CN101492611A - Supported palladium/carbon catalyst for hydrogen refining and method for preparing the same - Google Patents
Supported palladium/carbon catalyst for hydrogen refining and method for preparing the same Download PDFInfo
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- CN101492611A CN101492611A CNA2008100329206A CN200810032920A CN101492611A CN 101492611 A CN101492611 A CN 101492611A CN A2008100329206 A CNA2008100329206 A CN A2008100329206A CN 200810032920 A CN200810032920 A CN 200810032920A CN 101492611 A CN101492611 A CN 101492611A
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Abstract
The invention relates to a load type palladium/carbon catalyst used for hydrogen refining and a preparation method, mainly solving the problems in the prior art that Pd dispersity of Pd/c catalyst is low, microcrystal content is low, thermal stability is weak, and conversion rate of p-carboxyl benzaldehyde raw material is low . In the invention, palladium loaded on carrier active carbon is in microcrystal form, wherein the microcrystal less than 2.5 nanometer accounts for 90wt% of the total weight of the microcrystal palladium, and solution used for dipping or spraying the active carbon carrier contains Pd compound. In a COOH(CH2)nCOOH additive and a BCH3(CH2)m(CH3)3NBr additive, n is an integer ranging from 0 to 3 and m is an integer ranging from 8 to 20, wherein, the technical proposal that m is an integer ranging from 8 to 20 well solves the problems. The invention can be applied to the industrial production of terephthalic acid hydrobon catalyst.
Description
Technical field
The present invention relates to a kind of hydrorefined supported palladium/carbon catalyst and preparation method thereof that is used for.
Background technology
Supported palladium/carbon catalyst is widely used in the selective hydrogenation of unsaturated compounds.Especially, supported palladium/carbon catalyst is applicable to the refining of crude terephthalic acid, wherein some impurity in the crude terephthalic acid is as changing other compound to carboxyl benzaldehyde (be called for short 4-CBA) etc. into by hydrogenation, and terephthalate product can be separated purification with the crystalline method subsequently.Because palladium/carbon catalyst usually adopts single active ingredient, in the prior art its improvement research is mainly concentrated on the structure and the distribution situation of metal Pd on carrier of carrier, and these aspects can produce very big influence to the performance of catalyzer really.
Because terephthalic acid hydrofining reaction process is a first order reaction, speed of response is fast, and react the inside that reactant is difficult to be penetrated into granules of catalyst in the reaction process, and this just makes the active ingredient of granule interior not play a role.Therefore, in order to make full use of precious metal, palladium/carbon catalyst is made eggshell type usually, promptly allows the basic load of active ingredient precious metal in the surface of carrier.
Because hydrogenation reaction is to carry out on the surface of metal Pd, therefore usually for the identical catalyzer of metal Pd charge capacity, the dispersity of metal Pd the heal thermostability of height and/or catalyzer of the content of crystallite of the metal Pd of load in height and/or the catalyzer that heals is good more in the catalyzer, then activity of such catalysts is just higher, and work-ing life is also longer.
