CN106622255A - Alkyne selective hydrogenation catalyst as well as preparation method and application thereof - Google Patents
Alkyne selective hydrogenation catalyst as well as preparation method and application thereof Download PDFInfo
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- CN106622255A CN106622255A CN201510712244.7A CN201510712244A CN106622255A CN 106622255 A CN106622255 A CN 106622255A CN 201510712244 A CN201510712244 A CN 201510712244A CN 106622255 A CN106622255 A CN 106622255A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
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Abstract
The invention relates to the field of hydrogenation and in particular provides an alkyne selective hydrogenation catalyst as well as a preparation method and application thereof. The alkyne selective hydrogenation catalyst contains a carrier as well as a nickel component and a copper component which are loaded on the carrier, the carrier is nano silica, content of the carrier is 5-80wt% by taking the total weight of the catalyst as the benchmark; calculated by oxide, the content of the nickel component is 5-60wt%, and the content of the copper component is 3-40wt%. The preparation method of the alkyne selective hydrogenation catalyst comprises the following steps: (1) mixing a precipitating agent, soluble nickel salt, soluble copper salt and silica sol; (2) aging the mixture obtained in the step (1), and successively drying and roasting precipitate obtained after aging. The catalyst provided by the invention is obviously improved in activity and selectivity, the service life of the catalyst is also obviously prolonged, and the catalyst is especially applicable to a selective hydrogenation alkyne removal process of C5 fraction.
Description
Technical field
The present invention relates to catalyst field, in particular it relates to a kind of selective acetylene hydrocarbon hydrogenation catalyst, should
The application of the preparation method of catalyst and the catalyst during C5 fraction selects acetylene hydrogenation.
Background technology
Cracked C 5 fraction is the pair of naphtha and other heavy cracking stock preparing ethylene by steam cracking processes
Product, component isoprene, cyclopentadiene and the pentadiene that value is higher and content is more is about
Account for the 40%～60% of cracked C 5 fraction.Wherein, isoprene is in synthetic rubber and synthetic resin industry
In have huge demand.Isoprene is typically passed through the technique of separating-purifying, reaches certain purity
After effectively could rationally be utilized.In foreign matter diene purification and separation process, cracked C 5 fraction
In a small amount of alkynes can reduce the activity of catalyst, and the deterioration in physical properties of polymer is made, so must
Alkynes content in cracked C 5 fraction must be dropped to below certain value, can synthetic high polymer list
Body.The general alkynes removed using this both economical method of selective hydrogenation in cracked C 5 fraction
Hydrocarbon.
CN1188494C discloses a kind of selective hydrocatalyst and preparation method thereof and in C 5 fraction
In application, the preparation method of catalyst is：First with the salpeter solution of the salt of I B-group metal and the
The salpeter solution oxide impregnation alumina supporter of the salt of the race's metals of V III, then with the aqueous solution of alkali metal compound
Dipping；It is dried within the temperature range of 50-200 DEG C after each step dipping, in 250-650 DEG C of temperature
Roasting is carried out in the range of degree.The method has properly increased the selectivity of catalyst, but it is former not provide reaction
The content of alkynes and alkadienes in material, and in raw material the content of alkadienes and alkynes how many pairs of catalyst
Performance can produce a very large impact.
CN102649063A discloses a kind of Selective Hydrogenation Catalyst Phenylacetylene, and catalyst is mainly adopted
Metallic nickel or its oxide are metal active constituent, and lanthana, zinc oxide are its auxiliary agent, using leaching
Stain method is prepared, and cinnamic loss late is 0.1%, and the content of phenylacetylene is in reaction effluent
3ppm.The catalyst is primarily adapted for use in the selective hydrogenation of phenylacetylene.
