CN101347726A - Process for preparing catalyst Pd/TiO2 for hydrogenation of p-carboxybenzaldehyde - Google Patents
Process for preparing catalyst Pd/TiO2 for hydrogenation of p-carboxybenzaldehyde Download PDFInfo
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Abstract
The invention relates to a Pd/TiO2 catalyst used in the hydrogenation of 4-carboxybenzaldehyde; the catalyst takes TiO2 forming material, which is doped with ground alkali-free glass fibers and adopts titanium-containing precursors for surface modification, as the carrier, and is loaded with an active component, metal Pd; the content of metal Pd in the catalyst is 0.2-1.0%, the titanium-containing precursor can be any one of or the combination of tetrabutyl titanate, tetraisopropyl titanate and tetraethyl titanate. The compressive strength of the catalyst is 110-160N/cm; after reaction, the compressive strength of the catalyst is reduced by less than 13%; in the high-temperature and high-pressure water phase environment, the hydrogenation activity of the catalyst is high, and the transformation rate of 4-carboxybenzaldehyde is higher than 99.0%. The preparation method of the catalyst of the invention has simple technique, and the adopted method does not cause any negative impact on the catalyst and is suitable for the industrial production.
Description
Technical field
The present invention relates to a kind of Pd/TiO that is used for hydrogenation reaction
2The Preparation of catalysts method particularly is used under the HTHP loading type Pd/TiO to carboxyl benzaldehyde hydrogenation process
2The Preparation of catalysts method.
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, 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., crude terephthalic acid after refining contains the 4-CBA of 25 μ g/g, to satisfy the needs of production of polyester.
The Pd/C catalyst is generally adopted in crude terephthalic acid hydrofinishing, describes the problem of aspects such as 4-CBA hydrogenation Pd/C Preparation of catalysts and Pd/C activity of such catalysts, selectivity among U.S. Pat 4415479, US4476242 and the US4605763 in detail.4-CBA hydrogenation Pd/C Preparation of catalysts is to adopt 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 24h 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 determine 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, BP company has applied for the Pd/SiC catalyst that is used for the crude terephthalic acid unifining process as carrier with SiC, but energy consumption height (900～1400 ℃) in the SiC preparing carriers process, catalyst cost height.It is the catalyst of carrier with the carbon nano-fiber that Chinese patent CN1695805 adopt the organic mode of gas phase catalysis thermal cracking low carbon chain to prepare to be used for terephthalic acid (TPA) hydrorefined, the carbon fiber production process complexity, the production cost height, and 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).Jhung S H etc. report with CCM (charcoal-carbon composite) as the crude terephthalic acid Hydrobon catalyst of preparing carriers (Applied Catalysis A:General, 2002,225:131-139) also have the defective identical 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-middle strong toxicity, acid and alkali-resistance, and can " strong interaction " take place (SMSI) between energy 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 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 1MPa, 4-CBA, the 4-CBA conversion ratio reaches as high as 99.8% behind the reaction 1h; 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%.Amoco company has applied for two with the Pd/TiO of titanium dioxide as carrier
2Catalyst patent US5616792 and US5756833 have obtained good catalytic effect in catalysis purification and recovery dicarboxylic aromatic acids, reduced the content of 4-CBA in the crude terephthalic acid solution.Under the condition of 277 ℃ of reaction temperatures, pressure 7.2MPa, 4-CBA initial content 2944 μ g/g, the conversion ratio of 4-CBA can reach 98.1%.
Pd/TiO in above United States Patent (USP)
2The high temperature active of catalyst is relatively poor, and does not all mention Pd/TiO
2The situation of change of catalyst compression strength in HTHP water environment.Pd/TiO
2TiO in the catalyst
2Carrier is a kind of fragile material, and when catalyst is used for liquid-phase hydrogenatin when reaction under the HTHP, the liquid phase in the catalyst pores expands, and makes catalyst produce micro-crack, significantly reduces the compression strength of catalyst.The report that does not also address this problem at present.
Summary of the invention
At in the prior art to the Pd/TiO of carboxyl benzaldehyde hydrogenation process
2Catalyst compression strength in HTHP water environment significantly reduces, and shortcoming such as the high temperature active of catalyst is relatively poor, the invention provides a kind of high compressive strength and high activity Pd/TiO that is used for the carboxyl benzaldehyde hydrogenation reaction
2The Preparation of catalysts method.
