CN205874280U - Low nine hydrogenation petroleum resin's in colourity carbon apparatus for producing - Google Patents

Abstract

The utility model provides a low nine hydrogenation petroleum resin's in colourity carbon apparatus for producing, including the nine pretreatment of raw material systems in the carbon that the order links to each other, cold reaction system, two segmentation hydrogenation system and the rectification system of gathering, nine pretreatment of raw material systems in the carbon are hydrogenation catalyst's fixed bed reactor including loading nickel. The device provided by the utility model with nine pretreatment of raw material in the carbon, cold gather the reaction and two segmentation hydrogenation make up, impurity such as partial diolefin among nine pretreatment of raw material removing raw material in the accessible carbon, impurity such as degree of depth desorption sulphur, chlorine and gel in one section hydrogenation, it makes the alkene saturation to carry out degree of depth hydrogenation in the two -stage process hydrogenation. The device provided by the utility model can production colourity be 0#~1# look, good, the satisfied standard nine hydrogenation petroleum resin in the carbon that require both at home and abroad of heat stability.

Description

A kind of process units of low colourity carbon nine hydrogenated petroleum resin

Technical field

This utility model relates to hydrogenated petroleum resin production technical field, is specifically related to a kind of low colourity carbon nine hydrotreated petroleum The process units of resin.

Background technology

Along with developing rapidly of China's oil chemical industry, the production capacity of ethylene improves year by year, promotes the by-product of ethylene unit Thing cracking of ethylene C 9 distillate is also constantly increasing, and it accounts for the 10%～20% of ethylene total output.China's ethylene in 2010 Aggregated capacity is 1476.5 ten thousand t/a, cracks carbon nine total amount about 1,400,000 t, ends today, and cracking carbon nine total amount is estimated will be more than 2,000,000 t.The level of comprehensive utilization of domestic cracking C 9 fractioning is relatively low, mainly or is gone out as cheap primary raw materials by C 9 distillate Sell, or small part be used for producing Petropols or being carried out initial processing after as gasoline, diesel component or solvent naphtha.Carbon nine Petropols be C 9 distillate through pre-treatment, be polymerized, a kind of thermoplastic resin that the technique such as distillation produces.Due to carbon nine oil tree Not polar functionalities in fat molecular structure, good with oil product, oils and fats, the synthetic resin compatibility, tool has been widely used.But due to carbon Containing higher unsaturated bond in 9 petroleum resin, easily react under oxygen or other action of chemicals, make the carbon of synthesis 9 petroleum resin is easily poor with color and photo and thermal stability, and its form and aspect can only achieve 4～No. 5, greatly limit it Range of application.Petropols are modified by the most employing hydrofinishings, and hydrogenation modification has become raising synthesis Petropols quality or the Main Means of grade.

External C 9 petroleum resin commercial production and application are carried out relatively early, and the most large-scale production, product is Cover and to high-end hydrogenation colourless resin and become producing in serial form from low side colouring resin, such as Yi Siman and the Exxon of the U.S., day This auspicious father-in-law, the Cologne etc. of Korea S.The C 9 petroleum resin commercial production of China is started late, due to the deficiency of Technology, Existing Petropols manufacturer is also concentrated mainly on the production of low side colouring resin, and its application and value are nothing like external High-end product.Some the most domestic state-owned enterprises and private enterprise have applied for the patent of invention that various hydrogenated petroleum resin produces, but The most do not complete the production of industrial scale.The current high-end hydrogenation basic dependence on import of colourless resin product of China simultaneously, along with The modernization of road traffic and improving constantly of people's living standard, in the field such as traffic paint and adhesive in the urgent need to state-owned enterprise of state Industry breaks through the technical bottleneck of hydrogenated petroleum resin, it is achieved the domestic autonomous industrial scale metaplasia of high-end colourless carbon nine hydrogenation resin Produce.

In prior art, there is a following report about the production of C 9 petroleum resin:

Patent documentation CN102002131A relates to the preparation method of a kind of high-quality hydrogenated carbon 9 petroleum resin, and the method will After thick C 9 petroleum resin uses solvent to dissolve, carry out filtering separation, fixed bed High-pressure Hydrogenation Unit carries out hydrotreating. The method is one section of high pressure fixed bed hydrogenation technology, and catalyst consumption is bigger.

