CN1267188C - Palladium catalyst method of resisting CO poisoning - Google Patents
Palladium catalyst method of resisting CO poisoning Download PDFInfo
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- CN1267188C CN1267188C CN 03122846 CN03122846A CN1267188C CN 1267188 C CN1267188 C CN 1267188C CN 03122846 CN03122846 CN 03122846 CN 03122846 A CN03122846 A CN 03122846A CN 1267188 C CN1267188 C CN 1267188C
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Abstract
The present invention relates to a palladium catalyst method of resisting CO poisoning in a hydrogenation reaction with a carbonyl compound. A load type cocatalyst or a raney type cocatalyst which uses ruthenium as a main active constituent is added in a reaction system; the addition quantity of the cocatalyst of the ruthenium is calculated as ruthenium/palladium =0.001-10 by a weight proportion; when the load type cocatalyst of the ruthenium is adopted, the load quantity of the ruthenium is calculated as 3.0% to 6.0% by the weight of the cocatalyst of the ruthenium. The method obviously reduces the possibility of palladium catalyst poisoning and enhances the activity and the stability of the catalyst in a reaction process.
Description
Technical field
The invention relates to a kind of method that the palladium catalyst anti-carbon monoxide is poisoned.More particularly, the invention relates to a kind of method that the palladium catalyst anti-carbon monoxide is poisoned in containing the hydrogenation reaction of carbonyls.
Technical background
As good hydrogenation catalyst, palladium catalyst is widely used in the numerous areas of industries such as PETROLEUM PROCESSING, pharmacy, fine chemistry industry.Especially prepare the SNIA technology of caprolactam, the terephthalic acid (TPA) technology in the polyester industrial in chemical fibre industry, the consumption of palladium catalyst is all very big.
In the catalytic reaction of the compound that contains carbonyl, since the decarboxylation side reaction tend to produce carbon monoxide, if what at this moment reaction was used is palladium catalyst, the carbon monoxide meeting strong adsorption that then produces is on the surface of palladium metal, cause the poisoning of catalyst, and then reduce activity of such catalysts.
For example, the toluene method of SNIA company prepares the process route of caprolactam, and promptly SNIA technology comprises that mainly toluene oxidation system benzoic acid, benzoic acid hydrogenation prepare processes such as cyclohexane-carboxylic acid, cyclohexane-carboxylic acid amidatioon system caprolactam.Benzoic acid hydrogenation wherein is an important step, and what this process was used is the precious metals palladium catalyst (brief note is Pd/C) that loads on the active carbon.Recycling catalyst Pd/C in the benzoic acid hydrogenation reaction system must cause active reduction gradually owing to adsorb carbon monoxide, consequently not only producing load can not improve, and must regularly add fresh catalyst to system, and the recovery frequency of the quantity delivered of the fresh catalyst that sharply increases and palladium has increased the possibility of production cost and precious metal palladium loss without doubt.So the performance of benzoic acid hydrogenation catalyst P d/C is the key of restriction benzoic acid hydrogenation technical development and SNIA technological development always.
Similarly, in the technology of isopropyl acid and ethyl benzoate hydrogenation preparing isopropyl cyclohexane carboxylic acid and ethyl cyclohexane carboxylic acid, the carbon monoxide that side reaction produces can make palladium catalyst poison and shorten its service life.Therefore taking some countermeasures prolongs the service life of expensive palladium catalyst, and industrial production is had important and practical meanings.
Summary of the invention
The objective of the invention is in order to solve above-mentioned problems of the prior art, a kind of method that the precious metals palladium catalyst anti-carbon monoxide is poisoned in containing the hydrogenation reaction of carbonyls is provided.
Method provided by the invention is: adding with the ruthenium in the hydrogenation reaction that contains carbonyls that with the palladium is catalyst is the co-catalyst of main active component, and the addition of ruthenium auxiliary agent is counted ruthenium/palladium=0.001-10 with the weight metal ratio, preferred 0.01-2.0.
