CN106268725B - The hydrogenation catalyst and preparation method and application of the DCPD resins of dicyclopentadiene hot polymerization in cracking of ethylene carbon 9 - Google Patents
The hydrogenation catalyst and preparation method and application of the DCPD resins of dicyclopentadiene hot polymerization in cracking of ethylene carbon 9 Download PDFInfo
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Abstract
The present invention relates to the hydrogenation catalysts and preparation method and application of the DCPD resins of dicyclopentadiene hot polymerization in cracking of ethylene carbon 9；For catalyst using gamma-alumina as carrier, catalyst activity component is palladium, molybdenum and manganese；In terms of total catalyst weight 100%, Pd 0.5%~1.2%, Mo2O310.0%~15.0%, MnO5.0%~10.0%, surplus are gamma-alumina；Catalyst is stripe shape, trifolium-shaped or the ball-type of 3 × 3~5mm of Φ, 100~150m of specific surface area2/g.Component step load is restored on carrier in hydrogen atmosphere, and activation process is easy；Using fixed bed hydrogenation technique, resin does not need desulfurization pretreatment, and desulfurization and one step of saturation are completed.Hydrogenation reaction is optimized the condition of DCPD resin solutions concentration, feeding temperature, reaction temperature, pressure, volume liquid hourly space velocity (LHSV) and hydrogen-oil ratio in adiabatic or calandria type fixed bed reactor.
Description
Technical field
The present invention relates to one kind being based on cracking of ethylene C9DCPD (dicyclopentadiene) resin of middle dicyclopentadiene hot polymerization
The hydrogenation catalyst and methods for making and using same of the DCPD resins of hydrogenation catalyst, especially high sulfur content.
Background technology
When ethylene unit is using raw materials producing ethylene by cracking, propylene such as lighter hydrocarbons, naphtha, diesel oil, hydrogenation tail oils, by-product is split
Solve C9, account for about the 10~20% of ethylene yield, crack C9Composition with cracking stock, cracking technology, cracking severity difference and become
Change, the cracking C of different manufacturers9Composition there is also larger differences.But from the angle of synthesis, two classes can be divided into：One
Class is active constituent, such as the ring penta 2 generated after Styrene and its derivatives, indenes and its derivative, dicyclopentadiene and its decomposition
Alkene passes through polymerization C9Petropols.Another kind of is inert ingredient, such as alkylbenzene and condensed-nuclei aromatics, in polymerization process
It is middle to be used as polymer solvent, through distillation and C9Petropols detach, and obtain 120# solvent naphthas, midbarrel, No. 200 solvents
Oil.
C9Petropols are a kind of light yellow to dun functional resins, and relative molecular weight is generally 200~3000,
Softening point is glassy thermoplastic's solid between 60~140 DEG C, under room temperature.It is most heavy in many physico-chemical properties of Petropols
What is wanted is softening point, form and aspect, and the two directly influences the performance and purposes of resin.
High-quality C on international market9Petropols, coloration is general≤and No. 5, softening point >=9O DEG C, for adhesive, road sign
Coating and high-grade paint, ink, rubber product etc..China C9Petroleum resin products colour difference (it is light at 6~No. 13,
It is dark at 14~No. l8), the primary quality measures such as softening point are unstable, application range is narrow, can only be in low and middle-grade paint, ink
And it is applied in rubber product.
Synthesis C 9 petroleum resin method has three kinds of catalytic polymerization, thermal polymerization and free radical polymerization.The polymerization methods of fraction
To the production method of C 9 petroleum resin, the form and aspect of product, softening point are affected.
C9Dicyclopentadiene activity is higher in fraction, be cause resin form and aspect deteriorate and generate gelatinous mass it is main because
Element, external general requirement are not more than 2%.China C9Raw material dicyclopentadiene content is higher, in order to improve C9Petropols quality,
Except using two sections of polymerizations and twice in addition to polymerization catalyzed polymerization technique, 2003《Chemical industry is in progress》Introduce a kind of C of the exploitations such as Zhang Shaojun9
Petropols production new technique is reduced operation temperature with rectification under vacuum mode, while being contracted as possible using the tower of special designing
Short material cuts into three phenylethylene, dicyclopentadiene class and indene fraction sections in the residence time of hot-zone, by raw material.Benzene second
Alkene section and indene fraction section use acid catalyzed polymerisation technique productions resin, dicyclopentadiene fraction section in 2l0~280 DEG C, 0.2~
4~20h Continuous Heat consor is reacted under 2.0Mpa produces resin.Due to refined and reaction process the improvement of raw material, new process can
Produce Gardner colorations≤9#, light dicyclopentadiene petroleum resin (the DCPD oil trees that softening point is 90~120 DEG C
Fat), the product yield of comonomer can reach 95% or more, solve highly concentrated cracking C9Fraction cannot make light oil
The technical barrier of resin, but color of resin is still relatively deep, limits the application range of resin.