If directly will contain Pd compound (as chlorine palladium acid sodium or Palladous chloride) solution loads on the gac, activated carbon surface can the very thin glossiness metal Pd layer of very fast appearance, this mainly is that they very easily make the Pd ion be reduced into the non-valent metal Pd because activated carbon surface contains reduction group and the unbound electron just like aldehyde radical.Therefore, the catalyzer that so makes has very low metal Pd dispersity.A kind of method that overcomes this problem is to be transformed into insoluble compound at the Pd ion that dipping will contain before the operation in the steeping fluid of Pd compound.For example, at room temperature the water-soluble cpds hydrolysis of Pd is changed into insoluble Pd (OH)
2Or PdOH
2O, and then load on the gac, subsequently with the reduction of reductive agents such as formaldehyde, sodium formiate, glucose, formic acid or hydrogen, can prevent migration and the grain growth of Pd like this.As U.S. Pat 3,138,560 have instructed in steeping fluid and to add hydrogen peroxide and make the water-soluble cpds hydrolysis of Pd generate insoluble compound, flood then.But because hydrogen peroxide itself also has oxidisability, it can be with the activated carbon surface radical oxidation, thereby will change the Surface Physical Chemistry character of carrier, promptly change the surface group structure of carrier, this has stronger uncertain negative impact, can damage other performance of catalyzer, as carrying palladium intensity, catalyst life, selectivity etc.U.S. Pat 4; 476; the steeping fluid that contains the Pd compound is prepared in 242 propositions with organic solvents such as methyl alcohol or pyridines; it is said that this is also very effective to the migration and the grain growth that prevent Pd; but production process use methyl alcohol or pyridine are this in human body harmful's organic compound, all are disadvantageous from environment protection or labour protection.In addition, there is patent report chlorine palladium acid solution to be transformed into and contains palladium colloidal solution by adjustment pH value, the reduction group that allegedly can prevent activated carbon surface directly is reduced into the non-valent metal Pd with the Pd ion, but glue stability is bad, be difficult to uniform distribution on carrier active carbon, this can influence dispersiveness and the thermostability of Pd equally.
Summary of the invention
One of technical problem to be solved by this invention is that the Pd dispersity of Pd/C catalyzer in the prior art is low, content of crystallite is low, poor heat stability, the problem that raw material is low to the carboxyl benzaldehyde transformation efficiency provides a kind of new hydrorefined supported palladium/carbon catalyst that is used for.This catalyzer has higher Pd dispersity and high content of crystallite and thermostability preferably, and the treating process that is used for crude terephthalic acid has the characteristics high to the carboxyl benzaldehyde transformation efficiency.Two of technical problem to be solved by this invention provides one of a kind of and the technical solution problem corresponding preparation method who is used for hydrorefined supported palladium/carbon catalyst.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind ofly be used for hydrorefined supported palladium/carbon catalyst, the palladium that wherein is carried on carrier active carbon exists with the crystallite form, and wherein accounts for more than the 90 weight % of palladium crystallite total amount less than the crystallite of 2.5 nanometers.
In the technique scheme, the palladium of load is enriched in the upper layer of carrier active carbon, to such an extent as to be under the situation of 0.50 ± 0.30 weight % of total catalyst weight at the palladium content of palladium/carbon catalyst, palladium metal under the carrier active carbon surface in the layer of the 5 nanometer degree of depth accounts for more than the 40 weight % of total atom weight in this layer, more than the preferred 50 weight %; Palladium metal under the carrier active carbon surface in the layer of the 300 nanometer degree of depth accounts for more than the 10 weight % of total atom weight in this layer, more than the preferred 20 weight %.The palladium preferred version of load is for to be the high dispersing state on the carrier active carbon surface, and its dispersity is not less than 20%.500 ℃, at bubbling by roasting in the nitrogen gas stream of 25 ℃ of water after 10 hours, the average crystal grain size of the palladium of load is not more than 60 nanometers.Based on the gross weight meter of catalyzer, described catalyzer contains the metal Pd of 0.05～5 weight %, preferably contains the metal Pd of 0.2～3.5 weight %.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: prepare the described method that is used for hydrorefined supported palladium/carbon catalyst, may further comprise the steps:
A) at first gac is washed with inorganic acid aqueous solution, be washed with water to neutrality then, and dry this washed gac, absorbent charcoal carrier got;
B) usefulness contains the aqueous solution dipping of Pd compound and additive A and B or sprays described absorbent charcoal carrier, makes the compound loaded catalyst precursor that obtains on absorbent charcoal carrier of Pd; Described additive A is COOH (CH
2)
nCOOH, wherein n is 0～3 integer, the mol ratio of Pd is 0.01: 1～5.0: 1 in additive A and the Pd compound; Described additive B is CH
3(CH
2)
m(CH
3)
3NBr, wherein m is 8～20 integer, the addition of additive B is the 0.05-5% of described aqueous solution weight;
C) catalyst precursor is reduced processing with reductive agent, described supported palladium/carbon catalyst.
