CN102626621A - 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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- CN102626621A CN102626621A CN2012100813794A CN201210081379A CN102626621A CN 102626621 A CN102626621 A CN 102626621A CN 2012100813794 A CN2012100813794 A CN 2012100813794A CN 201210081379 A CN201210081379 A CN 201210081379A CN 102626621 A CN102626621 A CN 102626621A
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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
The present invention relates to honeycomb titanium dioxide is the hydrogenation catalyst and the preparation method of carrier, particularly be used for crude terephthalic acid or hydrorefined to aromatic aldehydes such as carboxyl benzaldehydes be the hydrogenation catalyst and the preparation method of carrier with honeycomb titanium dioxide.
Background technology
P-phthalic acid (PTA) is a kind of crucial Organic Chemicals, and its downstream converted products mainly is polyester fiber, polyester film, Packaging Bottle and PET engineering plastics etc.In the crude terephthalic acid of producing with paraxylene (PX) liquid phase oxidation (CTA); The major impurity that generally contains 2000～3000 μ g/g is to carboxyl benzaldehyde (4-CBA); Because its aldehyde radical is more active, can influence the color and luster of polyester fiber, the p-methylbenzoic acid that need under 270～285 ℃ of high temperature, adopt hydrorefined method that 4-CBA is changed into to be soluble in hot water etc.; Terephthalic acid (TPA) after refining contains the 4-CBA of 25 μ g/g, to satisfy the needs of production of polyester.
The 0.5%Pd/C catalyst is generally adopted in crude terephthalic acid hydrofinishing, has introduced Pd/C Preparation of catalysts method in detail among U.S. Pat 4476242 (Process for preparing palladium on carbon catalyst for purification of crude terephthalic acid) and the US4605763 (Process for the purification of terephthalic acid).The Pd/C Preparation of catalysts adopts infusion process basically, at first active carbon is used the strong acid immersion treatment, filters then, washes, dries.With PdCl
2Become H with the hydrochloric acid heating for dissolving
2PdCl
4Solution adds certain water in active carbon, drip H while stirring
2PdCl
4, NaOH and formalin, leave standstill, filter, wash solid to neutral; Or directly with active carbon at PdCl
2Soak 24 h in the solution, reduce preparation Pd/C catalyst with hydrogen then.
The Pd/C catalyst of prior art, employing be natural or the activity carbon carrier of 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 adverse effects such as reaction rate decline, side reaction increase, selectivity reduction.Confirm the specification difficulty of activated carbon simultaneously, the performance repeatability of every batch of active carbon cannot say for sure to demonstrate,prove, and catalyst strength is relatively poor, bulk density is little, the catalytic performance less stable under harsh conditions.
With TiO
2Catalyst as the carrier exploitation has characteristics such as active high and low temperature activity is good, heat endurance is good, anti-toxic strong, acid and alkali-resistance, and can " strong interaction " take place (SMSI) between ability and the noble metal, TiO
2Therefore carrier also is described as the SiO that continues
2, Al
2O
3" third generation carrier " afterwards.U.S. Pat 5387726 (Selective catalytic hydrogenation of aromatic aldehydes) is with TiO
2As preparing carriers to the Pd/TiO of carboxyl benzaldehyde selective hydrogenation
2Catalyst is at 150 ℃ of reaction temperatures, H
2Under the condition of the initial concentration 1.0% of dividing potential drop 1 MPa, 4-CBA, react 1 h after the 4-CBA conversion ratio reach as high as 99.8%; But the high temperature active of this catalyst is not good enough, and when reaction temperature was brought up to 270 ℃, the 4-CBA conversion ratio was reduced to 90.1%.This patent gives the activity of such catalysts data of eggshell type and even type Pd distribution, but does not relate to the preparation method of egg-shell catalyst.In the U.S. Pat 5616792 (Catalytic pufification of dicarboxylic aromatic acid) with TiO
2Carrier is used to prepare the Pd/TiO that catalysis is purified and reclaimed dicarboxylic aromatic acids through 900～1200 ℃ of roastings
2Catalyst has reduced the content of 4-CBA in the 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 is if direct carried noble metal Pd then is unfavorable for the dispersion of active component Pd.The inventor discloses a kind of hydrorefined noble metal/TiO of crude terephthalic acid that is used for
2-C Catalysts and its preparation method (application number: 201010106170.X), adopt resin to TiO
2Powder is modified, the carrier after the moulding under the high-temperature process condition, TiO
2The carbon that generates on the hole wall plays supporting role, stops TiO
2Caving in of the reduction of specific area, pore structure also can be suppressed TiO
2Crystalline structure from the transformation of anatase titanium dioxide to rutile-type.On the other hand, TiO
2And have cooperative effect between the carbon that generates, can strengthen and contain palladium compound and TiO
2The affinity interaction power of-C complex carrier prevents Pd gathering at high temperature, helps improving the hydrogenation performance of catalyst.But in the Preparation of catalysts process; Resin need at first be dissolved in the organic solvent, and need remove unnecessary organic solvent under reduced pressure, causes the volatilization of organic solvent easily; Bring environmental pollution, also do not relate to the impregnating depth problem of precious metals pd in this patent.
