CN106673938B - A method of cyclopentene is produced by cyclopentadiene selective hydrogenation - Google Patents
A method of cyclopentene is produced by cyclopentadiene selective hydrogenation Download PDFInfo
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- 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
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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Abstract
The present invention discloses a kind of method by cyclopentadiene selective hydrogenation production cyclopentene, include the following steps: to be used as hydrogenation reaction raw material after (1) raw material containing cyclopentadiene is mixed with solvent, then continues through the fixed bed reactors for being filled with selective hydrocatalyst after mixing with hydrogen；The selective hydrocatalyst is made of the amorphous nickel phosphide of active component, alumina support and auxiliary agent cerium, without Ni in the XRD spectra of the catalyst2P or Ni12P5Diffraction maximum；(2) it is passed through first rectifying column after step (1) hydrogenation products being isolated hydrogen, tower bottom produces heavy constituent impurity, and overhead is produced as the charging of Second distillation column；(3) step (2) first rectifying column overhead is passed through Second distillation column, tower bottom produces cyclopentene product, and as circulation solvent, return step (1) is middle to be recycled overhead extraction light component.This method can be improved the conversion ratio of cyclopentadiene and the selectivity of cyclopentene.
Description
Technical field
The present invention relates to a kind of methods by cyclopentadiene selective hydrogenation production cyclopentene.
Background technique
Cyclopentene is a kind of important fine chemical material, can be used for preparing cyclopentanol, cyclopentanone, glutaraldehyde, bromo ring
The high value added products such as pentane, chlorocyclopentane, but also be the primary raw material of polycyclic alkene high molecular polymer.
It is made currently, cyclopentene mainly passes through cyclopentadiene process for selective hydrogenation.Cyclopentadiene mostlys come from ethylene
Crack by-product C5 fraction.Because at room temperature, cyclopentadiene is easy to happen self-polymeric reaction and generates relatively more stable bicyclic penta
Diene, therefore industrial cyclopentadiene is usually stored with dimeric forms.In use, only needing dicyclopentadiene carrying out the normal of routine
Pressure distillation collects tower top temperature in 40~44 DEG C of fraction, cyclopentadiene can be obtained.
Active double bond there are two containing in cyclopentadiene molecules, under typical hydroconversion condition, a double bond is hydrogenated first
Cyclopentene, the double bond in the cyclopentene molecule of generation are generated, it also occur that further hydrogenation reaction generates pentamethylene.Due to ring
The reaction activity that pentadiene is hydrogenated to cyclopentene is more slightly lower than the reaction activity that cyclopentene is hydrogenated to pentamethylene, therefore only
Have and react at a lower temperature, reaction could more advantageously be made to rest on the stage for generating cyclopentene.
Cyclopentadiene hydrogenating can be divided into autoclave interval hydrogenation technique and fixed bed continuously hydrogen adding technique by type of reactor.Example
Such as CN1417179, CN1462734 and CN102728386, a kind of cyclopentadiene interval using tank reactor is individually disclosed
Hydrogenation technique.Above-mentioned interval hydrogenation technique is not easy point due to using powdered or catalyst particle there are catalyst and product
From problem, be not suitable for large-scale continuous production.
Cyclopentadiene fixed bed hydrogenation technique can be divided into gas phase hydrogenation technique and liquid-phase hydrogenatin technique by reaction condition.Document
(gas chemical industry, 2012,37, 20) and document (Hebei University of Technology's journal, 2011,40, 40) and a kind of ring penta is reported respectively
The method that diene gas phase hydrogenation prepares cyclopentene, this method reaction temperature are unfavorable because reaction temperature is higher usually above 100 DEG C
The reaction of pentamethylene is generated in the further hydrogenation reaction of control cyclopentene, the pentamethylene of generation will definitely increase follow-up separation process
Load.In addition, reactor volume needed for gas phase hydrogenation technique is larger, equipment investment is costly.
Cyclopentadiene fixed bed liquid-phase hydrogenatin is the preferred technical solution in this field.For example, US3994986, CN1011877
With document (petrochemical technology and application, 2009,27,218), a kind of cyclopentadiene using load type palladium catalyst is individually disclosed
The method that fixed bed hydrogenation produces cyclopentene, it is expensive because of precious metals pd, prior art there are catalyst cost compared with
High deficiency.