In the technique scheme, described mineral acid preferred version is to be selected from least a in hydrochloric acid, nitric acid or the phosphoric acid; Pickling time preferable range is 0.5～8 hour, and more preferably scope is 0.5～4 hour; The acid concentration preferable range of inorganic acid solution is 0.01～5.0 mol, and more preferably scope is 0.01～3.0 mol; The drying temperature preferable range is 80～150 ℃, and time of drying, preferable range was 0.5～10 hour, and more preferably scope is 0.5～6 hour.Described Pd compound preferred version is at least a in the subsalt of the halogenide that is selected from Pd, acid chloride, Palladous nitrate, the acid of chlorine palladium, the acid of chlorine palladium or the palladium amine complex, and more preferably scheme is to be selected from least a in acid chloride or the acid of chlorine palladium; The weight percent concentration preferable range of Pd is 0.01～5% in the described aqueous solution, and more preferably scope is 0.2～3.6%; The mol ratio preferable range of Pd is 0.05: 1～3.0: 1 in additive A and the Pd compound, and the addition preferable range of additive B is 0.3～3% of a described aqueous solution weight.Described catalyst precursor preferred version is that elder generation wore out 1～50 hour under 0～80 ℃ of condition of temperature before reduction is handled, and more preferably scheme is to wear out 1～24 hour under 0～80 ℃ of condition earlier before reduction is handled; The reductive agent preferred version is to be selected from least a in formic acid, sodium formiate, formaldehyde, hydrazine hydrate, glucose or the hydrogen, and more preferably scheme is for being selected from sodium formiate or hydrazine hydrate; Reduction treatment temp preferable range is 0～200 ℃, and more preferably scope is 50～120 ℃; Reduction treatment time preferable range is 0.5～24 hour, and more preferably scope is 1～10 hour.
The preparation method of the supported palladium/carbon catalyst in the technique scheme, catalyzer is a carrier with particle or pressed active carbon, supported active component metal Pd, the content of metal Pd is 0.05～5 weight % in the catalyzer, the preparation method may further comprise the steps successively:
A) at first gac is washed with inorganic acid aqueous solution, be washed with water to neutrality then, and dry this washed gac, absorbent charcoal carrier got;
B) usefulness contains the aqueous solution dipping of Pd compound and additive A and B or sprays described absorbent charcoal carrier, makes the compound loaded catalyst precursor that obtains on absorbent charcoal carrier of Pd; Described additive A is COOH (CH
2)
nCOOH, wherein n is 0～3 integer, the mol ratio of Pd is 0.01: 1～5.0: 1 in additive A and the Pd compound; Described additive B is CH
3(CH
2)
m(CH
3)
3NBr, wherein m is 8～20 integer, the addition of additive B is the 0.05-5% of described aqueous solution weight;
Additive A: COOH (CH
2)
nCOOH, n are 0～3 integer,
Be COOHCOOH during n=0 wherein, be designated as additive A 1;
During n=3 COOH (CH
2)
3COOH is designated as additive A 2;
Additive B: CH
3(CH
2)
m(CH
3)
3NBr, m are 8～20 integer,
Be CH during m=8 wherein
3(CH
2)
8(CH
3)
3NBr is designated as additive B 1;
During m=12 CH
3(CH
2)
12(CH
3)
3NBr is designated as additive B 2;
During m=20 CH
3(CH
2)
20(CH
3)
3NBr is designated as additive B 3;
C) catalyst precursor is reduced processing with reductive agent, described supported palladium/carbon catalyst.
In aforesaid method, add during except that the preparation of Pd solution the additive, other parts are then basic identical with existing general palladium/carbon catalyst preparation method, and these preparation process are that those skilled in the art are known.
