CN102936317B - Catalytic hydrogenation method for C5 petroleum resin - Google Patents
Catalytic hydrogenation method for C5 petroleum resin Download PDFInfo
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- CN102936317B CN102936317B CN201110234154.3A CN201110234154A CN102936317B CN 102936317 B CN102936317 B CN 102936317B CN 201110234154 A CN201110234154 A CN 201110234154A CN 102936317 B CN102936317 B CN 102936317B
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Abstract
The invention provides a catalytic hydrogenation method for a C5 petroleum resin. The C5 petroleum resin is transferred into a C5 hydrogenation petroleum resin under the catalytic action of a palladium bimetallic catalyst, wherein the catalyst comprises an alumina-titanium oxide compounded carrier and metal palladium and metal molybdenum or metal tungsten which are loaded on the compounded carrier. The content of metal palladium is 0.2-0.4% based on the weight of the catalyst; and the weight ratio of metal palladium to the molybdenum or metal tungsten is 1 : 0.8-2. The process conditions of catalytic hydrogenation of the C5 petroleum resin are as follows: a reaction temperature is 70-150 DEG C; a reaction pressure is 3-8 MPa; and a feeding space velocity is 1-3 h<-1>; The prepared C5 hydrogenation petroleum resin has a bromine index smaller than 1, a Gardner chromaticity smaller than 2, a softening point higher than 100 DEG C and a hydrogenation transformation rate reaching as high as 93-98%; and can be applied to various industries of adhesive, traffic paint, printing ink, rubber, etc.
Description
Technical field
The present invention relates to a kind of C
5petroleum resin catalytic hydrogenation method, is specifically related to a kind of palladium series hydrocatalyst catalysis C that uses
5hydrogenation of petroleum resin method.
Background technology
Along with the development of China's oil chemical industry, also increase year after year of the throughput of ethene.C
5petroleum resin are the by product C with ethylene unit
5cut is main raw material, the lower polymkeric substance of solid-state or thick relative molecular mass being polymerized under catalyzer exists, and its average molecular mass is generally between 1000-3000.This resin price is cheap, has the excellent performance such as acidproof, alkaline-resisting and anti-aging, is therefore widely used in adhesive tape, thermosol, the aspect such as coating, ink and rubber for road.Existing C
5petroleum resin are generally reddish-brown, and softening temperature is 120 DEG C of left and right; But along with the development in the each field of industry, the quality of people to petroleum resin, especially its form and aspect and softening temperature require more and more higher; Such as the need sharp increase of the field such as thermosol and paint of coating to the low white high-quality petroleum resin of softening temperature; And reddish-brown C
5petroleum resin range of application is very limited.Therefore, external many companies take hydrogenation technique to make C
5petroleum resin are converted into C
5hydrogenated petroleum resin.
C
5hydrogenated petroleum resin is to make C by shortening
5two keys in petroleum resin are saturated, and deviate from resin residual halogen element and making in polymerization process.Shortening process improvement colourity and the photo and thermal stability of resin, solved C
5the smell of petroleum resin and oxidative stability problem, widened C greatly
5the Application Areas of petroleum resin.C
5hydrogenated petroleum resin has been widely used in the every profession and trades such as tackiness agent, traffic paint, ink and rubber.According to external experience, C
5hydrogenation of petroleum resin will be China C
5petroleum resin are realized seriation, commercial important channel, are also the important means of increasing economic efficiency; Therefore, accelerate C
5the research and development of hydrogenated petroleum resin are very important.
