CN111234056A - Catalyst for hydrogenation of hydrocarbon-containing petroleum resin - Google Patents

Catalyst for hydrogenation of hydrocarbon-containing petroleum resin Download PDF

Info

Publication number
CN111234056A
CN111234056A CN202010062711.7A CN202010062711A CN111234056A CN 111234056 A CN111234056 A CN 111234056A CN 202010062711 A CN202010062711 A CN 202010062711A CN 111234056 A CN111234056 A CN 111234056A
Authority
CN
China
Prior art keywords
catalyst
hydrogenation
petroleum resin
resin
mesoporous molecular
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.)
Pending
Application number
CN202010062711.7A
Other languages
Chinese (zh)
Inventor
孙向东
王斌
李爱元
彭振博
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henghe Materials and Science Technology Co Ltd
Original Assignee
Henghe Materials and Science Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henghe Materials and Science Technology Co Ltd filed Critical Henghe Materials and Science Technology Co Ltd
Priority to CN202010062711.7A priority Critical patent/CN111234056A/en
Publication of CN111234056A publication Critical patent/CN111234056A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/02—Carriers therefor
    • C08F4/025—Metal oxides
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/26—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of manganese, iron group metals or platinum group 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group 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 relates to a catalyst for hydrogenation of carbon five petroleum resin, which takes mesoporous molecular sieve as a carrier to load palladium and platinum. The catalyst has good thermal stability, high catalytic activity and long service life; the method is applied to hydrogenation of carbon five petroleum resin, and the prepared hydrogenated resin not only obviously reduces the content of unsaturated hydrocarbon bonds, but also improves the color phase of the resin to be water white, thereby having good application prospect.