CN101428228B discloses a kind of selective hydrocatalyst and preparation method thereof, the catalyst
Comprising alumina catalyst support, active component palladium, Cu additives, auxiliary agent X1 and auxiliary agent X2 is total with catalyst
Weight 100% is counted：Containing palladium 0.1～0.5%, copper 2.0～5.5%, X10.5～15%, X20.5～
5%, 0～2% one or more be selected from cobalt, nickel, molybdenum, tungsten, lanthanum, silver, cerium, samarium, neodymium is helped
Agent metal；Wherein X1 is selected from IVA elements, and X2 is selected from alkali metal, alkaline-earth metal or its mixture.
The catalyst is particularly well-suited to the selective hydrogenation of C 4 fraction.
As fully visible, although above-mentioned preparation method can to a certain extent improve the hydrogenation of catalyst
Can, but, further research has been found that catalyst still suffers from catalyst activity obtained in prior art
It is relatively low, selective poor, the shorter defect of catalyst life, and containing more miscellaneous in cracking c_5
Matter, to isoprene selective hydrogenation except alkynes catalyst is put forward higher requirement.Therefore, develop
Activity is high, selectivity is got well and can keep the selective acetylene hydrocarbon hydrogenation catalyst compared with dominance energy the long period
It is particularly important.
The content of the invention
Use for relatively low, the selective poor or catalyst of existing selective acetylene hydrocarbon hydrogenation catalyst activity
The shortcoming of short life, the present invention provides a kind of new selective acetylene hydrocarbon hydrogenation catalyst, selective acetylene hydrocarbon hydrogenation and urges
The preparation method of agent, selective acetylene hydrocarbon hydrogenation catalyst obtained by this method and the catalyst are in carbon five
Fraction selective hydrogenation is except the application during alkynes.Catalyst obtained by this method not only activity and selectivity
It is significantly improved, and the service life of catalyst is also obviously improved, and it is particularly well-suited to carbon five
The selection acetylene hydrogenation process of cut.
The present inventor is had found by studying, in selective acetylene hydrocarbon hydrogenation catalyst preparation process,
The active component of selective acetylene hydrocarbon hydrogenation catalyst prepared using coprecipitation is more evenly distributed, and is catalyzed
The bigger advantage of agent specific surface area and pore volume, thus it is speculated that its reason is probably：Using coprecipitation by activity
Component is loaded on the silica support in the form of colloidal sol, and silica plays the work of skeletal support
With, it is possible to increase the specific surface area and pore volume of obtained catalyst, while enhancing active component with activity
Interaction between component, between active component and carrier.Therefore, method provided by the present invention
The selective acetylene hydrocarbon hydrogenation catalyst active component of preparation is uniformly dispersed, and is more likely formed greater number of activity
Good catalytic active center, significantly improves the activity and selectivity of catalyst, and effectively extends
The service life of catalyst.
Thus, the present invention provides a kind of new selective acetylene hydrocarbon hydrogenation catalyst, and the catalyst contains carrier
With load nickel component on this carrier and copper component, the carrier is nano silicon, to be catalyzed
On the basis of the gross weight of agent, the content of the carrier is 5-80 weight %, in terms of oxide, nickel component
Content be 5-60 weight %, the content of copper component is 3-40 weight %.
Present invention also offers a kind of preparation method of selective acetylene hydrocarbon hydrogenation catalyst, the method includes following
Step：
(1) precipitating reagent, soluble nickel salt, soluble copper salt and Ludox are mixed；
(2) mixture that step (1) is obtained is carried out it is aging, and will be aging after the sediment that obtains according to
It is secondary be dried, roasting.
Present invention also offers by obtained in said method selective acetylene hydrocarbon hydrogenation catalyst.
Additionally, present invention also offers above-mentioned selective acetylene hydrocarbon hydrogenation catalyst selects to be hydrogenated with C5 fraction
Except the application during alkynes.
The selective acetylene hydrocarbon hydrogenation catalyst main advantage compared with prior art of the present invention is：
(1) catalyst has higher activity and selectivity；
(2) method for preparing catalyst is simple, it is easy to industrialize；
(3) service life of catalyst is effectively extended, productivity effect is improve.
