CN102489335B - Preparation method of high-solid-content amorphous silicon aluminium - Google Patents
Preparation method of high-solid-content amorphous silicon aluminium Download PDFInfo
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- CN102489335B CN102489335B CN 201110427387 CN201110427387A CN102489335B CN 102489335 B CN102489335 B CN 102489335B CN 201110427387 CN201110427387 CN 201110427387 CN 201110427387 A CN201110427387 A CN 201110427387A CN 102489335 B CN102489335 B CN 102489335B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000004411 aluminium Substances 0.000 title abstract description 9
- 229910021417 amorphous silicon Inorganic materials 0.000 title abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000007787 solid Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 19
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 12
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 5
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 57
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 34
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000032683 aging Effects 0.000 abstract description 8
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000004115 Sodium Silicate Substances 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 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 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 4
- 229910001593 boehmite Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000010881 fly ash Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910000632 Alusil Inorganic materials 0.000 description 1
- 101100179824 Caenorhabditis elegans ins-17 gene Proteins 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101150089655 Ins2 gene Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004567 concrete 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
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a preparation method of high-solid-content amorphous silicon aluminium. The preparation method is characterized by comprising the following steps: after the temperature of a 25-40wt% silica solution rises to 30-50 DEG C, adding alumina and/or aluminium hydroxide powder under a stirring state according to the condition that the mole ratio of SiO2/Al2O3 is 10-20; reacting for 10-60 minutes under stirring, then adding ammonium salt accounting for 1-10% of the total weight of materials, and stirring for 20-60 minutes, wherein the pH of the materials is 7.5-9.0; ageing for 1-24 hours at the temperature of 40-60 DEG C, and drying until the solid content is more than or equal to 80%; after grinding, using water at the temperature of 30-90 DEG C to clean for 10-60 minutes at the weight ratio of 1:(3-10) in twice; and after drying, roasting for 0.5-4 hours. In the obtained amorphous silicon aluminium, the alumina is 10-20wt%, the sodium oxide is less than 0.2wt%, the pore volume is larger than 0.55ml/g, the specific surface is larger than 500m<2>/g, and the apparent bulk density is 0.5-0.6g/ml. Compared with the existing method, the preparation method disclosed by the invention has the advantages that the solid content in the preparation process is greatly improved, the energy consumption and the water consumption are reduced, the whole preparation process is simple and efficient and raw materials are easily obtained.
Description
Technical field
The present invention relates to a kind of preparation method of amorphous aluminum silicide, relate to a kind of high solids content amorphous aluminum silicide preparation method with the high pore volume of high surface area or rather.
Background technology
Amorphous aluminum silicide is widely used in preparing the support material of petroleum refining catalyst and adsorbent, particularly hydrocracking and Hydrobon catalyst, also can be used as raw material or the carrier of chemical catalyst.For guaranteeing the dispersiveness of catalyst activity component on amorphous aluminum silicide, the character of the dried glue of amorphous aluminum silicide is very important just, how to obtain enough big specific area, suitable pore volume, acidity, suitable silica alumina ratio and the efficient in the raising preparation process and be always the emphasis in the research work.
Industrial general normal employing carbonizatin method or the preparation of aluminum sulfate method, a kind of method of Carbonization Preparation amorphous aluminum silicide is disclosed as CN1282499C, CN100390055C, be that carbon dioxide is fed in sodium metasilicate and the sodium aluminate solution, and adopted the pH method of waving, sodium silicate solution is substep adding reaction, through stablizing, filter, wash and dry the acquisition; CN101239328B also adopts carbonizatin method and amorphous aluminum silicide to adopt and the stream coprecipitation method obtains, and has used wind to stir measure in the preparation process; CN1597093A has introduced a kind of method that adopts the production of batch (-type) carbonizatin method to prepare amorphous aluminum silicide; Also related to a kind of amorphous aluminum silicide of Carbonization Preparation among the CN1015638B, raw material is sodium metaaluminate and carbon dioxide, adds minor amount of silicon, and product acidity is lower, and specific surface and pore volume are also low; The amorphous aluminum silicide that the carbonizatin method of CN102039197A obtains has carried out hydrothermal treatment consists, makes it have higher specific surface and pore volume, and pore size distribution and acid the distribution all improve; CN102218350A, CN102218351A then adopt carbonizatin method to make the dried glue of amorphous aluminum silicide of fluorine-containing and titaniferous respectively.
