CN103708511B - A kind of technique producing pseudo-boehmite - Google Patents
A kind of technique producing pseudo-boehmite Download PDFInfo
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- CN103708511B CN103708511B CN201310705529.9A CN201310705529A CN103708511B CN 103708511 B CN103708511 B CN 103708511B CN 201310705529 A CN201310705529 A CN 201310705529A CN 103708511 B CN103708511 B CN 103708511B
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- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 74
- 239000000047 product Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000010009 beating Methods 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 239000003002 pH adjusting agent Substances 0.000 claims description 7
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- -1 alkyl carboxylic acid Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 10
- 230000008859 change Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 37
- 230000001276 controlling effect Effects 0.000 description 22
- 238000004131 Bayer process Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 14
- 229910017604 nitric acid Inorganic materials 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 229910001593 boehmite Inorganic materials 0.000 description 11
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 8
- 229910001679 gibbsite Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 229910002706 AlOOH Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 239000001433 sodium tartrate Substances 0.000 description 2
- 229960002167 sodium tartrate Drugs 0.000 description 2
- 235000011004 sodium tartrates Nutrition 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 241000446313 Lamella Species 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- CMNWUCGLNTVCSI-UHFFFAOYSA-J [Na+].[Na+].[Na+].[Na+].[Cl-].[O-]P([O-])([O-])=O Chemical compound [Na+].[Na+].[Na+].[Na+].[Cl-].[O-]P([O-])([O-])=O CMNWUCGLNTVCSI-UHFFFAOYSA-J 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
The present invention relates to a kind of technique producing pseudo-boehmite, comprise the steps: that adding pH value regulator, control agent and water in aluminum-containing raw material reacts; Mix under room temperature, stir making beating; It is incubated under mixed pulp 100-400 DEG C of condition and stirs making beating 0.5-30 hour; Filtered and recycled product, the filtrate after filtration is reclaimed and is reacted; Product is dried; Product powder grinds. Multiple alumina-bearing material can be used as raw materials for production, applied widely, only need the kind by change pH value regulator, control agent or consumption need not change production unit and step, the quality product that can meet the different market requirements and production is qualified. As long as the filtrate after filtration adjusts the kind of pH value and other control agent and quantity just can reclaim use, minimizing blowdown, very environmental protection; Product does not need repeatedly to wash.
Description
Technical field
The present invention relates to field of aluminum oxide production, it is specifically related to a kind of technique producing pseudo-boehmite.
Background technology
Pseudo-boehmite (pseudoboehmite) a kind of forms chemical aluminum oxide uncertain, that crystallization is imperfect, thus performance is controlled, and chemical formula is ��-AlOOH nH2O (n=0.08��0.62), its crystalline structure is similar with boehmite (��-AlOOH), is typical very thin fold lamella. Product ��-the Al of pseudo-boehmite roasting between 400-700 DEG C2O3It is widely used as support of the catalyst, catalyzer and sorbent material etc.; And calcining can obtain nanometer alpha-Al between 1100-1200 DEG C2O3, it is widely used as paint additive, high-grade ceramic, the effective catalyst of petrochemical complex, submicron/nanometer level abrasive substance and polishing material, makeup filler and inorganic material film etc., it is the type material that a class has wide development prospect.
The preparation of pseudo-boehmite comprise alcohol aluminium hydrolysis method, the alkaline neutralisation of acid aluminium salt, aluminate acidifying method, softening learn tensio-active agent assembling method and microemulsion method etc., which kind of method all also exists very big defect, some costs are very high and processing parameter slightly fluctuates just produces mutually assorted or produces other materials, it is very difficult to industrialization; Even the alkali method taking alumina producer intermediate sodium aluminate solution as raw material that everybody generally adopts, not only need the processing parameters such as strict controlling temperature, concentration, pH value, and technical process is complicated, even if also can not get the pseudo-boehmite of different crystallization series like this; In addition, pseudo-boehmite prepared by this method extracts the strong alkali solution from certain alumina concentration (i.e. sodium aluminate solution), and product alkalescence is very strong, it is necessary to just can reach index with a large amount of water washings; In addition, this method can't carry out carbonating thoroughly, and all the time containing a certain amount of aluminum oxide and a large amount of sodium carbonate in mother liquor, this has increased the weight of Production Flow Chart and burden undoubtedly.