Owing to producing C
5, there are two keys, and contain halogenide, hydrogen sulfide in the reason of raw material and polymerization technique when petroleum resin, partial synthesis technique also has gel to generate on it, therefore, and C
5hydrogenation of petroleum resin difficulty is very large.The existing catalyst system using is mainly precious metal and the large class of base metal two.The C that prior art Literature is introduced
5hydrogenation of petroleum resin catalyzer has Ni/Al
2o
3, Pd/Al
2o
3, Ni/Si etc.As patent CN100389874C discloses a kind of C
5hydrogenation of petroleum resin catalyzer, taking aluminum oxide as carrier, taking palladium as active ingredient, its weight percentage is 1-1.5%; Catalyst adjuvant X
1for one or more in lithium, sodium, potassium, its weight percentage is 0.5-5%; Auxiliary agent X
2for molybdenum and/or tungsten, its weight percentage is 1-5%.When described catalyzer application, hydrogenation temperature is 150-300 DEG C, and pressure is 10-20Mpa, liquid hourly space velocity 0.5-1.5h
-1, hydrogen/oil mol ratio is 0.5-2.5.This invention has solved that domestic C 5 petroleum resin hydrogenation unit all adopts import palladium series catalyst and derivative expense is high and the large problem of cost; But this catalyzer is in when application, it is under comparatively high temps and pressure, to carry out hydrogenation reaction that processing condition require, and such processing condition make hydrogenation unit energy and material consumption very high, and running cost is very large.
A kind of preparation method of C 5 hydrogenated petroleum resin is provided for another patent CN200510080028, and the temperature of its hydrogenation reaction is 150-350 DEG C, and pressure is 6-20Mpa, and liquid air speed is 0.5-2h
-1; Preferable reaction temperature is 280-320 DEG C, and pressure is 10-17Mpa.The catalytic hydrogenation component weight ratio wherein adopting is: catalyst carrier alumina is 100 parts, and palladium content is 0.8 part, and transition metal copper content is 0.2 part, and rare earth metal cerium content is 0.5 part, and the 4th main group element tin content is 1 part.This catalyzer is applied to C 5 petroleum resin hydrogenation, has obtained that bromine valency is low, form and aspect are low, and outward appearance is colourless product.But hydrogenation reaction temperature and pressure is higher in this patent equally, be not easy to the safety operation of device.
China is to C
5the research of petroleum resin shortening is started late, most of C
5hydrogenation of petroleum resin device industrial scale is little, and quality product is not high, and particularly the main quality index such as product colourity, softening temperature is unstable; And many devices are in end-of-life stage.For this present situation, domestic C
5in hydrogenation of petroleum resin device, all adopt import catalyzer to produce; Therefore, be badly in need of C
5petroleum resin catalytic hydrogenation method carries out innovation research.Because C 5 petroleum resin is a kind of heat-sensitive substance, the research and development of the catalyzer with low temperature hydrogenation activity are seemed to particularly important.
Summary of the invention
Contriver is at C
5hydrogenation of petroleum resin catalyzer Application Areas has been carried out research extensively and profoundly, to finding a kind of C
5the saturate catalytic hydrogenation method of hydrogenation of petroleum resin.Found that, use a kind of palladium series duplex metal catalyzer, and under certain processing condition, can make C
5the saturation ratio of petroleum resin increases greatly, and product colourity is greatly improved, and presents white or colourless; And the catalyzer Heat stability is good using, the life-span is long.
The invention provides a kind of C
5petroleum resin catalytic hydrogenation method, i.e. C
5petroleum resin hydrocracking under palladium series duplex metal catalyst is C
5hydrogenated petroleum resin, described catalyzer comprises aluminium oxide-titanium oxide complex carrier and loads on palladium metal and metal molybdenum or the tungsten on described complex carrier; Wherein the weight of the content of palladium metal based on described catalyzer is 0.2-0.4%; And palladium metal and metal molybdenum or with the weight ratio of tungsten be 1: 0.8-1: 2; C
5the processing condition of petroleum resin shortening are: temperature of reaction 70-150 DEG C, and reaction pressure is 3-8MPa, charging air speed is 1-3h
-1.Preferred described processing condition are: temperature of reaction 90-110 DEG C, and reaction pressure is 3.5-6.0MPa, charging air speed is 1.5-2.5h
-1.
