CN103100385A - Preparation method and application of palladium/bamboo charcoal catalyst - Google Patents
Preparation method and application of palladium/bamboo charcoal catalyst Download PDFInfo
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- CN103100385A CN103100385A CN2011103523835A CN201110352383A CN103100385A CN 103100385 A CN103100385 A CN 103100385A CN 2011103523835 A CN2011103523835 A CN 2011103523835A CN 201110352383 A CN201110352383 A CN 201110352383A CN 103100385 A CN103100385 A CN 103100385A
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Abstract
The invention relates to a preparation method and application of a palladium/bamboo charcoal catalyst. The palladium/bamboo charcoal catalyst is used for selective hydrogenation of crude m-phthalic acid and mainly overcomes the problems of poor dispersion of metal Pd and low minicrystal content in and poor thermal stability of a catalyst in the prior art. According to the invention, bamboo charcoal is used as a carrier, a Pd-containing solution is used for dipping of or is sprinkled on pretreated bamboo charcoal to prepare the palladium/bamboo charcoal catalyst, palladium is uniformly dispersed on the surface and secondary surface of bamboo charcoal, and a reducing agent is used for reduction so as to obtain the palladium/bamboo charcoal catalyst with high activity. Compared with a traditional palladium/charcoal catalyst, the palladium/bamboo charcoal catalyst provided by the invention has better activity, a longer service life and higher mechanical compressive strength.
Description
Technical field
The present invention relates to a kind of preparation method and application of palladium/bamboo charcoal catalyst, be used for the coarse isophthalic acid selective hydrogenation.
Background technology
The support type Pd/carbon catalyst is mainly used in the selective hydrogenation of unsaturated compounds.Contain a certain amount of by-product impurities in the coarse isophthalic acid that is obtained by the meta-xylene oxidation, the existence of carboxyl benzaldehyde in the middle of it (being called for short 3-CBA) affect quality and the color and luster of polyester, and is difficult to common crystallization separating method removal.But after the selective hydrogenation by the support type Pd/carbon catalyst changes m-methyl benzoic acid into, can be with the method separating-purifying of crystallization.Because Pd/carbon catalyst usually adopts single active component, its improvement research is concentrated on always structure and the distribution situation of metal Pd on carrier of carrier, this is the one of the main reasons that affects catalyst performance.Because hydrogenation reaction is to carry out on the surface of metal Pd, generally speaking, for the identical catalyst of metal Pd load capacity, the decentralization of its metal Pd is higher, crystallite (crystallite dimension is less than the 2.5 nanometers) content that is the metal Pd of load in catalyst is higher, the activity of catalyst is better, and service life is also longer.If directly will contain Pd compound (as chlorine palladium acid sodium or palladium bichloride) loads on charcoal, very thin glossiness metal Pd layer can appear in activated carbon surface very soon, this is mainly because activated carbon surface contains just like reproducibility groups such as aldehyde radical, free electrons, very easily make the Pd ion be reduced into the metal Pd of zeroth order, in the catalyst that makes like this, the decentralization of metal Pd is very low.And load type palladium/bamboo charcoal catalyst is better dispersed, and the palladium element is evenly distributed on carrier.Therefore, the effect with load type palladium/bamboo charcoal catalyst selective hydrogenation is better than with common support type Pd/carbon catalyst.Before the reduction operation, the Pd ion that will contain in the maceration extract of Pd compound is transformed into the effect that insoluble compound can be obtained.As at room temperature the hydrolysis of the water soluble compound of Pd being generated insoluble Pd (OH)
2Or PdO-H
20, back loading and then with the reducing agents such as aldehyde, sodium formate, glucose, formic acid or hydrogen reduction, can prevent migration and the grain growth of Pd on bamboo charcoal, introduce as US3138560.But this maceration extract stability that contains the Pd compound is very poor, and this has just improved the requirement of catalyst preparation process relatively.US4476242 proposes to prepare with organic solvents such as methyl alcohol or pyridines the maceration extract that contains the Pd compound; it is said that this is also very effective to the migration and the grain growth that prevent Pd; being harmful to organic compound but production process is used methyl alcohol or pyridine is this in human body, is all disadvantageous from ring environment protection or labour protection.