The Pd/TiO of prior art
2Catalyst, the method for control reactive metal impregnating depth are not very desirable, or impregnating depth is a bigger scope, or impregnating depth is near the surface, and decentralization is not high.In fact, the impregnating depth that realizes 1～100 μ m is difficulty very, and influence factor is numerous, and maceration extract pH value, impregnation concentration and different preparation parameters such as dip time, competitive adsorbate and drying condition all have very big influence to the impregnating depth of reactive metal.
In recent years, ceramic honey comb has had application widely as supporter at catalytic field.But because little, the smooth surface of ceramic honey comb specific area; Load capacity is little when causing direct metallizing catalyst; In order to improve the coating problem of ceramic honey comb and catalyst; Chinese patent CN1451475 (cellular catalyst for treating waste gas is with titania powder and catalyst for treating waste gas) provides a kind of extrusion molding property cellular catalyst for treating waste gas good, that be made up of the powder of titanium dioxide and/or titanium composite oxide with raw material and the catalyst that uses the active and high denitrification activity of high de-agglomeration this raw material, that have organic halogen compound, but contains 0.3～5.0% sulfate radical (SO in the honeycomb titanium dioxide of this catalyst
4 2-), cause poisoning when adopting this carrier-supported precious metal easily, the defective that specific area reduced when this carrier existed high-temperature roasting equally.Chinese patent CN1962061 (TiO
2Photochemical catalyst is in the preparation method of ceramic honey comb area load) the employing cordierite-quality honeycombed ceramics is carrier, adopts sol-gel process that metatitanic acid colloidal sol is loaded on and obtains photochemical catalyst on the ceramic honey comb, be used for the purification of air formaldehyde or kill airborne bacterium.But the thickness of loaded film is for being merely 300～400 nm in this catalyst, and the conjugation between titanium coating and the ceramic honey comb is lower, and loaded film is prone to come off.Cheng Chunchun etc. (preparation and the sign of structuring carbon nano-fiber catalysis material. Jiangsu Polytechnic University's journal, 2008,20 (4): be base material 1-5) with cordierite type ceramic honey comb; After the coating of titanium dioxide modification, dipping 4%Ni is a carbon source with methane; On cordierite type ceramic honey comb base material, grow the carbon nano-fiber of about 70 nm of diameter; Obtain the structuring nano catalytic material, and, prepare structuring Pd catalyst as carrier.Its shortcoming is that in the growth course of carbon nano-fiber, the carbon that the cracking of carbon and diffusion rate imbalance can cause generating wraps 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 fields such as denitrating flue gas, purifying vehicle exhaust and photocatalysis; The conjugation that in the preparation process of honeycomb catalyst, also exists between coating and the ceramic honey comb is lower, and coating is prone to defectives such as be full of cracks, expulsion rate height.
Summary of the invention
Pd/TiO to crude terephthalic acid unifining process in the prior art
2The not good shortcoming of decentralization of the undesirable and reactive metal of the reactive metal impregnating depth that catalyst exists; It is the hydrogenation catalyst of carrier that one of the object of the invention provides with honeycomb titanium dioxide, controls the reactive metal impregnating depth through the coating layer thickness of control honeycomb titania support; Two of the object of the invention provides conjugation height between a kind of coating and the honeycomb substrate, and what expulsion rate was low is the hydrogenization catalyst preparation method of carrier with honeycomb titanium dioxide.
Technical scheme of the present invention is following:
With honeycomb titanium dioxide is the hydrogenation catalyst of carrier, it is characterized in that described catalyst is by honeycomb titania support, TiO
2-C composite coating and precious metals pd are formed, TiO
2-C composite coating load capacity is 1～10% of a honeycomb titania support quality, and the load capacity of precious metals pd is 0.1～1.0% of a honeycomb titania support quality.
TiO
2The thickness of-C composite coating is 1～100 μ m, and the coating load capacity is 1～10% of a honeycomb titania support quality, the expulsion rate of coating≤3%.The load capacity of precious metals pd is 0.1～1.0% of a honeycomb titania support quality, and the load degree of depth is 1～100 μ m.
