CN102698744A - Sandwich cylindrical catalyst and preparation method thereof - Google Patents
Sandwich cylindrical catalyst and preparation method thereof Download PDFInfo
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- CN102698744A CN102698744A CN2012101761886A CN201210176188A CN102698744A CN 102698744 A CN102698744 A CN 102698744A CN 2012101761886 A CN2012101761886 A CN 2012101761886A CN 201210176188 A CN201210176188 A CN 201210176188A CN 102698744 A CN102698744 A CN 102698744A
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Abstract
The invention discloses a sandwich cylindrical catalyst and a preparation method thereof. The catalyst consists of a sandwich part and an outer ring part, wherein the sandwich part consists of a dense TiO2 material; the outer ring part consists of a TiO2-C compound material with a plenty of pores, and a noble metal Pd; and the mass content of the noble metal Pd is 0.1-1.0 percent. The catalyst has high compression strength, and the TiO2-C compound material on the outer ring cylinder part of the catalyst has a large specific area and a plenty of pores, so that carrying of palladium and storing of palladium are facilitated. Moreover, preparation of nanometer palladium particles through liquid phase uniform deposition under a hydrothermal condition is combined with a hydrothermal dispersing technology, and the mass transfer advantage of a hydrothermal solution is used for uniformly dispersing nanometer palladium particles onto a carrier, so that the dispersing degree and the activity of the catalyst are increased.
Description
Technical field
The present invention relates to a kind of sandwich cylindrical catalyst and preparation method, particularly a kind of hydrorefined sandwich cylindrical catalyst of crude terephthalic acid and preparation method of being used for.
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 with hydrogen then.Though the Pd/C catalyst is active high; But active carbon is as the carrier of Pd/C catalyst; Major defect is to confirm that the performance repeatability of their specification difficulty, every batch of active carbon cannot say for sure card, and catalyst strength is relatively poor, bulk density is little, the catalytic performance less stable under harsh conditions.For overcoming above-mentioned shortcoming, have some with SiC, charcoal fiber, CCM (charcoal-carbon composite), TiO
2Deng research as the crude terephthalic acid hydrofinishing palladium catalyst of carrier.But generally, the research of the charcoal non activated carrier of crude terephthalic acid Hydrobon catalyst report still seldom.
In patent WO200671407 (Process for purification of aromatic carboxylic acids); BP company has applied for the Pd/SiC catalyst that is used for the crude terephthalic acid unifining process as carrier with SiC; But the specific area of SiC carrier is lower, is unfavorable for the dispersion of metal Pd.It is the catalyst of carrier with the carbon nano-fiber that Chinese patent CN1695805 (being used for terephthalic acid (TPA) hydrorefined is the catalyst of carrier with the carbon nano-fiber) adopt the organic mode of gas phase catalysis thermal cracking low carbon chain to prepare to be used for crude terephthalic acid hydrorefined; Carbon fiber production process is complicated; Production cost is high; And the forming process difficulty, support strength is poor, abrasion are high, and the catalyst performance after the load can not satisfy the hydrorefined requirement of terephthalic acid (TPA).Report such as Jhung S H (Applied Catalysis A:General, 2002,225:131 – 139) also have the defective identical with CCM (charcoal-carbon composite) as the crude terephthalic acid Hydrobon catalyst of preparing carriers with carbon fiber.
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) with titanium dioxide as 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%.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 causes the pore structure of carrier to cave in after 900～1200 ℃ of high-temperature roastings, and specific area reduces, and the specific area of carrier is lower than 10 m
2/ g is unfavorable for the dispersion of active component Pd and fixing, is prone to cause the loss of active component and growing up of Pd crystal grain.