The use of carbonizatin method is subjected to equipment, raw material and becomes effects limit such as glue pH tuning range is little, can not finely satisfy the raising of amorphous aluminum silicide performance and the requirement that industry is promoted, and be difficult to improve the solid content of material in the preparation process, to such an extent as in preparation processes such as follow-up drying, cause energy consumption too high, owing to require it to possess certain acidity as catalysis material, also need to cause water consumption height and quantity of wastewater effluent big by the sodium ion in a large amount of water washing removal sodium silicoaluminates.
It also is a kind of method commonly used that the aluminum sulfate legal system is equipped with amorphous aluminum silicide, and GB2166971 discloses a kind of preparation method of amorphous aluminum silicide, is to form mixed liquor with composite alkali aluminum salt and silicate about pH12, reacts the preparation silica-alumina supports afterwards with aluminum sulfate; CN1081478C, CN1172850C then disclose in DL formula prilling granulator, with sodium metasilicate and acidifying inorganic acid aluminum solutions mist projection granulating, and through aging, acidifying, washing, surface treatment and the dry silica-alumina gel micelle that makes good sphericity; Similarly adopt the synthesis of molecular sieve mother liquor of silicon oxide-containing as raw material in addition with it, adopt coprecipitation in salic solution, to introduce siliceous synthesis of molecular sieve mother liquor as CN1306977C, after aging, dry, obtain silica-alumina; CN102050469A then adopts in the synthetic crystallization mother liquor of molecular sieve and adds directed agents and aluminium salt, filters the wet Alusil of gained as the raw material of synthesis of molecular sieve.Similar to carbonizatin method is that preparation process and products therefrom solid content are all very low, contains a large amount of sodium oxide molybdenas in the product, if need massive laundering to remove for the preparation of catalyst or carrier.
The method for preparing amorphous aluminum silicide of various improvement, remodeling has a large amount of reports in prior art, after the solution of silicon oxide-containing and aluminium oxide being mixed and adds hydrochloric acid and obtain colloidal sol as CN1074303C, add NaOH again and obtain gel, reaction obtains the powdery alumino-silicate under high temperature, the high pressure; CN101491774B discloses the sial coprecipitation and has adopted the high-silicon amorphous silica aluminum preparation method of organic-silicon-modified method preparation; CN1210755A discloses a kind of amorphous aluminum silicide and preparation method thereof, and its preparation process is to introduce the silicon source again after ammoniacal liquor and sodium aluminate form aluminium oxide earlier.These preparation methods and carbonizatin method and aluminum sulfate method be similar all to exist material solid content defective low and that need massive laundering to remove by the sodium ion that silicon/aluminate is brought into.
The technology that adopts cheap scrap feed material to prepare silica-alumina material also has report, disclose as CN101746976A and to have utilized flyash to produce the silica-alumina gel material, be with gangue pulverize after the roasting mix with lime and calcined kaolin ball milling and can, be mainly used in architectural moulding by casting and use; CN101717214A prepares silicon-aluminium aerogel with flyash for the raw material constant pressure and dry, be that the flyash combined grinding is calcined, with the filtrate of its gained of dissolving with hydrochloric acid leave standstill aging after, water, ethanol and organic silicide soak the back drying and make, as heat preserving and insulating material.This class is very high with the prepared silica-alumina material impurity content of the cheap scrap feed material of flyash class, character is unstable, generally is difficult to prepare catalyst, adsorbent or carrier.
Reported among USP4758338, the USP4721696 to adopt and waved the aluminium oxide that the pH method makes siliceous modification; CN102139204A with amorphous aluminum silicide slurries and boehmite slurries mixed siliceous boehmite; CN1267187C introduces silicon-containing compound solution and stream in the boehmite slurries, makes siliceous aluminium oxide.Though these prior art for preparing processes have certain similarity with preparation amorphous silicon aluminum, but the product that obtains still is alumina material, rather than amorphous aluminum silicide of the present invention, it is that physicochemical properties or catalytic performance and purposes all have marked difference with the amorphous silicon aluminum.