Preferred described catalyst specific surface is 70-210m
2/ g, pore volume is 0.6-1.6ml/g.
Preferably products C described in the present invention
5hydrogenated petroleum resin bromine valency < 1, Gardner colourity < 2, and softening temperature is higher than 100 DEG C, and hydrogenation conversion is 93-98%.
Embodiment
Bromine valency: bromine valency is used for weighing oil samples presence of unsaturates, represents with the grams of 100 grams of bromines that oil samples was consumed; Bromine valency is higher, and the contained unsaturated hydrocarbons of oil samples is more.It detects and adopts quality of chemical products index, adopts microcoulomb method to analyze oil samples.
We describe the hydrogenation saturation ratio of product conventionally with hydrogenation conversion; Hydrogenation conversion=[(raw material bromine valency-product bromine valency)/raw material bromine valency] * 100%.
Colourity is the appearance index of sample, and what its reacted is the color harmony saturation ratio of color.With platinum cobalt colorimetric method for determining.
Charging air speed is inlet amount/catalyst quality per hour, and unit is h
-1.
Softening temperature refers to the temperature that material is softening.Temperature when mainly referring to amorphous polymer and starting deliquescing.The test of employing ring and ball method.The steel ball of definite quality is placed on the metal ring that fills up sample, under the Elevated Temperature Conditions of regulation, steel ball enters sample, fall from certain height, temperature in the time that steel ball touches underlying metal baffle plate, is considered as its softening temperature, with centigradetemperature represent (DEG C).
The present invention describes the present invention in detail by following examples, can make the present invention of those skilled in the art comprehend, but these embodiment does not form any restriction to scope of the present invention.
In the present invention, the preparation of catalyzer adopts pickling process, palladium metal and molybdenum or tungsten is immersed on complex carrier, then makes through super-dry and roasting.The using method of catalyzer of the present invention is to make C
5the charging of petroleum resin and hydrogen contacts with described catalyzer in reaction unit.
Any suitable reactions device that the present invention's reaction unit used is known to those skilled in the art, for example, use isothermal bed hydroprocessing reaction unit.In the described charging of following examples, hydrogen and C
5the volume ratio of petroleum resin is 800: 1, before described charging is dropped into reaction unit, first utilize hydrogen by the catalyst reduction being loaded in reaction unit, for example, under the constant temperature of 120 DEG C, utilize hydrogen reducing 10 hours, then under suitable processing condition to C
5petroleum resin carry out hydrotreatment.Suitable processing condition are as follows: temperature in 70-150 DEG C, and preferably 90-110 DEG C, reaction pressure is 3-8MPa, preferably 3.5-6.0MPa, charging air speed is 1-3h
-1, preferably 1.5-2.5h
-1.
Embodiment 1
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 85g composite carrier load bimetallic catalyst of the present invention into, this catalyzer is trifolium shape, and active ingredient is palladium: 0.2%, and molybdenum: 0.2%; Catalyst specific surface is 70m
2/ g, pore volume is 0.6ml/g.Temperature of reaction is 70 DEG C, and reaction pressure is 6.0MPa, and charging air speed is 1h
-1, reacted C
5hydrogenated petroleum resin character is in table 1.
Embodiment 2
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 85g composite carrier load bimetallic catalyst of the present invention into, this catalyzer is trifolium shape, and active ingredient is palladium 0.2%, tungsten: 0.2%; Catalyst specific surface is 80m
2/ g, pore volume is 0.7ml/g.Temperature of reaction is 80 DEG C, and reaction pressure is 5.0MPa, and charging air speed is 1.5h
-1, reacted C
5hydrogenated petroleum resin character is in table 1.