Technical scheme of the present invention is as follows:
A kind of Pd/TiO that is used for carboxyl benzaldehyde hydrogenation process
2Catalyst, this catalyst be mix to grind alkali-free glass fibre, the TiO after the finishing of titaniferous predecessor
2Article shaped is a carrier, the load active component metal Pd, and the content of metal Pd is 0.2～1.0% in the catalyst, described titaniferous predecessor can be any or its combination in butyl titanate, isopropyl titanate, the tetraethyl titanate.
Above-mentioned catalyst, the described alkali-free glass fibre that grinds is that filament diameter is 5～15 μ m, draw ratio is 5～30 alkali-free glass fibre.
A kind of method for preparing above-mentioned catalyst, it is made up of following steps:
1. step 1. will grind 0.2～5 part of alkali-free glass fibre mass fraction, 2. TiO
220 parts of powder quality umbers, 3. 8～20 parts of water quality umbers, as after 0.1～3 part of the methylcellulose mass fraction of binding agent, 0.1～2 part of mixing of nitric acid mass fraction as peptizing agent, mediate evenly; The rectangular of 5～6mm is cut in extrusion molding then, after the described rectangular drying, through 600～800 ℃ of roasting 1～10h, obtains grinding the TiO that alkali-free glass fibre mixes
2The article shaped carrier,
Step 2. is dissolved in the titaniferous predecessor in the absolute ethyl alcohol of 1～5 times of volume, obtains the solution of homogeneous transparent,
Step 3. is with the TiO of step 1 gained
2Shaping carrier floods the alcoholic solution of the titaniferous predecessor of isopyknic step 2 gained, and dip time is 1～10h; Drying obtains the TiO of titaniferous predecessor finishing
2Shaping carrier,
The TiO of step 4. after with the finishing of step 3 gained
2Shaping carrier dipping or spraying contain the solution of Pd compound, make to contain palladium compound and be carried on TiO
2Shaping carrier obtains catalyst precarsor,
After the catalyst precarsor drying of step 5. with step 4 gained,, use hydrogen reducing at 30～300 ℃ then, promptly get the Pd/TiO that is used for carboxyl benzaldehyde hydrogenation process at 300～600 ℃ of roasting 1～10h
2Catalyst.
Above-mentioned method for preparing catalyst, the described doping way that grinds alkali-free glass fibre are any or its combination of following several modes:
(1) will 1. grind alkali-free glass fibre, 2. TiO earlier
2Powder, the gel that 3. contains water, binding agent methylcellulose and peptizing agent nitric acid directly mix, and mediate again;
(2) will 1. grind alkali-free glass fibre and 2. TiO earlier
2Powder mixes, and mixes with the gel that 3. contains water, binding agent methylcellulose, peptizing agent nitric acid again, mediates at last;
(3) will 1. grind alkali-free glass fibre earlier and mix, again with 2. TiO with the gel that 3. contains water, binding agent methylcellulose, peptizing agent nitric acid
2Powder mixes, and mediates at last;
(4) first 2. TiO
2Powder and the gel that 3. contains water, binding agent methylcellulose, peptizing agent nitric acid mix, again with 1. grind alkali-free glass fibre and mix, mediate at last;
(5) first 2. TiO
2Powder, the gel that 3. contains water, binding agent methylcellulose, peptizing agent nitric acid directly mix, and add 1. to grind alkali-free glass fibre in kneading process;
Above-mentioned method for preparing catalyst, described TiO
2The particle diameter of powder is 20～100 μ m.
Above-mentioned method for preparing catalyst, the described Pd of containing compound can be taken from a kind of or its combination in the complex of palladium bichloride, palladium, palladium nitrate, the acid of chlorine palladium or ammonium chloropalladate, and the concentration that contains the solution of Pd compound is generally 0.1～10%.These are that those skilled in the art are known.
