CN102626621B - Hydrogenation catalyst using cellular titanium dioxide as carrier and preparation method thereof - Google Patents
Hydrogenation catalyst using cellular titanium dioxide as carrier and preparation method thereof Download PDFInfo
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- CN102626621B CN102626621B CN201210081379.4A CN201210081379A CN102626621B CN 102626621 B CN102626621 B CN 102626621B CN 201210081379 A CN201210081379 A CN 201210081379A CN 102626621 B CN102626621 B CN 102626621B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 47
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 230000001413 cellular effect Effects 0.000 title abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 77
- 238000000576 coating method Methods 0.000 claims abstract description 77
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 239000010970 precious metal Substances 0.000 claims abstract description 22
- 230000001105 regulatory effect Effects 0.000 claims abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 53
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 46
- 238000007598 dipping method Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 230000009467 reduction Effects 0.000 claims description 21
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- 230000007935 neutral effect Effects 0.000 claims description 19
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 13
- 239000011247 coating layer Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 150000001722 carbon compounds Chemical class 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002941 palladium compounds Chemical class 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 229920000609 methyl cellulose Polymers 0.000 claims description 5
- 239000001923 methylcellulose Substances 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004375 Dextrin Substances 0.000 claims description 4
- 229920001353 Dextrin Polymers 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 4
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 235000019425 dextrin Nutrition 0.000 claims description 4
- 239000008101 lactose Substances 0.000 claims description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- -1 carboxyl benzaldehyde aromatic aldehyde Chemical class 0.000 claims 1
- 150000003934 aromatic aldehydes Chemical class 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
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- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 abstract 2
- 230000006578 abscission Effects 0.000 abstract 2
- 241000264877 Hippospongia communis Species 0.000 description 85
- 239000000243 solution Substances 0.000 description 29
- 238000000034 method Methods 0.000 description 24
- 230000008569 process Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 12
- 239000012535 impurity Substances 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 239000004280 Sodium formate Substances 0.000 description 9
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 9
- 235000019254 sodium formate Nutrition 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
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- 230000003197 catalytic effect Effects 0.000 description 4
- 230000021615 conjugation Effects 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- 102000002322 Egg Proteins Human genes 0.000 description 2
- 108010000912 Egg Proteins Proteins 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 210000003278 egg shell Anatomy 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZDPALFHDPFYJDY-UHFFFAOYSA-N [Na].OC=O Chemical compound [Na].OC=O ZDPALFHDPFYJDY-UHFFFAOYSA-N 0.000 description 1
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a hydrogenation catalyst using a cellular titanium dioxide as a carrier and a preparation method thereof. The catalyst is characterized by comprising cellular titanium dioxide carrier, TiO2-C composite coating and precious metal Pd. The TiO2-C composite coating has a thickness of 1-100 mum, a load of 1-10% of the weight of the cellular titanium dioxide carrier and an abscission rate no more than 3%. The precious metal Pd has a load of 0.1-1% of the weight of the cellular titanium dioxide carrier and a load depth of 1-100 muM. Compared with a prior art, the invention has the following advantages: first, the TiO2-C composite coating has high adhesion rate with cellular titanium dioxide carrier, and has smooth coating surface, no crack and low coating abscission rate; second, immersion depth of the precious metal Pd can be effectively regulated by controlling the thickness of the TiO2-C composite coating; and third, the catalyst has the advantages of simple preparation technology, good hydrogenation performance and suitability for industrialized production. The hydrogenation catalyst of the invention is suitable to be used as a hydrogenation catalyst for aromatic aldehydes like crude terephthalic acid or p-carboxy benzaldehyde.
Description
Technical field
Hydrogenation catalyst and preparation method that to the present invention relates to take honeycomb titanium dioxide be carrier, particularly take for crude terephthalic acid or to the aromatic aldehydes such as carboxyl benzaldehyde are hydrorefined hydrogenation catalyst and the preparation method that honeycomb titanium dioxide is carrier.
Background technology
P-phthalic acid (PTA) is a kind of very important Organic Chemicals, and its Downstream processing product is mainly polyester fiber, polyester film, Packaging Bottle and PET engineering plastics etc.In the crude terephthalic acid (CTA) of producing with paraxylene (PX) liquid phase oxidation, generally contain the major impurity of 2000～3000 μ g/g to carboxyl benzaldehyde (4-CBA), because its aldehyde radical is more active, can affect the color and luster of polyester fiber, need under 270～285 ℃ of high temperature, adopt hydrorefined method 4-CBA to be changed into p-methylbenzoic acid being soluble in hot water etc., the 4-CBA that terephthalic acid (TPA) after refining contains 25 μ g/g, to meet the needs of production of polyester.
Hydrofining crude terephthalic acid generally adopts 0.5%Pd/C catalyst, describes the preparation method of Pd/C catalyst in US Patent No. 4476242 (Process for preparing palladium on carbon catalyst for purification of crude terephthalic acid) and US4605763 (Process for the purification of terephthalic acid) in detail.The preparation of Pd/C catalyst adopts infusion process substantially, first active carbon is used to strong acid immersion treatment, then filters, washes, dries.By PdCl
2by hydrochloric acid heating for dissolving, become H
2pdCl
4solution adds certain water in active carbon, drips while stirring H
2pdCl
4, NaOH and formalin, standing, filter, washing solid is to neutral; Or directly by active carbon at PdCl
2in solution, soak 24 h, then with hydrogen, reduce and prepare Pd/C catalyst.