Embodiment 3
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 85g composite carrier load bimetallic catalyst of the present invention into, this catalyzer is trifolium shape, and active ingredient is palladium: 0.2%, and molybdenum: 0.16%; Catalyst specific surface is 100m
2/ g, pore volume is 0.8ml/g.Temperature of reaction is 90 DEG C, and reaction pressure is 4.0MPa, and charging air speed is 2h
-1, reacted C
5hydrogenated petroleum resin character is in table 1.
Embodiment 4
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 85g composite carrier load bimetallic catalyst of the present invention into, this catalyzer is trifolium shape, and active ingredient is palladium: 0.3%, and molybdenum: 0.3%; Catalyst specific surface is 130m
2/ g, pore volume is 0.9ml/g.Temperature of reaction is 100 DEG C, and reaction pressure is 3.5MPa, and charging air speed is 2.5h
-1, reacted C
5hydrogenated petroleum resin character is in table 1.
Embodiment 5
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 85g composite carrier load bimetallic catalyst of the present invention into, this catalyzer is trifolium shape, and active ingredient is palladium: 0.3%, and tungsten: 0.3%; Catalyst specific surface is 130m
2/ g, pore volume is 0.9ml/g.Temperature of reaction is 100 DEG C, and reaction pressure is 5.0MPa, and charging air speed is 2h
-1, reacted C
5hydrogenated petroleum resin character is in table 1.
Embodiment 6
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 85g composite carrier load bimetallic catalyst of the present invention into, this catalyzer is trifolium shape, and active ingredient is palladium: 0.3%, and molybdenum: 0.5%; Catalyst specific surface is 140m
2/ g, pore volume is 0.9ml/g.Temperature of reaction is 110 DEG C, and reaction pressure is 4.5MPa, and charging air speed is 2.5h
-1, reacted C
5hydrogenated petroleum resin character is in table 1.
Embodiment 7
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 85g composite carrier load bimetallic catalyst of the present invention into, this catalyzer is trifolium shape, and active ingredient is palladium: 0.4%, and molybdenum: 0.4%; Catalyst specific surface is 150m
2/ g, pore volume is 1.1ml/g.Temperature of reaction is 130 DEG C, and reaction pressure is 4.0MPa, and charging air speed is 1.5h
-1, reacted C
5hydrogenated petroleum resin character is in table 1.
Embodiment 8
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 85g composite carrier load bimetallic catalyst of the present invention into, this catalyzer is trifolium shape, and active ingredient is palladium: 0.4%, and tungsten: 0.4%; Catalyst specific surface is 180m
2/ g, pore volume is 1.4ml/g.Temperature of reaction is 150 DEG C, and reaction pressure is 3.0MPa, and charging air speed is 3h
-1, reacted C
5hydrogenated petroleum resin character is in table 1.
Embodiment 9
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 85g composite carrier load bimetallic catalyst of the present invention into, this catalyzer is trifolium shape, and active ingredient is palladium: 0.4%, and molybdenum: 0.6%; Catalyst specific surface is 190m
2/ g, pore volume is 1.2ml/g.Temperature of reaction is 120 DEG C, and reaction pressure is 6.0MPa, and charging air speed is 2h
-1, reacted C
5hydrogenated petroleum resin character is in table 1.
Embodiment 10
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 85g composite carrier load bimetallic catalyst of the present invention into, this catalyzer is trifolium shape, and active ingredient is palladium: 0.3%, and tungsten: 0.4%; Catalyst specific surface is 170m
2/ g, pore volume is 0.9ml/g.Temperature of reaction is 100 DEG C, and reaction pressure is 8.0MPa, and charging air speed is 1.5h
-1, reacted C
5hydrogenated petroleum resin character is in table 1.
Table 1 hydroconversion condition and C
5hydrogenated petroleum resin character
Comparative example 1
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 86g catalyzer into, this catalyzer is import PGC catalyzer, and this catalyzer is spherical in shape, and active ingredient is palladium: 1.0%; Catalyst specific surface is 140m
2/ g, pore volume is 0.54ml/g.Temperature of reaction is 120 DEG C, and reaction pressure is 5.0MPa, and charging air speed is 3.0h
-1, reacted C
5hydrogenated petroleum resin character is in table 2.
