CN1955256A - Acetylene selected hydrogenation catalyst and its preparation method - Google Patents
Acetylene selected hydrogenation catalyst and its preparation method Download PDFInfo
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Abstract
This invention discloses an acetylene hydrocarbon hydrogenation selected accelerant and its preparation. This accelerant includes carrier, main active component palladium, stannum as co-active substance. The carrier chooses from diatomite, SiO2, TiO2 and Al2O3, and its shape includes particle, globular, lamellar, Dentate or strip, whose specific surface is 1-200m2/g; The weight amount of main active component palladium in the form of simple substance is 0.01-1.0% that of total carrier weight. The weight amount of co-active component stannum is 0.01-3.0%. The Pd layer of this accelerant distributes rationally. The precious metal Pd distributes between 0 and 200 mum of the carrier outer shell, which improves the utilization rate of main active component Pd and reduces the possibility of side reaction.
Description
Technical field
The present invention relates to a kind of selective acetylene hydrocarbon hydrogenation catalyst and preparation method thereof, particularly a kind of simple substance palladium catalyst that directly prepares by chemical plating method and preparation method thereof.
Background technology
At the petrochemical complex industrial circle, contain 0.3～3% acetylene in the cracking centrifugal station in the ethene cut, this acetylene impurity is the poisonous substance of polyethylene catalysts, influences ethylene polymerization and normally carries out.Produce for fear of above-mentioned poisoning of catalyst phenomenon occurring, adopt catalyzer to select the method for hydrogenation to make that acetylene conversion is an ethene in the ethene cut usually.But selecting hydrogenation to remove in the reaction of acetylene, being adsorbed on acetylene on the catalyst surface, to be easy to deep hydrogenation be ethane, or generate unsaturated C such as 1,3-butadiene by the hydrogenation dimerization reaction
4Hydrocarbon, and they continue reaction again, generate C
6～C
24Superpolymer is commonly called as green oil.Green oil sticks on the selective acetylene hydrocarbon hydrogenation catalyst can cause catalyst deactivation.
It is that main body impregnated on the inorganic materials carrier that present alkynes and diolefin hydrogenate catalyzer generally adopt the oxide compound of precious metal palladium.For example, by adjusting the crystal plane structure of Pd, (100) and (110) face is exposed to skin and the catalyzer (US6084140) made; Add the catalyst component IB Pd-Au of family (EP1372843), Pd-Ag (US4404124), basic metal or alkaline-earth metal (US548824) etc. in the catalyzer; VA family catalyst component forms fluorochemical (US6465391); Carrier has aluminum oxide, silicon oxide (US5856262), honeycomb cordierite (CN1176291) and reticular fiber structure aluminum oxide (US6388150).
Preparation method's length not only consuming time that selective acetylene hydrocarbon hydrogenation catalyst is traditional, and calcining or when reduction the temperature condition height, make energy consumption big, production cost height and process control factor are many.At the problems referred to above, US6509292 discloses the technology that adopts reductive agents such as sodium formiate, formic acid the Pd-Ag catalyzer to be carried out original position prereduction; Though this patented technology can reduce high temperature reduction, but to after having flooded Pd and Ag, carry out high-temperature calcination respectively.CN1511634A discloses a kind of method of deactivated catalyst, with high energy active specy in the radio frequency plasma to the Pd series catalysts before species carry out discharge process; But this method is owing to the equipment requirements strictness, and there is big problem in large-scale commercial production.
From the spreading depth of palladium layer on carrier, it mainly is by the dipping diffusion that traditional method prepares palladium series catalyst, makes palladium enter the carrier duct than the depths, reached at the 400um that has.In the selective hydrogenation reaction process, the hydrogenation reaction utilization ratio of Pd that is in the depths, duct is very low, and after acetylene molecule enters the duct, is easy to cause reactions such as acetylene secondary hydrogenation, oligomerisation, blocks the duct, reduces reactive behavior and selectivity.
