CN108689792A - A kind of C4The method that fraction selective hydrogenation prepares 1- butylene - Google Patents
A kind of C4The method that fraction selective hydrogenation prepares 1- butylene Download PDFInfo
- Publication number
- CN108689792A CN108689792A CN201710223973.5A CN201710223973A CN108689792A CN 108689792 A CN108689792 A CN 108689792A CN 201710223973 A CN201710223973 A CN 201710223973A CN 108689792 A CN108689792 A CN 108689792A
- Authority
- CN
- China
- Prior art keywords
- nickel
- catalyst
- selective hydrogenation
- fraction
- copper base
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of C4The method that fraction selective hydrogenation prepares 1- butylene, including:In the reactor by nickel-copper base Catalyst packing, it is passed through hydrogen and reduction treatment is carried out to nickel-copper base catalyst;It is passed through liquid phase diluent and conditioning agent the nickel-copper base catalyst after reduction treatment is carried out stablizing processing;In the presence of the nickel-copper base catalyst through the reduction treatment and the stable processing, by C4After fraction, liquid phase diluent, conditioning agent and hydrogen mixing, it is passed through in reactor and carries out selective hydrogenation reaction, make C4Alkynes and di-olefins in fraction are 1- butylene;Wherein, the conditioning agent is carbon monoxide.It can be removed in time using the method for the present invention reaction heat, selectivity improves, and alkynes and di-olefins rate are high, 1- butylene can be prepared with high selectivity, and the activity of catalyst is high, and stability is good, catalyst life greatly prolongs, while the also impurity such as sulfur resistive and arsenic are to catalyst the advantages that poisoning.
Description
Technical field
The present invention relates to alkene preparation fields, and in particular to a kind of C4The method that fraction selective hydrogenation prepares 1- butylene.
Background technology
In cracking petroleum hydrocarbon ethylene process, as by-product, a large amount of mixing C-4-fraction (C will produce4Fraction), it should
1,3-butadiene containing 40-60wt% or so in fraction, the vinylacetylene (VA) and ethyl acetylene of 0.5-2.0wt%
(EA), remaining group is divided into butane, butylene and a small amount of 1,2- butadiene, carbon three and C5 fraction.In general, industrially passing through two sections
Solvent extraction rectifying and one section of direct rectification process carry out being refining to obtain product butadiene to cracking mixing C-4-fraction, isolate
In the raffinate of butadiene other than the 1,3-butadiene containing 20-40wt%, also VA and EA containing 10-20wt%, this stock
Material is exactly so-called high alkynes C4Fraction.In industrial processes, the considerations of for factors such as safety, usually by high alkynes C4It evaporates
Divide after using the material containing butane etc. to dilute and used as fuel, this not only causes the waste of resource, also creates environment dirt
Dye.
In the prior art, generally use adds the method for hydrogen to carry out effectively profit to the salvage stores that Butadiene Extraction tail gas generates
With.It is in place of the deficiencies in the prior art, on the one hand, selective acetylene hydrocarbon hydrogenation process is strong exothermal reaction, is released in reaction process big
The heat of amount, leads to catalyst blockage and inactivation;On the other hand, hydrogenation reaction heat release causes the raising of reaction temperature, and can be into
One step accelerates polymer in the deposition velocity of catalyst surface, while can reduce the selectivity of purpose product.This alkynes selection
Hydrogenation technique operation is not only absolutely unsafe but also the service life of catalyst is shorter, if C4Alkynes and butadiene concentration in fraction are more
Height, consequence will be more serious.In addition, the problem of precious metals palladium catalyst is easy to be lost in there is also active component, thereby results in and urges
Agent is permanently poisoned, and the service life of catalyst is short, every half a year needs to regenerate once, and operating cost is higher.
Therefore, develop suitable selective hydrogenation catalyst and coordinate suitable selection Hydrogenation for 1- butylene technique particularly
It is important.