Description

Catalyst for hydrogenation of hydrocarbon-containing petroleum resin
Technical Field
The invention belongs to the field of petroleum resin production, and particularly relates to a catalyst for hydrogenation of carbon five petroleum resin.
Background
The petroleum resin is a solid or viscous liquid polymer with lower relative molecular weight prepared by polymerization of byproducts of carbon five and carbon nine fractions of an ethylene plant as main raw materials. The monomers and molecular structures constituting the resin can be roughly classified into aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins, and the like.
The carbon five petroleum resin, also called aliphatic petroleum resin, is a functional resin obtained by taking carbon five fraction which is a byproduct of cracking ethylene as a raw material and carrying out cationic catalytic polymerization, has the number average molecular weight of 300-3000, has good compatibility with oil products, grease and synthetic resin, has good water resistance and acid resistance, low melting point and good adhesiveness when being mixed with other substances, and is mainly used as an adhesive, a road marking paint, a rubber assistant, a coating and printing ink. The petroleum resin containing five carbon atoms generally has the defects of deep hue, smelly smell, high unsaturated hydrocarbon bond content, poor thermal stability and oxidation resistance, poor cohesive force and the like, and greatly limits the application range of the petroleum resin. The color of carbon five petroleum resin is mainly formed by unsaturated bonds inside the resin molecules, and the saturated bonds are also the cause of the deterioration of the thermal stability and the light stability of petroleum resin products. The hydrogenated C-V petroleum resin is prepared by saturating unsaturated bonds in the C-V petroleum resin through a hydrogenation method, has performance advantages in the aspects of chromaticity, thermal stability, zinc oxidation resistance, good weather resistance, no skin sensitization and the like, and has important application in the aspects of medical adhesives, electronic product assembly, colorless adhesives, polymer modification and the like.
Patents US 4384080 and US 4952639 report hydrogenation catalysts using single-component noble metals such as nickel, palladium, platinum, rhenium, ruthenium and the like as active components for hydrogenation of petroleum resins. Patent US 4540480 describes a process for the hydrogenation of petroleum resins, using a catalyst whose active components use the above-mentioned noble metals in combination, the support of which is alumina. Patent WO 2003/106019 describes a catalyst for hydrogenation of petroleum resin, the active components of the catalyst being palladium and platinum, and the carrier of the catalyst being silica, alumina, silica-alumina, titania, alumina-boria, zeolite, etc. These methods are effective in reducing the unsaturated bond content of petroleum resin, but are not ideal in improving the hue of the resin because the Color of petroleum resin is related to unsaturated bonds, and there are other Color-producing principles which have not been recognized so far, such as "Color Improvement of C9Hydrocarbon Resin by Hydrogenation Over 2% Pd/gamma-aluminum Catalyst, Effect of development of Aromatic Rings, 117: 2862-2869 (2010)' document reports that both color bodies and benzene Rings may cause oil treesThe color of the fat darkens. Meanwhile, the noble metal catalysts such as palladium, platinum and the like have the defects of poor antitoxic property and short service life, and the phenomenon is more prominent particularly when the catalyst is used at higher temperature. Researches show that the main reasons for the short service life of the noble metal catalyst are as follows: poisoning and deactivation of the catalyst; at higher temperature, smaller noble metal crystal grains are heated to agglomerate and agglomerate to deactivate the catalyst. In the production of carbon five petroleum resin, because the raw materials are complex, components such as chlorine, sulfur, nitrogen, gel and the like exist in the production process, and the impurities can cause adverse effects on the activity and the service life of the catalyst.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst for hydrogenating hydrocarbon resin, the content of unsaturated hydrocarbon bonds of the hydrogenated resin is obviously reduced, the color phase of the resin is improved to be water white, and the catalyst has good application prospect.
The invention provides a catalyst for hydrogenation of carbon five petroleum resin, which takes mesoporous molecular sieve as a carrier to load palladium and platinum.
The mesoporous molecular sieve is selected from one or more of MCM-41, MCM-48, FSM-16, SBA-15, KIT-1, HMS and MSU.
The mesoporous molecular sieve has the following remarkable characteristics:
① has uniform and regular pore structure, and is suitable for dispersing large-sized molecules such as hydrogenated carbon penta-petroleum resin in time to avoid polymerization and coking, and the mesoporous molecular sieve can effectively regulate and control pore size and distribution by selecting proper surfactant, auxiliary guiding agent and reaction parameters, ② has high thermal stability, ③ has moderate acid strength, ④ has extremely high BET specific surface area (large specific surface area)>700m2Per g) and pore volume>0.7mL/g), ⑤ the catalyst using the medium pore molecular sieve as the carrier has good catalytic activity and shape selective catalytic performance, the medium pore molecular sieve has wide application in the fields of catalysis, adsorption, nanometer, optical material, environmental protection, etc., the aperture of the medium pore molecular sieve is preferably 5 nm-50 nm, more preferably 20 nm-40 nm.
The content of palladium in the catalyst is 0.01-5.0 wt%, preferably 0.05-4 wt%, and most preferably 0.1-3.0 wt%; the platinum content is 0.005 to 2.5 wt%, preferably 0.01 to 2.0 wt%, and more preferably 0.05 to 1.0 wt%. The mass ratio of palladium to platinum is preferably 0.5 to 9.5:1, and most preferably 1.5 to 4.5: 1.
The key points of the invention are as follows: the catalyst selects a proper active component and selects a mesoporous molecular sieve with a proper physical structure as a carrier. Experiments show that the catalyst shows an unexpected effect on the aspect of improving the hue of the C-V petroleum resin, and the prepared hydrogenated petroleum resin not only has obviously reduced unsaturated hydrocarbon bond content, but also has the hue improved to be water white.
The catalyst can be prepared by any one of the following methods: the "immersion method" includes preparing an aqueous solution of a compound or the like as a precursor of the catalyst component, and immersing the carrier in the prepared loading solution; "spray coating" involves spraying a loading solution onto a support; and "impregnation method" which comprises preparing a loading solution in an amount corresponding to the amount of water taken in by the support and then impregnating the support with the whole of the thus prepared solution.
