CN109939676A - Monatomic palladium catalyst and its preparation and the application in selective hydrogenation of acetylene - Google Patents
Monatomic palladium catalyst and its preparation and the application in selective hydrogenation of acetylene Download PDFInfo
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Abstract
Present invention relates particularly to a kind of monatomic palladium catalyst and its preparations and the application in selective hydrogenation of acetylene, the monatomic palladium catalyst is prepared by the following method: under ultra-low temperature surroundings, reducing agent solution is added in palladium salt precursor solution and is reacted, metal-sol is made, then carrier is added, and the reaction was continued, after fully reacting, washing, it is dry, monatomic palladium catalyst is made.Its active component palladium of the catalyst in high degree of dispersion and is evenly distributed on carrier in a manner of monoatomic；Wherein, the content of palladium is 0.01~1wt%, partial size 0.01-1nm.It is used in selective hydrogenation of acetylene technique, the stable in catalytic performance of catalyst, and has high conversion of alkyne in lower reaction temperature.
Description
Technical field
The present invention relates to a kind of monatomic palladium catalyst and its preparations and the application in selective hydrogenation of acetylene, belong to essence
Thin chemical field.
Background technique
The production capacity of ethylene is the important symbol of a national oil chemical industry development level.Industrial production ethylene master
If Long carbon chain hydrogen compound Pintsch process is limited by preparation process, product ethylene can inevitably contain about 1%
Acetylene, existing will lead to catalyst poisoning used in ethylene polymerization generation polyethylene and inactivates, and lead to polyethylene
The decline of product oxidation resistance, therefore the trace acetylene in ethylene raw material gas how is removed with important economy and industrial valence
Value.
Industrial at present mainly to use catalytic hydrogenation method, catalyst is Pd base catalyst.Traditional Pd catalyst is will to carry
Body is impregnated into palladium salt solution, and high-temperature hydrogen reduction after drying, it is big that there are metal particle sizes, bad dispersibility, is easy reunion etc. and lacks
Point, leading to catalyst, stability is poor in process of production, and the service life is shorter, causes the significant wastage of resource, and improves production
Cost.It is therefore desirable to the big, bad dispersibility to the metal particle size in existing Pd catalyst, it is easy to be changed the problem of reunion
Into, and then improve the stability of catalytic performance of the catalyst in selective hydrogenation of acetylene technique and the service life of catalyst.
Summary of the invention
To solve the above-mentioned problems, an object of the present invention is to provide a kind of monatomic palladium catalyst, metal partial size
It is small, dispersed high and be not susceptible to reunite, thus stable in catalytic performance.
To achieve the goals above, technical scheme is as follows:
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and load is evenly distributed in a manner of monoatomic
On body；Wherein, the content of palladium is 0.01~1wt%, partial size 0.01-1nm.
The second object of the present invention is to provide the preparation method of above-mentioned monatomic palladium catalyst, this method is in ultralow temperature
Under, monatomic palladium catalyst is prepared by oxidation-reduction method, simple process is easy to industrialize.
To achieve the goals above, technical scheme is as follows:
The preparation method of above-mentioned monatomic palladium catalyst, which comprises the following steps: under ultra-low temperature surroundings,
Reducing agent solution is added in palladium salt precursor solution and is reacted, metal-sol is made, carrier is then added, and the reaction was continued, instead
After answering completely, wash, it is dry, obtain monatomic palladium catalyst.
Preferably, the ultra-low temperature surroundings are -120-0 DEG C.
Preferably, the palladium salt is one of palladium chloride, palladium nitrate, palladium acetate or chlorine palladium acid sodium or a variety of.
The molar concentration of the palladium salt precursor solution is 0.01-0.1mol/L；The solvent of the palladium salt precursor solution
It is mixed in proportion for any one or more of pure water, ethyl alcohol, ethylene glycol, acetone and glycerine.
It is furthermore preferred that the palladium salt precursor solution is surfactant modified palladium salt precursor solution, by following
Method is prepared to obtain: adding the surfactant of the 1-10% of palladium salt quality in palladium salt precursor solution, is sufficiently stirred
It is uniformly dispersed to obtain surfactant modified palladium salt precursor solution；The surfactant is polyvinyl alcohol, poly- second
One of alkene pyrrolidone and cetyl trimethylammonium bromide are a variety of.
Preferably, the reducing agent is in ascorbic acid, hydrazine hydrate, formaldehyde, formic acid, sodium borohydride and potassium borohydride
It is any one or more of；The molar ratio of palladium in the reducing agent and palladium salt is 5:1-500:1.