USP3357791 has prepared boehmite or the boehmite of colloidal particle size by raw material of aluminum ethylate and acetic acid higher than 150 DEG C of heating; USP5194243 is taking nano level aqueous alumina as raw material, it is desired to taking the boehmite of the median diameter 50nm of harshness as Spawn preparation boehmite; USP4797139 when controlling pH with lower than the boehmite of 20-100nm or ��-Al2O3For seed produces boehmite or pottery split; Aforesaid method or technique or taking expensive aluminum ethylate as raw material, or need the very little nano level boehmite of median diameter to be seed, during this kind of Spawn preparation, flow process is very long, and cost is also very high; Filippou etc. once proposed to separate boehmite from Bayer process wrought aluminum acid sodium solution kind taking the boehmite of the gibbsite hydrothermal product-complete crystallization at 115��145 DEG C as crystal seed, produce metallurgical-grade aluminum oxide after roasting. According to a preliminary estimate, the total energy consumption that the latter produces aluminum oxide is only the former 1/4. They think simultaneously, and between 100��250 DEG C, boehmite is that unique kind divides a product, can not get pseudo-boehmite.
Visible pseudo-boehmite production method of the prior art has the defects such as cost height, process parameter control difficulty, ingredient requirement is harsh, the different demands that are difficult to meet in different industrial application to pseudo-boehmite, it is very difficult to suitability for industrialized production.
Summary of the invention
In order to solve above technical problem, the present invention provides a kind of technique producing pseudo-boehmite, solves the problem that ingredient requirement is harsh and product can not meet in industrial application the different demands to pseudo-boehmite.
The present invention is achieved through the following technical solutions:
Produce a technique for pseudo-boehmite, comprise the steps:
(1) in aluminum-containing raw material, add pH value regulator and/or control agent, add water and react;
(2) mix under room temperature, stir making beating;
(3) mixed pulp is incubated and stirs making beating;
(4) filtered and recycled product, the filtrate after filtration is recovered to step (1) again and reacts;
(5) product is dried;
(6) product powder mill.
In technique scheme, described aluminum-containing raw material accounts for the 90%-99.99% of reactant gross weight.
In technique scheme, the mol ratio of described pH adjusting agent and aluminum-containing raw material is 0.1:1��1:90.
In technique scheme, described control agent comprises one or more in crystalline controlling agent, guiding control agent, specific surface control agent and stability control agent.
In technique scheme, described crystalline controlling agent comprises one or more in sodium salt, ammonium salt, acid or alkali.
One in technique scheme, in described guiding control agent comprises aluminum nitrate, the molar content of crystal water is 0.08��2.2 hydrated aluminum oxide, formic acid or acetic acid.
In technique scheme, described specific surface control agent comprises the one in non-ionic type specific surface control agent, anionic specific surface control agent, alkyl benzene sulphonate (ABS) analogy granule surface contral agent or alkyl carboxylic acid analogy granule surface contral agent.
In technique scheme, described stability control agent comprises rare earth element and transition metal.
In technique scheme, described mixed pulp holding temperature is 100-400 DEG C, and stirring beating time is 0.5-30 hour.
In technique scheme, described product bake out temperature 80-150 DEG C, drying time 1-8h.
The present invention is owing to can use multiple alumina-bearing material as raw materials for production, applied widely, only needing the kind by change pH value regulator, control agent or consumption need not change production unit and step, the quality product that can meet the different market requirements and production is qualified. As long as the filtrate after filtration adjusts the kind of pH value and other control agent and quantity just can reclaim use, minimizing blowdown, very environmental protection; Product does not need repeatedly to wash, and direct filtration just can obtain qualified product after completion of the reaction.
