CN102002130B - Preparation method of hydrogenated C9 petroleum resin - Google Patents
Preparation method of hydrogenated C9 petroleum resin Download PDFInfo
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- CN102002130B CN102002130B CN2010102869812A CN201010286981A CN102002130B CN 102002130 B CN102002130 B CN 102002130B CN 2010102869812 A CN2010102869812 A CN 2010102869812A CN 201010286981 A CN201010286981 A CN 201010286981A CN 102002130 B CN102002130 B CN 102002130B
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Abstract
The invention relates to a preparation method of hydrogenated C9 petroleum resin, which is characterized by comprising the following steps of: (1) preparation of supported noble metal hydrogenated catalyst: preparing by using a coating method, selecting noble metal palladium and platinum and transition metal cobalt or nickel as metal active components, preparing a spherical alumina supporter, then coating the active components of palladium and platinum and transition metal on the alumina supporter, and activating to obtain a hydrogenated catalyst; (2) selective hydrogenation: desulfurizing and denitrifying; (3) high pressure hydrogenation reaction: controlling the weight ratio of resin to solvent to ensure that the concentration of resin is 20-40% by weight, taking chain-like or annular saturated hydrocarbon or aromatic hydrocarbon or hydrocarbon mixture as a solvent, and taking a supported noble metal hydrogenated catalyst as a catalyst, wherein the temperature of the high pressure hydrogenation reaction is 250-350 DEG C, the pressure is 8.0-20.0 MPa and the liquid volume space velocity is 0.5-2h<-1>. The properties of the final product hydrogenated C9 petroleum resin are as follows: Gardner is not more than 1, and the softening point is not smaller than 100 DEG C.
Description
Technical field
The present invention relates to the petrochemical technology field.Be a kind of preparation method of hydrogenated carbon 9 petroleum resin, the C 9 fraction of cracking that particularly relates to the cracking of ethylene by-product is the preparation method that raw material prepares the hydrogenated carbon 9 petroleum resin.
Background technology
As everyone knows, tackiness agent plays important effect for human daily life, and for example they are used for strap, bandage, envelope, scratch paper and other many article used in everyday.The preparation of these tackiness agents then need be used resin, and requires resin to have good performance, and for example look shallow is, stable, free from extraneous odour etc.In industry, petroleum resin promptly are the important sources of such use resin.
Petroleum resin are that carbon five or the C 9 fraction of cracking by-product when producing ethene is through AlCl
3Or BF
3Resulting product after complex catalysis polymerization or the employing thermopolymerization.But these product colours are dark, poor stability, particularly to heat and oxidation instability, when being heated, can produce bad smell, seriously hindered their application in the high-end product field.In order to address the above problem, the method that people adopt hydrogenation is given two keys remaining in the resin and part phenyl ring saturated, with color and the stability of improving petroleum resin.
USP 2,824,860; 2,911,395 and 3,040,009 and the resin described by the petroleum fractions of thermopolymerization steam cracking (preferred boiling range is 20～280 ℃) gained of English Patent 1,202,802 carry out the resin that shortening obtains to have high softening-point and light color.Wherein said petroleum fractions normally has the compound of one or more unsaturated rings, for example cyclic diolefine, cyclenes and indenes in the molecule.
English Patent 1,176,443 unsaturated hydrocarbons that to have described at least 50 heavy % wherein be atomatic olefins, cyclic monoolefins or cyclic diene hydrocarbon carry out polymerization, and particularly the resin of catalyzed polymerization gained carries out the method for hydrogenation.
Used hydrogenation catalyst comprises nickel, reduced nickel, moly-sulfide in above-mentioned these patents, preferably in preparatory activation diatomite support on the catalyzer of about 58% nickel of load.The specific surface of this live catalyst is about 140m
2/ g, reduced nickel is 2～20% with the weight ratio of total nickel on the catalyzer, is preferably 7～13%.Carry out before the hydrogenation reaction, preferably the resin with thermopolymerization is dissolved in saturated hydrocarbon solvent earlier, for example in the heptane; Then at 200～260 ℃, preferred 210～230 ℃, (2.0～12.1MPa), preferred 30～90 normal atmosphere (carried out hydrogenation reaction 5～7 hours to 20～120 normal atmosphere under 3.0～9.1MPa); The hydrogenation resin productive rate of gained is 90～95% (are benchmark in raw material thermopolymerization resin); The saybolt colorimeter value is about 25, and softening temperature is 150～180 ℃, and bromine number is 1～3.Insufficient is that the amount of the hydrogenation resin of preparation receives the restriction of through-put and catalyst life to a great extent in this way, and product colour is also treated further improvement.