Existing in recent years report confirms that carbon can suppress TiO
2The growing up of phase transformation and crystal grain, avoid the reduction with specific area of caving in of pore structure.Patent CN101322937 (order mesoporous nano-crystalline titanium dioxide/carbon composite and synthetic method thereof) discloses a kind of ordered nano crystal titanium dioxide/carbon composite; This mesoporous nanocrystalline titania/carbon composite has higher content of titanium dioxide, and this composite material by adopting mixed with titanium source, organic polymer and triblock copolymer induce the self assembly preparation to get through solvent evaporates.Patent CN100998934 (handle phenol liguid phase pollutant loaded photocatalyst and its production and application method) be that binding agent is fixed in the NACF surface with nano-titanium dioxide powder with the resin, then under nitrogen atmosphere 400～550 ℃ of roastings to make the titanium dichloride load amount be titanium dioxide/carbon composite of 25～55%.These composites are usually as photochemical catalyst; Exist with Powdered or fibrous form; Do not possess certain molding structure, can't satisfy of filling and the instructions for use of Industrial Catalysis reaction unit catalysis material, can not be as the carrier of crude terephthalic acid Hydrobon catalyst.Active carbon after patent CN101244383 (a kind of preparation method of absorbent charcoal loading titanium dioxide photocatalyst) will handle joins in the metatitanic acid colloidal sol; After stirring, leaving standstill active carbon is leached; Roasting obtains required titanium dioxide/carbon composite under inert gas shielding; Wherein the mass ratio of active carbon and metatitanic acid is 1:1～3:1, and its weak point is TiO
2Load capacity is not high, and in the preparation process TiO
2Can stop up the aperture of active carbon.
TiO to crude terephthalic acid unifining process in the prior art
2Carrier poor heat stability, pore structure in roasting process are caved in easily, specific area and pore volume sharply reduces, crystalline structure be prone to change, and Pd/TiO
2Shortcomings such as the high temperature active of catalyst is relatively poor, the inventor discloses a kind of hydrorefined noble metal/TiO of crude terephthalic acid that is used for
2(application number: 201010106170.X), this invention adopts macromolecular compound to TiO to-C Catalysts and its preparation method
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, macromolecular compound 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, brings environmental pollution.Do not provide TiO in the patent yet
2Concrete C content in the-C complex carrier, the compression strength of catalyst await further to improve.
Summary of the invention
Pd/TiO to crude terephthalic acid unifining process in the prior art
2Compression strength that catalyst exists and specific area are difficult to compatible shortcoming; One of the object of the invention provides the compression strength height; The sandwich cylindrical catalyst that specific area is big, two of the object of the invention provides the method for preparing the sandwich cylindrical catalyst.
Technical scheme of the present invention is following:
The sandwich cylindrical catalyst, described catalyst is made up of sandwich and outer ring portion, and sandwich is by the TiO of densification
2Material is formed, and the outer annulated column part of catalyst is by the abundant TiO of hole
2-C composite and precious metals pd are formed, and the content of precious metals pd is 0.1～1.0% in the catalyst.
Described catalyst is to adopt hydro-thermal method that precious metals pd is deposited on the cylindric carrier of sandwich to make.
The preparation method of sandwich cylindrical catalyst is characterized in that may further comprise the steps:
(1) will contain solution, macromolecular compound and the urea of palladium compound, mix wiring solution-forming.
(2) the cylindric carrier of sandwich is added in the solution of step (1) gained, stir, carry out hydro-thermal reaction, reaction finishes to reduce to room temperature and gets logistics 1.
(3) aqueous solution of reducing agent is added reduce processings in the logistics 1, reduction finishes filtration afterwards, washing, drying, and to obtain Pd content be 0.1～1.0% sandwich cylindrical catalyst.
The TiO of the sandwich of described catalyst
2Material is a rutile-type, the TiO of outer annulated column part
2Material is any or its combination in anatase titanium dioxide, the rutile-type.
The TiO of the outer annulated column part of described catalyst
2The content of C is 10～20% in the-C composite.
Step (1) is described to be contained palladium compound and is selected from any or its combination in palladium bichloride, palladium, palladium nitrate, palladium sulfate or the ammonium chloropalladate; The described consumption that contains the solution of palladium compound is 1～5 times of sandwich cylindrical catalyst carrier quality.
The described macromolecular compound of step (1) is selected from any or its combination in polyethylene glycol, polyvinyl alcohol, APEO or the PVP; The consumption of described macromolecular compound is 0.1～1.0% of a sandwich cylindrical catalyst carrier quality.