Patent documentation CN102382259A provides the industrially preparing process of a kind of hydrogenated petroleum resin.The method uses two-stage nitration Hydrogenation, merges in alkali cleaning and technique, and under conditions of suitable hydrogenation catalyst and solvent exist, by cracking c5, C9 fraction gathers Close the Petropols generation hydrogenation reaction obtained, the unsaturated composition hydrogenated minimizing double bond content in Petropols, have color base Group is hydrogenated and decolours, and the chlorine that hydrogenated removing remains in the course of the polymerization process, then through alkali cleaning, washing, stabilizer injects, de- Light color or colourless hydrogenated petroleum resin is obtained after solvent.

Method disclosed in patent documentation CN102746458A includes sulfur removal technology and hydrogenation technique；Described sulfur removal technology step It is to put into thiacyclohexane, toluene and BTX aromatics in blender to be sufficiently mixed, by the heating of mixed resin solution and hydrogen Gas enters in desulfurization-hydrogenation reactor, desulfurization under catalyst action, by high score, low point of separation, then through stripping tower air stripping, de- Desulfurization resin liquid is obtained after vulcanisation hydrogen.Hydrogenation technique is by heated for above-mentioned desulfurization resin liquid and enter together with hydrogen and add In hydrogen reactor, react under the effect of hydrogenation catalyst, by high score, low point of separation, obtain hydrogenation resin liquid, then will hydrogenation Resin liquid obtains hydrogenating C9 Petropols finished product through distillation.

Patent documentation CN102924659A discloses a kind of method of C9 hydrogenated petroleum resin.C9 Petropols are dissolved in and have In machine solvent, mass fraction is 5%～30%, through filtering and removing insoluble matter, then at one-stage hydrogenation desulfurization, secondary hydrogenation decolouring Reason, after last rectification under vacuum recycling design, obtains C9 hydrogenated petroleum resin.

But, mainly use one section of prior art and secondary hydrogenation technique for hot polymerization and catalytic polymerization Petropols, Can be from raw material imurity-removal, polymerization and hydrogenation technique are completely separate simultaneously, it is difficult to fundamentally improve product The colourity of product, is also not easy to large-scale industrialized production.

Utility model content

The purpose of this utility model is the defect overcoming prior art, it is provided that the production of a kind of low colourity carbon nine hydrogenation resin Device.

In the technical scheme that this utility model provides, described carbon nine raw material refers to: the C9 fraction of petroleum cracking institute by-product, Without pre-treatment, it is polymerized or the PROCESS FOR TREATMENT such as distillation, and directly uses as raw material.

Specifically, this utility model provides a kind of low colourity carbon nine hydrogenation resin process units, is connected including order Carbon nine feedstock pre-processing system, cold poly-response system, two-part hydrogenation reaction system and distillation system.

Carbon nine feedstock pre-processing system described in the utility model includes the fixed bed reactors loading nickel series hydrogenating catalyst. Described fixed bed reactors are preferably filled with high appearance sulfur, high selectivity, SA nickel-base catalyst.This utility model passes through carbon nine Feedstock pre-processing system, first carries out selective hydrogenation pretreatment, from feed stage just removing glial component and partial desulfurization etc., same Time with hydrofinishing combine, it is ensured that two-stage nitration catalytic hydrogenation activity and hydrogenation depth, it is to avoid constantly deposit because of impurity and quick coking Covering catalyst active center, causes the operation cycle the shortest, it is impossible to maintain the minimum economic operation that course of industrialization requires Cycle.

Cold poly-response system described in the utility model include order be connected feed cooler, cold poly-reactor, at least one Platform caustic treater, at least one water washing tank and treatment tank.Temperature in described cold poly-reactor controls to be cooled down by reacting kettle jacketing And/or the cooling of external circulation heat exchanging device realizes.Described caustic treater and water washing tank are all at least provided with one, in order to improve washing removing The effect of impurity, it is possible to multiple stage is set.One in activated alumina, active hargil and activated carbon is loaded in described treatment tank Plant or several.