Other features and advantages of the present invention will give specifically in subsequent specific embodiment part
It is bright.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place
The specific embodiment of description is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of selective acetylene hydrocarbon hydrogenation catalyst, the catalyst contains carrier and is supported on
Nickel component and copper component on the carrier, the carrier is nano silicon, with the gross weight of catalyst
On the basis of amount, the content of the carrier is 5-80 weight %, and in terms of oxide, the content of nickel component is
5-60 weight %, the content of copper component is 3-40 weight %.
In accordance with the present invention it is preferred that, it is described in terms of oxide on the basis of the gross weight of catalyst
The content of carrier is 30-70 weight %, and the content of nickel component is 10-50 weight %, the content of copper component
For 5-20 weight %.
In accordance with the present invention it is preferred that, the catalyst also contains auxiliary agent.
The metallic element of heretofore described auxiliary agent can be selected from metallic element commonly used in the art, preferably
Ground, the metallic element of the auxiliary agent is selected from lanthanide element, vib metals element and VIII
One kind in one or more in race's metallic element, preferably lanthanum, molybdenum, neodymium, cobalt, samarium and Ce elements
Or it is various.
In accordance with the present invention it is preferred that, it is described to help in terms of oxide on the basis of the gross weight of catalyst
The content of agent is 1-10 weight %.
In accordance with the present invention it is preferred that, the nano silicon is made up of Ludox as presoma, excellent
Choosing is made up of acidic silicasol as presoma.
As long as there is the catalyst of the present invention above-mentioned composition to be capable of achieving the purpose of the present invention, the present invention is to it
Preparation method without particular/special requirement, in order to further improve the activity of catalyst, the catalyst of the preferred present invention
Preparation process include：
(1) precipitating reagent, soluble nickel salt, soluble copper salt and Ludox are mixed；
(2) mixture that step (1) is obtained is carried out it is aging, and will be aging after the sediment that obtains according to
It is secondary be dried, roasting.
In the present invention, mixing described in step (1) adds water or does not add water according to needs, it is however generally that,
Because the water content in Ludox may be fewer than the dissolving precipitating reagent, soluble nickel salt, solubility
Mantoquita, it is therefore desirable to additionally add water, wherein it is preferred that, the consumption of water with precipitating reagent, soluble nickel salt, can
Dissolubility mantoquita is all dissolved as standard.
The present inventor has found that silica is added in catalyst in the form of colloidal sol, can by studying
To play skeletal support effect, it is possible to increase the specific surface area of catalyst, broadening pore passage structure, in addition, adopting
More conducively live on the silica support for loading in the form of colloidal sol by active component with coprecipitation
Property component is uniformly distributed, so as to improve the activity and selectivity of catalyst.
In the present invention, Ludox can be this area routine Ludox, preferably acidic silicasol.
In the present invention, it is preferred to soluble nickel salt and soluble copper salt are instilled described mixing be carried out in Ludox
Close, wherein, for the mode that soluble nickel salt and soluble copper salt instill Ludox has no particular limits,
Preferably, Ludox is placed in constant temperature oil bath, keeps oil bath temperature between 20-90 DEG C, in rotating speed
Under 50-500 rev/min of mixing speed, soluble nickel salt and soluble copper salt are instilled into Ludox, adopted
This preferred embodiment is more beneficial for the generation of coprecipitation reaction.
According to method of the present invention, soluble nickel salt is the conventional soluble nickel salt in this area, example
Such as can be one or more in nickel nitrate, nickel sulfate, nickel acetate and nickel chloride, preferably nitric acid
Nickel.
According to method of the present invention, soluble copper salt is the conventional soluble copper salt in this area, example
Such as can be one or more in copper nitrate, copper chloride and copper acetate, preferably copper nitrate.
According to method of the present invention, it is preferable that the consumption of the soluble nickel salt and soluble copper salt
So that, on the basis of the gross weight of catalyst, in terms of oxide, the content of nickel component is 5-60 weights
Amount %, the content of copper component is 3-40 weight %.
