CN101862653B - Acetylene selective hydrogenation catalyst and preparation method and application thereof - Google Patents
Acetylene selective hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN101862653B CN101862653B CN2009100824212A CN200910082421A CN101862653B CN 101862653 B CN101862653 B CN 101862653B CN 2009100824212 A CN2009100824212 A CN 2009100824212A CN 200910082421 A CN200910082421 A CN 200910082421A CN 101862653 B CN101862653 B CN 101862653B
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Abstract
The invention discloses an acetylene selective hydrogenation catalyst and a preparation method and application thereof. The catalyst comprises a carrier and active metal components supported on the carrier, wherein the main active metal component palladium is elemental palladium under the conditions of room temperature and air and is prepared by reducing a palladium precursor supported on the carrier through ionizing radiation. The catalyst can be directly used in hydrogenation reaction without reduction in advance by hydrogen; the active ingredients have uniform particle size; and the catalyst has higher activity and selectivity compared with catalysts prepared by the conventional methods.
Description
Technical field
The present invention relates to select hydrogenation catalyst; Concrete, relate to Catalysts and its preparation method and application that a kind of acetylene selective hydrogenation that is used for ethylene streams generates ethene.
Background technology
Ethene is one of most important basic material of petrochemical industry, in petrochemical industry, is that raw material uses cracking process production with gaseous state or liquefied hydrocarbon.Contain a spot of alkynes in the ethene that uses cleavage method to prepare, it is harmful to for follow-up reactions such as polymerization.As when preparing polyethylene, the existence of alkynes not only can make the polymer performance variation, also possibly cause explosion danger.Therefore, in the ethylene production flow process, use the selective catalytic hydrogenation method usually, alkynes concentration is removed to very low level (molar fraction＜1 * 10
-6), to satisfy the requirement of polymer raw; Also can increase the output of ethene simultaneously, improve resource utilization.Along with the progress of production technology and subsequent technique improve constantly what material purity required, petroleum chemical industry has also proposed increasingly high requirement to the performance of acetylene selective hydrogenation catalyst.
Mostly acetylene selective hydrogenation catalyst is load type metal catalyst, generally by carrier, main active component with help active component to form.Carrier commonly used has aluminium oxide, silica, molecular sieve, active carbon, magnesia, titanium oxide, diatomite or the like; Main active component is the metallic element with high active of hydrogenation catalysis, is generally VIII family element, and like Pd, Pt, Ni etc., Pd is the most frequently used selection hydrogenation activity component; Help active component to be used to regulate activity of such catalysts or selectivity, auxiliary agent commonly used such as Cu, Ag, Au etc.
Acetylene selective hydrogenation catalyst is the production of many employing dipping-roasting methods in industry; The solution (being mostly salting liquid) that is about to contain active component fully contacts with the carrier for preparing; Make active constituent loading to carrier, dry back roasting under high temperature makes slaine be decomposed into corresponding oxide.Active component in the catalyst after the roasting exists with oxide form usually, need just can be used for hydrogenation reaction with hydrogen reducing before use.Make the catalyst of preparation in this way, maximum problem is that the high temperature in the roasting process may cause the active component sintering, makes the degradation of catalyst.
At present, some new method for preparing catalyst have been removed calcination steps, use instead method such as electronation make active component under temperate condition by directly reduction, obtained to have more high activity and optionally catalyst.U.S. Pat 5968860 discloses a kind of hydrogenization catalyst preparation method that the gaseous ethene legal system is equipped with vinylacetate that is used for.With Pd, Au active constituent loading behind carrier, use sodium borohydride, hydrazine or formic acid at room temperature to accomplish reduction process, and in the preparation process, introduce the ultrasonic wave radiation, the selectivity of the hydrogenation catalyst of acquisition is higher than the sample that uses the conventional method preparation.Introduced a kind of preparation method of supported metal catalyst among the Chinese patent CN 1579618.This method is a thermal source with the microwave radiation, is reducing agent and protective agent with the polyalcohol, and can prepare load capacity fast is the polynary supported catalyst of 1～99wt%, and the metallic particle diameter can be controlled in 0.5～10nm.