The Pd/C catalyst of prior art, employing be the activity carbon carrier of natural or artificial moulding, its specific area is easy to reach 800～1500 m
2/ g, and wherein most of micropore, 2～3 nm or following pore diameter range have been contributed most specific area.The aperture of this part body of activated carbon and surface area, totally unfavorable for the mass transfer of reaction, can cause the adverse effects such as reaction rate declines, side reaction increases, elective reduction.The specification difficulty of simultaneously determining activated carbon, the performance repeatability of every batch of active carbon is difficult to ensure card, catalyst strength is poor, bulk density is little, the catalytic performance less stable under harsh conditions.
With TiO
2catalyst as carrier exploitation has the features such as active high and low temperature activity is good, heat endurance is good, anti-Poisoning strong, acid and alkali-resistance, and between energy and noble metal, can " strong interaction " occur (SMSI), TiO
2therefore carrier is also described as the SiO that continues
2, Al
2o
3" third generation carrier " afterwards.US Patent No. 5387726 (Selective catalytic hydrogenation of aromatic aldehydes) is with TiO
2as carrier, prepared the Pd/TiO to carboxyl benzaldehyde selective hydrogenation
2catalyst, at 150 ℃ of reaction temperatures, H
2under the condition of the initial concentration 1.0% of dividing potential drop 1 MPa, 4-CBA, after reaction 1 h, 4-CBA conversion ratio reaches as high as 99.8%; But the high temperature active of this catalyst is not good enough, when reaction temperature is brought up to 270 ℃, 4-CBA conversion ratio is reduced to 90.1%.This patent gives the activity data of eggshell type and the catalyst that evenly type Pd distributes, but does not relate to the preparation method of egg-shell catalyst.In US Patent No. 5616792 (Catalytic pufification of dicarboxylic aromatic acid) by TiO
2carrier is through 900～1200 ℃ of roastings, for the preparation of the Pd/TiO of catalysis purification and recovery dicarboxylic aromatic acids
2catalyst, has reduced the content of 4-CBA in crude terephthalic acid solution, but TiO
2carrier is after 900～1200 ℃ of high-temperature roastings, and the specific area of carrier is lower than 10 m
2/ g, if direct carried noble metal Pd is unfavorable for the dispersion of active component Pd.The inventor discloses a kind of noble metal/TiO for hydrofining crude terephthalic acid
2-C Catalysts and its preparation method (application number: 201010106170.X), adopt resin to TiO
2powder is modified, the carrier after moulding under high-temperature process condition, TiO
2the carbon generating on hole wall plays supporting role, stops TiO
2caving in of the reduction of specific area, pore structure, also can suppress TiO
2the transformation of crystalline structure from anatase titanium dioxide to rutile-type.On the other hand, TiO
2and there is cooperative effect between the carbon generating, can strengthen containing palladium compound and TiO
2the affinity interaction power of-C complex carrier, prevents Pd gathering at high temperature, is conducive to improve the Hydrogenation of catalyst.But in the preparation process of catalyst, first resin need to be dissolved in organic solvent, and need to remove unnecessary organic solvent under reduced pressure, easily causes the volatilization of organic solvent, bring environmental pollution, in this patent, also do not relate to the impregnating depth problem of precious metals pd.
The Pd/TiO of prior art
2catalyst, the method for controlling active metal impregnating depth is not very desirable, or impregnating depth is a larger scope, or impregnating depth approaches surface, decentralization is not high.In fact, the impregnating depth that realizes 1～100 μ m is very difficult, and influence factor is numerous, and maceration extract pH value, impregnation concentration all have a great impact the impregnating depth of active metal from different preparation parameters such as dip time, competitive adsorbate and drying conditions.
In recent years, ceramic honey comb has had application widely as supporter at catalytic field.But because ceramic honey comb specific area is little, smooth surface, while causing direct metallizing catalyst, load capacity is little, in order to improve the coating problem of ceramic honey comb and catalyst, Chinese patent CN1451475 (titania powder and catalyst for treating waste gas for cellular catalyst for treating waste gas) provides a kind of extrusion molding good, the cellular catalyst for treating waste gas that consists of the powder of titanium dioxide and/or titanium composite oxide is with raw material and use this raw material, there is the high de-agglomeration activity of organic halogen compound and the catalyst of high denitrification activity, but in the honeycomb titanium dioxide of this catalyst, contain 0.3～5.0% sulfate radical (SO
4 2-), while adopting this carrier-supported precious metal, easily cause poisoning, the defect that when this carrier exists high-temperature roasting equally, specific area reduces.Chinese patent CN1962061 (TiO
2photochemical catalyst is in the preparation method of ceramic honey comb area load) employing cordierite-quality honeycombed ceramics is carrier, adopt sol-gel process that metatitanic acid colloidal sol is loaded on and on ceramic honey comb, obtains photochemical catalyst, for the purification of air formaldehyde or kill airborne bacterium.But in this catalyst, the thickness of loaded film is for being only 300～400 nm, and the conjugation between titanium coating and ceramic honey comb is lower, and loaded film easily comes off.Cheng Chunchun etc. (preparation and characterization of structuring carbon nano-fiber catalysis material. Total, 2008,20 (4): 1-5) take cordierite type ceramic honey comb is base material, after coating of titanium dioxide modification, dipping 4%Ni, take methane as carbon source, on cordierite type ceramic honey comb base material, grow the carbon nano-fiber of diameter 70 nm, obtain structuring nano catalytic material, and as carrier, prepare structuring Pd catalyst.Its shortcoming is that, in the growth course of carbon nano-fiber, the cracking of carbon and diffusion rate imbalance can cause the carbon generating to wrap up Ni and inactivation, so the load capacity of carbon nano-fiber is limited.