Japanese Patent is put down 4-110, and 304, flat 1-165,604, flat 1-101,347 peaceful 2-6,791 have also all described the catalytic hydrogenation method of petroleum resin, and catalyst system therefor mainly is the catalyzer that monometallic nickel, monometallic palladium and platinum and alkali metal are composited.The characteristics of these catalyzer are active high, but they are comparatively responsive to the impurity in the petroleum resin, especially in aromatic petroleum resin, use, easily poisoning and deactivation.
A kind of method of petroleum resin shortening described, the use therein Ni-W/Al that has vulcanized in the European Patent Application No. 81303319.8
2O
3, the specific surface of catalyzer is 120～300m
2/ g wherein contains the heavy % in Ni2～10, the heavy % in W10～25.Hydrogenation conditions is: 200～320 ℃, 20～300 normal atmosphere (2.0～30.4MPa), preferred 30～50 normal atmosphere (3.0～5.1MPa).
Used in the disclosed petroleum resin catalytic hydrogenation method in the European patent 82,726 and to have contained the Ni-W/Al that has vulcanized
2O
3Catalyzer, its fresh specific surface area is 120～300m
2/ g.This catalyzer contains the heavy % in Ni2～10, the heavy % in W10～25.Hydroconversion condition is: temperature is that 250～330 ℃, hydrogen pressure are 150～200 normal atmosphere (15.2～20.3MPa).Wherein used raw material petroleum resin are that thermopolymerization or the catalyzed polymerization by C5/C9 alkene and/or diolefine makes, or are made by the catalyzed polymerization of C8/C9 atomatic olefins, and its softening temperature is 85～150 ℃.The saybolt colorimeter value of gained hydrogenated petroleum resin is 20～30
+, softening temperature is 50～150 ℃, bromine number is about 0, and has improved hot tinting stability.
Chinese patent CN 1,199,742A disclose a kind of method of hydrotreating of C5/C9 petroleum resin, be make the solution of petroleum resin in resin solvent at hydrogen pressure be under the condition of 220～350 ℃ of 2～15MPa, temperature of reaction with through prevulcanized NiO-WO
3-MgO/Al
2O
3Catalyzer contact, Separation and Recovery product then, solvent cycle is used.This loaded catalyst that contains Ni and W has following composition: 1.0～10.0 heavy %, 15.0～32.0 heavy %WO
3, the MgO of 0.2～3.5 heavy % and the carrier A l of surplus
2O
3, its specific surface area is 120～250m
2Within/g the scope, pore volume is 0.4～0.9ml/g, and wherein the pore volume in the hole of diameter＞1000 dusts should account for more than 6% of total pore volume.
Used hydrogenation catalyst uses sulphided state to contain the loaded catalyst of Ni and W in above-mentioned these patents, and hydrogenated petroleum resin is produced in the hydrotreatment of adopting single reaction vessel to carry out thick C 9 petroleum resin.Because present development along with the C 9 petroleum resin polymerization technique; Thick C 9 petroleum resin output increases substantially; Meanwhile bring foreign matter content height in the petroleum resin, sulphur, nitrogen content height, the increase of especially insoluble sol content; What cause above-mentioned patent weak point is; Because raw material impurity content height makes the amount of hydrogenation resin receive the restriction of through-put and catalyst life to a great extent, signs of degradation takes place in resin in hydrogenation process, and product colour is also treated further improvement.
Summary of the invention
The objective of the invention is on the basis of above-mentioned prior art; Providing a kind of adopts the complete processing improved and improves the method that active and novel noble metal hydrogenation catalyst optionally carry out the C 9 petroleum resin hydrogenation; This method both can make that colourity is good, the bromine valency is low, the hydrogenated petroleum resin of Heat stability is good, can obtain higher product yield again.
The objective of the invention is to reach through following proposal: the C 9 fraction with commercially available cracking of ethylene by-product is a raw material; Through selective hydrogenation; Again through hot polymerization, separation, dissolving, filtration; In the presence of the high-pressure hydrogenation catalyzer, carry out hydrogenation reaction, isolate solvent more at last and obtain final hydrogenated petroleum resin product.
