CN1803871A - Kettle type catalytic hydrogenation of C5 and C9 petroleum resin for removing color and foreign flavour - Google Patents
Kettle type catalytic hydrogenation of C5 and C9 petroleum resin for removing color and foreign flavour Download PDFInfo
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- CN1803871A CN1803871A CN 200610045624 CN200610045624A CN1803871A CN 1803871 A CN1803871 A CN 1803871A CN 200610045624 CN200610045624 CN 200610045624 CN 200610045624 A CN200610045624 A CN 200610045624A CN 1803871 A CN1803871 A CN 1803871A
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Abstract
The disclosed hydrogenation and discolor method relates mainly to catalyze the C5 and C9 petroleum resin with modified frame nickel on mild condition. This invention reduces unsaturated bond in product obviously, and improves the resin hue to water white.
Description
Technical field
The invention belongs to skeleton nickel catalyzed C
5And C
9The hydrogenation of petroleum resin applied technical field is a kind of C
5And C
9The decolouring of petroleum resin still formula shortening, the method that eliminates the unusual smell
Background technology
Petroleum resin are the by-product C with ethylene unit
5, C
9Cut is a main raw material, polymerization in the presence of catalyzer, or itself and aldehydes, aromatic hydrocarbons, terpene compound carried out copolymerization and the thermoplastic resin that makes.Its molecular weight is generally less than 2000, and 5～150 ℃ of softening temperatures are thermoplasticity thick liquid or solid.Difference according to raw material sources and polymerization process generally is divided into: C-5 (aliphatic hydrocarbon resin), C-5/C-9 (aliphatic hydrocarbon, aromatic hydrocarbon resin), C-9 (aromatic hydrocarbon resin) and dcpd resin (DCPD).Petroleum resin have tackifying, cohesiveness and with the consistency of other resins, thereby often blend such as itself and other high polymer material are improved the performance of various products, be mainly used in fields such as coating, printing ink and tackiness agent.But along with the continuous development in each field, to the quality of petroleum resin, especially form and aspect, softening temperature require more and more higher.General C
5Or C
9Petroleum resin are reddish-brown or lurid, become white or transparent behind the hydrogenation.Application in hot melt adhesive and sealing tape, the transparency of resin is very important.Hydrogenation also can improve binding property, weathering resistance, stability and consistency etc.The hydrogenation catalyst of document introduction has Ni, Pd/Al
2O
3, Ni/Si etc., catalyst levels is 1%～35% of a petroleum resin weight, hydrogenation carries out in solvent, solvent can be hexanaphthene, ethyl cyclohexane, methyl cyclohexane, heptane and octane etc., hydrogenation pressure is 5～25MPa; Hydrogenation temperature is 100～270 ℃; Reaction times is 1～10h.Hydrogenated petroleum resin has solved smell, colourity and the oxidative stability problem of petroleum resin, has widened the Application Areas of petroleum resin greatly.
The U.S. is the country that researchs and develops petroleum resin the earliest, begins one's study in 1910, and the forties in 20th century, Picoo company was at first with its industrialization.After the sixties, the petroleum resin industry of states such as the U.S., West Europe, Japan is developed rapidly.To the end of the eighties, the overall throughput of state's petroleum resin such as U.S., day, English, method reaches 45.1 ten thousand t/a, and wherein the throughput of hydrogenated petroleum resin is 6.64 ten thousand t/a.In recent years, along with updating and the needs of market competition of technology, petroleum resin have developed into many kinds, many trades mark, broad-spectrum functional synthetic resins.China developed petroleum resin since 1964, had successively built up some small-sized production equipments, but since raw material sources and technical problem, slower development.Along with the raising year by year of developing rapidly of China's Petrochemical, particularly ethylene production capacity, cracking C
9The quantity of cut makes full use of this part resource and develops the attention that derived product more and more causes people in continuous increase.Lanzhou chemical industrial company is with the C in the pyrolysis fuel oil
5～C
9Cut is that raw material has successfully been developed the petroleum resin production technology, thereafter organic institute of the Chinese Academy of Sciences, evolution factory of Yanshan Petrochemical company, chemical industry institute of Shanghai Petrochemicals Company Ltd, Zibo chemical institute, Anshan chemical institute, Daqing Petrochemical institute etc. once carried out research, and built up the production equipment of a few cover kilotons.