The consumption of the described urea of step (1) is 1～10% of a sandwich cylindrical catalyst carrier quality.
The described mixing temperature of step (1) has no particular limits, and generally adopts conventional temperature, mixes such as under the room temperature.
The preparation method of the cylindric carrier of the described sandwich of step (2) is following:
(a) with TiO
2After powder and phenolic resins, epoxy resin, Petropols or polyurethane resin powder mix, mediate evenly, get material 1 with the gel that contains water, binding agent methylcellulose, peptizing agent nitric acid.
(b) with TiO
2Powder is mediated evenly with the gel that contains water, binding agent methylcellulose, peptizing agent nitric acid, gets material 2.
(c) material 1 is placed the outside charging aperture position of sandwich banded extruder, material 2 is placed the charging aperture position, inside of sandwich banded extruder, extrusion molding gets material 3.
(d) material 3 roasting under drying, nitrogen atmosphere obtains sandwich cylindrical catalyst carrier.
The sandwich of the cylindric carrier of the described sandwich of step (2) is by the TiO of densification
2Material is formed, and the outer annulated column part of carrier is by the abundant TiO of hole
2-C composite is formed, and the compression strength of carrier is 150～250 N/cm, and the specific area of carrier is 100～200 m
2/ g.
The TiO of the sandwich of the cylindric carrier of the described sandwich of step (2)
2Material is a rutile-type, the TiO of outer annulated column part
2Material is any or its combination in anatase titanium dioxide, the rutile-type.The TiO of the outer annulated column part of described carrier
2The content of C is 10～20% in the-C composite.
The described hydrothermal temperature of step (2) is 100～200 ℃, and reaction pressure is 0.1～1.5 MPa, and the reaction time is 1～30 h.
The described reducing agent of step (3) is selected from any or its combination in formaldehyde, formic acid, hydrazine hydrate, paraformaldehyde, glucose, sodium formate or the sodium borohydride.
The described reduction of step (3), the dry conventional method that adopts are carried out; Like ℃ reduction in room temperature～100; 100～150 ℃ of dryings, there are not described recovery time, drying time special qualification, can use the conventional time of this area as required; Generally reduce at 1～5 h, dry at 1～10 h.
Sandwich cylindrical catalyst of the present invention, the compression strength of catalyst are 150～250 N/cm, and the specific area of catalyst is 100～200 m
2/ g.Described catalyst is used for crude terephthalic acid or to the Hydrobon catalyst of aromatic aldehydes such as carboxyl benzaldehyde.
Sandwich cylindrical catalyst of the present invention, described compression strength are on the big connection intelligent testing machine ZQJ-of factory II granule strength testing machine, to measure by chemical industry standard HG/T2782-1996.Described specific area is on the U.S. ASAP2010 of Micromeritics company physical adsorption appearance, to measure.Described carbon content is measured on the German Analytik Jena Multi EA2000 of company type carbon sulphur appearance.Described pattern is on the Dutch Philips XL-30 TMP of company SEM, to measure.Described crystalline structure is on the German Bruker Bruker D8 Advance of company X-ray diffractometer, to measure.Described Pd content is the standard test of on the U.S. J-A1100 of Jarrell-Ash company type ICP, adopting RIPP128-90.
Sandwich cylindrical catalyst of the present invention, the method for testing and the above-mentioned catalyst of the compression strength of the cylindric carrier of described sandwich, specific area, carbon content, crystalline structure are basic identical.
Sandwich cylindrical 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.
With respect to prior art, advantage of the present invention is: one of which, the catalyst sandwich is by the TiO of the rutile-type of densification
2Material is formed, and as " keel " of catalyst, has improved the compression strength of catalyst greatly.Its two, the TiO of the outer annulated column part of catalyst
2The specific area of-C composite is big, hole abundant, helps carrying palladium and hides palladium.Its three, liquid phase uniform deposition under the hydrothermal condition is prepared nanometer palladium particle and hydro-thermal dispersion technology combines, utilize the mass transfer advantage of hydrothermal solution that nanometer palladium uniform particles is dispersed on the carrier, thereby improve decentralization and activity of such catalysts.