In step (1) of the present invention, for precipitating reagent, soluble nickel salt, soluble copper salt and Ludox
There is no particular limitation for the mode of mixing, and step (1) can first by soluble nickel salt and soluble copper salt
Wiring solution-forming instills Ludox, is subsequently adding precipitating reagent, it is also possible to first precipitating reagent is instilled into Ludox, so
The solution for being afterwards made into soluble nickel salt and soluble copper salt is instilled, it is also possible to by precipitating reagent, soluble nickel
Salt and soluble copper salt cocurrent instill Ludox simultaneously, preferably by precipitating reagent, soluble nickel salt and solubility
Mantoquita cocurrent instills Ludox simultaneously.Using this preferred embodiment, solution local concentration overrich can be avoided,
Precipitation process is more stable.
In the present invention, it is preferred to, the precipitating reagent is alkali compounds, preferably NaOH, hydrogen
One or more in potassium oxide, sodium carbonate and sodium acid carbonate, more preferably sodium carbonate.
Preparation in accordance with the present invention, it is preferable that the method is also including the introducing of auxiliary agent.
In the present invention, for the occasion of introduction of auxiliary agent has no particular limits, as long as can ensure that auxiliary agent has
Effect plays a role, and for example, auxiliary agent can be collectively incorporated in step (1) with nickel component and copper component,
Can also introduce after nickel component and copper component are introduced, can introduce before step (2) ageing process,
Can also introduce before dry run after ageing process.
A preferred embodiment of the invention, before the roasting process of step (2), introduces
Auxiliary agent.
For the incorporation way of auxiliary agent has no particular limits, preferably infusion process, the infusion process can be with
For this area conventional impregnation method.
Heretofore described metal promoter element can be selected from auxiliary agent commonly used in the art, it is preferable that described
The metallic element of auxiliary agent is selected from lanthanide element, vib metals element and group VIII metal unit
One or more in element, the further preferably one kind in lanthanum, molybdenum, neodymium, cobalt, samarium and Ce elements
Or it is various.
Preparation in accordance with the present invention, it is preferable that the consumption of the auxiliary agent is caused, with the total of catalyst
On the basis of weight, in terms of oxide, the content of the auxiliary agent is 1-10 weight %.
Preparation in accordance with the present invention, step (2) the aging condition includes：Aging temperature is excellent
Elect 20-90 DEG C, more preferably 40-80 DEG C as.
Preparation in accordance with the present invention, step (2) the aging condition includes：Ageing time is excellent
Elect 0.5-5 hours, more preferably 1-3 hours as.
Preparation in accordance with the present invention, step (2) drying condition can be with this area conventional drying
Condition.
Preferably, the condition of the drying includes：Baking temperature is 60-120 DEG C, preferably 80-120 DEG C.
Preferably, the condition of the drying includes：Drying time is 3-12 hours, preferably 3-6 hours.
Preparation in accordance with the present invention, the condition of step (2) roasting includes：Sintering temperature is excellent
Elect 300-600 DEG C, more preferably 350-500 DEG C as.
Preparation in accordance with the present invention, the condition of step (2) roasting includes：Roasting time is excellent
Elect 2-10 hours, more preferably 3-6 hours as.
Present invention also offers the selective acetylene hydrocarbon hydrogenation catalyst prepared by above-mentioned preparation method, the alkynes
The activity of hydrocarbon selective hydrogenation catalyst is higher, and selective more preferable, service life is longer.
Present invention also offers above-mentioned selective acetylene hydrocarbon hydrogenation catalyst selects acetylene hydrogenation mistake in C5 fraction
Application in journey.Apply when the selective acetylene hydrocarbon hydrogenation catalyst of the present invention selects hydrogenation to remove in C5 fraction
When during alkynes, can be in the case where less isoprene be lost, effectively in removing C5 fraction
Alkynes.
The following examples are used to be described in further detail the specific embodiment of the present invention, but this
The protection domain of invention is not limited thereto.