With respect to prior art, improvements of the present invention are that high resiliency, the high-intensity alkali-free glass fibre that grinds are doped to TiO
2In the shaping carrier, when catalyst is used for liquid-phase hydrogenatin when reaction under the HTHP, when the micro-crack extension that produces runs into the high strength alkali-free glass fibre, on near the alkali-free glass fibre crack tip and catalyst matrix interface, there is bigger shear stress, very easily cause the cracking that separates at alkali-free glass fibre and interface, make crackle expand along the interface, alkali-free glass fibre can be extracted from matrix, consumes the energy of extraneous load because of interface friction.After reaching certain distance along interface expansion, crackle can pass or walk around alkali-free glass fibre to be continued to expand in matrix material, the bridging that alkali-free glass fibre forms between crack surface produces closure stress at crack tip and has reduced the stress field intensity factor of crack tip, thereby has improved catalyst compression strength in the aqueous environment under HTHP.
Compared with prior art, the present invention be advantageous in that TiO
2Shaping carrier further carries out finishing with titaniferous predecessor alcoholic solution to carrier with after grinding the alkali-free glass fibre doping, can increase TiO
2Carrier surface and the affinity interaction power that contains palladium compound prevent Pd gathering at high temperature, thereby have improved the hydrogenation performance of catalyst.
The compression strength of catalyst of the present invention is 110～160N/cm, and the compression strength of catalyst reduces in 13% before and after the reaction, but also can further dwindle the ratio that compression strength reduces.In HTHP water environment, the hydrogenation activity height of catalyst is higher than 99.0% to the conversion ratio of carboxyl benzaldehyde.Preparation method's technology of the present invention is simple, and the method that adopts can not produce any negative effect to catalyst, suitability for industrialized production.
The specific embodiment
The technical characterictic that the invention is further illustrated by the following examples, but be not limited to embodiment.In embodiment and comparative example, the activity of such catalysts evaluation is carried out in 1L magnetic agitation autoclave, adds 4-CBA 0.7g in the still, and deionized water 700ml, 1.0g catalyst are seated in the special catalyst frame, and the catalytic reaction temperature is 280 ℃, H
2Dividing potential drop 0.6MPa, reaction time 1.0h.4-CBA content behind the hydrogenation adopts Tianjin, island LC-10 high performance liquid chromatograph, and (the C18 post, flowing is the CH of mass fraction 10% mutually
3The NH of CN and 0.25mol/L
4H
2PO
4, flow 1ml/min detects wavelength 240nm, sample size 15uL) to analyze, external standard method is quantitative.
Activity of such catalysts is calculated with the conversion ratio of 4-CBA.
The compression strength of catalyst is by the specification requirement of chemical industry standard HG/T2782-1996 regulation, calculates with the arithmetic mean of instantaneous value of 40 measurement results.
Embodiment 1
(1) grinds alkali-free glass fibre with 1 part and join 20 parts of TiO
2In the powder, on high speed disintegrator, mix 30min.1 part of binding agent methylcellulose joined in 10 parts 85 ℃ the deionized water, treat the methylcellulose swelling after, be cooled to room temperature, add 0.3 part of peptizing agent nitric acid again, stir, form gel.The gained gel is joined above-mentioned alkali-free glass fibre and TiO
2Powder in, after mediating 1h on the kneader,, be cut into the rectangular of 5～6mm with banded extruder extrusion molding (extrudate diameter 1.5mm), again at 100 ℃ of dry 10h, be warming up to make behind 700 ℃ and the constant temperature 5h with the heating rate of 2.5 ℃/min and grind the TiO that alkali-free glass fibre mixes
2Shaping carrier.
(2) be 1: 1 by titaniferous predecessor butyl titanate with absolute ethyl alcohol volume parts ratio, butyl titanate is joined in the absolute ethyl alcohol, stir 30min, obtain the solution of homogeneous transparent.
(3) with the TiO of above-mentioned (1) gained
2The alcoholic solution of the butyl titanate of shaping carrier dipping isopyknic (2) gained, dip time is 1h; Obtain the TiO of titaniferous predecessor finishing through 100 ℃ of dryings
2Shaping carrier.