Accompanying drawing explanation
The process flow sheet of the production pseudo-boehmite that Fig. 1 provides for the embodiment of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the technical scheme of the present invention is described in detail.
Embodiment 1
Count in molar ratio, Bayer process produce dry gibbsite 25.6 moles, 0.25 mol sulfuric acid ammonium as crystalline controlling agent, 5.12 moles containing aluminium hydrate (its crystal water be 0.56 mole as guiding control agent), add water and mix, be about 3 by pH value regulator nitric acid adjust ph; Above-mentioned substance is mixed, compound at room temperature 100 revs/min stir 20 minutes, be warming up to 180 DEG C thereafter again with the rotating speed of 100 revs/min insulation 5h; Reactant filters, dries, bake out temperature 80-150 degree, time 1-8h; Wherein in reaction system, solid-to-liquid ratio is 2:1.
Embodiment 2
Counting in molar ratio, the wet gibbsite 38 moles that Bayer process is produced, 1 mol sulfuric acid sodium, as crystalline controlling agent, after suitable quantity of water mixes, is about 3 by pH adjusting agent nitric acid adjust ph; Stir 20 minutes under the lower 100 revs/min of rotating speeds of compound room temperature, then it is warming up to 180 DEG C again with the rotating speed insulation 5h of 100 revs/min; Reactant filters, dries, bake out temperature 80-150 degree, time 1-8h; Wherein in reaction system, solid-to-liquid ratio is 3:1.
Embodiment 3
Count in molar ratio, the Bayer process of high-temperature roasting produces gibbsite 15 moles, 1.0 mol sulfuric acid ammoniums are as crystalline controlling agent, after suitable quantity of water mixes, stirring when being about 3 by pH adjusting agent nitric acid adjust ph, mixing speed 150-400 rev/min stirs 20 minutes, it is warming up to 200 DEG C again with 150-400 rev/min of rotating speed insulation 2h, reactant filters, dries, bake out temperature 80-150 degree, time 1-8h; In reaction system, solid-to-liquid ratio is 4:1.
Embodiment 4
Count in molar ratio, the Bayer process of 1.15 moles of dry three water-aluminum hydroxides of Bayer process product, 0.15 mole of high-temperature roasting produces three water-aluminum hydroxides as guiding control agent, ammonium sulfate and sodium sulfate mixing salt be three water-aluminum hydroxide mole numbers of high-temperature roasting 1% as crystalline controlling agent, after suitable quantity of water mixes, by pH adjusting agent nitric acid adjust ph about 3, mixing speed 150-400 rev/min stirs 20 minutes, it is warming up to 200 DEG C again with 150-400 rev/min of rotating speed insulation 3h, reactant filters, dries, bake out temperature 80-150 degree, time 1-8h; In reaction system, solid-to-liquid ratio is 4:1.
Embodiment 5
Count in molar ratio, three water-aluminum hydroxides of 1.15 moles of Bayer process products, the Bayer process of 0.15 mole of high-temperature roasting produce three water-aluminum hydroxides as guiding control agent, 0.007 mole, sodium sulfate is as crystalline controlling agent, after suitable quantity of water mixes, by pH value regulator ammoniacal liquor and sodium hydroxide adjust ph about 11, mixing speed 150-400 rev/min stirs 20 minutes, it is warming up to 220 DEG C again with 150-400 rev/min of rotating speed insulation 2h, reactant filters, dries, bake out temperature 80-150 degree, time 1-8h; In reaction system, solid-to-liquid ratio is 2:1.
Embodiment 6
Count in molar ratio, the Bayer process of 0.196 mole of high-temperature roasting produces three water-aluminum hydroxides, after suitable quantity of water mixes, by pH value regulator bicarbonate of ammonia adjust ph about 8, mixing speed 150-400 rev/min stirs 20 minutes, is warming up to 200 DEG C again with 150-400 rev/min of rotating speed insulation 3h, and reactant filters, dries, bake out temperature 80-150 degree, time 1-8h; In reaction system, solid-to-liquid ratio is 3:1.