Description of drawings
Accompanying drawing 1 is the SEM pattern of the sandwich of catalyst.
Accompanying drawing 2 is the SEM pattern of the outer annulated column part of catalyst.
The specific embodiment
The technical characterictic that the invention is further illustrated by the following examples, but be not limited to embodiment.
The performance of the cylindric carrier of sandwich that present embodiment adopts is:
The sandwich of carrier is by the TiO of densification
2Material is formed, and the outer annulated column part of carrier is by the abundant TiO of hole
2-C composite is formed.The compression strength of carrier is 205 N/cm, and specific area is 142 m
2/ g.The TiO of the sandwich of carrier
2Material is a rutile-type, the TiO of outer annulated column part
2Material is an anatase titanium dioxide, the TiO of outer annulated column part
2The content of C is 14% in the-C composite.
The preparation method of the sandwich cylindrical catalyst of present embodiment may further comprise the steps:
(1) 200 g is contained solution, 0.5 g polyethylene glycol and the 5 g urea of palladium bichloride, mix wiring solution-forming.
(2) the cylindric carrier of 100 g sandwiches is added in the solution of step (1) gained, stir, carry out hydro-thermal reaction, reaction temperature is 150 ℃, and reaction pressure is 0.5 MPa, and the reaction time is 20 h, reduces to room temperature after reaction finishes and gets logistics 1.
(3) aqueous solution of sodium formate is added in the logistics 1,2 h are handled in reduction at room temperature, and reduction finishes that the back is filtered, to obtain Pd content be 0.5% sandwich cylindrical catalyst for washing, 100 ℃ of drying 5 h.
The sandwich cylindrical catalyst that present embodiment obtains has following performance:
The sandwich of catalyst is by the TiO of densification
2Material is formed, and the outer annulated column part of catalyst is by the abundant TiO of hole
2-C composite and precious metals pd are formed, and the content of precious metals pd is 0.5% in the catalyst, and the compression strength of catalyst is 205 N/cm, and specific area is 142 m
2/ g.The TiO of the sandwich of catalyst
2Material is a rutile-type, the TiO of outer annulated column part
2Material is an anatase titanium dioxide, the TiO of outer annulated column part
2The content of C is 14% in the-C composite.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 pattern of the sandwich of the catalyst that present embodiment obtains is seen Fig. 1, and the pattern of outer annulated column part is seen Fig. 2.
Embodiment 2
The performance of the cylindric carrier of sandwich that present embodiment adopts is:
The sandwich of carrier is by the TiO of densification
2Material is formed, and the outer annulated column part of carrier is by the abundant TiO of hole
2-C composite is formed.The compression strength of carrier is 150 N/cm, and specific area is 200 m
2/ g.The TiO of the sandwich of carrier
2Material is a rutile-type, the TiO of outer annulated column part
2Material is an anatase titanium dioxide, the TiO of outer annulated column part
2The content of C is 10% in the-C composite.
The preparation method of the sandwich cylindrical catalyst of present embodiment may further comprise the steps:
(1) 100 g is contained solution, 0.1 g polyvinyl alcohol and the 1 g urea of palladium, mix wiring solution-forming.
(2) the cylindric carrier of 100 g sandwiches is added in the solution of step (1) gained, stir, carry out hydro-thermal reaction, reaction temperature is 100 ℃, and reaction pressure is 0.1 MPa, and the reaction time is 30 h, reduces to room temperature after reaction finishes and gets logistics 1.
(3) aqueous solution of formaldehyde is added in the logistics 1,5 h are handled in reduction at room temperature, and reduction finishes that the back is filtered, to obtain Pd content be 0.1% sandwich cylindrical catalyst for washing, 100 ℃ of drying 10 h.