The honeycomb ceramic carrier of prior art is mainly used in the fields such as denitrating flue gas, purifying vehicle exhaust and photocatalysis, the conjugation also existing between coating and ceramic honey comb in the preparation process of honeycomb catalyst is lower, the defects such as coating easily chaps, expulsion rate height.
Summary of the invention
Pd/TiO for hydrofining crude terephthalic acid process in prior art
2the not good shortcoming of decentralization of the undesirable and active metal of active metal impregnating depth that catalyst exists, one of object of the present invention is to provide take the hydrogenation catalyst that honeycomb titanium dioxide is carrier, by controlling the coating layer thickness of honeycomb titania support, controls active metal impregnating depth; Two of object of the present invention is to provide between a kind of coating and honeycomb substrate that conjugation is high, and expulsion rate is low take the preparation method of the hydrogenation catalyst that honeycomb titanium dioxide is carrier.
Technical scheme of the present invention is as follows:
The hydrogenation catalyst that the honeycomb titanium dioxide of take is carrier, is characterized in that described catalyst is by honeycomb titania support, TiO
2-C composite coating and precious metals pd form, TiO
2-C composite coating load capacity is 1～10% of honeycomb TiO 2 carrying weight, and the load capacity of precious metals pd is 0.1～1.0% of honeycomb TiO 2 carrying weight.
TiO
2the thickness of-C composite coating is 1～100 μ m, and coating load amount is 1～10% of honeycomb TiO 2 carrying weight, expulsion rate≤3% of coating.The load capacity of precious metals pd is 0.1～1.0% of honeycomb TiO 2 carrying weight, and the load degree of depth is 1～100 μ m.
The preparation method of the hydrogenation catalyst that the honeycomb titanium dioxide of take is carrier, comprises the following steps:
(1) by honeycomb titania support densified sintering product, ash content and the impurity of carrier surface is removed in pickling, with deionized water washing, to neutral, floods the solution of non-ionic surface active agent, drying for standby.
(2) nanoscale titanium hydroxide and carbon compound are added in deionized water, stir, regulate pH value 0.5～5, obtain transparent colloidal sol.In described colloidal sol, the content of nanoscale titanium hydroxide is 1～20%, and the content of carbon compound is 1～10%.
(3) the honeycomb titania support of step (1) gained is immersed in the colloidal sol of step (2), after taking out, remove the raffinate in duct, dry, optionally, repeated impregnations is with dry as required, until meet the requirements of coating load amount, under nitrogen atmosphere, roasting acquisition coating layer thickness is the honeycomb titania support of 1～100 μ m.
(4) the honeycomb titania support of step (3) gained is flooded to solution 0.1～1 h containing palladium compound, dipping finishes the raffinate in rear removal duct, through reducing, wash, being dried, obtains hydrogenation catalyst of the present invention.
The specific area of described catalyst is 5～50 m
2/ g, the specific area of described honeycomb titania support is 0.01～1 m
2/ g.
The described carrier sintering temperature of step (1) is 950～1250 ℃.
The pickling of the carrier that step (1) is described is that the art those of ordinary skill is known, and the acid of employing can be nitric acid, hydrochloric acid, phosphoric acid etc., is preferably nitric acid, and acid concentration is 0.1～5 mol/L, and pickling time is 1～5 h.
The described non-ionic surface active agent of step (1) is any or its combination in polyethylene glycol, polyvinyl alcohol, glycerine, APEO or carboxymethyl cellulose; The concentration of described non-ionic surface active agent is 1～10%.
Described the dry of carrier of step (1) is that the art those of ordinary skill is known, normally 100～150 ℃ of baking temperatures, and drying time is 1～10 h normally.
The described nanoscale titanium hydroxide of step (2) is that the art those of ordinary skill is known, and normally any in titanium tetrachloride, butyl titanate or isopropyl titanate prepared by method for hydrolysis.
The described carbon compound of step (2) is any or its combination in glucose, sucrose, maltose, fructose, lactose, dextrin or methylcellulose.
The pH value of the colloidal sol that step (2) is described is 0.5～5.
The described dip time of step (3) is 0.1～1 h.
Described repeated impregnations and the dry number of times of step (3) is 1～10 time.
The described coating load amount of step (3) is 1～10% of honeycomb TiO 2 carrying weight.
What step (4) was described is any or its combination in palladium bichloride, palladium, palladium nitrate, palladium sulfate or ammonium chloropalladate containing palladium compound.