Chinese patent CN 1511634 discloses a kind of preparation of ethylene through selective hydrogenation of acetylene Preparation of catalysts method.Use the high energy active specy in the radio frequency plasma and load on Modification on Al
2O
3On the effect of palladium series catalyst precursor, can under temperate condition, make the rapid activation of catalyst; Advantages such as the catalyst of preparation has the low temperature active height, ethylene selectivity is high, green oil yields poorly, good stability.Use the ultraviolet light reducing process to prepare hydrogenation catalyst in the U.S. Pat 6268522, its active component is eggshell state and distributes, and shell thickness can be controlled through conditions such as ultraviolet wavelength, radiant power, radiated times.The catalyst of preparation shows good activity and selectivity in the gaseous ethene legal system is equipped with the reaction of vinylacetate.
Though above-mentioned improving one's methods omitted calcination steps, make the performance of catalyst be improved, but still exist many deficiencies that be in particular in: (1) needs to use a large amount of compounds as reducing agent or protective agent, makes the production cost raising and causes the wasting of resources; (2) ultra-violet radiation and plasma penetration ability, high to equipment requirements, only can be used for Preparation of catalysts in a small amount, be difficult to realize commercial production.
In sum; Provide a kind of and can realize commercial production, have the novel selection hydrogenization catalyst preparation method of operability; To improve the weak point in the traditional preparation process method; And prepare the activity that improves acetylene selective hydrogenation catalyst and catalyst optionally, the technological progress of ethylene industry is had crucial meaning.
Summary of the invention
The object of the present invention is to provide a kind of novel acetylene selective hydrogenation catalyst.
Concrete, selective hydrocatalyst of acetylene of the present invention comprises carrier and is carried on the active component on the carrier, and wherein said active component comprises main active component palladium and the optional active component that helps.Described main active component palladium is elemental under normal temperature and air atmosphere, and said main active component palladium makes through the reducing loaded palladium precursor on carrier of ionising radiation.
In catalyst of the present invention, the content of preferred said main active component palladium is 0.01～1wt% of carrier gross weight, and its average grain diameter is 1～100nm; It is said that to help the content of active component be 0～20wt% of carrier gross weight.
In catalyst of the present invention, preferred described active component comprises:
A) described main active component palladium is present in said carrier surface with the elemental particle shape under room temperature and air conditions; Its content is 0.01～1wt% of carrier gross weight, and its average grain diameter is 1～100nm;
B) optional, help active component, be selected from least a among group VIII, IB family element, Bi, Sb, Pb, In, Cs, Rb, K and the Mg, its content is 0～20wt% of carrier gross weight.
In catalyst of the present invention, said main active component palladium is present in said carrier surface, and preferred palladium layer thickness is between 1-500 μ m.
In catalyst of the present invention, the content of described main active component palladium is 0.01～1wt% of carrier gross weight, is preferably 0.01～0.2wt% of carrier gross weight, more preferably 0.01～0.06wt%.
In catalyst of the present invention, the average grain diameter of described main active component palladium is 1～100nm, is preferably 1～40nm, more preferably 1～10nm.
In catalyst of the present invention, for described distribution and the not restriction of existence that helps active component, the said active component that helps can be distributed in carrier surface, also can be distributed in the carrier; Its existence can be elemental or oxidation state, also can be the coexistence of elemental and oxidation state, and its content is 0～20wt% of carrier gross weight; Be preferably 0～5wt%.
In another preferred implementation of catalyst of the present invention, described to help the content of active component be 0.001～2wt% of carrier gross weight.
In catalyst of the present invention, preferred described main active component palladium and described to help the weight ratio of active component be 0.01-50.
In addition, also can add in the hydrogenation catalyst commonly used other and regulate the auxiliary agent of catalyst performances, like halogen etc.
In the present invention, do not have special restriction for used carrier, the carrier that uses in the existing hydrogenation catalyst all can be used for catalyst of the present invention.In practical implementation of the present invention, said carrier is preferably from Al
2O
3, SiO
2, TiO
2, one or both and two or more mixtures among the MgO, diatomite, molecular sieve; Preferred use be shaped as that spherical, sheet, tooth are spherical, the carrier of special-shaped strips such as strip, clover or bunge bedstraw herb, more preferably using specific area is 1～200m
3The carrier of/g.
Selection hydrogenation catalyst of the present invention uses ionising radiation to reduce described main active component palladium precursor and obtains the palladium active component of elemental.Preferred described ionising radiation reduction is selected from one of following method, uses ionising radiation irradiation, and described main active component palladium precursor is reduced to metal simple-substance:
A) load is had the carrier of the active component precursor that comprises said main active component palladium precursor to use to contain the solution-wet of free radical scavenger after, irradiation under wetting state, preferably irradiation under vacuum or inert atmosphere;
B) there is the carrier of the active component precursor that comprises said main active component palladium precursor to add load and contains in the solution of free radical scavenger irradiation under the solution submerged state;
C) said carrier is added in the maceration extract that contains free radical scavenger and the active component precursor that comprises said main active component palladium precursor irradiation under the solution submerged state.