Embodiment 1
Weigh the water nickel nitrates of 113.2g six to be put in 100g deionized waters with 8.8g nitrate trihydrate copper, stir
Dissolving obtains solution A, weighs 54.1g sodium carbonate and is put in 100g deionized waters, and stirring and dissolving obtains molten
Liquid B, the acidic silicasol of weight % of 100g 25 is placed in constant temperature oil bath and is stirred continuously, and keeps oil
Bath temperature is 60 DEG C, and mixing speed is 150 revs/min, and solution A and solution B cocurrent are instilled into above-mentioned acid
It is aging 1 hour at 60 DEG C in property Ludox, after being washed with deionized, then in 110 DEG C of dryings 6
Hour, gained filter cake will be dried and be ground to powder, 1.2g powder lanthanas are added thereto to, mix
After uniform, in 500 DEG C of roastings 3 hours, catalyst S1 is obtained.In S1, in terms of oxide, nickel group
The content divided is 50 weight %, and the content of copper component is 5 weight %, and the content of auxiliary agent lanthanum is 2 weight %.
Embodiment 2
Weigh the water nickel nitrates of 59.6g six, 23.1g nitrate trihydrates copper and 8.1g lanthanum nitrate hexahydrates and be put into 100g
In deionized water, stirring and dissolving obtains solution A, weighs 40.7g sodium carbonate and is put in 100g deionized waters,
Stirring and dissolving obtains solution B, and the acidic silicasol of weight % of 100g 25 is placed in constant temperature oil bath not
Disconnected stirring, keeps oil bath temperature to be 80 DEG C, and mixing speed is 200 revs/min, by solution A and solution B
Cocurrent is instilled in above-mentioned acidic silicasol, aging 3 hours at 80 DEG C, after being washed with deionized, then
In 120 DEG C of dryings 3 hours, 450 DEG C of roastings obtained catalyst S2 in 6 hours.In S2, in terms of oxide,
The content of nickel component is 30 weight %, and the content of copper component is 15 weight %, and the content of auxiliary agent lanthanum is 6
Weight %.
Embodiment 3
Weigh the water nickel nitrates of 16.2g six, 25.2g nitrate trihydrates copper and 11.1g lanthanum nitrate hexahydrates and be put into 100g
In deionized water, stirring and dissolving obtains solution A, weighs 25.0g potassium hydroxide and is put into 100g deionized waters
In, stirring and dissolving obtains solution B, and the acidic silicasol of weight % of 100g 25 is placed in constant temperature oil bath
And be stirred continuously, keep oil bath temperature to be 40 DEG C, mixing speed is 100 revs/min, by solution A and molten
Liquid B cocurrents are instilled in above-mentioned acidic silicasol, aging 2 hours at 60 DEG C, after being washed with deionized,
Then in 80 DEG C of dryings 5 hours, 350 DEG C of roastings 4 hours obtain catalyst S3.In S3, with oxygen
Compound meter, the content of nickel component is 10 weight %, and the content of copper component is 20 weight %, auxiliary agent lanthanum
Content is 10 weight %.
Embodiment 4
Weigh the water nickel nitrates of 90.6g six to be put in 100g deionized waters with 26.4g nitrate trihydrate copper, stir
Dissolving obtains solution A, weighs 53.6g sodium carbonate and is put in 100g deionized waters, and stirring and dissolving obtains molten
Liquid B, the acidic silicasol of weight % of 100g 25 is placed in constant temperature oil bath and is stirred continuously, and keeps oil
Bath temperature is 60 DEG C, and mixing speed is 150 revs/min, and solution A and solution B cocurrent are instilled into above-mentioned acid
It is aging 1 hour at 60 DEG C in property Ludox, after being washed with deionized, then in 110 DEG C of dryings 4
Hour, gained filter cake will be dried and be ground to powder, 1.2g powder neodymia is added thereto to, mix
After uniform, in 400 DEG C of roastings 3 hours, catalyst S4 is obtained.In S4, in terms of oxide, nickel group
The content divided is 40 weight %, and the content of copper component is 15 weight %, and the content of auxiliary agent neodymium is 2 weight %.
