CN100404568C - Prepn of C5 hydrogenated petroleum resin - Google Patents
Prepn of C5 hydrogenated petroleum resin Download PDFInfo
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- CN100404568C CN100404568C CNB2005100800281A CN200510080028A CN100404568C CN 100404568 C CN100404568 C CN 100404568C CN B2005100800281 A CNB2005100800281 A CN B2005100800281A CN 200510080028 A CN200510080028 A CN 200510080028A CN 100404568 C CN100404568 C CN 100404568C
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Abstract
The preparation process of C5 hydrogenated petroleum resin with the C5 fraction as the side product of cracking ethylene includes the steps of: pre-treating material, neutralizing, water washing, eliminating chlorine ion impurity from crude resin product at 200-300 deg.c under the action of modified alumina as catalyst, and hydrogenation at 150-350 deg.c and 6.0-20.0 MPa in the presence of hydrogenation catalyst. The hydrogenation catalyst is prepared through spraying process and consists of catalyst carrier alumina 100 weight portions, Pd 0.2-1.2 weight portions, transition metal 0.06-0.48 weight portion, RE metal 0.001-0.05 weight portion and IV element 0.06-2.4 weight portions. The present invention is used in producing C5 hydrogenated petroleum resin with the material possessing relatively high cyclopentadiene and arene content.
Description
Affiliated technical field
The present invention relates to mix the preparation method of C 5 hydrogenated petroleum resin, particularly relating to mixing C5 fractions such as m-pentadiene with the cracking of ethylene by-product, isoprene, cyclopentadiene, amylene is the preparation method of feedstock production C 5 hydrogenated petroleum resin.
Background technology
C 5 petroleum resin is a kind of low-molecular-weight thermoplastic resin, C5 fraction by the ethylene unit by-product is polymerized under catalyst actions such as aluminum chloride, molecular-weight average is between 1000～3000, with oil product, grease, synthetic resins good consistency is arranged, good be mixed water tolerance, acid resistance of other materials, molten point is low, and binding property is good, and petroleum resin are mainly as tackiness agent, traffic paint, rubber ingredients, coating and printing ink.C 5 petroleum resin ubiquity form and aspect are dark, and defective such as smell is smelly, thermostability and oxidative stability are low has limited its range of application.The color of C 5 petroleum resin mainly is that the unsaturated link(age) of molecular resin inside forms, and these unsaturated link(age)s also are the reasons that causes petroleum resin products thermostability and light stability to worsen.It is saturated that C 5 hydrogenated petroleum resin is that the method by hydrogenation makes in the C 5 petroleum resin unsaturated link(age) be able to, and its color, thermostability, consistency etc. are greatly improved, and have good use properties, thereby obtain using more widely.
U.S. Pat 4,384,080 has reported that single component precious metals such as nickel, palladium, platinum, rhenium, ruthenium make the preparation method of the hydrogenated petroleum resin of hydrogenation catalyst.U.S. Pat 4,540,480 have introduced a kind of hydrogenation of petroleum resin method, and the active ingredient of catalyst system therefor is for using above-mentioned precious metal composite, and the carrier of catalyzer adopts Al
2O
3, the hydrogenated petroleum resin iodine number≤60g/100g that obtains.These methods are in that to reduce aspect the petroleum resin unsaturated link(age) content effect obvious, but improve aspect the form and aspect of resin not very good, this be because the color of petroleum resin remove have with unsaturated link(age) outside the Pass, also have at present as yet not other chromophores of understanding.There are shortcomings such as toxin immunity is poor, the life-span is short in noble metal catalyst simultaneously, all kinds of single noble metal catalyst long easy poisoning and deactivations of reason first catalyzer in work-ing life that studies show that, it two is easy coalescent inactivations of precious metal crystal grain at high temperature, this just causes catalyzer cost height, influences the economic benefit of product.In addition, C 5 hydrogenated petroleum resin belongs to heat-sensitive substance, and treating process is improper also can to influence performance.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of C 5 hydrogenated petroleum resin its objective is to obtain the petroleum resin products that the bromine valency is low, form and aspect are shallow, performance is good, and has reasonable benefit.Overcome low and the problem that form and aspect are high of the medium-term and long-term bromine valency that exists of actual production.
