CN102725063A - Titania-containing extrudate - Google Patents
Titania-containing extrudate Download PDFInfo
- Publication number
- CN102725063A CN102725063A CN2010800578488A CN201080057848A CN102725063A CN 102725063 A CN102725063 A CN 102725063A CN 2010800578488 A CN2010800578488 A CN 2010800578488A CN 201080057848 A CN201080057848 A CN 201080057848A CN 102725063 A CN102725063 A CN 102725063A
- Authority
- CN
- China
- Prior art keywords
- extrudate
- alkyl cellulose
- titanium dioxide
- cellulose
- hydroxy alkyl
- 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.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 claims abstract description 28
- 125000004181 carboxyalkyl group Chemical group 0.000 claims abstract description 24
- 239000004408 titanium dioxide Substances 0.000 claims description 42
- 229920013820 alkyl cellulose Polymers 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 14
- -1 2-hydroxypropyl Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- CWSZBVAUYPTXTG-UHFFFAOYSA-N 5-[6-[[3,4-dihydroxy-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxymethyl]-3,4-dihydroxy-5-[4-hydroxy-3-(2-hydroxyethoxy)-6-(hydroxymethyl)-5-methoxyoxan-2-yl]oxyoxan-2-yl]oxy-6-(hydroxymethyl)-2-methyloxane-3,4-diol Chemical compound O1C(CO)C(OC)C(O)C(O)C1OCC1C(OC2C(C(O)C(OC)C(CO)O2)OCCO)C(O)C(O)C(OC2C(OC(C)C(O)C2O)CO)O1 CWSZBVAUYPTXTG-UHFFFAOYSA-N 0.000 claims 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims 2
- 229920002678 cellulose Polymers 0.000 abstract description 16
- 239000001913 cellulose Substances 0.000 abstract description 16
- 238000001125 extrusion Methods 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000001354 calcination Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 229920003091 Methocel™ Polymers 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 210000003746 feather Anatomy 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 235000010894 Artemisia argyi Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 244000030166 artemisia Species 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 238000007598 dipping method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B30/00—Compositions for artificial stone, not containing binders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/38—Polysaccharides or derivatives thereof
- C04B24/383—Cellulose or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/28—Polysaccharides or derivatives thereof
- C04B26/285—Cellulose or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
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Abstract
An extrudate comprising titania, a carboxyalkyl cellulose, and a hydroxyalkyl cellulose is disclosed. The extrudates have a smooth outer surface when they exit the extruder. The extrusion processibility is improved.
Description
Technical field
The present invention relates to a kind of extrudate that comprises titanium dioxide, carboxyl alkyl cellulose and hydroxy alkyl cellulose.
Background of invention
Titanium dioxide (titania) (or titanium dioxide (titanium dioxide)) is well-known white inorganic pigment.Except as the pigment, titanium dioxide also has other purposes.For example, titanium dioxide useful as catalysts or catalyst carrier (Stiles, A.B., " Supports Other Than Alumina, "
Catalyst Supports and Supported Catalysts(1987) Butterworths Publishers, pp.57-85).Commercial, titanium dioxide is produced with the form of fine powder.When titanium dioxide is used as catalyst or catalyst carrier, often need make it be configured as particle, for example sphere, sheet shape, extrudate or the like.Although on the preparation method of development titanium dioxide extrudate, make many effort, because its machinability method far short of what is expected is inappropriate for and commercially produces.Therefore, need to continue the new method of development and preparation titanium dioxide extrudate, in particular as catalyst carrier (referring to the common pending application file number 01-2768A [still unallocated sequence number] that for example submitted on December 16th, 2009).
Summary of the invention
The present invention is a kind of extrudate that comprises titanium dioxide, carboxyl alkyl cellulose and hydroxy alkyl cellulose; The preparation method of said extrudate comprises that (a) mixes titanium dioxide, carboxyl alkyl cellulose and hydroxy alkyl cellulose to form material group (dough); And (b) said material group is extruded with the preparation extrudate.This method has the machinability of improvement and prepares the extrudate with smooth outer surface.
