CN106673938A - Method for producing cyclopentene by selective hydrogenation of cyclopentadiene - Google Patents
Method for producing cyclopentene by selective hydrogenation of cyclopentadiene Download PDFInfo
- Publication number
- CN106673938A CN106673938A CN201510750175.9A CN201510750175A CN106673938A CN 106673938 A CN106673938 A CN 106673938A CN 201510750175 A CN201510750175 A CN 201510750175A CN 106673938 A CN106673938 A CN 106673938A
- Authority
- CN
- China
- Prior art keywords
- cyclopentadiene
- catalyst
- column
- nickel
- temperature
- 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
- C07C5/03—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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
Abstract
The invention discloses a method for producing cyclopentene by selective hydrogenation of cyclopentadiene. The method comprises the following steps: (1) a cyclopentadiene-containing raw material is mixed with a solvent to be used as a raw material of a hydrogenation reaction, and then the raw material is mixed with hydrogen and the mixture continuously passes through a fixed bed reactor filled with a selective hydrogenation catalyst consisting of an active component amorphous nickel phosphide, an alumina carrier and a promoter cerium and with no diffraction peak of Ni2P or Ni12P5 in the XRD spectrogram thereof; (2) the hydrogenated product in the step (1) is isolated from hydrogen and then introduced into a first rectification column, heavy component impurities are extracted out of the bottom of the column, and a distillate at the top of the column is withdrawn as feedstock of a second rectification column; and (3) a distillate at the top of the first rectification column is introduced into the second rectification column, a cyclopentene product is withdrawn at the bottom of the column, and a light component is withdrawn from the top of the column to be used as a recycle solvent and return to step (1) for recycling. By the method, the conversion rate of cyclopentadiene and the selectivity of cyclopentene can be enhanced.
Description
Technical field
The present invention relates to a kind of method for producing cyclopentenes by cyclopentadiene selective hydrogenation.
Background technology
Cyclopentenes are a kind of important fine chemical materials, can be used to prepare the high value added products such as cyclopentanol, Ketocyclopentane, glutaraldehyde, bromocyclopentane, chlorocyclopentane, but also are the primary raw materials of polycyclic alkene high molecular polymer.
At present, cyclopentenes are mainly obtained by cyclopentadiene process for selective hydrogenation.Cyclopentadiene mostlys come from cracking of ethylene by-product C5 fraction.Because at room temperature, cyclopentadiene is susceptible to self-polymeric reaction and generates relatively more stable dicyclopentadiene, therefore industrial cyclopentadiene generally with dimeric forms storage.When using, it is only necessary to which dicyclopentadiene is carried out into conventional air-distillation, fraction of the tower top temperature at 40～44 DEG C is collected, you can obtain cyclopentadiene.
Containing two active double bonds in cyclopentadiene molecules, under typical hydroconversion condition, one first double bond is hydrogenated generation cyclopentenes, the double bond in the cyclopentenes molecule of generation, it also occur that further hydrogenation reaction generates Pentamethylene..Because the reaction activity that cyclopentadiene hydrogenating generates cyclopentenes is more lower slightly than the reaction activity that cyclopentenes are hydrogenated to Pentamethylene., therefore only react at a lower temperature, could more advantageously make reaction rest on the stage for generating cyclopentenes.
Cyclopentadiene hydrogenating can be divided into autoclave interval hydrogenation technique and fixed bed continuously hydrogen adding technique by type of reactor.Such as CN1417179, CN1462734 and CN102728386, individually disclose a kind of cyclopentadiene interval hydrogenation technique of employing tank reactor.Above-mentioned interval hydrogenation technique is not suitable for large-scale continuous production due to using powder or catalyst particle, there is the difficult problem that catalyst is not readily separated with product.
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）A kind of method that cyclopentadiene gas phase hydrogenation prepares cyclopentenes is reported respectively, the method reaction temperature is usually above 100 DEG C, because reaction temperature is higher, it is unfavorable for controlling the reaction that the further hydrogenation reaction of cyclopentenes generates Pentamethylene., the Pentamethylene. of generation will certainly increase the load of follow-up separation process.Additionally, the reactor volume needed for gas phase hydrogenation technique is larger, equipment investment is costly.