The technology used in the present invention: this method is a raw material with the C5 fraction of cracking of ethylene by-product, through raw materials pretreatment, with active ingredient m-pentadiene, isoprene, cyclopentadiene, amylene etc. under the aluminum trichloride catalyst effect, pass through cationic polymerization, again through neutralizing, wash, remove the impurity operation, in the presence of hydrogenation catalyst, carry out hydrogenation reaction, remove solvent through underpressure distillation and obtain finished product.It is 200-300 ℃ that this method removes the impurity temperature.Removing the impurity catalyzer is modified aluminas.The hydrogenation reaction temperature is 150-350 ℃, and pressure is 6.0-20.0MPa, liquid air speed 0.5-2h
-1Activity of hydrocatalyst component weight ratio is: 100 parts in aluminum oxide; Palladium 0.2-1.2 part; Transition metal 0.060.48 part, transition metal comprises: copper, nickel, cobalt, zinc; Rare earth metal is 0.1-5 part, and rare earth metal comprises: cerium, lanthanum, protactinium; The 4th main group element is 0.06-2.4 part, and the 4th main group element comprises: tin, germanium, lead.Aluminum oxide is a support of the catalyst, and its specific surface area is 80-150m
2/ g, pore volume are 0.2-0.4ml/g; Thin-film evaporator, distillation temperature 280-350 ℃, pressure 0-10kPa are adopted in underpressure distillation.
This invention found through experiments, increase crude resin and remove the impurity operation, to hydrogenation reaction with to improve the product form and aspect very favourable, judge thus, system's impurity chlorine element etc. may have restraining effect to the hydrogenation of palladium catalyst, is present in the form and aspect that influence resin on the molecular resin simultaneously.Remove preferably 260-280 ℃ of impurity temperature.
This invention is discovered, adds a small amount of rare earth ion and can improve the hydrogenation activity of palladium to C 5 petroleum resin, and the 4th main group element can obviously prolong the life-span of palladium catalyst.Above-mentioned activity of hydrocatalyst component is preferably: catalyst carrier alumina is 100 parts, and palladium is 0.8-1.0 part, and copper is 0.06-0.4 part, and cerium is 0.5-2.8 part, and tin is 0.06-2 part; The hydrogenation reaction temperature is preferably 280-320 ℃; Hydrogenation pressure is 10.0-17.0Mpa.
This invention considers that C 5 petroleum resin belongs to heat-sensitive substance, adopts thin-film evaporator when refining, and the residence time is short, and is very favourable to the product form and aspect.Preferably distillation temperature 290-300 ℃ of above-mentioned purification condition, pressure 0-10kPa.
Hydrogenation catalyst adopts the spraying method preparation, and the starting material of palladium, cerium, tin can adopt corresponding muriate.Carry out the preparation of carrier earlier, alumina balls are soaked, calcine the support of the catalyst that makes the rare earth processing in Cerium II Chloride; Palladium, cerium, tin isoreactivity component are being sprayed on the carrier, activatedly obtaining hydrogenation catalyst of the present invention.
The invention has the beneficial effects as follows: key of the present invention is that the catalyzer that is adopted selected to remove earlier before suitable active ingredient and the hydrogenation impurity such as chlorion, simultaneously the thin film evaporation technology is applied to the preparation of C 5 hydrogenated petroleum resin, the contriver found through experiments, during the C 5 hydrogenated petroleum resin that this method is applied to the higher raw material of cyclopentadiene, aromaticity content is produced, preferably resolve low and the problem that form and aspect are high of the medium-term and long-term bromine valency that exists of actual production, product not only unsaturated link(age) content obviously reduces, and outward appearance is colourless.
Embodiment
Below be representative embodiment and the comparative example of from a large amount of explorations experiment, picking out, further describe details of the present invention, but embodiment does not mean limitation of the present invention.
Embodiment:
The preparation hydrogenation catalyst adopts the spraying method preparation earlier.Catalyst carrier alumina weight is 100 parts, gets 0.8 part of palladium; 0.2 part of transition metal copper; 0.5 part of rare earth metal cerium; 1 part in the 4th main group element tin.Carry out the preparation of carrier earlier, alumina balls are soaked, calcine the support of the catalyst that makes the rare earth processing in Cerium II Chloride; Palladium, cerium, tin isoreactivity component are being sprayed on the carrier, activatedly obtaining hydrogenation catalyst of the present invention.