Summary of the invention
For deficiency existing for existing cyclopentadiene fixed bed liquid phase hydrogenation technology, the present invention provides a kind of using non-expensive
The method by cyclopentadiene selective hydrogenation production cyclopentene of metallic catalyst.
A kind of method by cyclopentadiene selective hydrogenation production cyclopentene of the present invention, includes the following steps:
(1) it is used as hydrogenation reaction raw material after raw material containing cyclopentadiene is mixed with solvent, then is continued through after being mixed with hydrogen
It is filled with the fixed bed reactors of selective hydrocatalyst；The selective hydrocatalyst is by the amorphous phosphatization of active component
Nickel, alumina support and auxiliary agent cerium form, without Ni in the XRD spectra of the catalyst2P or Ni12P5Diffraction maximum, finally urging
In agent, the weight content of nickel accounts for the 10-15% of total catalyst weight, phosphorus in terms of metallic nickel in the amorphous nickel phosphide of active component
It is 2.0-2.4:1 with the molar ratio of nickel, the molar ratio of auxiliary agent cerium and nickel is 0.01-0.05:1, remaining is carrier；
(2) it is passed through first rectifying column after step (1) hydrogenation products being isolated hydrogen, tower bottom produces heavy constituent impurity, tower
The charging that distillate is pushed up as Second distillation column produces；
(3) step (2) first rectifying column overhead is passed through Second distillation column, tower bottom produces cyclopentene product, tower
As circulation solvent, return step (1) is middle to be recycled top extraction light component.
In the method for the present invention step (1), selective hydrocatalyst the preparation method is as follows:
(1) acid nickel salt aqueous solution is prepared, the salt and citric acid of diammonium hydrogen phosphate, the X containing auxiliary agent is then added, makes phosphorus/nickel
Molar ratio is 2.5-3.0, and X/ nickel molar ratio is 0.01-0.05:1, and citric acid/nickel molar ratio is 1.0-2.0:1, obtains solution A,
The aluminium oxide or aluminium hydroxide of metering are added into acquired solution A, forms slurries B, then slow evaporating water, forms dry glue C；
(2) gained dry glue C in step (1) is placed under the atmosphere of inert gases continuously flowed, is warming up to 250-350 DEG C
Under, and in handling 5-10 hours at this temperature, make the citric acid in dry glue that pyrolysis occur, obtains catalyst precursor D；
(3) catalyst precursor D obtained in step (2) is formed, molding rear catalyst after drying, is obtained into
Type catalyst precursor E；
(4) preformed catalyst presoma E obtained in step (3) is restored in atmosphere of hydrogen, reduction temperature is
300-400 DEG C, it is the blunt of 0.5-1.0% with oxygen concentration that the recovery time, which is that 1-10 h is cooled to room temperature after catalyst reduction,
Change gas and 0.5-1 h is passivated to catalyst at room temperature, obtains selectivity hydrogenation catalyst.
In the method for the present invention step (1), ethyl methyl ether and 20~90% that the solvent is 10~80% by mass fraction
Ether composition.As the further preferred of the method for the present invention, solvent as described in step (1) is 20~80% by mass fraction
Ethyl methyl ether and 20~80% ether composition.
In the method for the present invention step (1), the raw material containing cyclopentadiene cracks institute or methyl from dicyclopentadiene
The cracking of cycle pentadiene dimer, wherein the mass fraction of cyclopentadiene or methyl cyclopentadiene is 98% or more.
In the method for the present invention step (1), in the hydrogenation reaction raw material, the mass fraction of cyclopentadiene is 1~25%,
It is preferred that 10~25%.
In the method for the present invention step (1), the reaction condition: reactor inlet temperature is 20~60 DEG C, reaction pressure
For 0.5~1.1 MPa, mass space velocity is 1~4 h-1, the molar ratio of hydrogen and cyclopentadiene is 1.1~2.0；Preferred reactor
Inlet temperature is 40~60 DEG C, and reaction pressure is 0.9~1.1 MPa, and mass space velocity is 2~4 h-1, hydrogen and cyclopentadiene
Molar ratio is 1.1~1.3.
Bottom temperature is 215~255 DEG C in the method for the present invention step (2), and tower top temperature is 60~85 DEG C, and tower top pressure is
0.50~0.65 MPa.
In the method for the present invention step (2), the theoretical cam curve of the first rectifying column is 10~20 pieces.As the present invention
Method it is further preferred, the theoretical cam curve of the first rectifying column is 15 pieces, column plate can be set in first rectifying column,
Filler can also be loaded.