Method a) and b) in, at first use the active component precursor maceration extract impregnated carrier comprise the palladium precursor, add the solution that contains free radical scavenger again, it is under moisture state or the solution submerged state carries out irradiation; At method c) in, be carrier directly to be immersed in contain free radical scavenger and comprise in the active component precursor maceration extract of palladium precursor.In above-mentioned irradiance method, described palladium precursor maceration extract can one go on foot dipping simultaneously with other activity component impregnation liquid, also can step impregnation.
Another object of the present invention provides a kind of selection hydrogenization catalyst preparation method.
Concrete, Preparation of catalysts method of the present invention may further comprise the steps:
(1) one or more described active component precursors is loaded on the carrier;
(2) add free radical scavenger, use ionising radiation to carry out irradiation under wetting state or under the solution submerged state, to reduce described active component precursor.
In Preparation of catalysts method of the present invention, described ionising radiation is gamma-rays, X ray or electron beam, and radiation source is optional
60Co (γ source),
137Cs (γ source), x-ray source or electron accelerator (electron beam), preferred
60Co, x-ray source or electron accelerator, more preferably
60Co.
In catalyst of the present invention, main active component palladium is an elemental; Helping active component can be elemental, can be oxidation state, also can be two kinds of form coexistences; Therefore, in preparation method of the present invention, radiation absorbed dose preferably reduces needed dosage fully with the main active component palladium precursor and controls.According to the difference of composition, pH and the radiation parameter of maceration extract, make main active component palladium reduced the required optional 5～100kGy of absorbed dose of radiation fully.This professional can confirm to make main active component palladium to be reduced required appropriate dose fully easily.
In Preparation of catalysts method of the present invention, the absorbed dose rate of preferred described ionising radiation is 10～10000Gy/min; More preferably 20～100Gy/min.
In Preparation of catalysts process of the present invention, when comprising two or more active component in the catalyst, help active component and main active component palladium can adopt a step infusion process or step impregnation method to load on the carrier.Use a step during infusion process, several kinds of active component precursors are dissolved in the same solution carrier is flooded.For the active component precursor that can not be formulated in the same solution, then preferably adopt the method for step impregnation.When using step impregnation method; Several kinds of active component precursors are mixed with solution respectively to be flooded carrier; Help the active component can load before or after main active component palladium, can be as required help carrier after the active component to carry out roasting and make it to change into corresponding oxide load.The radiation reduction step is all being carried out after the loading process completion usually, no longer carries out roasting usually after the radiation reduction.
In preparation method of the present invention, described active component precursor can use dipping method commonly used in the Preparation of Catalyst to load on the carrier, like spraying, incipient impregnation, supersaturation impregnating.When using the supersaturation infusion process, the active component precursor in the maceration extract then should be confirmed the volume and the active component concentration of maceration extract according to the absorption ratio if can not adsorb fully by suppressed by vector, satisfies predetermined requirement with proof load to the active component content on the carrier.Active component precursor of the present invention is the corresponding metallic compound of described active component, can be preferably from chloride, nitrate, acetate, sulfate and metallo-organic compound.
In Preparation of catalysts of the present invention, preferred described active component precursor is formulated as solution in advance, and solvent is selected from one or more the mixing in water, hydrochloric acid, nitric acid, acetate, the alcohols; More preferably water.
In Preparation of catalysts, the pH value of maceration extract can impact particle size and the distribution situation that makes the catalyst activity component.Thereby, can regulate and control activity of such catalysts and selectivity through the pH that regulates maceration extract.In catalyst of the present invention, the pH scope of control maceration extract is 1-12, preferred 2-8.The pH value of maceration extract can use solution such as NaOH, potassium hydroxide, ammoniacal liquor, sodium carbonate or sodium acid carbonate to regulate.
In another preferred embodiment of Preparation of catalysts method of the present invention, before carrying out the irradiation reduction step, use fixative to handle the carrier of described carrier or said load active component precursor; Wherein said fixative is an alkali compounds, preferred NaOH, potassium hydroxide, sodium acid carbonate, sodium carbonate etc. and ammoniacal liquor etc.Generally can adopt the mode of spraying that fixative is mixed with carrier, its objective is that making soluble metal salt change insoluble metallic compound into is fixed on carrier surface.