Through to the research of existing various alkynes hydrogenation catalysts, investigators generally believe that elemental metals Pd is the active specy in the selective acetylene hydrocarbon hydrogenation catalyst, and this active specy present stage generally obtains by the high temperature reduction PdO of hydrogenation reaction initial stage.
Use the method for electroless plating the palladium metal of simple substance can be deposited on surfaces of various materials at present, as palladium being deposited on the inner wire in the electronic component (CN1351359); The composition metal palladium film (CN1640530) that is used for hydrogen; Chemical palladium-plating is made the liquid crystalline polymers (CN1550124) of metal inoculation in the liquid crystalline polymers substrate.But require the Pd content of load a small amount of (as 0.01～0.5 weight %) on inorganic carrier for selective acetylene hydrocarbon hydrogenation catalyst, and the Pd layer is evenly distributed on the carrier, in the prior art, also can't be by the method realization of simple electroless plating.
Summary of the invention
In order to address the above problem, prepare the selective acetylene hydrocarbon hydrogenation catalyst that the simple substance palladium is an active ingredient, the inventor has carried out intensive research, found a kind of elder generation to carry out pre-treatment, then realized the method for preparing selective acetylene hydrocarbon hydrogenation catalyst of the electroless plating Pd of trace again by sensitization, activation method.
An object of the present invention is to provide a kind of hydrogenation activity height, selective acetylene hydrocarbon hydrogenation simple substance palladium catalyst that selectivity is good.
Selective acetylene hydrocarbon hydrogenation catalyst of the present invention comprises carrier, main active component palladium, helps active ingredient tin,
Wherein, carrier is selected from diatomite, SiO
2, TiO
2, Al
2O
3, that its shape is selected from is granular, spherical, sheet, dentation or strip, and its specific surface is 1～200m
2/ g;
In total weight of carrier, the content of main active component palladium is 0.01～1.0 weight %, preferred 0.01～0.5 weight %;
The content that helps active ingredient tin is 0.01～3.0 weight %, preferred 0.1～2.5 weight %;
And main active component palladium is present in the catalyst body with the simple substance form.
In the preferred selective acetylene hydrocarbon hydrogenation catalyst of the present invention, described main active component palladium exists with the simple substance form, and be distributed in from carrier surface to the degree of depth less than 200 microns catalyst body in.
Preferred described carrier is Al
2O
3, it is shaped as strip or spherical, and its specific surface is 5～120m
2/ g, more preferably specific surface is at 70m
2Below/the g.
Preferred described catalyzer is to prepare by the method that comprises the following steps:
1) uses SnCl
2Solution sensitization carrier is used PdCl again
2The acidic solution activated carrier, and repeat described carrier sensitization activation step 1～8 time;
2) carrier through after the sensitization activation that step 1) is obtained joins [Pd (NH
3)
2+] in the solution, and add reductive agent, carry out electroless plating 2～30min;
3) with step 2) carrier after the electroless plating that obtains do not have Cl with deionized water wash to washing lotion
-, drying obtains catalyzer of the present invention.
In catalyzer of the present invention, can also add in other hydrogenation catalyst the active ingredient that helps of adjusting catalyst performance commonly used, as basic metal or alkaline-earth metal, silver, copper etc.
Another object of the present invention provides a kind of method that the simple substance palladium is the selective acetylene hydrocarbon hydrogenation catalyst of active ingredient for preparing.
Because the method for existing electroless plating can not realize the elemental metals palladium is deposited on the inorganic carrier, the inventor found a kind of by sensitization, the activation inorganic carrier is carried out pre-treatment, and then carry out the method for electroless plating, the simple substance palladium is deposited on the inorganic carrier.