The wherein said hydrogenation reaction that contains carbonyls mainly comprises the hydrogenation reaction etc. of hydrogenation reaction, terephthalic acid (TPA) hydrofining reaction, aliphatic unsaturated carboxylic acid or its ester of benzoic acid or substituted benzoic acid.For example benzoic hydrogenation reaction is the reaction that benzoic acid prepares cyclohexane-carboxylic acid; The hydrogenation reaction of substituted benzoic acid is C
1-C
5The benzoic acid hydrogenation that alkyl replaces prepares C
1-C
5The reaction of the naphthenic acid that alkyl replaces, isopropyl acid or to the reaction of ethyl benzoate hydrogenation preparing isopropyl cyclohexane formic acid and ethyl cyclohexane formic acid etc.
Wherein said is that the co-catalyst of main active component can be a non-loading type with the ruthenium, for example thunder Buddhist nun ruthenium; Also can be the porous carrier support type, be carrier loaded ruthenium auxiliary agent with silica, aluminium oxide, titanium dioxide, active carbon etc. for example.
When the ruthenium auxiliary agent adopted support type, the load capacity of ruthenium was counted 3.0-6.0% with ruthenium auxiliary agent weight and is advisable.The carrier of supported ruthenium auxiliary agent should be preferably consistent with the carrier of used palladium catalyst in the reaction system.
Because containing the hydrogenation reaction of carbonyls many is the palladium catalyst of carrier in order to active carbon, so in the inventive method emphasis to be disclosed in detail with the active carbon be the ruthenium auxiliary agent of carrier.
Absorbent charcoal carrier as ruthenium/charcoal auxiliary agent in the inventive method should be consistent with the absorbent charcoal carrier of employed Pd/carbon catalyst in the reaction system, promptly adopts the shell base, the active carbon of preferred coconut husk base and/or walnut shell base, and they should have 700-1000m
2The specific area of/g, granularity should be less than 200 microns.
Non-loading type thunder Buddhist nun ruthenium auxiliary agent can prepare according to the preparation method of the Raney's nickel of classics.
For the ruthenium auxiliary agent of support type, when the material that adopts beyond the active carbon, as silica, aluminium oxide, when titanium dioxide is carrier, the preparation process of this ruthenium auxiliary agent comprises the load of ruthenium and the activation step after the load.Concrete operations are as follows:
A. the load of ruthenium: ruthenic chloride or nitric acid ruthenium are made the solution that concentration is 10-100g/l, with the material that is selected from one of water, acetone and acetonitrile is medium, at 10-100 ℃ of following impregnated carrier 2-48 hour, make the load capacity of ruthenium on the carrier account for the 3.0-6.0% of ruthenium auxiliary agent gross weight;
B. the activation after the load: the ruthenium/carrier after the load was reduced 4-6 hour in 400-600 ℃ under hydrogen atmosphere.
When adopting active carbon to be carrier, the preparation process of this ruthenium auxiliary agent comprises impurity elimination and oxidation, the load of ruthenium and the activation step after the load of active carbon.Concrete operations are as follows:
A. the impurity elimination of active carbon: with concentration is the hydrochloric acid solution of 5-20 weight %, weight ratio according to active carbon and hydrochloric acid is 1: 0.5-1: 5 consumption, commercially available active carbon is handled 2-12 hour down to remove inorganic impurity wherein at normal temperature to 100 ℃, and the washing back is 100-120 ℃ of drying.
B. the oxidation of active carbon: this unit operations both can be undertaken by the liquid phase mode, also can be undertaken by the gas phase mode.
The liquid phase mode is: with concentration is the salpeter solution of 5-50 weight %, is 1 according to the weight ratio of active carbon and nitric acid: 0.5-1: 5 consumption, the active carbon after the impurity elimination ℃ to be handled 2-12 hour down at normal temperature to 100, and the washing back is 100-120 ℃ of drying.
The gas phase mode is: with (2-10%) O
2+ (98-90%) N
2Or the gaseous mixture of other inert gas, handled 10-12 hour down at 400-500 ℃ according to the gas flow of the 10-100ml/min active carbon after with impurity elimination.
C. the load of ruthenium: ruthenic chloride or nitric acid ruthenium are made the solution that concentration is 10-100g/l, with the material that is selected from one of water, acetone and acetonitrile is medium, 10-100 ℃ of following dipping active carbon 2-48 hour after impurity elimination and oxidation, make the load capacity of ruthenium on the active carbon account for the 3.0-6.0% of ruthenium auxiliary agent gross weight.