With honeycomb titanium dioxide is the hydrogenization catalyst preparation method of carrier, may further comprise the steps:
(1) with honeycomb titania support densified sintering product, the ash content and the impurity of carrier surface is removed in pickling, spends deionised water to neutral, the solution of dipping non-ionic surface active agent, drying for standby.
(2) nanoscale titanium hydroxide and carbon compound are added in the deionized water, stir, regulate pH value 0.5～5, obtain transparent colloidal sol.The content of nanoscale titanium hydroxide is 1～20% in the described colloidal sol, and the content of carbon compound is 1～10%.
(3) the honeycomb titania support with step (1) gained is immersed in the colloidal sol of step (2); Take out the back and remove the raffinate in the duct; Drying, randomly, repeated impregnations and drying as required; Up to meeting the requirements of the coating load capacity, roasting acquisition coating layer thickness is the honeycomb titania support of 1～100 μ m under the nitrogen atmosphere.
(4) the honeycomb titania support with step (3) gained floods solution 0.1～1 h that contains palladium compound, and dipping finishes the back and removes the raffinate in the duct, obtains hydrogenation catalyst of the present invention through reduction, washing, drying.
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 described carrier of step (1) is that present technique field 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 the 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 the carboxymethyl cellulose; The concentration of described non-ionic surface active agent is 1～10%.
The drying of the described carrier of step (1) is that present technique field 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 present technique field those of ordinary skill is known, normally by in titanium tetrachloride, butyl titanate or the isopropyl titanate any through method for hydrolysis preparation.
The described carbon compound of step (2) is any or its combination in glucose, sucrose, maltose, fructose, lactose, dextrin or the methylcellulose.
The pH value of the described colloidal sol of step (2) is 0.5～5.
The described dip time of step (3) is 0.1～1 h.
The described repeated impregnations of step (3) is 1～10 time with dry number of times.
The described coating load capacity of step (3) is 1～10% of a honeycomb titania support quality.
Step (4) is described, and to contain palladium compound be any or its combination in palladium bichloride, palladium, palladium nitrate, palladium sulfate or the ammonium chloropalladate.
The reduction of the described catalyst of step (4) is that present technique field those of ordinary skill is known; Reducing agent is any in formaldehyde, formic acid, hydrazine hydrate, paraformaldehyde, glucose, sodium formate or the sodium borohydride normally; Preferable formic acid sodium; Reduction temperature is room temperature～100 ℃, and the recovery time is 1～5 h.
The drying of the described catalyst of step (4) is that present technique field those of ordinary skill is known, normally 100～150 ℃ of baking temperatures, and drying time is 1～10 h normally.
Above-mentioned is the hydrogenation catalyst of carrier with honeycomb titanium dioxide, and described catalyst is used for crude terephthalic acid or to the Hydrobon catalyst of aromatic aldehydes such as carboxyl benzaldehyde.
Hydrogenation catalyst of the present invention, the specific area of described catalyst and carrier are on the U.S. ASAP2010 of Micromeritics company physical adsorption appearance, to measure.Described coating layer thickness is on the Dutch Philips XL-30 TMP of company SEM, to measure.The load capacity of described metal Pd is on the U.S. J-A1100 of Jarrell-Ash company type ICP, to adopt the standard test of RIPP128-90.The load degree of depth of described metal Pd is on the Quantum of U.S. Physical electronics company 2000 type X-ray scanning microprobe electron spectrometers, to measure.The expulsion rate of described coating is on the Kunshan ultrasonic instrument KQ-50DB of Co., Ltd type numerical control supersonic cleaning apparatus, to measure, and obtains according to computes.
Hydrogenation catalyst of the present invention, described activity rating are in 1 L magnetic agitation autoclave, to carry out.In agitated reactor, add 250 g crude terephthalic acids (impurity 4-CBA content is 2400 μ g/g), 700 mL deionized waters, 1.0 g catalyst are seated in the 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 behind the hydrogenation adopts Tianjin, island LC-10 high performance liquid chromatograph, and (C18 post, flowing phase are 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 honeycomb titania support that the present invention is fine and close with high temperature sintering carries out pickling; Remove the ash content and the impurity of carrier surface; Increased the step of dipping nonionic surfactant solution; Help improving the conjugation of colloidal sol and honeycomb TiO 2 carrying surface, collosol coating surfacing in the process of drying, do not chap, the expulsion rate of coating is low.In the process for preparation of colloidal sol, added carbon compound, the carbon that under nitrogen atmosphere, generates in the roasting process is coated on TiO
2The surfaces externally and internally of pore structure has reduced the loss of the coating specific area that causes because of high-temperature roasting, has improved the heat endurance of coating effectively, and the carbon that generates simultaneously 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 to pass through control TiO
2The thickness of-C composite coating effectively regulates the impregnating depth of precious metals pd.Because the honeycomb titania support is fine and close, contains palladium compound and can only load on TiO
2On-C the 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 of which, TiO
2Conjugation between-C composite coating and the honeycomb titania support is high, and coating surface is smooth, do not chap, and the expulsion rate of coating is low.Its two, can through control TiO
2The thickness of-C composite coating effectively regulates the impregnating depth of precious metals pd.Its three, Preparation of catalysts technology is simple, the hydrogenation performance is good, suitability for industrialized production.