Because effects of ionizing radiation is when aqueous solvent, water is generated hydrated electron (e by radiolysis
Aq -), hydrogen atom (H), hydroxy radical products such as (OH).E wherein
Aq -Be strong reductant, can most of metal ion be reduced to simple substance.The metallic that is reduced is stable in carrier surface growth and final suppressed by vector, forms the metallic with catalytic activity.But H, OH that the water radiolysis generates are oxidative free radical, can make the metallic atom that has just generated in the radiation reduction process heavily be oxidized to ion.Take place for fear of this reaction, need in system, to add a certain amount of free radical scavenger at predose, free radical scavenger is generally alcohols; Can react with H or OH; Generate the pure free radical of reproducibility, thereby improve the radiation reduction yield of metal ion, improve the reducing power of system.
In preparation method of the present invention, free radical scavenger can be selected from alcohols and the derivative thereof of C1-C5, like methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol, tert-butyl alcohol or derivatives thereof etc., also can use formic acid; Preferred isopropyl alcohol and ethylene glycol.When specifically adding free radical scavenger, use its aqueous solution usually, the concentration of control radicals scavenging agent solution can realize the present invention in certain scope.In containing the solution of free radical scavenger, the volume ratio of free radical scavenger optional 1%～100%, preferred 20%～50%.
At method for using c) when flooding, can confirm the adding dosage of free radical scavenger through the volume ratio of free radical scavenger-maceration extract, the concentration of solution is got final product in above-mentioned scope.
When using preparation method's radiation of the present invention to reduce, described carrier can be wetting state or solution submerged state.In the present invention, described wetting state or solution submerged state are not had special requirement, those skilled in the art can judge through prior art and operating experience.Usually can adopt following method: when wetting state irradiation, in advance with soaked carrier in the mixed solution of free radical scavenger and water fully wetting after, with carrier irradiation in vacuum or inert gas (like nitrogen) of surface wettability.When solution submerged state irradiation, soaked carrier is packed in the container, add the mixed solution submergence carrier of free radical scavenger and water after, seal irradiation.For the carrier that uses supersaturation infusion process dipping, can directly in maceration extract, add a certain amount of free radical scavenger, seal irradiation after mixing and make solution submergence carrier.
Ionising radiation reduction process of the present invention can be carried out under room temperature or low temperature, preferably at room temperature carries out.
In preparation method of the present invention, preferably use appropriate amount of deionized water to wash 1～6 time in the carrier after the ionising radiation reduction to remove foreign ion, fully dry afterwards.Drying can be carried out under air atmosphere or vacuum, preferably under air atmosphere, carries out.Optional 50～200 ℃ of baking temperature, preferred 50～100 ℃.Optional 5～48 hours of drying time, preferred 5～24 hours.Promptly obtain catalyst of the present invention after the drying.
Selection hydrogenation catalyst of the present invention can use x-ray photoelectron power spectrum (XPS) to analyze, and confirms the chemical valence state of activity of such catalysts component; Can use transmission electron microscope (TEM) to observe the particle diameter and the particle diameter distribution situation of particles of active components; Can use SEM (SEM) to observe the distribution situation of active component on carrier surface and cross section.
A further object of the present invention is in the selective hydrogenation with alkynes in the ethylene streams of catalyst applications of the present invention in ethylene industry, is preferably applied in the back end hydrogenation, front-end deethanization front-end hydrogenation, predepropanization front-end hydrogenation flow process in the cracking separating technology selectively removing of acetylene in the ethylene streams.
In the time of in the selective hydrogenation of catalyst applications of the present invention alkynes in ethylene streams, need not use hydrogen reducing before the use.
Acetylene selective hydrogenation catalyst of the present invention and preparation method thereof has the following advantages:
(1) main active component palladium of catalyst of the present invention is the metal simple-substance attitude, and the particle diameter homogeneous is compared with the catalyst of conventional method preparation, to C
2The selective hydrogenation of cracking cut removes in the alkynes and shows higher activity and selectivity;
(2) because the main active component palladium of catalyst of the present invention exists with the simple substance form, can directly come into operation, not need to use hydrogen to reduce in advance;
(3) the present invention uses ionising radiation irradiation to be impregnated with the carrier of active component precursor; Promptly use the radiation reducing process to replace the high-temperature roasting-hydrogen reducing in the conventional method; Avoided the active component sintering that causes in the roasting process; Thereby make catalyst of the present invention have more performance, and simplified preparation technology, lowered the discharging of energy consumption and gas pollutant;
(4) because in the catalyst preparation process, condition such as the kind of carrier state, free radical scavenger and content, radiation reducing agent dose rate all can exert an influence to particle size and the distribution that makes the catalyst activity component when kind of carrier, maceration extract pH, dip time, dipping method, irradiation.Therefore, use method of the present invention to prepare catalyst, to be adapted to the needs of multiple choices property hydrogenation reaction easily through the above-mentioned preparation condition of regulation and control with different qualities.