Detailed Description Of The Invention
The present invention is a kind of extrudate that comprises titanium dioxide.The titanium dioxide that is fit to can be rutile, anatase, brockite or its mixture.Titanium dioxide can prepare through chloridising, sulfate process, hydro-thermal method or titanium tetrachloride flame hydrolysis.The example of suitable titanium dioxide comprises TiONA
DT-51, DT-52, DT-51D, DT-40 and the DT-20 of Millennium Inorganic Chemicals company.
Extrudate comprises carboxyl alkyl cellulose.Shown in scheme I, cellulose is to have formula (C
6H
10O
5)
nOrganic compound, the polysaccharide that a kind of linear chain by β-1,4 connecting key is formed, n=50-20 wherein, 000.Cellulose is the constituent of green plants primary cell wall.Cellulose can be transformed into many derivatives.
Scheme I
Carboxyl alkyl cellulose is a kind of cellulose derivative, and shown in scheme II, its carboxyalkyl that has is connected with some hydroxyls of the glucopyranose monomer that constitutes cellulose skeleton, wherein R=H, carboxyalkyl, m=50-20000.Often use its sodium salt, carboxyl alkyl cellulose sodium.The functional characteristic of carboxyl alkyl cellulose depends on the substitution value (promptly having how many hydroxyls to participate in substitution reaction) of cellulosic structure and the chain length and the substituent concentration class of cellulose skeleton.The average of the substituted hydroxyl of every glucose unit is called substitution value (DS) in cellulose derivative.Replacement can be provided as 3 DS fully.Preferably, use carboxymethyl cellulose.Preferred carboxymethyl cellulose have 0.5-0.9 substitution value (D.B.Braun and M.R.Rosen,
Rheology is repaiied Positive handbook (Rheology Modifiers Handbook):
Actual use and use (Practical Use and Applications) (2000) William Andrew Publishing, the 109-131 page or leaf).Known carboxymethyl cellulose is as extrusion aid (extrusion aids) (United States Patent(USP) No. 5,884,138 and 6,709,570; The open No.2008/0146721 of U.S. Patent application).
Scheme II
Extrudate also comprises hydroxy alkyl cellulose.Hydroxy alkyl cellulose is a cellulose derivative, and wherein some hydroxyls in the glucose unit that repeats are by hydroxyalkylation.Some hydroxyls in the hydroxy alkyl cellulose also can be by alkylation.Shown in the typical structure of hydroxy alkyl cellulose such as the scheme II, wherein R=H, alkyl, hydroxyalkyl, m=50-20,000.Preferably, hydroxyalkyl is selected from 2-ethoxy, 2-hydroxypropyl and their mixture.More preferably, hydroxy alkyl cellulose is by alkylation.Most preferably, hydroxy alkyl cellulose is selected from 2-HEMC, 2-hydroxypropyl methylcellulose and their mixture.Preferably, the methyl substituted degree is 1-2, more preferably 1.5-1.8; 2-ethoxy or 2-hydroxypropyl molar substitution are 0.1-0.3.The preferred METHOCEL that uses Dow Chemical (DOW Chemical) company
TMK4M cellulose derivative, the methyl substituted degree that it has are 1.4, the hydroxypropyl molar substitution is 0.21.Known hydroxy alkyl cellulose is as extrusion aid (United States Patent(USP) No. 5884138,6316383 and 6709570).
Extrudate can comprise other inorganic oxide except that titanium dioxide, for example silica, aluminium oxide, zirconia, magnesia, silica-alumina, silica-magnesia, zeolite, clay etc. and composition thereof.The silica that is fit to comprises for example silica gel, precipitated silica and fumed silica.The weight ratio of other inorganic matter oxide and titanium dioxide is more preferably less than 20: 80 preferably less than 50: 50, most preferably less than 10: 90.