The present invention is a kind of preparation method of hydrogenated carbon 9 petroleum resin, it is characterized in that:
1, the preparation of carried noble metal hydrogenation catalyst:
The carried noble metal hydrogenation catalyst adopts the cladding process preparation; Metal active constituent is selected from precious metal palladium and platinum, and transition metals cobalt or nickel, and the metal active constituent starting material adopts corresponding muriate or nitrate salt; Carry out the preparation of ball-aluminium oxide carrier earlier; Again with palladium and platinum, transition metal activity component impregnation on alumina powder jointed, or spray on the alumina supporter, activatedly obtain hydrogenation catalyst of the present invention; Components by weight: be aluminum oxide in the support of the catalyst; Carrier A l
2O
3Select the transition aluminas of high-ratio surface for use, be selected from γ-Al
2O
3, θ-Al
2O
3Or δ-Al
2O
3, so that the specific surface area of catalyst that is made by this carrier is at 80～120m
2Within/g the scope, Al wherein
2O
3Other foreign matter content is lower than 1% weight in the carrier; With carrier A l
2O
3100 parts of meters of weight, precious metal palladium is 0.4～0.8 part, and noble metal platinum is 0.4～0.8 part, and transition metal is a kind of in cobalt or the nickel; Transition metal is 1.0～5.0 parts;
2, selective hydrogenation operation:
It at first is the desulfurization removing nitric operation; For removing impurity such as sulphur nitrogen in the C 9 fraction, temperature is 180～320 ℃, and pressure is 1.0～6.0MPa; The liquid volume air speed is 1～6h
-1, selective hydrogenation catalyst is a base metal cobalt molybdenum hydrogenation catalyst;
3, high-pressure hydrogenation reaction process
When carrying out the high-pressure hydrogenation reaction, thick C 9 petroleum resin is with the solution form charging in resin solvent; The weight ratio of resin and solvent makes that the concentration of resin is 20～40% weight in the reaction solution; Used resin solvent is chain or cyclic stable hydrocarbon; Perhaps be aromatic hydrocarbons; Or hydrocarbon mixture, be selected from: normal heptane, cyclohexane, toluene, mineral essential oil, reforming raffinate oil wherein one or more;
Catalyzer is preceding system carried noble metal hydrogenation catalyst; The high-pressure hydrogenation temperature of reaction is 250-350 ℃, and pressure is 8.0～20.0MPa, and the liquid volume air speed is 0.5～2h
-1
The finished product hydrogenated carbon 9 petroleum resin character is: Gardner Gardner form and aspect≤1, softening temperature>=100 ℃.
According to preparation method of the present invention, its preferred version is characterised in that:
1, the preparation of carried noble metal hydrogenation catalyst:
Carried noble metal hydrogenation catalyst components by weight: be aluminum oxide in the support of the catalyst; Carrier A l
2O
3Select the transition aluminas γ-Al of high-ratio surface for use
2O
3, so that the specific surface area of catalyst that is made by this carrier is at 90～120m
2Within/g the scope, Al wherein
2O
3Other foreign matter content is lower than 1% weight in the carrier; With carrier A l
2O
3100 parts of meters of weight, precious metal palladium is 0.6～0.8 part, and noble metal platinum is 0.6～0.8 part, and transition metal is a kind of in cobalt or the nickel; Transition metal is 1.6～5.0 parts;
2, selective hydrogenation operation:
It at first is the desulfurization removing nitric operation; For removing impurity such as sulphur nitrogen in the C 9 fraction, temperature is 250～300 ℃, and pressure is 1.5～5.0MPa; The liquid volume air speed is 1.5～4h
-1, selective hydrogenation catalyst is a base metal cobalt molybdenum hydrogenation catalyst;
3, high-pressure hydrogenation reaction process:
When carrying out hydrogenation reaction, thick C 9 petroleum resin is with the solution form charging in resin solvent; The weight ratio of resin and solvent makes that the concentration of resin is 25～35% weight in the reaction solution; Used resin solvent is chain or cyclic stable hydrocarbon, perhaps is aromatic hydrocarbons, or hydrocarbon mixture, is selected from: normal heptane, cyclohexane, mineral essential oil, reforming raffinate oil wherein one or more;
Catalyzer is preceding system carried noble metal hydrogenation catalyst; The high-pressure hydrogenation temperature is 270～320 ℃, and pressure is 10.0～18.0MPa; The liquid volume air speed is 0.5～2h
-1
It is feedstock production hydrogenated carbon 9 petroleum resin that the inventive method is applied to C 9 fraction of cracking, and this flow process good stability is easy to realize that hydrogenated carbon 9 petroleum resin bromine index is low, and outward appearance is colourless.