Embodiment 5
Weigh the water nickel nitrates of 113.2g six to be put in 100g deionized waters with 8.8g nitrate trihydrate copper, stir
Dissolving obtains solution A, weighs 54.1g sodium carbonate and is put in 100g deionized waters, and stirring and dissolving obtains molten
Liquid B.A, B solution cocurrent are instilled and be placed in the beaker of oil bath, keeps oil bath temperature to be 60 DEG C, stirred
Speed is mixed for 150 revs/min.It is aging 1 hour at 60 DEG C, after being washed with deionized, then at 110 DEG C
It is dried 6 hours, gained filter cake will be dried and be ground to powder, by itself and 25g powder nanometer titanium dioxides
Silicon (particle diameter is 50nm-100nm), the mixing of 1.2g powders lanthana, in 500 DEG C of roastings 3 hours,
Obtain catalyst S5.In S5, in terms of oxide, the content of nickel component is 50 weight %, and copper component contains
Measure as 5 weight %, the content of auxiliary agent lanthanum is 2 weight %.
Comparative example 1
Method according to CN102649063A prepares catalyst, specially：Weigh aluminum oxide and oxygen
The weight ratio of SiClx is 5:20 grams of 1 composite carrier, it is 12 weight % to be added to nitric acid nickel content,
The content of lanthanum nitrate is 3 weight %, and the content of zinc nitrate is in the solution of 1 weight %, to carry out equivalent leaching
Stain, in 120 DEG C of dryings 6 hours, 400 DEG C of roastings 8 hours were obtained nickel-base catalyst D1 so that nickel
Content is the 8% of vehicle weight, and lanthanum content is 0.2%, and the content of zinc is 0.2%.
Comparative example 2
According to the method for embodiment 2, except for the difference that, the carrier for being used is aluminum oxide, specially：
Weigh the water nickel nitrates of 59.6g six, 23.1g nitrate trihydrates copper and 8.1g lanthanum nitrate hexahydrates and be put into 100g
In deionized water, stirring and dissolving obtains solution A, by aluminum oxide incipient impregnation 1 hour in solution A,
Then in 120 DEG C of dryings 8 hours, 450 DEG C of roastings obtain catalyst D2 in 6 hours.In D2, to aoxidize
Thing meter, the content of nickel component is 31 weight %, and the content of copper component is 15.3 weight %, auxiliary agent lanthanum
Content is 6.1 weight %.
Comparative example 3
According to the method for embodiment 5, except for the difference that, using powdered alumina is (commercial) powder is replaced
Shape nano silicon, obtains catalyst D3.In D3, in terms of oxide, the content of nickel component is 50.4
Weight %, the content of copper component is 5 weight %, and the content of auxiliary agent lanthanum is 2.1 weight %.
Test example 1
In this test example, to the acetylene selective hydrogenation catalyst prepared using method provided by the present invention
The performance of the acetylene selective hydrogenation catalyst provided with comparative example is evaluated in accordance with the following methods, evaluates knot
It is really as shown in table 1 below.
Reaction raw materials composition is as follows：
| Isoprene | 99.59 weight % |
| Pentone | 0.17 weight % |
| 2- butine | 0.04% |
| N-pentene | 0.01% |
The performance evaluation of catalyst is carried out on fixed bed device, by 20mL Catalyst packings to reactor
In, the catalyst is being reduced 4 hours using front use hydrogen at 400 DEG C, is lowered the temperature using after nitrogen displacement
To room temperature, reaction raw materials are passed through into reactor carries out selective hydrogenation reaction.Reaction condition includes：Reaction
Device inlet temperature is 35 DEG C, and hydrogen flowing quantity is 8.4mL/min, and reaction pressure is 1.0MPa, liquid space-time
Speed is 6h-1。
The evaluation result of catalyst is as shown in table 1 obtained by each embodiment and comparative example.