The present invention is owing to added additive during the preparation of Pd solution, additive can produce stronger interaction and generate a kind of complex compound with Pd, so can reduce the redox-potential of Pd, when Pd loads on the gac, the Pd ion just can not reduced by the activated carbon surface group, thereby the Pd ion can be distributed in activated carbon surface very equably.Compared with prior art, the invention has the advantages that metal Pd has higher dispersity in the catalyzer that makes, content of crystallite is higher, on use properties, show active high, long service life, and the step that increases in the preparation process is very simple, the raw material that adopts is easy to environmental protection treatment, and the method that adopts can not produce any negative impact to catalyzer, has obtained better technical effect.
Among the present invention, adopted following testing method:
(1) dispersity of palladium metal:
The dispersity of palladium metal uses the chemisorption instrument, adopts the hydroxide titration method to measure.Dispersity calculates by following formula:
Dispersity=((2 * V
Inhale* M
Pd)/(3 * 22400 * W
Sample* C
Pd)) * 100%
Wherein: V
InhaleThe hydrogen adsorptive capacity of expression sample,
M
PdThe nucleidic mass of expression palladium,
W
SampleThe weight of expression sample,
C
PdThe content of palladium in the expression sample.
(2) content of crystallite:
The term of Shi Yonging " content of crystallite " is meant the crystalline content of particle diameter less than 2.5 nanometers in the present invention.
Measure the content of palladium in the catalyzer by the X-fluorescence spectrophotometer, record the particle diameter of palladium metal crystal grain with x-ray diffractometer (XRD), then by following formula calculating content of crystallite:
Content of crystallite=(particle diameter is less than the palladium metal crystal grain amount/palladium metal total amount of 2.5 nanometers) * 100%
(3) thermostability:
Measure the median size of the palladium crystal grain of palladium/carbon catalyst by x-ray diffractometer (XRD).Then with this catalyzer at 500 ℃, after 10 hours, measure the median size of palladium crystal grain by roasting in the nitrogen gas stream of 25 ℃ of water again by x-ray diffractometer (XRD) at bubbling.The thermostability of catalyzer has been indicated in the variation of the median size of the median size of palladium crystal grain and roasting front and back palladium crystal grain after the roasting.The median size of palladium crystal grain is more little after the roasting, illustrates that the thermostability of catalyzer is good more.Simultaneously, the variation of the median size of roasting front and back palladium crystal grain is more little, illustrates that the thermostability of catalyzer is good more.
(4) content of palladium in the layer of different depths under the catalyst surface:
Catalyst surface is carried out the argon etching.Behind the etching certain depth, measure the content of palladium in the upper layer that exposes after the etching with photoelectron spectrum XPS and auger spectrum AES, get final product the content of palladium in the layer of different depths under the catalyst surface.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
With 100 grams by 4 mesh sieves but be retained on 8 mesh sieves, 1100 meters of specific surfaces
2The cocoanut active charcoal of/gram washed 2 hours with the aqueous nitric acid of 200 milliliter of 0.4 mol.After removing acid solution, described gac is washed till neutrality with deionized water, following dry 6 hours in 120 ℃ then.
The preparation of Pd solution.Get chlorine palladium aqueous acid 3.2 gram that contains palladium 16 weight %, add deionized water to 40 milliliter, add additive A 1 aqueous solution of 2.16 grams, 10 weight % more therein, and to add deionized water to liquor capacity be 60 milliliters that this moment, solution weight was 61 grams.After stablizing 180 minutes, add additive B 10.3 grams again, and stir.Above-mentioned treated gac is contained the Pd solution impregnation 3 hours with this, obtain catalyst precursor.With catalyst precursor aged at room temperature 24 hours, then in the reduced liquid that hydrazine hydrate aqueous solutions and 200 gram pure water by 20 grams, 5 weight % are mixed with at 30 ℃ of dippings 3 hours down.After removing by filter liquid, with pure water that the solids washing is extremely neutral, and dry, obtain catalyst prod.