The weight ratio of carboxyl alkyl cellulose and titanium dioxide is preferably 0.2: 100-5: 100, more preferably 0.5: 100-4: 100, most preferably 1: 100-3: 100.The weight ratio of hydroxy alkyl cellulose and titanium dioxide is preferably 0.1: 100-2.5: 100, more preferably 0.2: 100-2: 100, most preferably 0.5: 100-1: 100.Carboxyl alkyl cellulose and hydroxy alkyl cellulose weight ratio are preferably 5: 1-1: 2, more preferably 3: 1-1: 1.
In order to prepare extrudate, titanium dioxide, carboxyl alkyl cellulose and hydroxy alkyl cellulose are processed well-mixed material group.If be necessary, can use solvent.The solvent that is fit to comprises water, alcohol, ether, ester, acid amides, aromatic compound, halogenated compound etc. and composition thereof.Preferred solvent is water, pure and mild their mixture.Suitable alcohol comprises methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol and phenmethylol.
TiO 2 sol can be as the titanium dioxide source.TiO 2 sol is the soliquid of titanium dioxide granule in liquid.Can be through the titanium dioxide precursor hydrolysis be prepared TiO 2 sol.Suitable titanium dioxide precursor comprises titanium salt, titanium halide, titanium alkoxide, titanium oxyhalide etc.
Extrudate of the present invention makes through extruding, and its process is to push material group to make it pass mould or aperture (orifice) to produce the long materials of constant cross-section.Extrude and generally be used for processing plastic or food, and be used to form adsorbent, catalyst or catalyst carrier.Can use the extruder of any routine." particle diameter enlarges (Particle Size Enlargement), "
The powder technology handbook (Handbook of Powder Technology), among vol.1 (1980) pp.112-22 a kind of suitable screw-type extruder has been described.
Carboxyl alkyl cellulose and hydroxy alkyl cellulose use as extrusion aid.Extrusion aid helps to mix, grind and extrude operation, and can improve the machinery and/or the physical property of extrudate, like crushing strength, surface area, hole dimension or pore volume.The extrudate that contains titanium dioxide, carboxyl alkyl cellulose and hydroxy alkyl cellulose has smooth outer surface.When by moulding, drying and calcining, they are not easy to stick to each other, and are fit to large-scale production.In addition, the combination of carboxyl alkyl cellulose and hydroxy alkyl cellulose (feathering) minimizes " emergence ".Term " emergence " is meant that extrudate is not to have smooth outer surface, but crackle occurs on its surface, the flakelet of extrudate or " feather (feather) " and surface isolation." emergence " not only causes the loss of utility, but also is easy to damage the physical strength of extrudate.
Extrudate can comprise other extrusion aid, for example comprises alkylamine, carboxylic acid, alkyl ammonium compound, amino alcohol, starch, polyacrylate, polymethacrylates, gathers (vinyl alcohol), gathers (vinyl pyrrolidone), gathers (amino acid), polyethers, gathers (oxolane), metal carboxylate etc. and composition thereof.Preferably gathering (alkylene oxide) is the copolymer that gathers (oxirane), gathers (expoxy propane) or oxirane and expoxy propane.Usually remove organic extrusion aid through calcining.
Extrudate carries out drying usually after moulding.Most of solvent (for example greater than 90%) is generally removed in drying process from extrudate.Said drying process can be carried out in 30-200 ℃ under atmospheric pressure or vacuum.Said drying can be carried out in air or inert atmosphere.Sometimes the preferred baking temperature that slowly improves makes extrudate not by cracking or damage.
The present invention includes the calcining extrudate.Preferably, in oxygen-containing gas, calcine the organic substance (for example residual solvent and extrusion aid) that is included in the extrudate to burn.Calcining can be at 400-1000 ℃, more preferably 450-800 ℃, most preferably carries out under 650-750 ℃.Sometimes, in inert gas (for example nitrogen, helium), extrudate is initially calcined will be included in the organic compound thermal decomposition in this extrudate, it is favourable in oxygen-containing gas, burning organic substance then.Usually, the burnt extrudate after the calcining contains the carbon that is less than 0.5wt%.Preferably, it contains the carbon that is less than 0.1wt%.