(4) with the TiO of (3) gained
2Shaping carrier dipping or spraying contain the solution of PdCl2, make to contain palladium compound and be carried on TiO
2Shaping carrier obtains catalyst precarsor;
(5) with the catalyst precarsor of (4) gained through 100 ℃ of dryings, 500 ℃ of roasting 4h, 200 ℃ of hydrogen reducings obtain to be used for the 0.5%Pd/TiO to carboxyl benzaldehyde hydrogenation process
2Catalyst.
Embodiment 2
Is 1: 3 by titaniferous predecessor isopropyl titanate with absolute ethyl alcohol volume parts ratio, and isopropyl titanate is joined in the absolute ethyl alcohol, stirs 30min, obtains the solution of homogeneous transparent.Other step makes 0.5%Pd/TiO of the present invention with embodiment 1
2Catalyst.
Embodiment 3
Is 1: 5 by titaniferous predecessor tetraethyl titanate with absolute ethyl alcohol volume parts ratio, and tetraethyl titanate is joined in the absolute ethyl alcohol, stirs 30min, obtains the solution of homogeneous transparent.Other step makes 0.5%Pd/TiO of the present invention with embodiment 1
2Catalyst.
Embodiment 4
Grind alkali-free glass fibre with 5 parts and join 20 parts of TiO
2In the powder, on high speed disintegrator, mix 30min.Other step makes 0.5%Pd/TiO of the present invention with embodiment 1
2Catalyst.
Embodiment 5
1 part of binding agent methylcellulose joined in 10 parts 85 ℃ the deionized water, treat the methylcellulose swelling after, be cooled to room temperature, add 0.3 part of peptizing agent nitric acid again, stir, form gel.Grind alkali-free glass fibre, 20 parts of TiO with 0.2 part
2Powder and above-mentioned gel directly mix, then after mediating 1h on the kneader, with banded extruder extrusion molding (extrudate diameter 1.5mm), be cut into the rectangular of 5～6mm, again at 100 ℃ of dry 10h, make the TiO that alkali-free glass fibre of the present invention mixes after being warming up to 800 ℃ and constant temperature 5h with the heating rate of 2.5 ℃/min
2Shaping carrier.Other step makes 0.5%Pd/TiO of the present invention with embodiment 1
2Catalyst.
Embodiment 6
(1) grind alkali-free glass fibre and 1 part of binding agent methylcellulose with 1 part and add in 10 parts 85 ℃ the deionized water, treat the methylcellulose swelling after, be cooled to room temperature, add 0.3 part of peptizing agent nitric acid again, stir, form gel.The gained gel is joined 20 parts of TiO
2In the powder powder, after mediating 1h on the kneader,, be cut into the rectangular of 5～6mm with banded extruder extrusion molding (extrudate diameter 3.0mm), again at 100 ℃ of dry 10h, make the TiO that alkali-free glass fibre of the present invention mixes after being warming up to 700 ℃ and constant temperature 5h with the heating rate of 2.5 ℃/min
2Shaping carrier.
(2) be 1: 3 with butyl titanate with absolute ethyl alcohol volume parts ratio by the titaniferous predecessor, butyl titanate is joined in the absolute ethyl alcohol, stir 30min, obtain the solution of homogeneous transparent.
(3) with the TiO of above-mentioned (1) gained
2The alcoholic solution of the butyl titanate of shaping carrier dipping isopyknic (2) gained, dip time is 10h; Obtain the TiO of titaniferous predecessor finishing through 100 ℃ of dryings
2Shaping carrier.
(4) with the TiO of (3) gained
2Shaping carrier dipping or spraying contain PdCl
2Solution, make to contain palladium compound and be carried on TiO
2Shaping carrier obtains catalyst precarsor;
(5) with the catalyst precarsor of (4) gained through 100 ℃ of dryings, 300 ℃ of roasting 5h, 100 ℃ of hydrogen reducings obtain to be used for the 0.5%Pd/TiO to carboxyl benzaldehyde hydrogenation process
2Catalyst.
