CN1485352A - Hydrogenation catalyst for preparing dicyclopentadiene hydrogenated petroleum resin - Google Patents
Hydrogenation catalyst for preparing dicyclopentadiene hydrogenated petroleum resin Download PDFInfo
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- CN1485352A CN1485352A CNA021371148A CN02137114A CN1485352A CN 1485352 A CN1485352 A CN 1485352A CN A021371148 A CNA021371148 A CN A021371148A CN 02137114 A CN02137114 A CN 02137114A CN 1485352 A CN1485352 A CN 1485352A
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- petroleum resin
- catalyst
- dicyclopentadiene
- resin
- hydrogenation
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Abstract
A hydrogenation catalyst for preparing dicyclopentadiene hydrogenant petroleum resin by dicyclopentadiene petroleum resin. The active components of the resin are Pd and Pt. The contents of Pd and Pt are 0.1- 1.0 wt% and 0.05-0.5 wt%, respectively. The carrier of the catalyst is gamma-Al2O3, the specific surface are is 150-250m2/g, the volume is 0.5-0.9ml/g. Hydrogenant resin prepared from dicyclopentadiene petroleum resin through the catalyst has a lowered content of unsaturated hydrocarbon bonds, and the color of the resin is improved to water-white.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst, particularly be used for preparing by shortening the catalyzer of dicyclopentadiene hydrogenated petroleum resin by dicyclopentadiene petroleum resin.
Background technology
Dicyclopentadiene petroleum resin is made by hot polymerization by dicyclopentadiene usually, it is the relatively low thermoplastic hydrocarbon resin of a kind of number-average molecular weight, utilize it and other resin to have this characteristic of consistency preferably, be often used as tackifier and binding agent, obtained at aspects such as hot melt adhesive, Pressuresensitive Tape, ink printing and rubber using widely.Dicyclopentadiene derives from the C5 fraction separated product of petroleum cracking system ethylene by-product greatly at present, the petroleum resin ubiquity form and aspect that this dicyclopentadiene makes are dark, flavor is smelly, unsaturated hydrocarbons linkage content height, thermostability and defective such as oxidative stability is low, cohesive force is relatively poor, with a lot of resinous substrates can not be compatible well, relatively poor as the tackifier result of use.Usually people adopt the method for hydrogenation to improve the performance of dicyclopentadiene petroleum resin, can reduce the content of unsaturated hydrocarbons key effectively by hydrogenation, thereby improve the thermostability of dicyclopentadiene petroleum resin and consistency etc.
Patent US4,384,080 and US4,952,639 have described the hydrogenation of petroleum resin method of making hydrogenation catalyst with precious metals such as nickel, palladium, platinum, rhenium, rutheniums, and generally adopting the single component metal is the catalyst activity component.Patent US4,540,480 have introduced a kind of hydrogenation of petroleum resin method, and the active ingredient of catalyst system therefor is used in combination above-mentioned precious metal, and the carrier of catalyzer generally adopts Al
2O
3, it is said that the catalyzer that adopts has higher active and long work-ing life, the hydrogenated petroleum resin iodine number≤60g/100g that obtains, gardner form and aspect≤1.The catalyzer that existing these hydrogenation of petroleum resin methods are adopted is remarkable for the unsaturated hydrocarbons linkage content effect that reduces dcpd resin, but improve aspect the form and aspect of resin not very good.Particularly separate in the dicyclopentadiene that obtains and contain more impurity by the C5 fraction of petroleum cracking system ethylene by-product, usually purity only is 75～85wt%, other impurity that contains comprises unknown dipolymer, trimer, indenes class, isoprene dimer, benzene and toluene etc., the dicyclopentadiene petroleum resin that makes is unsaturated hydrocarbons linkage content height not only, and form and aspect are darker.This dicyclopentadiene petroleum resin carries out hydrogenation reaction with existing general hydrogenation of petroleum resin catalyzer can not obtain form and aspect ideal hydrogenation resin.