The present invention comprises the preparation method of extrudate in addition, and this method comprises that (a) mixes titanium dioxide, carboxyl alkyl cellulose and hydroxy alkyl cellulose to form material group; (b) said material group is extruded with the preparation extrudate.Describe said method in the chapters and sections in front in detail.
Embodiment 1
In Chinese mugwort formula blender (Eirich mixer) with D-T51 titanium dioxide (2500g), a kind of high-purity WALOCEL
TMThe sodium carboxymethylcellulose of C (Dow Chemical, 52.5g), gather (oxirane) (MW=100,000,35g) with 2-hydroxypropyl cellulose (METHOCEL
TMK4M 25g) mixed 5 minutes.With water (1005g), water-based ammonium hydroxide (14.8M, 100g) and phenmethylol (17.5g) join in this mixer.They were mixed 5 minutes under " low " speed is set, under " height " speed is set, mixed 10 minutes then.The material group that produces is placed in the hopper of 2 inches extruders of Bonnot, and said extruder has been equipped with the die face (Bonnot company) of 1/8 inch of one 25 hole dia.Speed with about 0.25 kg/min is extruded.The extrudate that makes has smooth outer surface, and it is minimum to stick to each other.Almost do not observe emergence.
Extrudate is piled up 1 inch thickness on collection tray, and in air in 80 ℃ dry 12 hours down, in air, calcine then.Calcining heat is elevated to 500 ℃ with 2 ℃/minute speed from room temperature, keeps 2 hours at 500 ℃, is elevated to 700 ℃ with 10 ℃/minute speed from 500 ℃, keeps 3 hours at 700 ℃, reduces to room temperature then.
Some physical properties of burnt titanium dioxide extrudate are listed in table 1.Adopt Chatillon crushing strength analyzer (DPP 50 types) to measure the crushing strength of burnt titanium dioxide extrudate.Average so that report value to be provided to destroying needed power in 25 measurements.Measure bulk density through the burnt extrudate of 40g being put into 100mL graduated cylinder (1 inch nominal outside diameter).Rap graduated cylinder and no longer change, should be worth then divided by quality to calculate bulk density up to apparent volume.Be filled to confirm voidage through in the 50mL of second graduated cylinder water, adding particle and rapping then until all spaces.The volume sum that water and particle occupy separately deducts the water yield that obtains, with the voidage of confirming to be occupied by water., then wet extrudate is weighed so that it passes basket, shakes to remove excessive water through mixture is toppled over, confirm total pore volume thus.The quality that will on initial 40g extrudate basis, be increased is divided by the density of the water measured value as pore volume.
Comparative Examples 2
Operation with the prescription repetition embodiment 1 shown in the table 1.This extrudate is sagging and when they drop on the collection tray, trends towards mutual adhesion when extrudate leaves the die face of extruder.
Comparative Examples 3
Operation with the prescription repetition embodiment 1 shown in the table 1.This extrudate is sagging and when they drop on the collection tray, trends towards mutual adhesion when extrudate leaves the die face of extruder.
Table 1
| Embodiment | 1 | Comparative Examples 2 | Comparative Examples 3 |
| Prescription | |||
| Titanium dioxide (g) | 2500 | 2500 | 2500 |
| Water (g) | 1005 | 1250 | 1005 |
| Gather (oxirane) (g) | 35 | 35 | 35 |
| WALOCEL TMC cellulose (g) | 52.5 | 52.5 | 52.5 |
| Phenmethylol (g) | 17.5 | 17.5 | 17.5 |
| Ammonium hydroxide (g) | 100 | 100 | 100 |
| METHOCEL TMK4M cellulose (g) | 25 | 0 | 0 |
| Extrude machinability | Good | Difference | Difference |
| The performance of calcining extrudate | |||
| Crushing strength (Ib/mm) | 1.68 | 1.37 | 1.43 |
| Surface area (m 2/g) | 27.2 | n/a | n/a |
| Pore volume (mL/g) | 0.32 | 0.30 | 0.30 |
Comparative Examples 4
Repeat the operation of embodiment 1, difference is prescription as follows: DT51 (2000g), TAMOL
TM1124 dispersants (from the hydrophily polyelectrolyte copolymer of Dow Chemical, 32.6g), METHOCEL
TMK4M (54.6g), lactic acid (6g), water (950g), ammonium hydroxide aqueous solution (14.8M, 70g).