The C 9 fraction of cracking raw material that the present invention was suitable for is for the not restriction of sulphur nitrogen impurity content; That sells in the market all can be used to processing treatment without the hydrotreatment C 9 fraction of cracking; Wherein selective hydrogenation operation can be selected for use at present for the well-known selective hydrodesulfurization mature technology comparatively commonly used of catalytically cracked gasoline; Under the condition that guarantees sulphur nitrogen maximum conversion, the unsaturated link(age) in the C 9 fraction of cracking is not as much as possible by hydrocracking.After cracking carbon nine was handled through selective hydrogenation, the sulphur nitrogen content can be reduced to the level that is lower than 10 μ g/g, to guarantee the hydrogenation performance of follow-up noble metal hydrogenation catalyst.
The present invention finds through experiment, increases cracking carbon nine selective hydrogenation operations, to follow-up precious metal adding hydrogen into resin reaction with to improve the product form and aspect are necessary operations, otherwise after the thermopolymerization sulphur nitrogen impurity in the resin for the toxic effect of adding hydrogen into resin catalyzer.
Thick C 9 petroleum resin technology is produced in the C 9 fraction thermopolymerization of the present invention after for selective hydrogenation does not have special demands, takes existing sophisticated carbon nine resin thermopolymerization industrial technologies to meet the demands, and obtains the higher thick C 9 petroleum resin of softening temperature.Resin carries out separation circuit behind the hot polymerization, removes unpolymerized C 9 fraction oil.
The high-pressure hydrogenation reaction of the thick C 9 petroleum resin that uses among the present invention adopts the fixed bed high-pressure hydrogenation to handle, and described hydrogenation reaction temperature is preferably 270～320 ℃, and pressure is 10.0～18.0MPa, and the liquid volume air speed is 0.5～2h
-1
Carrier A l in the above-mentioned adding hydrogen into resin catalyzer
2O
3Should select the transition aluminas of high-ratio surface for use, like γ-Al
2O
3, so that the specific surface area of catalyst that is made by this carrier is at 80～120m
2Within/g the scope, Al wherein
2O
3Other foreign matter content is lower than 1 heavy % in the carrier.Since the HMW of petroleum resin with and molecule in have a large amount of undersaturated pair of keys, so carrier A l
2O
3Pore structure be vital to the influence of catalyst performance, the new catalyst that the present invention uses should have the pore volume of requirement, its median pore diameter should be enough greatly, but avoid influential to the intensity of catalyzer.
The Separation and Recovery of product is through reaching through distillation or stripping the hydrogenation after product with solvent recuperation.What particularly point out is, reclaim solvent and must not surpass 320 ℃ the temperature of petroleum resin solution, in order to avoid cause the cracking condensation of petroleum resin, and then cause the petroleum resin color to be gone up.Cool off after the broken or resin that gets product of cutting into slices with the hydrogenated petroleum resin after the separated from solvent.
In the method provided by the invention owing to used C 9 fraction of cracking selective hydrogenation and removing sulphur nitrogen impurity and novel noble metal support hydrogenation catalyst; Reactive behavior and selectivity and anti-impurity ability have been improved; Thereby has a following beneficial effect: for by C 9 fraction of cracking being feedstock production hydrogenated carbon 9 petroleum resin technology, because the employing of selective hydrogenation operation, make the wide adaptability of polymerization with the C 9 fraction of cracking raw material; The resin high-pressure hydrogenation catalyst is selected noble metal hydrogenation catalyst for use simultaneously; Make that the hydrogenated carbon 9 petroleum resin form and aspect that finally obtain are high, product not only unsaturated link(age) content obviously reduces, and outward appearance is colourless; And palliating degradation degree is low in the adding hydrogen into resin process, and the hydrogenated resin softening temperature is high.The thick C 9 petroleum resin that adopts thermopolymerization or catalyzed polymerization to obtain, no matter foreign matter content height in the resin solution all can adopt method provided by the invention to carry out the segmentation hydrotreatment and get high performance hydrogenated petroleum resin.