Description of drawings
The stereoscan photograph of the catalyst coat that accompanying drawing 1 obtains for embodiment 1 said method.
The stereoscan photograph of the catalyst coat that accompanying drawing 2 obtains for comparative example 1 said method.
Embodiment
The technical characterictic that the invention is further illustrated by the following examples, but be not limited to embodiment.
(1) with the honeycomb titania support at 1050 ℃ of densified sintering products, make its specific area reduce to 0.5 m
2/ g adopts rare nitric acid acidwashing 2 h of 1 mol/L then, removes the ash content and the impurity of carrier surface, spends deionised water to neutral, and dipping concentration is the solution of 5% polyethylene glycol, and is subsequent use at 120 ℃ of drying 5 h;
(2) nanoscale titanium hydroxide and glucose are added in the deionized water, in the process that stirs, drip the nitre acid for adjusting pH value, obtain transparent pH value and be 1 colloidal sol.The content of nanoscale titanium hydroxide is 10% in the described colloidal sol, and the content of glucose is 5%;
(3) the honeycomb titania support of step (1) gained is immersed in 0.5 h in the colloidal sol of step (2); Take out the back and remove the raffinate in the duct; At 70 ℃ of drying 2 h; Repeated impregnations and drying are 3 times as required, and up to meeting the requirements of the coating load capacity, roasting acquisition coating layer thickness is the honeycomb titania support of 40 μ m under 400 ℃ of nitrogen atmospheres then;
(4) the honeycomb titania support with step (3) gained floods solution 0.5 h that contains palladium bichloride; Dipping finishes the back and removes the raffinate in the duct; 2 h are handled in reduction under the solution room temperature of employing sodium formate; Spend deionised water after reduction finishes to neutral, obtain the hydrogenation catalyst of present embodiment through 120 ℃ of drying 5 h.
The hydrogenation catalyst that present embodiment obtains has following performance: TiO in the catalyst
2The thickness of-C composite coating is 40 μ m, and the load capacity of coating is 5% of a honeycomb titania support quality, and the expulsion rate of coating is 1.3%.The load capacity of precious metals pd is 0.5% of a honeycomb titania support quality, and the load degree of depth is 40 μ m.The specific area of catalyst is 39 m
2/ g, activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 12 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that present embodiment obtains is seen Fig. 1, the surfacing of coating, no crack performance.
Embodiment 2
(1) with the honeycomb titania support at 950 ℃ of densified sintering products, make its specific area reduce to 1 m
2/ g adopts rare nitric acid acidwashing 2 h of 1 mol/L then, removes the ash content and the impurity of carrier surface, spends deionised water to neutral, and dipping concentration is the solution of 1% polyvinyl alcohol, and is subsequent use at 120 ℃ of drying 5 h;
(2) nanoscale titanium hydroxide and sucrose are added in the deionized water, in the process that stirs, drip the nitre acid for adjusting pH value, obtain transparent pH value and be 5 colloidal sol.The content of nanoscale titanium hydroxide is 1% in the described colloidal sol, and the content of sucrose is 1%;
(3) the honeycomb titania support of step (1) gained is immersed in 0.1 h in the colloidal sol of step (2); Take out the back and remove the raffinate in the duct; At 50 ℃ of drying 5 h; Repeated impregnations and drying are 10 times as required, and up to meeting the requirements of the coating load capacity, roasting acquisition coating layer thickness is the honeycomb titania support of 1 μ m under 300 ℃ of nitrogen atmospheres then;
(4) the honeycomb titania support with step (3) gained floods solution 0.1 h that contains palladium; Dipping finishes the back and removes the raffinate in the duct; 2 h are handled in reduction under the solution room temperature of employing sodium formate; Spend deionised water after reduction finishes to neutral, obtain the hydrogenation catalyst of present embodiment through 120 ℃ of drying 5 h.