Summary of the invention
Low for the decentralization that has metal Pd in the catalyst make in prior art, the problem that content of crystallite is low the invention provides a kind of preparation method of Pd/ bamboo charcoal catalyst, and the Pd/ bamboo charcoal catalyst of the inventive method preparation is used for hydrofinishing of coarse isophthalic acid.Palladium/bamboo charcoal catalyst that the inventive method prepares has in catalyst that the decentralization of metal Pd is high, the advantage such as content of crystallite is higher, and preparation process is simple, and the raw material sources of employing are wide and with low cost.
The preparation method of palladium/bamboo charcoal catalyst of the present invention comprises the steps:
(1) the carrier bamboo charcoal first carries out pickling, and the acid concentration of pickle is 0.05～5mol/L;
(2) washing of the carrier bamboo charcoal water that obtains of step (1) or aqueous slkali is to neutral, and is then dry;
(3) the carrier bamboo charcoal that obtains of step (2) is with the aqueous solution dipping that contains nitrite ion, and the nitrite ion concentration of maceration extract is 0.05～3 mol/L, and dip time is 2～10h;
(4) the carrier bamboo charcoal that obtains with the solution impregnation step (3) that contains the Pd compound obtains the catalyst precarsor of load P d compound, and catalyst precarsor reduces processing with reducing agent after aging, gets catalyst prod.
In the inventive method, step (1), (2), (4) and existing common Pd/carbon catalyst preparation method are basic identical, and described below is only that the present invention recommends.The bamboo charcoal raw material can adopt the commercially available prod, and the specific surface of general bamboo charcoal is 100 ~ 800m
2/ g, pore volume are 0.4 ~ 1.2mL/g, can make as required the carrier granular of suitable shape and size.The pickling of step (1) adopts acid solution to process, acid cleaning process and condition be under 60 ~ 90 ℃ through 0.2 ~ 5.0 mol/L pickling 1 ~ 4 time, each processing time is 0.1 ~ 8h, solid (bamboo charcoal) volume ratio of liquid (acid) is 10:1 ~ 1:1.Preferably wash after pickling and remove floating acid.In final catalyst take the content of the weighing scale of Pd as 1%～5%.
At least a in the complex of the basic salt that contains halide that Pd compound preferred version is selected from Pd, acetate, nitrate, the acid of vinegar palladium, the acid of chlorine palladium, the acid of chlorine palladium described in step (4) or palladium ammonia, more preferably scheme is selected from the basic salt of the acid of chlorine palladium or the acid of chlorine palladium.Reducing agent preferred version described in step (4) is selected from least a in formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or hydrogen, and more preferably scheme is selected from sodium formate or hydrazine hydrate.Acid in step (1) is selected from least a in hydrochloric acid, nitric acid or phosphoric acid.
Get and contain Pd compound water and be mixed with dipping solution, weight concentration is generally 0.01%～5%, and the pH value of regulating dipping solution is 4～6.Then adopt dipping method that Pd is carried on carrier, infusion process can adopt conventional saturated infusion process (equi-volume impregnating), supersaturation infusion process, unsaturated infusion process, spray method etc., is preferably the method for spraying, and the time of spraying is about 5～30 minutes.Then with catalyst precarsor in air aging approximately 10～30 hours.Catalyst precarsor after aging is processed with the reducing agent reduction, and reduction temperature is 70～150 ℃ of left and right.The consumption of reducing agent depends on the dosage of active component Pd, is generally 2～10 times of left and right of reduction reaction equivalent, and the recovery time is 2～6 hours.