Any compound containing palladium and platinum components may be used as long as the compound is soluble in water. Compounds that can be used include chlorides such as palladium chloride and chloroplatinic acid, nitrates such as palladium nitrate and platinum nitrate, and organic compounds of palladium and platinum.
Advantageous effects
The catalyst has good thermal stability, high catalytic activity and long service life; the method is applied to hydrogenation of carbon five petroleum resin, and the prepared hydrogenated resin not only obviously reduces the content of unsaturated hydrocarbon bonds, but also improves the color phase of the resin to be water white, thereby having good application prospect.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
In the examples, the test method for each index is as follows:
softening point: the method defined in GB/T2294-1997 (method A) was used.
Hue: the method specified in GB/T22295-.
Bromine number: the assay was carried out according to the method specified in appendix A of GB/T24138-.
Figure BDA0002375000140000031
Example 1
Preparation of mesoporous molecular sieves
Adding 25L of deionized water and 5kg of structural template cetyl trimethyl ammonium bromide into a 100L horizontal reactor at room temperature, controlling the stirring speed to be 100rpm, dropwise adding an acid regulator HCl into the reactor under full stirring to ensure that the pH value of the system is 6, adding 3.01kg of sodium silicate and 30g of sodium metaaluminate into the reactor, continuously stirring for 12h, then aging for 45h, and transferring the obtained material into an autoclave for crystallization at the crystallization temperature of 175 ℃ for 80 h. In the crystallization process, the solid content is gradually increased, the reaction kettle needs to be stirred to ensure that the obtained granularity is more uniform, and the stirring speed is adjusted to 60 rpm. And cooling the obtained liquid-solid mixture, taking out, filtering, washing, drying and roasting to obtain the powder MCM-41 mesoporous molecular sieve. The pore size of the mesoporous molecular sieve is about 15 nm.
Preparation of hydrogenation catalyst
Weighing palladium chloride and chloroplatinic acid, dissolving the palladium chloride and the chloroplatinic acid in hydrochloric acid, taking the MCM-41 mesoporous molecular sieve as a carrier, pouring the carrier into the solution, aging the solution in a reaction kettle for 4 hours, drying the solution at the temperature of 120 ℃ while stirring, placing the catalyst precursor in a muffle furnace, roasting the catalyst precursor for 2 hours at the temperature of 350 ℃, and roasting the catalyst precursor for 3 hours at the temperature of 550 ℃ to obtain the catalyst for later use. The material indexes of the raw materials of the catalyst and the amount of the catalyst are shown in Table 1.
Evaluation of hydrogenation catalyst
Adding 300ml of cyclohexane into a 1L autoclave with magnetic stirring, adding 200g of powdered carbon five petroleum resin raw material and a required amount of catalyst into a kettle, sealing the kettle, replacing air in the kettle with nitrogen for 3 times, replacing nitrogen in the kettle with hydrogen for 3 times, heating the reaction kettle to 250-280 ℃, and reacting for 4-6 hours under the condition that the hydrogen pressure is increased to 7.0-9.0 MPa. After the reaction is finished, the product is subjected to the processes of recovering the catalyst by centrifugal filtration, recovering the solvent by desolventizing, removing light by stripping, reducing pressure, dehydrating, cooling and forming and the like to obtain the hydrogenated petroleum resin product. The product was tested and analyzed for various indexes, and the results are shown in table 2.
Example 2
Preparation of mesoporous molecular sieves
MCM-48 mesoporous molecular sieves having pore sizes around 5nm were prepared according to the literature "Beck J S, et al, a new family of molecular devices with liquid crystals templates, journal of the American Chemical Society,1992,114: 10834-.
The other steps and conditions were the same as in example 1, and the indexes and the product test results are shown in tables 1 and 2, respectively.
Example 3
Preparation of mesoporous molecular sieves
SBA-15 mesoporous molecular sieves having pore sizes around 20nm were prepared according to the literature "ZHao D, et al, triblock copolymer synthesis of mesoporous silica with periodic50 to 300 and strain stress, science,1998,279: 548-.
The other steps and conditions were the same as in example 1, and the indexes and the product test results are shown in tables 1 and 2, respectively.
Example 4
Preparation of mesoporous molecular sieves
FSM-16 mesoporous molecular sieves having pore sizes around 10nm were prepared according to the literature "Inagaki S, et al.
The other steps and conditions were the same as in example 1, and the indexes and the product test results are shown in tables 1 and 2, respectively.
Example 5
Preparation of mesoporous molecular sieves
KIT-1 mesoporous molecular sieves having pore sizes around 60nm were prepared according to the literature "Ryoo R, et al, Synthesis and Hydraulic stability of adsorbed mesoporous molecular size. Studies in Surface Science and catalysis,1997,105: 45-52".
The other steps and conditions were the same as in example 1, and the indexes and the product test results are shown in tables 1 and 2, respectively.
Example 6
Preparation of mesoporous molecular sieves
HMS mesoporous molecular sieves having a pore size of around 2nm were prepared according to the literature "Tanev P T, et al.
The other steps and conditions were the same as in example 1, and the indexes and the product test results are shown in tables 1 and 2, respectively.
Example 7
Preparation of mesoporous molecular sieves
MSU mesoporous molecular sieves with pore sizes around 30nm were prepared according to the literature "Zhang X M, et al. Synthesis of transition-metal conjugation MSUmeso pore molecular sieves. catalysis Letters,1996, 38: 3".
The other steps and conditions were the same as in example 1, and the indexes and the product test results are shown in tables 1 and 2, respectively.
TABLE 1
Figure BDA0002375000140000051
TABLE 2
Figure BDA0002375000140000052
Figure BDA0002375000140000061
Comparative example
Active alumina is used as a carrier, and a hydrogenation catalyst loaded with palladium and platinum is obtained by an impregnation method. The other steps and conditions were the same as in example 1, and the main indices of the catalyst and the results of the product test are shown in tables 3 and 4.
TABLE 3
Figure BDA0002375000140000062
TABLE 4
Softening Point (. degree. C.) Bromine number (g bromine/100 g) Color phase Hydrogenation ratio (%)
Comparative example 1 95 3.3 Water white colour 90
Comparative example 2 98 4.8 Water white colour 88
Comparative example 3 113 6.2 Light yellow 83
As can be seen from the above comparative examples, gamma-Al is activated with alumina2O3And β -Al2O3The hydrogenation degree of hydrogenated hydrocarbon-penta petroleum resin obtained by hydrogenation is relatively low, and the hydrogenation degree is gamma-Al2O3The carrier is easy to cause violent degradation of the resin, so that the softening point of the resin is greatly reduced.