Because the raw material supply instability, quality fluctuation is bigger, and the reasons such as quality of the competition of natural rosin and petroleum resin itself make that the production of petroleum resin and application development are slower in addition.The China's oil resin production plant is with C
9Petroleum resin are main, account for 70% of overall throughput, C
5Petroleum resin account for 30%.Most of device industrial scale is little, and kind is single, and quality product is not high, main quality index instability such as product colourity, softening temperature particularly, and many devices are in and stop production or half end-of-life state.About 7.6 ten thousand t of national output in 1999, apparent consumption is 9.5 ten thousand t.The import volume of China's oil resin increases year by year in recent years, reaches 2.8 ten thousand t in 2000, and imported product is high-grade private-use class petroleum resin.At this situation, domestic large-scale petrochemical company takes technology introduction and joint mode, accelerates the development of China's oil resin, builds the C of golden gloomy petroleum resin 0.2 ten thousand t/a of company limited in 1998 at the Shanghai sino-america joint-venture
5The hydrogenated petroleum resin device.Raise the C of 1.8 ten thousand t/a of sub-petrochemical industry industrial corporation and the joint construction of U.S. Eastman
5The hydrogenated petroleum resin device is now gone into operation.The C of 0.8 ten thousand t/a of Lanzhou petrochemical industry chemical industry company
5Hydrogenated petroleum resin is produced high-grade C before being installed on year in 2002
5Petroleum resin.
Summary of the invention
The invention provides a kind of C
5And C
9The decolouring of petroleum resin still formula shortening, the method that eliminates the unusual smell, not only the unsaturated hydrocarbons linkage content is low for the hydrogenated petroleum resin that makes, thermostability and good in oxidation resistance, and also form and aspect are also improved completely.
Technical solution of the present invention is a kind of C
5And C
9The decolouring of petroleum resin still formula shortening, the method that eliminates the unusual smell, this method as catalyzer, adopts relatively mild reaction conditions with modified raney ni, and resin is carried out hydrogenation reaction, makes hydrogenated petroleum resin, and the resin form and aspect are improved to and are water white and free from extraneous odour.Its method steps is:
In still formula high-pressure reactor, put into C
5Or C
9Petroleum resin, solvent, modified skeletal nickel catalyst, the ratio of solvent and petroleum resin is 1: 1-10: 1, the modified skeletal nickel catalyst consumption is the 1-20wt% of petroleum resin, airtight rear substitution air charges into the hydrogen of 1.0-2.0MPa then, puts into oil bath and slowly is heated to temperature of reaction, temperature of reaction is 100-250 ℃, adjust hydrogen valve, making system pressure reach pressure is 1.0-10.0MPa, then hold-time 2-10h.Described modified skeletal nickel catalyst, its precursor is made up of Primary Catalysts and promotor, and Primary Catalysts is a nickel, and promotor is made up of Al and M, and integral body is expressed as NiAlM, and wherein component M is one or more the mixture among Fe, Mn, Mo or the Cr; The weight percent of the pressed powder of Ni, Al, M is Ni:5-60%, Al:10-70%, M:0-20%, and catalyst precursor launches according to a conventional method.When temperature of reaction is 180-200 ℃, when system pressure was 3.5-8.0MPa, reaction effect was better.Solvent of the present invention be in perhydronaphthalene, dioxane, sherwood oil, ether, methyl ethyl ether, tetrahydrofuran (THF), methyl-formiate, ethyl formate, ethyl acetate, the methyl acetate one or more mixture.
The invention has the beneficial effects as follows, 1, adopt cheap modified raney ni to make the hydrogenation of petroleum resin catalyzer, have with precious metal palladium and make the close reactive behavior of catalyzer, greatly reduce the production cost of water white hydrogenated petroleum resin.2, make in the reaction of water white hydrogenated petroleum resin at the petroleum resin shortening, adopt relatively mild reaction conditions: 100～200 ℃ of temperature, pressure 1.0～10.0MPa, overcome traditional technology high temperature, the highly compressed shortcoming makes production technique operation become simple like this, and the requirement of equipment is reduced greatly, reduced the investment of energy consumption and hydrogenator simultaneously, Financial cost can significantly descend.