Preferably, the reducing agent is added before palladium salt precursor solution, by palladium salt precursor solution stirring condition
Under be placed in ultra-low temperature surroundings；The temperature is -120-0 DEG C, mixing time 0.5-2h, stirring rate 10-2000r/
min。
Preferably, the carrier is one of aluminium oxide, molecular sieve, diatomite or metal composite oxide or a variety of.
Preferably, the carrier, which is added in metal-sol, is stirred to react 1-4h；The washing is to be washed with deionized；
The drying is in 60-120 DEG C of oven drying 12-24h.
The third object of the present invention is to provide the application of above-mentioned monatomic palladium catalyst, is used for selective hydrogenation of acetylene
In technique, the stable in catalytic performance of catalyst, and have high conversion of alkyne in lower reaction temperature.
To achieve the goals above, technical scheme is as follows:
The application of above-mentioned monatomic palladium catalyst, which is characterized in that the monatomic palladium catalyst is used for selective acetylene
In hydrogenation technique.
Preferably, in the selective hydrogenation of acetylene technique, the relative pressure of reaction system is 0.2-0.6MPa, reaction temperature
Degree is 30-180 DEG C, reaction velocity 8041h-1。
It is furthermore preferred that the relative pressure of reaction system is 0.3MPa, reaction temperature in the selective hydrogenation of acetylene technique
It is 50 DEG C, reaction velocity 8041h-1。
Advantageous effects of the invention:
The present invention prepares monatomic palladium catalyst under ultra-low temperature surroundings, through redox, and ultralow reaction temperature can be with
Effectively inhibit metal nucleation, to improve monodispersed metal atom concentration, and simple process, is suitable for industrial applications, is made
Monatomic palladium catalyst, metal partial size is small, dispersed high and be not susceptible to reunite, thus stable in catalytic performance, is used for
In selective hydrogenation of acetylene technique, when reaction temperature is 50 DEG C, conversion of alkyne reaches 90% or more.
In a preferred embodiment, monatomic palladium catalyst of the invention is used in selective hydrogenation of acetylene technique,
When reaction temperature is 50 DEG C, conversion of alkyne is up to 100%；And industrial palladium catalyst need to be when reaction temperature be 150 DEG C, acetylene
Conversion ratio is 100%.
Specific embodiment:
Combined with specific embodiments below, the present invention is described in more detail.
A kind of monatomic palladium catalyst, active component palladium is in high degree of dispersion and load is evenly distributed in a manner of monoatomic
On body；Wherein, the content of palladium is 0.01~1wt%, partial size 0.01-1nm.
The preparation method of above-mentioned monatomic palladium catalyst, comprising the following steps: under ultra-low temperature surroundings, by reducing agent solution
It is added in palladium salt precursor solution and is reacted, metal-sol is made, carrier is then added, and the reaction was continued, after fully reacting, washes
It washs, it is dry, obtain monatomic palladium catalyst.
Preferably, the ultra-low temperature surroundings are -120-0 DEG C.
Preferably, the palladium salt is one of palladium chloride, palladium nitrate, palladium acetate or chlorine palladium acid sodium or a variety of；
The molar concentration of the palladium salt precursor solution is 0.01-0.1mol/L；The solvent of the palladium salt precursor solution
It is mixed in proportion for any one or more of pure water, ethyl alcohol, ethylene glycol, acetone and glycerine.
It is furthermore preferred that the palladium salt precursor solution is surfactant modified palladium salt precursor solution, by following
Method is prepared to obtain: adding the surfactant of the 1-10% of palladium salt quality in palladium salt precursor solution, is sufficiently stirred
It is uniformly dispersed to obtain surfactant modified palladium salt precursor solution；The surfactant is polyvinyl alcohol, poly- second
One of alkene pyrrolidone and cetyl trimethylammonium bromide are a variety of.
Preferably, the reducing agent is in ascorbic acid, hydrazine hydrate, formaldehyde, formic acid, sodium borohydride and potassium borohydride
It is any one or more of；The reducing agent is 5:1-500:1 according to the molar ratio of the palladium in palladium salt.
Preferably, the reducing agent is added before palladium salt precursor solution, by palladium salt precursor solution stirring condition
Under be placed in ultra-low temperature surroundings；The temperature is -120-0 DEG C, mixing time 0.5-2h, stirring rate 10-2000r/
min。
Preferably, the carrier is one of aluminium oxide, molecular sieve, diatomite or metal composite oxide or a variety of.