Concrete, at first make Sn in the solution by sensitization technology
2+Be adsorbed on carrier surface, again through washing with part Sn
2+Hydrolysis forms the surface that tindihydroxide is deposited on carrier; Add Pd again
2+Acidic activated liquid, under acidic conditions, be deposited on the tindihydroxide of carrier surface, with Pd in the solution
2+Be reduced to metal Pd, and occupy original Sn
2+The position be deposited on carrier surface, and Sn
2+Be oxidized to Sn
4+, enter solution.
Sensitization, activation back through repeated multiple times have deposited a spot of simple substance Pd at carrier surface.By the method for electroless plating, be the active centre at last, at the even metal Pd thin layer of carrier superficial deposit with the Pd on being activated.
The preparation method of selective acetylene hydrocarbon hydrogenation catalyst of the present invention, it may further comprise the steps:
1) carrier sensitization, activation
Use SnCl
2Solution sensitization carrier is used PdCl again
2The acidic solution activated carrier, and repeat described carrier sensitization activation step;
2) electroless plating Pd
The carrier through after the sensitization activation that step 1) is obtained joins [Pd (the NH of metering
3)
2+] in the solution, and add reductive agent, carry out electroless plating 2～30min;
3) aftertreatment
With step 2) carrier after the electroless plating that obtains do not have Cl with deionized water wash to washing lotion
-, drying obtains catalyzer of the present invention.
In a preferred embodiment of the invention,
In described step 1), earlier with 1～15g/L SnCl
2Solution sensitization carrier, SnCl
2The total consumption of solution is 1.01～20 times of required tin content in the catalyzer; Use 0.005～0.25g/L PdCl again
2The acidic solution activated carrier, PdCl
2Total consumption of activation solution is that to make palladium content in the described solution be 0.010～1.0 times of Catalyst Design palladium content; And repeat carrier sensitization activation step 1～8 time;
In described step 2) in, the carrier through after the sensitization activation that step 1) is obtained adds plating bath [Pd (NH
3)
2+] in the solution, the concentration of plating bath is 0.5～20g/L, palladium content is Catalyst Design palladium content and actual 1～20 times of activating palladium amount difference on the carrier in the used plating bath, be preferably 1～8 times, 1～100 times the reductive agent that adds Catalyst Design palladium content then, under 40～90 ℃ of conditions, stir electroless plating 2～30min
In described step 3), to washing lotion, there is not Cl with the deionized water rinse solution
-Under 90～200 ℃ of conditions, dry 5～20h obtains catalyzer of the present invention again.
Preferred described reductive agent is selected from hydrazine, NaH
2PO
2, formaldehyde, H
2And KH
2PO
2, more preferably hydrazine or NaH
2PO
2, add-on is 2～50 times of Catalyst Design palladium content.
Preferred described SnCl
2The concentration of sensitizing solution is 2～10g/L; Described PdCl
2The concentration of activation solution is 0.010～0.1g/L, PdCl
2Palladium content is 0.05～1.0 times of Catalyst Design palladium content in the total consumption of activation solution; And repeat the sensitization activation step 2～7 times of described carrier.
When concrete enforcement prepares catalyzer, in described step 2) in, at first use the atomic absorption spectrophotometer test to activate the content of the simple substance Pd on the carrier, thereby determine the palladium content in the plating bath, and then after the concentration of selected plating bath, determine consumption of plating.
In specific embodiments of the present invention, alkynes selective hydrogenation catalyst carrier of the present invention can be diatomite, Al
2O
3, SiO
2, TiO
2, preferred Al
2O
3Support shapes can or be extruded bar shaped for granular, spherical, sheet, strip.The Al that the present invention is used
2O
3The preparation approach to the not influence of the character of this catalyzer.
The catalyzer of the present invention's preparation can use photoelectron spectrum (XPS) test to confirm that activity of such catalysts component palladium is the simple substance form; Can confirm that it is distributed in the catalyzer outside surface of 0-200 μ m by of the distribution of scanning electron microscope test active component palladium at the catalyzer outside surface; A large amount of Pd is enriched in the catalyzer outside surface of 5-200 μ m.