Summary of the invention
The invention provides a kind of hydrogenation catalyst that is used for by dicyclopentadiene petroleum resin hydrogenation preparing dicyclopentadiene hydrogenated petroleum resin, its technical problem to be solved is after hydrogenation reaction adopts this hydrogenation catalyst, the hydrogenated petroleum resin that makes not only requires the unsaturated hydrocarbons linkage content low, thermostability and oxidative stability are good, and form and aspect also should be improved completely.It is that the dicyclopentadiene petroleum resin that raw material makes carries out hydrotreatment that this hydrogenation catalyst is used for the C5 fraction with petroleum cracking system ethylene by-product is separated the dicyclopentadiene that obtains, and can obtain the ideal effect equally.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of hydrogenation catalyst that is used for by dicyclopentadiene petroleum resin hydrogenation preparing dicyclopentadiene hydrogenated petroleum resin, this catalyst activity component is Pd and Pt, the content of Pd is 0.1～1.0wt%, and the content of Pt is 0.05～0.5wt%, and support of the catalyst is γ-Al
2O
3, its specific surface is 150～250m
2/ g, pore volume are 0.5～0.9ml/g.
The content of above-mentioned catalyst activity component Pd is preferably 0.3～0.5wt%; The content of Pt is preferably 0.1～0.2wt%.
Catalyst consumption is generally dicyclopentadiene petroleum resin: catalyzer=100: 1.0～4.0 (weight ratio).
The pickling process that catalyzer can adopt those skilled in the art to know prepares, and the starting material of Pd can adopt PdCl
2, the starting material of Pt can adopt H
2PtCl
6Elder generation is with PdCl during preparation
2And H
2PtCl
6Be dissolved in the HCl solution, then with γ-Al
2O
3Pour in the solution and flood.Oven dry while stirring just can make finished catalyst behind the mixture ageing after high-temperature roasting.
Key of the present invention is that catalyzer selected suitable active ingredient and selected the suitable γ-Al of physical structure
2O
3As carrier, the contriver found through experiments, this catalyzer has demonstrated beyond thought effect aspect the form and aspect of dicyclopentadiene petroleum resin improving, even the dicyclopentadiene petroleum resin that obtains with the relatively poor dicyclopentadiene hot polymerization that is obtained by the C5 fraction separation of form and aspect is a raw material, adopt this catalyzer to carry out hydrogenation reaction, the hydrogenation resin that makes not only unsaturated hydrocarbons linkage content obviously reduces, and the resin form and aspect are improved to and are water white.
Embodiment
In an embodiment, the testing method of each index is as follows:
Softening temperature: ring and ball method (GB4507-84)
Form and aspect: iron-cobalt colorimetry, i.e. gardner method (GB1722-79)
Bromine number: volumetry (SH/T0236-92)
Hydrogenation ratio:
Dicyclopentadiene petroleum resin raw material index:
Softening temperature (℃) 118
Bromine number (g bromine/100g) 83.7
Form and aspect 7
[embodiment 1～8]
One, Preparation of catalysts:
Take by weighing a certain amount of PdCl
2And H
2PtC
16, it is dissolved among the HCl of 0.1N, getting specific surface is 150～250m
2/ g, pore volume are γ-Al of 0.5～0.9ml/g
2O
3As carrier.With this Al
2O
3Pour in the above-mentioned solution aging 2 hours into.With infrared lamp it is dried while stirring, this catalyst precursor is placed chamber type electric resistance furnace in 300 ℃ of following roastings 1 hour again, in 500 ℃ of following roastings 3 hours, it was standby to obtain finished catalyst again.Catalyzer index and the catalyst consumption of each embodiment see Table 1.
Two, evaluating catalyst:
At a capacity is that 2L is with adding 200ml hexanaphthene in the autoclave that stirs, and the dicyclopentadiene petroleum resin raw material of the broken shape of 200g, the catalyzer of aequum is added in the still again.With nitrogen and hydrogen the air in the still fully being replaced successively, is 280～300 ℃ in temperature then, and the reaction hydrogen pressure is to react 2～6 hours under the condition of 8.0～10.0MPa.Hydrogenation products reclaims after filtration that catalyzer, precipitation reclaim solvent, stripping takes off light and processes such as decompression dehydration and cooling forming, obtains the hydrogenated petroleum resin product.Product carries out index analysis, and the product index of each embodiment sees Table 2.