With the C5 fraction of cracking of ethylene by-product is raw material, through raw materials pretreatment, after polymerization under the aluminum trichloride catalyst effect, neutralization, washing, with the crude product C 5 petroleum resin in the reactor of hydrogenation catalyst is housed, 280 ℃ after dechlorination etc. removes the impurity reaction, in the fixed-bed reactor of hydrogenation catalyst are housed, carry out hydrogenation reaction, the hydrogenation reaction temperature is 160 ℃, pressure is 13MPa, liquid air speed 0.5h
-1, again through the thin-film evaporator underpressure distillation, 290 ℃ of distillation liquidus temperatures, pressure 10kPa removes solvent and obtains water white C 5 hydrogenated petroleum resin product, 110 ℃ of softening temperatures, bromine valency 0.6gBr2/100g, Gardner (Gardner) form and aspect are No. 0 look.
Comparative example 1:
With the C5 fraction of cracking of ethylene by-product is that the crude product C 5 petroleum resin of raw material after polymerization under the aluminum trichloride catalyst effect, neutralization, washing do not carry out the impurity removal operation, directly in being housed, the fixed-bed reactor of hydrogenation catalyst of the present invention carry out hydrogenation reaction, the hydrogenation reaction temperature is 160 ℃, pressure is 13MPa, liquid air speed 0.5h
-1, again through the thin-film evaporator underpressure distillation, 290 ℃ of distillation liquidus temperatures, pressure 10kPa removes solvent and obtains the C 5 hydrogenated petroleum resin product, 109 ℃ of softening temperatures, bromine valency 1.2gBr
2/ 100g, Gardner (Gardner) form and aspect are No. 3 looks.
Comparative example 2:
With the C5 fraction of cracking of ethylene by-product is that raw material is being equipped with in the modified aluminas reactor at the crude product C 5 petroleum resin after polymerization under the aluminum trichloride catalyst effect, neutralization, the washing, at 280 ℃ after dechlorination etc. removes the impurity reaction, in being housed, the fixed-bed reactor of hydrogenation catalyst of the present invention carry out hydrogenation reaction, the hydrogenation reaction temperature is 160 ℃, pressure is 13MPa, liquid air speed 0.5h
-1, again through conventional underpressure distillation, 290 ℃ of distillation liquidus temperatures, pressure 10kPa removes solvent and obtains the C 5 hydrogenated petroleum resin product, 106 ℃ of softening temperatures, bromine valency 1.6gBr
2/ 100g, Gardner (Gardner) form and aspect are No. 2 looks.
Comparative example 3:
With the C5 fraction of cracking of ethylene by-product is that raw material is being equipped with in the reactor of the present invention at the crude product C 5 petroleum resin after polymerization under the aluminum trichloride catalyst effect, neutralization, the washing, at 280 ℃ after dechlorination etc. removes the impurity reaction, in the fixed-bed reactor of the single component hydrogenation catalyst that palladium 1.0% is housed, carry out hydrogenation reaction, the hydrogenation reaction temperature is 160 ℃, pressure is 13MPa, liquid air speed 0.5h
-1, again through the thin-film evaporator underpressure distillation, 290 ℃ of distillation liquidus temperatures, pressure 10kPa removes solvent and obtains the C 5 hydrogenated petroleum resin product, 108 ℃ of softening temperatures, bromine valency 3.6gBr
2/ 100g, Gardner (Gardner) form and aspect are No. 5 looks.
Through contrast, reach a conclusion: by the C 5 hydrogenated petroleum resin that the embodiment of the invention is produced, Gardner (Gardner) form and aspect are No. 0 look.By the C 5 hydrogenated petroleum resin that comparative example is produced, Gardner (Gardner) form and aspect height.
Claims (3)
1. a hydrogenation catalyst that adopts the spraying method preparation is mainly used in the preparation process of C 5 hydrogenated petroleum resin, and it is characterized in that: its each component weight ratio is: catalyst carrier alumina is 100 parts; Palladium is 0.2-1.2 part; Transition metal is 0.06-0.48 part, and rare earth metal is 0.5-2.8 part, and the 4th main group element is 0.06-2.4 part, and wherein: transition metal is a copper, and rare earth metal is a cerium, and the 4th main group element is a tin.