The reduction of the catalyst that step (4) is described is that the art those of ordinary skill is known, reducing agent is any in formaldehyde, formic acid, hydrazine hydrate, paraformaldehyde, glucose, sodium formate or sodium borohydride normally, preferable formic acid sodium, reduction temperature is room temperature～100 ℃, and the recovery time is 1～5 h.
Described the dry of catalyst of step (4) is that the art those of ordinary skill is known, normally 100～150 ℃ of baking temperatures, and drying time is 1～10 h normally.
Above-mentioned take the hydrogenation catalyst that honeycomb titanium dioxide is carrier, described catalyst is for crude terephthalic acid or the Hydrobon catalyst to aromatic aldehydes such as carboxyl benzaldehydes.
Hydrogenation catalyst of the present invention, measures on the specific area Shi U.S. ASAP2010 of the Micromeritics company physical adsorption appearance of described catalyst and carrier.Described coating layer thickness is to measure in the Dutch Philips XL-30 TMP of company SEM.On the load capacity Shi U.S. J-A1100 of the Jarrell-Ash company type ICP of described metal Pd, adopt the standard test of RIPP128-90.On the load degree of depth Shi U.S. Physical electronics Quantum of the company 2000 type X-ray scanning microprobe electron spectrometers of described metal Pd, measure.The expulsion rate of described coating is to measure on the KQ-50DB of the ultrasonic instrument Co., Ltd type numerical control supersonic cleaning apparatus of Kunshan, according to following formula, calculates.
Hydrogenation catalyst of the present invention, described activity rating is to carry out in 1 L magnetic agitation autoclave.In reactor, add 250 g crude terephthalic acids (impurity 4-CBA content is 2400 μ g/g), 700 mL deionized waters, 1.0 g Catalyst packings in special catalyst frame, 280 ℃ of the reaction temperatures of hydrogenation process, H
2dividing potential drop 0.6 MPa, reaction time 1.0 h.4-CBA content after hydrogenation adopts Shimadzu LC-10 high performance liquid chromatograph, and (C18 post, mobile phase is the CH of mass fraction 10%
3the NH of CN and 0.25 mol/L
4h
2pO
4, flow 1 mL/min, detects wavelength 240 nm, sample size 15
ul) analyze, external standard method is quantitative.
The present invention carries out pickling by the honeycomb titania support of high temperature sintering densification, remove ash content and the impurity of carrier surface, increased the step of dipping nonionic surfactant solution, be conducive to improve the conjugation of colloidal sol and honeycomb TiO 2 carrying surface, collosol coating surfacing in dry process, do not chap, the expulsion rate of coating is low.In the process for preparation of colloidal sol, added carbon compound, the carbon generating in roasting process under nitrogen atmosphere is coated on TiO
2the surfaces externally and internally of pore structure, has reduced the loss of the coating specific area causing because of high-temperature roasting, has effectively improved the heat endurance of coating, and the carbon simultaneously generating also helps and prevents the be full of cracks of coating in roasting process, greatly reduces the expulsion rate of coating.In addition, the present invention also finds can pass through to control TiO
2the thickness of-C composite coating effectively regulates the impregnating depth of precious metals pd.Because honeycomb titania support is fine and close, containing palladium compound, can only load on TiO
2on-C composite coating, the impregnating depth of Pd depends on TiO
2the thickness of-C composite coating.So just, simplify the load process of precious metals pd, adopted conventional carrying method also can access the controlled hydrogenation catalyst of impregnating depth.
With respect to prior art, advantage of the present invention is: one, TiO
2conjugation between-C composite coating and honeycomb titania support is high, and coating surface is smooth, do not chap, and the expulsion rate of coating is low.Its two, can be by controlling TiO
2the thickness of-C composite coating effectively regulates the impregnating depth of precious metals pd.Its three, the preparation technology of catalyst is simple, Hydrogenation is good, suitability for industrialized is produced.
Accompanying drawing explanation
The stereoscan photograph of the catalyst coat that accompanying drawing 1 obtains for method described in embodiment 1.
The stereoscan photograph of the catalyst coat that accompanying drawing 2 obtains for method described in comparative example 1.
Embodiment
The technical characterictic that the invention is further illustrated by the following examples, but be not limited to embodiment.
(1) by honeycomb titania support at 1050 ℃ of densified sintering products, make its specific area be down to 0.5 m
2/ g, then adopts rare nitric acid acidwashing 2 h of 1 mol/L, removes ash content and the impurity of carrier surface, with deionized water washing to neutral, the solution of the polyethylene glycol that dipping concentration is 5%, standby at 120 ℃ of dry 5 h;
(2) nanoscale titanium hydroxide and glucose are added in deionized water, in the process stirring, drip nitre acid for adjusting pH value, obtain the colloidal sol that transparent pH value is 1.In described colloidal sol, the content of nanoscale titanium hydroxide is 10%, and the content of glucose is 5%;
(3) the honeycomb titania support of step (1) gained is immersed in to 0.5 h in the colloidal sol of step (2), after taking out, remove the raffinate in duct, at 70 ℃ of dry 2 h, repeated impregnations and dry 3 times as required, until meet the requirements of coating load amount, then under 400 ℃ of nitrogen atmospheres, roasting acquisition coating layer thickness is the honeycomb titania support of 40 μ m;
(4) by solution 0.5 h of the honeycomb titania support dipping chloride containing palladium of step (3) gained, dipping finishes the raffinate in rear removal duct, under the solution room temperature of employing sodium formate, 2 h are processed in reduction, reduction finishes rear extremely neutral with deionized water washing, obtains the hydrogenation catalyst of the present embodiment through 120 ℃ of dry 5 h.