Beneficial effect of the present invention is as follows:
1) the invention provides the selective acetylene hydrocarbon hydrogenation catalyst that a kind of rational Pd layer distributes.Precious metals pd is enriched between carrier shell 5～200 μ m in catalyzer, has improved the utilization ratio of Primary Catalysts Pd, reduces the possibility that side reaction takes place.
2) method for preparing catalyst of the present invention has been avoided highly energy-consuming, the expensive technology such as high-temperature calcination, reduction in traditional hydrogenation catalyst preparation method, has saved the energy greatly, has shortened preparation cycle.
3) catalyzer of the present invention is used for the selective acetylene hydrocarbon hydrogenation reaction, under the close situation of active component content, can significantly improve selectivity of catalyst.
Description of drawings
Fig. 1 is the XPS spectrum figure of the catalyzer D of the embodiment of passing through 4 preparations of the present invention.
Embodiment
The following examples are to describe in further detail of the present invention, but the present invention is not subjected to the restriction of embodiment.
Embodiment 1
Take by weighing 50g ball-type Al
2O
3Carrier is added to the 3g/L SnCl of 50ml
2Sensitization in the sensitizing solution then joins carrier the 0.01g/L PdCl of 50ml
2Acidic solution in activate, the carrier of taking-up cleans with distilled water, above step repeats 5 times.Contain palladium 0.0035g through sensitization, activation back carrier.
The carrier that activation is good joins 2.5g/L[Pd (NH
3)
2+] palladium plating solution in, the total Pd amount in the plating bath is 0.0175g, under 45 ℃ of conditions, adds hydrazine reducing agent 2ml, stirs, electroless plating 10min after the plating, does not have Cl with the deionized water rinse solution to washing lotion
-Under last 105 ℃ of conditions, dry 18h obtains described catalyst A, Pd content 0.035% (wt) wherein, Sn content 0.7% (wt).
Embodiment 2
Take by weighing 50g and extrude stripe shape Al
2O
3Carrier is added to the 11g/L SnCl of 40ml
2Sensitization in the sensitizing solution then joins carrier the 0.05g/L PdCl of 80ml
2Acidic solution in activate, the carrier of taking-up cleans with distilled water, above step repeats 6 times.Contain palladium 0.012g through sensitization, activation back carrier.
The carrier that activation is good joins 0.5g/L[Pd (NH
3)
2+] palladium plating solution in, the total Pd amount in the plating bath is 0.0055g, under 40 ℃ of conditions, adds hydrazine reducing agent 2ml, stirs, electroless plating 5min after the plating, does not have Cl with the deionized water rinse solution to washing lotion
-Under last 120 ℃ of conditions, dry 10h obtains described catalyst B, Pd content 0.035% (wt) wherein, Sn content 2.7% (wt).
Embodiment 3
Take by weighing 50g flute profile Al
2O
3Carrier is added to the 5g/L SnCl of 100ml
2Sensitization in the sensitizing solution then joins carrier the 0.1g/L PdCl of 100ml
2Acidic solution in activate, the carrier of taking-up cleans with distilled water, above step repeats 3 times.Contain palladium 0.02g through sensitization, activation back carrier.
The carrier that activation is good joins 3g/L[Pd (NH
3)
2+] palladium plating solution in, the total Pd amount in the plating bath is 0.015g, under 75 ℃ of conditions, adds reductive agent NaH
2PO
20.10g, stirring, electroless plating 20min after the plating, does not have Cl with the deionized water rinse solution to washing lotion
-Under last 120 ℃ of conditions, dry 5h obtains described catalyzer C, Pd content 0.05% (wt) wherein, Sn content 1.5% (wt).
Embodiment 4
Take by weighing 50g ball-type Al
2O
3Carrier is added to the 9g/L SnCl of 40ml
2Sensitization in the sensitizing solution then joins carrier the 0.05g/L PdCl of 80ml
2Acidic solution in activate, the carrier of taking-up cleans with distilled water, above step repeats 6 times.Contain palladium 0.018g through sensitization, activation back carrier.