Claims (6)

1. A catalyst for hydrogenation of a hydrocarbon-containing petroleum resin, characterized in that: the catalyst is prepared by loading palladium and platinum on a mesoporous molecular sieve serving as a carrier.
2. The catalyst of claim 1, wherein: the mesoporous molecular sieve is selected from one or more of MCM-41, MCM-48, FSM-16, SBA-15, KIT-1, HMS and MSU.
3. The catalyst of claim 1, wherein: the pore diameter range of the mesoporous molecular sieve is 2-60 nm.
4. The catalyst of claim 3, wherein: the pore diameter range of the mesoporous molecular sieve is 20-40 nm.
5. The catalyst of claim 1, wherein: the palladium content is 0.01-5.0 wt%, the platinum content is 0.005-2.5 wt%, and the mass ratio of palladium to platinum is 0.5-9.5: 1.
6. The catalyst of claim 5, wherein: the palladium content is 0.1-3.0 wt%, the platinum content is 0.05-1.0 wt%, and the mass ratio of palladium to platinum is 1.5-4.5: 1.
CN202010062711.7A 2020-01-20 2020-01-20 Catalyst for hydrogenation of hydrocarbon-containing petroleum resin Pending CN111234056A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010062711.7A CN111234056A (en) 2020-01-20 2020-01-20 Catalyst for hydrogenation of hydrocarbon-containing petroleum resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010062711.7A CN111234056A (en) 2020-01-20 2020-01-20 Catalyst for hydrogenation of hydrocarbon-containing petroleum resin

Publications (1)

Publication Number Publication Date
CN111234056A true CN111234056A (en) 2020-06-05

Family

ID=70862844

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010062711.7A Pending CN111234056A (en) 2020-01-20 2020-01-20 Catalyst for hydrogenation of hydrocarbon-containing petroleum resin

Country Status (1)