Adopt the sial raw material preparing amorphous aluminum silicide that does not contain sodium ion that report is also arranged in the prior art, adopt tetraalkylammonium hydroxide, tri-alkoxy aluminium and positive silicic acid tetraalkyl fat hydrolysis and gel to obtain amorphous silicon oxide-alumina gel as CN1049957C, shortcoming be raw material too costliness make manufacturing cost increase substantially; CN1300061C discloses a kind of preparation method of silica alumina gel bonding agent for corundum-mullite composite ceramic, mainly be as raw material with Ludox and aluminium colloidal sol, pH value by the control aluminium glue, prepare silica-alumina gel through sol-gel process, this method products therefrom is mainly as binding agent, surface area and pore volume are all low, be difficult to as catalysis material, and the solid content in the preparation process are all very low.
Summary of the invention
In order to solve existing deficiency in the prior art, increase substantially the efficient of preparation process, the invention provides a kind of high solids content amorphous aluminum silicide preparation method with the high pore volume of high surface area.
Preparation process concrete in the technical solution of the present invention is as follows:
A kind of high solids content amorphous aluminum silicide preparation method of the present invention is after Ludox with concentration 25～40 heavy % is warmed up to 30～50 ℃ of degree, to press SiO under stirring
2/ Al
2O
3Mol ratio 10～20 adds aluminium oxide and/or aluminium hydrate powder, is by SiO under the preferable case
2/ Al
2O
3The ratio of mol ratio 13～16 adds; Described Ludox, aluminium oxide, aluminium hydroxide can pass through commercially available, aluminium oxide and aluminium hydroxide have the product of the extensive stock trade mark and different types of structure, but those skilled in the art generally classify as aluminium oxide, aluminium hydroxide respectively with it, and this is conventionally known to one of skill in the art.
Among a kind of high solids content amorphous aluminum silicide preparation method of the present invention, material stirs reaction down 10～60 minutes, and stirring reaction is 20～40 minutes under the preferable case; In the ratio of material gross weight 1～10 heavy %, in the ratio of 3～6 heavy %, the adding ammonium salt also stirred 20～60 minutes under the preferable case afterwards; Described ammonium salt is selected from ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium oxalate, ammonium acetate and ammonium carbonate, and these ammonium salts all can be by commercially available.
Adding the reacted material pH of ammonium salt among a kind of high solids content amorphous aluminum silicide preparation method of the present invention is 7.5～9.0, and the pH under the preferable case is 8.0～8.5; Material wore out 1～24 hour under 40～60 ℃ of degree and dries the heavy % to solid content 〉=80, dried the heavy % to solid content 〉=85 under the preferable case.
Material after aging among a kind of high solids content amorphous aluminum silicide preparation method of the present invention is after grinding, at twice by 1: 3～10 part by weight with 30～90 ℃ of water washings 10～60 minutes, press 1: 4～6 part by weight under the preferable case at twice with 40～70 ℃ of water washings 20～40 minutes.
Dried material is 400～550 ℃ of roastings 0.5～4 hour among a kind of high solids content amorphous aluminum silicide preparation method of the present invention, and 450～520 ℃ of roastings are 1～2 hour under the preferable case.
Reaction described in the present invention, making beating, drying and baking operation are the known basic operation of chemical field those skilled in the art, and drying mode comprises and adopts the method for spray-drying, expansion drying and oven drying all to be well known to those skilled in the art among the present invention; The roasting mode comprises that employing rotary kiln, tunnel cave and vertical heater roasting also are well known to those skilled in the art among the present invention.
The aluminium oxide of the amorphous aluminum silicide that preparation method of the present invention obtains is that 10～20 heavy %, the heavy % in sodium oxide molybdena＜0.20, pore volume＞0.55 milliliter/gram, specific surface＞500 meters squared per gram, apparent bulk density are 0.5～0.6 grams per milliliter; The aluminium oxide of prepared amorphous aluminum silicide is that 13～17 heavy %, the heavy % in sodium oxide molybdena＜0.15, pore volume＞0.60 milliliter/gram, specific surface＞550 meters squared per gram, apparent bulk density are 0.52～0.58 grams per milliliter under the preferable case.