Invention content
In view of the deficiencies of the prior art, the present invention is intended to provide a kind of C4The method that fraction selective hydrogenation prepares 1- butylene,
By carrying out reduction treatment and stablizing to handle to nickel-copper base catalyst, then in the collective effect of liquid phase diluent and conditioning agent
Under make C4Alkynes and di-olefins in fraction are 1- butylene, can significantly improve the selectivity, activity and stabilization of catalyst
Property, the service life of catalyst and service life also greatly increase.
Therefore, the purpose of the present invention is to provide a kind of C4The method that fraction selective hydrogenation prepares 1- butylene, including:
In the reactor by nickel-copper base Catalyst packing, it is passed through hydrogen and reduction treatment is carried out to nickel-copper base catalyst;
It is passed through liquid phase diluent and conditioning agent the nickel-copper base catalyst after reduction treatment is carried out stablizing processing;
In the presence of the nickel-copper base catalyst through the reduction treatment and the stable processing, by C4Fraction, liquid phase dilution
After agent, conditioning agent and hydrogen mixing, it is passed through in reactor and carries out selective hydrogenation reaction, make C4Alkynes and alkadienes in fraction turn
Turn to 1- butylene;
Wherein, the conditioning agent is carbon monoxide.
Due to catalyst preparation process and the needs of storage, custom catalysts are stored and are transported usually in the form of oxidation state
It is defeated, but its high active of hydrogenation catalysis of oxidation state metal is very low, it is difficult to play significant catalytic action.Present inventor couple
C4The method that fraction selective hydrogenation prepares 1- butylene has carried out research extensively and profoundly, as a result, it has been found that, by using hydrogen to nickel-
After copper-based catalysts carry out reduction treatment, nickel-copper base catalyst is carried out stablizing place by using conditioning agent and liquid phase diluent
Reason can be more conducive to the selectivity for improving the stability and reaction product of catalyst, so as to avoid the prior art
Middle reaction speed is fast, is difficult to control the defects of release strength of reaction heat;And using this method to high alkynes C4Fraction selection adds
When hydrogen, the service life of catalyst and service life also greatly increase, and increase up to one times or more.The present invention is based on the above discovery
It is accomplished.
In the preferred embodiment of the present invention, in the reduction treatment, hydrogen gas space velocity 100-250h-1;
Processing pressure is 1.5-5.0MPa, preferably 1.8-3.0MPa;130-280 DEG C for the treatment of temperature;Processing time is 10-30 hours,
Preferably 15-26 hours.
In another preferred embodiment of the present invention, in the stable processing, conditioning agent air speed 3-10h-1;Liquid
Phase dilution agent air speed is 5-15h-1;Processing pressure is 1-3.5MPa;20-100 DEG C for the treatment of temperature;Processing time is 3-8 hours.
The present invention another preferred embodiment in, in the selective hydrogenation reaction, the carbon monoxide with
The molar ratio of hydrogen is 1:(20-100), preferably 1:(30-80), more preferably 1:(40-70).
In another preferred embodiment of the present invention, in the selective hydrogenation reaction, the hydrogen and C4It evaporates
The molar ratio divided is (0.5-8):1, preferably (1-5):1, more preferably (1.2-3.0):1.
In another preferred embodiment of the present invention, in the selective hydrogenation reaction, the C4Fraction and liquid
The weight ratio of phase dilution agent is 1:(5-12), catalyst loading is calculated as 3-20h with liquid material-1, preferably 5-15h-1。
In another preferred embodiment of the present invention, the temperature of the selective hydrogenation reaction is 0-155 DEG C, preferably
It is 15-120 DEG C, more preferably 30-80 DEG C;Reaction pressure is 0.1-5.0MPa, preferably 0.5-3MPa.
In another preferred embodiment of the present invention, in the selective hydrogenation reaction, the liquid phase diluent
For ester type compound, preferably methyl formate, butyl formate, ethyl acetate, butyl acetate, isopropyl acetate, sec-butyl acetate,
It is one or more in pentyl acetate, isoamyl acetate, methyl amyl acetate, n-butyl propionate and ethyl acetoacetate, it is more excellent
It is selected as one or more in ethyl acetate, pentyl acetate and ethyl acetoacetate.