The hydrogenation catalyst that the present embodiment obtains has following performance: TiO in catalyst
2the thickness of-C composite coating is 40 μ m, and the load capacity of coating is 5% of honeycomb TiO 2 carrying weight, and the expulsion rate of coating is 1.3%.The load capacity of precious metals pd is 0.5% of honeycomb TiO 2 carrying weight, and the load degree of depth is 40 μ m.The specific area of catalyst is 39 m
2/ g, the activity of catalyst can make the 4-CBA content in crude terephthalic acid be down to 12 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that the present embodiment obtains is shown in Fig. 1, and the surfacing of coating, without crack performance.
Embodiment 2
(1) by honeycomb titania support at 950 ℃ of densified sintering products, make its specific area be down to 1 m
2/ g, then adopts rare nitric acid acidwashing 2 h of 1 mol/L, removes ash content and the impurity of carrier surface, with deionized water washing to neutral, the solution of the polyvinyl alcohol that dipping concentration is 1%, standby at 120 ℃ of dry 5 h;
(2) nanoscale titanium hydroxide and sucrose are added in deionized water, in the process stirring, drip nitre acid for adjusting pH value, obtain the colloidal sol that transparent pH value is 5.In described colloidal sol, the content of nanoscale titanium hydroxide is 1%, and the content of sucrose is 1%;
(3) the honeycomb titania support of step (1) gained is immersed in to 0.1 h in the colloidal sol of step (2), after taking out, remove the raffinate in duct, at 50 ℃ of dry 5 h, repeated impregnations and dry 10 times as required, until meet the requirements of coating load amount, then under 300 ℃ of nitrogen atmospheres, roasting acquisition coating layer thickness is the honeycomb titania support of 1 μ m;
(4) solution 0.1 h containing palladium by the honeycomb titania support dipping of step (3) gained, dipping finishes the raffinate in rear removal duct, under the solution room temperature of employing sodium formate, 2 h are processed in reduction, reduction finishes rear extremely neutral with deionized water washing, obtains the hydrogenation catalyst of the present embodiment through 120 ℃ of dry 5 h.
The hydrogenation catalyst that the present embodiment obtains has following performance: TiO in catalyst
2the thickness of-C composite coating is 1 μ m, and the load capacity of coating is 1% of honeycomb TiO 2 carrying weight, and the expulsion rate of coating is 0.7%.The load capacity of precious metals pd is 0.1% of honeycomb TiO 2 carrying weight, and the load degree of depth is 1 μ m.The specific area of catalyst is 5 m
2/ g, the activity of catalyst can make the 4-CBA content in crude terephthalic acid be down to 66 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that the present embodiment obtains has the feature of Fig. 1, and the surfacing of coating, without crack performance.
Embodiment 3
(1) by honeycomb titania support at 1250 ℃ of densified sintering products, make its specific area be down to 0.01 m
2/ g, then adopts rare nitric acid acidwashing 2 h of 1 mol/L, removes ash content and the impurity of carrier surface, with deionized water washing to neutral, the solution of the glycerine that dipping concentration is 10%, standby at 120 ℃ of dry 5 h;
(2) nanoscale titanium hydroxide and maltose are added in deionized water, in the process stirring, drip nitre acid for adjusting pH value, obtain the colloidal sol that transparent pH value is 0.5.In described colloidal sol, the content of nanoscale titanium hydroxide is 20%, and the content of maltose is 10%;
(3) the honeycomb titania support of step (1) gained is immersed in to 1 h in the colloidal sol of step (2), after taking out, remove the raffinate in duct, at 120 ℃ of dry 1 h, repeated impregnations and dry 1 time as required, until meet the requirements of coating load amount, then under 500 ℃ of nitrogen atmospheres, roasting acquisition coating layer thickness is the honeycomb titania support of 100 μ m;
(4) solution 1 h containing palladium nitrate by the honeycomb titania support dipping of step (3) gained, dipping finishes the raffinate in rear removal duct, under the solution room temperature of employing sodium formate, 2 h are processed in reduction, reduction finishes rear extremely neutral with deionized water washing, obtains the hydrogenation catalyst of the present embodiment through 120 ℃ of dry 5 h.
The hydrogenation catalyst that the present embodiment obtains has following performance: TiO in catalyst
2the thickness of-C composite coating is 100 μ m, and the load capacity of coating is 10% of honeycomb TiO 2 carrying weight, and the expulsion rate of coating is 3.0%.The load capacity of precious metals pd is 1.0% of honeycomb TiO 2 carrying weight, and the load degree of depth is 100 μ m.The specific area of catalyst is 50 m
2/ g, the activity of catalyst can make the 4-CBA content in crude terephthalic acid be down to 10 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that the present embodiment obtains has the feature of Fig. 1, and the surfacing of coating, without crack performance.