The carrier that activation is good joins 9g/L[Pd (NH
3)
2+] palladium plating solution in, the total Pd amount in the plating bath is 0.038g, under 85 ℃ of conditions, adds reductive agent NaH
2PO
20.25g, stirring, electroless plating 25min after the plating, does not have Cl with the deionized water rinse solution to washing lotion
-Under last 120 ℃ of conditions, dry 18h obtains described catalyzer D, Pd content 0.1% (wt) wherein, Sn content 2.0% (wt).
Embodiment 5
Take by weighing 50g ball-type Al
2O
3Carrier is added to the 5g/LSnCl of 80ml
2Sensitization in the sensitizing solution then joins carrier the 0.02g/L PdCl of 80ml
2Acidic solution in activate, the carrier of taking-up cleans with distilled water, above step repeats 3 times.Contain palladium 0.0012g through sensitization, activation back carrier.
The carrier that activation is good joins 1.2g/L[Pd (NH
3)
2+] palladium plating solution in, the total Pd amount in the plating bath is 0.008g, under 40 ℃ of conditions, adds hydrazine reducing agent 1ml, stirs, electroless plating 2min after the plating, does not have Cl with the deionized water rinse solution to washing lotion
-Under last 120 ℃ of conditions, dry 24h obtains described catalyzer E, Pd content 0.01% (wt) wherein, Sn content 2.3% (wt).
Embodiment 6
Take by weighing 50g flute profile Al
2O
3Carrier is added to the 2g/L SnCl of 100ml
2Sensitization in the sensitizing solution then joins carrier the 0.02g/L PdCl of 100ml
2Acidic solution in activate, the carrier of taking-up cleans with distilled water, above step repeats 4 times.Contain palladium 0.004g through sensitization, activation back carrier.
The carrier that activation is good joins 14g/L[Pd (NH
3)
2+] palladium plating solution in, the total Pd amount in the plating bath is 0.05g, under 56 ℃ of conditions, adds reductive agent formaldehyde 30ml, stirs, electroless plating 10min after the plating, does not have Cl with the deionized water rinse solution to washing lotion
-Under last 120 ℃ of conditions, dry 15h obtains described catalyzer F, Pd content 0.04% (wt) wherein, Sn content 0.5% (wt).
Embodiment 7
Take by weighing 50g flute profile Al
2O
3Carrier is added to the 1g/L SnCl of 100ml
2Sensitization in the sensitizing solution then joins carrier the 0.02g/L PdCl of 100ml
2Acidic solution in activate, the carrier of taking-up cleans with distilled water, above step repeats 4 times.Contain palladium 0.004g through sensitization, activation back carrier.
The carrier that activation is good joins 20g/L[Pd (NH
3)
2+] palladium plating solution in, the total Pd amount in the plating bath is 0.8g, under 40 ℃ of conditions, adds reductive agent hydrogen flow rate 30ml/min, stirs, electroless plating 15min after the plating, does not have Cl with the deionized water rinse solution to washing lotion
-Under last 120 ℃ of conditions, dry 20h obtains described catalyzer G, Pd content 0.4% (wt) wherein, Sn content 0.1% (wt).
Comparative Examples
Take by weighing 100g flute profile Al
2O
3Carrier adopts pickling process, with the Palladous nitrate impregnated carrier, makes after the drying calcining and consists of 0.035%Pd/Al
2O
3Catalyzer is referred to as catalyzer X.