Preferably, the carrier, which is added in metal-sol, is stirred to react 1-4h；The washing is to be washed with deionized；
The drying is in 60-120 DEG C of oven drying 12-24h.
The monatomic palladium catalyst of preparation is used in selective hydrogenation of acetylene technique, the relative pressure of reaction system is
0.2-0.6MPa, reaction temperature are 30-180 DEG C, reaction velocity 8041h-1.0.01-0.5g catalyst sample is weighed, and in stone
Sand mixing, loaded in crystal reaction tube.Reactor feed gas contains the acetylene of 0.1-1%, and N2 is Balance Air.Gas after reaction
Ingredient is analyzed using gas chromatograph, and detector is hydrogen flame detector.
A specific embodiment of the invention is further described below with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
Embodiment 1:
It is spare that molecular sieve carrier is put in 80 DEG C of oven drying 12h first.60mL 0.01mol/L palladium chloride solution is configured,
Polyvinyl alcohol is added according to the 1% of palladium chloride quality, is put in -120 DEG C of high/low temperature reaction chamber stirrings, the solvent of palladium chloride solution is pressed
According to ethyl alcohol: water volume ratio is 8:2 configuration.Molar ratio according to the palladium in ascorbic acid and palladium chloride is that 5:1 is added to palladium chloride
Solution stirs 1h at -120 DEG C, and palladium metal colloidal sol is made.The dried molecular sieve carrier of 10g is weighed, metal-sol is added to
In, 2h, stirring rate 200r/min are stirred, is filtered at -120 DEG C after reaction and cleans product with deionized water, so
After be put in 70 DEG C of oven drying 12h, monatomic palladium catalyst is prepared.
Catalyst prepared by embodiment 1 is used in selective hydrogenation of acetylene technique, the relative pressure of reaction system is
0.3MPa, reaction velocity 8041h-1, reactor feed gas contains 1% acetylene, and N2 is Balance Air.Gas componant after reaction is adopted
It is analyzed with gas chromatograph, when reaction temperature is 50 DEG C, conversion of alkyne reaches 93%.
Embodiment 2:
It is spare that molecular sieve carrier is put in 80 DEG C of oven drying 12h first.60mL 0.1mol/L palladium chloride solution is configured,
Polyvinylpyrrolidone is added according to the 1% of palladium chloride quality, is put in -120 DEG C of high/low temperature reaction chamber stirring 30min, solution
Solvent is according to ethyl alcohol: water volume ratio is 8:2 configuration.Molar ratio according to palladium in ascorbic acid and palladium chloride is that 5:1 is added to chlorine
Change palladium solution, stir 1h at -120 DEG C, palladium metal colloidal sol is made.The dried molecular sieve carrier of 10g is weighed, it is molten to be added to metal
In glue, 2h, stirring rate 200r/min are stirred, filters under cryogenic after reaction and cleans production with deionized water
Then product are put in 70 DEG C of oven drying 12h, monatomic palladium catalyst are prepared.
Catalyst prepared by embodiment 2 is used in selective hydrogenation of acetylene technique, the relative pressure of reaction system is
0.3MPa, reaction velocity 8041h-1, reactor feed gas contains 1% acetylene, and N2 is Balance Air.Gas componant after reaction is adopted
It is analyzed with gas chromatograph, when reaction temperature is 50 DEG C, conversion of alkyne reaches 100%.
Embodiment 3:
It is spare that molecular sieve carrier is put in 80 DEG C of oven drying 12h first.60mL 0.01mol/L palladium nitrate solution is configured,
Polyvinylpyrrolidone is added according to the 1% of chlorine palladium acid sodium quality, is put in -120 DEG C of high/low temperature reaction chamber stirring 30min, solution
Solvent according to ethyl alcohol: water volume ratio be 8:2 configuration.Add according to the molar ratio of ascorbic acid and the palladium in chlorine palladium acid sodium for 5:1
Enter to palladium nitrate solution, stir 1h at -120 DEG C, palladium metal colloidal sol is made.The dried molecular sieve carrier of 10g is weighed, is added to
In metal-sol, 2h, stirring rate 200r/min are stirred, filters at -120 DEG C and is cleaned with deionized water after reaction
Then product is put in 70 DEG C of oven drying 12h, monatomic palladium catalyst is prepared.
Catalyst prepared by embodiment 3 is used in selective hydrogenation of acetylene technique, the relative pressure of reaction system is
0.3MPa, reaction velocity 8041h-1, reactor feed gas contains 1% acetylene, and N2 is Balance Air.Gas componant after reaction is adopted
It is analyzed with gas chromatograph, when reaction temperature is 50 DEG C, conversion of alkyne reaches 98%.