Dicyclopentadiene petroleum resin (DCPD Petropols) has softening point high, and Efficient Adhesive Promotion is good, the strong spy of stability
Point.Stability in order to reduce the color and raising resin of resin improves the saturation degree of resin to resin progress hydrogenation modification,
The coloration for reducing resin, improves the stability of resin, to meet requirement of the downstream to high-performance dcpd resin.
Major producing country of DCPD hydrogenated petroleum resins foreign countries is the U.S., Japan, South Korea etc., the DCPD hydrotreated petroleum trees in the U.S.
Fat production capacity reaches ten thousand t/a of 1O, and Exxon Corporation is to be best, production capacity 6.5 ten thousand t/a, Hercules in the world
0.5 ten thousand t/a of 3.0 ten thousand t/a, Goodyear；Auspicious about 2.2 ten thousand t/a of father-in-law's production capacity of Japan；It voluntarily researches and develops DCPD and adds in South Korea Cologne
Hydrogen resin, about 2.7 ten thousand t/a of production capacity.Domestic enterprise does not have the production of DCPD hydrogenated petroleum resins.
DCPD Petropols are divided into two kinds according to raw material sources：One is based on cracking of ethylene C5Isolated ring
The DCPD Petropols of pentadiene/dicyclopentadiene hot polymerization production, due to cracking C5Middle sulfur content is low, the DCPD trees thus produced
Fat also has the characteristics that low-sulfur content, but cost of material is high；Another kind is to be based on cracking of ethylene C9Isolated bicyclic penta 2
The DCPD Petropols of alkene hot polymerization production, it is cheap, there is price competitiveness, but 400~500 μ g/g of sulfur content, hydrogen is added to change
It must take into consideration the influence of high sulfur content when property.
Catalyst is the key that hydrogenated petroleum resin technology, and hydrogenation of petroleum resin catalyst has powdery nickel according to technique difference
Catalyst also has loaded noble metal catalyst, load-type nickel series catalysts and supported sulfided nickel-tungsten system or sulphurating nickel-molybdenum
Series catalysts.
Supported catalyst agent carrier is usually aluminium oxide and diatomite, using fixed bed hydrogenation technique.Load-type nickel system urges
Agent hydrogenation temperature is relatively low, generally at 260 DEG C or so.Load type palladium series catalysts, palladium content is in 0.5~2.O%, reaction temperature
280~290 DEG C.Many companies external at present use palladium catalyst, it can effectively inhibit adding hydrogen into resin degradation side reaction.It is negative
The nickel-tungsten or sulphurating nickel-molybdenum adding hydrogen into resin catalyst of the sulphided state of load type, activity is higher, but using being preceding required for being vulcanized
Activation, activation process is cumbersome, and resin degradation is than more serious, and product yield only has 80% or so, and softening point drops to 9O from 120 DEG C
℃。
CN1237117A discloses a kind of method of hydrotreating of unsaturated hydrocarbons, to number-average molecular weight more than 180 hydrocarbon molecule into
Row catalytic hydrogenation, active component are the NiO and 15~25.0 (wt) %WO of 7 (wt) %3, and the alkali of 0.25~10 (wt) % is added
Property metallic promoter agent improve resistance to halogen, alkali metal includes 1-3 races and group of the lanthanides, Actinium systems metal, typically lanthanum, potassium, magnesium, rubidium,
Caesium, rubidium, zinc and calcium, but resin degradation is serious when nickel catalyst is to adding hydrogen into resin, and softening point reduces more.CN1432026A is public
A kind of hydrogenation treatment method, the monometallic based on 6,7,8,9,10,11 race's element of catalyst or bimetallic catalysis are opened
Agent system, based on cobalt, nickel, tungsten, palladium, copper, zinc, to content of halogen 50~2000ppm one or more halogen residues
Resin carries out plus hydrogen, and color perfecting is very big, and resin softening point, which declines, is no more than 8 DEG C.But using preceding need carry out cure activation,
Activation process is cumbersome.