The sandwich cylindrical catalyst that present embodiment obtains has following performance:
The sandwich of catalyst is by the TiO of densification
2Material is formed, and the outer annulated column part of catalyst is by the abundant TiO of hole
2-C composite and precious metals pd are formed, and the content of precious metals pd is 0.1% in the catalyst, and the compression strength of catalyst is 150 N/cm, and specific area is 200 m
2/ g.The TiO of the sandwich of catalyst
2Material is a rutile-type, the TiO of outer annulated column part
2Material is an anatase titanium dioxide, the TiO of outer annulated column part
2The content of C is 10% in the-C composite.Activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 35 μ g/g by 2400 μ g/g.
The pattern of the sandwich of the catalyst that present embodiment obtains has the characteristic of Fig. 1, and the pattern of outer annulated column part has the characteristic of Fig. 2.
Embodiment 3
The performance of the cylindric carrier of sandwich that present embodiment adopts is:
The sandwich of carrier is by the TiO of densification
2Material is formed, and the outer annulated column part of carrier is by the abundant TiO of hole
2-C composite is formed.The compression strength of carrier is 250 N/cm, and specific area is 100 m
2/ g.The TiO of the sandwich of carrier
2Material is a rutile-type, the TiO of outer annulated column part
2Material is a rutile-type, the TiO of outer annulated column part
2The content of C is 20% in the-C composite.
The preparation method of the sandwich cylindrical catalyst of present embodiment may further comprise the steps:
(1) 500 g is contained solution, 1 g APEO and the 10 g urea of palladium nitrate, mix wiring solution-forming.
(2) the cylindric carrier of 100 g sandwiches is added in the solution of step (1) gained, stir, carry out hydro-thermal reaction, reaction temperature is 200 ℃, and reaction pressure is 1.5 MPa, and the reaction time is 1 h, reduces to room temperature after reaction finishes and gets logistics 1.
(3) aqueous solution of formic acid is added in the logistics 1,100 ℃ down reduction handle 1 h, reduction finishes that the back is filtered, to obtain Pd content be 1.0% sandwich cylindrical catalyst for washing, 150 ℃ of drying 1 h.
The sandwich cylindrical catalyst that present embodiment obtains has following performance:
The sandwich of catalyst is by the TiO of densification
2Material is formed, and the outer annulated column part of catalyst is by the abundant TiO of hole
2-C composite and precious metals pd are formed, and the content of precious metals pd is 1.0% in the catalyst, and the compression strength of catalyst is 250 N/cm, and specific area is 100 m
2/ g.The TiO of the sandwich of catalyst
2Material is a rutile-type, the TiO of outer annulated column part
2Material is a rutile-type, the TiO of outer annulated column part
2The content of C is 20% in the-C composite.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 pattern of the sandwich of the catalyst that present embodiment obtains has the characteristic of Fig. 1, and the pattern of outer annulated column part has the characteristic of Fig. 2.
Embodiment 4
The performance of the cylindric carrier of sandwich that present embodiment adopts is:
The sandwich of carrier is by the TiO of densification
2Material is formed, and the outer annulated column part of carrier is by the abundant TiO of hole
2-C composite is formed.The compression strength of carrier is 235 N/cm, and specific area is 155 m
2/ g.The TiO of the sandwich of carrier
2Material is a rutile-type, the TiO of outer annulated column part
2Material is the combination of anatase titanium dioxide, rutile-type, the TiO of outer annulated column part
2The content of C is 15% in the-C composite.
The preparation method of the sandwich cylindrical catalyst of present embodiment may further comprise the steps:
(1) with solution, 0.6 g polyvinylpyrrolidone and the 4 g urea of 300 g sulfur acid palladiums, mixes wiring solution-forming.
(2) the cylindric carrier of 100 g sandwiches is added in the solution of step (1) gained, stir, carry out hydro-thermal reaction, reaction temperature is 130 ℃, and reaction pressure is 0.3 MPa, and the reaction time is 20 h, reduces to room temperature after reaction finishes and gets logistics 1.
(3) aqueous solution of hydrazine hydrate is added in the logistics 1,2 h are handled in reduction at room temperature, and reduction finishes that the back is filtered, to obtain Pd content be 0.5% sandwich cylindrical catalyst for washing, 100 ℃ of drying 5 h.