Embodiment 4
(1) by honeycomb titania support at 1150 ℃ of densified sintering products, make its specific area be down to 0.1 m
2/ g, then adopts rare nitric acid acidwashing 2 h of 1 mol/L, removes ash content and the impurity of carrier surface, with deionized water washing to neutral, the solution of the APEO that dipping concentration is 7%, standby at 120 ℃ of dry 5 h;
(2) nanoscale titanium hydroxide and fructose are added in deionized water, in the process stirring, drip nitre acid for adjusting pH value, obtain the colloidal sol that transparent pH value is 2.In described colloidal sol, the content of nanoscale titanium hydroxide is 10%, and the content of fructose is 3%;
(3) the honeycomb titania support of step (1) gained is immersed in to 0.5 h in the colloidal sol of step (2), after taking out, remove the raffinate in duct, at 70 ℃ of dry 2 h, repeated impregnations and dry 6 times as required, until meet the requirements of coating load amount, then under 400 ℃ of nitrogen atmospheres, roasting acquisition coating layer thickness is the honeycomb titania support of 52 μ m;
(4) by solution 0.5 h of the honeycomb titania support dipping sulfur acid palladium of step (3) gained, dipping finishes the raffinate in rear removal duct, under the solution room temperature of employing sodium formate, 2 h are processed in reduction, reduction finishes rear extremely neutral with deionized water washing, obtains the hydrogenation catalyst of the present embodiment through 120 ℃ of dry 5 h.
The hydrogenation catalyst that the present embodiment obtains has following performance: TiO in catalyst
2the thickness of-C composite coating is 52 μ m, and the load capacity of coating is 6% of honeycomb TiO 2 carrying weight, and the expulsion rate of coating is 2.2%.The load capacity of precious metals pd is 0.7% of honeycomb TiO 2 carrying weight, and the load degree of depth is 52 μ m.The specific area of catalyst is 43 m
2/ g, the activity of catalyst can make the 4-CBA content in crude terephthalic acid be down to 8 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that the present embodiment obtains has the feature of Fig. 1, and the surfacing of coating, without crack performance.
Embodiment 5
(1) by honeycomb titania support at 1050 ℃ of densified sintering products, make its specific area be down to 0.5 m
2/ g, then adopts rare nitric acid acidwashing 2 h of 1 mol/L, removes ash content and the impurity of carrier surface, with deionized water washing to neutral, the solution of the carboxymethyl cellulose that dipping concentration is 3%, standby at 120 ℃ of dry 5 h;
(2) nanoscale titanium hydroxide and lactose are added in deionized water, in the process stirring, drip nitre acid for adjusting pH value, obtain the colloidal sol that transparent pH value is 1.In described colloidal sol, the content of nanoscale titanium hydroxide is 7%, and the content of lactose is 7%;
(3) the honeycomb titania support of step (1) gained is immersed in to 0.5 h in the colloidal sol of step (2), after taking out, remove the raffinate in duct, at 70 ℃ of dry 2 h, repeated impregnations and dry 2 times as required, until meet the requirements of coating load amount, then under 450 ℃ of nitrogen atmospheres, roasting acquisition coating layer thickness is the honeycomb titania support of 18 μ m;
(4) solution 0.5 h containing ammonium chloropalladate by the honeycomb titania support dipping of step (3) gained, dipping finishes the raffinate in rear removal duct, under the solution room temperature of employing sodium formate, 2 h are processed in reduction, reduction finishes rear extremely neutral with deionized water washing, obtains the hydrogenation catalyst of the present embodiment through 120 ℃ of dry 5 h.
The hydrogenation catalyst that the present embodiment obtains has following performance: TiO in catalyst
2the thickness of-C composite coating is 18 μ m, and the load capacity of coating is 2% of honeycomb TiO 2 carrying weight, and the expulsion rate of coating is 1.1%.The load capacity of precious metals pd is 0.3% of honeycomb TiO 2 carrying weight, and the load degree of depth is 18 μ m.The specific area of catalyst is 17 m
2/ g, the activity of catalyst can make the 4-CBA content in crude terephthalic acid be down to 25 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that the present embodiment obtains has the feature of Fig. 1, and the surfacing of coating, without crack performance.
Embodiment 6
(1) by honeycomb titania support at 1200 ℃ of densified sintering products, make its specific area be down to 0.05 m
2/ g, then adopts rare nitric acid acidwashing 2 h of 1 mol/L, removes ash content and the impurity of carrier surface, and with deionized water washing, to neutral, polyethylene glycol and the mixed solution of APEO that dipping concentration is 5%, be dried 5 h at 120 ℃ standby;
(2) nanoscale titanium hydroxide and dextrin are added in deionized water, in the process stirring, drip nitre acid for adjusting pH value, obtain the colloidal sol that transparent pH value is 1.In described colloidal sol, the content of nanoscale titanium hydroxide is 10%, and the content of dextrin is 5%;
(3) the honeycomb titania support of step (1) gained is immersed in to 0.5 h in the colloidal sol of step (2), after taking out, remove the raffinate in duct, at 70 ℃ of dry 2 h, repeated impregnations and dry 2 times as required, until meet the requirements of coating load amount, then under 350 ℃ of nitrogen atmospheres, roasting acquisition coating layer thickness is the honeycomb titania support of 35 μ m;
(4) by solution 0.5 h of the honeycomb titania support dipping chloride containing palladium of step (3) gained, dipping finishes the raffinate in rear removal duct, under the solution room temperature of employing sodium formate, 2 h are processed in reduction, reduction finishes rear extremely neutral with deionized water washing, obtains the hydrogenation catalyst of the present embodiment through 120 ℃ of dry 5 h.