CN1199742A discloses a kind of C5Or C9The method of hydrotreating of Petropols, in a solvent by Petropols dissolving,
Under conditions of 2~15MPa of Hydrogen Vapor Pressure, 220~350 DEG C of reaction temperature, the NiO-WO with presulfurization3-MgO/Al2O3Catalysis
Agent contacts, and then separates and recovers product, and solvent recycles.The catalyst group becomes 1.0~10.0%NiO, 15~32%
WO3, 0.2~3.5% MgO and balance carriers aluminium oxide, specific surface area be 120~250m20.4~0.9ml/ of/g, Kong Rongwei
g。
CN101967214A discloses a kind of method producing hydrogenation C 9 petroleum resin by thick C 9 petroleum resin, to second
Alkene cracks C9The thick C 9 petroleum resin supernatant liquor that fraction polymerize uses fixed bed high-pressure hydrogenation, and remaining liq is using anti-
Autoclave is answered to add hydrogen.Fixed bed high-pressure hydrogenation catalyst composition is as follows：NiO 2~10 (wt) %, WO310~25.0 (wt) %, MoO3
1~5 (wt) %, CuO 5~10 (wt) %, 250~350 DEG C, 8.0~20Mpa of reaction pressure of reaction temperature, liquid air speed 0.5
~2.8h-1.It is as follows to react autoclave hydrogenation catalyst composition：NiO 5~15 (wt) %, WO310~25.0 (wt) %, Mo2O31~
5 (wt) %, ZnO 5~10 (wt) %, 200~300 DEG C of reaction temperature, 8.0~20MPa of reaction pressure.
Above-mentioned support type nickel-tungsten system or nickel-molybdenum series catalysts add hydrogen for carbon nine or C 5 petroleum resin, be required for by
Presulfurization is handled, and active component is carried out with sulphided state plus hydrogen.Some patents disclose the resin hydrogen using noble metal as active component
Change catalyst, catalyst is made to be operated from cure activation, and reduces resin softening point caused by due to degradation and decline.
CN1887927A discloses a kind of preparation method of C 5 hydrogenated petroleum resin, and catalyst is with aluminium oxide (100 parts)
For carrier, active component includes 0.2-1.2 points of palladium, 0.06-0.48 parts of transition metal (copper), 0.1-5 parts of rare earth metal
(cerium), 0.06-2.4 parts of major element (tin), for cyclopentadiene, the higher C 5 hydrogenated petroleum resin production of arene content
In, resin unsaturated bond content is substantially reduced, and appearance is colourless.CN1978447A, which is disclosed, a kind of preparing C 5 hydrogenated oil tree
Catalyst of fat and preparation method thereof, constituent content is consistent with CN1887927A, is only copper, nickel, cobalt, zinc by transition metal,
Rare earth metal is cerium, lanthanum, protactinium, and the 4th major element is tin, germanium, lead.
CN1485352A discloses a kind of hydrogenation catalyst being used to prepare dicyclopentadiene hydrogenated petroleum resin, catalyst
Active component is Pd and Pt, and Pd contents are that 0.1~1.0 (wt) %, Pt contents are 0.05~0.5 (wt) %, for being evaporated by light dydrocarbon
Divide isolated dicyclopentadiene hot polymerization dcpd resin to add hydrogen, obtains water white Petropols.CN101157029A
It discloses one kind and being used to prepare dicyclopentadiene hydrogenation special-purpose catalyzer and preparation method thereof, provide bicyclic in a kind of C5 fraction
Pentadiene adds the catalyst and preparation method thereof of hydrogen production Petropols, and catalyst activity component is one kind in Pd or Pt, single
Component Pd contents 0.3~1.3%, one pack system Pt contents 0.5~1.0% or Pd and Pt combinations, palladium platinum ratio are 4：1~1：1, always
Amount 0.3~1.3%, carrier include aluminium oxide, silica, molecular sieve, kaolin porous inorganic material, are used for C5It is bicyclic in fraction
Pentadiene hydrogenation of petroleum resin, 150~280 DEG C, 6.0~12.0MPa of reaction pressure, 0.5~4.0h of liquid hourly space velocity (LHSV) of reaction temperature-1, hydrogen-oil ratio 100：1~500：1, resin water white obtained.
Above-mentioned patent is using noble metal as catalyst, or has been properly added the resistance to halogen of alkali metal promoter improvement, is used for C5Stone
Oleoresin adds hydrogen, but adds hydrogen for thioretinite, it is also necessary to desulfurization process is carried out, to prevent catalyst poisoning.
CN101628956A discloses a kind of preparation method of hydrogenated carbon five petroleum resin, is more than 20 μ to sulfide content
It is carried out in the domestic C 5 petroleum resins of g/g plus hydrogen, specific steps includes：(1) oxidation sweetening：Existed using 1%~20% hydrogen peroxide
Sulfide in 40~90 DEG C of oxidation removal C 5 petroleum resins；(2) one sections of low pressure adsorbents：Existed with improved silica adsorbent
Chlorion and last traces sulfide in 0.2~1.0MPa, 80~280 DEG C of adsorbing and removing crude resins；(3) two sections of high-pressure hydrogenations：
Using aluminium oxide-titanium oxide as carrier, 0.4-1.2 parts of palladium, 1.0-8.0 parts of transition metal is active component, 12~
18MPa, 270~320 DEG C, 0.8~1.8h of liquid air speed-1Lower carry out hydrogenation reaction.Preferably solves thick C 5 petroleum resin
Raw material sulphur, chlorinity height can not use noble metal hydrogenation processing the problem of, product degree of unsaturation is substantially reduced, appearance be it is colourless,
Resin yield is not less than 90%.
The 5th phase of chemical science and technology 2013 reports《Dicyclopentadiene petroleum resin autoclave hydrogenation technique is studied》, with
Gardner colorations 10,130 DEG C of softening point dicyclopentadiene petroleum resin be raw material carry out autoclave add hydrogen to study, using BASF
Catalyst, palladium mass fraction 1.0%, 200~260 DEG C, 4.0~6.0MPa of reaction pressure of reaction temperature, it is relatively low to prepare form and aspect
DCPD hydrogenated petroleum resins.
Although above-mentioned patent and document all use Pd systems noble metal catalyst to carry out adding hydrogen to DCPD resins, or contain to sulphur
It measures the isolated dicyclopentadiene hot polymerization resin of lower C5 fraction to carry out adding hydrogen, or 20 μ g/g is more than to sulfide content
Domestic C 5 petroleum resin adds hydrogen by being carried out after oxidation sweetening, or has only carried out autoclave hydroconversion condition exploratory development.For base
In C9The DCPD resins of dicyclopentadiene hot polymerization obtained by fraction seperation, because sulfur content is up to 400~500 μ g/g, therefore on
It states Pd systems noble metal catalyst and cannot meet it and add hydrogen demand.
Invention content
The present invention provides one kind being based on cracking of ethylene C9The hydrogenation of the DCPD resins of dicyclopentadiene hot polymerization is urged in fraction
Agent, the catalyst activity component are Pd, Mo and Mn, improve the sulfur resistance of catalyst；Using fixed bed hydrogenation technique, base
In cracking of ethylene C9The DCPD resins of middle dicyclopentadiene hot polymerization do not need desulfurization pretreatment, hydrodesulfurization and plus hydrogen saturation process
One step is completed；Catalyst is after hydrogen atmosphere restores, you can for being based on cracking of ethylene C9The DCPD of middle dicyclopentadiene hot polymerization
The hydrogenation reaction of resin, does not need cure activation, and activation process is easy.
The present invention provides one kind being based on cracking of ethylene C9The hydrogenation catalyst of the DCPD resins of middle dicyclopentadiene hot polymerization,
Catalyst is using gama-alumina as carrier, catalyst activity component Pd, Mo and Mn, in terms of total catalyst weight 100%, Pd
0.5%~1.2%, Mo2O310.0%~15.0%, MnO 5.0%~10.0%, surplus are gama-alumina；Catalyst is Φ
Stripe shape, trifolium-shaped or the ball-type of 3 × 3~5mm, 100~150m of specific surface area2/g。
The content of active component is in terms of total catalyst weight 100%, preferably Pd 0.5%~1.0%, Mo2O312.0%~
15.0%, MnO 6.0%~8.0%.
The preparation method of catalyst is to be carried on into active component by way of dipping using gama-alumina as carrier
It is obtained by drying, roasting on carrier after type.
Active component is introduced in a manner of salting liquid, and the soluble-salt of palladium is palladium bichloride；The soluble-salt of molybdenum is ammonium molybdate；
The soluble-salt of manganese is manganese nitrate.
Component step load is loaded on carrier, first loads molybdenum and manganese, load active component palladium again after drying, roasting, so
Afterwards again drying, roasting finished product catalyst.
Load molybdenum and manganese group timesharing, 118~120 DEG C of drying temperature, 500~600 DEG C of calcination temperature.
When supported palladium, 118~120 DEG C of drying temperature, 400~420 DEG C of calcination temperature.
Catalyst is restored using preceding in hydrogen atmosphere, first rises to 120 DEG C, constant temperature 2h~3h with 3~5 DEG C/min, then with 3
~5 DEG C/min rises to 300 DEG C, then bed temperature is down to 260 DEG C by constant temperature 4h~6h in hydrogen atmosphere, for adding hydrogen anti-
It answers.
Based on cracking of ethylene C9The hydrogenation reaction of the DCPD resins of middle dicyclopentadiene hot polymerization is fixed in adiabatic or shell and tube
In bed reactor, process conditions are：DCPD resin solutions concentration 10~20%, 250~260 DEG C of feeding temperature, reaction temperature
260~280 DEG C, 6.0~8.0MPa of reaction pressure, 1.5~3.0h of volume liquid hourly space velocity (LHSV)-1, hydrogen-oil ratio (v/v) 100~300：1.
Dissolve the one kind of the organic solvent of DCPD resins in normal heptane, hexahydrotoluene or normal octane.
It is an advantage of the invention that：Catalyst obtained by the present invention is especially suitable for being based on cracking of ethylene C9In bicyclic penta 2
The DCPD resins of alkene hot polymerization add hydrogen, by addition Mo, Mn He Fen Bu load process, improves the sulfur resistance of catalyst, tree
Fat need not carry out pre- desulfurization process；Hydrogen is added to be carried out in adiabatic or calandria type fixed bed reactor, catalyst is only needed using preceding
It is restored in hydrogen atmosphere, is not required to vulcanizing treatment, activation process relative ease；Using fixed bed hydrogenation technique, resin is not
It needs to carry out pre- desulfurization process, desulfurization and one step of saturation are completed.
Specific implementation mode
Further illustrated the present invention below by embodiment, but the present invention is not limited to embodiment, permission of the invention with
Subject to claims.
The preparation of catalyst：The preparation of 3 catalyst of table and evaluation data：
A certain amount of gamma-aluminium oxide carrier after molding is weighed, is made of the soluble-salt of the soluble-salt of molybdenum, manganese and carrier
Carrier is soaked in certain time in the loading solution by isometric loading solution at room temperature, pours out remaining soak, is passed through
Drying roasts, after cooling, then it is impregnated certain time with the soluble salt solutions of isometric palladium, using drying, roasting
It burns, required catalyst is made.
Catalyst restores in hydrogen atmosphere, first rises to 120 DEG C, constant temperature 2h~3h with 3~5 DEG C/min, then with 3~5 DEG C/
Min rises to 300 DEG C, then bed temperature is down to 260 DEG C by constant temperature 4h~6h in hydrogen atmosphere, is used for hydrogenation reaction.
Catalyst hydrogenation reaction condition：DCPD resin solutions concentration 10~20%, 250~260 DEG C of feeding temperature, reaction temperature
260~280 DEG C, 6.0~8.0MPa of reaction pressure of degree, 1.5~3.0h of volume liquid hourly space velocity (LHSV)-1, hydrogen-oil ratio (v/v) 100~300：
1, dissolve the one kind of the organic solvent of DCPD resins in normal heptane, hexahydrotoluene or normal octane.
Add the resin solution after hydrogen after falling film evaporator removes solvent and oligomer, obtain adding the DCPD resins after hydrogen,
And tested and analyzed, analytical instrument and execution standard are shown in Table 1.
The detecting instrument and method of 1 resin raw material of table and product
Based on cracking of ethylene C9The DCPD Petropols feedstock specifications of middle dicyclopentadiene hot polymerization are shown in Table 2.
Table 2 is based on cracking of ethylene C9The DCPD Petropols feedstock specifications of middle dicyclopentadiene hot polymerization
Embodiment 1-8
Embodiment 1-8 is catalyst preparation and evaluation experimental.