Cyclopentadiene fixed bed liquid-phase hydrogenatin is the preferred technical scheme in this area.For example, US3994986, CN1011877 and document（Petrochemical technology and application, 2009,27,218）, the method that a kind of cyclopentadiene fixed bed hydrogenation of employing load type palladium catalyst produces cyclopentenes is individually disclosed, expensive because of precious metals pd, there is the relatively costly deficiency of catalyst in prior art.
The content of the invention
For the deficiency that existing cyclopentadiene fixed bed liquid phase hydrogenation technology is present, the invention provides a kind of method for producing cyclopentenes by cyclopentadiene selective hydrogenation of employing non-precious metal catalyst.
A kind of method for producing cyclopentenes by cyclopentadiene selective hydrogenation of the present invention, comprises the steps：
（1）Raw material containing cyclopentadiene mix with solvent after as hydrogenation reaction raw material, then the fixed bed reactors for being filled with selective hydrocatalyst are continued through after mixing with hydrogen；The selective hydrocatalyst is made up 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, in the final catalyst, 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, and phosphorus is 2.0-2.4 with the mol ratio of nickel:1, auxiliary agent cerium is 0.01-0.05 with the mol ratio of nickel:1, remaining is carrier；
（2）By step（1）Hydrogenation products are isolated and be passed through after hydrogen first rectifying column, and bottom of towe extraction heavy constituent impurity, overhead is produced as the charging of Second distillation column；
（3）By step（2）First rectifying column overhead is passed through Second distillation column, and bottom of towe produces cyclopentenes product, and overhead extraction light component is used as circulating solvent, return to step（1）Middle recycling.
The inventive method step（1）In, the preparation method of selective hydrocatalyst is as follows：
（1）Acid nickel salt aqueous solution is prepared, diammonium phosphate, the salt containing auxiliary agent X and citric acid is subsequently adding, makes phosphorus/nickel mol ratio be 2.5-3.0, X/ nickel mol ratio is 0.01-0.05:1, citric acid/nickel mol ratio is 1.0-2.0:1, solution A is obtained, the aluminium oxide or aluminium hydroxide of metering are added in resulting solution A, serosity B is formed, then slow evaporating water, form dry glue C；
（2）By step（1）Middle gained dry glue C is placed under the atmosphere of inert gases of continuous flowing, is warming up at 250-350 DEG C, and in 5-10 hours are processed at this temperature, makes the citric acid in dry glue that pyrolysis to occur, and obtains catalyst precursor D；
（3）By step（2）In the catalyst precursor D that obtains carry out molding, after molding rear catalyst drying, obtain preformed catalyst presoma E；
（4）By step（3）In the preformed catalyst presoma E that obtains reduced in atmosphere of hydrogen, reduction temperature is 300-400 DEG C, recovery time is 1-10 h, after catalyst reduction, it is cooled to room temperature, passivating gas with oxygen concentration as 0.5-1.0% are passivated at room temperature 0.5-1 h to catalyst, obtain selectivity hydrogenation catalyst.
The inventive method step（1）In, described solvent is made up of the ethyl methyl ether and 20～90% ether that mass fraction is 10～80%.As the further preferred of the inventive method, step（1）Described in solvent be made up of the ethyl methyl ether and 20～80% ether that mass fraction is 20～80%.
The inventive method step（1）In, described raw material containing cyclopentadiene come from dicyclopentadiene cracking institute or methyl cycle pentadiene dimer cracking, wherein the mass fraction of cyclopentadiene or methyl cyclopentadiene be more than 98%.
The inventive method step（1）In, in described hydrogenation reaction raw material, the mass fraction of cyclopentadiene is 1～25%, preferably 10～25%.
The inventive method step（1）In, described reaction condition：Reactor inlet temperature is 20～60 DEG C, and reaction pressure is 0.5～1.1 MPa, and mass space velocity is 1～4 h-1, hydrogen is 1.1～2.0 with the mol ratio of cyclopentadiene；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 is 1.1～1.3 with the mol ratio of cyclopentadiene.