In the inventive method, the nitrite ion preferred version described in step (3) is from the alkali metal salt of nitrous acid, and more preferably scheme is natrium nitrosum.The amount of aqueous solution used that contains nitrite ion is 0.2～1.2 times of carrier bamboo charcoal carrier adsorption capacity.
The application of catalyst in the coarse isophthalic acid selective hydrogenation of the inventive method preparation.Take coarse isophthalic acid as raw material, the selective hydrogenation condition is: 270～370 ℃ of reaction temperatures, reaction pressure is 2～10MPa, and the volume ratio of hydrogen and liquid phase feed (under standard state) is 100:1～2000:1, and during the liquid of liquid phase feed, volume space velocity is 0.2～10h
-1
Key of the present invention has been to increase step wherein (3), and the carrier bamboo charcoal with the aqueous solution dipping that contains nitrite ion, makes nitrite ion be adsorbed in the bamboo charcoal surface after pickling.Because nitrite ion can be distributed in the bamboo charcoal surface very equably, and nitrite ion and palladium and bamboo charcoal surface all have affinity interaction power preferably, this has just increased the bamboo charcoal surface to the fixation of palladium, thereby the migratory movement that can reduce palladium is to stop or to delay the grain growth of Metal Palladium.Compared with prior art, the invention has the advantages that in the catalyst that makes, metal Pd has higher decentralization, content of crystallite is higher, shows active high, long service life on serviceability, and the step that increases in preparation process is very simple, and the raw material of employing is easy to get and is cheap; Belong to natural regenerated resources; Be not subjected to the restriction of mining deposits; The catalyst cost can obviously reduce; Obtained technique effect preferably.
The specific embodiment
In catalyst preparation process of the present invention, carrier can be prepared into the particle of suitable shape and size as required.Be generally bar shaped as shape, as be generally the cylindrical bars of diameter 3 ~ 8mm or clover bar etc.At 100 ~ 130 ℃ of drying 3 ~ 20h, the roasting of catalyst carrier preparation process is generally at 400 ~ 550 ℃ of roasting 2 ~ 10h for generally for the drying condition of catalyst and carrier preparation process.Further describe the present invention below by example.
Embodiment 1
Get the commercially available bamboo charcoal material of 500g, specific area is 550m
2/ g, pore volume are 0.9mL/g, and footpath, average hole (directly) is 6.5nm.With 1.5 mol/L sulfuric acid washing 2 times, each processing time is 2h to this bamboo charcoal under 75 ℃, and liquid-solid volume ratio is 3:1, and then washing is dry after neutral.Prepare with NO with natrium nitrosum and water
2Meter concentration is the dipping solution of 0.05mol/L, incipient impregnation absorbent charcoal carrier 8 hours, preparation palladium weight content is 100 milliliters of 0.5% chlorine palladium acid solutions, with alkali, the pH value is adjusted between 4～6 again, after stablizing 10～200 minutes, adopt the method load that sprays to contain palladium compound and obtain catalyst precarsor.Catalyst precarsor after aging 12 hours sodium formate 20 grams and pure water 200 grams with weighing scale 5% be mixed with reducing solution, catalyst precarsor is immersed in reducing solution 3 hours, then with the pure water washing to neutral, get catalyst prod A-1.
Embodiment 2
Bamboo charcoal washs with the nitric acid of 3 mol/L, and wash temperature is 75 ℃, then washes with water to neutrality, and all the other are with embodiment 1.Get catalyst prod A-2.
Embodiment 3
The bamboo charcoal phosphoric acid washing of 5mol/L, wash temperature is 80 ℃, then washes with water to neutrality, all the other are with embodiment 1.Get catalyst prod A-3.
Embodiment 4
With natrium nitrosum and water preparation NO
2Concentration is the maceration extract of 0.2mol/L, incipient impregnation active carbon 8 hours, and all the other are with embodiment 1.Get catalyst prod A-4.