A fact known in those skilled in the art is: be difficult to improve the solid content of material in the amorphous aluminum silicide preparation process, all be difficult to reach 10 heavy % generally speaking, to such an extent as to cause energy consumption too high in preparation processes such as follow-up drying, operating procedure is numerous and diverse; Owing to require it to possess certain acidity as catalysis material, also need to cause the water consumption too high huge with quantity of wastewater effluent by the sodium ion in a large amount of water washing removal sodium silicoaluminates; Compare with existing method, the present invention has increased substantially the solid content in the preparation process, can make in the preparation process material solid content bring up to 40 heavy %, greatly reduce energy consumption and water consumption in the preparation process, and simple, the efficient and raw material of whole process of preparation technology is easy to get.
The specific embodiment
The following examples will the present invention is further illustrated, but protection scope of the present invention is not subjected to the restriction of these embodiment.
In each embodiment, the specific surface of sample and pore volume adopt low-temperature nitrogen adsorption method to measure with reference to the GB/T5816-1995 method; Constituent content adopts x-ray fluorescence analyzer to measure according to GB/T12690.5-90; The pH value adopts pH meter to measure.
Other detect referring to (" oil and oil product test method national standard " China Standard Press published 1989).
Embodiment 1
Present embodiment is the preparation process that high solids content amorphous aluminum silicide provided by the present invention will be described.
Get Ludox 300 gram (industrial goods, Qingdao Marine Chemical Co., Ltd., silica 40 heavy %), under stirring, add macroporous aluminium oxide 20.0 gram (industrial goods after being warmed up to 40 ℃, Shandong Aluminum Plant of China Aluminum Co., Ltd, solid content 69.1 heavy %), stir and added ammonium chloride 7.6 gram (chemical pures in 20 minutes, Beijing reagent company), stirring and surveying pH after 30 minutes is 8.3,50 ℃ of static burn ins 20 hours, oven dry is to more than the solid content 85 heavy %, after levigate at twice with 55 ℃ hot water by water: amorphous aluminum silicide is 5: 1 weight ratio exchange 30 minutes, after the oven dry, 480 ℃ of roastings 1 hour; Record 0.62 milliliter/gram of aluminium oxide 15.0 heavy %, sodium oxide molybdena 0.13 heavy %, pore volume, specific surface 570 meters squared per gram, apparent bulk density 0.56 grams per milliliter of product amorphous aluminum silicide.
Comparative Examples 1
This Comparative Examples is the preparation process that the amorphous aluminum silicide that provides by traditional carbonizatin method will be described.
Method by CN102039197A embodiment 1 is prepared amorphous aluminum silicide, at 10 liters of sodium aluminate solution (industrial goods, Shandong Aluminum Plant of China Aluminum Co., Ltd, concentration 20 grams per liters) add 0.3 liter of (industrial goods of sodium silicate solution in, Shandong Aluminum Plant of China Aluminum Co., Ltd, concentration 100 grams per liters), 24 ℃ of control reaction temperatures, the feeding volumetric concentration is 55% carbon dioxide (industrial goods, sea, Beijing spectrum gas Co., Ltd), behind the carbon dioxide of feeding 80%, feed carbon dioxide gas on one side, add 0.6 liter of sodium silicate solution (the same) on one side, the pH value of control cemented into bundles is 10.0, ventilate then and stablized 10 minutes, dope filtration also is washed till neutrality with 75 ℃ of deionized waters, the gained filter cake adds the water making beating by the solid-liquid volume ratio at 1: 8, at 120 ℃, handled 2 hours under the 1MPa water vapour pressure, again after under 120 ℃ dry 8 hours, crushing screening gets the amorphous aluminum silicide product of Comparative Examples 1, its aluminium oxide 70 heavy %, sodium oxide molybdena 0.95 heavy %, 0.87 milliliter/gram of pore volume, specific surface 435 meters squared per gram, apparent bulk density 0.65 grams per milliliter.
Comparative Examples 2
This Comparative Examples is the preparation process that the amorphous aluminum silicide that provides by traditional aluminum sulfate method will be described.