D. the activation after the load: this unit operations both can be undertaken by the liquid phase mode, also can be undertaken by the gas phase mode.
The liquid phase mode is: with one or more the mixture that is selected from formaldehyde, hydrazine hydrate, formic acid, potassium borohydride and the sodium borohydride is activator, mol ratio according to activator and ruthenium is 2: 1-10: 1, preferred 2: 1-4: 1 consumption, ruthenium/charcoal was handled 2-10 hour down at 0-100 ℃, spent deionised water after the filtration to Cl
-＜10
-6M is 1.013 * 10 at temperature 100-120 ℃, vacuum again
-3-1.013 * 10
-4Dry under the condition of Pa, under nitrogen protection, preserve.
The gas phase mode is: ruthenium/charcoal was handled 2-10 hour down at 0-100 ℃ according to the hydrogen flowing quantity of 10-100ml/min with hydrogen, preserved under nitrogen protection, perhaps hygrometric state is preserved under atmosphere.
Method provided by the invention is compared with the existing method that does not add the ruthenium auxiliary agent, because the carbon monoxide that reaction produces is absorbed by the ruthenium auxiliary agent or transforms, greatly reduce the possibility that palladium catalyst is poisoned, thereby the activity of palladium catalyst and stability are obviously improved, and operational stability and production efficiency also improve greatly.Simultaneously owing to reduced the additional speed of fresh palladium catalyst, thereby reduced palladium catalyst the recovery frequency, reduced the possibility of palladium metal loss.In addition, since the reduction of carbon monoxide quantity in the system, the load that the transformation that must reduce needs for the processing carbon monoxide is adsorbed.In a word, adopt method provided by the invention that palladium catalyst is accelerated to contain the operability of the hydrogenation reaction of carbonyls greatly to improve, and cost obviously reduce.
The specific embodiment
The following examples will be described further method provided by the invention, but not thereby limiting the invention.
Embodiment 1
The preparation of employed ruthenium/charcoal auxiliary agent in present embodiment explanation the inventive method.
Get powdered activated carbon 50 gram (Shanghai active carbon Co., Ltd product, analyze pure, specific surface 860m
2/ g, moisture content 10%, the pH value is 3.5, granularity be the 40-60 micron account for 50%, all the other are the 60-160 micron), after following preliminary treatment as the carrier of ruthenium auxiliary agent:
(1) active carbon is that the aqueous hydrochloric acid solution of 10 weight % is added a cover in water-bath and boiled 6 hours with 500ml concentration, removes soluble impurity, ash and the aperture tamper on surface, to filtrate neutrality, filters the back in 110 ℃ of oven dry with deionized water drip washing;
(2) be that the salpeter solution of 20 weight % carried out oxidation processes 6 hours at normal temperatures with the active carbon after the impurity elimination with 150ml concentration, use deionized water drip washing to filtrate neutrality then, 110 ℃ of oven dry.
In 100ml concentration is to add in the ruthenium chloride aqueous solution of 40g/l through above-mentioned pretreated active carbon, constant temperature is 3 hours under 10 ℃ of also powerful stirrings, leaving standstill after 10 hours with 60ml concentration is hydrazine hydrate (Tianjin good fortune chemical reagent in the morning factory product of 5 weight %, analyze pure) under 4 ℃, its dipping was carried out activation processing in 2 hours, spend deionised water after the filtration to Cl
-Concentration is less than 10
-6M is 1.013 * 10 at 110 ℃, vacuum then
-3-1.013 * 10
-4Carried out drying under the condition of Pa 4 hours, the preservation of under nitrogen protection, coming out of the stove.
Ruthenium content is 3.5 weight % in the prepared auxiliary agent, and it is numbered and helps-1.
Embodiment 2
The preparation of employed ruthenium/charcoal auxiliary agent in present embodiment explanation the inventive method.