Embodiment 7
(1) 1 part of binding agent methylcellulose is joined in 10 parts 85 ℃ the deionized water, treat the methylcellulose swelling after, be cooled to room temperature, add 0.3 part of peptizing agent nitric acid again, stir, form gel.Earlier with gained gel and 20 parts of TiO
2Powder mixes, grind alkali-free glass fibre and mix with 1 part again, after mediating 1h on the kneader, with banded extruder extrusion molding (extrudate diameter 3.0mm), be cut into the rectangular of 5～6mm, again at 100 ℃ of dry 10h, be warming up to make behind 600 ℃ and the constant temperature 5h with the heating rate of 2.5 ℃/min and grind the TiO that alkali-free glass fibre mixes
2Shaping carrier.
(2) be 1: 3 by titaniferous predecessor butyl titanate and isopropyl titanate with absolute ethyl alcohol volume parts ratio, butyl titanate and isopropyl titanate (the two volume parts ratio is 1: 1) are joined in the absolute ethyl alcohol, stir 30min, obtain the solution of homogeneous transparent.
(3) with the TiO of above-mentioned (1) gained
2The butyl titanate of shaping carrier dipping isopyknic (2) gained and the alcoholic solution of isopropyl titanate, dip time is 1h; Obtain the TiO of titaniferous predecessor finishing through 100 ℃ of dryings
2Shaping carrier.
(4) with the TiO of (3) gained
2Shaping carrier dipping or spraying contain PdCl
2Solution, make to contain palladium compound and be carried on TiO
2Shaping carrier obtains catalyst precarsor;
(5) with the catalyst precarsor of (4) gained through 100 ℃ of dryings, 600 ℃ of roasting 2h, 300 ℃ of hydrogen reducings obtain to be used for the 0.2%Pd/TiO to carboxyl benzaldehyde hydrogenation process
2Catalyst.
Embodiment 8
(1) 1 part of binding agent methylcellulose is joined in 10 parts 85 ℃ the deionized water, treat the methylcellulose swelling after, be cooled to room temperature, add 0.3 part of peptizing agent nitric acid again, stir, form gel.Earlier with gained gel and 20 parts of TiO
2Powder directly mixes, and adds 1 part and grind alkali-free glass fibre in kneading process.After mediating 1h,, be cut into the rectangular of 5～6mm,, be warming up to make behind 750 ℃ and the constant temperature 5h with the heating rate of 2.5 ℃/min and grind the TiO that alkali-free glass fibre mixes again at 100 ℃ of dry 10h with banded extruder extrusion molding (extrudate diameter 1.5mm)
2Shaping carrier.
(2) be 1: 3 by titaniferous predecessor butyl titanate and tetraethyl titanate with absolute ethyl alcohol volume parts ratio, butyl titanate and tetraethyl titanate (the two volume parts ratio is 1: 1) are joined in the absolute ethyl alcohol, stir 30min, obtain the solution of homogeneous transparent.
(3) with the TiO of above-mentioned (1) gained
2The butyl titanate of shaping carrier dipping isopyknic (2) gained and the alcoholic solution of tetraethyl titanate, dip time is 5h; Obtain the TiO of titaniferous predecessor finishing through 100 ℃ of dryings
2Shaping carrier.
(4) with the TiO of (3) gained
2Shaping carrier dipping or spraying contain PdCl
2Solution, make to contain palladium compound and be carried on TiO
2Shaping carrier obtains catalyst precarsor;
(5) with the catalyst precarsor of (4) gained through 100 ℃ of dryings, 400 ℃ of roasting 6h, 100 ℃ of hydrogen reducings obtain to be used for the 1.0%Pd/TiO to carboxyl benzaldehyde hydrogenation process
2Catalyst.
Comparative Examples 1
Compare TiO with embodiment 1
2Shaping carrier does not adopt and grinds the alkali-free glass fibre doping, but adopts the titaniferous predecessor to carry out finishing.
1 part of binding agent methylcellulose joined in 10 parts 85 ℃ the deionized water, treat the methylcellulose swelling after, be cooled to room temperature, add 0.3 part of peptizing agent nitric acid again, stir, form gel.The gained gel is joined 20 parts of TiO
2Powder in, after mediating 1h on the kneader,, be cut into the rectangular of 5～6mm with banded extruder extrusion molding (extrudate diameter 1.5mm), again at 100 ℃ of dry 10h, make TiO after being warming up to 700 ℃ and constant temperature 5h with the heating rate of 2.5 ℃/min
2Shaping carrier.Other step makes the 0.5%Pd/TiO of this comparative example with embodiment 1
2Catalyst.