Comparative Examples 5
Repeat the operation of embodiment 4; Difference is to use aluminium oxide (DISPERAL
P2; Derive from Sasol, 20g).This extrudate is sagging and when they drop on the metal tray, trends towards mutual adhesion when extrudate leaves the die face of extruder.Burnt extrudate contains the aluminium oxide of 1wt% and the titanium dioxide of 99wt%.
Table 2
Embodiment 6
Repeat the operation of embodiment 1, difference is prescription as follows: DT51 (300g), TAMOL
TM1124 dispersants (5g), WALOCEL
TMC cellulose (6g), METHOCEL
TMK4M cellulose (6g), lactic acid (4.5g), water (155g) and water-based ammonium hydroxide (14.8M, 11g).Extrudate has smooth outer surface.It is minimum to observe emergence.Almost do not observe the mutual adhesion of extrudate.
Comparative Examples 7
Repeat the operation of embodiment 6, difference is to fill a prescription as shown in table 3.Slump when extrudate leaves die face.They are adhesion mutually on collection tray.
Comparative Examples 8
Repeat the operation of embodiment 6, difference is to fill a prescription as shown in table 3., extrudate do not trend towards mutual adhesion after dropping on the collection tray.Yet they look and occur having sprouted wings.
Table 3
| Embodiment | 6 | Comparative Examples 7 | Comparative Examples 8 |
| Prescription | |||
| DT-51 titanium dioxide (g) | 300 | 300 | 300 |
| Water (g) | 155 | 145 | 145 |
| TAMOL TM1124 dispersants (g) | 5 | 5 | 5 |
| WALOCEL TMC cellulose (g) | 6 | 0 | 6 |
| Lactic acid (g) | 4.5 | 4.5 | 4.5 |
| Ammonium hydroxide (g) | 11 | 11 | 11 |
| METHOCEL TMK4M cellulose (g) | 6 | 6 | 0 |
| Extrude machinability | Good | Difference | Difference |
Embodiment 9
With NaHCO
3Powder (27 gram) slowly joins and contains Na
2PdCl
43H
2O (31.4 gram), NaAuCl
42H
2In the aqueous solution of O (11.3 gram) and water (235.4 gram).With this mixture stirring at room 10 minutes.The burnt titanium dioxide extrudate (1000 gram) that uses pipette that this spray solution is prepared in embodiment 1 is gone up and they is overturn in rotary flask.In case accomplish dipping, use heat gun that this rotary flask is heated to about 100 ℃.Under 100 ℃, impregnated extrudate was overturn 30 minutes again, before they being cooled to room temperature, in 80 ℃ baking box, placed 2 hours then.
Wash dry extrudate till not determining chloride with warm water (50-80 ℃), said mensuration is carried out through wash filtrate being mixed with the silver nitrate of 1wt% to observe sediment.After accomplishing washing, dry said catalyst anhydrates to remove under 80-100 ℃.Then with they in air in 230 ℃ the heating 3 hours, nitrogen flow down in 230 ℃ the heating 30 minutes.Before extrudate is cooled to room temperature, make it in the stream of nitrogen gas that contains 10mol% hydrogen, temperature is increased to 500 ℃ and kept 3 hours.
The aqueous solution (10 liters) washing extrudate with the potassium hydroxide that contains 10wt% potassium acetate and 1wt%.With the extrudate after the washing under nitrogen in 125 ℃ of dryings 2 hours.Obtain palladium-gold catalyst.It contains 0.93wt% palladium, 0.54wt% gold and 1.5wt% potassium.