Country Link
CN (1) CN111234056A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113769739A (en) * 2021-09-17 2021-12-10 中化泉州石化有限公司 Hydrocatalyst for C-V petroleum resin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101254472A (en) * 2008-04-17 2008-09-03 中国石油天然气集团公司 Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same
CN101298052A (en) * 2008-06-20 2008-11-05 华东理工大学 Copper zinc catalyst and precursor, preparation and use thereof
CN102558444A (en) * 2010-12-17 2012-07-11 中国石油天然气股份有限公司 Method for preparing dicyclopentadiene hydrogenated petroleum resin
CN105032476A (en) * 2015-05-22 2015-11-11 浙江工业大学 Biological alkane hydroisomerization catalyst, preparation method and applications thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101254472A (en) * 2008-04-17 2008-09-03 中国石油天然气集团公司 Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same
CN101298052A (en) * 2008-06-20 2008-11-05 华东理工大学 Copper zinc catalyst and precursor, preparation and use thereof
CN102558444A (en) * 2010-12-17 2012-07-11 中国石油天然气股份有限公司 Method for preparing dicyclopentadiene hydrogenated petroleum resin
CN105032476A (en) * 2015-05-22 2015-11-11 浙江工业大学 Biological alkane hydroisomerization catalyst, preparation method and applications thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
宋盘龙 等: "改性MCM-41沸石负载的Pd-Pt催化剂上萘的加氢活性及耐硫性研究", 《石油学报（石油加工）》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113769739A (en) * 2021-09-17 2021-12-10 中化泉州石化有限公司 Hydrocatalyst for C-V petroleum resin
CN113769739B (en) * 2021-09-17 2023-11-28 中化泉州石化有限公司 Carbon five petroleum resin hydrogenation catalyst

Similar Documents

Publication Publication Date Title
CN111527184B (en) Process for selective hydrogenation
CN102391426B (en) Method for performing hydrogenating pretreatment on C9 petroleum resin
CN110013854B (en) Preparation of supported nickel catalyst and application of supported nickel catalyst in catalytic hydrogenation of C5/C9 petroleum resin
CN101157029A (en) A dicyclopentadiene hydrogenation special-purpose catalyzer and its preparing method
CN1962706A (en) Process for preparing hydrogenated C5/C9 copolymerized petroleum resin
CN108452840A (en) A kind of isomerization catalyst and preparation method
CN103752306B (en) Preparation method of a kind of prepared from benzene and hydrogen thiacyclohexane catalyst and products thereof and application
CN102558444B (en) Method for preparing dicyclopentadiene hydrogenated petroleum resin
CN111234056A (en) Catalyst for hydrogenation of hydrocarbon-containing petroleum resin
CN113939548B (en) Process for preparing hydrogenated petroleum resin
CN112439433B (en) Catalyst with hydrogenation and dimerization functions and preparation method and application thereof
CN108262060A (en) A kind of gasoline catalyzing and olefine reducing aromatized catalyst and its preparation method and application
CN111574645A (en) Hydrogenation method for high-sulfur petroleum resin
CN108003291A (en) A kind of method that hydrogenated petroleum resin is prepared using dicyclopentadiene as raw material
CN101745383A (en) Deeply hydrodearomatized catalyst and preparation method
CN109569634B (en) Hydrogenation method for C-V petroleum resin
CN112275311A (en) Heavy aromatic hydrocarbon lightening catalyst based on VIII group metal elements and preparation method and application thereof
CN112934232B (en) Catalyst for selective hydrogenation of carbon three fractions
CN109395738B (en) Hydrogenation catalyst for carbon five petroleum resin and preparation method thereof
CN109395739B (en) Petroleum resin hydrogenation catalyst and preparation method thereof
CN111100244A (en) Modified pentadiene hydrogenated petroleum resin and preparation method thereof
CN111068728B (en) Aromatic hydrocarbon hydrogenation catalyst, preparation method and application thereof
CN109400808B (en) Hydrogenation method for carbon-nine petroleum resin
CN111100243A (en) Modified carbon-acanthopanax hydrogen petroleum resin and preparation method thereof
CN117164425A (en) Selective hydrogenation method for preparing olefin by ethane pyrolysis

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
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20200605

WD01 Invention patent application deemed withdrawn after publication