The inventive method step（2）Middle bottom temperature is 215～255 DEG C, and tower top temperature is 60～85 DEG C, and tower top pressure is 0.50～0.65 MPa.
The inventive method step（2）In, the theoretical cam curve of described first rectifying column is 10～20 pieces.Used as the further preferred of the inventive method, the theoretical cam curve of described first rectifying column is 15 pieces, column plate can be arranged in first rectifying column, it is also possible to load filler.
The inventive method step（3）In, 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,
The inventive method step（3）In, the theoretical cam curve of described Second distillation column is 60～70 pieces.Used as the further preferred of the inventive method, the theoretical cam curve of described Second distillation column is 65 pieces, column plate can be arranged in Second distillation column, it is also possible to load filler.
It is strong exothermal reaction that cyclopentadiene hydrogenating generation cyclopentenes and cyclopentenes are hydrogenated to Pentamethylene., and under the conditions of typical liquid-phase hydrogenatin, the reaction heat of the two is above 100
KJ/mol, the thermal discharge of the latter is bigger.It has been generally acknowledged that, if reaction temperature is higher than 120 DEG C, cyclopentenes are hydrogenated to the response speed of Pentamethylene. can be dramatically speeded up, on the one hand cyclopentenes selectivity is caused to decline, order can affect cyclopentenes product quality and increase the separating difficulty of subsequent product on the one hand because Pentamethylene. is close with product cyclopentenes boiling point.Therefore, taking reaction heat and control reaction away is carried out at a lower temperature, will be the key of production and separating-purifying cyclopentenes with high selectivity.
One of key of the present invention is to employ to constitute base metal selective hydrocatalyst by the amorphous nickel phosphide of active component, alumina support and auxiliary agent cerium.Compare compared with the precious metals pd catalyst adopted in technical scheme, catalyst of the present invention has low cost, the high advantage of cyclopentenes selectivity.
Additionally, one of another key of the present invention is the solvent that the present invention is adopted being made up of ethyl methyl ether and ether.Ethyl methyl ether the present invention adopt reaction pressure under boiling point for 79.0～87.9 DEG C.Under the reaction condition that the present invention is adopted, cyclopentadiene hydrogenating heat release makes ethyl methyl ether gasify, and using the gasification latent heat of dimethyl ether reaction bed temperature is controlled.The content of ethyl methyl ether in by adjusting solvent, reaction bed temperature can be made stably to control at 80～90 DEG C, the selective hydrocatalyst that ensure that present invention employing has given full play to itself superior catalytic performance, Pentamethylene. by-product selectivity is controlled below 0.5%.
Because the solvent that the present invention is adopted is made up of ethyl methyl ether and ether, the two boiling point at ambient pressure is below cyclopentadiene raw material and cyclopentenes product so that product separation process is greatly simplified.Compared with the existing technology, the inventive method eliminates solvent separating step, solvent and unreacted cyclopentadiene raw material are produced with the tower top light component of Second distillation column jointly, on the one hand on the other hand also unreacted cyclopentadiene raw material can be taken back hydrogenation reactor and continue to react as the circulating solvent of the present invention.After device reaches stable state, the unreacted cyclopentadiene raw material of solvent and part is circulated in a device, can improve the conversion ratio of cyclopentadiene in fresh feed, and without the need for supplementing fresh solvent.
Description of the drawings
Fig. 1 is schematic flow sheet of the present invention.
In Fig. 1,1- raw material storage tanks, 2- feed pumps, 3- hydrogenation reactors, 4- gas-liquid separators, 5- feed pumps, 6- first rectifying columns, 7- Second distillation columns.
101～111 is logistics in Fig. 1, wherein 101- raw materials containing cyclopentadiene, 102- fresh solvents, 103- hydrogenation reaction raw materials, 104- hydrogen, 105- hydrogenation reaction effluents, 106- circulating hydrogens, the charging of 107- first rectifying columns, 108- heavy constituent impurity, 109- Second distillation columns feed, 110- cyclopentenes products, 111- circulating solvents.