Comparative Examples 2
Compare TiO with embodiment 1
2Shaping carrier adopts and grinds the alkali-free glass fibre doping, but does not adopt the titaniferous predecessor to carry out finishing.
Grind alkali-free glass fibre with 1 part and join 20 parts of TiO
2In the powder, on high speed disintegrator, mix 30min.1 part of binding agent methylcellulose joined in 10 parts 85 ℃ the deionized water, treat the methylcellulose swelling after, be cooled to room temperature, add 0.3 part of peptizing agent nitric acid again, stir, form gel.The gained gel is joined above-mentioned alkali-free glass fibre and TiO
2Powder in, after mediating 1h on the kneader,, be cut into the rectangular of 5～6mm with banded extruder extrusion molding (extrudate diameter 1.5mm), again at 100 ℃ of dry 10h, be warming up to make behind 700 ℃ and the constant temperature 5h with the heating rate of 2.5 ℃/min and grind the TiO that alkali-free glass fibre mixes
2Shaping carrier.Gained carrier impregnation or spraying are contained PdCl
2Solution, make to contain palladium compound and be carried on TiO
2Shaping carrier obtains catalyst precarsor; The catalyst precarsor of gained is through 100 ℃ of dryings, 500 ℃ of roasting 4h, and 200 ℃ of hydrogen reducings make the 0.5%Pd/TiO of this comparative example
2Catalyst.Comparative Examples 3
Compare TiO with embodiment 1
2Shaping carrier neither adopts and grinds the alkali-free glass fibre doping, does not also adopt the titaniferous predecessor to carry out finishing.
1 part of binding agent methylcellulose joined in 10 parts 85 ℃ the deionized water, treat the methylcellulose swelling after, be cooled to room temperature, add 0.3 part of peptizing agent nitric acid again, stir, form gel.The gained gel is joined 20 parts of TiO
2Powder in, after mediating 1h on the kneader,, be cut into the rectangular of 5～6mm with banded extruder extrusion molding (extrudate diameter 1.5mm), again at 100 ℃ of dry 10h, make TiO after being warming up to 700 ℃ and constant temperature 5h with the heating rate of 2.5 ℃/min
2Shaping carrier.Gained carrier impregnation or spraying are contained PdCl
2Solution, make to contain palladium compound and be carried on TiO
2Shaping carrier obtains catalyst precarsor; The catalyst precarsor of gained is through 100 ℃ of dryings, 500 ℃ of roasting 4h, and 200 ℃ of hydrogen reducings make the 0.5%Pd/TiO of this comparative example
2Catalyst.
Comparative Examples 4
This comparison example is to prepare catalyst by the method that US 5387726A describes.
With 0.7 part of binding agent methylcellulose, 0.3 part of peptizing agent lactic acid is dissolved in 12 parts of deionized waters and forms gel.The gained gel is joined 20 parts of TiO
2Powder in, after mediating 1h on the kneader,, be cut into the rectangular of 5～6mm with banded extruder extrusion molding (extrudate diameter 3.0mm), again at 70 ℃ of dry 24h, make TiO after being warming up to 700 ℃ and constant temperature 5h with the heating rate of 2.5 ℃/min
2Shaping carrier.Gained carrier impregnation or spraying are contained PdCl
2Solution, make to contain palladium compound and be carried on TiO
2Shaping carrier obtains catalyst precarsor; The catalyst precarsor of gained is through 120 ℃ of dryings, 400 ℃ of roasting 4h, and 280 ℃ of hydrogen reducings make the 0.5%Pd/TiO of this comparative example
2Catalyst.
Measure the compression strength of the catalyst that the various embodiments described above and Comparative Examples obtain, and catalyst is carried out activity rating, it the results are shown in Table 1.
Compression strength before and after table 1 activity of such catalysts and the reaction
Claims (6)
1. Pd/TiO who is used for carboxyl benzaldehyde hydrogenation process
2Catalyst is characterized in that: this catalyst be mix to grind alkali-free glass fibre, the TiO after the finishing of titaniferous predecessor
2Article shaped is a carrier, the load active component metal Pd, and the mass content of metal Pd is 0.2～1.0% in the catalyst, described titaniferous predecessor can be any or its combination in butyl titanate, isopropyl titanate, the tetraethyl titanate.