Strip gamma-aluminium oxide carrier 30g after molding is weighed, according to loading required Mo on 3 catalyst of table2O3, MnO weight
Amount percentage composition weighs required ammonium molybdate tetrahydrate, 50% manganese nitrate, is made into 45ml solution.Carrier is soaked at room temperature molten
12 hours in liquid, remaining soak is poured out.In 118~120 DEG C drying after, 500~600 DEG C roasting 6h, load high-content molybdenum,
Manganese, catalyst have the performance of sulfur poisoning-resistant and the Hydrogenation to sulfide.Molybdenum, the gamma-aluminium oxide carrier after manganese will be carried,
Impregnating 12 hours with isometric palladium chloride solution again, (amount that palladium bichloride is converted into according to the palladium content needed for load is claimed
Take), catalyst is made using drying, roasting, carried palladium catalyst has preferably plus hydrogen is saturated performance, reduces the insatiable hunger of resin
With degree and coloration.
The catalyst of preparation is restored and evaluated in 10ml fixed bed reactors.Catalyst reduction is in hydrogen atmosphere
Middle progress first rises to 120 DEG C, constant temperature 2h with 5 DEG C/min, then rises to 300 DEG C with 5 DEG C/min, constant temperature 4h, then in hydrogen atmosphere
It is middle that bed temperature is down to 260 DEG C.DCPD resins are made into 15% solution with hexahydrotoluene, be preheated to 250~260 DEG C into
Enter reactor.260 DEG C of reaction temperature, pressure 8.0MPa, volume liquid hourly space velocity (LHSV) 2.0h-1, hydrogen-oil ratio (v/v) 300：1.Catalyst
It prepares and garbled data concludes such as table 3.
The preparation of 3 catalyst of table and evaluation data
The catalyst prepared using table 3, to being based on cracking of ethylene C9The DCPD Petropols of middle dicyclopentadiene hot polymerization into
Row hydrogenation reaction adds the bromine valency of resin after hydrogen to be reduced to 0.65~1.5gBr/100g from 35.8gBr/100g, and sulfur content is from 456 μ
G/g is down to 0.7~2.0 μ g/g, and resin does not need desulfurization pretreatment, and desulfurization and one step of saturation are completed, prepared catalyst tool
There are good hydrogenation capability and desulphurizing ability, resin softening point to reduce by 4~8 DEG C, resin degradation is low.
Embodiment 9-20
Embodiment 9-20 is based on cracking of ethylene C9The reaction condition of the DCPD Petropols of middle dicyclopentadiene hot polymerization is real
It tests, catalyst is the catalyst in embodiment 5.
The evaluation of catalyst carries out in 10ml fixed bed reactors.
The catalyst of preparation is restored in 10ml fixed bed reactors in hydrogen atmosphere, is first risen to 3~5 DEG C/min
120 DEG C, constant temperature 2h~3h, then 300 DEG C, constant temperature 4h~6h are risen to 3~5 DEG C/min, then by bed temperature in hydrogen atmosphere
Degree is down to 260 DEG C, is used for hydrogenation reaction.
Catalyst hydrogenation reaction condition experimentation is as follows：With a kind of general in normal heptane, hexahydrotoluene or normal octane
DCPD resins are made into the solution of concentration 10~20%, are preheated to 250~260 DEG C and enter fixed bed reactors, control reactor temperature
260~280 DEG C, 6.0~8.0MPa of reaction pressure of degree, 1.5~3.0h of volume liquid hourly space velocity (LHSV)-1, hydrogen-oil ratio (v/v) 100~300：
1.Pair plus hydrogen after resin solution after falling film evaporator removes solvent and oligomer, obtain plus hydrogen after DCPD resins, go forward side by side
Row detection and analysis.Based on cracking of ethylene C9The hydrogenation reaction Data induction such as table of the DCPD Petropols of middle dicyclopentadiene hot polymerization
4。
Table 4 is based on cracking of ethylene C9The hydrogenation reaction data of the DCPD Petropols of middle dicyclopentadiene hot polymerization
The catalyst prepared using table 3, to being based on cracking of ethylene C9The DCPD Petropols of middle dicyclopentadiene hot polymerization into
Row hydrogenation reaction, from the reaction condition of table 4 and after adding hydrogen, response data can be seen that hexahydrotoluene, normal octane, normal heptane all
DCPD hydrogenation of petroleum resin solvents, resin concentration 10~20% can be used as to be preheated to 250~260 DEG C and enter fixed bed reaction
Device, 260~280 DEG C, 6.0~8.0MPa of reaction pressure of reaction temperature, 1.5~3.0h of volume liquid hourly space velocity (LHSV)-1, hydrogen-oil ratio (v/v)
100~300：1, add the bromine valency of resin after hydrogen to be reduced to 0.63~1.0gBr/100g from 35.8gBr/100g, sulfur content is from 456 μ
G/g is down to 0.7~1.2 μ g/g, and resin does not need desulfurization pretreatment, and desulfurization and one step of saturation are completed, prepared catalyst tool
There are good hydrogenation capability and desulphurizing ability, resin softening point to reduce by 4~6 DEG C, resin degradation is low.