Embodiment 7
Count in molar ratio, the dry gibbsite 25.6 moles that Bayer process is produced, 0.25 mol sulfuric acid ammonium is as crystalline controlling agent, 5.12 moles containing aluminium hydrate (its crystal water is 0.56 mole), after suitable quantity of water mixes, by pH value regulator nitric acid adjust ph about 3, mixing speed 100 revs/min stirs 20 minutes, it is warming up to 180 DEG C again with 100 revs/min of rotating speed insulation 5h, after reaction terminates, it is 8��11 that slurries are adjusted to pH while stirring, in about room temperature to 90 DEG C, temperature stirs 1��8h, reactant filters, dry, bake out temperature 80-150 degree, time 1-8h, in reaction system, solid-to-liquid ratio is 2:1.
Embodiment 8
Count in molar ratio, the wet gibbsite 38 moles that Bayer process is produced, 1 mol sulfuric acid sodium is as crystalline controlling agent, 5.12 moles containing aluminium hydrate (its crystal water is 0.56 mole), after suitable quantity of water mixes, it is about 3 by pH value regulator nitric acid adjust ph, mixing speed 100 revs/min stirs 20 minutes, it is warming up to 180 DEG C again with 100 revs/min of rotating speed insulation 5h, after reaction terminates, it is 8��11 that slurries are adjusted to pH while stirring, in about room temperature to 90 DEG C, temperature stirs 1��8h, reactant carries out taking out filter separation, dry filter cake, bake out temperature 80-150 degree, time 1-8h, in reaction system, solid-to-liquid ratio is 3:1.
Embodiment 9
Count in molar ratio, the Bayer process of high-temperature roasting produces gibbsite 15 moles, 1.0 mol sulfuric acid sodium as crystalline controlling agent, after suitable quantity of water mixes, it is about 4 by pH value regulator nitric acid adjust ph, mixing speed 150-400 rev/min stirs 20 minutes, and after reaction terminates, it is 8��11 that slurries are adjusted to pH while stirring, in about room temperature to 90 DEG C, temperature stirs 1��8h, reactant carries out taking out filter separation, drying filter cake, bake out temperature 90 DEG C, time 6h; In reaction system, solid-to-liquid ratio is 4:1.
Embodiment 10
Count in molar ratio, 1.15 moles of Bayer process produce dry three water-aluminum hydroxides, the Bayer process of 0.15 mole of high-temperature roasting produces three water-aluminum hydroxides as guiding control agent, ammonium sulfate and sodium sulfate mixing salt be three water-aluminum hydroxide mole numbers of high-temperature roasting 0.1% as crystalline controlling agent, after suitable quantity of water mixes, it is about 5 by pH value regulator nitric acid adjust ph, mixing speed 150-400 rev/min stirs 20 minutes, after reaction terminates, it is 8��11 that slurries are adjusted to pH while stirring, in about room temperature to 90 DEG C, temperature stirs 1��8h, reactant carries out taking out filter separation, dry filter cake, bake out temperature 90 DEG C, time 1-8h, in reaction system, solid-to-liquid ratio is 4:1.
Embodiment 11
2L water adds three water-aluminum hydroxides of 160g high-temperature roasting, then 32g guiding control agent (hydrated aluminum oxide containing crystal water 0.08 mole) is added, after suitable quantity of water mixes, by pH adjusting agent nitric acid adjust ph about 5, control temperature of reaction is 150 DEG C, stirring velocity is 200 revs/min, reaction 3h. After reaction terminates, regulate pH to be 9, carry out filtering separation subsequently, by filter cake in 100 DEG C of dry 3h. In reaction system, solid-to-liquid ratio is 4:1.