(5) used gamma-rays, X ray or the electron beam of ionising radiation irradiation reducing process of the present invention has stronger penetration capacity, can be used for the production of a large amount of catalyst.
Description of drawings
Fig. 1 and Fig. 2 are the XPS spectrum figure of the catalyst D of embodiments of the invention 4.Wherein the absworption peak of Pd3d is positioned at the 334.90eV place, explains that Pd exists and catalyst surface with the simple substance form; The Ag3d peak position explains that in the 366.83eV place Ag is present in catalyst surface with oxidation state.
Fig. 3 is to use the Pd3d XPS spectrum figure of the catalyst of conventional method preparation, and wherein curve a is a sample after the roasting, and curve b is a sample behind the hydrogen reducing.Can find out that by figure the Pd3d peak position of sample is PdO in 336.76eV after the roasting; The Pd3d peak position is simple substance Pd in 335.03eV behind the hydrogen reducing.
Fig. 4 is transmission electron microscope (TEM) photo of the catalyst B of embodiments of the invention 2, and by finding out among the figure, Pd metallic size is evenly added up to such an extent that its average grain diameter is 3.2nm, less than 10nm.
Fig. 5 has represented embodiments of the invention 3,4,5 and the catalyst of Comparative Examples 2 catalytic performance in the experiment of front-end deethanization front-end hydrogenation flowsheeting.From figure, can clearly be seen that under uniform temp, the selectivity of embodiment is better than Comparative Examples; Embodiment 3,5 also shows good resisting temperature fluctuating nature.
The specific embodiment
Following examples are to more detailed the describing for example of the present invention, but the present invention is not limited to these embodiment.
Embodiment 1
Getting concentration is the Pd (NO of 2mg/ml
3)
2Solution 5.25ml evenly is sprayed at 30g Al
2O
3Carrier surface sprays the NaOH solution of 6.0ml 0.5mol/L again.Add afterwards after an amount of 50% aqueous isopropanol makes carrier surface wetting, under vacuum, use
60The Co gamma emitter is irradiation 15h under the 30Gy/min close rate.Sample behind the irradiation uses deionized water washing 4 times, and 50 ℃ were descended dry 12 hours, obtained said catalyst A, and its Pd content is 0.035wt%.
Embodiment 2
Get 5.0ml 10mg/ml PdCl
2Solution after use 1mol/L NaOH solution is regulated pH to 4.0, evenly is sprayed at 50g Al
2O
3Carrier surface adds after an amount of 50% aqueous isopropanol makes carrier surface wetting afterwards, under vacuum, uses
60The Co gamma emitter is irradiation 15h under the 30Gy/min close rate.Sample behind the irradiation uses deionized water washing 4 times, and 50 ℃ were descended dry 12 hours, obtained said catalyst B, and its Pd content is 0.1wt%.
Embodiment 3
Get 5.25ml 2mg/ml Pd (NO
3)
2Solution is with 6.0ml 3.5mg/ml AgNO
3Solution mixes, and evenly sprays to 30g Al
2O
3Carrier surface sprays the NaOH solution of 6.0ml 0.5mol/L again.Add afterwards after an amount of 50% aqueous isopropanol makes carrier surface wetting, under vacuum, use
60The Co gamma emitter is irradiation 25h under the 30Gy/min close rate.Sample behind the irradiation uses deionized water washing 4 times, and 50 ℃ were descended dry 12 hours, obtained said catalyst C, and its Pd content is 0.035wt%, and Ag content is 0.7wt%.