The hydrogenation catalyst that the present embodiment obtains has following performance: TiO in catalyst
2the thickness of-C composite coating is 35 μ m, and the load capacity of coating is 4% of honeycomb TiO 2 carrying weight, and the expulsion rate of coating is 1.8%.The load capacity of precious metals pd is 0.5% of honeycomb TiO 2 carrying weight, and the load degree of depth is 35 μ m.The specific area of catalyst is 32 m
2/ g, the activity of catalyst can make the 4-CBA content in crude terephthalic acid be down to 15 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that the present embodiment obtains has the feature of Fig. 1, and the surfacing of coating, without crack performance.
Embodiment 7
(1) by honeycomb titania support at 1050 ℃ of densified sintering products, make its specific area be down to 0.5 m
2/ g, then adopts rare nitric acid acidwashing 2 h of 1 mol/L, removes ash content and the impurity of carrier surface, with deionized water washing to neutral, the solution of the polyethylene glycol that dipping concentration is 5%, standby at 120 ℃ of dry 5 h;
(2) nanoscale titanium hydroxide, glucose and methylcellulose are added in deionized water, in the process stirring, drip nitre acid for adjusting pH value, obtain the colloidal sol that transparent pH value is 1.In described colloidal sol, the content of nanoscale titanium hydroxide is 10%, and the content of glucose and methylcellulose is 5%;
(3) the honeycomb titania support of step (1) gained is immersed in to 0.5 h in the colloidal sol of step (2), after taking out, remove the raffinate in duct, at 70 ℃ of dry 2 h, repeated impregnations and dry 3 times as required, until meet the requirements of coating load amount, then under 400 ℃ of nitrogen atmospheres, roasting acquisition coating layer thickness is the honeycomb titania support of 45 μ m;
(4) by the honeycomb titania support dipping chloride containing palladium of step (3) gained and mixed solution 0.5 h of palladium nitrate, dipping finishes the raffinate in rear removal duct, under the solution room temperature of employing sodium formate, 2 h are processed in reduction, reduction finishes rear extremely neutral with deionized water washing, obtains the hydrogenation catalyst of the present embodiment through 120 ℃ of dry 5 h.
The hydrogenation catalyst that the present embodiment obtains has following performance: TiO in catalyst
2the thickness of-C composite coating is 45 μ m, and the load capacity of coating is 6% of honeycomb TiO 2 carrying weight, and the expulsion rate of coating is 1.5%.The load capacity of precious metals pd is 0.5% of honeycomb TiO 2 carrying weight, and the load degree of depth is 45 μ m.The specific area of catalyst is 41 m
2/ g, the activity of catalyst can make the 4-CBA content in crude terephthalic acid be down to 7 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that the present embodiment obtains has the feature of Fig. 1, and the surfacing of coating, without crack performance.
Comparative example 1
This comparison example is compared with embodiment 1, does not flood the solution of non-ionic surface active agent, in the process of preparation colloidal sol, does not also add carbon compound;
(1) by honeycomb titania support at 1050 ℃ of densified sintering products, make its specific area be down to 0.5 m
2/ g, then adopts rare nitric acid acidwashing 2 h of 1 mol/L, removes ash content and the impurity of carrier surface, to neutral, standby at 120 ℃ of dry 5 h with deionized water washing;
(2) nanoscale titanium hydroxide is added in deionized water, in the process stirring, drip nitre acid for adjusting pH value, obtain the colloidal sol that transparent pH value is 1, in described colloidal sol, the content of nanoscale titanium hydroxide is 10%;
(3) the honeycomb titania support of step (1) gained is immersed in to 0.5 h in the colloidal sol of step (2), after taking out, remove the raffinate in duct, at 70 ℃ of dry 2 h, repeated impregnations and dry 3 times as required, until meet the requirements of coating load amount, then under 400 ℃ of nitrogen atmospheres, roasting acquisition coating layer thickness is the honeycomb titania support of 40 μ m;
(4) by solution 0.5 h of the honeycomb titania support dipping chloride containing palladium of step (3) gained, dipping finishes the raffinate in rear removal duct, under the solution room temperature of employing sodium formate, 2 h are processed in reduction, reduction finishes rear extremely neutral with deionized water washing, obtains the hydrogenation catalyst of the present embodiment through 120 ℃ of dry 5 h.
The hydrogenation catalyst that this comparative example obtains has following performance: TiO in catalyst
2the thickness of coating is 40 μ m, and the load capacity of coating is 5.5% of honeycomb TiO 2 carrying weight, and the expulsion rate of coating is 7.8%.The load capacity of precious metals pd is 0.5% of honeycomb TiO 2 carrying weight, and the load degree of depth is 40 μ m.The specific area of catalyst is 12 m
2/ g, the activity of catalyst can make the 4-CBA content in crude terephthalic acid be down to 57 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that this comparative example obtains is shown in Fig. 2, and the surface irregularity of coating has obvious crack performance to produce.