Two-part hydrogenation reaction system described in the utility model include order be connected material mixer, feed preheater, One-stage hydrogenation reactor, one section of knockout drum, second-stage hydrogenation reactor and two-stage nitration knockout drum.Preferably, described one Section hydrogenation reactor includes the fixed bed reactors filling nickel series hydrogenating catalyst.Preferably, described second-stage hydrogenation reactor bag Include the fixed bed reactors filling palladium series hydrocatalyst.In described two-part hydrogenation reaction system, fixed bed hydrogenation reactor Bed all uses cloverleaf pattern, column or spheric catalyst multistage hierarchical arrangement, and its upper strata is provided with inert catalyst bed and dirt Dirt retracting device.

Described device is under actual motion environment, and carbon nine raw material passes through pretreatment system, selective hydrogenation and removing colloid Component and fractional saturation carbon-carbon double bond, pretreated raw material mixes with modifying agent, through polymer raw cooler, is cooled to anti- Answer temperature to enter cold poly-reactor and obtain polymer fluid, then pass through caustic treater and water washing tank, terminate polyreaction and remove unnecessary Catalyst, by treatment tank removing polymer fluid in moisture, reach certain after the mixing with circulating solvent and fresh solvent Ratio, enters hydrogenation head tank, hydrogenation feed preheater enter one-stage hydrogenation reactor after being heated to reaction temperature, and one section adds Hydrogen reactor and one section of knockout drum are connected, and one section of knockout drum is connected with second-stage hydrogenation reactor, and secondary hydrogenation reacts Device is connected with two-stage nitration knockout drum, and described two-stage nitration knockout drum is preferably by high-pressure gas-liquid knockout drum and low-pressure gas-liquid knockout drum Being in series, two-stage nitration knockout drum is connected with distillation system and granulating system subsequently.

In order to realize recycling of environmental protection and the energy, described one section of knockout drum, two-stage nitration high-pressure gas-liquid knockout drum with And the respective gaseous phase outlet of two-stage nitration low-pressure gas-liquid knockout drum is respectively through the entrance phase of hydrogen purification system with circulating hydrogen compressor Even；The outlet of described circulating hydrogen compressor is connected with one-stage hydrogenation reactor and second-stage hydrogenation reactor respectively, for hydrogenation reaction Hydrogen is provided.Additionally, new hydrogen source can also be connected with the entrance of described circulating hydrogen compressor after compressor.

This utility model provides the production method of a kind of low colourity carbon nine hydrogenated petroleum resin simultaneously.Described method is main Pretreatment of raw material, cold poly-reaction bonded two-part hydrogenation reaction combined method is used to carry out C 9 petroleum resin hydrogenation, this practicality The novel polymerization being applicable to C 9 petroleum resin and hydrotreating overall process, have that flow process is flexible, catalyst consumption is low, and resin produces The features such as the good colourity of quality is low.

Specifically, said method comprising the steps of:

(1) by carbon nine raw material and hydrogen with volume ratio 1:100～500, preferred 1:100～300 mix, use nickel series hydrogenating Catalyst carries out selective hydrogenation, obtains pretreated feedstock；

(2) described pretreated feedstock uses polymerization catalyst to carry out cold poly-reaction, obtains polymerizate；

(3) described polymerizate mixes with volume ratio 1:500～1000 with hydrogen, uses nickel series hydrogenating catalyst to carry out one Section hydrogenation reaction, products therefrom is after gas-liquid separation, and liquid phase component uses palladium series hydrocatalyst to carry out secondary hydrogenation reaction, institute Product after gas-liquid separation, liquid phase component is hydrogenation products；

(4) described hydrogenation products carries out rectification process, to obtain final product.

In step described in the utility model (1), described nickel series hydrogenating catalyst is preferably multicomponent skeleton nickel catalyst, Wherein, the content of Ni is 0.1～3%.Possibly together with other gold insoluble in alkali that content is 0.05～10% in described catalyst Belong to one or more in component, preferably Sn, Pb, Mn, Cu, Ag, Mo, Cr, Fe, Co, more preferably copper.Described catalysis By the addition of other component element in agent, the activity of catalyst can be increased, improve selectivity of catalyst and stability.Described Selective hydrogenation condition is: 80 DEG C～150 DEG C, 1.0MPa～2.5MPa.

Due to extremely complex through carbon obtained by petroleum cracking nine raw material composition, there are about kind more than 200, and disperse very much, contain There is a large amount of polymerisable unsaturated component, mainly have Styrene and its derivatives, dicyclopentadiene and derivant thereof, indenes and spread out Biological etc., bromine valency about 150gBr₂/ 100g, diene value about 6gI₂/ 100g, easily forms colloid；By storage time, place (temperature Degree factor) impact, the gum level of carbon nine raw material changes between 400～7000mg/100mL.This utility model is through former Material pretreatment system processes, and the strict hydrogen-oil ratio that controls, 100～500:1, is preferably controlled in 100～300:1, by temperature 80 ～150 DEG C, carry out selective hydrogenation under the conditions of pressure 1.0～2.5MPa, alkynes can be removed and gel generates component, reduce raw material The impact on postorder polyreaction of the middle impurity, the favourable low colourity ensureing product.

Step described in the utility model (2) is preferably: described pretreated feedstock mixes with weight ratio 1:0.1～1 with modifying agent Close, under the conditions of using polymerization catalyst, 10 DEG C～50 DEG C, 100Kpa～500Kpa, carry out cold poly-reaction, fully after reaction, It is passed through sig water under the conditions of 40～90 DEG C and terminates reaction, then be passed through after water fully washs, carry out dehydration refined, obtain polymerizate. Described reaction temperature is preferably 10～30 DEG C.

Wherein, described modifying agent selected from C4～C8 isomeric olefine or/and C8～C10 aromatic hydrocarbons；It is preferably isobutene., isoamyl The mixture of one or more in alkene, dissident's alkene, iso-heptene, isooctene, styrene, methyl styrene, divinylbenzene.This reality Resin melting viscosity can be regulated by each component ratio in adjustment modifying agent with novel.

Wherein, described polymerization catalyst is aluminum chloride or its complex formed with ether/toluene, or is boron trifluoride Or its complex formed with ether/toluene, preferably boron trifluoride.The consumption of catalyst is preferably the 0.1 of material liquid weight ～5%.

In described step (2), through step (1) gained pretreated feedstock according to component need preferably to be properly added change Property agent, after being cooled to reaction temperature, in the catalyst being continuously injected into, temperature 10～50 DEG C, the condition of pressure 100～500Kpa Under carry out polyreaction.After polyreaction, (concentration is 0.5～5% to products therefrom, preferably 0.5～3% with sig water；Described dilute Alkali liquor also can add demulsifier) it is sufficiently mixed, under conditions of temperature 40～90 DEG C, preferably 80～90 DEG C, terminate polymerization anti- Should, the hot water that the resin liquid after alkali cleaning controls with temperature at 40～90 DEG C, preferably 70～90 DEG C mixes, and water elution removed repeatedly The alkali liquor of amount and catalyst residue etc..Resin liquid after washing refines, and removes unnecessary moisture, it is ensured that downstream catalyst Activity and service life.Product water content after described refined dehydration is 100～500ppm, preferably 100～300ppm.

In this utility model step (3), described one-stage hydrogenation reaction condition be preferably: 150 DEG C～200 DEG C, 5MPa～ 20MPa, in further preferred described course of reaction, liquid hourly space velocity (LHSV) is 0.3～1h^-1.Described nickel catalyst is preferably high activity nickel Series catalysts, preferably Ni content be 15～30%, with refractory aluminium oxide and silicon oxide the catalyst as carrier.

In the reaction of described secondary hydrogenation, liquid phase component is preferably 1:500～1000 with the volume ratio of hydrogen.Secondary hydrogenation is anti- Condition is answered to be preferably: 250 DEG C～350 DEG C, 10MPa～20MPa, in further preferred described course of reaction, liquid hourly space velocity (LHSV) is 0.3 ～2h^-1.Described palladium series hydrocatalyst preferably Pd content be 1～5%, the catalysis as carrier with refractory aluminium oxide and silicon oxide Agent.