[embodiment 2～11]
Select for use different Pd compounds and different additives to prepare and contain Pd solution, all the other are with [embodiment 1].It is 1 listed that mol ratio, the weight percent of additive B in described Pd solution of concrete Pd compound, the content (in Pd) that contains Pd compound in the Pd solution, concrete additive and additive A and Pd sees Table.
[embodiment 12～18]
According to the program of [embodiment 1], but select different additives to prepare to contain Pd solution (the concrete additive that uses sees Table 1) for use, and will contain the Pd spray solution on gac to obtain catalyst precursor.Adopt mineral acid as shown in table 2, inorganic acid concentration, pickling time, time of drying, temperature, reductive agent, reduction treatment temp and reduction treatment time in addition.
[comparative example]
Not doping when preparation contains Pd solution, all the other are with [embodiment 1].
[embodiment 19]
The catalyzer that each embodiment and comparative example are made carries out palladium Determination on content in the layer of different depths under dispersity, content of crystallite, thermostability and the catalyst surface, and estimates described catalyzer under following appreciation condition, the results are shown in Table 3 and table 4.
Catalyst consumption: 2.0 grams
Thick p-Xylol amount: 30.0 grams
4-CBA amount: 1.0 grams
Reaction pressure: 7.0MPa
Hydrogen partial pressure: 0.50MPa
Reaction times: 1.0 hours
Temperature of reaction: 270 ℃
Table 1
*The weight percent that contains the Pd aqueous solution
Table 2
Table 3
| Embodiment | Pd content (weight %) in the catalyzer | Dispersity (%) | Content of crystallite (%) | Average crystal grain size (nm) | Grain size (nm) after 500 ℃ of roastings | 4-CBA transformation efficiency (%) |
| Embodiment 1 | 0.51 | 20 | 91 | 3.6 | 5.8 | 99.8 |
| Embodiment 2 | 0.49 | 21 | 90 | 3.4 | 6.0 | 99.9 |
| Embodiment 3 | 0.20 | 28 | 93 | 2.9 | 5.5 | 90.2 |
| Embodiment 4 | 0.60 | 20 | 90 | 3.6 | 6.0 | 99.9 |
| Embodiment 5 | 0.51 | 22 | 91 | 3.7 | 5.9 | 99.7 |
| Embodiment 6 | 3.53 | 20 | 90 | 3.9 | 5.9 | 100 |
| Embodiment 7 | 0.40 | 28 | 93 | 3.8 | 5.7 | 99.5 |
| Embodiment 8 | 0.54 | 20 | 92 | 3.5 | 6.0 | 99.9 |
| Embodiment 9 | 0.49 | 20 | 91 | 3.2 | 5.8 | 99.7 |
| Embodiment 10 | 0.50 | 22 | 92 | 3.9 | 5.7 | 99.8 |
| Embodiment 11 | 0.49 | 25 | 90 | 3.7 | 5.9 | 99.7 |
| Embodiment 12 | 0.48 | 28 | 91 | 3.3 | 5.8 | 99.6 |
| Embodiment 13 | 0.50 | 20 | 90 | 3.5 | 6.0 | 99.7 |
| Embodiment 14 | 0.40 | 21 | 92 | 3.2 | 6.1 | 99.5 |
| Embodiment 15 | 0.47 | 26 | 91 | 3.5 | 5.9 | 99.8 |
| Embodiment 16 | 0.50 | 23 | 91 | 3.0 | 5.8 | 99.9 |
| Embodiment 17 | 0.47 | 22 | 93 | 3.3 | 5.9 | 99.8 |
| Embodiment 18 | 0.48 | 26 | 90 | 3.2 | 5.7 | 100 |
| Comparative example | 0.49 | 4 | 52 | 4.6 | 11.1 | 66.2 |
Table 4
| Embodiment | Pd content (weight %) in the catalyzer | Palladium content (weight %) under the activated carbon surface in the layer of the 5nm degree of depth | Palladium content (weight %) under the activated carbon surface in the layer of the 300nm degree of depth |
| Embodiment 1 | 0.51 | 55.3 | 22.1 |
| Embodiment 2 | 0.49 | 54.3 | 23.5 |
| Embodiment 3 | 0.20 | 43.1 | 11.8 |
| Embodiment 4 | 0.60 | 61.3 | 24.9 |
| Embodiment 5 | 0.51 | 57.6 | 23.7 |
| Embodiment 6 | 3.53 | 63.5 | 29.3 |
