is shown in figure 10.
Comparative example 2:
(10) The temperature of the sodium aluminate solution of (6) in example 2 was raised to 70 ℃, other conditions were not changed, the obtained slurry was filtered, and the obtained filter cake was washed and dried, and the obtained product contained Gibbsite (α -aluminum hydroxide) XRD as shown in fig. 6, and the crystal morphology as shown in fig. 11.
The embodiments chosen for the purpose of this invention are to be considered as illustrative and not restrictive, the scope of the invention being indicated by the claims. It will be apparent to those skilled in the art that certain insubstantial modifications and adaptations of the present invention can be made without departing from the spirit and scope of the invention.
Claims (12)
1. A process for the industrial preparation of bayer stone, comprising the steps of:
1) Introducing CO into the sodium aluminate solution 2 in the presence of a seed crystal 2 2 Carrying out carbon decomposition to obtain slurry 1;
2) Filtering the slurry 1 to obtain a filter cake 1 and a filtrate 1, washing the filter cake 1, and drying and dispersing to obtain a bayer stone powder;
3) Introducing CO into the filtrate 1 2 Obtaining slurry 2, and filtering the slurry 2 to obtain filtrate 2 and a filter cake 2;
4) Introducing CO into the filtrate 2 2 Obtaining sodium bicarbonate solution;
5) Mixing the sodium bicarbonate solution with a sodium aluminate solution 1 to prepare a seed crystal, wherein the seed crystal at least comprises the seed crystal 2 in the step 1).
2. The preparation method of claim 1, wherein the seed crystal in the step 5) further comprises a seed crystal 1, and the seed crystal 1 is used for preparing the ultra-fine aluminum hydroxide and has a particle size of 0.1-0.7 μm.
3. The preparation process according to claim 1, wherein α of said sodium aluminate solution 1 in step 5) is k Is 1.4-1.6.
4. The method according to claim 1, wherein in step 5), naHCO is added to the sodium bicarbonate solution 3 The molar ratio of the number of moles to OH < - > in the sodium aluminate solution 1 is 2-4: 1.
5. The production method according to claim 1, wherein, in the step 5), the temperature at which the seed crystal 2 is produced is not higher than 30 ℃.
6. The production method according to claim 1, wherein the seed crystal 2 has a particle diameter of 1 to 2 μm.
7. The method for preparation according to claim 1, wherein in step 1), the temperature of the sodium aluminate solution 2 is maintained between 20-50 ℃.
8. The method for preparing as claimed in claim 7, wherein, in step 1), α of sodium aluminate solution 2 is k The value is 1.4-1.6, and the Nk value is 80-150g/L.
9. The production method according to claim 8, wherein, in the step 1), the seed crystal 2 is introduced in an amount of 0.3 to 1.0% by mass as N based on the mass of the sodium aluminate solution 2 k When the value decreases to the range of 10-25g/L, the reaction is stopped.
10. The production method according to claim 2, wherein, in the step 5), the temperature at which the seed crystal 1 is produced is not higher than 40 ℃.
11. The method for preparing as claimed in claim 10, further comprising a step 6) of preparing ultra fine aluminum hydroxide by using the seed crystal 1 of the sodium aluminate solution 3.
12. The method for preparing sodium aluminate solution 3 according to claim 11, wherein, in step 6), α of sodium aluminate solution 3 is k Is 1.4-1.6.
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