In the method for the present invention step (3), bottom temperature is 95~120 DEG C, and tower top temperature is 55~80 DEG C, and tower top pressure is
0.45~0.70 MPa,
In the method for the present invention step (3), the theoretical cam curve of the Second distillation column is 60~70 pieces.As the present invention
Method it is further preferred, the theoretical cam curve of the Second distillation column is 65 pieces, column plate can be set in Second distillation column,
Filler can also be loaded.
It is strong exothermal reaction that cyclopentadiene hydrogenating generation cyclopentene and cyclopentene, which are hydrogenated to pentamethylene, in typical liquid
Under phase hydroconversion condition, the reaction heat of the two is above 100 kJ/mol, and the thermal discharge of the latter is bigger.Generally, it is considered that if reaction
Temperature is higher than 120 DEG C, and the reaction speed that cyclopentene is hydrogenated to pentamethylene can be dramatically speeded up, and on the one hand causes cyclopentene selective
On the one hand decline is enabled because pentamethylene is close with product cyclopentene boiling point, will affect cyclopentene product quality and increase subsequent product
Separating difficulty.Therefore, it takes reaction heat away and control reaction carries out at a lower temperature, will produce and divide with high selectivity
Key from purification cyclopentene.
One of key of the invention is to use by the amorphous nickel phosphide of active component, alumina support and auxiliary agent cerium group
At base metal selective hydrocatalyst.It is compared compared with the precious metals pd catalyst used in technical solution, the present invention urges
Agent has at low cost, the selectively high advantage of cyclopentene.
In addition, the solvent that one of another key of the invention is that the present invention uses is made of ethyl methyl ether and ether.First and second
Ether boiling point under the used reaction pressure of the present invention is 79.0~87.9 DEG C.Under the reaction condition that the present invention uses, ring penta 2
Alkene adds hydrogen heat release that ethyl methyl ether is made to gasify, and controls reaction bed temperature using the gasification latent heat of dimethyl ether.By adjusting solvent
The content of middle ethyl methyl ether can make reaction bed temperature steadily control the selection that ensure that the present invention is used at 80~90 DEG C
Property hydrogenation catalyst given full play to itself superior catalytic performance, make pentamethylene by-product selectively control below 0.5%.
Since the solvent that the present invention uses is made of ethyl methyl ether and ether, the boiling point of the two under normal pressure is below ring penta 2
Alkene raw material and cyclopentene product, so that product separation process greatly simplifies.Compared with the existing technology, the method for the present invention eliminates molten
Agent separating step, solvent and unreacted cyclopentadiene raw material are produced jointly with the tower top light component of Second distillation column, on the one hand
It can be used as circulation solvent of the invention, on the other hand unreacted cyclopentadiene raw material can also be taken back to hydrogenator continue instead
It answers.After device reaches stable state, the unreacted cyclopentadiene raw material of solvent and part recycles in a device, and fresh feed can be improved
The conversion ratio of middle cyclopentadiene, and without supplementing fresh solvent.
Detailed description of the invention
Fig. 1 is flow diagram of the present invention.
In Fig. 1,1- raw material storage tank, 2- feed pump, 3- hydrogenator, 4- gas-liquid separator, 5- feed pump, the first essence of 6-
Evaporate tower, 7- Second distillation column.
101~111 be logistics in Fig. 1, wherein 101- raw material containing cyclopentadiene, 102- fresh solvent, 103- hydrogenation reaction
Raw material, 104- hydrogen, 105- hydrogenation reaction effluent, 106- circulating hydrogen, the charging of 107- first rectifying column, 108- heavy constituent are miscellaneous
Matter, the charging of 109- Second distillation column, 110- cyclopentene product, 111- recycle solvent.
Fig. 2 is the XRD spectra for the selective hydrocatalyst that the present invention uses.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and embodiments.It is below only the present invention preferably specific implementation
Mode, but protection scope of the present invention is not limited to this, and anyone skilled in the art can readily occur in variation
Or replacement, it should all cover in the protection scope of this patent.