Method with reference to the CN1172850C preferred embodiment is prepared amorphous aluminum silicide, with aluminum sulfate solution (Beijing chemical reagent company reagent preparation, concentration 10 heavy %), dilution heat of sulfuric acid (Beijing chemical reagent company reagent preparation, the heavy % of concentration 10) and sodium silicate solution (the same, concentration 10 heavy %) also stream mixes in the making beating jar, stirring to pulp, 18 ℃ of control reaction temperatures, the pH value is about 9.0, and at 25 times aging 3 hours, after the dilute sulfuric acid acidification, with 3 times washings 12 times, oven dry back its aluminium oxide 8.4 heavy %, sodium oxide molybdena 0.78 heavy %, 0.46 milliliter/gram of pore volume, specific surface 730 meters squared per gram, apparent bulk density 0.62 grams per milliliter.
Comparative Examples 3
This Comparative Examples is that the process for preparing amorphous aluminum silicide by the available technology adopting silicon-aluminum sol will be described.
Method with reference to the CN1300061C specific embodiment prepares silica-alumina gel, with aluminium colloidal sol (industrial goods, Shandong Aluminum Plant of China Aluminum Co., Ltd, concentration 20 heavy %) be added in deionized water (the pH value 2.5) container that fills the acetic acid acidifying and dilute, it is standby that stirring is mixed with the aluminium colloidal sol of the heavy % of concentration 5, with quadrat method that Ludox is (the same, the heavy % of concentration 20) it is standby to be diluted to the colloidal sol of 5 heavy %, with aluminium colloidal sol stirring and refluxing half an hour in 80 ℃ of reactors, be cooled to 40 ℃, add Ludox, the limit edged stirs, and controls pH value≤3 simultaneously, stir and make silicon-aluminum sol after 2 hours, dehydration obtains silica-alumina gel; Oven dry back its sodium oxide molybdena 0.20 heavy %, pore volume＜0.1 milliliter/gram, specific surface 30 meters squared per gram.
Embodiment 2
Present embodiment is the preparation process that high solids content amorphous aluminum silicide provided by the present invention will be described.
It is (the same to get Ludox 400 grams, silica 30 heavy %), under stirring, add aluminium hydrate powder 20.0 gram (industrial goods, Shandong Aluminum Plant of China Aluminum Co., Ltd after being warmed up to 40 ℃, solid content 70.5 heavy %), stir and added ammonium nitrate 8 grams (chemical pure, Beijing reagent company) in 20 minutes, stirring and surveying pH after 30 minutes is 8.2,50 ℃ of static burn ins 2 hours, oven dry is to more than the solid content 85 heavy %, after levigate at twice with 60 ℃ hot water by water: amorphous aluminum silicide is 4.5: 1 weight ratio exchange 30 minutes, after the oven dry, 500 ℃ of roastings 1 hour; Record 0.64 milliliter/gram of aluminium oxide 14.8 heavy %, sodium oxide molybdena 0.12 heavy %, pore volume, specific surface 560 meters squared per gram, apparent bulk density 0.55 grams per milliliter of product amorphous aluminum silicide.
Embodiment 3
Present embodiment is the preparation process that high solids content amorphous aluminum silicide provided by the present invention will be described.
It is (the same to get Ludox 300 grams, silica 40 heavy %), under stirring, add boehmite 10.0 gram (industrial goods after being warmed up to 40 ℃, Shandong Aluminum Plant of China Aluminum Co., Ltd, solid content 70.5 weighs %) and 10 gram aluminium hydrate powders (the same), stir and added ammonium sulfate 8 gram (chemical pures in 20 minutes, Beijing reagent company), stirring and surveying pH after 30 minutes is 8.1,50 ℃ of static burn ins 14 hours, oven dry is to more than the solid content 85 heavy %, after levigate at twice with 45 ℃ hot water by water: amorphous aluminum silicide is 5.5: 1 weight ratio exchange 20 minutes, after the oven dry, 480 ℃ of roastings 2 hours; Record 0.63 milliliter/gram of aluminium oxide 14.8 heavy %, sodium oxide molybdena 0.14 heavy %, pore volume, specific surface 565 meters squared per gram, apparent bulk density 0.57 grams per milliliter of product amorphous aluminum silicide.
Embodiment 4
Present embodiment is noted that the embodiment of the invention 1～3 and Comparative Examples 1～3 preparation process contrast situation, and the gel solid content refers to the solid content of aging back filter cake, and the process water consumption refers to slurry amount in every gram amorphous aluminum silicide preparation process, sees Table 1.
Table 1, embodiment 1～3 and the contrast of Comparative Examples 1～3 preparation process
As can be seen from Table 1, preparation method provided by the present invention is that the solid content of material in the preparation process or the solid content of the aging back of gained gel are all far above the solid content of corresponding material and gel in the art methods, thereby make the energy consumption in the follow-up dry run reduce greatly, and the technical scheme that adopts has also reduced the water consumption of washing removal sodium ion significantly, the products therefrom sodium content is also lower, the catalytic performance requirement when having satisfied it for the preparation of catalyst or carrier.
Need to prove at last, above embodiment is only unrestricted for explanation technical scheme of the present invention, although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not break away from the spirit and scope of technical solution of the present invention.
Claims (10)
1. high solids content amorphous aluminum silicide preparation method, it is characterized in that Ludox with concentration 25～40 heavy % is warmed up to 30～50 ℃ after, under stirring, press SiO
2/ Al
2O
3Mol ratio 10～20 adds aluminium oxide and/or aluminium hydrate powder, stirring reaction down adds ammonium salt in the ratio of material gross weight 1～10 heavy % after 10～60 minutes and stirred 20～60 minutes, the pH of material is 7.5～9.0,40～60 ℃ were worn out 1～24 hour down, dry the heavy % to solid content 〉=80, after the grinding at twice by 1: 3～10 part by weight with 30～90 ℃ of water washings 10～60 minutes, 400～550 ℃ of roastings in dry back 0.5～4 hour, aluminium oxide 10～20 heavy % of gained amorphous aluminum silicide, the heavy % in sodium oxide molybdena＜0.20, pore volume＞0.55 milliliter/gram, specific surface＞500 meters squared per gram, apparent bulk density is 0.5～0.6 grams per milliliter.
2. high solids content amorphous aluminum silicide preparation method according to claim 1, it is characterized in that described in Ludox by SiO
2/ Al
2O
3The ratio of mol ratio 13～16 adds aluminium oxide and/or aluminium hydrate powder.
3. high solids content amorphous aluminum silicide preparation method according to claim 1 is characterized in that behind described adding aluminium oxide and/or the aluminium hydrate powder stirring reaction 20～40 minutes.
4. high solids content amorphous aluminum silicide preparation method according to claim 1, the addition that it is characterized in that described ammonium salt are material gross weight 3～6 heavy %.
5. high solids content amorphous aluminum silicide preparation method according to claim 4 is characterized in that described ammonium salt is selected from ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium phosphate, ammonium oxalate, ammonium acetate and ammonium carbonate.
6. high solids content amorphous aluminum silicide preparation method according to claim 1 is characterized in that the reacted material pH of described adding ammonium salt is 8.0～8.5.
7. high solids content amorphous aluminum silicide preparation method according to claim 1 is characterized in that drying materials to solid content 〉=85 after described the wearing out weigh %.
8. high solids content amorphous aluminum silicide preparation method according to claim 1 is characterized in that behind the described improved grinding at twice by 1: 4～6 part by weight with 40～70 ℃ of water washings 20～40 minutes.
9. high solids content amorphous aluminum silicide preparation method according to claim 1 is characterized in that behind the dry materials after the described washing 450～520 ℃ of roastings 1～2 hour.
10. high solids content amorphous aluminum silicide preparation method according to claim 1, the aluminium oxide that it is characterized in that prepared amorphous aluminum silicide is that 13～17 heavy %, the heavy % in sodium oxide molybdena＜0.15, pore volume＞0.60 milliliter/gram, specific surface＞550 meters squared per gram, apparent bulk density are 0.52～0.58 grams per milliliter.
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|---|---|---|---|---|
| CN1210755A (en) * | 1997-09-10 | 1999-03-17 | 中国石油化工总公司 | Amorphous silica-alumina and its preparing method |
| CN102039197A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Amorphous silicon aluminium and preparation method thereof |
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| CN1210755A (en) * | 1997-09-10 | 1999-03-17 | 中国石油化工总公司 | Amorphous silica-alumina and its preparing method |
| CN102039197A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Amorphous silicon aluminium and preparation method thereof |
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