In another preferred embodiment of the present invention, in the selective hydrogenation reaction, with the gross weight of catalyst
Amount is 100% meter, and the content of nickel is 1-25wt%, preferably 3-20wt%, more preferably 5-15wt%;The content of copper is 0.1-
8wt%, preferably 0.5-6wt%, more preferably 2-5wt%.
In another preferred embodiment of the present invention, the nickel-copper base catalyst includes being supported on carrier
Nickel and copper, and optionally contain and help active metal.
According to the present invention it is possible to as the nickel of catalytically-active metals component, copper and optional active metal will be helped to pass through
Method well known in the art, such as dipping, co-precipitation, cogelledization or ion exchange, primary or described being dispersed in batches
On titanium dioxide-aluminum oxide composite carrier.
It is described to help active metal in Ag, Au, Li, Na, K, Cs, Ca, Mg, Ba, La, Ce and Nd according to the present invention
It is one or more, it is preferably one or more in K, Mg and Ag.
It is to help the content of active metal for 0-3wt% in terms of 100% by the total weight of catalyst, preferably according to the present invention
0-2.0wt%, more preferably 0.01-1.0wt%, further preferably 0.05-1.0wt%.
According to the present invention, the carrier is titanium dioxide-aluminum oxide composite material.Preferably, the titanium dioxide-aluminum oxide is multiple
The surface area of condensation material (before load active component) is 120-150m2/ g, Kong Rongwei 0.5-1.0ml/g, most several apertures are 10-
14nm.In addition, the shape of titanium dioxide-aluminum oxide composite material is not particularly limited, such as can be spherical shape, cloverleaf pattern, column
Shape, bar shaped, zigzag, preferably cloverleaf pattern.
According to the present invention, the titanium dioxide-aluminum oxide composite material can be prepared by the method for this field routine, such as
It can be prepared according to method disclosed in Chinese patent CN1184289C.
According to the present invention, in the titanium dioxide-aluminum oxide composite carrier, the content of titanium oxide is based on alumina weight
3-25wt%, preferably 5-20wt%, more preferably 6-16wt%.
In the specific embodiment of the present invention, in the reactor by nickel-copper base Catalyst packing, pressed in processing
It is 100-300h with air speed under conditions of power is 1.5-3.5MPa and treatment temperature is 150-260 DEG C-1Hydrogen is passed through to nickel-copper
Base catalyst carries out reduction treatment 15-30 hours;Then empty with liquid phase diluent again under the conditions of pressure is 0.05-2.0MPa
Speed is 5-15h-1It is passed through ethyl acetate, is 3-10h with conditioning agent air speed-1CO is added, stablizes processing 3-8 hours;Hereafter, make second
Sour pentyl ester, C4Fraction, hydrogen and CO enter after being mixed in the oil-gas mixer at reactor inlet is filled with the catalysis of nickel-copper base
It it is 15-80 DEG C in hydrogenation temperature, reaction pressure is the reaction condition of 0.1-3.0MPa in the reactor of the catalyst bed of agent
Under, C4Selection plus hydrogen occur for fraction, and generation includes the reaction product of 1- butylene, and reaction product is discharged from reactor discharge port.
Feeding is sent to gas-chromatography and carries out composition analysis, other enter centrifugal station.
By using the C of the present invention4The method that fraction selective hydrogenation prepares 1- butylene can solve to react in the prior art
The problems such as heat is difficult to remove in time, poor selectivity and short catalyst life;Improve 1- butylene selectivity, catalyst activity and steady
Qualitative height, catalyst life greatly prolong, in addition, this method, which also overcomes precious metals pd, is easy to loss and the impurity such as sulphur and arsenic
Catalyst is poisoned.
Description of the drawings
Fig. 1 is the process flow chart of embodiment 1.
Specific implementation mode
The present invention is further described with embodiment below, it is noted that these embodiments are exemplary only,
The spirit and scope of the present invention are not limited in any way.