Get powdered activated carbon 50 gram (Shanghai active carbon Co., Ltd product, analyze pure, specific surface 860m
2/ g, moisture content 10%, the pH value is 3.5, granularity be the 40-60 micron account for 50%, all the other are the 60-160 micron), after following preliminary treatment as the carrier of ruthenium auxiliary agent:
(1) active carbon is that the aqueous hydrochloric acid solution of 15 weight % is added a cover in water-bath and boiled 6 hours with 600ml concentration, removes soluble impurity, ash and the aperture tamper on surface, to filtrate neutrality, filters the back in 110 ℃ of oven dry with deionized water drip washing;
(2) at gas flow the 5%O of 50ml/min with the active carbon after the impurity elimination
2+ 95%N
2Gaseous mixture atmosphere in be warming up to 425 ℃ and constant 11 hours and carry out oxidation processes, be cooled to room temperature after the processing.
In 100ml concentration is to add in the ruthenium chloride aqueous solution of 40g/l through above-mentioned pretreated active carbon, constant temperature is 3 hours under 10 ℃ of also powerful stirrings, leaving standstill after 10 hours with 60ml concentration is that the hydrazine hydrate of 5 weight % carried out activation processing in 2 hours to its dipping under 4 ℃, spends deionised water after the filtration to Cl
-Concentration is less than 10
-6M is 1.013 * 10 at 110 ℃, vacuum then
-3-1.013 * 10
-4Carried out drying under the condition of Pa 4 hours, the preservation of under nitrogen protection, coming out of the stove.
Ruthenium content is 3.5 weight % in the prepared auxiliary agent, and it is numbered and helps-2.
Embodiment 3
The preparation of employed ruthenium/charcoal auxiliary agent in present embodiment explanation the inventive method.
Get powdered activated carbon 50 gram (Shanghai active carbon Co., Ltd product, analyze pure, specific surface 860m
2/ g, moisture content 10%, the pH value is 3.5, granularity be the 40-60 micron account for 50%, all the other are the 60-160 micron), after following preliminary treatment as the carrier of ruthenium auxiliary agent:
(1) active carbon is that the aqueous hydrochloric acid solution of 20 weight % is added a cover in water-bath and boiled 2 hours with 150ml concentration, removes soluble impurity, ash and the aperture tamper on surface, to filtrate neutrality, filters the back in 110 ℃ of oven dry with deionized water drip washing;
(2) be that the salpeter solution of 20 weight % carried out oxidation processes 10 hours at normal temperatures with the active carbon after the impurity elimination with 150ml concentration, use deionized water drip washing to filtrate neutrality then, 110 ℃ of oven dry.
In 100ml concentration is to add in the ruthenium chloride aqueous solution of 60g/l through above-mentioned pretreated active carbon, constant temperature is 2 hours under 20 ℃ of also powerful stirrings, leaving standstill after 15 hours with 92ml concentration is that the hydrazine hydrate of 5 weight % carried out activation processing in 3 hours to its dipping under 4 ℃, spends deionised water after the filtration to Cl
-Concentration is less than 10
-6M is 1.013 * 10 at 110 ℃, vacuum then
-3-1.013 * 10
-4Carried out drying under the condition of Pa 4 hours, the preservation of under nitrogen protection, coming out of the stove.
Ruthenium content is 5.5 weight % in the prepared auxiliary agent, and it is numbered and helps-3.
Embodiment 4
The preparation of employed ruthenium/charcoal auxiliary agent in present embodiment explanation the inventive method.
Get powdered activated carbon 50 gram (Shanghai active carbon Co., Ltd product, analyze pure, specific surface 860m
2/ g, moisture content 10%, the pH value is 3.5, granularity be the 40-60 micron account for 50%, all the other are the 60-160 micron), after following preliminary treatment as the carrier of ruthenium auxiliary agent:
(1) active carbon is that the aqueous hydrochloric acid solution of 20 weight % is added a cover in water-bath and boiled 2 hours with 150ml concentration, removes soluble impurity, ash and the aperture tamper on surface, to filtrate neutrality, filters the back in 110 ℃ of oven dry with deionized water drip washing;
(2) be that the salpeter solution of 20 weight % carried out oxidation processes 12 hours at normal temperatures with the active carbon after the impurity elimination with 150ml concentration, use deionized water drip washing to filtrate neutrality then, 110 ℃ of oven dry.
In 100ml concentration is to add in the ruthenic chloride acetone soln of 60g/l through above-mentioned pretreated active carbon; in fluid bed reactor the dipping 3 hours colourless to raffinate; the gained impregnation product is activated 6 hours down for 60 ℃ with hydrogen in reduction furnace; hydrogen flowing quantity is 30ml/min; comes out of the stove under nitrogen protection in cooling back, product is stored in the drier under the nitrogen protection.