2. hydrogenation catalyst according to claim 1, it is characterized in that: its each component weight ratio is: catalyst carrier alumina is 100 parts, palladium content is 0.8-1.0 part, transition metal copper content is 0.06-0.4 part, the rare earth metal cerium content is 0.5-2.8 part, and the 4th main group element tin content is 0.06-2 part.
3. hydrogenation catalyst according to claim 1, it is characterized in that: its each component weight ratio is: catalyst carrier alumina is 100 parts, and palladium content is 0.8 part, and transition metal copper content is 0.2 part, the rare earth metal cerium content is 0.5 part, and the 4th main group element tin content is 1 part.
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| CNB2005100800281A CN100404568C (en) | 2005-06-28 | 2005-06-28 | Prepn of C5 hydrogenated petroleum resin |
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| CNB2005100800281A CN100404568C (en) | 2005-06-28 | 2005-06-28 | Prepn of C5 hydrogenated petroleum resin |
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| CN1887927A CN1887927A (en) | 2007-01-03 |
| CN100404568C true CN100404568C (en) | 2008-07-23 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372598B (en) * | 2007-08-20 | 2012-01-11 | 北京路桥瑞通养护中心 | Energy-storing self-luminescent road marking coating |
| CN103450401B (en) * | 2012-06-01 | 2016-04-06 | 中国石油天然气股份有限公司 | A kind of C5 hydrogenated petroleum resin raw material and its preparation method and application |
| CN106279538A (en) * | 2015-09-25 | 2017-01-04 | 中国石油化工股份有限公司 | It is applicable to dechlorination method and the device of C5 hydrogenation of petroleum resin process |
| CN109718808B (en) * | 2019-01-09 | 2022-04-15 | 山东玉皇化工有限公司 | Selective hydrogenation catalyst, method for preparing hydrogenated petroleum resin, hydrogenated petroleum resin prepared by method, and hot-melt pressure-sensitive adhesive |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540480A (en) * | 1982-10-23 | 1985-09-10 | Arakawa Kagaku Kogyo Kabushiki Kaisha | Process for preparing hydrogenated petroleum resin |
| JP2001172323A (en) * | 1999-12-15 | 2001-06-26 | Arakawa Chem Ind Co Ltd | Hydrogenation method of hydroxyl group-containing petroleum resin and hydroxyl group-containing petroleum resin hydride obtained by the method |
| CN1485353A (en) * | 2002-09-24 | 2004-03-31 | 中国石化上海石油化工股份有限公司 | Method for production of dicyclopentadiene hydrogenated petroleum resin |
| CN1485352A (en) * | 2002-09-24 | 2004-03-31 | 中国石化上海石油化工股份有限公司 | Hydrogenation catalyst for preparing dicyclopentadiene hydrogenated petroleum resin |
| CN1563127A (en) * | 2004-03-23 | 2005-01-12 | 倪才国 | Method for preparing petroleum resin of piperyene |
-
2005
- 2005-06-28 CN CNB2005100800281A patent/CN100404568C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4540480A (en) * | 1982-10-23 | 1985-09-10 | Arakawa Kagaku Kogyo Kabushiki Kaisha | Process for preparing hydrogenated petroleum resin |
| JP2001172323A (en) * | 1999-12-15 | 2001-06-26 | Arakawa Chem Ind Co Ltd | Hydrogenation method of hydroxyl group-containing petroleum resin and hydroxyl group-containing petroleum resin hydride obtained by the method |
| CN1485353A (en) * | 2002-09-24 | 2004-03-31 | 中国石化上海石油化工股份有限公司 | Method for production of dicyclopentadiene hydrogenated petroleum resin |
| CN1485352A (en) * | 2002-09-24 | 2004-03-31 | 中国石化上海石油化工股份有限公司 | Hydrogenation catalyst for preparing dicyclopentadiene hydrogenated petroleum resin |
| CN1563127A (en) * | 2004-03-23 | 2005-01-12 | 倪才国 | Method for preparing petroleum resin of piperyene |
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