Raw material containing cyclopentadiene (101) as shown in Figure 1 and fresh solvent (102) and circulation solvent (111) are in raw material storage tank 1
After middle mixing, form hydrogenation reaction raw material (103)；The flow for adjusting each stock material, makes the quality of cyclopentadiene in hydrogenating materials
Score is 10~25%, and the mass fraction of ethyl methyl ether is 20~80% in solvent；Hydrogenation reaction raw material (103) warp and hydrogen (104)
Enter hydrogenator 2 after mixing, be 40~60 DEG C in reactor inlet temperature under the action of selective hydrocatalyst,
Reaction pressure is 0.9~1.1 MPa, and mass space velocity is 2~4 h-1, item that the molar ratio of hydrogen and cyclopentadiene is 1.1~1.3
Under part, cyclopentadiene selective hydrogenation occurs；The hydrogenation reaction effluent (105) of generation carries out in knockout drum 4
Gas-liquid separation, isolating hydrogen (106) can be recycled；Isolate charging of the liquid-phase hydrogenatin product as first rectifying column 6
(107), bottom temperature is 215~255 DEG C, and tower top temperature is 60~85 DEG C, and tower top pressure is the condition of 0.50~0.65 MPa
Lower operation, tower bottom produce heavy constituent impurity (108)；Charging (109) of the first rectifying column overhead as Second distillation column,
Bottom temperature is 95~120 DEG C, and tower top temperature is 55~80 DEG C, and tower top pressure operates under conditions of being 0.45~0.70 MPa,
Tower bottom produces cyclopentene product (110), and tower top distillates light component as circulation solvent (111), and returning to recycle in raw material storage tank 1 makes
With.
Effect of the invention is further illustrated with reference to embodiments.
Embodiment 1-4
Catalyst preparation step (1)
Six water nickel nitrates being weighed by weight shown in table 1,500 ml deionized waters being added, 0.05 mol/L nitric acid is then added
PH value is adjusted to 2-3, diammonium hydrogen phosphate, cerium nitrate hexahydrate, Citric Acid Mono then is added by weight shown in table 1 again, then exists
It stirs 1 hour at room temperature, respectively obtains solution A 1-A4.
Table 1
Aluminium hydrate powder 77g, 72g, 67g and 78g is added into solution A 1-A4 respectively, is allowed to dispersion in the solution, respectively
Obtain slurries B1-B4, then by gained slurries move into Rotary Evaporators at 85 DEG C evaporating water, then dried at 120 DEG C
It is 24 hours dry, obtain dry glue C1-C4.
Catalyst preparation step (2)
Dry glue C1-C4 is placed in tubular heater, in the N continuously flowed2In atmosphere, 3- is handled at 250-300 DEG C
10 hours, make the citric acid in dry glue that pyrolysis occur made temperature be reduced to room temperature after the required processing time to be achieved
(25 DEG C) taking-ups, respectively obtain catalyst precursor D1-D4.Treatment conditions are shown in Table 2.
Table 2
Catalyst preparation step (3)
By catalyst precursor D1-D4 and suitable nitric acid, water, sesbania powder mixer kneader, extruded moulding.Extruded moulding
Afterwards, gained extrudate is first dried 24 hours at room temperature, is dried 24 hours then at 120 DEG C, is respectively obtained preformed catalyst forerunner
Body E1-E4.
Catalyst preparation step (4)
By condition listed by table 3, preformed catalyst presoma E1-E4 is respectively placed in tubular heater, in continuous flow
Dynamic H2In atmosphere, restored 5-10 hours at 350-400 DEG C.After the required recovery time to be achieved, temperature is made to be reduced to room
Warm (25 DEG C), the O for being then 0.75% with oxygen volumetric concentration2/N2Passivating gas is passivated processing 0.8 hour to catalyst, obtains
To the catalyst F1-F4 of final passivation state.
Table 3
Passivation state catalyst F1-F4 is characterized using X-ray diffraction (XRD), the results showed that nickel phosphide on catalyst
In amorphous state.Fig. 2 shows the XRD spectras of F1-F4 catalyst.
Passivation state catalyst composition is measured using inductively coupled plasma atomic emission (ICP).Ni loading is with Ni gold
Belong to weight and account for total catalyst weight percentages, P content and Ce content are indicated respectively with P/Ni, Ce/Ni molar ratio.F1 catalysis
Agent: Ni content 10.12%, P/Ni=2.35, Ce/Ni=0.01；F2 catalyst: Ni content 12.51%, P/Ni=2.24, Ce/Ni=
0.03；F3 catalyst: Ni content 14.96%, P/Ni=2.06, Ce/Ni=0.05；F4 catalyst: Ni content 10.23%, P/Ni=
2.14, Ce/Ni=0.02.