Ruthenium content is 5.5 weight % in the prepared auxiliary agent, and it is numbered and helps-4.
Embodiment 5-8
These embodiment illustrate the beneficial effect of the method for employing ruthenium auxiliary agent provided by the invention to the Pd/C catalyst.
For Evaluation on effect is to illustrate that by estimating the hydrogenation effect that adds the forward and backward Pd/C catalyst of ruthenium auxiliary agent used Pd/C catalyst is the recycling catalyst sample on the benzoic acid hydrogenation production line.
The hydrogenation effect is with Z
0Value representation, it is that the Pd/C activity of such catalysts characterizes the hydrogen-absorption speed of representation unit time catalyst.Usually the depletion rate according to beginning hydrogen calculates.
Z
0The assay method of value can be with reference to described in " caprolactam device analysis method compilation " (chemical fibre Co., Ltd in Shijiazhuang writes).Basic step is: get Pd/C catalyst 2g, add that (or not adding) ruthenium auxiliary agent mixes and the autoclave of packing in, add the 200g benzoic acid again, with high purity nitrogen displacement 3-4 time, begin heating when filling nitrogen to 20 atmospheric pressure, replace 3-4 time with High Purity Hydrogen during to 150 ℃, fill hydrogen to 110 atmospheric pressure, start stirring and pick up counting simultaneously, when reducing to 90 atmospheric pressure, recording reacting time and reaction temperature.Fill simultaneously hydrogen to 110 atmospheric pressure rapidly, according to identical method, repetitive operation repeatedly, and continuation recording reacting time (reducing to 90 atmospheric pressure) from 110 atmospheric pressure, catalyst sample is finished circular response usually 7 times, utilizes γ=Δ P/ Δ t formula to calculate the wear rate of hydrogen, is abscissa with time, γ is ordinate mapping, is the hydrogen consumption speed γ of beginning with the ordinate intersection point
0, catalyst activity is Z
0=γ
0/ 4.
Table 1 has been listed the method provided by the invention that adopts, and promptly adds Pd/C activity of such catalysts behind the ruthenium auxiliary agent.
Comparative Examples 1
For the effect of the method for the invention provides is described, estimate simultaneously according to the method for the embodiment 5-8 Pd/C activity of such catalysts when not adding the ruthenium auxiliary agent, gained result one is listed in table 1.
Table 1.
| Embodiment | Adjuvant used | Ruthenium content in the auxiliary agent, weight % | Ruthenium/palladium weight ratio | The active Z of Pd/C 0 |
| Embodiment 5 embodiment 6 embodiment 7 embodiment 8 Comparative Examples 1 | Help-1 to help-2 to help-3 to help-4 | 3.5 3.5 5.5 5.5 | 0.05 0.10 0.50 1.00 | 0.40 0.50 0.60 0.70 0.16 |
Embodiment 9-15
These embodiment illustrate the implementation result that the ruthenium promoter addition the invention provides method to the influence and the employing of Pd/C catalyst activity.
Method according to embodiment 5-8 is estimated for the Pd/C activity of such catalysts that adds the ruthenium auxiliary agent, and evaluation result is as shown in table 2.
Comparative Examples 2
For the effect of the method for the invention provides is described, estimate simultaneously according to the method for the embodiment 5-8 Pd/C activity of such catalysts when not adding the ruthenium auxiliary agent, gained result one is listed in table 2.
Table 2.
| Embodiment | Adjuvant used | The Pd/C catalyst concn, % | Ruthenium/palladium weight ratio | The active Z of Pd/C 0 |
| Embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 embodiment 14 embodiment 15 Comparative Examples 2 | Help-4 to help-4 to help-4 to help-4 to help-4 to help-4 to help-4 | 1.0 1.0 1.0 1.0 1.0 0.5 0.5 0.5 | 0.02 0.03 0.04 0.05 0.1 1.0 2.0 | 0.32 0.37 0.41 0.50 0.60 0.30 0.50 0.08 |
Embodiment 16
The preparation of employed ruthenium/titanium dioxide auxiliary agent in present embodiment explanation the inventive method.