Reactor is fixed bed reactors, and the position of material inlet and outlet is not limited to as shown in the figure.From raw material
Liquid phase material diluent, the C of tank4Fraction, conditioning agent and hydrogen enter catalyst bed after oil-gas mixer mixes, go out
The material of autoreactor enters separation phase, and hydrogenation products is selected to be analyzed using gas chromatograph.Experiment is in trickle bed reality
It is carried out in experiment device, Catalyst packing volume is 200ml, C used4Feedstock is obtained by commercial channel, and hydrogen is
Tube hydrogen, carbon monoxide are commercially available acquisition.C4Fractional composition is shown in Table 1.
Table 1C4Fractional composition
Note:Arsenic, sulfur content in material are respectively:3.45×10-6,1.8×10-4。
In the following embodiments, the definition of catalyst loading, conversion ratio and selectivity is:
When di-olefins rate is less than 85%, and alkynes conversion ratio is less than 93%, Catalyst Definitions are failure.The catalyst longevity
Life refers to that catalyst is kept for the time of non-failure state.
Embodiment 1:
For catalyst using titanium dioxide-aluminum oxide composite material as carrier, nickel-copper is active component, the gross weight based on catalyst
Amount, nickel content 20wt%, copper content 5.0wt%, it is 0.15wt% to help the content of active metal K.
Reduction treatment:In the reactor by nickel-copper base Catalyst packing, it is 2.5MPa in processing pressure and treatment temperature is
It is 200h with air speed under conditions of 220 DEG C-1It is passed through hydrogen and reduction treatment 20 hours is carried out to nickel-copper base catalyst.
Stablize processing:It is 12h with liquid phase diluent air speed under the conditions of pressure is 1.0MPa-1It is passed through liquid phase diluent, with
Adjusting agent flux is 8h-1It is passed through CO, stablizes processing 8 hours.
Selective hydrogenation reaction:Make pentyl acetate, C4Fraction, hydrogen and CO are mixed in the oil-gas mixer at reactor inlet
Enter after conjunction in the reactor for the catalyst bed for being filled with nickel-copper base catalyst, under reaction condition as shown in Table 2, C4
Selection plus hydrogen occur for fraction, and generation includes the reaction product of 1- butylene, and reaction product is discharged from reactor discharge port.Feeding is sent
Composition analysis is carried out to gas-chromatography, other enter centrifugal station.Other process conditions are shown in Table 2 and table 3.It is carried according to embodiment 1
The method continuous operation of confession 800 hours, catalyst performance does not have any change.
Embodiment 2
For catalyst using titanium dioxide-aluminum oxide composite material as carrier, nickel-copper is active component, the gross weight based on catalyst
Amount, nickel content 15wt%, copper content 3wt%.Reduction treatment is carried out in the way of embodiment 1, stablizes processing and selection
Hydrogenation reaction, specific process conditions and reaction result are as shown in table 2 and table 3.
Embodiment 3
For catalyst using titanium dioxide-aluminum oxide composite material as carrier, nickel-copper is active component, the gross weight based on catalyst
Amount, nickel content 12wt%, copper content 4.0wt%, it is 0.15wt% to help the content of active metal Ag.According to embodiment 1
Mode carries out reduction treatment, stablizes processing and selective hydrogenation reaction, 3 institute of specific process conditions and reaction result such as table 2 and table
Show.
Embodiment 4
For catalyst using titanium dioxide-aluminum oxide composite material as carrier, nickel-copper is active component, the gross weight based on catalyst
Amount, nickel content 20wt%, copper content 3.0wt%, it is 0.1wt% to help the content of active metal Mg.According to the side of embodiment 1
Formula carries out reduction treatment, stablizes processing and selective hydrogenation reaction, specific process conditions and reaction result as shown in table 2 and table 3.