In embodiment 13, lower heating rate is used when reduction, longer constant temperature time, hydrogenation reaction is using higher
Reaction pressure, moderate reaction temperature and charging liquid hourly space velocity (LHSV), adding hydrogen into resin best results.
Claims (10)
1. the hydrogenation catalyst of the DCPD resins of dicyclopentadiene hot polymerization in a kind of cracking of ethylene carbon 9, it is characterised in that：Catalyst
Using gama-alumina as carrier, catalyst activity component is palladium, molybdenum and manganese；In terms of total catalyst weight 100%, Pd 0.5%~
1.2%, Mo2O310.0%~15.0%, MnO 5.0%~10.0%, surplus are gama-alumina；Catalyst be Φ 3 × 3~
Stripe shape, trifolium-shaped or the ball-type of 5mm, 100~150m of specific surface area2/g。
2. hydrogenation catalyst according to claim 1, it is characterised in that：The content of active component is with total catalyst weight
100% meter, Pd 0.5%~1.0%, Mo2O312.0%~15.0%, MnO 6.0%~8.0%.
3. the preparation method of catalyst according to claim 1, it is characterized in that catalyst passes through using gama-alumina as carrier
Active component is carried on carrier after molding by the mode of dipping, obtained by drying, roasting.
4. according to the method described in claim 3, it is characterized in that, active component is introduced in a manner of salting liquid, the solubility of palladium
Salt is palladium bichloride；The soluble-salt of molybdenum is ammonium molybdate；The soluble-salt of manganese is manganese nitrate.
5. according to the method described in claim 4, it is characterized in that load component step load first loads molybdenum and manganese on carrier,
Load active component palladium again after drying, roasting, then drying, roasting finished product catalyst again.
6. according to the method described in claim 5, it is characterized in that load molybdenum and manganese group timesharing, 118~120 DEG C of drying temperature, roasting
Burn 500~600 DEG C of temperature.
7. according to the method described in claim 5, it is characterized in that when load active component palladium, 118~120 DEG C of drying temperature, roasting
Burn 400~420 DEG C of temperature.
8. the application of catalyst described in claim 1, it is characterized in that catalyst is restored using preceding in hydrogen atmosphere, first with 3~5
DEG C/min rises to 120 DEG C, constant temperature 2h~3h, then rises to 300 DEG C with 3~5 DEG C/min, constant temperature 4h~6h, then in hydrogen atmosphere
It is middle that bed temperature is down to 260 DEG C, it is used for hydrogenation reaction.
9. application according to claim 8, it is characterised in that：Hydrogenation reaction is in adiabatic or calandria type fixed bed reactor
In, process conditions are：DCPD resin solutions concentration 10~20%, 250~260 DEG C of feeding temperature, reaction temperature 260~280
DEG C, 6.0~8.0MPa of reaction pressure, 1.5~3.0h of volume liquid hourly space velocity (LHSV)-1, hydrogen-oil ratio v/v is 100~300：1.
10. application according to claim 9, it is characterised in that：The organic solvent for dissolving DCPD resins is selected from normal heptane, first
One kind in butylcyclohexane or normal octane.
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| 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 |
| CN101628956A (en) * | 2009-08-19 | 2010-01-20 | 中国海洋石油总公司 | Preparation method of hydrogenated carbon five petroleum resin |
| CN102921428A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Sulfur-containing coking liquefied gas high-temperature hydrogenation catalyst and its preparation method and use |
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| CN101628956A (en) * | 2009-08-19 | 2010-01-20 | 中国海洋石油总公司 | Preparation method of hydrogenated carbon five petroleum resin |
| CN102921428A (en) * | 2012-10-26 | 2013-02-13 | 中国石油化工股份有限公司 | Sulfur-containing coking liquefied gas high-temperature hydrogenation catalyst and its preparation method and use |
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