Embodiment 5-9
Raw material containing cyclopentadiene used in various embodiments of the present invention is cracked from dicyclopentadiene, wherein cyclopentadiene
Mass fraction is 98%, remaining is dicyclopentadiene.
The process flow that various embodiments of the present invention use is as shown in Figure 1.Table 4 lists the hydrogenation reaction raw material of each embodiment
(103) composition.
Table 4
Table 5 lists the operating condition of various embodiments of the present invention hydrogenator.
Table 5
In order to illustrate the effect of the method for the present invention, using cyclopentadiene conversion per pass, cyclopentene one way selectivity and
Beneficial effect of the one way selective presentation the method for the present invention of pentamethylene to cyclopentadiene selective hydrogenation.
Table 6 lists various embodiments of the present invention cyclopentadiene selective hydrogenation one way reaction result.The method of the present invention passes through
The mass fraction for controlling ethyl methyl ether in solvent makes ethyl methyl ether absorb cyclopentadiene hydrogenating reaction under the conditions of the reaction according to the invention and releases
Heat and gasify, reaction bed temperature is controlled using the gasification latent heat of ethyl methyl ether, maintains hydrogenation reaction lower
At a temperature of carry out.As shown in table 6, the control of hydrogenator outlet temperature can be made at 80~90 DEG C using the method for the present invention, favorably
Itself superior catalytic performance has been given full play in the selective hydrocatalyst that uses of the present invention, therefore by cyclopentadiene depth
The one way for being hydrogenated to pentamethylene is selectively controlled 0.5% hereinafter, obtaining higher cyclopentene product selectivity.
Table 6
Table 7 lists hydrogenation products separation and process for refining condition, the process flow such as Fig. 1 institute of various embodiments of the present invention
Show.The theoretical cam curve of first rectifying column is 15 pieces, and the theoretical cam curve of Second distillation column is 65 pieces.Various embodiments of the present invention institute
Distillation tray can be set in the rectifying column of use, can also load filler.Plate column and packed tower are those skilled in the art
Known technology contents.Various embodiments of the present invention are all made of packed tower, and filler used is metal Pall ring filler.
Table 7
Table 8 lists cyclopentene product (110) and recycles the composition of solvent (111).The dress invested to build using the method for the present invention
It sets after reaching stable state, without being supplemented fresh solvent.As shown in table 9, another beneficial effect of the present invention is unreacted rings penta
Diene returns hydrogenator the reaction was continued with circulation solvent, the total conversion of cyclopentadiene can be improved 99% or more, ring penta
Alkene total yield of products is improved to 97% or more.
Table 8
Table 9
Claims (11)
1. a kind of method by cyclopentadiene selective hydrogenation production cyclopentene, characterized by the following steps:
(1) it is used as hydrogenation reaction raw material after raw material containing cyclopentadiene is mixed with solvent, then continues through filling after mixing with hydrogen
The fixed bed reactors of selective hydrogenation catalyst；The selective hydrocatalyst by the amorphous nickel phosphide of active component,
Alumina support and auxiliary agent cerium form, without Ni in the XRD spectra of the catalyst2P or Ni12P5Diffraction maximum, be finally catalyzed
In agent, the weight content of nickel accounts for the 10-15% of total catalyst weight in terms of metallic nickel in the amorphous nickel phosphide of active component, phosphorus with
The molar ratio of nickel is 2.0-2.4:1, and the molar ratio of auxiliary agent cerium and nickel is 0.01-0.05:1, remaining is carrier；
(2) it is passed through first rectifying column after step (1) hydrogenation products being isolated hydrogen, tower bottom produces heavy constituent impurity, and tower top evaporates
Object is produced as the charging of Second distillation column out；
(3) step (2) first rectifying column overhead is passed through Second distillation column, tower bottom produces cyclopentene product, and tower top is adopted
As circulation solvent, return step (1) is middle to be recycled light component out；
Wherein, reactor inlet temperature is 20~60 DEG C in step (1), and reaction pressure is 0.5~1.1 MPa, mass space velocity 1
~4 h-1, the molar ratio of hydrogen and cyclopentadiene is 1.1~2.0；The first that solvent is 10~80% by mass fraction in step (1)
Ether and 20~90% ether composition；In step (1), selective hydrocatalyst the preparation method is as follows:
(1) acid nickel salt aqueous solution is prepared, the salt and citric acid of diammonium hydrogen phosphate, the cerium containing auxiliary agent is then added, makes phosphorus/nickel mole
Than for 2.5-3.0, cerium/nickel molar ratio is 0.01-0.05:1, citric acid/nickel molar ratio is 1.0-2.0:1, obtains solution A, to
The aluminium oxide or aluminium hydroxide of metering are added in acquired solution A, forms slurries B, then slow evaporating water, forms dry glue C；
(2) gained dry glue C in step (1) is placed under the atmosphere of inert gases continuously flowed, is warming up at 250-350 DEG C, and
In handling 5-10 hours at this temperature, makes the citric acid in dry glue that pyrolysis occur, obtain catalyst precursor D；
(3) catalyst precursor D obtained in step (2) is formed, molding rear catalyst after drying, obtains molding and urges
Agent presoma E；
(4) preformed catalyst presoma E obtained in step (3) is restored in atmosphere of hydrogen, reduction temperature 300-
400 DEG C, it is the passivating gas of 0.5-1.0% with oxygen concentration that the recovery time, which is that 1-10 h is cooled to room temperature after catalyst reduction,
0.5-1 h is passivated to catalyst at room temperature, obtains selectivity hydrogenation catalyst.