Embodiment 11
Use 100ml isothermal bed hydroprocessing reaction evaluating device, pack 85g composite carrier load bimetallic catalyst of the present invention into, this catalyzer is trifolium shape, and active ingredient is palladium: 0.3%, and molybdenum: 0.3%; Catalyst specific surface is 160m
2/ g, pore volume is 0.9ml/g.Use the processing condition same with comparative example 1 to C
5petroleum resin carry out shortening, and temperature of reaction is 120 DEG C, and reaction pressure is 5.0MPa, and charging air speed is 3.0h
-1, reacted C
5hydrogenated petroleum resin character is in table 2.
Table 2 C
5hydrogenated petroleum resin character
From table 2, under same appreciation condition, the C of catalyst described in the application of the invention
5the bromine valency of hydrogenated petroleum resin and colourity are all less than the C with PGC catalyst
5hydrogenated petroleum resin, same hydrogenation conversion is also higher, illustrates and uses catalyzer of the present invention at C
5hydrogenation activity in petroleum resin is higher than import PGC catalyzer.
Import PGC catalyzer is the spheroidal particle that alumina catalyst support load has 1.0% active component palladium weighing, and its particle diameter is at 2-3mm, and the basic load of palladium particle is at the extexine of carrier.Catalyzer of the present invention is compared with PGC catalyzer, active ingredient becomes two component metals (containing palladium 0.2-0.4%) catalysis from single palladium metal (1.0%), and increase titanium oxide and form complex carrier, be conducive to the dispersion of active ingredient on carrier, bimetallic synergy has improved catalyst activity, has especially improved the low-temperature catalytic activity of catalyzer.In addition, catalyzer pore volume of the present invention is larger, and macropore is not only conducive to the macromolecular reactant mass transfer of resene, is also conducive to the desorption of colloid, thus extending catalyst life cycle.
Claims (6)
1. a C
5petroleum resin catalytic hydrogenation method, is characterized in that, C
5petroleum resin hydrocracking under palladium series duplex metal catalyst is C
5hydrogenated petroleum resin, described catalyzer comprises aluminium oxide-titanium oxide complex carrier and loads on palladium metal and metal molybdenum or the tungsten on described complex carrier; Wherein the weight of the content of palladium metal based on described catalyzer is 0.2-0.4%; And palladium metal and metal molybdenum or with the weight ratio of tungsten be 1: 0.8-1: 2; Described C
5the processing condition of petroleum resin shortening are: temperature of reaction 70-150 DEG C, and reaction pressure is 3-8MPa, charging air speed is 1-3h
-1.
2. method according to claim 1, is characterized in that, described temperature of reaction is 90-110 DEG C.
3. method according to claim 1, is characterized in that, described reaction pressure is 3.5-6.0MPa.
4. method according to claim 1, is characterized in that, described charging air speed is 1.5-2.5h
-1.
5. according to the method described in any one in claim 1 to 4, it is characterized in that, described catalyst specific surface is 70-210m
2/ g, pore volume is 0.6-1.6ml/g.
6. according to the method described in any one in claim 1 to 4, it is characterized in that described C
5the bromine valency < 1 of hydrogenated petroleum resin, Gardner colourity < 2, and softening temperature is higher than 100 DEG C, and hydrogenation conversion is 93-98%.
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|---|---|---|---|
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429890A (en) * | 2001-12-31 | 2003-07-16 | 北京燕山石油化工公司研究院 | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use |
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|---|---|---|---|---|
| MXPA05012893A (en) * | 2005-11-29 | 2007-11-23 | Mexicano Inst Petrol | Catalyst for the hydrodesulfurization of residues and heavy crudes. |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429890A (en) * | 2001-12-31 | 2003-07-16 | 北京燕山石油化工公司研究院 | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use |
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