Embodiment 5
For catalyst using titanium dioxide-aluminum oxide composite material as carrier, nickel-copper is active component, the gross weight based on catalyst
Amount, nickel content 15wt%, copper content 2.5wt%, it is 0.5wt% to help the content of active metal Mg.According to the side of embodiment 1
Formula carries out reduction treatment, stablizes processing and selective hydrogenation reaction, specific process conditions and reaction result as shown in table 2 and table 3.
Embodiment 6
The catalyst provided using embodiment 1, and carry out reduction treatment in the way of embodiment 1, stablize processing and choosing
Hydrogenation reaction, specific process conditions and reaction result are selected as shown in table 2 and table 3.
Embodiment 7
The catalyst provided using embodiment 1, and carry out reduction treatment in the way of embodiment 1, stablize processing and choosing
Hydrogenation reaction, specific process conditions and reaction result are selected as shown in table 2 and table 3.
Embodiment 8
The catalyst provided using embodiment 1, and carry out reduction treatment in the way of embodiment 1, stablize processing and choosing
Hydrogenation reaction, specific process conditions and reaction result are selected as shown in table 2 and table 3.
Comparative example 1
The catalyst provided using embodiment 1, and carry out reduction treatment in the way of embodiment 1, stablize processing and choosing
Hydrogenation reaction is selected, difference is that liquid phase diluent uses dodecane, and carbon monoxide tune is not used in selective hydrogenation reaction
Agent is saved, after 400 hours, catalyst indices are begun to decline continuous operation.Specific process conditions and reaction result such as table 2
Shown in table 3.
The catalyst that comparative example 2 is provided using embodiment 1, and at carrying out in the way of embodiment 1 reduction treatment, stablizing
Reason and selective hydrogenation reaction, the difference is that the molar ratio of carbon monoxide conditioning agent and hydrogen is 1:110.Specific technique item
Part and reaction result are as shown in table 2 and table 3.
Comparative example 3
The catalyst provided using embodiment 1 is directly carried out selection and added without stablizing the step of handling after reduction treatment
Hydrogen reacts.Specific process conditions and reaction result are as shown in table 2 and table 3.
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that various aspects, different specific implementation mode that the present invention records
Each section and the various features enumerated can be combined or all or part of exchange.In above-mentioned each specific implementation mode, that
A little embodiments with reference to another embodiment can be combined suitably with other embodiment, this is will be by this field skill
Art personnel are to understand.In addition, it will be understood to those of skill in the art that the description of front is only exemplary mode, not purport
In the limitation present invention.
Claims (10)
1. a kind of C4The method that fraction selective hydrogenation prepares 1- butylene, including:
In the reactor by nickel-copper base Catalyst packing, it is passed through hydrogen and reduction treatment is carried out to nickel-copper base catalyst;
It is passed through liquid phase diluent and conditioning agent the nickel-copper base catalyst after reduction treatment is carried out stablizing processing;
In the presence of the nickel-copper base catalyst through the reduction treatment and the stable processing, by C4Fraction, is adjusted liquid phase diluent
After saving agent and hydrogen mixing, it is passed through in reactor and carries out selective hydrogenation reaction, make C4Alkynes and di-olefins in fraction are
1- butylene;Wherein, the conditioning agent is carbon monoxide.
2. according to the method described in claim 1, it is characterized in that, in the reduction treatment, hydrogen gas space velocity 100-250h-1;Processing pressure is 1.5-5.0MPa, preferably 1.8-3.0MPa;130-280 DEG C for the treatment of temperature;Processing time is that 10-30 is small
When, preferably 15-26 hours.
3. method according to claim 1 or 2, which is characterized in that in the stable processing, conditioning agent air speed is 3-
10h-1;Liquid phase diluent air speed is 3-15h-1;Processing pressure is 0.05-2.0MPa;20-100 DEG C for the treatment of temperature;Processing time
It is 3-8 hours.
4. according to the method described in any one of claim 1-3, which is characterized in that in the selective hydrogenation reaction, institute
The molar ratio for stating carbon monoxide and hydrogen is 1:(20-100), preferably 1:(30-80), more preferably 1:(40-70).