Table 1
From table 1 it follows that under the same reaction conditions, the catalyst that the present invention is provided can be only
In the case of having a small amount of isoprene to lose, the alkynes being stripped of in reaction raw materials as much as possible, this
The catalyst of bright offer has preferable activity and selectivity.The data of contrast reaction 4h and reaction 200h can
With find, using the present invention provide catalyst, reaction 4h and reaction 200h isoprene loss late and
The change of alkynes surplus is not that amplitude is little, and is used after the catalyst reaction 200h that comparative example is provided,
Isoprene loss late is substantially more, and the alkynes removing ability of catalyst has also declined.Above-mentioned knot
Fruit fully shows that the catalyst obtained by preparation method provided by the present invention has existing other catalyst
Incomparable superiority.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned
Detail in embodiment, in the range of the technology design of the present invention, can be to the skill of the present invention
Art scheme carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid not
Necessary repetition, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as
, without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention for it.
Claims (11)
1. a kind of selective acetylene hydrocarbon hydrogenation catalyst, it is characterised in that the catalyst contains carrier and load
Nickel component on this carrier and copper component, the carrier is nano silicon, with the gross weight of catalyst
On the basis of amount, the content of the carrier is 5-80 weight %, and in terms of oxide, the content of nickel component is
5-60 weight %, the content of copper component is 3-40 weight %.
2. catalyst according to claim 1, wherein, on the basis of the gross weight of catalyst,
The content of the carrier is 30-70 weight %, and in terms of oxide, the content of nickel component is 10-50 weight %,
The content of copper component is 5-20 weight %.
3. catalyst according to claim 1 and 2, wherein, the catalyst also contains auxiliary agent,
The metallic element of the auxiliary agent is selected from lanthanide element, vib metals element and group VIII gold
One or more in category element, the preferably one kind or many in lanthanum, molybdenum, neodymium, cobalt, samarium and Ce elements
Kind, on the basis of the gross weight of catalyst, in terms of oxide, the content of the auxiliary agent is 1-10 weight %.
4. catalyst according to claim 1 and 2, wherein, the nano silicon is by silicon
Colloidal sol is made as presoma, is preferably made up as presoma of acidic silicasol.
5. a kind of preparation method of selective acetylene hydrocarbon hydrogenation catalyst, it is characterised in that the method include with
Lower step：
(1) precipitating reagent, soluble nickel salt, soluble copper salt and Ludox are mixed；
(2) mixture that step (1) is obtained is carried out it is aging, and will be aging after the sediment that obtains according to
It is secondary be dried, roasting.
6. method according to claim 5, wherein, the method also includes：In step (2)
Before roasting process, auxiliary agent is introduced, the metallic element of the auxiliary agent is selected from lanthanide element, VIB
One or more in race's metallic element and group VIII metallic element, preferably lanthanum, molybdenum, neodymium, cobalt,
One or more in samarium and Ce elements, the consumption of the auxiliary agent is caused, and the gross weight with catalyst is as base
Standard, in terms of oxide, the content of the auxiliary agent is 1-10 weight %.
7. method according to claim 5, wherein, the precipitating reagent is alkali compounds, excellent
Elect one or more in NaOH, potassium hydroxide, sodium carbonate and sodium acid carbonate as.
8. method according to claim 5, wherein, the soluble nickel salt selected from nickel nitrate,
One or more in nickel sulfate, nickel acetate and nickel chloride, the soluble copper salt is selected from copper nitrate, chlorine
Change one or more in copper and copper acetate；The consumption of the soluble nickel salt and soluble copper salt is caused,
On the basis of the gross weight of catalyst, in terms of oxide, the content of nickel component is 5-60 weight %, copper group
The content divided is 3-40 weight %.
9. method according to claim 5, wherein, the aging condition includes：Aging temperature
Spend for 20-90 DEG C, preferably 40-80 DEG C；Ageing time is 0.5-5 hours, preferably 1-3 hours；
The condition of the roasting includes：Sintering temperature is 300-600 DEG C, preferably 350-500 DEG C；Roasting time
For 2-10 hours, preferably 3-6 hours.
10. selective acetylene hydrocarbon hydrogenation obtained in the preparation method by described in any one in claim 5-9 is urged
Agent.
