CN110961127A - Method for preparing loaded DCPD resin hydrogenation catalyst by using hydrotalcite-like compound as precursor - Google Patents

Method for preparing loaded DCPD resin hydrogenation catalyst by using hydrotalcite-like compound as precursor Download PDF

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CN110961127A
CN110961127A CN201911249144.XA CN201911249144A CN110961127A CN 110961127 A CN110961127 A CN 110961127A CN 201911249144 A CN201911249144 A CN 201911249144A CN 110961127 A CN110961127 A CN 110961127A
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reaction
hydrotalcite
compound
hydrogenation
dcpd resin
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梁长海
白宗宣
陈霄
李闯
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Jinzhou Kaiten Technology Co Ltd
Dalian University of Technology
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Jinzhou Kaiten Technology Co Ltd
Dalian University of Technology
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    • 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
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B01J27/236—Hydroxy carbonates
    • 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
    • B01J23/007—Mixed salts
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/58—Platinum group metals with alkali- or alkaline earth metals
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation

Abstract

The invention discloses a method for preparing a hydrogenation catalyst of a loaded DCPD resin by using hydrotalcite-like compound as a precursor, belonging to the technical field of petroleum resin hydrogenation. The supported catalyst is prepared by using hydrotalcite-like compound as a precursor, the obtained catalytic particles are uniformly distributed, active components are not easy to lose, the catalyst shows higher catalytic activity when being used for the hydrogenation reaction of DCPD resin, and the prepared hydrogenated resin has high hydrogenation saturation and obviously improved hue. The method has the advantages of mild reaction conditions, simple catalyst preparation process, low cost, higher activity, good stability and high added value of the obtained product, and is suitable for industrial application.

Description

Method for preparing loaded DCPD resin hydrogenation catalyst by using hydrotalcite-like compound as precursor
Technical Field
The invention belongs to the technical field of petroleum resin hydrogenation, and relates to preparation of a supported DCPD resin hydrogenation catalyst taking hydrotalcite-like compound as a precursor.
Background
Dicyclopentadiene (DCPD) resin is a high-performance thermosetting high-molecular polymer. The resin has good processing performance, mechanical performance and acid and alkali resistance, and is easy to dissolve in organic substances, so that the resin is widely applied to various manufacturing fields of the automobile industry, equipment pipelines, medical instruments, coatings, printing industry and the like. However, the molecular structure of the DCPD resin after simple polymerization also contains more double bonds and impurities, which causes the defects of dark color, bad smell, poor thermal stability, poor oxidation resistance and the like, and limits the application range of the DCPD resin. At present, a catalytic hydrogenation mode is generally adopted at home and abroad to saturate double bonds in molecules and remove impurities, the unsaturated degree of a product subjected to hydrogenation modification is greatly reduced, the resin is colorless and has no special smell, the performances such as adhesiveness, stability and the like are improved, and the application range of the resin is greatly widened. At present, the foreign DCPD resin is represented by American Exxon, Japanese Ralskion, Korea Kelong and other companies, and the hydrogenated petroleum resin has a considerable production scale and mature technology. Compared with the relatively backward technology of domestic enterprises, low yield and poor quality, the application of the DCPD resin in various fields is greatly limited. Therefore, the hydrogenation technology of DCPD resin is receiving more and more attention from researchers, and the core of the research on the catalyst is to improve the hydrogenation technology of petroleum resin. At present, the active metal components of the catalyst used in the resin hydrogenation reaction are mainly classified into two major types, namely palladium-based catalysts and nickel-based catalysts. Chinese patent, publication No.: CN 107252688A, introduction of a DCPD petroleum resin hydrogenation catalystAn agent, a preparation method and application thereof. The catalyst is gamma-Al modified by alkali metal2O3As a carrier, Ni active components are loaded, and the loading amount is 12-30%. The method comprises mixing gamma-Al2O3The carrier is soaked in a Ni-containing solution and then dried and roasted, so that the active components are unevenly dispersed on the carrier, and even agglomeration phenomenon occurs, and the activity of the catalyst is further influenced. Chinese patent, publication No.: CN 106268725B discloses a hydrogenation catalyst of DCPD resin thermally polymerized by dicyclopentadiene in ethylene cracking carbon 9, a preparation method and application thereof. The method is to use gamma-Al2O3The catalyst is prepared by loading active components Pd, Mo and Mn on a formed carrier step by step in an impregnation mode, drying and roasting, and the catalyst is prepared by adopting gamma-Al2O3The supported active metal is low, so that the hydrogenation rate is low when the DCPD petroleum resin hydrogenation catalyst is used for hydrogenation reaction of DCPD petroleum resin, and the active metal is easy to lose.
Disclosure of Invention
The invention provides a method for preparing a hydrogenation catalyst of a loaded DCPD resin by using hydrotalcite-like compound as a precursor. Aiming at the defects that the active metal of the existing catalyst is easy to agglomerate and run off, the novel method for preparing the supported catalyst by using the hydrotalcite-like compound as the precursor is used for the hydrogenation reaction of the DCPD resin, so that the hydrogenation efficiency and the service life of the catalyst are greatly improved, the content of unsaturated bonds in the obtained product is obviously reduced, the chroma is also greatly improved, the softening point is reduced less, the process is simple, and the investment is saved.
The technical scheme of the invention is as follows:
a method for preparing a loaded DCPD resin hydrogenation catalyst by using hydrotalcite-like compound as a precursor is characterized in that the loaded hydrogenation catalyst obtained by using the hydrotalcite-like compound is subjected to hydrogenation reaction on a DCPD resin solution with the concentration of 10% -40% at the temperature of 150-270 ℃, the hydrogen pressure of 1-9 MPa, the reaction time of 0.5-6 h and the stirring paddle rotation speed of 700r/min to obtain the hydrogenated DCPD resin.
The hydrotalcite-like compound is: [ (X)2+)x(Mg2+)y]2(Al3+)(OH)6(CO3 2-)1/2·mH2O, wherein x, y and m satisfy 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, x + y ≤ 1, 0 ≤ m ≤ 1.5, and are calcined at 500 deg.C and Ar at 400 deg.C and H2And (4) reducing and activating under the condition.
In the hydrotalcite-like compound, X is one or the combination of more than two of Pd, Ni and Cu.
The mass ratio of the supported hydrogenation catalyst to the DCPD resin solution is 1: 160.
The invention has the beneficial effects that: the method has simple process, is green and environment-friendly, is easy for industrial production, and the prepared hydrogenated resin has improved hue to water white and little reduction of softening point.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1 (influence of active Metal component)
The effect of active components in the catalyst used on the reaction results was examined using a 10 wt.% DCPD resin cyclohexane solution as substrate. The reaction was carried out in a batch reactor.
Reaction conditions are as follows: the reaction temperature is 210 ℃, the reaction pressure is 5MPa, the reaction time is 3h, and the hydrogenation reaction is carried out under the condition that the rotating speed of a stirring paddle is 700r/min, wherein the mass ratio of the hydrogenation catalyst to the reaction liquid is 1: 160. The catalyst needs to pass through 400 ℃ and H before reaction2The reaction is carried out for 2h under the following conditions:
Figure BDA0002308532130000031
example 2 (influence of temperature)
The effect of the reaction temperature on the reaction result was examined using a 10 wt% DCPD resin cyclohexane solution as a substrate. The reaction was carried out in a batch reactor.
Reaction conditions are as follows: the reaction temperature is 150-270 ℃, the reaction pressure is 5MPa, the reaction time is 3h, and the rotating speed of a stirring paddle is 700r/minAnd (3) hydrogenation reaction, wherein the mass ratio of the Pd-MgAl catalyst to the reaction liquid is 1: 160. The catalyst needs to pass through 400 ℃ and H before reaction2The reaction is carried out for 2h under the following conditions:
Figure BDA0002308532130000041
example 3 (influence of Hydrogen pressure)
The effect of the reaction pressure on the reaction result was examined using a 10 wt% DCPD resin cyclohexane solution as a substrate. The reaction was carried out in a batch reactor.
Reaction conditions are as follows: the reaction temperature is 210 ℃, the reaction pressure is 1-9 MPa, the reaction time is 3h, the hydrogenation reaction is carried out under the condition that the rotating speed of a stirring paddle is 700r/min, and the mass ratio of the Pd-MgAl catalyst to the reaction liquid is 1: 160. The catalyst needs to pass through 400 ℃ and H before reaction2The reaction is carried out for 2h under the following conditions:
Figure BDA0002308532130000042
example 4 (influence of reaction time)
The effect of the reaction time on the reaction result was examined using a 10 wt% DCPD resin cyclohexane solution as a substrate. The reaction was carried out in a batch reactor.
Reaction conditions are as follows: the reaction temperature is 210 ℃, the reaction pressure is 5MPa, the reaction time is 0.5-6 h, the hydrogenation reaction is carried out under the condition that the rotating speed of a stirring paddle is 700r/min, and the mass ratio of the Pd-MgAl catalyst to the reaction liquid is 1: 160. The catalyst needs to pass through 400 ℃ and H before reaction2The reaction is carried out for 2h under the following conditions:
Figure BDA0002308532130000051
example 5 (influence of solvent type)
The effect of the solvent used on the reaction results was examined using a 10 wt% DCPD resin solution as a substrate. The reaction was carried out in a batch reactor.
Reaction conditions are as follows: the reaction temperature is 210 ℃, the reaction pressure is 5MPa,the reaction time is 3 hours, the hydrogenation reaction is carried out under the condition that the rotating speed of a stirring paddle is 700r/min, and the mass ratio of the hydrogenation catalyst to the reaction liquid is 1: 160. The catalyst needs to pass through 400 ℃ and H before reaction2The reaction is carried out for 2h under the following conditions:
Figure BDA0002308532130000061
example 6 (influence of raw Material concentration)
The effect of the raw material concentration on the reaction result was examined by using 10-40 wt% DCPD resin cyclohexane solution as a substrate. The reaction was carried out in a batch reactor.
Reaction conditions are as follows: the reaction temperature is 210 ℃, the reaction pressure is 5MPa, the reaction time is 3h, and the hydrogenation reaction is carried out under the condition that the rotating speed of a stirring paddle is 700r/min, wherein the mass ratio of the hydrogenation catalyst to the reaction liquid is 1: 160. The catalyst needs to pass through 400 ℃ and H before reaction2The reaction is carried out for 2h under the following conditions:
Figure BDA0002308532130000062
example 7 (influence of preparation method)
The influence of the preparation method of the catalyst on the reaction result is examined by using a 10 wt% DCPD resin cyclohexane solution as a substrate. The reaction was carried out in a batch reactor.
Reaction conditions are as follows: the reaction temperature is 210 ℃, the reaction pressure is 5MPa, the reaction time is 3h, and the hydrogenation reaction is carried out under the condition that the rotating speed of a stirring paddle is 700r/min, wherein the mass ratio of the hydrogenation catalyst to the reaction liquid is 1: 160. The catalyst needs to pass through 400 ℃ and H before reaction2The reaction is carried out for 2h under the following conditions:
Figure BDA0002308532130000071

Claims (4)

1. a method for preparing a hydrogenation catalyst of a loaded DCPD resin by using hydrotalcite-like compound as a precursor is characterized by comprising the following steps: a supported hydrogenation catalyst obtained from hydrotalcite-like compound is prepared by carrying out hydrogenation reaction on DCPD resin solution with the concentration of 10-40 wt% at the temperature of 150-270 ℃, the hydrogen pressure of 1-9 MPa, the reaction time of 0.5-6 h and the rotation speed of a stirring paddle of 700r/min to obtain hydrogenated DCPD resin.
2. The method for preparing the DCPD resin hydrogenation catalyst supported by hydrotalcite-like compound as the precursor according to claim 1, wherein said hydrotalcite-like compound is [ (X)2+)x(Mg2+)y]2(Al3+)(OH)6(CO3 2-)1/2·mH2O, wherein x, y and m satisfy 0 ≤ x ≤ 1, 0 ≤ y ≤ 1, x + y ≤ 1, 0 ≤ m ≤ 1.5, and are calcined at 500 deg.C and Ar at 400 deg.C and H2And (4) reducing and activating under the condition.
3. The method for preparing the DCPD resin hydrogenation catalyst supported by hydrotalcite-like compound as the precursor according to claim 2, wherein X in the hydrotalcite-like compound is one or a combination of two or more of Pd, Ni and Cu.
4. The method for preparing the hydrogenation catalyst of the supported DCPD resin by using the hydrotalcite-like compound as the precursor according to any one of claims 1 to 3, characterized in that the mass ratio of the supported hydrogenation catalyst to the DCPD resin solution is 1: 160.
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Citations (7)

* Cited by examiner, † Cited by third party
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CN1322217A (en) * 1999-01-15 2001-11-14 埃克森美孚化学专利公司 Hydrogenation process for hydrocarbon resins
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WO2017078905A1 (en) * 2015-11-04 2017-05-11 Exxonmobil Chemical Patents Inc. Processes and systems for converting hydrocarbons to cyclopentadiene
CN106866331A (en) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 A kind of method that cyclopentadiene or dicyclopentadiene are prepared by furfuryl alcohol
CN107252688A (en) * 2017-05-15 2017-10-17 北京石油化工学院 A kind of DCPD hydrogenation of petroleum resin catalyst and its preparation method and application
CN107417485A (en) * 2017-08-21 2017-12-01 大连理工大学 A kind of method that hanging type tetrahydrochysene dicyclopentadiene is directly prepared by dicyclopentadiene
CN108117475A (en) * 2016-11-30 2018-06-05 中国科学院大连化学物理研究所 A kind of method that JP-10 aviation fuel is prepared by furfuryl alcohol

Patent Citations (7)

* Cited by examiner, † Cited by third party
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CN1322217A (en) * 1999-01-15 2001-11-14 埃克森美孚化学专利公司 Hydrogenation process for hydrocarbon resins
CN106268725A (en) * 2015-08-10 2017-01-04 中国石油化工股份有限公司 The hydrogenation catalyst of the DCPD resin of dicyclopentadiene hot polymerization and preparation method and application in cracking of ethylene carbon 9
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CN106866331A (en) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 A kind of method that cyclopentadiene or dicyclopentadiene are prepared by furfuryl alcohol
CN108117475A (en) * 2016-11-30 2018-06-05 中国科学院大连化学物理研究所 A kind of method that JP-10 aviation fuel is prepared by furfuryl alcohol
CN107252688A (en) * 2017-05-15 2017-10-17 北京石油化工学院 A kind of DCPD hydrogenation of petroleum resin catalyst and its preparation method and application
CN107417485A (en) * 2017-08-21 2017-12-01 大连理工大学 A kind of method that hanging type tetrahydrochysene dicyclopentadiene is directly prepared by dicyclopentadiene

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