Embodiment 10
Palladium-gold catalyst with embodiment 9 preparations in fixed bed reactors (stainless steel, 1 inch of external diameter) is used for vinyl acetate production so that it is tested.This reactor is mounted with catalyst (10g) and inertia alpha-aluminium oxide cylindrical particle (1/8 inch of diameter, surface area 4m
2/ g, pore volume 0.25mL/g, mixture 25g).Charging comprises the helium of 46.1mol%, the ethene of 33.9mol%, the acetate of 11.48mol%, the oxygen of 4.2mol% and the nitrogen of 4.2mol%.Reactor pressure be 80psig and under standard temperature and pressure (STP) the air speed with respect to catalyst volume be 3050h
-1Adopt this reactor of fluidized bed sand bath cooling, and the sand bath temperature is set at 130 ℃.Flow through gas-chromatography (GC) assay products.By GC result calculate logistics between 75 to 100 hours to the oxygen conversion of vinyl acetate, oxygen selectivity, oxygen productive rate with to the ethylene selectivity of vinyl acetate, be listed in the table 4.The amount of oxygen that consumes is calculated oxygen conversion divided by the amount of oxygen that is fed into reactor.The oxygen selectivity of vinyl acetate is that the amount of oxygen that consumes in the vinyl acetate of preparation is divided by the amount of oxygen that consumes.The oxygen productive rate of vinyl acetate is an optionally product of oxygen conversion and oxygen.The ethylene selectivity of vinyl acetate is that the ethene amount that consumes in the vinyl acetate of preparation is divided by the ethene total amount that consumes.Catalyst productivity is the gram number of the vinyl acetate per hour produced of every liter of catalyst.
Table 4
| Oxygen conversion (%) | 63.7 |
| The oxygen selectivity (%) of vinyl acetate | 86.3 |
| The oxygen productive rate (%) of vinyl acetate | 54.9 |
| The ethylene selectivity of vinyl acetate (%) | 97.4 |
| Catalyst productivity (gL -1·h -1) | 492.2 |
Claims (15)
1. extrudate, it comprises titanium dioxide, carboxyl alkyl cellulose and hydroxy alkyl cellulose.
2. the extrudate of claim 1, the carboxyl alkyl cellulose of this extrudate and the weight ratio of titanium dioxide are 1: 100-3: 100.
3. the extrudate of claim 1, wherein said carboxyl alkyl cellulose is a carboxymethyl cellulose.
4. the extrudate of claim 1, the hydroxy alkyl cellulose of this extrudate and the weight ratio of titanium dioxide are 0.5: 100-1: 100.
5. the extrudate of claim 1, the carboxyl alkyl cellulose of this extrudate and the weight ratio of hydroxy alkyl cellulose are 5: 1-1: 2.
6. the extrudate of claim 1, the carboxyl alkyl cellulose of this extrudate and the weight ratio of hydroxy alkyl cellulose are 3: 1-1: 1.
7. the extrudate of claim 1, wherein said hydroxy alkyl cellulose is selected from 2-hydroxypropyl cellulose, 2-hydroxyethylcellulose and their mixture.
8. the extrudate of claim 1, wherein said hydroxy alkyl cellulose is selected from 2-hydroxypropyl methylcellulose, 2-HEMC and their mixture.
9. the extrudate of claim 1, wherein titanium dioxide accounts for 10% of said extrudate weight at least.
10. the extrudate of claim 1, this extrudate also comprises the inorganic oxide except that titanium dioxide.
11. the extrudate of claim 10, the inorganic oxide of this extrudate and the weight ratio of titanium dioxide were less than 10: 90.
12. a method for preparing extrudate, this method comprise that (a) mixes titanium dioxide, carboxyl alkyl cellulose and hydroxy alkyl cellulose to form material group; And (b) said material group is extruded with the preparation extrudate.
13. the process of claim 1 wherein that said extrudate has 3: 1-1: 1 the carboxyl alkyl cellulose and the weight ratio of hydroxy alkyl cellulose.