Embodiment
The present invention is further illustrated below in conjunction with embodiment,
Embodiment 1
In being 75 milliliters still formula high-pressure reactor, puts into volume 11.2 gram C
5Petroleum resin, 30 milliliters of solvent orange 2 As, the modified skeletal nickel catalyst after the 1.5 gram activation, airtight rear substitution air, charge into the hydrogen of 2.0MPa then, put into slowly heat temperature raising to 180 degree of oil bath, adjust hydrogen valve, make system pressure reach 6.0MPa, kept C then 6 hours
5The resin form and aspect are improved to and are pale yellow near water white.
Embodiment 2
In being 75 milliliters still formula high-pressure reactor, puts into volume 11.2 gram C
9Petroleum resin, 30 milliliters of solvent orange 2 As, the modified skeletal nickel catalyst after the 1.5 gram activation, airtight rear substitution air, charge into the hydrogen of 2.0MPa then, put into slowly heat temperature raising to 200 degree of oil bath, adjust hydrogen valve, make system pressure reach 6.0MPa, kept C then 4 hours
9The resin form and aspect are improved to and are pale yellow near water white.
Embodiment 3
In being 75 milliliters still formula high-pressure reactor, puts into volume 8 gram C
5Petroleum resin, 25 milliliters of solvent B, the modified skeletal nickel catalyst after the 2 gram activation, airtight rear substitution air, charge into the hydrogen of 3.0MPa then, put into slowly heat temperature raising to 200 degree of oil bath, adjust hydrogen valve, make system pressure reach 7.5MPa, kept C then 4 hours
5The resin form and aspect are improved to and are water white.
Embodiment 4
In being 75 milliliters still formula high-pressure reactor, puts into volume 8 gram C
9Petroleum resin, 25 milliliters of solvent B, the modified skeletal nickel catalyst after the 2 gram activation, airtight rear substitution air, charge into the hydrogen of 3.0MPa then, put into slowly heat temperature raising to 180 degree of oil bath, adjust hydrogen valve, make system pressure reach 7.5MPa, kept C then 3 hours
9The resin form and aspect are improved to and are water white.
Embodiment 5
In being 75 milliliters still formula high-pressure reactor, puts into volume 11.2 gram C
5Petroleum resin, 30 milliliters of solvent C, the modified skeletal nickel catalyst after the 2 gram activation, airtight rear substitution air, charge into the hydrogen of 3.0MPa then, put into slowly heat temperature raising to 200 degree of oil bath, adjust hydrogen valve, make system pressure reach 7.0MPa, kept C then 4 hours
5The resin form and aspect are improved to water white.
Embodiment 6
In being 75 milliliters still formula high-pressure reactor, puts into volume 11.2 gram C
9Petroleum resin, 30 milliliters of solvent C, the modified skeletal nickel catalyst after the 2 gram activation, airtight rear substitution air, charge into the hydrogen of 3.0MPa then, put into slowly heat temperature raising to 180 degree of oil bath, adjust hydrogen valve, make system pressure reach 7.0MPa, kept C then 3 hours
9The resin form and aspect are improved to water white.
Embodiment 7
In being the Chinese style autoclave of 1 liter, puts into volume 200 gram C
5Petroleum resin, 600 milliliters of solvent B, the modified skeletal nickel catalyst after the 30 gram activation, airtight rear substitution air charges into the hydrogen of 4.0MPa then, and slowly heat temperature raising to 180 degree is adjusted hydrogen valve, makes system pressure reach 8.0MPa, keeps C then 3 hours
5The resin form and aspect are improved to and are water white.
Embodiment 8
In being the Chinese style autoclave of 1 liter, puts into volume 200 gram C
9Petroleum resin, 600 milliliters of solvent B, the modified skeletal nickel catalyst after the 30 gram activation, airtight rear substitution air charges into the hydrogen of 4.0MPa then, and slowly heat temperature raising to 160 degree is adjusted hydrogen valve, makes system pressure reach 8.0MPa, keeps C then 2 hours
9The resin form and aspect are improved to and are water white.
Embodiment 9
In being the Chinese style autoclave of 50 liters, volume puts into 8 kilograms of C
5Petroleum resin, 25 liters of solvent B, the modified skeletal nickel catalyst after 2 kilograms of activation, airtight rear substitution air charges into the hydrogen of 4.0MPa then, and slowly heat temperature raising to 200 degree is adjusted hydrogen valve, makes system pressure reach 8.0MPa, keeps C then 4 hours
5The resin form and aspect are improved to and are water white.