Embodiment 5
With natrium nitrosum and water preparation NO
2Concentration is the maceration extract of 0.5mol/L, incipient impregnation active carbon 8 hours, and all the other are with embodiment 1.Get catalyst prod A-5.
Embodiment 6
With natrium nitrosum and water preparation NO
2Concentration is the maceration extract of 0.5mol/L, and the sodium nitrite in aqueous solution consumption is the carrier bamboo Charcoal Adsorption capacity Immesion active carbon 2 hours of 0.3 times, and all the other are with embodiment 1.Get catalyst prod A-6.
Comparative example
Get 500g modification bamboo charcoal material, specific area is 550m
2/ g, pore volume are 0.9mL/g, and footpath, average hole (directly) is 6.5nm.With 0.5 mol/L pickling 2 times, each processing time is 2h to this bamboo charcoal under 75 ℃, then wash with water to neutrality, under 120 ℃ dry 5～10 hours standby.
Then preparation conversion palladium content is 200 milliliters of the chlorine palladium acid solutions of 2.5 % by weight, with alkali, the pH value is adjusted between 4～6, after stablizing 2 hours, sprays on above-mentioned treated bamboo charcoal and obtains catalyst precarsor.Catalyst precarsor is mixed with reducing solution with 1 kilogram of sodium formate 100 grams of 20 % by weight and pure water after aging 12 hours, and catalyst precarsor is immersed in reducing solution 5 hours, then with the pure water washing to neutral catalyst prod B.
Embodiment 7
Decentralization and the x-ray diffraction method of the Metal Palladium of the catalyst prod load that mensuration the various embodiments described above and comparative example obtain record Pd content of crystallite (quality), and catalyst is carried out activity rating.
The assay method of the decentralization of Metal Palladium is chemiadsorption:
In formula, D is decentralization,
M Pd Relative atomic mass (106) for Pd;
WWeight (g) for Pd/ bamboo charcoal catalyst sample;
PMass fraction for Pd in catalyst.
Conversion ratio=((adding 3-CBA quality-residue 3-CBA quality)/add 3-CBA quality) * 100%.
Catalyst activity evaluation test of the present invention, evaluation is carried out on the 10mL micro-reactor, and appreciation condition is reaction pressure 4.5MPa, hydrogen to oil volume ratio 800:1, volume space velocity 1.0h during liquid
-1The results are shown in Table 1.
Table 1 catalyst property and proof valency result.
| ? | The Pd(% by weight) | Decentralization (%) | Content of crystallite (%) | Conversion ratio (%) |
| Embodiment 1 | 0.48 | 30 | 85 | 98.9 |
| Embodiment 2 | 0.49 | 28 | 87 | 98.7 |
| Embodiment 3 | 0.47 | 29 | 90 | 98.6 |
| Embodiment 4 | 0.48 | 26 | 86 | 98.5 |
| Embodiment 5 | 0.48 | 27 | 88 | 97.9 |
| Embodiment 6 | 0.49 | 28 | 86 | 98.5 |
| Comparative example | 0.51 | 15 | 76 | 95.2 |
Can find out from upper table data, catalyst good dispersion degree of the present invention, content of crystallite is high, and conversion ratio is high.
Claims (10)
1. the preparation method of a palladium/bamboo charcoal catalyst, is characterized in that comprising the steps:
(1) the carrier bamboo charcoal first carries out pickling, and the acid concentration of pickle is 0.05～5mol/L;
(2) washing of the carrier bamboo charcoal water that obtains of step (1) or aqueous slkali is to neutral, and is then dry;
(3) the carrier bamboo charcoal that obtains of step (2) is with the aqueous solution dipping that contains nitrite ion, and the nitrite ion concentration of maceration extract is 0.05～3 mol/L, and dip time is 2～10h;
(4) the carrier bamboo charcoal that obtains with the solution impregnation step (3) that contains the Pd compound obtains the catalyst precarsor of load P d compound, and catalyst precarsor reduces processing with reducing agent after aging, gets catalyst prod.