Embodiment 4
Get 6.0ml 3.5mg/ml AgNO
3Solution mixes, and evenly is sprayed at 30g Al
2O
3Carrier surface, dry back makes AgNO at 550 ℃ of following roasting 8h
3Decompose.Get 5.25ml 2mg/ml PdCl
2Solution uses 1mol/LNaOH solution to regulate its pH to 3, and it evenly is sprayed at the carrier surface that contains Ag.Add afterwards after an amount of 30% ethylene glycol solution makes carrier surface wetting, under vacuum, use
60The Co gamma emitter is irradiation 25h under the 30Gy/min close rate.Sample behind the irradiation uses deionized water washing 4 times, and 50 ℃ were descended dry 12 hours, obtained said catalyst D, and its Pd content is 0.035wt%, and Ag content is 0.7wt%.
Embodiment 5
Get 5.25ml 2mg/ml Pd (NO
3)
2Solution evenly is sprayed at 30g Al
2O
3Carrier surface; Get 6.0ml 3.5mg/ml AgNO after the drying again
3Solution is sprayed at carrier surface; Spray the NaOH solution of 6.0ml 0.5mol/L again.Add after an amount of 50% aqueous isopropanol makes carrier surface wetting, under vacuum, use
60The Co gamma emitter is irradiation 15h under the 40Gy/min close rate.Sample behind the irradiation uses deionized water washing 4 times, and 50 ℃ were descended dry 12 hours, obtained said catalyst E, and its Pd content is 0.035wt%, and Ag content is 0.7wt%.
Embodiment 6
Get 5.25ml 2mg/ml Pd (NO
3)
2Solution is with 6.0ml 3.5mg/ml Pb (NO
3)
2The solution mixing is sprayed at 30g Al
2O
3Carrier surface sprays the NaOH solution of 6.0ml 0.5mol/L again.Add after an amount of 50% aqueous isopropanol makes carrier surface wetting, under vacuum, use
60The Co gamma emitter is irradiation 25h under the 30Gy/min close rate.Sample behind the irradiation uses deionized water washing 4 times, and 50 ℃ were descended dry 12 hours, obtained said catalyst F, and its Pd content is 0.035wt%, and Pb content is 0.7wt%.
Embodiment 7
Get 5.25ml 2mg/ml Pd (NO
3)
2Solution is with 3.0ml 3.5mg/ml Ag (NO
3)
2Solution, 1.12ml2.70mg/ml Bi (NO
3)
3Solution is sprayed at 30g Al after mixing
2O
3Carrier surface sprays the NaOH solution of 5.0ml 1mol/L again.Add after an amount of 50% aqueous isopropanol makes carrier surface wetting, under vacuum, use
60The Co gamma emitter is irradiation 40h under the 30Gy/min close rate.Sample behind the irradiation uses deionized water washing 4 times, and 50 ℃ were descended dry 12 hours, obtained said catalyst G, and its Pd content is 0.035wt%, and Ag content is 0.035wt%, and Bi content is 0.01%.
Comparative Examples 1
Get 5.25ml 2mg/ml Pd (NO
3)
2Solution evenly is sprayed at 30g Al
2O
3Carrier surface.At 550 ℃ of following roasting 8h, obtain catalyst H after the carrier drying, wherein Pd content is 0.035wt%.
Comparative Examples 2
Get 5.25ml 2mg/ml Pd (NO
3)
2Solution is with 6.0ml 3.5mg/ml AgNO
3Solution mixes, and evenly sprays to 30g Al
2O
3Carrier surface.At 550 ℃ of following roasting 8h, obtain catalyst J after the carrier drying, wherein Pd content is 0.035wt%, and Ag content is 0.7wt%.
Comparative Examples 3
Industrial catalyst BC-H-20 (Sinopec Beijing Research Institute of Chemical Industry's production), carrier is Al
2O
3, active component is Pd and Ag, and Pd content is 0.035wt%, and Ag content is 0.7wt%.