14. the process of claim 1 wherein that said hydroxy alkyl cellulose is selected from 2-hydroxypropyl cellulose, 2-hydroxyethylcellulose and their mixture.
15. the process of claim 1 wherein that said hydroxy alkyl cellulose is selected from 2-hydroxypropyl methylcellulose, 2-HEMC and their mixture.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/653592 | 2009-12-16 | ||
| US12/653563 | 2009-12-16 | ||
| US12/653,563 US8329611B2 (en) | 2009-12-16 | 2009-12-16 | Titania-containing extrudate |
| US12/653,592 US8273682B2 (en) | 2009-12-16 | 2009-12-16 | Preparation of palladium-gold catalyst |
| PCT/US2010/057365 WO2011075277A1 (en) | 2009-12-16 | 2010-11-19 | Titania-containing extrudate |
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| CN2010800578473A Pending CN102740964A (en) | 2009-12-16 | 2010-11-19 | Preparation of palladium-gold catalyst |
| CN2010800578488A Pending CN102725063A (en) | 2009-12-16 | 2010-11-19 | Titania-containing extrudate |
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| EP (2) | EP2512655A1 (en) |
| JP (2) | JP2013514174A (en) |
| KR (2) | KR20120102079A (en) |
| CN (2) | CN102740964A (en) |
| BR (2) | BR112012014795A2 (en) |
| SG (4) | SG181640A1 (en) |
| TW (2) | TW201129455A (en) |
| WO (2) | WO2011075278A1 (en) |
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| US8273682B2 (en) | 2009-12-16 | 2012-09-25 | Lyondell Chemical Technology, L.P. | Preparation of palladium-gold catalyst |
| EP2512655A1 (en) * | 2009-12-16 | 2012-10-24 | Lyondell Chemical Technology, L.P. | Titania-containing extrudate |
| US8507720B2 (en) | 2010-01-29 | 2013-08-13 | Lyondell Chemical Technology, L.P. | Titania-alumina supported palladium catalyst |
| US8329611B2 (en) | 2009-12-16 | 2012-12-11 | Lyondell Chemical Technology, L,P. | Titania-containing extrudate |
| EP2703078A1 (en) * | 2012-09-03 | 2014-03-05 | Saudi Basic Industries Corporation | Photocatalyst comprising gold-palladium alloy, method for preparation, photolysis system |
| US20140081040A1 (en) * | 2012-09-20 | 2014-03-20 | Lyondell Chemical Technology, L.P. | Process for pre-treatment of a catalyst support and catalyst prepared therefrom |
| KR101964275B1 (en) | 2015-09-01 | 2019-04-01 | 주식회사 엘지화학 | Manufacturing method of catalyst for production of acrylic acid and the catalyst therefrom |
| US11452995B2 (en) | 2017-12-20 | 2022-09-27 | Basf Se | Catalyst and process for preparing dimethyl ether |
| CN112517065B (en) * | 2019-09-18 | 2023-05-02 | 中国石油化工股份有限公司 | Preparation method of catalyst for vinyl acetate process by ethylene gas phase method |
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| TW201129455A (en) | 2011-09-01 |
| EP2512654A1 (en) | 2012-10-24 |
| SG181647A1 (en) | 2012-07-30 |
| BR112012014697A2 (en) | 2016-04-12 |
| JP2013514175A (en) | 2013-04-25 |
| SG189707A1 (en) | 2013-05-31 |
| KR20120102080A (en) | 2012-09-17 |
| CN102740964A (en) | 2012-10-17 |
| EP2512655A1 (en) | 2012-10-24 |
| WO2011075278A1 (en) | 2011-06-23 |
| WO2011075277A1 (en) | 2011-06-23 |
| TW201129642A (en) | 2011-09-01 |
| KR20120102079A (en) | 2012-09-17 |
| SG181640A1 (en) | 2012-07-30 |
| JP2013514174A (en) | 2013-04-25 |
| SG188923A1 (en) | 2013-04-30 |
| BR112012014795A2 (en) | 2016-06-21 |
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