Embodiment 12
2L water adds three water-aluminum hydroxides of 160g high-temperature roasting, then add 32g lead control agent (hydrated aluminum oxide containing crystal water 0.08 mole) and 5g cetyl trimethylammonium bromide as specific surface control agent, suitable quantity of water mixes abundant stirring, by pH value regulator nitric acid adjust ph about 5, control temperature of reaction is 150 DEG C, stirring velocity is 200 revs/min, reaction 3h. After reaction terminates, regulate pH to be 9, carry out filtering separation subsequently, by filter cake in 100 DEG C of dry 3h. In reaction system, solid-to-liquid ratio is 3:1.
Embodiment 13
Count in molar ratio, the dry gibbsite 25.6 moles that Bayer process is produced, 0.25 mol sulfuric acid ammonium is as crystalline controlling agent, 5.12 moles containing aluminium hydrate (its crystal water is 0.56 mole) as guiding control agent, the PEG-4000 of 0.1 mole is as specific surface control agent, after suitable quantity of water mixes, by pH value regulator nitric acid adjust ph about 3; At room temperature 100 revs/min are stirred 20 minutes, are then warming up to 180 DEG C again with the rotating speed insulation 5h of 100 revs/min. After reaction terminates, being adjusted to pH by pH adjusting agent is 9, carries out filtering separation subsequently, by filter cake in 100 degree of dry 3h. In reaction system, solid-to-liquid ratio is 4:1.
Embodiment 14
Count in molar ratio, 1.15 moles of Bayer process produce dry three water-aluminum hydroxides, the Bayer process of 0.15 mole of high-temperature roasting produces three water-aluminum hydroxides as guiding control agent, ammonium sulfate and sodium sulfate mixing salt be three water-aluminum hydroxide mole numbers of high-temperature roasting 1% as crystalline controlling agent, the sodium tartrate of 0.1 mole, as specific surface control agent, after suitable quantity of water mixes, regulates PH value about 5 by pH value regulator nitric acid, mixing speed 150-400 rev/min, is incubated 4h at 200 DEG C; After reaction terminates, it is 8��11 that slurries are adjusted to pH while stirring, and the temperature spent in room temperature to 90 stirs 1��8h, mixing speed 150-400 rev/min. Carry out taking out filter separation subsequently, by filter cake 90 DEG C of dry 6h. Wherein in reaction system, solid-to-liquid ratio is 4:1.
Embodiment 15
2L water adds three water-aluminum hydroxides of 160g high-temperature roasting, then add 32g lead control agent (hydrated aluminum oxide containing crystal water 0.08 mole) and 5g cetyl trimethylammonium bromide as specific surface control agent, after suitable quantity of water mixes, by pH value regulator nitric acid adjust ph about 5, fully stir, mixing speed 200 revs/min, control temperature of reaction is 170 DEG C, reaction 3h. Reaction terminates rear filtering separation, by filter cake in 100 degree of dry 3h. In reaction system, solid-to-liquid ratio is 3:1.
Embodiment 16
The reaction system of above-described embodiment 1-15 adds stability control agent rare earth, wherein the kind of rare earths material and addition are determined according to the performance of required pseudo-boehmite, usual add-on is that the 0.1-3%(of aluminum-containing raw material is in alumina weight), such as lanthanum nitrate, preparation process middle-weight rare earths becomes branch to stay in pseudo-boehmite with the carrying out of reaction, contribute to regulating the physics of pseudo-boehmite, chemistry and catalytic performance, as: thermostability, specific density, surface-area, pore volume, pore size distribution, the type in density and active centre, basicity and acidity, crushing strength, polishing machine etc., thus determine that pseudo-boehmite is as catalyzer, the suitability in other field such as sorbent material or polishing.
The crystalline controlling agent of the present invention is used for controlling the grain fineness number of pseudo-boehmite, when aluminium hydroxide or alumina solid are converted in the process of pseudo-boehmite product, due to the difference of the conditions such as the soda acid pH value of the kind of raw material, solution, temperature of reaction, the pseudo-boehmite grain fineness number of production is different; If not having crystalline controlling agent, the grain fineness number of product can reach 300-400 dust; After adding crystalline controlling agent, within the grain fineness number of product can be controlled in 25-60 dust. Conventional crystalline controlling agent has sodium salt, such as sodium sulfate, sodium-chlor, sodium phosphate etc.; Ammonium salt, such as ammonium sulfate, ammonium chloride, ammonium phosphate etc.; Acid, such as acetic acid, formic acid, phosphoric acid etc.; Alkali, such as sodium hydroxide, urea, ammoniacal liquor etc.
The effect of control agent of leading in the present invention guides solid product to transform to required pseudo-boehmite product, instead of is converted into other undesired products; If the pH value regulator used is the acid of the class such as formic acid, acetic acid, it is not necessary to use guiding control agent; If the pH value regulator used is the acid of the class such as nitric acid, sulfuric acid, it is necessary to use guiding control agent; If the pH value regulator used is the strong alkaloids such as sodium hydroxide, potassium hydroxide, it is necessary to use guiding control agent.
In the present invention, the effect of specific surface control agent is the specific surface area increasing pseudo-boehmite raw material in early stage in reaction process, to prevent the pseudo-boehmite specific surface area generated is excessively little. Its effect principle be: the surface being adsorbed in solid particulate, reduce liquid-solid between interfacial tension, solid particles surface is easily soaked; Or form adsorption layer in solid particles surface, the electric charge of solid particles surface is increased, it is to increase form the reactive force between the particle of steric hindrance; Or making solid particle surfaces form bilayer structure, outer dispersion agent polar end and water have relatively strong affinity, add the degree that solids are spontaneously wet out by water, between solid particulate because of electrostatic repulsion away from; Or making system even, suspension property increases, and does not precipitate, makes whole system physico-chemical property identical.
Conventional specific surface control agent comprises: non-ionic type specific surface control agent, such as polyethylene glycols; Cationic specific surface control agent, such as Trimethyllaurylammonium bromide; Anionic specific surface control agent, such as sodium lauryl sulphate; Alkyl benzene sulphonate (ABS) analogy granule surface contral agent, such as Sodium dodecylbenzene sulfonate; Alkyl carboxylic acid analogy granule surface contral agent, sodium tartrate etc.;
The present invention can add some rare earths and/or transition metal in preparation process, compared with additive method (such as pickling process), the rare earth and the transition metal that add are evenly dispersed in pseudo-boehmite product, x light shows that these addition element can characterize out in x light, this shows that these addition element do not form single separation phase, this kind of feature makes the product of this explained hereafter be applicable to very much catalysis object, or it is suitable as the initial material making catalyzer, or it is suitable as very much polishing material, or it is suitable as very much sorbing material, such as element silicon add the quantity that can increase acid activity position (acid sites) in product, adding of transition metal can increase absorption agent, such as the adsorptive power of oxysulfide, oxides of nitrogen gas, or increase the speed of hydrogenation, hydrocracking and gas/solid surface reaction.
The effect of rare earth element and transition metal is:
1. (reason is: under high temperature, the introducing of rare earth element species can improve anti-agglutinatting property and the high-temperature stability of aluminum oxide significantly to significantly improve the anti-agglutinatting property of alumina product that calcining pseudo-boehmite obtains and high-temperature stability; Effectively prevent the bulk diffusion in alumina particle; The loss of inhibited oxidation aluminium specific surface area and �� phase transformation; The membership that adds of rare earth element changes between aluminum oxide phase the controlling mechanism changed, it is to increase low-temperature oxidation aluminium phase in version is the transformation temperature of alpha phase, makes low-temperature oxidation aluminium keep high temperature active);
2. (reason is: rare earth element is preferentially anchored on after adding in alumina body phase and surface imperfection to significantly improve the specific surface area stability of alumina product that calcining pseudo-boehmite obtains, occupy Adsorption, reduce surface energy, thus effectively inhibit the generation of aluminum oxide phase and sintering, it is to increase surface-area thermostability; The membership that adds of rare earth element changes between aluminum oxide phase the controlling mechanism changed, improve the transformation temperature that low-temperature oxidation aluminium phase in version is alpha phase, low-temperature oxidation aluminium is made to keep high temperature active, inversion of phases not easily occurs at service temperatures, and therefore nature can keep specific surface area stability at service temperatures);
3. (reason is: the dispersity that improve catalytic elements and transition metal in catalyzer after adding rare-earth oxidation thing, makes catalytic elements and transition metal more be enriched in surface to significantly improve the catalytic performance of the calcining alumina product that obtains of pseudo-boehmite; When reaction activity does not reduce, add the active centre number of reaction, there occurs structure effect; But the effect of different rare earth element is different, and this may be relevant with the character of rare earth element and transition metal itself).