| Embodiment 7 | 0.40 | 50.1 | 21.0 |
| Embodiment 8 | 0.54 | 57.5 | 22.3 |
| Embodiment 9 | 0.49 | 56.3 | 20.7 |
| Embodiment 10 | 0.50 | 53.4 | 23.6 |
| Embodiment 11 | 0.49 | 52.3 | 23.6 |
| Embodiment 12 | 0.48 | 51.6 | 21.7 |
| Embodiment 13 | 0.50 | 54.3 | 23.3 |
| Embodiment 14 | 0.40 | 50.4 | 20.2 |
| Embodiment 15 | 0.47 | 54.9 | 21.3 |
| Embodiment 16 | 0.50 | 56.3 | 23.3 |
| Embodiment 17 | 0.47 | 53.9 | 22.4 |
| Embodiment 18 | 0.48 | 54.2 | 25.3 |
| Comparative example | 0.49 | 30.6 | 12.5 |
。
Claims (10)
1, a kind ofly be used for hydrorefined supported palladium/carbon catalyst, the palladium that wherein is carried on carrier active carbon exists with the crystallite form, and wherein accounts for more than the 90 weight % of palladium crystallite total amount less than the crystallite of 2.5 nanometers.
2, be used for hydrorefined supported palladium/carbon catalyst according to claim 1 is described, the palladium that it is characterized in that load is enriched in the upper layer of carrier active carbon, to such an extent as to be that the palladium metal under the carrier active carbon surface in the layer of the 5 nanometer degree of depth accounts for more than the 40 weight % of total atom weight in this layer under the situation of 0.50 ± 0.30 weight % of total catalyst weight at the palladium content of palladium/carbon catalyst; Palladium metal under the carrier active carbon surface in the layer of the 300 nanometer degree of depth accounts for more than the 10 weight % of total atom weight in this layer.
3, be used for hydrorefined supported palladium/carbon catalyst according to claim 2 is described, the palladium that it is characterized in that load is enriched in the upper layer of carrier active carbon, to such an extent as to be that the palladium metal under the carrier active carbon surface in the layer of the 5 nanometer degree of depth accounts for more than the 50 weight % of total atom weight in this layer under the situation of 0.50 ± 0.30 weight % of total catalyst weight at the palladium content of palladium/carbon catalyst; Palladium metal under the carrier active carbon surface in the layer of the 300 nanometer degree of depth accounts for more than the 20 weight % of total atom weight in this layer.
4, be used for hydrorefined supported palladium/carbon catalyst according to claim 1 is described, it is characterized in that the palladium of load is the high dispersing state on the carrier active carbon surface, its dispersity is not less than 20%.
5, be used for hydrorefined supported palladium/carbon catalyst according to claim 1 is described, it is characterized in that with described catalyzer 500 ℃, at bubbling by roasting in the nitrogen gas stream of 25 ℃ of water after 10 hours, the average crystal grain size of the palladium of load is not more than 6.0 nanometers.
6, be used for hydrorefined supported palladium/carbon catalyst according to claim 1 is described, it is characterized in that the gross weight meter based on catalyzer, described catalyzer contains the metal Pd of 0.05～5 weight %.
7, be used for hydrorefined supported palladium/carbon catalyst according to claim 6 is described, it is characterized in that the gross weight meter based on catalyzer, described catalyzer contains the metal Pd of 0.2～3.5 weight %.