2. according to the method described in claim 1, reaction pressure is it is characterized by: reactor inlet temperature is 40~60 DEG C
0.9~1.1 MPa, mass space velocity are 2~4 h-1, the molar ratio of hydrogen and cyclopentadiene is 1.1~1.3.
3. according to the method described in claim 1, it is characterized by: the ethyl methyl ether and 20 that solvent is 20~80% by mass fraction
~80% ether composition.
4. according to the method described in claim 1, it is characterized by: raw material containing cyclopentadiene is from bicyclic penta in step (1)
Diene cracking, wherein the mass fraction of cyclopentadiene is 98% or more.
5. according to the method described in claim 1, it is characterized by: in step (1) in hydrogenation reaction raw material, the matter of cyclopentadiene
Measuring score is 1~25%.
6. according to the method described in claim 1, it is characterized by: in step (2) bottom temperature be 215~255 DEG C, tower top temperature
Degree is 60~85 DEG C, and tower top pressure is 0.50~0.65 MPa.
7. according to the method described in claim 1, it is characterized by: the theoretical cam curve of first rectifying column is 10 in step (2)
~20 pieces.
8. according to the method described in claim 1, it is characterized by: column plate or filling is arranged in step (2) in first rectifying column
Filler.
9. according to the method described in claim 1, it is characterized by: in step (3) bottom temperature be 95~120 DEG C, tower top temperature
Degree is 55~80 DEG C, and tower top pressure is 0.45~0.70 MPa.
10. according to the method described in claim 1, it is characterized by: the theoretical cam curve of step (3) Second distillation column be 60~
70 pieces.
11. according to the method described in claim 1, it is characterized by: column plate or filling is arranged in step (3) in Second distillation column
Filler.
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| CN107684919B (en) * | 2017-08-03 | 2020-05-19 | 大连理工大学 | Loaded Ni3P catalyst and preparation method and application thereof |
| CN109865519B (en) * | 2017-12-01 | 2021-11-30 | 中国石化扬子石油化工有限公司 | Ruthenium modified activated carbon supported nickel catalyst, preparation method and application thereof |
| CN111085273B (en) * | 2018-10-24 | 2023-02-28 | 中国石油化工股份有限公司 | Hydrogenation catalyst for preparing cyclopentene by cyclopentadiene hydrogenation, preparation method and hydrogenation method thereof |
| CN111889036B (en) * | 2019-05-05 | 2023-01-10 | 中国石油集团工程股份有限公司 | Cyclopentadiene fixed bed catalytic hydrogenation reaction device, system and method |
| CN115806462A (en) * | 2021-09-14 | 2023-03-17 | 中国科学院大连化学物理研究所 | Cyclopentanol production process, device and method |
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| CN1417179A (en) * | 2001-11-08 | 2003-05-14 | 中国石化上海石油化工股份有限公司 | Cyclopentadiene hydrogenating precess of preparing cyclopentene |
| CN101474568A (en) * | 2009-01-14 | 2009-07-08 | 大连理工大学 | Duplex metal phosphide catalyst for selective hydrogenation and olefin hydrocarbon removal as well as preparation method thereof |
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| Influence of TiO2 and CeO2 on the hydrogenation activity of bulk Ni2P;Xiang Li et al.;《Catalysis Communications》;20100613;第11卷;第1129-1132页 |
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