5. according to the method described in any one of claim 1-4, which is characterized in that in the selective hydrogenation reaction, institute
State hydrogen and C4The molar ratio of fraction is (0.5-8):1, preferably (1-5):1, more preferably (1.2-3.0):1.
6. method according to any one of claims 1-5, which is characterized in that in the selective hydrogenation reaction, the C4
The weight ratio of fraction and liquid phase diluent is 1:(5-12), catalyst loading is calculated as 3-20h with liquid material-1, preferably 5-
15h-1。
7. according to the method described in any one of claim 1-6, which is characterized in that the temperature of the selective hydrogenation reaction is 0-
155 DEG C, preferably 15-120 DEG C, more preferably 30-80 DEG C;Reaction pressure is 0.1-5.0MPa, preferably 0.5-3MPa.
8. according to the described method of any one of claim 1-7, which is characterized in that described in the selective hydrogenation reaction
Liquid phase diluent be ester type compound, preferably methyl formate, butyl formate, ethyl acetate, butyl acetate, isopropyl acetate,
One kind in sec-butyl acetate, pentyl acetate, isoamyl acetate, methyl amyl acetate, n-butyl propionate and ethyl acetoacetate
Or it is a variety of, it is more preferably one or more in ethyl acetate, pentyl acetate and ethyl acetoacetate.
9. according to the method described in any one of claim 1-8, which is characterized in that in the selective hydrogenation reaction, to urge
The total weight of agent is 100% meter, and the content of nickel is 1-25wt%, preferably 3-20wt%, more preferably 5-15wt%;Copper
Content is 0.1-8wt%, preferably 0.5-6wt%, more preferably 2-5wt%.
10. according to the method described in claim 9, it is characterized in that, the nickel-copper base catalyst includes being supported on carrier
Nickel and copper, and optionally contain and help active metal;It is described help active metal be selected from Ag, Au, Li, Na, K, Cs, Ca, Mg, Ba, La,
It is one or more in Ce and Nd, it is preferably one or more in K, Mg and Ag;By the total weight of catalyst be 100% in terms of,
It is 0-3wt%, preferably 0-2.0wt%, more preferably 0.01-1.0wt% to help the content of active metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710223973.5A CN108689792B (en) | 2017-04-07 | 2017-04-07 | C4Method for preparing 1-butene by selective hydrogenation of fraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710223973.5A CN108689792B (en) | 2017-04-07 | 2017-04-07 | C4Method for preparing 1-butene by selective hydrogenation of fraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108689792A true CN108689792A (en) | 2018-10-23 |
| CN108689792B CN108689792B (en) | 2021-07-30 |
Family
ID=63842244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710223973.5A Active CN108689792B (en) | 2017-04-07 | 2017-04-07 | C4Method for preparing 1-butene by selective hydrogenation of fraction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108689792B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232155A (en) * | 2018-10-31 | 2019-01-18 | 内蒙古中煤蒙大新能源化工有限公司 | A method of 1- butylene yield is improved in mixing four selective hydrogenation reaction of carbon |
| CN111978140A (en) * | 2019-05-21 | 2020-11-24 | 中国石油化工股份有限公司 | Method for preparing 1-butene and application thereof |
| CN114160054A (en) * | 2022-02-14 | 2022-03-11 | 南京禾勤生物医药科技有限公司 | Continuous flow hydrogenation reaction device and selective reduction method of unsaturated aldehyde ketone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS595127A (en) * | 1982-06-29 | 1984-01-12 | Sumitomo Chem Co Ltd | Method for hydrogenating hydrocarbon without causing isomerization thereof |
| CN102285859A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Selective hydrogenation process for C4 material flow with high concentration of butadiene |
| CN103664457A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Selective hydrogenation method of crude isopentene |
| CN104689830A (en) * | 2013-12-09 | 2015-06-10 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of alkyne and dialkene in mixed olefins |
-
2017