Embodiment 4:
It is spare that molecular sieve carrier is put in 80 DEG C of oven drying 12h first.It is molten to configure 60mL 0.01mol/L chlorine palladium acid sodium
Polyvinylpyrrolidone is added according to the 1% of chlorine palladium acid sodium quality in liquid, is put in 0 DEG C of high/low temperature reaction chamber stirring 30min, solution
Solvent according to ethyl alcohol: water volume ratio be 8:2 configuration.Add according to the molar ratio of ascorbic acid and the palladium in chlorine palladium acid sodium for 5:1
Enter to chlorine palladium acid sodium solution, stir 1h at 0 DEG C, palladium metal colloidal sol is made.The dried molecular sieve carrier of 10g is weighed, is added to
In metal-sol, 2h, stirring rate 200r/min are stirred, is filtered at 0 DEG C after reaction and cleans production with deionized water
Then product are put in 70 DEG C of oven drying 12h, monatomic palladium catalyst are prepared.
Catalyst prepared by embodiment 4 is used in selective hydrogenation of acetylene technique, the relative pressure of reaction system is
0.3MPa, reaction velocity 8041h-1, reactor feed gas contains 1% acetylene, and N2 is Balance Air.Gas componant after reaction is adopted
It is analyzed with gas chromatograph, when reaction temperature is 50 DEG C, conversion of alkyne reaches 82%.
Embodiment 5:
It is spare that molecular sieve carrier is put in 80 DEG C of oven drying 12h first.Configure 60mL 0.01mol/L chlorine palladium acid sodium-salt
Polyvinylpyrrolidone is added according to the 1% of chlorine palladium acid sodium quality in solution, is put in -120 DEG C of high/low temperature reaction chamber stirring 30min,
The solvent of solution is according to ethyl alcohol: water volume ratio is 8:2 configuration.It is 5 according to the molar ratio of the palladium in sodium borohydride and chlorine palladium acid sodium:
1 is added to chlorine palladium acid sodium solution, stirs 1h at -120 DEG C, and palladium metal colloidal sol is made.The dried molecular sieve carrier of 10g is weighed,
It is added in metal-sol, stirs 2h, stirring rate 200r/min is filtered at -120 DEG C after reaction and used deionization
Water cleans product, is then put in 70 DEG C of oven drying 12h, the monatomic palladium catalyst of selective hydrogenation of acetylene is prepared.
Catalyst prepared by embodiment 5 be used in selective hydrogenation of acetylene technique, the relative pressure of reaction system
For 0.3MPa, reaction velocity 8041h-1, reactor feed gas contains 1% acetylene, and N2 is Balance Air.Gas componant after reaction
It is analyzed using gas chromatograph, when reaction temperature is 50 DEG C, conversion of alkyne reaches 98%.
Embodiment 6:
It is spare that molecular sieve carrier is put in 80 DEG C of oven drying 12h first.It is molten to configure 60mL 0.01mol/L chlorine palladium acid sodium
Polyvinylpyrrolidone is added according to the 10% of chlorine palladium acid sodium quality in liquid, is put in -120 DEG C of high/low temperature reaction chamber stirring 30min,
The solvent of solution is according to ethyl alcohol: water volume ratio is 8:2 configuration.It is 5 according to the molar ratio of the palladium in sodium borohydride and chlorine palladium acid sodium:
1 is added to chlorine palladium acid sodium solution, stirs 1h at -120 DEG C, and palladium metal colloidal sol is made.The dried molecular sieve carrier of 10g is weighed,
Be added in metal-sol, stir 2h, stirring rate 200r/min, filter under cryogenic after reaction and spend from
Sub- water cleans product, is then put in 70 DEG C of oven drying 12h, monatomic palladium catalyst is prepared.
Catalyst prepared by embodiment 6 is used in selective hydrogenation of acetylene technique, the relative pressure of reaction system is
0.3MPa, reaction velocity 8041h-1, reactor feed gas contains 1% acetylene, and N2 is Balance Air.Gas componant after reaction is adopted
It is analyzed with gas chromatograph, when reaction temperature is 50 DEG C, conversion of alkyne reaches 92%.