The hydrogenation catalyst that present embodiment obtains has following performance: TiO in the catalyst
2The thickness of-C composite coating is 1 μ m, and the load capacity of coating is 1% of a honeycomb titania support quality, and the expulsion rate of coating is 0.7%.The load capacity of precious metals pd is 0.1% of a honeycomb titania support quality, and the load degree of depth is 1 μ m.The specific area of catalyst is 5 m
2/ g, activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 66 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that present embodiment obtains has the characteristic of Fig. 1, the surfacing of coating, no crack performance.
Embodiment 3
(1) with the honeycomb titania support at 1250 ℃ of densified sintering products, make its specific area reduce to 0.01 m
2/ g adopts rare nitric acid acidwashing 2 h of 1 mol/L then, removes the ash content and the impurity of carrier surface, spends deionised water to neutral, and dipping concentration is the solution of 10% glycerine, and is subsequent use at 120 ℃ of drying 5 h;
(2) nanoscale titanium hydroxide and maltose are added in the deionized water, in the process that stirs, drip the nitre acid for adjusting pH value, obtain transparent pH value and be 0.5 colloidal sol.The content of nanoscale titanium hydroxide is 20% in the described colloidal sol, and the content of maltose is 10%;
(3) the honeycomb titania support of step (1) gained is immersed in 1 h in the colloidal sol of step (2); Take out the back and remove the raffinate in the duct; At 120 ℃ of drying 1 h; Repeated impregnations and drying are 1 time as required, and up to meeting the requirements of the coating load capacity, roasting acquisition coating layer thickness is the honeycomb titania support of 100 μ m under 500 ℃ of nitrogen atmospheres then;
(4) the honeycomb titania support with step (3) gained floods solution 1 h that contains palladium nitrate; Dipping finishes the back and removes the raffinate in the duct; 2 h are handled in reduction under the solution room temperature of employing sodium formate; Spend deionised water after reduction finishes to neutral, obtain the hydrogenation catalyst of present embodiment through 120 ℃ of drying 5 h.
The hydrogenation catalyst that present embodiment obtains has following performance: TiO in the catalyst
2The thickness of-C composite coating is 100 μ m, and the load capacity of coating is 10% of a honeycomb titania support quality, and the expulsion rate of coating is 3.0%.The load capacity of precious metals pd is 1.0% of a honeycomb titania support quality, and the load degree of depth is 100 μ m.The specific area of catalyst is 50 m
2/ g, activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 10 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that present embodiment obtains has the characteristic of Fig. 1, the surfacing of coating, no crack performance.
Embodiment 4
(1) with the honeycomb titania support at 1150 ℃ of densified sintering products, make its specific area reduce to 0.1 m
2/ g adopts rare nitric acid acidwashing 2 h of 1 mol/L then, removes the ash content and the impurity of carrier surface, spends deionised water to neutral, and dipping concentration is the solution of 7% APEO, and is subsequent use at 120 ℃ of drying 5 h;
(2) nanoscale titanium hydroxide and fructose are added in the deionized water, in the process that stirs, drip the nitre acid for adjusting pH value, obtain transparent pH value and be 2 colloidal sol.The content of nanoscale titanium hydroxide is 10% in the described colloidal sol, and the content of fructose is 3%;
(3) the honeycomb titania support of step (1) gained is immersed in 0.5 h in the colloidal sol of step (2); Take out the back and remove the raffinate in the duct; At 70 ℃ of drying 2 h; Repeated impregnations and drying are 6 times as required, and up to meeting the requirements of the coating load capacity, roasting acquisition coating layer thickness is the honeycomb titania support of 52 μ m under 400 ℃ of nitrogen atmospheres then;
(4) with solution 0.5 h of the honeycomb titania support of step (3) gained dipping sulfur acid palladium; Dipping finishes the back and removes the raffinate in the duct; 2 h are handled in reduction under the solution room temperature of employing sodium formate; Spend deionised water after reduction finishes to neutral, obtain the hydrogenation catalyst of present embodiment through 120 ℃ of drying 5 h.
The hydrogenation catalyst that present embodiment obtains has following performance: TiO in the catalyst
2The thickness of-C composite coating is 52 μ m, and the load capacity of coating is 6% of a honeycomb titania support quality, and the expulsion rate of coating is 2.2%.The load capacity of precious metals pd is 0.7% of a honeycomb titania support quality, and the load degree of depth is 52 μ m.The specific area of catalyst is 43 m
2/ g, activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 8 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that present embodiment obtains has the characteristic of Fig. 1, the surfacing of coating, no crack performance.