Embodiment 8
The above-mentioned catalyst of preparation is carried out the little anti-experiment of ethene back end hydrogenation reaction simulation, and reaction condition is following:
The 1ml catalyst is loaded in the stainless steel tube reactor that internal diameter is 7.8mm, use nitrogen replacement after, feed reactor after simulation joined hydrogen from the unstripped gas of deethanization cat head.The composition of unstripped gas (molar fraction) is an ethane 7%, ethene 92.64%, and acetylene 0.36%, hydrogen alkynes ratio is 2: 1; The experiment air speed is 10000h
-1
Above-mentioned catalyst is estimated the selection hydrogenation catalyst performance of acetylene; Wherein the catalyst A of embodiment, C, D, E, G directly estimate, and Comparative Examples catalyst H, J and BC-H-20 use hydrogen purge to make it reduction in 2 hours down in 150 ℃ before evaluation and estimate.Under 120～130 ℃, each catalytic reaction acetylene hydrogenation is that the conversion ratio and the selectivity of ethene listed in table 1.The computational methods of conversion ratio of ethene (Conversion) and selectivity (Selectivity) are:
Table 1 back end hydrogenation flowsheeting experimental result (120-130 ℃ of following mean value)
Embodiment 9
Above-mentioned catalyst C, D, E, the J of preparation are simulated the little anti-experiment of front-end deethanization front-end hydrogenation, and reaction condition is following:
The 1ml catalyst is loaded in the stainless steel tube reactor that internal diameter is 7.8mm, behind the use nitrogen replacement, the unstripped gas feeding reactor of simulation from the deethanization cat head.The composition of unstripped gas (molar fraction) is a methane 41.85%, ethane 8.15%, and ethene 49%, acetylene 0.93%, propane 0.07%, hydrogen content (with respect to unstripped gas) is about 20%; The experiment air speed is 10000h
-1
Above-mentioned catalyst is carried out the selection hydrogenation catalyst performance of acetylene and estimate, the computational methods of conversion ratio of ethene (Conversion) and selectivity (Selectivity) are the same.Evaluation result is that embodiments of the invention and the catalytic performance of Comparative Examples in the experiment of front-end deethanization front-end hydrogenation flowsheeting are listed among Fig. 5.
Experimental result shows, compares with conventional preparation method, uses the catalyst of radiation method of reducing preparation of the present invention, reveals good selectivity for the acetylene hydrogenation reaction table.In the reaction of front-end deethanization front-end hydrogenation flowsheeting, the selectivity of Embodiment C, E is much higher than Comparative Examples J, also shows good resisting temperature fluctuating nature simultaneously.
Table 2 front-end deethanization front-end hydrogenation simulated experiment result
Claims (14)
1. one kind is used for the catalyst that selective hydrogenation of acetylene is an ethene, comprises carrier and the active component that is carried on carrier, and the main active component of said catalyst is a palladium, and it is elemental under room temperature and air conditions; And said main active component palladium makes through the reducing loaded palladium precursor on carrier of ionising radiation; It is characterized in that in said catalyst preparation process; Use ionising radiation to carry out irradiation; The precursor of main active component palladium is reduced to the metal simple-substance attitude; Irradiance method is: after load was had the carrier of the active component precursor that comprises said main active component palladium precursor to use to contain the solution-wet of free radical scavenger, at wetting state irradiation under vacuum or inert atmosphere, described free radical scavenger was selected from the alcohols of C1-C5 and in the formic acid one or more.
2. catalyst according to claim 1 is characterized in that: described active component comprises
A) described main active component palladium is present in carrier surface with the elemental particle under room temperature and air conditions, its content is 0.01～1wt% of carrier gross weight, and its average grain diameter is 1～100nm;
B) the optional active component that helps is selected from least a among group VIII element, IB family element, Bi, Sb, Pb, In, Cs, Rb, K and the Mg, and its content is 0～20wt% of carrier gross weight.
3. catalyst according to claim 2, the content that it is characterized in that described main active component palladium is 0.01～0.2wt% of carrier gross weight.
4. catalyst according to claim 3, the content that it is characterized in that described main active component palladium is 0.01～0.06wt% of carrier gross weight.
5. catalyst according to claim 2 is characterized in that described main active component palladium and described to help the weight ratio of active component be 0.01-50.
6. catalyst according to claim 1 is characterized in that described main active component palladium is present in carrier surface with the elemental particle shape, and its average grain diameter is 1～40nm.
7. catalyst according to claim 6 is characterized in that described main active component palladium is present in carrier surface with the elemental particle shape, and its average grain diameter is 1～10nm.
8. catalyst according to claim 1 is characterized in that described free radical scavenger is selected from a kind of in methyl alcohol, ethanol, ethylene glycol, isopropyl alcohol and the formic acid.
9. according to the described catalyst of one of claim 1-8, it is characterized in that described carrier is selected from Al
2O
3, SiO
2, TiO
2, a kind of in MgO, diatomite and the molecular sieve or two or more mixture in them.
10. the described Preparation of catalysts method of one of claim 1～9, it may further comprise the steps:
The active component precursor that (1) will comprise the main active component palladium precursor loads on the carrier;
(2) add free radical scavenger, under wetting state, use ionising radiation to carry out irradiation, so that the main active component palladium precursor is reduced to elemental.