The sandwich cylindrical catalyst that present embodiment obtains has following performance:
The sandwich of catalyst is by the TiO of densification
2Material is formed, and the outer annulated column part of catalyst is by the abundant TiO of hole
2-C composite and precious metals pd are formed, and the content of precious metals pd is 0.5% in the catalyst, and the compression strength of catalyst is 235 N/cm, and specific area is 155 m
2/ g.The TiO of the sandwich of catalyst
2Material is a rutile-type, the TiO of outer annulated column part
2Material is the combination of anatase titanium dioxide, rutile-type, the TiO of outer annulated column part
2The content of C is 15% in the-C composite.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 pattern of the sandwich of the catalyst that present embodiment obtains has the characteristic of Fig. 1, and the pattern of outer annulated column part has the characteristic of Fig. 2.
Embodiment 5
The performance and the embodiment 1 of the cylindric carrier of sandwich that present embodiment adopts are basic identical.
The preparation method of the sandwich cylindrical catalyst of present embodiment may further comprise the steps:
(1) 200 g is contained solution, 0.5 g polyethylene glycol and the 6 g urea of ammonium chloropalladate, mix wiring solution-forming.
(2) the cylindric carrier of 100 g sandwiches is added in the solution of step (1) gained, stir, carry out hydro-thermal reaction, reaction temperature is 150 ℃, and reaction pressure is 0.5 MPa, and the reaction time is 15 h, reduces to room temperature after reaction finishes and gets logistics 1.
(3) aqueous solution of sodium borohydride is added in the logistics 1,2 h are handled in reduction at room temperature, and reduction finishes that the back is filtered, to obtain Pd content be 0.3% sandwich cylindrical catalyst for washing, 100 ℃ of drying 5 h.
The sandwich cylindrical catalyst that present embodiment obtains has following performance:
The sandwich of catalyst is by the TiO of densification
2Material is formed, and the outer annulated column part of catalyst is by the abundant TiO of hole
2-C composite and precious metals pd are formed, and the content of precious metals pd is 0.3% in the catalyst, and the compression strength of catalyst is 205 N/cm, and specific area is 142 m
2/ g.The TiO of the sandwich of catalyst
2Material is a rutile-type, the TiO of outer annulated column part
2Material is an anatase titanium dioxide, the TiO of outer annulated column part
2The content of C is 14% in the-C composite.Activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 17 μ g/g by 2400 μ g/g.
The pattern of the sandwich of the catalyst that present embodiment obtains has the characteristic of Fig. 1, and the pattern of outer annulated column part has the characteristic of Fig. 2.
Embodiment 6
The performance and the embodiment 1 of the cylindric carrier of sandwich that present embodiment adopts are basic identical.
The preparation method of the sandwich cylindrical catalyst of present embodiment may further comprise the steps:
(1) 200 g is contained the solution of palladium bichloride, solution, 0.5 g polyethylene glycol and the 5 g urea that 100 g contain palladium nitrate, mix wiring solution-forming.
(2) the cylindric carrier of 100 g sandwiches is added in the solution of step (1) gained, stir, carry out hydro-thermal reaction, reaction temperature is 150 ℃, and reaction pressure is 0.5 MPa, and the reaction time is 10 h, reduces to room temperature after reaction finishes and gets logistics 1.
(3) aqueous solution of paraformaldehyde is added in the logistics 1,2 h are handled in reduction at room temperature, and reduction finishes that the back is filtered, to obtain Pd content be 0.7% sandwich cylindrical catalyst for washing, 100 ℃ of drying 5 h.
The sandwich cylindrical catalyst that present embodiment obtains has following performance:
The sandwich of catalyst is by the TiO of densification
2Material is formed, and the outer annulated column part of catalyst is by the abundant TiO of hole
2-C composite and precious metals pd are formed, and the content of precious metals pd is 0.7% in the catalyst, and the compression strength of catalyst is 205 N/cm, and specific area is 142 m
2/ g.The TiO of the sandwich of catalyst
2Material is a rutile-type, the TiO of outer annulated column part
2Material is an anatase titanium dioxide, the TiO of outer annulated column part
2The content of C is 14% in the-C composite.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 pattern of the sandwich of the catalyst that present embodiment obtains has the characteristic of Fig. 1, and the pattern of outer annulated column part has the characteristic of Fig. 2.
Embodiment 7
The performance and the embodiment 1 of the cylindric carrier of sandwich that present embodiment adopts are basic identical.
The preparation method of the sandwich cylindrical catalyst of present embodiment may further comprise the steps:
(1) 200 g is contained solution, 0.3 g polyethylene glycol, 0.3 g APEO and the 5 g urea of palladium bichloride, mix wiring solution-forming.
(2) the cylindric carrier of 100 g sandwiches is added in the solution of step (1) gained, stir, carry out hydro-thermal reaction, reaction temperature is 150 ℃, and reaction pressure is 0.5 MPa, and the reaction time is 20 h, reduces to room temperature after reaction finishes and gets logistics 1.
(3) aqueous solution of sodium formate and glucose is added in the logistics 1,2 h are handled in reduction at room temperature, and reduction finishes that the back is filtered, to obtain Pd content be 0.5% sandwich cylindrical catalyst for washing, 100 ℃ of drying 5 h.
The sandwich cylindrical catalyst that present embodiment obtains has following performance:
The sandwich of catalyst is by the TiO of densification
2Material is formed, and the outer annulated column part of catalyst is by the abundant TiO of hole
2-C composite and precious metals pd are formed, and the content of precious metals pd is 0.5% in the catalyst, and the compression strength of catalyst is 205 N/cm, and specific area is 142 m
2/ g.The TiO of the sandwich of catalyst
2Material is a rutile-type, the TiO of outer annulated column part
2Material is an anatase titanium dioxide, the TiO of outer annulated column part
2The content of C is 14% in the-C composite.Activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 14 μ g/g by 2400 μ g/g.
The pattern of the sandwich of the catalyst that present embodiment obtains has the characteristic of Fig. 1, and the pattern of outer annulated column part has the characteristic of Fig. 2.
Comparative example 1
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.
Specific area 300 m with 20 g
2/ g, pore volume 0.6 cm
3/ g, anatase titanium dioxide TiO
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.120 ℃ of dryings of catalyst precarsor warp of gained, 400 ℃ of roastings, 200 ℃ of hydrogen reducings make the 0.5%Pd/TiO of this comparative example
2Catalyst.
The catalyst that this comparative example obtains has following performance: the content of precious metals pd is 0.5% in the catalyst, and the compression strength of catalyst is 142 N/cm, and specific area is 20 m
2/ g, TiO
2Crystalline structure be anatase titanium dioxide and rutile-type.Activity of such catalysts can make the 4-CBA content in the crude terephthalic acid reduce to 138 μ g/g by 2400 μ g/g.
Claims (13)
1. sandwich cylindrical catalyst, it is characterized in that: said catalyst is made up of sandwich and outer ring portion, and sandwich is by the TiO of densification
2Material is formed, and outer ring portion is by the abundant TiO of hole
2-C composite and precious metals pd are formed, and the mass content of precious metals pd is 0.1～1.0%.
2. the preparation method of claim 1 a described sandwich cylindrical catalyst is characterized in that may further comprise the steps:
(1) will contain solution, macromolecular compound and the urea of palladium compound, mix wiring solution-forming;
(2) the cylindric carrier of sandwich is added in the solution of step (1) gained, stir, carry out hydro-thermal reaction, reduce to room temperature after reaction finishes and get logistics 1;
(3) aqueous solution of reducing agent is added reduce processings in the logistics 1, reduction finishes filtration afterwards, washing, drying, and to obtain Pd content be 0.1～1.0% sandwich cylindrical catalyst.
3. sandwich cylindrical catalyst according to claim 1 is characterized in that: the TiO of the sandwich of described catalyst
2Material is a rutile-type, the TiO of outer ring portion
2Material is any or its combination in anatase titanium dioxide, the rutile-type.
4. sandwich cylindrical catalyst according to claim 1 is characterized in that: the TiO of the outer annulated column part of described catalyst
2The mass content of C is 10～20% in the-C composite.