Select the foregoing description and Comparative Examples to prepare catalyzer and carry out the acetylene hydrogenation reaction experiment, reaction conditions is as follows:
The lml catalyzer is packed in the tubular reactor, and beds is filled the porcelain ring up and down.Behind nitrogen replacement, from top to bottom pass through reactor after simulation joined hydrogen from the unstripped gas of deethanizing cat head.Hydrogen alkynes ratio is 1.5, inlet concentration of acetylene 0.1lmol%, air speed 15000hr
-1
Catalyst A～G and catalyzer X are carried out the examination of catalyzer selection hydrogenation, the highest conversion of alkyne and the corresponding selection such as the table 1 of each catalyzer.
Test-results shows, by the simple substance palladium catalyst of electroless plating gained, need not pass through hydrogen reducing, has good acetylene selective hydrogenation catalytic performance equally, and its active single palladium catalyst with immersion process for preparing is fair, but selectivity is higher.
The highest conversion of alkyne and the corresponding selection thereof of table 1 catalyzer of the present invention
| Catalyzer | Form | Peak rate of conversion and corresponding selection | |
| Transformation efficiency (%) | Selectivity (%) | ||
| A | Pd content 0.035% (wt), Sn content 0.7% (wt) | 81 | 94 |
| B | Pd content 0.035% (wt), Sn content 2.7% (wt) | 90 | 83 |
| C | Pd content 0.05% (wt), Sn content 1.5% (wt) | 91 | 78 |
| D | Pd content 0.1% (wt), Sn content 2.0% (wt) | 90 | 80 |
| E | Pd content 0.01% (wt), Sn content 2.3% (wt) | 86 | 72 |
| F | Pd content 0.04% (wt), Sn content 0.5% (wt) | 89 | 79 |
| G | Pd content 0.4% (wt), Sn content 0.1% (wt) | 92 | 82 |
| X | Pd content 0.035% (wt) | 90 | 74 |
Claims (12)
1. a selective acetylene hydrocarbon hydrogenation catalyst comprises carrier, main active component palladium, helps active ingredient tin, and wherein, carrier is selected from diatomite, SiO
2, TiO
2, Al
2O
3, that its shape is selected from is granular, spherical, sheet, dentation or strip, and its specific surface is 1～200m
2/ g;
In total weight of carrier, the content of main active component palladium is 0.01～1.0 weight %, and the content that helps active ingredient tin is 0.01～3.0 weight %;
And main active component palladium is present in the catalyst body with the simple substance form.
2. catalyzer according to claim 1 is characterized in that: described main active component palladium exists with the simple substance form, and be distributed in from carrier surface to the degree of depth less than 200 microns catalyst body in.
3. catalyzer according to claim 1 is characterized in that: the content of described main active component palladium is 0.01～0.5 weight %, in total weight of carrier.
4. catalyzer according to claim 1 is characterized in that: described to help the content of active ingredient tin be 0.1～2.5 weight %, in total weight of carrier.
5. catalyzer according to claim 1 is characterized in that: described carrier is Al
2O
3, it is shaped as strip or spherical, and its specific surface is 5～120m
2/ g.
6. according to the described catalyzer of one of claim 1～5, it is characterized in that described catalyzer is to prepare by the method that comprises the following steps:
1) uses SnCl
2Solution sensitization carrier is used PdCl again
2The acidic solution activated carrier, and repeat described carrier sensitization activation step 1～8 time;
2) carrier through after the sensitization activation that step 1) is obtained joins [Pd (NH
3)
2+] in the solution, and add reductive agent, carry out electroless plating 2～30min;
3) with step 2) carrier after the electroless plating that obtains do not have Cl with deionized water wash to washing lotion
-, drying obtains catalyzer of the present invention.
7. the described Preparation of catalysts method of one of claim 1～6, it may further comprise the steps:
1) uses SnCl
2Solution sensitization carrier is used PdCl again
2The acidic solution activated carrier, and repeat described carrier sensitization activation step;
2) carrier through after the sensitization activation that step 1) is obtained joins [Pd (NH
3)
2+] in the solution, and add reductive agent, carry out electroless plating 2～30min;
3) with step 2) carrier after the electroless plating that obtains do not have Cl with deionized water wash to washing lotion
-, drying obtains catalyzer of the present invention.