Get titanium dioxide powder 50 gram (Deqing chemical industry technological development Co., Ltd product, analyze pure, specific surface 81.9m
2/ g, granularity be the 40-60 micron account for 50%, all the other are the 60-160 micron) through 600 ℃ of roastings carrier as the ruthenium auxiliary agent after 6 hours.
In 100ml concentration is to add above-mentioned carrier in the ruthenic chloride acetone soln of 60g/l; in fluid bed reactor the dipping 3 hours colourless to raffinate; the gained impregnation product is activated 6 hours down for 400 ℃ with hydrogen in reduction furnace; hydrogen flowing quantity is 30ml/min; comes out of the stove under nitrogen protection in cooling back, product is stored in the drier under the nitrogen protection.
Ruthenium content is 5.5 weight % in the prepared auxiliary agent, and it is numbered and helps-5.
Embodiment 17-20
These embodiment illustrate the beneficial effect of the method for employing ruthenium auxiliary agent provided by the invention to palladium/titanium catalyst.
For Evaluation on effect is to add the forward and backward Pd/TiO of ruthenium auxiliary agent by estimating
2The hydrogenation effect of catalyst illustrates.Used Pd/TiO
2Catalyst is to prepare according to " Hankbook Heterogeneous CatalyticHydrogenation for Organic Synthesis " (SHIGEO NISHIMURA compiles, and Wiley-Interscience publishing house publishes, the 36th page).
The hydrogenation effect is with Z
0Value representation, it is Pd/TiO
2Activity of such catalysts characterizes, the hydrogen-absorption speed of representation unit time catalyst.Usually the depletion rate according to beginning hydrogen calculates.
Z
0The assay method of value is as follows: get Pd/TiO
2Catalyst 2g, add that (or not adding) ruthenium auxiliary agent mixes and the autoclave of packing in, add again 200g trans-the 4-isopropyl acid, with high purity nitrogen displacement 3-4 time, begin heating when filling nitrogen to 2MPa, replace 3-4 time with High Purity Hydrogen during to 150 ℃, fill hydrogen to 18MPa, start stirring and pick up counting simultaneously, when reducing to 16MPa, recording reacting time and reaction temperature.Simultaneously fill hydrogen rapidly to 18MPa, according to identical method, repetitive operation repeatedly, and continuation recording reacting time (reducing to 16MPa) from 18MPa, catalyst sample is finished circular response usually 7 times, utilizes γ=Δ P/ Δ t formula to calculate the wear rate of hydrogen, is abscissa with time, γ is ordinate mapping, is the hydrogen consumption speed γ of beginning with the ordinate intersection point
0, catalyst activity is Z
0=γ
0/ 4.
Table 3 has been listed the method provided by the invention that adopts, and promptly adds Pd/TiO behind the ruthenium auxiliary agent
2Activity of such catalysts.
Comparative Examples 3-4
For the effect of the method for the invention provides is described, according to the method for the embodiment 17-20 Pd/TiO when not adding the ruthenium auxiliary agent
2Activity of such catalysts is estimated simultaneously, and gained result one is listed in table 3.
Table 3.
| Embodiment | Adjuvant used | Pd/TiO 2Catalyst concn, % | Ruthenium/palladium weight ratio | Pd/TiO 2Active Z 0 |
| Embodiment 17 embodiment 18 embodiment 19 embodiment 20 Comparative Examples 3 Comparative Examples 4 | Help-5 to help-5 to help-5 to help-5 | 1.0 1.0 0.5 0.5 1.0 0.5 | 0.1 0.3 1.0 2.0 | 0.40 0.50 0.34 0.40 0.30 0.16 |
Claims (5)
1, a kind of method that in the benzoic acid hydrogenation reaction that with the palladium is being catalyst, makes the poisoning of palladium catalyst anti-carbon monoxide, it is characterized in that: adding with the ruthenium in reaction is the co-catalyst and the mixing of main active component, the addition of ruthenium auxiliary agent is counted ruthenium/palladium=0.001-10 with the weight metal ratio, described co-catalyst is a support type, its carrier is selected from silica, aluminium oxide, titanium dioxide or active carbon, and the load capacity of ruthenium is counted 3.0-6.0% with ruthenium auxiliary agent weight.