- 2017-04-07 CN CN201710223973.5A patent/CN108689792B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS595127A (en) * | 1982-06-29 | 1984-01-12 | Sumitomo Chem Co Ltd | Method for hydrogenating hydrocarbon without causing isomerization thereof |
| CN102285859A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Selective hydrogenation process for C4 material flow with high concentration of butadiene |
| CN103664457A (en) * | 2012-09-25 | 2014-03-26 | 中国石油化工股份有限公司 | Selective hydrogenation method of crude isopentene |
| CN104689830A (en) * | 2013-12-09 | 2015-06-10 | 中国石油化工股份有限公司 | Catalyst for selective hydrogenation of alkyne and dialkene in mixed olefins |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232155A (en) * | 2018-10-31 | 2019-01-18 | 内蒙古中煤蒙大新能源化工有限公司 | A method of 1- butylene yield is improved in mixing four selective hydrogenation reaction of carbon |
| CN111978140A (en) * | 2019-05-21 | 2020-11-24 | 中国石油化工股份有限公司 | Method for preparing 1-butene and application thereof |
| CN111978140B (en) * | 2019-05-21 | 2022-11-18 | 中国石油化工股份有限公司 | Method for preparing 1-butene and application thereof |
| CN114160054A (en) * | 2022-02-14 | 2022-03-11 | 南京禾勤生物医药科技有限公司 | Continuous flow hydrogenation reaction device and selective reduction method of unsaturated aldehyde ketone |
| CN114160054B (en) * | 2022-02-14 | 2022-04-26 | 南京禾勤生物医药科技有限公司 | Continuous flow hydrogenation reaction device and selective reduction method of unsaturated aldehyde ketone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108689792B (en) | 2021-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106861691B (en) | A kind of preparation of hydrogenation catalyst and hydrogenation catalyst and application | |
| CN102847544B (en) | Catalytic agent for preparing ethanol by using acetic acid hydrogenation and preparation method thereof | |
| CN102285859B (en) | Selective hydrogenation process for C4 material flow with high concentration of butadiene | |
| CN101884922B (en) | Method for preparing propylene catalyst by propane dehydrogenation process | |
| CN100553770C (en) | The Raney nickel that is used for selective hydrogenation | |
| CN104096573B (en) | Preparation method of high-coking-resistance selective hydrogenation catalyst | |
| CN104096572B (en) | Selective hydrogenation catalyst with improved coking resistance | |
| CN103121896B (en) | Method for converting polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons | |
| CN108689792A (en) | A kind of C4The method that fraction selective hydrogenation prepares 1- butylene | |
| CN101279279B (en) | Method for selective hydrogenation | |
| CN102206132B (en) | Carbon three-fraction selective hydrogenation method | |
| CN106582706B (en) | Selective hydrogenation of butadiene catalyst | |
| CN102614870B (en) | Vinylacetylene hydrogenation catalyst and preparation method thereof | |
| CN104098425A (en) | Selective hydrogenation method for carbon-dioxide fraction | |
| CN104098427A (en) | Carbon three-fraction selective hydrogenation method | |
| CN102847535A (en) | Catalyst for preparation of ethanol through acetic acid hydrogenation and preparation method thereof | |
| CN103127935B (en) | Mesoporous carbon supported type copper-based catalyst, preparation method thereof and application thereof | |
| CN104098426A (en) | Method for selective hydrogenation of carbon-containing distillate | |
| CN105642324B (en) | A kind of base metal selective hydrocatalyst and its preparation method and application | |
| CN101906014B (en) | Selective hydrogenation method for carbon-containing fraction | |
| CN108689789A (en) | A kind of C4The method that fraction selective hydrogenation prepares 1- butylene | |
| CN105363484B (en) | Catalyst for dehydrogenating low-carbon alkane producing light olefins and its application | |
| CN105536808B (en) | A kind of hydrogenation catalyst and its preparation method and application | |
| CN105582922B (en) | Catalyst for dehydrogenating low-carbon alkane | |
| CN105582920B (en) | Catalyst for dehydrogenation of low-carbon paraffin and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |