CN1267187C - Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method - Google Patents
Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method Download PDFInfo
- Publication number
- CN1267187C CN1267187C CN 03157163 CN03157163A CN1267187C CN 1267187 C CN1267187 C CN 1267187C CN 03157163 CN03157163 CN 03157163 CN 03157163 A CN03157163 A CN 03157163A CN 1267187 C CN1267187 C CN 1267187C
- Authority
- CN
- China
- Prior art keywords
- silica
- alumina
- aluminum
- silicon
- containing compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000002360 preparation method Methods 0.000 title claims description 15
- VIJYFGMFEVJQHU-UHFFFAOYSA-N aluminum oxosilicon(2+) oxygen(2-) Chemical compound [O-2].[Al+3].[Si+2]=O VIJYFGMFEVJQHU-UHFFFAOYSA-N 0.000 title description 3
- 229910001583 allophane Inorganic materials 0.000 title 1
- 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 99
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 8
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 37
- 230000032683 aging Effects 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 239000002210 silicon-based material Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 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 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000012736 aqueous medium Substances 0.000 claims description 7
- 235000019353 potassium silicate Nutrition 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- -1 alkoxy aluminum Chemical compound 0.000 claims description 5
- 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 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical group O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical group [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims 2
- 150000003377 silicon compounds Chemical class 0.000 claims 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 claims 1
- 238000004026 adhesive bonding Methods 0.000 claims 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 claims 1
- 238000010304 firing Methods 0.000 claims 1
- 239000011736 potassium bicarbonate Substances 0.000 claims 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims 1
- 235000015497 potassium bicarbonate Nutrition 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 235000011181 potassium carbonates Nutrition 0.000 claims 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 238000004523 catalytic cracking Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- 229910001648 diaspore Inorganic materials 0.000 description 30
- 239000000047 product Substances 0.000 description 28
- 239000008367 deionised water Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000003054 catalyst Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 239000004411 aluminium Substances 0.000 description 10
- 239000012065 filter cake Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 229910001593 boehmite Inorganic materials 0.000 description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- 241000640882 Condea Species 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- 241001502050 Acis Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WAKTWVHWRCNIKU-UHFFFAOYSA-N S(=O)(=O)(O)O.[AlH3] Chemical compound S(=O)(=O)(O)O.[AlH3] WAKTWVHWRCNIKU-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
Abstract
一种具有拟薄水铝石结构的氧化硅-氧化铝，其焙烧后含有5-60重量%的氧化硅，40-95重量%的氧化铝，其特征在于，所述氧化硅-氧化铝的N值为0.2-1；所述的N＝P1/P2，P1为所述氧化硅-氧化铝的固体27Al NMR谱图中化学位移为60±0.1-0.2ppm处的峰面积，P2为所述氧化硅-氧化铝的固体27Al NMR谱图中化学位移为5±0.1-0.2ppm处的峰面积。本发明提供的具有拟薄水铝石结构的氧化硅-氧化铝的N值高，经高温活化后具有更高的催化裂化活性。A silica-alumina having a pseudo-boehmite structure, which contains 5-60% by weight of silica and 40-95% by weight of alumina after roasting, characterized in that the silica-alumina The N value is 0.2-1; the N=P1/P2, P1 is the peak area at the chemical shift of 60±0.1-0.2ppm in the solid 27 Al NMR spectrum of the silica-alumina, and P2 is the peak area at the place where the chemical shift is 60±0.1-0.2ppm. The peak area at the chemical shift of 5±0.1-0.2ppm in the solid 27 Al NMR spectrum of the above silica-alumina. The silicon oxide-alumina with pseudo-boehmite structure provided by the invention has a high N value, and has higher catalytic cracking activity after being activated at high temperature.
Description
Technical field
The invention relates to a kind of silica-alumina and preparation method thereof, more specifically say so about a kind of silica-alumina and preparation method thereof with structure of similar to thin diaspore.
Background technology
With respect to molecular sieve, certain acid catalysis activity can be got well and have to the activated back of silica-alumina specific surface height, anti-agglutinatting property with divergence hole distribution, and Chang Zuowei carrier and active component are used to prepare various dissimilar catalyst.In the existing method, silica-alumina is often by alkali silicate with contain aluminium salt glue or substep become the method for glue to prepare altogether.Silica-alumina by these method preparations mostly is amorphous silicon oxide-aluminium oxide.For amorphous silicon oxide-aluminium oxide, ubiquitous problem is the poor operability of constant product quality and moulding.For example, in actual applications, silica-alumina adopts oil ammonia column to drip ball forming method usually and makes carrier, and its yield rate and production efficiency are low.
USP 5045519 discloses a kind of preparation method of the catalyst carrier based on alumina silicate.This method is in aqueous medium a kind of aluminum contained compound to be mixed with silicic acid, and dry then and roasting obtains product.Its used aluminum contained compound is by C
2-C
20 +The aluminum alkoxide hydrolysis obtains, and simultaneously or will join in the aluminum contained compound through the positive silicic acid of ion-exchange process purifying subsequently, comprising one the 90-235 ℃ of process that mixture is heat-treated.The x-ray analysis result shows to have structure of similar to thin diaspore before the silica-alumina roasting by this method preparation.This easy moulding of silica-alumina with structure of similar to thin diaspore is even when silica content during up to 40 weight %, still can pass through the moulding of extruded moulding mode.But, be raw material owing to adopt aluminum alkoxide and positive silicic acid, this method preparation cost height.In addition, its preparation is carried out under the condition that is bordering on neutrality, is unfavorable for that the reaction of silica and aluminium oxide generates the acid site.
Aluminium in alumina silicate or the silica-alumina mainly contain two kinds of four-coordination and hexa-coordinates different have a form.Adopt solid-state nuclear magnetic resonance to characterize, four-coordination aluminium and hexa-coordinate aluminium exist
27Characteristic peak occurs on the Al NMR spectrogram, wherein, the peak of 5 ± 0.1-0.2ppm chemical shift place belongs to the aluminium of hexa-coordinate, and the peak of 60 ± 0.1-0.2ppm chemical shift place belongs to the aluminium of four-coordination.Acid site number in alumina silicate or the silica-alumina is by the wherein content decision of contained four-coordination aluminium.Be that four-coordination aluminium content is big more, the acid site number is many more.The shortcoming of the silica-alumina with structure of similar to thin diaspore that existing method provides is that four-coordination aluminium content is low.
Summary of the invention
The objective of the invention is at the low shortcoming of four-coordination aluminium content in the existing silica-alumina with structure of similar to thin diaspore, provide a kind of new four-coordination aluminium content higher have silica-alumina of structure of similar to thin diaspore and preparation method thereof.
Silica-alumina with structure of similar to thin diaspore provided by the invention contains the silica of 5-60 weight % after its roasting, the aluminium oxide of 40-95 weight %, and its N value is 0.2-1; Described N=P1/P2, P1 are the solid of described silica-alumina
27Chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the Al NMR spectrogram, and P2 is the solid of described silica-alumina
27Chemical shift is the peak area at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
Preparation method with silica-alumina of structure of similar to thin diaspore provided by the invention comprises the mixed liquor of a kind of boehmite of preparation and water, introduce a kind of solution of silicon-containing compound, aging and drying afterwards, described aging condition: the pH value be 7.5-11, temperature be carry out under the 75-120 ℃ of condition, the time is 6-24 hour, the condition of described drying: temperature is that 80-300 ℃, time are 2-24 hour, and it is 5-60 weight % that the introducing amount of the solution of silicon-containing compound makes the content of silica in the final silica-alumina.
Compare with existing silica-alumina with structure of similar to thin diaspore, the N value height with silica-alumina of structure of similar to thin diaspore provided by the invention has higher catalytic cracking activity behind high-temperature activation.
For example, by a kind of silica content provided by the invention is that the N value of the silica-alumina with structure of similar to thin diaspore of 39 weight % is 0.78, in 600 ℃ of activation 4 hours, is raw material on pulse micro-inverse device estimate with n-C14 afterwards with it, and its cracking activity is 11%; And existing N value with silica-alumina of structure of similar to thin diaspore only is 0.12, and it in 600 ℃ of activation 4 hours, is used n-C afterwards
14For raw material is estimated on the pulse micro-inverse device, its cracking activity only is 5%.
Description of drawings
Fig. 1 for the silica-alumina with structure of similar to thin diaspore provided by the invention, existingly have the silica-alumina of structure of similar to thin diaspore and an x-ray diffraction spectra of boehmite.
The specific embodiment
According to the silica-alumina with structure of similar to thin diaspore provided by the invention, preferably contain the silica of 10-45 weight % after its roasting, the aluminium oxide of 55-90 weight %.The N value is preferably 0.2-0.8.
Several x-ray diffraction spectra with silica-alumina of structure of similar to thin diaspore provided by the invention is seen a, b, c, d, the e among Fig. 1.As a comparison, provided a kind of x-ray diffraction spectra (Fig. 1 f) of silica-alumina and a kind of x-ray diffraction spectra (Fig. 1 g) of boehmite of having now among Fig. 1 simultaneously with structure of similar to thin diaspore.
According to method provided by the invention, the method for the mixed liquor of a kind of boehmite of wherein said preparation and water is the conventional method for preparing boehmite.For example, can be the solution of at least a aluminum contained compound is mixed, becomes glue with the solution of a kind of alkali or acid and to wear out, described aging condition: pH is 7-8.5, temperature is that 30-75 ℃, time are 5-120 minute.
Described aluminum contained compound is selected from one or more in aluminum sulfate, sodium metaaluminate, aluminum nitrate, alchlor, aluminum alkoxide, the alkyl aluminum, is preferably in aluminum sulfate, sodium metaaluminate, aluminum nitrate, the alchlor one or more.
Described alkali be hydroxide or in aqueous medium hydrolysis make the aqueous solution be the salt of alkalescence, preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, the potassium hydroxide; Preferred salt is selected from one or more in carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, the potash.
Described acid is Bronsted acid or is acid oxide that in aqueous medium preferred Bronsted acid is selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid; Preferred oxide is a carbon dioxide.
According to method provided by the invention, the introducing of the solution of described silicon-containing compound is that the solution with silicon-containing compound mixes with the mixed liquor of water with prepared boehmite, for example, can be under agitation the solution of silicon-containing compound to be joined in the mixed liquor of boehmite and water, also can be to contain in the mixed liquor and stream adding reaction vessel of solution with boehmite and water of silicon-containing compound, the consumption of the solution of silicon-containing compound makes the silica that contains 5-60 weight % in the final silica-alumina, is preferably 10-45 weight %.
Described silicon-containing compound can be any water-soluble silicon-containing compound and the silicon-containing compound that can hydrolysis in aqueous medium forms silicon gel, colloidal sol.For example, one or more in the compounds such as waterglass, the hydrosol and esters of silicon acis.
Described aging condition is preferred: the pH value is that 8-10, temperature 80-98 ℃, time are 12-24 hour.
Described drying is conventional drying, preferred condition: temperature is that 100-150 ℃, time are 4-20 hour,
According to method provided by the invention, an embodiment preferred may further comprise the steps:
(1) a kind of solution that contains aluminium salt and a kind of aqueous slkali or acid solution and stream are joined be carried out to the glue reaction in the reaction vessel, reaction condition: the pH value is 6.5-8.5, and temperature is 30-75 ℃;
(2) product that step (1) is generated is at pH 7-8.5, and temperature 30-75 ℃ was worn out 5-120 minute down;
(3) under agitation, a kind of solution of silicon-containing compound is joined in the product that step (2) obtains;
(4) at pH 8-10,80-98 ℃ of product 12-24 hour of descending aging step (3) to obtain;
(5) product that wash, filtration step (4) obtains;
(6) product that obtains of drying steps (5) obtains product provided by the invention.
Have after silica-alumina with structure of similar to thin diaspore provided by the invention is activated conventional silica-alumina specific surface, pore volume, can several apertures, its specific surface is a 250-500 rice
2/ gram is preferably 300-420 rice
2/ gram, pore volume is 0.4-2 milliliter/gram, is preferably 0.5-1.5 milliliter/gram, can several apertures be the 4-20 nanometer, is preferably the 5-15 nanometer.Therefore, the silica-alumina with structure of similar to thin diaspore provided by the invention can be used as the matrix of various adsorbents, catalyst carrier and catalyst and/or the precursor use of binding agent.Be particularly suitable for the carrier precursor of catalyst such as hydrotreatment, hydrocracking, catalytic cracking, isomerization, alkylation, disproportionation.As a kind of matrix precursor, it can also with combination of components such as molecular sieve, clay, also can make the catalyst of various desired properties with the combination of molecular sieve and/or metal component.
The following examples are with the present invention is further illustrated.
Agents useful for same in the example except that specifying, is chemically pure reagent.
Example 1-5 explanation silica-alumina with structure of similar to thin diaspore provided by the invention and preparation method thereof.
Example 1
Take by weighing 515 gram alchlors (Beijing chemical reagent factory product), be dissolved into 1.6 liters of aluminum trichloride solution a1 (Al with deionized water
2O
3Concentration is 65 grams per liters); 500 milliliters of concentrated ammonia liquors (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b1 with deionized water; The modulus of getting technical grade is 3.26, SiO
2Content is 220 milliliters of the water glass solutions (Chang Ling refinery product) of 280 grams per liters, is diluted to 1000 ml soln c1 with deionized water; Get 75 gram NaOH, be dissolved into 150 ml soln d1 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 40 ℃, and stream adds solution a1 and b1, it is 7 that the adjusting flow makes the pH value of reaction system, and product is gone into ageing can and worn out, aging condition: pH is 7, temperature is 45 ℃, ageing time is 30 minutes, behind aging the end, under agitation adds solution c1 and d1 successively.This moment, the pH of reaction system was 8.9, and temperature is 50 ℃, was warming up to 85 ℃ and constant temperature and filtered after 23 hours.Filter cake spends deionised water 5 times, filter after each washing, the filter cake after the last washing 110 ℃ dry 20 hours down, promptly obtain silica-alumina M-1 provided by the invention.The x-ray diffraction spectra of M-1 is seen Fig. 1 a, the content of silica, aluminium oxide, N value and specific surface, can several holes, pore volume sees Table 1.
The X-ray diffracting spectrum is measured on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44KV, 40mA, sweep speed is 2 °/minute (down together).
Silica, alumina content adopt x-ray fluorescence spectrometry.Before the mensuration, sample is at first in 600 ℃ of roastings 2 hours (down together).
Specific surface, can several apertures, pore volume adopts B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature to measure.Before the mensuration, sample is at first in 600 ℃ of roastings 2 hours (down together).
27The chemical shift at each peak and each peak area are that reference is measured with saturated aluminum sulfate aqueous solution on Varian UnityInova 300M type nuclear magnetic resonance spectrometer in the Al NMR spectrogram.And according to formula N=P1/P2 calculating N value, P1 is the solid of silica-alumina
27Chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the Al NMR spectrogram, and P2 is the solid of silica-alumina
27Chemical shift is the peak area (down together) at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
Example 2
Take by weighing 800 gram aluminum nitrates (Beijing chemical reagent factory product), be dissolved into 1.6 liters of aluminum nitrate solution a2 (Al with deionized water
2O
3Concentration is 65 grams per liters); 500 milliliters of concentrated ammonia liquors (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b2 with deionized water; The modulus of getting technical grade is 3.26, SiO
2Content is 60 milliliters of the water glass solutions (Chang Ling refinery product) of 280 grams per liters, is diluted to 240 ml soln c2 with deionized water; Get 75 gram NaOH, be dissolved into 150 ml soln d2 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 50 ℃, and stream adds solution a2 and b2, it is 8 that the adjusting flow makes the pH value of reaction system, and product is gone into ageing can and worn out, and aging condition is that pH is 7.6, temperature is 60 ℃, ageing time is 30 minutes, behind aging the end, under agitation adds solution c2 and d2 successively.This moment, the pH of reaction system was 8.5, and temperature is 65 ℃, was warming up to 90 ℃ and constant temperature and filtered after 13 hours.Filter cake spends deionised water 5 times, filter after each washing, the filter cake after the last washing 150 ℃ dry 6 hours down, promptly obtain silica-alumina M-2 of the present invention.The x-ray diffraction spectra of M-2 is seen Fig. 1 b, the content of silica, aluminium oxide, N value and specific surface, can several apertures, pore volume sees Table 1.
Example 3
Take by weighing 800 gram aluminum nitrates (Beijing chemical reagent factory product), be dissolved into 1.6 liters of aluminum nitrate solution a3 (Al with deionized water
2O
3Concentration is 65 grams per liters); 500 milliliters of concentrated ammonia liquors (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b3 with deionized water; The modulus of getting technical grade is 3.26, SiO
2160 milliliters of the water glass solutions of content 280 grams per liters (Chang Ling refinery product) are diluted to 500 ml soln c3 with deionized water; Get 35 gram NaOH, be dissolved into 150 ml soln d3 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 40 ℃, and stream adds solution a3 and b3, it is 8 that the adjusting flow makes the pH value of reaction system, and product is gone into ageing can and worn out, and aging condition is that pH is 8, temperature is 45 ℃, ageing time is 60 minutes, behind aging the end, under agitation adds solution c3 and d3 successively.This moment, the pH of reaction system was 8.2, and temperature is 50 ℃, was warming up to 95 ℃ and constant temperature and filtered after 20 hours.Filter cake spends deionised water 4 times, filter after each washing, the filter cake after the last washing 120 ℃ dry 15 hours down, promptly obtain silica-alumina M-3 of the present invention.The x-ray diffraction spectra of M-3 is seen Fig. 1 c, the content of silica, aluminium oxide, N value and specific surface, can several apertures, pore volume sees Table 1.
Example 4
Take by weighing 800 gram aluminum nitrates (Beijing chemical reagent factory product), be dissolved into 1.6 liters of aluminum nitrate solution a4 (Al with deionized water
2O
3Concentration is 65 grams per liters); 500 milliliters of concentrated ammonia liquors (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b4 with deionized water; The modulus of getting technical grade is 3.26, SiO
2Content is 220 milliliters of the water glass solutions (Chang Ling refinery product) of 280 grams per liters, is diluted to 1000 ml soln c4 with deionized water; Get 120 gram NaOH, be dissolved into 150 ml soln d4 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 40 ℃, and stream adds solution a4 and b4, it is 7.3 that the adjusting flow makes the pH value of reaction system, and product is gone into ageing can and worn out, and aging condition is that pH is 7.6, temperature is 40 ℃, ageing time is 15 minutes, behind aging the end, under agitation adds solution c4 and d4 successively.This moment, the pH of reaction system was 9.7, and temperature is 35 ℃, was warming up to 98 ℃ and constant temperature and filtered after 18 hours.Filter cake spends deionised water 6 times, filter after each washing, the filter cake after the last washing 120 ℃ dry 15 hours down, promptly obtain silica-alumina M-4 of the present invention.The x-ray diffraction spectra of M-4 is seen Fig. 1 d, the content of silica, aluminium oxide, N value and specific surface, can several apertures, pore volume sees Table 1.
Example 5
Get 1.6 liters of (Al of industrial sulphuric acid aluminum solutions a5
2O
3Concentration is about 98 grams per liters, free acid content 1.5 grams per liters).500 milliliters of concentrated ammonia liquors (Beijing Yili Fine Chemicals Co., Ltd.'s product, concentration are 25%-28%) are diluted to 1500 ml soln b5 with deionized water.Get the modulus 3.26 of technical grade, SiO
2Content is 220 milliliters of the water glass solutions of 280 grams per liters, is diluted to 1000 milliliters with deionized water, obtains solution c5.Get 50 gram NaOH, be dissolved into 150 ml soln d5 with deionized water.
In one 2 liters retort, add 1.7 liters of deionized waters, stirring also is heated to 60 ℃, and stream adds solution a5 and b5, it is 7.5 that the adjusting flow makes the pH value of reaction system, and product is gone into ageing can and worn out, and aging condition is that pH is 7, temperature is 70 ℃, ageing time is 15 minutes, behind aging the end, under agitation adds solution c5 and d5 successively.This moment, the pH of reaction system was 8.5, and temperature is 70 ℃, was warming up to 98 ℃ and constant temperature and filtered after 16 hours.Filter cake spends deionised water 5 times, filter after each washing, the filter cake after the last washing 120 ℃ dry 15 hours down, promptly obtain silica-alumina M-5 of the present invention.The x-ray diffraction spectra of M-5 is seen Fig. 1 e, the content of silica, aluminium oxide, N value and specific surface, can several apertures, pore volume sees Table 1.
Comparative Examples 1
Directly get silica-alumina commodity Siral40 that Condea company has structure of similar to thin diaspore as reference.The x-ray diffraction spectra of this product is seen Fig. 1 f; The content of silica, aluminium oxide, N value and specific surface, can several apertures, pore volume sees Table 1.
Fig. 1 g is the x-ray diffraction spectra of boehmite (SB powder, German Condea company product).