Embodiment 5
(1) with the honeycomb titania support at 1050 ℃ of densified sintering products, make its specific area reduce to 0.5 m
2/ g adopts rare nitric acid acidwashing 2 h of 1 mol/L then, removes the ash content and the impurity of carrier surface, spends deionised water to neutral, and dipping concentration is the solution of 3% carboxymethyl cellulose, and is subsequent use at 120 ℃ of drying 5 h;
(2) nanoscale titanium hydroxide and lactose are added in the deionized water, in the process that stirs, drip the nitre acid for adjusting pH value, obtain transparent pH value and be 1 colloidal sol.The content of nanoscale titanium hydroxide is 7% in the described colloidal sol, and the content of lactose is 7%;
(3) the honeycomb titania support of step (1) gained is immersed in 0.5 h in the colloidal sol of step (2); Take out the back and remove the raffinate in the duct; At 70 ℃ of drying 2 h; Repeated impregnations and drying are 2 times as required, and up to meeting the requirements of the coating load capacity, roasting acquisition coating layer thickness is the honeycomb titania support of 18 μ m under 450 ℃ of nitrogen atmospheres then;
(4) the honeycomb titania support with step (3) gained floods solution 0.5 h that contains ammonium chloropalladate; Dipping finishes the back and removes the raffinate in the duct; 2 h are handled in reduction under the solution room temperature of employing sodium formate; Spend deionised water after reduction finishes to neutral, obtain the hydrogenation catalyst of present embodiment through 120 ℃ of drying 5 h.
The hydrogenation catalyst that present embodiment obtains has following performance: TiO in the catalyst
2The thickness of-C composite coating is 18 μ m, and the load capacity of coating is 2% of a honeycomb titania support quality, and the expulsion rate of coating is 1.1%.The load capacity of precious metals pd is 0.3% of a honeycomb titania support quality, and the load degree of depth is 18 μ m.The specific area of catalyst is 17 m
2/ g, activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 25 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that present embodiment obtains has the characteristic of Fig. 1, the surfacing of coating, no crack performance.
Embodiment 6
(1) with the honeycomb titania support at 1200 ℃ of densified sintering products, make its specific area reduce to 0.05 m
2/ g adopts rare nitric acid acidwashing 2 h of 1 mol/L then, removes the ash content and the impurity of carrier surface, spends deionised water to neutral, and dipping concentration is 5% the polyethylene glycol and the mixed solution of APEO, and is subsequent use at 120 ℃ of drying 5 h;
(2) nanoscale titanium hydroxide and dextrin are added in the deionized water, in the process that stirs, drip the nitre acid for adjusting pH value, obtain transparent pH value and be 1 colloidal sol.The content of nanoscale titanium hydroxide is 10% in the described colloidal sol, and the content of dextrin is 5%;
(3) the honeycomb titania support of step (1) gained is immersed in 0.5 h in the colloidal sol of step (2); Take out the back and remove the raffinate in the duct; At 70 ℃ of drying 2 h; Repeated impregnations and drying are 2 times as required, and up to meeting the requirements of the coating load capacity, roasting acquisition coating layer thickness is the honeycomb titania support of 35 μ m under 350 ℃ of nitrogen atmospheres then;
(4) the honeycomb titania support with step (3) gained floods solution 0.5 h that contains palladium bichloride; Dipping finishes the back and removes the raffinate in the duct; 2 h are handled in reduction under the solution room temperature of employing sodium formate; Spend deionised water after reduction finishes to neutral, obtain the hydrogenation catalyst of present embodiment through 120 ℃ of drying 5 h.
The hydrogenation catalyst that present embodiment obtains has following performance: TiO in the catalyst
2The thickness of-C composite coating is 35 μ m, and the load capacity of coating is 4% of a honeycomb titania support quality, and the expulsion rate of coating is 1.8%.The load capacity of precious metals pd is 0.5% of a honeycomb titania support quality, and the load degree of depth is 35 μ m.The specific area of catalyst is 32 m
2/ g, activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 15 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that present embodiment obtains has the characteristic of Fig. 1, the surfacing of coating, no crack performance.
Embodiment 7
(1) with the honeycomb titania support at 1050 ℃ of densified sintering products, make its specific area reduce to 0.5 m
2/ g adopts rare nitric acid acidwashing 2 h of 1 mol/L then, removes the ash content and the impurity of carrier surface, spends deionised water to neutral, and dipping concentration is the solution of 5% polyethylene glycol, and is subsequent use at 120 ℃ of drying 5 h;
(2) nanoscale titanium hydroxide, glucose and methylcellulose are added in the deionized water, in the process that stirs, drip the nitre acid for adjusting pH value, obtain transparent pH value and be 1 colloidal sol.The content of nanoscale titanium hydroxide is 10% in the described colloidal sol, and the content of glucose and methylcellulose is 5%;
(3) the honeycomb titania support of step (1) gained is immersed in 0.5 h in the colloidal sol of step (2); Take out the back and remove the raffinate in the duct; At 70 ℃ of drying 2 h; Repeated impregnations and drying are 3 times as required, and up to meeting the requirements of the coating load capacity, roasting acquisition coating layer thickness is the honeycomb titania support of 45 μ m under 400 ℃ of nitrogen atmospheres then;
(4) the honeycomb titania support with step (3) gained floods mixed solution 0.5 h that contains palladium bichloride and palladium nitrate; Dipping finishes the back and removes the raffinate in the duct; 2 h are handled in reduction under the solution room temperature of employing sodium formate; Spend deionised water after reduction finishes to neutral, obtain the hydrogenation catalyst of present embodiment through 120 ℃ of drying 5 h.
The hydrogenation catalyst that present embodiment obtains has following performance: TiO in the catalyst
2The thickness of-C composite coating is 45 μ m, and the load capacity of coating is 6% of a honeycomb titania support quality, and the expulsion rate of coating is 1.5%.The load capacity of precious metals pd is 0.5% of a honeycomb titania support quality, and the load degree of depth is 45 μ m.The specific area of catalyst is 41 m
2/ g, activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 7 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that present embodiment obtains has the characteristic of Fig. 1, the surfacing of coating, no 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) with the honeycomb titania support at 1050 ℃ of densified sintering products, make its specific area reduce to 0.5 m
2/ g adopts rare nitric acid acidwashing 2 h of 1 mol/L then, removes the ash content and the impurity of carrier surface, spends deionised water to neutral, and is subsequent use at 120 ℃ of drying 5 h;
(2) the nanoscale titanium hydroxide is added in the deionized water, in the process that stirs, drip the nitre acid for adjusting pH value, obtain transparent pH value and be 1 colloidal sol, the content of nanoscale titanium hydroxide is 10% in the described colloidal sol;
(3) the honeycomb titania support of step (1) gained is immersed in 0.5 h in the colloidal sol of step (2); Take out the back and remove the raffinate in the duct; At 70 ℃ of drying 2 h; Repeated impregnations and drying are 3 times as required, and up to meeting the requirements of the coating load capacity, roasting acquisition coating layer thickness is the honeycomb titania support of 40 μ m under 400 ℃ of nitrogen atmospheres then;
(4) the honeycomb titania support with step (3) gained floods solution 0.5 h that contains palladium bichloride; Dipping finishes the back and removes the raffinate in the duct; 2 h are handled in reduction under the solution room temperature of employing sodium formate; Spend deionised water after reduction finishes to neutral, obtain the hydrogenation catalyst of present embodiment through 120 ℃ of drying 5 h.
The hydrogenation catalyst that this comparative example obtains has following performance: TiO in the catalyst
2The thickness of coating is 40 μ m, and the load capacity of coating is 5.5% of a honeycomb titania support quality, and the expulsion rate of coating is 7.8%.The load capacity of precious metals pd is 0.5% of a honeycomb titania support quality, and the load degree of depth is 40 μ m.The specific area of catalyst is 12 m
2/ g, activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 57 μ g/g by 2400 μ g/g.
The stereoscan photograph of the catalyst coat that this comparative example obtains is seen Fig. 2, and the surface irregularity of coating has tangible crack performance to produce.
Comparative example 2
This comparison example is compared with embodiment 1, and the method for describing according to U.S. Pat 5387726 (Selective catalytic hydrogenation of aromatic aldehydes) prepares catalyst.
With 20 g specific areas is 200 m
2The TiO of/g
2Powder is mediated evenly extrusion molding with after 8 g deionized waters, 0.6 g binding agent methylcellulose, 0.4 g peptizing agent lactic acid mix on kneader.The gained article shaped obtains TiO at 70 ℃ of drying 24 h at 800 ℃ of roasting 4 h
2Carrier.The gained carrier impregnation is contained the solution of palladium bichloride, make 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 dryings, 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 a titania support quality, and the load degree of depth is 650 μ m.The specific area of catalyst is 18 m
2/ g, activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 142 μ g/g by 2400 μ g/g.