Selective acetylene hydrocarbon hydrogenation catalyst in 11. claims 1-4 and 10 described in any one evaporates in carbon five
Application during component selections acetylene hydrogenation.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970938A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preparation method and application |
| CN111085221A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silver-zinc doped Raney copper catalyst and preparation method and application thereof |
| CN111097445A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst, preparation method and application thereof, and method for removing alkyne through selective hydrogenation of isoprene |
| CN114471570A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Naphthalene selective hydrogenation catalyst, and preparation method and application thereof |
| CN115555001A (en) * | 2021-07-01 | 2023-01-03 | 中国石油天然气股份有限公司 | Alkyne-rich carbon four-selective hydrogenation catalyst and preparation method thereof |
| CN117065750A (en) * | 2023-10-13 | 2023-11-17 | 北京弗莱明科技有限公司 | Nickel-based catalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410515A (en) * | 2001-09-29 | 2003-04-16 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and its preparation method and application |
| CN101037613A (en) * | 2006-03-17 | 2007-09-19 | 中国石油天然气股份有限公司 | Nickel-based hydrogenation catalyst, and preparation method and application thereof |
| CN101664682A (en) * | 2008-09-05 | 2010-03-10 | 中国石油化工股份有限公司 | Non-noble metal supported selective hydrogenation catalyst and preparation method and application thereof |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
| CN102989477A (en) * | 2011-09-09 | 2013-03-27 | 中国石油天然气股份有限公司 | Nickel-based hydrogenation catalyst, preparation method thereof and reduction and regeneration method of catalyst |
-
2015
- 2015-10-28 CN CN201510712244.7A patent/CN106622255A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410515A (en) * | 2001-09-29 | 2003-04-16 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and its preparation method and application |
| CN101037613A (en) * | 2006-03-17 | 2007-09-19 | 中国石油天然气股份有限公司 | Nickel-based hydrogenation catalyst, and preparation method and application thereof |
| CN101664682A (en) * | 2008-09-05 | 2010-03-10 | 中国石油化工股份有限公司 | Non-noble metal supported selective hydrogenation catalyst and preparation method and application thereof |
| CN102989477A (en) * | 2011-09-09 | 2013-03-27 | 中国石油天然气股份有限公司 | Nickel-based hydrogenation catalyst, preparation method thereof and reduction and regeneration method of catalyst |
| CN102764656A (en) * | 2012-08-06 | 2012-11-07 | 久泰能源科技有限公司 | High-efficiency hydrogenation catalyst and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| 孙春水等: "Ni/Al2O3-SiO2催化剂对碳五馏分的加氢性能", 《石油炼制与化工》 * |
| 阮细强等: "碳五馏分选择性加氢除炔催化剂的研究", 《石油化工》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970938A (en) * | 2016-10-25 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its preparation method and application |
| CN111085221A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Silver-zinc doped Raney copper catalyst and preparation method and application thereof |
| CN111097445A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst, preparation method and application thereof, and method for removing alkyne through selective hydrogenation of isoprene |
| CN114471570A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Naphthalene selective hydrogenation catalyst, and preparation method and application thereof |
| CN114471570B (en) * | 2020-10-23 | 2024-01-30 | 中国石油化工股份有限公司 | Naphthalene selective hydrogenation catalyst and preparation method and application thereof |
| CN115555001A (en) * | 2021-07-01 | 2023-01-03 | 中国石油天然气股份有限公司 | Alkyne-rich carbon four-selective hydrogenation catalyst and preparation method thereof |
| CN115555001B (en) * | 2021-07-01 | 2023-12-26 | 中国石油天然气股份有限公司 | Alkyne-rich carbon four-selective hydrogenation catalyst and preparation method thereof |
| CN117065750A (en) * | 2023-10-13 | 2023-11-17 | 北京弗莱明科技有限公司 | Nickel-based catalyst and preparation method and application thereof |
| CN117065750B (en) * | 2023-10-13 | 2024-01-26 | 北京弗莱明科技有限公司 | Nickel-based catalyst and preparation method and application thereof |
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