Fig. 2 is the XRD spectra of the selective hydrocatalyst that the present invention is adopted.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment the invention will be further described.It is only below the present invention preferably specific embodiment, but protection scope of the present invention is not limited to this, and any those familiar with the art can readily occur in change or replacement, all should cover in the protection domain of this patent.
Raw material containing cyclopentadiene as shown in Figure 1（101）With fresh solvent（102）And circulating solvent（111）After mixing in raw material storage tank 1, hydrogenation reaction raw material is constituted（103）；The flow of each stock material is adjusted, the mass fraction for making cyclopentadiene in hydrogenating materials is 10～25%, the mass fraction of ethyl methyl ether is 20～80% in solvent；Hydrogenation reaction raw material（103）Jing and hydrogen（104）Hydrogenation reactor 2 is entered after mixing, is 40～60 DEG C in reactor inlet temperature in the presence of selective hydrocatalyst, reaction pressure is 0.9～1.1 MPa, and mass space velocity is 2～4 h-1, the mol ratio of hydrogen and cyclopentadiene is under conditions of 1.1～1.3, cyclopentadiene selective hydrogenation occurs；The hydrogenation reaction effluent of generation（105）Gas-liquid separation is carried out in knockout drum 4, hydrogen is isolated（106）Can be recycled；Liquid-phase hydrogenatin product is isolated as the charging of 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 to operate under conditions of 0.50～0.65 MPa, bottom of towe extraction heavy constituent impurity（108）；Charging of the first rectifying column overhead as Second distillation column（109）, bottom temperature is 95～120 DEG C, and tower top temperature is 55～80 DEG C, and tower top pressure is to operate under conditions of 0.45～0.70 MPa, bottom of towe extraction cyclopentenes product（110）, tower top distillates light component as circulating solvent（111）, return in raw material storage tank 1 and recycle.
The effect of the present invention is further illustrated with reference to embodiments.
Embodiment 1-4
Catalyst preparation step（
1
）
The weight as shown in table 1 weighs six water nickel nitrates and adds 500
Ml deionized waters, are subsequently adding 0.05 mol/L nitre acid for adjusting pH value to 2-3, then again as shown in table 1 weight adds diammonium phosphate, six water cerous nitrates, citric acid monohydrate, be then stirred at room temperature 1 hour, respectively obtain solution A 1-A4.
Table 1
Add aluminium hydrate powder 77g, 72g, 67g and 78g in solution A 1-A4 respectively, be allowed to dispersion in the solution, respectively obtain serosity B1-B4, then by gained serosity move into Rotary Evaporators at 85 DEG C evaporating water, then dry 24 hours at 120 DEG C, obtain dry glue C1-C4.
Catalyst preparation step（
2
）
Dry glue C1-C4 is placed in tubular heater, in the N of continuous flowing2In atmosphere, 3-10 hours are processed at 250-300 DEG C, make the citric acid in dry glue that pyrolysis to occur, after required process time to be achieved, make temperature be reduced to room temperature（25℃）Take out, 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 appropriate nitric acid, water, sesbania powder mixer kneader, extruded moulding.After extruded moulding, gained extrudate is first dried 24 hours at room temperature, dries 24 hours then at 120 DEG C, respectively obtains preformed catalyst presoma E1-E4.
Catalyst preparation step（
4
）
Condition as listed by table 3, preformed catalyst presoma E1-E4 is respectively placed in tubular heater, in the H of continuous flowing2In atmosphere, 5-10 hours are reduced at 350-400 DEG C.After recovery time needed for be achieved, temperature is set to be reduced to room temperature（25℃）, then with O that oxygen volumetric concentration is 0.75%2/N2Passivating gas are passivated process 0.8 hour to catalyst, are finally passivated the catalyst F1-F4 of state.
Table 3
Using X-ray diffraction（XRD）Characterize to being passivated state catalyst F1-F4, as a result show that nickel phosphide is in amorphous state on catalyst.Fig. 2 shows the XRD spectra of F1-F4 catalyst.
Using inductively coupled plasma atomic emission（ICP）Determine passivation state catalyst composition.Ni loadings account for total catalyst weight percentages with Ni weight metals, and P content and Ce contents are represented respectively with P/Ni, Ce/Ni mol ratio.F1 catalyst：Ni contents 10.12%, P/Ni=2.35, Ce/Ni=0.01；F2 catalyst：Ni contents 12.51%, P/Ni=2.24, Ce/Ni=0.03；F3 catalyst：Ni contents 14.96%, P/Ni=2.06, Ce/Ni=0.05；F4 catalyst：Ni contents 10.23%, P/Ni=2.14, Ce/Ni=0.02.
Embodiment 5-9
Raw material containing cyclopentadiene used by various embodiments of the present invention comes from dicyclopentadiene cracking, and the wherein mass fraction of cyclopentadiene is 98%, and remaining is dicyclopentadiene.
The technological process that various embodiments of the present invention are adopted 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 hydrogenation reactor.
Table 5
In order to illustrate the effect of the inventive method, using beneficial effect of the one way selective presentation the inventive method of cyclopentadiene conversion per pass, the one way selectivity of cyclopentenes and Pentamethylene. to cyclopentadiene selective hydrogenation.
Table 6 lists various embodiments of the present invention cyclopentadiene selective hydrogenation one way reaction result.The mass fraction that the inventive method passes through ethyl methyl ether in control solvent, ethyl methyl ether is set to absorb cyclopentadiene hydrogenating reaction liberated heat under the conditions of the reaction according to the invention and gasify, reaction bed temperature is controlled using the gasification latent heat of ethyl methyl ether, makes hydrogenation reaction maintain to carry out at a lower temperature.As shown in table 6, using the inventive method hydrogenation reactor outlet temperature can be made to control at 80～90 DEG C, the selective hydrocatalyst for being conducive to present invention employing has given full play to itself superior catalytic performance, therefore the one way selectivity that cyclopentadiene deep hydrogenation generates Pentamethylene. is controlled below 0.5%, to obtain higher cyclopentenes product selectivity.
Table 6
Table 7 lists the hydrogenation products of various embodiments of the present invention and separates and process for refining condition, and technological process is as shown in Figure 1.The theoretical cam curve of first rectifying column is 15 pieces, and the theoretical cam curve of Second distillation column is 65 pieces.The rectifying column that various embodiments of the present invention are adopted can arrange distillation tray, it is also possible to load filler.The technology contents that plate column and packed tower are well known to the skilled person.Various embodiments of the present invention adopt packed tower, and filler used is metal Pall ring filler.
Table 7
Table 8 lists cyclopentenes product（110）And circulating solvent（111）Composition.The device invested to build using the inventive method is reached after stable state, without the need for being supplemented with fresh solvent.As shown in table 9, another beneficial effect of the invention is that unreacted cyclopentadiene returns hydrogenation reactor and continues reaction with circulating solvent, the total conversion of cyclopentadiene can be improved into more than 99%, and cyclopentenes total yield of products is improved to more than 97%.
Table 8
Table 9
Claims (14)
1. it is a kind of by cyclopentadiene selective hydrogenation produce cyclopentenes method, it is characterised in that：Comprise the steps：
（1）Raw material containing cyclopentadiene mix with solvent after as hydrogenation reaction raw material, then the fixed bed reactors for being filled with selective hydrocatalyst are continued through after mixing with hydrogen；The selective hydrocatalyst is made up 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, in the final catalyst, 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, and phosphorus is 2.0-2.4 with the mol ratio of nickel:1, auxiliary agent cerium is 0.01-0.05 with the mol ratio of nickel:1, remaining is carrier；
（2）By step（1）Hydrogenation products are isolated and be passed through after hydrogen first rectifying column, and bottom of towe extraction heavy constituent impurity, overhead is produced as the charging of Second distillation column；
（3）By step（2）First rectifying column overhead is passed through Second distillation column, and bottom of towe produces cyclopentenes product, and overhead extraction light component is used as circulating solvent, return to step（1）Middle recycling.
2. method according to claim 1, it is characterised in that：Step（1）Middle reactor inlet temperature is 20～60 DEG C, and reaction pressure is 0.5～1.1 MPa, and mass space velocity is 1～4 h-1, hydrogen is 1.1～2.0 with the mol ratio of cyclopentadiene.