Embodiment 10
In being the Chinese style autoclave of 50 liters, volume puts into 8 kilograms of C
9Petroleum resin, 25 liters of solvent B, the modified skeletal nickel catalyst after 1.5 kilograms of activation, airtight rear substitution air charges into the hydrogen of 4.0MPa then, and slowly heat temperature raising to 200 degree is adjusted hydrogen valve, makes system pressure reach 8.0MPa, keeps C then 4 hours
9The resin form and aspect are improved to and are water white.
Claims (5)
1, a kind of C
5And C
9Petroleum resin still formula shortening decolouring, the method that eliminates the unusual smell is characterized in that, this method with modified raney ni as catalyzer, adopt relatively mild reaction conditions, resin is carried out hydrogenation reaction, make hydrogenated petroleum resin, the resin form and aspect are improved to and are water white and free from extraneous odour.Its method steps is:
In still formula high-pressure reactor, put into C
5Or C
9Petroleum resin, solvent, modified skeletal nickel catalyst, the ratio of solvent and petroleum resin is 1: 1-10: 1, the modified skeletal nickel catalyst consumption is the 1-20wt% of petroleum resin, airtight rear substitution air charges into the hydrogen of 1.0-2.0MPa then, puts into oil bath and slowly is heated to temperature of reaction, temperature of reaction is 100-250 ℃, adjust hydrogen valve, making system pressure reach pressure is 1.0-10.0MPa, then hold-time 2-10h.
2, a kind of C according to claim 1
5And C
9The decolouring of petroleum resin still formula shortening, the method that eliminates the unusual smell, it is characterized in that, described modified skeletal nickel catalyst, its precursor is made up of Primary Catalysts and promotor, Primary Catalysts is a nickel, promotor is made up of Al and M, and integral body is expressed as NiAlM, and wherein component M is one or more the mixture among Fe, Mn, Mo or the Cr; The weight percent of the pressed powder of Ni, Al, M is Ni:5-60%, Al:10-70%, M:0-20%, and catalyst precursor launches according to a conventional method.
3, a kind of C according to claim 2
5And C
9The decolouring of petroleum resin still formula shortening, the method that eliminates the unusual smell is characterized in that described temperature of reaction is 150-200 ℃.
4, a kind of C according to claim 2
5And C
9The decolouring of petroleum resin still formula shortening, the method that eliminates the unusual smell is characterized in that described system pressure is 3.5-8.0MPa.
5, a kind of C according to claim 2
5And C
9The decolouring of petroleum resin still formula shortening, the method that eliminates the unusual smell, it is characterized in that, described solvent be in perhydronaphthalene, dioxane, sherwood oil, ether, methyl ethyl ether, tetrahydrofuran (THF), methyl-formiate, ethyl formate, ethyl acetate, the methyl acetate one or more mixture.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100456240A CN100506864C (en) | 2006-01-06 | 2006-01-06 | Kettle type catalytic hydrogenation of C5 and C9 petroleum resin for removing color and foreign flavour |
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|---|---|---|---|
| CNB2006100456240A CN100506864C (en) | 2006-01-06 | 2006-01-06 | Kettle type catalytic hydrogenation of C5 and C9 petroleum resin for removing color and foreign flavour |
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| Publication Number | Publication Date |
|---|---|
| CN1803871A true CN1803871A (en) | 2006-07-19 |
| CN100506864C CN100506864C (en) | 2009-07-01 |
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|---|---|---|---|
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002131A (en) * | 2010-11-18 | 2011-04-06 | 中国海洋石油总公司 | Method for preparing high-quality hydrogenised C9 petroleum resin |
| CN102140153A (en) * | 2011-03-14 | 2011-08-03 | 杭州华品科技有限公司 | Preparation method for Carbon 5/Carbon 9 hydrogenated petroleum resin |