In the two-part hydrogenation reaction of this utility model step (3), one-stage hydrogenation reaction and secondary hydrogenation reaction are the most preferred Fixed bed reactors are carried out.Catalyst in two-stage reaction is formed by metal active constituent and carrier, and described carrier is Refractory aluminium oxide and silica support, provide distribution carrier for active component and molecular sieve.Described one section of fixed bed hydrogenation catalysis The active component of agent is mainly metallic nickel, uses cloverleaf pattern or spherical shape, and nickel catalyst has low-temp desulfurization denitrogenation The function of dechlorination；The active component of described two-stage nitration fixed bed hydrogenation catalyst is mainly Metal Palladium, uses cloverleaf pattern or spherical Shape.In described catalytic hydrogenation, using inert catalyst, its major function is guard catalyst the most simultaneously, removing Objectionable impurities, carries out the functions such as gas-liquid distribution, uses cloverleaf pattern or spherical form, can be added separately to one section, two-stage nitration adds The top of hydrogen reactor.

In step (3), preferably, to carry out one-stage hydrogenation again after first mixing with reaction dissolvent anti-for described polymerizate Should；Described reaction dissolvent is one or more in hexamethylene, hexahydrotoluene, normal heptane；Or be hexamethylene, methyl cyclohexane The combination of the pretreated feedstock reacted the most completely in one or more in alkane, normal heptane and step (2).

In described step (3), after polymerizate is sufficiently mixed with fresh solvent and/or circulating solvent, reach to be hydrogenated with institute The material rate needed, after being heated to reaction temperature, carries out one-stage hydrogenation reaction under the conditions of 5～20MPa, 150～200 DEG C, Removing sulfur, chlorine during Gai and carry out one-stage hydrogenation saturated reaction, hydrogen sulfide is isolated in reacted logistics after gas-liquid separation Deng light-component gas virose to secondary hydrogenation catalyst, under the conditions of 10～20MPa, 250～350 DEG C, there is secondary hydrogenation Reaction, i.e. deep hydrogenation saturated reaction, secondary hydrogenation product delivers to rectification system through gas-liquid separation, hydrogenation products liquid phase component System.The described secondary hydrogenation product isolated hydrogen of gas-liquid separation can carry out hydrogen cleaning Posterior circle utilization.

In hydrogenation process described in the utility model, one-stage hydrogenation reaction is on the basis of feed purification, utilizes nickel system Catalyst carry out effective low temperature hydrogenation demetalization, desulfurization, denitrogenation, dechlorination, Removal of catalyst poisonous substance be secondary hydrogenation provide The condition of long period operation；Secondary hydrogenation uses load type palladium series catalysts, and being mainly used for hydrofinishing, to carry out alkene saturated, Owing to have employed above-mentioned protective measure, the hydrogenation activity of the reaction of secondary hydrogenation is protected, and the hydrogenation of resin is thorough, therefore originally The hydrogenated petroleum resin colourity that utility model produces is low, and softening point slightly reduces, and photo and thermal stability and intersolubility are good.Described two sections Carry out gas-liquid separation in the middle of hydrogenation reaction, the catalyst poisons such as one section of hydrogen sulfide produced can be removed, protection secondary hydrogenation Activity, sulfur in product, nitrogen content is respectively less than 10ug/g, it is ensured that secondary hydrogenation stable operation.

In described step (4), hydrogenation reaction product is connected in series into decompression distillation through air-distillation, decompression distillation or normal pressure OK, abjection circulating solvent and oligomer obtain qualified carbon nine hydrogenation resin.Specifically, described distillation system can use often Pressure and the independent and tandem compound of hybrid combining, preferably normal pressure and depressurized system of decompression distillation, equipment uses packed tower or sudden strain of a muscle Steaming pot, successively removing circulating solvent and oligomer, carbon nine hydrogenated petroleum resin after being refined.Circulating solvent can follow Ring use or be further refined after as product.

Described step (4) also can farther include granulation step, after rectification product is carried out pelletize, i.e. can get finished product.