Comparative example 2
This comparison example is compared with embodiment 1, the method Kaolinite Preparation of Catalyst of describing according to US Patent No. 5387726 (Selective catalytic hydrogenation of aromatic aldehydes).
By 20 g specific areas, be 200 m
2the TiO of/g
2after powder mixes with 8 g deionized waters, 0.6 g binding agent methylcellulose, 0.4 g peptizing agent lactic acid, on kneader, mediate evenly extrusion molding.Gained article shaped, at 70 ℃ of dry 24 h, obtains TiO at 800 ℃ of roasting 4 h
2carrier.Solution by gained carrier impregnation chloride containing palladium, makes palladium bichloride be carried on TiO
2shaping carrier obtains catalyst precarsor.The catalyst precarsor of gained makes the 0.5%Pd/TiO of this comparative example through 120 ℃ of dry, 400 ℃ of roastings, 200 ℃ of hydrogen reducings
2catalyst.
The catalyst that this comparative example obtains has following performance: the load capacity of precious metals pd is 0.5% of TiO 2 carrying weight, and the load degree of depth is 650 μ m.The specific area of catalyst is 18 m
2/ g, the activity of catalyst can make the 4-CBA content in crude terephthalic acid be down to 142 μ g/g by 2400 μ g/g.
Claims (9)
1. the hydrogenation catalyst that the honeycomb titanium dioxide of take is carrier, is characterized in that: described catalyst is by honeycomb titania support, TiO
2-C composite coating and precious metals pd form, TiO
2-C composite coating load capacity is 1～10% of honeycomb TiO 2 carrying weight, and the load capacity of precious metals pd is 0.1～1.0% of honeycomb TiO 2 carrying weight, and this catalyst is prepared by following steps:
(1) by honeycomb titania support at 950～1250 ℃ of densified sintering products, pickling, with deionized water washing to neutral, the solution of dipping non-ionic surface active agent, drying for standby;
(2) nanoscale titanium hydroxide and carbon compound are added in deionized water, stir, regulating pH value is 0.5～5, obtains transparent colloidal sol; In described colloidal sol, the mass content of nanoscale titanium hydroxide is 1～20%, and the mass content of carbon compound is 1～10%;
(3) the honeycomb titania support of step (1) gained is immersed in the colloidal sol of step (2), after taking out, remove the raffinate in duct, dry, repeat above dipping and drying steps, until meet the requirements of coating load amount, under nitrogen atmosphere, roasting acquisition coating layer thickness is the honeycomb titania support of 1～100 μ m;
(4) solution containing palladium compound by the honeycomb titania support dipping of step (3) gained, dipping finishes the raffinate in rear removal duct, through reduction, washing, dryly obtain take the hydrogenation catalyst that honeycomb titanium dioxide is carrier;
The described non-ionic surface active agent of step (1) is any or its combination in polyethylene glycol, polyvinyl alcohol, glycerine, APEO or carboxymethyl cellulose.
2. hydrogenation catalyst according to claim 1, is characterized in that: the specific area of described catalyst is 5～50 m
2/ g, specific area 0.01～1 m of described honeycomb titania support
2/ g.
3. hydrogenation catalyst according to claim 1, is characterized in that: the mass concentration of the non-ionic surface active agent that step (1) is described is 1～10%.
4. hydrogenation catalyst according to claim 1, is characterized in that: the described carbon compound of step (2) is any or its combination in glucose, sucrose, maltose, fructose, lactose, dextrin or methylcellulose.
5. hydrogenation catalyst according to claim 1, is characterized in that: the described dip time of step (3) is 0.1～1 h.
6. hydrogenation catalyst according to claim 1, is characterized in that: described repeated impregnations and the dry number of times of step (3) is 1～10 time.
7. hydrogenation catalyst according to claim 1, is characterized in that: the described coating load amount of step (3) is 1～10% of honeycomb TiO 2 carrying weight.
8. catalyst according to claim 1, is characterized in that: what step (4) was described is any or its combination in palladium bichloride, palladium, palladium nitrate, palladium sulfate or ammonium chloropalladate containing palladium compound.
9. according to claim 1ly take the hydrogenation catalyst that honeycomb titanium dioxide is carrier, it is characterized in that: described catalyst is for crude terephthalic acid or the Hydrobon catalyst to carboxyl benzaldehyde aromatic aldehyde.
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| RU2602536C1 (en) * | 2015-09-25 | 2016-11-20 | Федеральное государственное бюджетное учреждение науки Институт органического синтеза им. И.Я. Постовского Уральского отделения Российской академии наук (ИОС УрО РАН) | Method of producing titanium dioxide/carbon composite |
| CN107855124A (en) * | 2017-11-16 | 2018-03-30 | 苏州甫众塑胶有限公司 | A kind of preparation method of honeycomb substrate coating |
| WO2020210295A1 (en) * | 2019-04-11 | 2020-10-15 | Basf Corporation | Selective ammonia oxidation catalyst |
| CN116173947B (en) * | 2021-11-29 | 2024-07-12 | 中国华能集团清洁能源技术研究院有限公司 | Hydrogenation catalyst and preparation method and application thereof |
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