5. method for preparing catalyst according to claim 2 is characterized in that: step (1) is described to be contained palladium compound and is selected from any or its combination in palladium bichloride, palladium, palladium nitrate, palladium sulfate or the ammonium chloropalladate; The described consumption that contains the solution of palladium compound is 1～5 times of sandwich cylindrical catalyst carrier quality.
6. Preparation of catalysts method according to claim 2 is characterized in that: the described macromolecular compound of step (1) is selected from any or its combination in polyethylene glycol, polyvinyl alcohol, APEO, the PVP; The consumption of described macromolecular compound is 0.1～1.0% of a sandwich cylindrical catalyst carrier quality.
7. the preparation method of sandwich cylindrical catalyst according to claim 2 is characterized in that: the consumption of the described urea of step (1) is 1～10% of a sandwich cylindrical catalyst carrier quality.
8. the preparation method of sandwich cylindrical catalyst according to claim 2 is characterized in that: the sandwich of the cylindric carrier of the described sandwich of step (2) is by the TiO of densification
2Material is formed, and the outer annulated column part of carrier is by the abundant TiO of hole
2-C composite is formed, and the compression strength of carrier is 150～250 N/cm, and the specific area of carrier is 100～200 m
2/ g.
9. the preparation method of sandwich cylindrical catalyst according to claim 2 is characterized in that: the TiO of the sandwich of the cylindric carrier of the described sandwich of step (2)
2Material is a rutile-type, the TiO of outer annulated column part
2Material is any or its combination in anatase titanium dioxide, the rutile-type.
10. the TiO of the outer annulated column of described carrier part
2The content of C is 10～20% in the-C composite.
11. the preparation method of sandwich cylindrical catalyst according to claim 2 is characterized in that: the described hydrothermal temperature of step (2) is 100～200 ℃, and reaction pressure is 0.1～1.5 MPa, and the reaction time is 1～30 h.
12. the preparation method of sandwich cylindrical catalyst according to claim 2 is characterized in that: the described reducing agent of step (3) is selected from any or its combination in formaldehyde, formic acid, hydrazine hydrate, paraformaldehyde, glucose, sodium formate or the sodium borohydride.
13. sandwich cylindrical catalyst according to claim 1 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107620619A (en) * | 2017-11-03 | 2018-01-23 | 成都赛伦斯环保科技有限公司 | A kind of exhaust gas cleaner using perovskite-based catalyst |
| CN109759005A (en) * | 2019-03-13 | 2019-05-17 | 郑州大学 | A kind of quick response Pd-TiO2The preparation method of the quick material of nano particle hydrogen |
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| US4601996A (en) * | 1984-11-13 | 1986-07-22 | Chevron Research Company | Hydrofinishing catalyst comprising palladium |
| CN102139211A (en) * | 2010-02-02 | 2011-08-03 | 中国石油化工股份有限公司 | Method for preparing noble metal/TiO2-C catalyst for hydrofining of crude terephthalic acid |
| CN102476051A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Noble metal/TiO2-C catalyst and preparation method thereof |
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2012
- 2012-05-31 CN CN201210176188.6A patent/CN102698744B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4601996A (en) * | 1984-11-13 | 1986-07-22 | Chevron Research Company | Hydrofinishing catalyst comprising palladium |
| CN102139211A (en) * | 2010-02-02 | 2011-08-03 | 中国石油化工股份有限公司 | Method for preparing noble metal/TiO2-C catalyst for hydrofining of crude terephthalic acid |
| CN102476051A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Noble metal/TiO2-C catalyst and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107620619A (en) * | 2017-11-03 | 2018-01-23 | 成都赛伦斯环保科技有限公司 | A kind of exhaust gas cleaner using perovskite-based catalyst |
| CN109759005A (en) * | 2019-03-13 | 2019-05-17 | 郑州大学 | A kind of quick response Pd-TiO2The preparation method of the quick material of nano particle hydrogen |
| CN109759005B (en) * | 2019-03-13 | 2021-09-14 | 郑州大学 | Quick response Pd-TiO2Preparation method of nano-particle hydrogen sensitive material |
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