2, according to the process of claim 1 wherein that the addition of ruthenium auxiliary agent counts ruthenium/palladium=0.01-2.0 with the weight metal ratio.
3, according to the process of claim 1 wherein that said carrier is that the preparation process of ruthenium auxiliary agent of silica, aluminium oxide or titanium dioxide is as follows:
A. the load of ruthenium: ruthenic chloride or nitric acid ruthenium are made the solution that concentration is 10-100g/l, with the material that is selected from one of water, acetone and acetonitrile is medium, at 10-100 ℃ of following impregnated carrier 2-48 hour, make the load capacity of ruthenium on the carrier account for the 3.0-6.0% of ruthenium auxiliary agent gross weight;
B. the activation after the load: the ruthenium/carrier after the load was reduced 4-6 hour in 400-600 ℃ under hydrogen atmosphere.
4, according to the process of claim 1 wherein that said carrier is that the preparation process of ruthenium auxiliary agent of active carbon is as follows:
A. the impurity elimination of active carbon: with concentration is the hydrochloric acid solution of 5-20 weight %, weight ratio according to active carbon and hydrochloric acid is 1: 0.5-1: 5 consumption, active carbon is handled 2-12 hour down to remove inorganic impurity wherein at normal temperature to 100 ℃, and the washing back is 100-120 ℃ of drying;
B. the oxidation of active carbon: can be undertaken by liquid phase mode or gas phase mode,
The liquid phase mode is: with concentration is the salpeter solution of 5-50 weight %, is 1 according to the weight ratio of active carbon and nitric acid: 0.5-1: 5 consumption, the active carbon after the impurity elimination ℃ to be handled 2-12 hour down at normal temperature to 100, and the washing back is 100-120 ℃ of drying;
The gas phase mode is: with (2-10%) O
2+ (98-90%) N
2Or the gaseous mixture of other inert gas, handled 10-12 hour down at 400-500 ℃ according to the gas flow of the 10-100ml/min active carbon after with impurity elimination;
C. the load of ruthenium: ruthenic chloride or nitric acid ruthenium are made the solution that concentration is 10-100g/l, with the material that is selected from one of water, acetone and acetonitrile is medium, 10-100 ℃ of following dipping active carbon 2-48 hour after impurity elimination and oxidation, make the load capacity of ruthenium on the active carbon account for the 3.0-6.0% of ruthenium auxiliary agent gross weight;
D. the activation after the load: can be undertaken by liquid phase mode or gas phase mode,
The liquid phase mode is: with one or more the mixture that is selected from formaldehyde, hydrazine hydrate, formic acid, potassium borohydride and the sodium borohydride is activator, mol ratio according to activator and ruthenium is 2: 1-10: 1 consumption, ruthenium/charcoal was handled 2-10 hour down at 0-100 ℃, spent deionised water after the filtration to Cl
-＜10
-6M is 1.013 * 10 at temperature 100-120 ℃, vacuum again
-3-1.013 * 10
-4Dry under the condition of Pa, under nitrogen protection, preserve;
The gas phase mode is: ruthenium/charcoal was handled 2-10 hour down at 0-100 ℃ according to the hydrogen flowing quantity of 10-100ml/min with hydrogen, preserved under nitrogen protection, perhaps hygrometric state is preserved under atmosphere.
5, according to the method for claim 4, wherein said active carbon is specific area 700-1000m
2/ g, granularity are less than 200 microns shell matrix activated carbon.
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|---|---|---|---|
| CN 03122846 CN1267188C (en) | 2003-04-29 | 2003-04-29 | Palladium catalyst method of resisting CO poisoning |
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|---|---|---|---|
| CN 03122846 CN1267188C (en) | 2003-04-29 | 2003-04-29 | Palladium catalyst method of resisting CO poisoning |
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| CN1267188C true CN1267188C (en) | 2006-08-02 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872859A (en) * | 2012-10-11 | 2013-01-16 | 厦门大学 | Sintering-resisting loading type nanometer palladium catalyst and preparing method and application thereof |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872859A (en) * | 2012-10-11 | 2013-01-16 | 厦门大学 | Sintering-resisting loading type nanometer palladium catalyst and preparing method and application thereof |
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