Claims (10)
1. be the hydrogenation catalyst of carrier with honeycomb titanium dioxide, it is characterized in that: described catalyst is by honeycomb titania support, TiO
2-C composite coating and precious metals pd are formed, TiO
2-C composite coating load capacity is 1～10% of a honeycomb titania support quality, and the load capacity of precious metals pd is 0.1～1.0% of a honeycomb titania support quality.
2. claim 1 is described is the hydrogenization catalyst preparation method of carrier with honeycomb titanium dioxide, it is characterized in that may further comprise the steps:
(1) with the honeycomb titania support at 950～1250 ℃ of densified sintering products, pickling spends deionised water to neutral, the solution of dipping non-ionic surface active agent, drying for standby;
(2) nanoscale titanium hydroxide and carbon compound are added in the deionized water, stir, regulating the pH value is 0.5～5, obtains transparent colloidal sol; The mass content of nanoscale titanium hydroxide is 1～20% in the said colloidal sol, and the mass content of carbon compound is 1～10%;
(3) the honeycomb titania support with step (1) gained is immersed in the colloidal sol of step (2); Take out the back and remove the raffinate in the duct; Dry; Repeat above dipping and drying steps; Up to meeting the requirements of the coating load capacity, roasting acquisition coating layer thickness is the honeycomb titania support of 1～100 μ m under the nitrogen atmosphere;
(4) the honeycomb titania support with step (3) gained floods the solution that contains palladium compound, and dipping finishes the back and removes the raffinate in the duct, obtains hydrogenation catalyst of the present invention through reduction, washing, drying.
3. 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.
4. hydrogenization catalyst preparation method according to claim 2 is characterized in that: the described non-ionic surface active agent of step (1) is any or its combination in polyethylene glycol, polyvinyl alcohol, glycerine, APEO or the carboxymethyl cellulose; The mass concentration of described non-ionic surface active agent is 1～10%.
5. hydrogenization catalyst preparation method according to claim 2 is characterized in that: the described carbon compound of step (2) is any or its combination in glucose, sucrose, maltose, fructose, lactose, dextrin or the methylcellulose.
6. hydrogenization catalyst preparation method according to claim 2 is characterized in that: the described dip time of step (3) is 0.1～1 h.
7. hydrogenization catalyst preparation method according to claim 2 is characterized in that: the described repeated impregnations of step (3) is 1～10 time with dry number of times.
8. hydrogenization catalyst preparation method according to claim 2 is characterized in that: the described coating load capacity of step (3) is 1～10% of a honeycomb titania support quality.
9. Preparation of catalysts method according to claim 2 is characterized in that: step (4) is described, and to contain palladium compound be any or its combination in palladium bichloride, palladium, palladium nitrate, palladium sulfate or the ammonium chloropalladate.
10. according to claim 1 is the hydrogenation catalyst of carrier with honeycomb titanium dioxide, it is characterized in that: described catalyst is used for crude terephthalic acid or to the Hydrobon catalyst of aromatic aldehydes such as carboxyl benzaldehyde.
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Cited By (5)
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| CN105126925A (en) * | 2015-09-18 | 2015-12-09 | 苏州顺唐化纤有限公司 | Catalyst for hydrogenation synthesis reaction |
| 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 |
| CN113646065A (en) * | 2019-04-11 | 2021-11-12 | 巴斯夫公司 | Selective ammonia oxidation catalyst |
| WO2023093000A1 (en) * | 2021-11-29 | 2023-06-01 | 中国华能集团清洁能源技术研究院有限公司 | Hydrogenation catalyst, and preparation method therefor and use thereof |
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| CN102125838A (en) * | 2011-01-12 | 2011-07-20 | 中国石油化工股份有限公司 | Method for preparing high-selectivity Pd/TiO2-C hydrogenation catalyst |
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| US5616792A (en) * | 1996-02-01 | 1997-04-01 | Amoco Corporation | Catalytic purification of dicarboxylic aromatic acid |
| CN1451475A (en) * | 2002-04-18 | 2003-10-29 | 触媒化成工业株式会社 | Titania powder for honeycomb waste gas treating catalyst, and waste gas treating catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105126925A (en) * | 2015-09-18 | 2015-12-09 | 苏州顺唐化纤有限公司 | Catalyst for hydrogenation synthesis reaction |
| 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 |
| CN113646065A (en) * | 2019-04-11 | 2021-11-12 | 巴斯夫公司 | Selective ammonia oxidation catalyst |
| WO2023093000A1 (en) * | 2021-11-29 | 2023-06-01 | 中国华能集团清洁能源技术研究院有限公司 | Hydrogenation catalyst, and preparation method therefor and use thereof |
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