8. preparation method according to claim 7 is characterized in that:
In described step 1), earlier with 1C～15g/L SnCl
2Solution sensitization carrier, SnCl
2The total consumption of solution is 1.01～20 times of required tin content in the catalyzer; Use 0.005～0.25g/L PdCl again
2The acidic solution activated carrier, PdCl
2Total consumption of activation solution is that to make palladium content in the described solution be 0.010～1.0 times of Catalyst Design palladium content; And repeat carrier sensitization activation step 1～8 time;
In described step 2) in, the carrier through after the sensitization activation that step 1) is obtained adds plating bath [Pd (NH
3)
2+] in the solution, the concentration of plating bath is 0.5～20g/L, palladium content is Catalyst Design palladium content and actual 1～20 times of activating palladium amount difference on the carrier in the used plating bath, 1～100 times the reductive agent that adds Catalyst Design palladium content then, under 40～90 ℃ of conditions, stir electroless plating 2～30min;
In described step 3), to washing lotion, there is not Cl with the deionized water rinse solution
-Under 90～200 ℃ of conditions, dry 5～20h obtains catalyzer of the present invention again.
9. according to claim 7 or 8 described preparation methods, it is characterized in that: described reductive agent is selected from hydrazine, NaH
2PO
2, formaldehyde, H
2And KH
2PO
2, add-on is 2～50 times of Catalyst Design palladium content.
10. preparation method according to claim 9 is characterized in that: described reductive agent is hydrazine or NaH
2PO
2
11. preparation method according to claim 8 is characterized in that: palladium content is Catalyst Design palladium content and the actual difference that activates the palladium amount on the catalyzer 1～8 times in the described plating bath.
12., it is characterized in that: described SnCl according to claim 7 or 8 described preparation methods
2The concentration of sensitizing solution is 2～10g/L; Described PdCl
2The concentration of activation solution is 0.010～0.1g/L, PdCl
2Palladium content is 0.05～1.0 times of Catalyst Design palladium content in the total consumption of activation solution; And repeat the sensitization activation step 2～7 times of described carrier.
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|---|---|---|---|
| CNB2005101167099A CN100457865C (en) | 2005-10-28 | 2005-10-28 | Acetylene selected hydrogenation catalyst and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101167099A CN100457865C (en) | 2005-10-28 | 2005-10-28 | Acetylene selected hydrogenation catalyst and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1955256A true CN1955256A (en) | 2007-05-02 |
| CN100457865C CN100457865C (en) | 2009-02-04 |
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ID=38062811
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549560A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Method for activating hydrogenation catalyst |
| CN109954500A (en) * | 2017-12-25 | 2019-07-02 | 沈阳三聚凯特催化剂有限公司 | A kind of compound membranous type hydrogenation catalyst of copper-based skeleton and preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998010863A1 (en) * | 1996-09-11 | 1998-03-19 | Nissan Girdler Catalyst Co., Ltd. | Catalyst for selective hydrogenation of highly unsaturated hydrocarbon compound in olefin compound |
| CN1081666C (en) * | 1998-07-17 | 2002-03-27 | 中国石化齐鲁石油化工公司 | Selective hydrogen catalyst having catalysis and fractional distillation functions |
-
2005
- 2005-10-28 CN CNB2005101167099A patent/CN100457865C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549560A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Method for activating hydrogenation catalyst |
| CN109954500A (en) * | 2017-12-25 | 2019-07-02 | 沈阳三聚凯特催化剂有限公司 | A kind of compound membranous type hydrogenation catalyst of copper-based skeleton and preparation method and application |
| CN109954500B (en) * | 2017-12-25 | 2023-05-05 | 沈阳三聚凯特催化剂有限公司 | Copper-based skeleton composite membrane type hydrogenation catalyst, and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN100457865C (en) | 2009-02-04 |
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