2. catalyst according to claim 1 is characterized in that: the described alkali-free glass fibre that grinds is that filament diameter is 5～15 μ m, and draw ratio is 5～30 alkali-free glass fibre.
3. method for preparing the described catalyst of claim 1 is characterized in that it is made up of following steps:
1. step 1. will grind 0.2～5 part of alkali-free glass fibre mass fraction, 2. TiO
220 parts of powder quality umbers, 3. 8～20 parts of water quality umbers, as after 0.1～3 part of the methylcellulose mass fraction of binding agent, 0.1～2 part of mixing of nitric acid mass fraction as peptizing agent, on kneader, mediate evenly; With the material extrusion molding on banded extruder after mediating, be cut into the rectangular of 5～6mm, after the described rectangular drying,, obtain grinding the TiO that alkali-free glass fibre mixes through 600～800 ℃ of roasting 1～10h
2The article shaped carrier,
Step 2. is dissolved in the titaniferous predecessor in the absolute ethyl alcohol of 1～5 times of volume, obtains the solution of homogeneous transparent,
Step 3. is with the TiO of step 1 gained
2Shaping carrier floods the alcoholic solution of the titaniferous predecessor of isopyknic step 2 gained, and dip time is 1～10h; Drying obtains the TiO of titaniferous predecessor finishing
2Shaping carrier,
The TiO of step 4. after with the finishing of step 3 gained
2Shaping carrier dipping or spraying contain the solution of Pd compound, make to contain palladium compound and be carried on TiO
2Shaping carrier obtains catalyst precarsor,
After the catalyst precarsor drying of step 5. with step 4 gained,, use hydrogen reducing at 30～300 ℃ then, promptly get the Pd/TiO that is used for carboxyl benzaldehyde hydrogenation process at 300～600 ℃ of roasting 1～10h
2Catalyst.
4. method for preparing catalyst according to claim 3 is characterized in that the described doping way that grinds alkali-free glass fibre is any or its combination of following several modes:
(1) will 1. grind alkali-free glass fibre, 2. TiO earlier
2Powder, the gel that 3. contains water, binding agent methylcellulose and peptizing agent nitric acid directly mix, and mediate again;
(2) will 1. grind alkali-free glass fibre and 2. TiO earlier
2Powder mixes, and mixes with the gel that 3. contains water, binding agent methylcellulose, peptizing agent nitric acid again, mediates at last;
(3) will 1. grind alkali-free glass fibre earlier and mix, again with 2. TiO with the gel that 3. contains water, binding agent methylcellulose, peptizing agent nitric acid
2Powder mixes, and mediates at last;
(4) first 2. TiO
2Powder and the gel that 3. contains water, binding agent methylcellulose, peptizing agent nitric acid mix, again with 1. grind alkali-free glass fibre and mix, mediate at last;
(5) first 2. TiO
2Powder, the gel that 3. contains water, binding agent methylcellulose, peptizing agent nitric acid directly mix, and add 1. to grind alkali-free glass fibre in kneading process;
5. method for preparing catalyst according to claim 3 is characterized in that: described TiO
2The particle diameter of powder is 20～100 μ m.
6. method for preparing catalyst according to claim 3 is characterized in that: the described Pd of containing compound can be taken from a kind of or its combination in the complex of palladium bichloride, palladium, palladium nitrate, the acid of chlorine palladium or ammonium chloropalladate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810124517A CN100594978C (en) | 2008-08-22 | 2008-08-22 | Process for preparing catalyst Pd/TiO2 for hydrogenation of p-carboxybenzaldehyde |
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| CN101474580B (en) * | 2009-02-13 | 2014-04-23 | 江苏龙源催化剂有限公司 | Carrier for supporting catalyst in condition with high concentration of powder dust and flue gas as well as preparation method thereof |
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| CN114425387B (en) * | 2020-09-28 | 2023-10-31 | 中国石油化工股份有限公司 | Boron-nitrogen co-doped titanium dioxide palladium-supported catalyst and preparation method and application thereof |
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