Table 1.
| Pd content (%) | Pt content (%) | Catalyst levels (resin/catalyst, weight ratio) | |
| Embodiment 1 | ????0.1 | ????0.48 | ????4.0 |
| Embodiment 2 | ????0.1 | ????0.40 | ????3.0 |
| Embodiment 3 | ????0.2 | ????0.35 | ????3.0 |
| Embodiment 4 | ????0.3 | ????0.20 | ????2.5 |
| Embodiment 5 | ????0.5 | ????0.10 | ????2.5 |
| Embodiment 6 | ????0.7 | ????0.10 | ????2.0 |
| Embodiment 7 | ????0.9 | ????0.08 | ????1.5 |
| Embodiment 8 | ????1.0 | ????0.05 | ????1.0 |
Table 2.
| Softening temperature (℃) | Bromine number (the g bromine/100g) | Form and aspect | Hydrogenation ratio (%) | |
| Embodiment 1 | ????108 | ????3.2 | Water white | ????96 |
| Embodiment 2 | ????113 | ????4.2 | Water white | ????95 |
| Embodiment 3 | ????105 | ????3.3 | Water white | ????96 |
| Embodiment 4 | ????105 | ????2.5 | Water white | ????97 |
| Embodiment 5 | ????111 | ????3.0 | Water white | ????96 |
| Embodiment 6 | ????108 | ????3.8 | Water white | ????95 |
| Embodiment 7 | ????104 | ????5.0 | Water white | ????94 |
| Embodiment 8 | ????101 | ????5.0 | Water white | ????94 |
Claims (3)
1, a kind of hydrogenation catalyst that is used for by dicyclopentadiene petroleum resin hydrogenation preparing dicyclopentadiene hydrogenated petroleum resin, this catalyst activity component is Pd and Pt, the content of Pd is 0.1～1.0wt%, and the content of Pt is 0.05～0.5wt%, and support of the catalyst is γ-Al
2O
3, its specific surface is 150～250m
2/ g, pore volume are 0.5～0.9ml/g.
2, hydrogenation catalyst according to claim 1, the content that it is characterized in that described catalyst activity component Pd is 0.3～0.5wt%.
3, hydrogenation catalyst according to claim 1, the content that it is characterized in that described catalyst activity component Pt is 0.1～0.2wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021371148A CN1189493C (en) | 2002-09-24 | 2002-09-24 | Hydrogenation catalyst for preparing dicyclopentadiene hydrogenated petroleum resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021371148A CN1189493C (en) | 2002-09-24 | 2002-09-24 | Hydrogenation catalyst for preparing dicyclopentadiene hydrogenated petroleum resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1485352A true CN1485352A (en) | 2004-03-31 |
| CN1189493C CN1189493C (en) | 2005-02-16 |
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ID=34146870
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021371148A Expired - Fee Related CN1189493C (en) | 2002-09-24 | 2002-09-24 | Hydrogenation catalyst for preparing dicyclopentadiene hydrogenated petroleum resin |
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|---|---|
| CN (1) | CN1189493C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404568C (en) * | 2005-06-28 | 2008-07-23 | 中国石油天然气集团公司 | Prepn of C5 hydrogenated petroleum resin |
| CN100451044C (en) * | 2005-11-29 | 2009-01-14 | 中国石油天然气集团公司 | Catalyst for preparing C5 hydrogenated petroleum resin, and its preparing method |
| CN101327453B (en) * | 2007-06-20 | 2011-05-11 | 中国石油天然气集团公司 | Aluminum-silicon-titanium composite oxide carrier and load type catalytic hydro-dearomatization catalyst |
| 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 |
| 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 |
| CN107096533A (en) * | 2017-06-02 | 2017-08-29 | 钦州学院 | A kind of benzene hydrogenating catalyst and preparation method |
-
2002
- 2002-09-24 CN CNB021371148A patent/CN1189493C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404568C (en) * | 2005-06-28 | 2008-07-23 | 中国石油天然气集团公司 | Prepn of C5 hydrogenated petroleum resin |
| CN100451044C (en) * | 2005-11-29 | 2009-01-14 | 中国石油天然气集团公司 | Catalyst for preparing C5 hydrogenated petroleum resin, and its preparing method |
| CN101327453B (en) * | 2007-06-20 | 2011-05-11 | 中国石油天然气集团公司 | Aluminum-silicon-titanium composite oxide carrier and load type catalytic hydro-dearomatization catalyst |
| 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 |
| CN102558444B (en) * | 2010-12-17 | 2013-07-31 | 中国石油天然气股份有限公司 | Method for preparing dicyclopentadiene hydrogenated petroleum resin |
| 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 |
| CN106268725B (en) * | 2015-08-10 | 2018-08-21 | 中国石油化工股份有限公司 | The hydrogenation catalyst and preparation method and application of the DCPD resins of dicyclopentadiene hot polymerization in cracking of ethylene carbon 9 |
| CN107096533A (en) * | 2017-06-02 | 2017-08-29 | 钦州学院 | A kind of benzene hydrogenating catalyst and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1189493C (en) | 2005-02-16 |
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