8, prepare the described method that is used for hydrorefined supported palladium/carbon catalyst of claim 1, may further comprise the steps:
A) at first gac is washed with inorganic acid aqueous solution, be washed with water to neutrality then, and dry this washed gac, absorbent charcoal carrier got;
B) usefulness contains the aqueous solution dipping of Pd compound and additive A and B or sprays described absorbent charcoal carrier, makes the compound loaded catalyst precursor that obtains on absorbent charcoal carrier of Pd; Described additive A is COOH (CH
2)
nCOOH, wherein n is 0～3 integer, the mol ratio of Pd is 0.01: 1～5.0: 1 in additive A and the Pd compound; Described additive B is CH
3(CH
2)
m(CH
3)
3NBr, wherein m is 8～20 integer, the addition of additive B is the 0.05-5% of described aqueous solution weight;
C) catalyst precursor is reduced processing with reductive agent, described supported palladium/carbon catalyst.
9, described according to Claim 8 preparation is used for the method for hydrorefined supported palladium/carbon catalyst, it is characterized in that described mineral acid is selected from least a in hydrochloric acid, nitric acid or the phosphoric acid; The pickling time is 0.5～8 hour; The acid concentration of inorganic acid solution is 0.01～5.0 mol; Drying temperature is 80～150 ℃, and be 0.5～10 hour time of drying;
Described Pd compound is selected from least a in the subsalt of halogenide, acid chloride, Palladous nitrate, the acid of chlorine palladium, the acid of chlorine palladium of Pd or the palladium amine complex; The weight percent concentration of Pd is 0.01～5% in the described aqueous solution, and the mol ratio of Pd is 0.05: 1～3.0: 1 in additive A and the Pd compound; The addition of additive B is 0.3～3% of a described aqueous solution weight;
Described catalyst precursor wore out 1～50 hour under 0～80 ℃ of condition of temperature earlier before reduction is handled; Reductive agent is selected from least a in formic acid, sodium formiate, formaldehyde, hydrazine hydrate, glucose or the hydrogen; The reduction treatment temp is 0～200 ℃, and the reduction treatment time is 0.5～24 hour.
10, described preparation is used for the method for hydrorefined supported palladium/carbon catalyst according to claim 9, it is characterized in that the pickling time is 0.5～4 hour; The acid concentration of inorganic acid solution is 0.01～3.0 mol; Be 0.5～6 hour time of drying;
Described Pd compound is selected from least a in acid chloride or the acid of chlorine palladium; The weight percent concentration of Pd is 0.2～3.6% in the described aqueous solution;
Described catalyst precursor wore out 1～24 hour under 0～80 ℃ of condition earlier before reduction is handled; Reductive agent is selected from sodium formiate or hydrazine hydrate; The reduction treatment temp is 50～120 ℃, and the reduction treatment time is 1～10 hour.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732554A (en) * | 2016-11-21 | 2017-05-31 | 湖北省宏源药业科技股份有限公司 | Low carrying capacity catalyst Pd/C of glyoxal air oxidation synthesizing glyoxalic acid and preparation method thereof |
| CN109092296A (en) * | 2018-08-17 | 2018-12-28 | 中国科学院长春应用化学研究所 | A kind of carbon load palladium oxide nanocluster catalyst and the preparation method and application thereof |
-
2008
- 2008-01-23 CN CNA2008100329206A patent/CN101492611A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732554A (en) * | 2016-11-21 | 2017-05-31 | 湖北省宏源药业科技股份有限公司 | Low carrying capacity catalyst Pd/C of glyoxal air oxidation synthesizing glyoxalic acid and preparation method thereof |
| CN106732554B (en) * | 2016-11-21 | 2019-03-08 | 湖北省宏源药业科技股份有限公司 | Low carrying capacity catalyst Pd/C of glyoxal air oxidation synthesizing glyoxalic acid and preparation method thereof |
| CN109092296A (en) * | 2018-08-17 | 2018-12-28 | 中国科学院长春应用化学研究所 | A kind of carbon load palladium oxide nanocluster catalyst and the preparation method and application thereof |
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Application publication date: 20090729 |