Embodiment
Embodiment 1,
Adding hydrogen into resin Preparation of Catalyst used among the embodiment is following:
Adopt cladding process to prepare hydrogenation catalyst.Catalyst carrier alumina weight is 85 parts, wherein Al
2O
3Content is 99.4 heavy %, in 100 parts of vehicle weight, gets 0.6 part of palladium, 0.4 part in platinum, 2 parts of transiting metal nickels.Carry out the preparation of alumina supporter earlier, its particle diameter is that Φ 2～3mm is spherical; With in 15 parts of alumina powder jointed aqueous solution that impregnated in Palladous chloride, Platinic chloride and nickelous nitrate of residue, be the underflow shape and spray on the spherical carrier of aluminum oxide again, 120 ℃ of oven dry of warp, 550 ℃ of calcination activations obtain hydrogenation catalyst of the present invention, are numbered H-1.
Catalyst carrier alumina weight is 85 parts, wherein Al
2O
3Content is 99.4 heavy %, in 100 parts of vehicle weight, gets 0.4 part of palladium, 0.6 part in platinum, 3 parts of transition metals cobalt.Carry out the preparation of alumina supporter earlier, its particle diameter is that Φ 2～3mm is spherical; With in 15 parts of alumina powder jointed aqueous solution that impregnated in Palladous chloride, Platinic chloride and Xiao Suangu of residue, be the underflow shape and spray on the spherical carrier of aluminum oxide again, 120 ℃ of oven dry of warp, 550 ℃ of calcination activations obtain hydrogenation catalyst of the present invention, are numbered H-2.
Embodiment 2,
C 9 fraction (sulphur content 65.6 μ g/g, nitrogen content 58.1 μ g/g, bromine valency 84gBr with the cracking of ethylene by-product
2/ 100g oil) be raw material, handle that selective hydrogenation catalyst is a base metal cobalt molybdenum hydrogenation catalyst through selective hydrogenation; Temperature of reaction is 270 ℃, and pressure is 3.5MPa, and the liquid volume air speed is 3h
-1The time, sulphur content is reduced to 5.2 μ g/g in the selective hydrogenation after product, nitrogen content is reduced to 1.1 μ g/g, and the bromine valency is 77gBr
2/ 100g oil.In autoclave, carry out heat polymerization, carry out rectifying then and remove not polymerization C 9 fraction, obtain thick C 9 petroleum resin; Its softening temperature is that 110 ℃, Gardner (Gardner) form and aspect are No. 12; Adopt mineral spirits to dissolve in the ratio of 1: 1.5 (portions of resin mineral spirits) then, sulphur content is that 2.4 μ g/g, nitrogen content are 0.5 μ g/g in the resin liquid after the dissolving, and thick C 9 petroleum resin liquid is carried out hydrogenation reaction in the fixed-bed reactor of hydrogenation catalyst are housed; Hydrogenation catalyst is selected H-1 for use; The hydrogenation reaction temperature is 280 ℃, and pressure is 16MPa, liquid volume air speed 1h
-1, handle through flash distillation, stripping again, remove solvent and obtain water white hydrogenated carbon 9 petroleum resin product, 105 ℃ of softening temperatures, Gardner (Gardner) form and aspect are No. 0 look.In the high-pressure hydrogenation processing reaction, steady running 1000 hours, hydrogenation catalyst remains high hydrogenation activity, and resin liquid is a colourless liquid behind the hydrogenation, and separating back resin form and aspect is No. 0 look.