2. it is characterized in that in accordance with the method for claim 1: the specific surface of bamboo charcoal is 100 ~ 800m
2/ g, pore volume are 0.4 ~ 1.2mL/g.
3. in accordance with the method for claim 1, it is characterized in that: step (1) pickling adopts acid solution to process, and acid cleaning process and condition are 60 ~ 90 ℃ of lower pickling 1 ~ 4 time, and each processing time is 0.1 ~ 8h, and is liquid-solid) volume ratio is 10:1 ~ 1:1.
4. it is characterized in that in accordance with the method for claim 1: in final catalyst take the content of the weighing scale of Pd as 1%～5%.
5. it is characterized in that in accordance with the method for claim 1: at least a in the complex of the basic salt that contains halide that the Pd compound is selected from Pd, acetate, nitrate, the acid of vinegar palladium, the acid of chlorine palladium, the acid of chlorine palladium described in step (4) or palladium ammonia.
6. it is characterized in that in accordance with the method for claim 1: the reducing agent described in step (4) is selected from least a in formic acid, sodium formate, formaldehyde, hydrazine hydrate, glucose or hydrogen.
7. in accordance with the method for claim 1, it is characterized in that: contain Pd compound water and be mixed with dipping solution, weight concentration is 0.01%～5%, the pH value of regulating dipping solution is 4～6, then adopts dipping method that Pd is carried on carrier, then in air aging 10～30 hours, catalyst precarsor after aging is processed with the reducing agent reduction, reduction temperature is 70～150 ℃ of left and right, and the consumption of reducing agent is 2～10 times of reduction reaction equivalent, and the recovery time is 2～6 hours.
8. in accordance with the method for claim 1, it is characterized in that: the nitrite ion described in step (3) is from the alkali metal salt of nitrous acid, and the amount of aqueous solution used that contains nitrite ion is 0.2～1.2 times of carrier bamboo charcoal carrier adsorption capacity.
9. the application of catalyst in the coarse isophthalic acid selective hydrogenation of the described method preparation of the arbitrary claim of claim 1 to 8.
10. according to application claimed in claim 9, it is characterized in that: selective hydrogenation is take coarse isophthalic acid as raw material, 270～370 ℃ of selective hydrogenation temperature, reaction pressure is 2～10MPa, the volume ratio of hydrogen and liquid phase feed is 100:1～2000:1, and during the liquid of liquid phase feed, volume space velocity is 0.2～10h
-1
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104941634A (en) * | 2015-06-03 | 2015-09-30 | 江苏清泉化学股份有限公司 | Palladium-carbon catalyst for preparing furan through furfural decarbonylation process, and preparation method thereof |
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| CN1565726A (en) * | 2003-06-12 | 2005-01-19 | 中国石化上海石油化工股份有限公司 | Method for preparing palladium/carbon catalyzer by hydrogenising and refining crude terephthalic acid |
| CN101347729A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for preparing Pd/carbon catalyst for hydrofinishing of coarse isophthalic acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1565726A (en) * | 2003-06-12 | 2005-01-19 | 中国石化上海石油化工股份有限公司 | Method for preparing palladium/carbon catalyzer by hydrogenising and refining crude terephthalic acid |
| CN101347729A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for preparing Pd/carbon catalyst for hydrofinishing of coarse isophthalic acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941634A (en) * | 2015-06-03 | 2015-09-30 | 江苏清泉化学股份有限公司 | Palladium-carbon catalyst for preparing furan through furfural decarbonylation process, and preparation method thereof |
| CN104941634B (en) * | 2015-06-03 | 2018-05-15 | 江苏清泉化学股份有限公司 | A kind of preparing furan through decarbonylation of furfural palladium carbon catalyst and preparation method thereof |
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