11. Preparation of catalysts method according to claim 10 is characterized in that described ionising radiation is gamma-rays, X ray or electron beam, its absorbed dose rate is 10～20000Gy/min.
12. Preparation of catalysts method according to claim 10 is characterized in that described active component precursor is selected from metallic element corresponding chloride, nitrate, sulfate and metallo-organic compound; Described active component precursor loads on the carrier through infusion process.
13. Preparation of catalysts method according to claim 10 is characterized in that, uses alkaline solution to handle the carrier of described carrier or said load active component precursor as fixative; Alkaline solution is selected from one or more the mixture in sodium hydroxide solution, potassium hydroxide solution, sodium bicarbonate solution and the ammoniacal liquor.
14. use in the selective hydrogenation of acetylene in the ethylene streams of the described catalyst of one of claim 1～9 in petrochemical industry is produced.
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| CN2009100824212A CN101862653B (en) | 2009-04-17 | 2009-04-17 | Acetylene selective hydrogenation catalyst and preparation method and application thereof |
| PCT/CN2009/001332 WO2010060281A1 (en) | 2008-11-26 | 2009-11-26 | Metal loaded catalyst and preparation method thereof |
| BRPI0920995-6A BRPI0920995B1 (en) | 2008-11-26 | 2009-11-26 | LOADED METAL CATALYST AND PREPARATION METHOD OF THE SAME. |
| EP09828542.2A EP2368629B1 (en) | 2008-11-26 | 2009-11-26 | Metal loaded catalyst and preparation method thereof |
| US13/131,226 US20110288353A1 (en) | 2008-11-26 | 2009-11-26 | Metal loaded catalyst and preparation method thereof |
| RU2011126193/04A RU2514438C2 (en) | 2008-11-26 | 2009-11-26 | Metal-loaded catalyst and method for preparation thereof |
| KR1020117014269A KR101605055B1 (en) | 2008-11-26 | 2009-11-26 | Metal loaded catalyst and preparation method thereof |
| US14/885,838 US9643172B2 (en) | 2008-11-26 | 2015-10-16 | Metal loaded catalyst and preparation method thereof |
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| CN102794204B (en) * | 2011-05-23 | 2014-11-26 | 中国石油天然气股份有限公司 | Reduction method of palladium catalyst |
| CN102794173A (en) * | 2011-05-27 | 2012-11-28 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for removing alkynes and preparation methods thereof |
| CN102794197B (en) * | 2011-05-27 | 2014-03-12 | 中国石油化工股份有限公司 | Hydrogenation catalyst, and preparation method and application thereof |
| CN103071491B (en) * | 2011-10-26 | 2015-03-11 | 中国石油化工股份有限公司 | Hydrogenation catalyst with large specific surface and low acid amount, and application thereof |
| CN103301838A (en) * | 2012-03-15 | 2013-09-18 | 清华大学 | Catalyst and application as well as preparation method thereof |
| CN103772126B (en) * | 2012-10-25 | 2016-03-30 | 中国石油化工股份有限公司 | Take oil refinery dry gas as the combined method of waste ethylbenzene |
| CN103772125B (en) * | 2012-10-25 | 2016-03-30 | 中国石油化工股份有限公司 | Take oil refinery dry gas as the method for waste ethylbenzene |
| CN106475094B (en) * | 2015-09-02 | 2020-07-24 | 中国石油化工股份有限公司 | Alkyne selective hydrogenation catalyst, preparation method and application thereof, and method for removing alkyne from carbon-containing fraction |
| CN106622223B (en) * | 2015-10-28 | 2019-09-27 | 中国石油化工股份有限公司 | A kind of acetylene hydrogenation catalyst and preparation method thereof |
| CN110876930B (en) * | 2018-09-06 | 2022-11-18 | 中国石油化工股份有限公司 | Supported metal catalyst, preparation method thereof and method for preparing ethylene by selective hydrogenation of acetylene |
| CN112705042A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Method for removing acetylene and ethylene in natural gas cracking tail gas |
| CN111545205B (en) * | 2020-05-29 | 2023-08-11 | 山东京博石油化工有限公司 | Catalyst for selective alkyne removal of catalytic cracking dry gas and preparation method and application thereof |
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| US4745094A (en) * | 1984-06-13 | 1988-05-17 | Centre National De La Recherche Scientifique | Mono- or multi-metal microaggregates, a method for their preparation and their application in the catalysis of the photoreduction of water |
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