Comparative example 1,
C 9 fraction with cracking of ethylene by-product among the embodiment 1 is a raw material; Handle without selective hydrogenation, in autoclave, carry out heat polymerization, carry out rectifying then and remove not polymerization C 9 fraction; Obtain thick C 9 petroleum resin; Its softening temperature is that 112 ℃, Gardner (Gardner) form and aspect are No. 13, adopts mineral spirits to dissolve in the ratio of 1: 1.5 (portions of resin mineral spirits) then, and sulphur content is that 46.5 μ g/g, nitrogen content are 23.1 μ g/g in the resin liquid after the dissolving.Thick C 9 petroleum resin liquid is carried out hydrogenation reaction in the fixed-bed reactor of hydrogenation catalyst are housed, the hydrogenation reaction temperature is 280 ℃, and pressure is 16MPa, liquid volume air speed 1h
-1, handle through flash distillation, stripping again, remove solvent and obtain hydrogenated carbon 9 petroleum resin product, 105 ℃ of softening temperatures, Gardner (Gardner) form and aspect are No. 3 looks.In the high-pressure hydrogenation processing reaction, turned round 100 hours, resin liquid colourity is identical with raw material behind the hydrogenation, and separating back resin form and aspect is No. 13 looks.
Comparative example 2,
With the thick C 9 petroleum resin of buying on the market (No. 11 looks of form and aspect; 110 ℃ of softening temperatures) dissolve with mineral spirits; The weight ratio of thick C 9 petroleum resin and mineral spirits is 1: 1.5, and sulphur content is 55.3 μ g/g in the solvent-laden thick C 9 petroleum resin, and nitrogen content is 46.7 μ g/g.Dissolving back resin liquid is carried out hydrogenation reaction in the fixed-bed reactor of hydrogenation catalyst are housed, the hydrogenation reaction temperature is 280 ℃, and pressure is 16MPa, liquid volume air speed 1h
-1, remove solvent and obtain hydrogenated carbon 9 petroleum resin product through flash distillation, stripping processing again, 105 ℃ of softening temperatures, Gardner (Gardner) form and aspect are No. 4 looks.In the high-pressure hydrogenation processing reaction, turned round 80 hours, resin liquid colourity is identical with raw material behind the hydrogenation, and separating back resin form and aspect is No. 12 looks.
Embodiment 3
C 9 fraction (sulphur content 67.1 μ g/g, nitrogen content 55.2 μ g/g, bromine valency 108gBr with the cracking of ethylene by-product
2/ 100g oil) be raw material, handle that selective hydrogenation catalyst is a base metal cobalt molybdenum hydrogenation catalyst through selective hydrogenation; Temperature of reaction is 260 ℃, and pressure is 3.0MPa, and the liquid volume air speed is 2.5h
-1The time, sulphur content is reduced to 6.2 μ g/g in the selective hydrogenation after product, nitrogen content is reduced to 1.8 μ g/g, and the bromine valency is 95gBr
2/ 100g oil.In autoclave, carry out heat polymerization, carry out rectifying then and remove not polymerization C 9 fraction, obtain thick C 9 petroleum resin; Its softening temperature is that 112 ℃, Gardner (Gardner) form and aspect are No. 13; Adopt reforming raffinate oil to dissolve in the ratio of 1: 2 (portions of resin reforming raffinate oil) then, sulphur content is that 3.5 μ g/g, nitrogen content are 0.8 μ g/g in the resin liquid after the dissolving, and thick C 9 petroleum resin liquid is carried out hydrogenation reaction in the fixed-bed reactor of hydrogenation catalyst are housed; Hydrogenation catalyst is selected H-1 for use; The hydrogenation reaction temperature is 320 ℃, and pressure is 10MPa, liquid volume air speed 1.2h
-1, handle through flash distillation, stripping again, remove solvent and obtain water white hydrogenated carbon 9 petroleum resin product, 108 ℃ of softening temperatures, Gardner (Gardner) form and aspect are No. 0.6 look.
Embodiment 4,
C 9 fraction (sulphur content 67.1 μ g/g, nitrogen content 55.2 μ g/g, bromine valency 108gBr with the cracking of ethylene by-product
2/ 100g oil) be raw material, handle that selective hydrogenation catalyst is a base metal cobalt molybdenum hydrogenation catalyst through selective hydrogenation; Temperature of reaction is 260 ℃, and pressure is 3.0MPa, and the liquid volume air speed is 3h
-1The time, sulphur content is reduced to 6.2 μ g/g in the selective hydrogenation after product, nitrogen content is reduced to 1.8 μ g/g, and the bromine valency is 95gBr
2/ 100g oil.In autoclave, carry out heat polymerization, carry out rectifying then and remove not polymerization C 9 fraction, obtain thick C 9 petroleum resin; Its softening temperature is that 112 ℃, Gardner (Gardner) form and aspect are No. 13; Adopt reforming raffinate oil to dissolve in the ratio of 1: 2 (portions of resin reforming raffinate oil) then, sulphur content is that 3.5 μ g/g, nitrogen content are 0.8 μ g/g in the resin liquid after the dissolving, and thick C 9 petroleum resin liquid is carried out hydrogenation reaction in the fixed-bed reactor of hydrogenation catalyst are housed; Hydrogenation catalyst is selected H-2 for use; The hydrogenation reaction temperature is 280 ℃, and pressure is 18MPa, liquid volume air speed 1.2h
-1, handle through flash distillation, stripping again, remove solvent and obtain water white hydrogenated carbon 9 petroleum resin product, 108 ℃ of softening temperatures, Gardner (Gardner) form and aspect are No. 0.2 look.