3. method according to claim 2, it is characterised in that：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 is 1.1～1.3 with the mol ratio of cyclopentadiene.
4. method according to claim 1, it is characterised in that：Step（1）Middle solvent is made up of the ethyl methyl ether and 20～90% ether that mass fraction is 10～80%.
5. method according to claim 4, it is characterised in that：Solvent is made up of the ethyl methyl ether and 20～80% ether that mass fraction is 20～80%.
6. method according to claim 1, it is characterised in that：Step（1）In raw material containing cyclopentadiene come from dicyclopentadiene cracking, wherein the mass fraction of cyclopentadiene be more than 98%.
7. method according to claim 1, it is characterised in that：Step（1）In middle hydrogenation reaction raw material, the mass fraction of cyclopentadiene is 1～25%.
8. method according to claim 1, it is characterised in that：Step（1）In, the preparation method of selective hydrocatalyst is as follows：
（1）Acid nickel salt aqueous solution is prepared, diammonium phosphate, the salt containing auxiliary agent X and citric acid is subsequently adding, makes phosphorus/nickel mol ratio be 2.5-3.0, X/ nickel mol ratio is 0.01-0.05:1, citric acid/nickel mol ratio is 1.0-2.0:1, solution A is obtained, the aluminium oxide or aluminium hydroxide of metering are added in resulting solution A, serosity B is formed, then slow evaporating water, form dry glue C；
（2）By step（1）Middle gained dry glue C is placed under the atmosphere of inert gases of continuous flowing, is warming up at 250-350 DEG C, and in 5-10 hours are processed at this temperature, makes the citric acid in dry glue that pyrolysis to occur, and obtains catalyst precursor D；
（3）By step（2）In the catalyst precursor D that obtains carry out molding, after molding rear catalyst drying, obtain preformed catalyst presoma E；
（4）By step（3）In the preformed catalyst presoma E that obtains reduced in atmosphere of hydrogen, reduction temperature is 300-400 DEG C, recovery time is 1-10 h, after catalyst reduction, it is cooled to room temperature, passivating gas with oxygen concentration as 0.5-1.0% are passivated at room temperature 0.5-1 h to catalyst, obtain selectivity hydrogenation catalyst.
9. method according to claim 1, it is characterised in that：Step（2）Middle bottom temperature is 215～255 DEG C, and tower top temperature is 60～85 DEG C, and tower top pressure is 0.50～0.65 MPa.
10. method according to claim 1, it is characterised in that：Step（2）The theoretical cam curve of middle first rectifying column is 10～20 pieces.
11. methods according to claim 1, it is characterised in that：Step（2）Column plate is set in middle first rectifying column or filler is loaded.
12. methods according to claim 1, it is characterised in that：Step（3）Middle 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.
13. methods according to claim 1, it is characterised in that：Step（3）The theoretical cam curve of Second distillation column is 60～70 pieces.