4. (in the activity of catalyzer and catalyzer, the electronic state on catalytic elements and transition metal surface is closely related significantly to accelerate to calcine the catalytic activity of the alumina product that obtains of pseudo-boehmite, the elements such as transition metal add the active surface area increasing catalyzer, improve dispersity, add active centre number, enhance poison resistance);
The additional proportion of rare earth and transition element is 0.1%-10%;
Above-described embodiment 1-15 gained product substance analysis of physical and chemical property detected result is in table 1:
Table 1
The physico-chemical property parameter of above embodiment products obtained therefrom meets or higher than the conventional standard in this area: specific surface 250m2/ g, hole holds 0.3ml/g, hydrogen aluminium content < 5%.
It should be noted last that, above embodiment only in order to illustrate this material technology implementation scheme but not restriction, although with reference to better embodiment to invention has been detailed explanation, it will be understood by those within the art that, the technical scheme of the present invention can be modified or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the right of the present invention.
Claims (6)
1. produce the technique of pseudo-boehmite for one kind, it is characterised in that: comprise the steps:
(1) in aluminum-containing raw material, add pH value regulator and control agent, add water and react;
(2) mix under room temperature, stir making beating;
(3) mixed pulp is incubated and stirs making beating;
(4) filtered and recycled product, the filtrate after filtration is recovered to step (1) again and reacts;
(5) product is dried;
(6) product powder mill;
Wherein, described control agent comprises crystalline controlling agent, guiding control agent, specific surface control agent and stability control agent;
Described guiding control agent comprises aluminum nitrate, the molar content of crystal water is the one in the hydrated aluminum oxide of 0.08��2.2;
Described stability control agent comprises rare earth element and transition metal, and wherein, described rare earth and transition metal are 0.1%-10% relative to the additional proportion of aluminum-containing raw material;
Described crystalline controlling agent comprises one or more in sodium salt, ammonium salt, acid or alkali.
2. the technique producing pseudo-boehmite as claimed in claim 1, it is characterised in that: described aluminum-containing raw material accounts for the 90%-99.99% of reactant gross weight.
3. the technique producing pseudo-boehmite as claimed in claim 1, it is characterised in that: the mol ratio of described pH adjusting agent and aluminum-containing raw material is 0.1:1��1:90.
4. the technique producing pseudo-boehmite as claimed in claim 1, it is characterised in that: described specific surface control agent comprises the one in non-ionic type specific surface control agent, anionic specific surface control agent or alkyl carboxylic acid analogy granule surface contral agent.
5. the technique producing pseudo-boehmite as claimed in claim 1, it is characterised in that: described mixed pulp holding temperature is 100-400 DEG C, and stirring beating time is 0.5-30 hour.
6. the technique producing pseudo-boehmite as claimed in claim 1, it is characterised in that: described product bake out temperature 80-150 DEG C, drying time 1-8h.
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Effective date of registration: 20170609 Address after: Nam Dinh Town, Zhangdian city of Zibo province Shandong 255052 five km road No. 1 Patentee after: China Aluminum Shandong New Material Co., Ltd. Address before: 100082 Beijing, Xizhimen, North Street, No. 62, No. Patentee before: Aluminum Corporation of China Limited |