Table 1
| Example | Numbering | SiO 2 ％ | Al 2O 3 ％ | The N value | Pore structure character | ||
| Specific surface m 2·g -1 | Can a few aperture | Pore volume cm 3·g -1 | |||||
| 1 | M-1 | 41 | 59 | 0.27 | 390 | 110 | 0.98 |
| 2 | M-2 | 15 | 85 | 0.21 | 320 | 58 | 0.63 |
| 3 | M-3 | 29 | 71 | 0.23 | 350 | 60 | 0.66 |
| 4 | M-4 | 39 | 61 | 0.78 | 342 | 100 | 1.07 |
| 5 | M-5 | 43 | 57 | 0.41 | 417 | 95 | 0.96 |
| Comparative Examples 1 | Siral40 | 40 | 60 | 0.12 | 437 | 75 | 0.89 |
The result that table 1 provides can show, by the N value of the silica-alumina with structure of similar to thin diaspore provided by the invention apparently higher than existing silica-alumina with structure of similar to thin diaspore.
Example 6-10
This example explanation is provided by the invention to have the silica-alumina of the structure of similar to thin diaspore pure hydrocarbon cracking performance after activated.
With M-1, M-2, M-3, M-4, M-5 respectively 600 ℃ of following roastings 4 hours.Afterwards, use n-C
14As raw material, on the pulse micro-inverse device, estimate, catalyst loading amount 0.1 gram, 480 ℃ of reaction temperatures, sample size is 0.3 microlitre.Nitrogen is done carrier gas, and flow velocity is 30 ml/min, fid detector.Use n-C
14Conversion ratio as cracking activity, the results are shown in Table 2.
Comparative Examples 2
Catalytic cracking performance after this Comparative Examples explanation Siral40 is activated.
Evaluation method the results are shown in Table 2 with example 6.
Table 2
| Example | Silica-alumina | n-C 14Cracking activity/% |
| 6 | M-1 | 7.0 |
| 7 | M-2 | 6.0 |
| 8 | M-3 | 6.5 |
| 9 | M-4 | 11.0 |
| 10 | M-5 | 8.5 |
| Comparative Examples 2 | Siral40 | 5.0 |
The result that table 2 provides can show, compares with existing silica-alumina with structure of similar to thin diaspore, and after the silica-alumina with structure of similar to thin diaspore provided by the invention was activated, its cracking activity obviously improved.
Example 11-12
This example explanation is provided by the invention to have the silica-alumina of the structure of similar to thin diaspore catalytic cracking performance after activated.
In this example, the evaluation of catalyst is carried out according to the method that RIPP 92-90 provides.M-1, M-3 are activated 4 hours down at 600 ℃ respectively, be broken into 20-40 purpose particle afterwards, feedstock oil is grand celebration VGO, catalyst 5 grams of in fixed bed reactors, packing into, and 500 ℃ of reaction temperatures, oil inlet quantity 1.7 grams, the oil-feed time is 70 seconds, conversion ratio sees Table 3.
Comparative Examples 3
Catalytic cracking performance after this Comparative Examples explanation Siral40 is activated.
Evaluation method the results are shown in Table 3 with example 11.
Example 13-14
This example illustrates that silica-alumina provided by the invention is through the catalytic cracking performance of 800 ℃ of steam treatment after 4 hours.
In this example, the evaluation of the evaluate catalysts of catalyst is carried out according to the method that RIPP 92-90 provides.Be specially, M-1, M-3 respectively 800 ℃ of following hydrothermal treatment consists 4 hours, are become catalyst breakage 20-40 purpose particle afterwards, catalyst 5 grams of in reactor, packing into, 500 ℃ of reaction temperatures, oil inlet quantity 1.7 grams, the results are shown in Table in 3 70 seconds oil-feed time.
Comparative Examples 4
This Comparative Examples explanation Siral40 is through through the catalytic cracking performance of 800 ℃ of steam treatment after 4 hours.
Evaluation method the results are shown in Table 3 with example 13.