| CN102382261A (en) * | 2011-08-22 | 2012-03-21 | 天津市兴源化工有限公司 | Preparation method for light-chroma aromatic petroleum resin |
| CN102453217A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrogenation and decoloration method for petroleum resin |
| CN102618326A (en) * | 2012-04-20 | 2012-08-01 | 江苏联东化工股份有限公司 | Method for hydrofining C9 petroleum resin |
| CN105413694A (en) * | 2015-12-04 | 2016-03-23 | 大连理工大学 | Catalyst for catalyzing hydrogenation of petroleum resin as well as preparation method and application thereof |
| CN105749972A (en) * | 2014-12-17 | 2016-07-13 | 中国科学院大连化学物理研究所 | Petroleum resin hydrogenation catalyst and preparation method and application thereof |
| CN106397673A (en) * | 2016-06-03 | 2017-02-15 | 中国石油化工股份有限公司 | Method and apparatus for continuous kettle type hydrogenation of petroleum resin |
| CN107163186A (en) * | 2017-07-07 | 2017-09-15 | 常州市天鑫新材料科技有限公司 | A kind of diolefin thermal polymerization method prepares the method that the method and the thermal polymerization method of mixing copolymerization light dydrocarbon carbon nine of Petropols produce Petropols |
| CN112427037A (en) * | 2020-07-24 | 2021-03-02 | 浙江环化科技有限公司 | Nano catalyst for hydrogenation of C5 or C9 petroleum resin and hydrogenation and decoloration method |
-
2006
- 2006-01-06 CN CNB2006100456240A patent/CN100506864C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453217B (en) * | 2010-10-15 | 2013-11-20 | 中国石油化工股份有限公司 | Hydrogenation and decoloration method for petroleum resin |
| CN102453217A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrogenation and decoloration method for petroleum resin |
| CN102002131A (en) * | 2010-11-18 | 2011-04-06 | 中国海洋石油总公司 | Method for preparing high-quality hydrogenised C9 petroleum resin |
| CN102002131B (en) * | 2010-11-18 | 2013-04-17 | 中国海洋石油总公司 | Method for preparing high-quality hydrogenised C9 petroleum resin |
| CN102140153A (en) * | 2011-03-14 | 2011-08-03 | 杭州华品科技有限公司 | Preparation method for Carbon 5/Carbon 9 hydrogenated petroleum resin |
| CN102140153B (en) * | 2011-03-14 | 2012-11-28 | 杭州华品科技有限公司 | Preparation method for Carbon 5/Carbon 9 hydrogenated petroleum resin |
| CN102382261A (en) * | 2011-08-22 | 2012-03-21 | 天津市兴源化工有限公司 | Preparation method for light-chroma aromatic petroleum resin |
| CN102382261B (en) * | 2011-08-22 | 2013-03-06 | 天津市兴源化工有限公司 | Preparation method for light-chroma aromatic petroleum resin |
| CN102618326A (en) * | 2012-04-20 | 2012-08-01 | 江苏联东化工股份有限公司 | Method for hydrofining C9 petroleum resin |
| CN102618326B (en) * | 2012-04-20 | 2013-12-11 | 江苏联东化工股份有限公司 | Method for hydrofining C9 petroleum resin |
| CN105749972A (en) * | 2014-12-17 | 2016-07-13 | 中国科学院大连化学物理研究所 | Petroleum resin hydrogenation catalyst and preparation method and application thereof |
| CN105749972B (en) * | 2014-12-17 | 2018-11-02 | 中国科学院大连化学物理研究所 | A kind of hydrogenation of petroleum resin catalyst and its preparation method and application |
| CN105413694A (en) * | 2015-12-04 | 2016-03-23 | 大连理工大学 | Catalyst for catalyzing hydrogenation of petroleum resin as well as preparation method and application thereof |
| CN106397673A (en) * | 2016-06-03 | 2017-02-15 | 中国石油化工股份有限公司 | Method and apparatus for continuous kettle type hydrogenation of petroleum resin |
| CN106397673B (en) * | 2016-06-03 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of method and device of continuous autoclave hydrogenation of petroleum resin |
| CN107163186A (en) * | 2017-07-07 | 2017-09-15 | 常州市天鑫新材料科技有限公司 | A kind of diolefin thermal polymerization method prepares the method that the method and the thermal polymerization method of mixing copolymerization light dydrocarbon carbon nine of Petropols produce Petropols |
| CN112427037A (en) * | 2020-07-24 | 2021-03-02 | 浙江环化科技有限公司 | Nano catalyst for hydrogenation of C5 or C9 petroleum resin and hydrogenation and decoloration method |
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| CN100506864C (en) | 2009-07-01 |
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