Embodiment 7:
It is spare that molecular sieve carrier is put in 80 DEG C of oven drying 12h first.It is molten to configure 60mL 0.01mol/L chlorine palladium acid sodium
Polyvinylpyrrolidone is added according to the 1% of chlorine palladium acid sodium quality in liquid, is put in -120 DEG C of high/low temperature reaction chambers and stirs 30min, molten
The solvent of liquid is according to ethyl alcohol: water volume ratio is 8:2 configuration.It is 500 according to the molar ratio of the palladium in sodium borohydride and chlorine palladium acid sodium:
1 is added to chlorine palladium acid sodium solution, stirs 1h at -120 DEG C, and palladium metal colloidal sol is made.The dried molecular sieve carrier of 10g is weighed,
Be added in metal-sol, stir 2h, stirring rate 200r/min, filter under cryogenic after reaction and spend from
Sub- water cleans product, is then put in 70 DEG C of oven drying 12h, the monatomic Pd catalyst of selective hydrogenation of acetylene is prepared.
Catalyst prepared by embodiment 7 is used in selective hydrogenation of acetylene technique, the relative pressure of reaction system is
0.3MPa, reaction velocity 8041h-1, reactor feed gas contains 1% acetylene, and N2 is Balance Air.Gas componant after reaction is adopted
It is analyzed with gas chromatograph, when reaction temperature is 50 DEG C, conversion of alkyne reaches 99%.
The above, preferable specific embodiment only of the invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and invention structure
Think of is subject to equivalent replacement or change, should be covered by the scope of protection of the present invention.
Claims (10)
1. a kind of monatomic palladium catalyst, including active component and carrier, which is characterized in that the active component palladium is in height point
It dissipates and is evenly distributed on carrier in a manner of monoatomic；Wherein, the content of palladium is 0.01~1wt%, partial size 0.01-1nm.
2. the preparation method of monatomic palladium catalyst according to claim 1, which comprises the following steps:-
At 120-0 DEG C, reducing agent is added in palladium salt precursor solution and is reacted, metal-sol is made, carrier is then added and continues
Reaction is washed after reaction, dry, obtains monatomic palladium catalyst.
3. the preparation method of monatomic palladium catalyst according to claim 2, which is characterized in that the palladium salt be palladium chloride,
One of palladium nitrate, palladium acetate or chlorine palladium acid sodium are a variety of；The molar concentration of the palladium salt precursor solution is 0.01-
0.1mol/L；The solvent of the palladium salt precursor solution is any one of pure water, ethyl alcohol, ethylene glycol, acetone and glycerine
Or it a variety of mixes in proportion.
4. the preparation method of monatomic palladium catalyst according to Claims 2 or 3, which is characterized in that the palladium salt presoma
Solution is surfactant modified palladium salt precursor solution, is prepared by the following method to be obtained: molten in palladium salt presoma
In liquid add palladium salt quality 1-10% surfactant, be sufficiently stirred be uniformly dispersed to obtain it is surfactant modified
Palladium salt precursor solution；The surfactant is polyvinyl alcohol, polyvinylpyrrolidone and cetyl trimethylammonium bromide
One of or it is a variety of.
5. the preparation method of monatomic palladium catalyst according to claim 2, which is characterized in that the reducing agent is anti-bad
Any one or more of hematic acid, hydrazine hydrate, formaldehyde, formic acid, sodium borohydride and potassium borohydride；In the reducing agent and palladium salt
Palladium molar ratio be 5:1-500:1.
6. the preparation method of monatomic palladium catalyst according to claim 2, which is characterized in that palladium salt is added in the reducing agent
Before precursor solution, palladium salt precursor solution is placed in ultra-low temperature surroundings under stirring conditions；The temperature is -120-
0 DEG C, mixing time 0.5-2h, stirring rate 10-2000r/min.
7. the preparation method of monatomic palladium catalyst according to claim 2, which is characterized in that the carrier be aluminium oxide,
One of molecular sieve, diatomite or metal composite oxide are a variety of.
8. the application of monatomic palladium catalyst according to claim 1, which is characterized in that the monatomic palladium catalyst is used for
In selective hydrogenation of acetylene technique.
9. the application of monatomic palladium catalyst according to claim 1, which is characterized in that the selective hydrogenation of acetylene technique
In, the relative pressure of reaction system is 0.2-0.6MPa, and reaction temperature is 30-180 DEG C, reaction velocity 8041h-1。
10. the application of monatomic palladium catalyst according to claim 1, which is characterized in that the selective hydrogenation of acetylene work
In skill, the relative pressure of reaction system is 0.3MPa, and reaction temperature is 350 DEG C, reaction velocity 8041h-1。
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Application publication date: 20190628 |