Embodiment 5,
C 9 fraction (sulphur content 67.1 μ g/g, nitrogen content 55.2 μ g/g, bromine valency 108gBr with the cracking of ethylene by-product
2/ 100g oil) be raw material, handle that selective hydrogenation catalyst is a base metal cobalt molybdenum hydrogenation catalyst through selective hydrogenation; Temperature of reaction is 200 ℃, and pressure is 5.0MPa, and the liquid volume air speed is 4h
-1The time selective hydrogenation after product in sulphur content be reduced to 8.1 μ g/g, nitrogen content is reduced to 2.8 μ g/g, the bromine valency is 97gBr
2/ 100g oil.In autoclave, carry out heat polymerization, carry out rectifying then and remove not polymerization C 9 fraction, obtain thick C 9 petroleum resin; Its softening temperature is that 110 ℃, Gardner (Gardner) form and aspect are No. 12; Adopt reforming raffinate oil to dissolve in the ratio of 1: 2 (portions of resin reforming raffinate oil) then, sulphur content is that 5.1 μ g/g, nitrogen content are 1.2 μ g/g in the resin liquid after the dissolving, and thick C 9 petroleum resin liquid is carried out hydrogenation reaction in the fixed-bed reactor of hydrogenation catalyst are housed; Hydrogenation catalyst is selected H-1 for use; The hydrogenation reaction temperature is 280 ℃, and pressure is 18MPa, liquid volume air speed 1.2h
-1, handle through flash distillation, stripping again, remove solvent and obtain water white hydrogenated carbon 9 petroleum resin product, 106 ℃ of softening temperatures, Gardner (Gardner) form and aspect are No. 0 look.
Claims (2)
1. the preparation method of a hydrogenated carbon 9 petroleum resin is characterized in that:
1) preparation of carried noble metal hydrogenation catalyst:
The carried noble metal hydrogenation catalyst adopts the cladding process preparation; Metal active constituent is selected from precious metal palladium and platinum, and transition metals cobalt or nickel, and the metal active constituent starting material adopts corresponding muriate or nitrate salt; Carry out the preparation of ball-aluminium oxide carrier earlier; Again with palladium and platinum, transition metal activity component impregnation on alumina powder jointed, or spray on the alumina supporter, activatedly obtain hydrogenation catalyst of the present invention; Weight percentages of components: be aluminum oxide in the support of the catalyst; Carrier A l
2O
3Select the transition aluminas of high-ratio surface for use, be selected from γ-Al
2O
3, θ-Al
2O
3Or δ-Al
2O
3, so that the specific surface area of catalyst that is made by this carrier is at 80～120m
2Within/g the scope, Al wherein
2O
3Other foreign matter content is lower than 1% weight in the carrier; With carrier A l
2O
3100 parts of meters of weight, precious metal palladium is 0.4～0.8 part, and noble metal platinum is 0.4～0.8 part, and transition metal is a kind of in cobalt or the nickel; Transition metal is 1.0～5.0 parts;
2) selective hydrogenation operation:
It at first is the desulfurization removing nitric operation; For removing sulphur nitrogen impurity in the C 9 fraction, temperature is 180～320 ℃, and pressure is 1.0～6.0MPa; The liquid volume air speed is 1～6h
-1, selective hydrogenation catalyst is a base metal cobalt molybdenum hydrogenation catalyst;
3) high-pressure hydrogenation reaction process
When carrying out the high-pressure hydrogenation reaction, thick C 9 petroleum resin is with the solution form charging in resin solvent; The weight ratio of resin and solvent makes that the concentration of resin is 20～40% weight in the reaction solution; Used resin solvent is chain or cyclic stable hydrocarbon; Perhaps be aromatic hydrocarbons; Or hydrocarbon mixture, be selected from: normal heptane, cyclohexane, toluene, mineral essential oil, reforming raffinate oil wherein one or more;
Catalyzer is preceding system carried noble metal hydrogenation catalyst; The high-pressure hydrogenation temperature of reaction is 250-350 ℃, and pressure is 8.0～20.0MPa, and the liquid volume air speed is 0.5～2h
-1
The finished product hydrogenated carbon 9 petroleum resin character is: Gardner Gardner form and aspect≤1, softening temperature>=100 ℃.
2. according to the described preparation method of claim 1, it is characterized in that:
1) preparation of carried noble metal hydrogenation catalyst:
Carried noble metal hydrogenation catalyst weight percentages of components: be aluminum oxide in the support of the catalyst; Carrier A l
2O
3Select the transition aluminas γ-Al of high-ratio surface for use
2O
3, so that the specific surface area of catalyst that is made by this carrier is at 90～120m
2Within/g the scope, Al wherein
2O
3Other foreign matter content is lower than 1% weight in the carrier; With carrier A l
2O
3100 parts of meters of weight, precious metal palladium is 0.6～0.8 part, and noble metal platinum is 0.6～0.8 part, and transition metal is a kind of in cobalt or the nickel; Transition metal is 1.6～5.0 parts;
2) selective hydrogenation operation:
It at first is the desulfurization removing nitric operation; For removing sulphur nitrogen impurity in the C 9 fraction, temperature is 250～300 ℃, and pressure is 1.5～5.0MPa; The liquid volume air speed is 1.5～4h
-1, selective hydrogenation catalyst is a base metal cobalt molybdenum hydrogenation catalyst;
3) high-pressure hydrogenation reaction process:
When carrying out hydrogenation reaction, thick C 9 petroleum resin is with the solution form charging in resin solvent; The weight ratio of resin and solvent makes that the concentration of resin is 25～35% weight in the reaction solution; Used resin solvent is chain or cyclic stable hydrocarbon, perhaps is aromatic hydrocarbons, or hydrocarbon mixture, is selected from: normal heptane, cyclohexane, mineral essential oil, reforming raffinate oil wherein one or more;
Catalyzer is preceding system carried noble metal hydrogenation catalyst; The high-pressure hydrogenation temperature is 270～320 ℃, and pressure is 10.0～18.0MPa; The liquid volume air speed is 0.5～2h
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| CN105254809A (en) * | 2015-10-19 | 2016-01-20 | 高大元 | Method for removing sulfur in petroleum resin |
| CN105664968B (en) * | 2015-12-29 | 2018-12-25 | 广东工业大学 | A kind of catalyst and preparation method thereof for the reaction of C9 hydrogenation of petroleum resin |
| CN105859965B (en) * | 2016-04-12 | 2019-06-14 | 抚顺新瑞催化剂有限公司 | The method of catalytic hydrogenation preparation high-quality resin |
| CN106832127B (en) * | 2017-02-10 | 2019-07-30 | 恒河材料科技股份有限公司 | A method of orientation plus hydrogen preparation hydrogenation C 9 petroleum resin |
| 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 |
| US11753566B2 (en) | 2019-01-31 | 2023-09-12 | Synthomer Adhesive Technologies Llc | Low volatile tackifier compositions |
| JP7292426B2 (en) * | 2019-06-03 | 2023-06-16 | ハンワ ソリューションズ コーポレイション | Method for producing hydrogenated petroleum resin |
| CN111333751B (en) * | 2020-02-28 | 2021-06-08 | 宁波工程学院 | Hydrogenation catalysis method of carbon nine resin |
| GB2595369B (en) * | 2020-02-28 | 2022-11-23 | Univ Ningbo Technology | Catalytic hydrogenation method for carbon nine resin |
| CN111978470A (en) * | 2020-10-10 | 2020-11-24 | 抚顺齐隆化工有限公司 | Method for deodorizing carbon-nine petroleum resin |
| CN114516926B (en) * | 2022-03-11 | 2023-11-17 | 广东新华粤石化集团股份公司 | Preparation method of hydrogenated C9 petroleum resin and hydrogenated C9 petroleum resin |
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