Table 3
| Example | 11 | 12 | Comparative Examples 3 | 13 | 14 | Comparative Examples 4 |
| Silica-alumina | M-1 | M-3 | Siral40 | M-1 | M-3 | Siral40 |
| Activation temperature/℃ | 600 | 600 | 600 | 800 | 800 | 800 |
| Conversion ratio/% | 77 | 80 | 70 | 75 | 77 | 68 |
The result that table 3 provides shows, compares with existing silica-alumina with structure of similar to thin diaspore, and is not only active high after the silica-alumina with structure of similar to thin diaspore provided by the invention is activated, has good hydrothermal stability simultaneously.
Claims (14)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03157163 CN1267187C (en) | 2003-09-17 | 2003-09-17 | Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03157163 CN1267187C (en) | 2003-09-17 | 2003-09-17 | Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597092A CN1597092A (en) | 2005-03-23 |
| CN1267187C true CN1267187C (en) | 2006-08-02 |
Family
ID=34660228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03157163 Expired - Lifetime CN1267187C (en) | 2003-09-17 | 2003-09-17 | Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1267187C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915485B (en) * | 2005-08-17 | 2010-05-12 | 中国石油化工股份有限公司 | A kind of alumina with additives |
| CN1915486B (en) * | 2005-08-17 | 2010-05-12 | 中国石油化工股份有限公司 | A kind of hydrated alumina with pseudo-boehmite structure containing additives |
| CN102139217B (en) * | 2010-02-03 | 2013-04-24 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN102160996B (en) * | 2010-02-24 | 2013-06-26 | 中国石油化工股份有限公司 | Composition of pseudo-boehmite and silicon-containing compound and silica-alumina prepared therefrom |
| CN109053418A (en) * | 2018-07-31 | 2018-12-21 | 菏泽华立新材料有限公司 | A kind of the organic acid processing method and its device of aluminium isopropoxide dead catalyst |
| CN117000222A (en) * | 2022-04-27 | 2023-11-07 | 中国石油化工股份有限公司 | A silicon oxide-pseudo-boehmite composition and its preparation method and application |
-
2003
- 2003-09-17 CN CN 03157163 patent/CN1267187C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1597092A (en) | 2005-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1091428C (en) | Preparation method of pseudo-boehmite | |
| CN1164494C (en) | Preparation method of γ-alumina | |
| CN1261217C (en) | A kind of mesoporous silicon aluminum material and preparation method thereof | |
| CN1275855C (en) | Nano-grade Y type zeolite synthesized from kaolin and its preparation metod | |
| EP3658503A1 (en) | Methods for producing hierarchical mesoporous zeolite beta | |
| CN116265107B (en) | A method for preparing a high-yield diesel catalytic cracking catalyst | |
| CN1068975A (en) | The preparation method of low-density, large pore volume, high-strength alumina carrier | |
| CN1803613A (en) | ZSM-5 type molecular sieve and method for preparing the same | |
| CN114425399A (en) | Catalytic cracking catalyst, preparation method and application thereof | |
| CN1901993A (en) | Catalyst, process for preparing the catalyst and process for producing lower hydrocarbon with the catalyst | |
| CN1048655C (en) | Alkyl catalyst and application thereof | |
| CN105268469B (en) | A kind of catalytic cracking catalyst and its preparation method and application | |
| CN1267187C (en) | Silicon oxide-aluminium oxide having pseudo thin allophane structure and its preparation method | |
| CN1072031C (en) | Preparation method for penta-basic cyclic molecular sieve composite | |
| CN116265108B (en) | Preparation method of catalytic cracking catalyst for producing more gasoline | |
| CN116265106B (en) | A method for preparing a catalyst for catalytic cracking of high-yield light olefins | |
| EP3661646B1 (en) | A zeolitic material having framework type cha and comprising a transition metal and one or more of potassium and cesium | |
| CN1915486A (en) | Hydrated alumina with structure of similar to thin diaspore of containing additive | |
| CN1608992A (en) | Modified molecular sieve and its prepn process | |
| CN1504409A (en) | A kind of ZSM-35/MCM-22 co-crystal molecular sieve and its preparation method | |
| CN1121979C (en) | Process for preparing ZSM-5 molecular sieve | |
| CN1335258A (en) | Synthesis of nanometer size beta-zeolite | |
| CN1417296A (en) | Phosphorus-containing aluminium sol adhesive for catalyst and its prepn | |
| CN1915485A (en) | Alumina of containing additive | |
| CN1024503C (en) | Rare earth Y molecular sieve cracking catalyst and its preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060802 |
|
| CX01 | Expiry of patent term |