14. methods according to claim 1, it is characterised in that：Step（3）Column plate is set in middle Second distillation column or filler is loaded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510750175.9A CN106673938B (en) | 2015-11-09 | 2015-11-09 | A method of cyclopentene is produced by cyclopentadiene selective hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510750175.9A CN106673938B (en) | 2015-11-09 | 2015-11-09 | A method of cyclopentene is produced by cyclopentadiene selective hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106673938A true CN106673938A (en) | 2017-05-17 |
| CN106673938B CN106673938B (en) | 2019-04-12 |
Family
ID=58858492
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510750175.9A Active CN106673938B (en) | 2015-11-09 | 2015-11-09 | A method of cyclopentene is produced by cyclopentadiene selective hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106673938B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107684919A (en) * | 2017-08-03 | 2018-02-13 | 大连理工大学 | Support type Ni3P catalyst and its preparation method and application |
| CN109865519A (en) * | 2017-12-01 | 2019-06-11 | 中国石化扬子石油化工有限公司 | A kind of ruthenium modified activated carbon supported nickel catalyst, preparation method and its application |
| CN111085273A (en) * | 2018-10-24 | 2020-05-01 | 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 |
| CN111889036A (en) * | 2019-05-05 | 2020-11-06 | 中国石油集团工程股份有限公司 | Cyclopentadiene fixed bed catalytic hydrogenation reaction device, system and method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2015
- 2015-11-09 CN CN201510750175.9A patent/CN106673938B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| WEI-JIANG WANG ET AL.: "Amorphous NiP/SiO2 aerogel: Its preparation, its high thermal stability and its activity during the selective hydrogenation of cyclopentadiene to cyclopentene", 《APPLIED CATALYSIS A: GENERAL》 * |
| XIANG LI ET AL.: "Influence of TiO2 and CeO2 on the hydrogenation activity of bulk Ni2P", 《CATALYSIS COMMUNICATIONS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107684919A (en) * | 2017-08-03 | 2018-02-13 | 大连理工大学 | Support type Ni3P catalyst and its preparation method and application |
| CN107684919B (en) * | 2017-08-03 | 2020-05-19 | 大连理工大学 | Loaded Ni3P catalyst and preparation method and application thereof |
| CN109865519A (en) * | 2017-12-01 | 2019-06-11 | 中国石化扬子石油化工有限公司 | A kind of ruthenium modified activated carbon supported nickel catalyst, preparation method and its application |
| 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 |
| CN111085273A (en) * | 2018-10-24 | 2020-05-01 | 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 |
| 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 |
| CN111889036A (en) * | 2019-05-05 | 2020-11-06 | 中国石油集团工程股份有限公司 | Cyclopentadiene fixed bed catalytic hydrogenation reaction device, system and method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106673938B (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9663426B2 (en) | Composite metal catalyst composition, and method and apparatus for preparing 1,4-cyclohexanedimethanol using same | |
| CN106673938A (en) | Method for producing cyclopentene by selective hydrogenation of cyclopentadiene | |
| CN106518608A (en) | A continuous preparing method and apparatus for cyclohexanedimethanol | |
| CN103420776B (en) | A kind of method preparing methyl cyclopentene | |
| CN112537998B (en) | Process for producing neopentyl glycol by continuous catalytic hydrogenation | |
| CN104557454B (en) | A kind of method of acetic acid Hydrogenation for high-quality ethanol | |
| CN109721469A (en) | A kind of preparation method of cyclopentanone | |
| CN109761819B (en) | Continuous preparation method of N, N-dimethylpropylamine | |
| CN110498732B (en) | Method for preparing ethanol by acetic acid hydrogenation | |
| CN106673951B (en) | A method of cyclopentene is produced by cyclopentadiene | |
| CN1249008C (en) | Method for preparing cyclopentanone from cyclopentanol | |
| CN114230453A (en) | Production method for synthesizing propionic acid by one-step hydrogenation | |
| CN105481649B (en) | A kind of method that acetic acid hydrogenation prepares ethanol | |
| CN107226771B (en) | Method for separating stream containing cyclohexane and acetic acid, method for producing cyclohexyl acetate and method for co-producing cyclohexanol and ethanol | |
| CN107226770B (en) | Distillation method, production method of cyclohexyl acetate and production method of cyclohexanol | |
| WO2019117759A1 (en) | Single-stage method of butadiene production | |
| CN104557453B (en) | A kind of method of acetic acid preparation of ethanol through hydrogenation | |
| CN114432724B (en) | Process system and method for isopropanol dehydration reaction and process system and method for preparing propylene from acetone | |
| CN110668927B (en) | Method for preparing 3-pentanone by dehydrogenating 3-pentanol | |
| CN116217349B (en) | Method for coproducing isopropyl ether by MIBK | |
| CN112661618B (en) | Copper catalysis preparation method of cyclopentanone | |
| CN114716325B (en) | Method for continuously preparing triethylamine | |
| CN109534954B (en) | Method and device for coproducing cyclohexanol and ethanol | |
| CN106701159A (en) | Fluidized bed hydrogenation system and method of high solid content coal tar | |
| CN116020351A (en) | Maleic anhydride hydrogenation reaction method and maleic anhydride hydrogenation reactor |
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 |