Owing to Petropols are the rock-steady structure groups that relative molecular mass is less than 2000, the main task of its hydrogenation process It is that the apparatus and method that this utility model provides are by material choice weighted BMO spaces and two by saturated to impurity removal, alkene Section hydrofinishing combination, not only reduces the gel generation component affecting product colourity, and ensures that two-stage nitration is catalyzed from feed stage Hydrogenation activity and hydrogenation depth, it is to avoid constantly deposit because of impurity and quick coking covering catalyst active center, cause operation week Phase is the shortest, it is impossible to maintain the minimum economic cycle of operation that course of industrialization requires.At hydrogenation according to this utility model method Reason process can be from running more than 1 year continuously, and resin conversion ratio reaches ＞ 95%, and after hydrogenation, resin colourity reaches 0#～1#.This The apparatus and method that utility model provides are for producing low colourity, and the high-performance hydrogenating carbon 9 petroleum resin of Heat stability is good provides one Plant technique simple, the processing method that catalyst activity is high.

Accompanying drawing explanation

Fig. 1 is the schematic diagram of low colourity carbon nine hydrogenation resin process units described in the utility model；Wherein: 1 is that carbon nine is former Material pretreatment system, 2 is feed cooler, and 3 is cold poly-reactor, and 4 is caustic treater, and 5 is water washing tank, and 6 is treatment tank, and 7 is former Feed mixer, 8 is hydrogenation head tank, and 9 is feed preheater, and 10 is one-stage hydrogenation reactor, and 11 is one section of knockout drum, 12 For second-stage hydrogenation reactor, 13 is two-stage nitration high-pressure gas-liquid knockout drum, and 14 is two-stage nitration low-pressure gas-liquid knockout drum, and 15 is distillation system, 16 is circulating hydrogen compressor, and 17 is hydrogen purification system, and 18 is granulating system, and remaining is pipeline.

Detailed description of the invention

Following example are used for illustrating this utility model, but are not limited to scope of the present utility model.

Embodiment 1

Present embodiments provide the process units of a kind of low colourity carbon nine hydrogenated petroleum resin, its structural representation such as Fig. 1 Shown in, including carbon nine feedstock pre-processing system 1 being sequentially connected, cold poly-response system, two-part hydrogenation reaction system, rectification system System 15 and granulating system 18；

Described carbon nine feedstock pre-processing system includes the fixed bed reactors loading nickel series hydrogenating catalyst；

Described cold poly-response system includes the feed cooler 2 being sequentially connected, cold poly-reactor 3, caustic treater 4, water washing tank 5 And treatment tank 6；

Described two-part hydrogenation reaction system includes material mixer 7, hydrogenation head tank 8, the feeding preheating being sequentially connected Device 9,10, one section of knockout drum 11 of one-stage hydrogenation reactor, second-stage hydrogenation reactor 12, two-stage nitration high-pressure gas-liquid knockout drum 13 with And two-stage nitration low-pressure gas-liquid knockout drum 14；Wherein, described one-stage hydrogenation reactor 10 includes filling the fixing of nickel series hydrogenating catalyst Bed reactor；Described second-stage hydrogenation reactor 12 includes the fixed bed reactors filling palladium series hydrocatalyst；

Described one section of knockout drum 11, two-stage nitration high-pressure gas-liquid knockout drum 13 and two-stage nitration low-pressure gas-liquid knockout drum 14 are respective Gaseous phase outlet be connected respectively through the entrance of hydrogen purification system 17 with circulating hydrogen compressor 16, new hydrogen source is after compressor Also the entrance with described circulating hydrogen compressor 16 is connected；The outlet of described circulating hydrogen compressor 16 respectively with one-stage hydrogenation reactor 10 are connected with second-stage hydrogenation reactor 12.

Described device is in actual mechanical process, by pretreatment system 1, selective hydrogenation and removing glial component and portion Dividing saturated carbon-carbon double bond, pretreated raw material mixes with modifying agent, through feed cooler 2, is cooled to reaction temperature and enters Cold poly-reactor 3 obtains polymer fluid, then passes through caustic treater 4 and water washing tank 5, is being removed the water in polymer fluid by treatment tank 6 Point, reach certain proportion after the mixing with circulating solvent and fresh solvent, enter hydrogenation head tank 8, by hydrogenation feed preheater 9 Entering one-stage hydrogenation reactor 10 after being heated to reaction temperature, one-stage hydrogenation reactor 10 is connected with one section of knockout drum 11, The liquid phase of one section of knockout drum 11 is connected with second-stage hydrogenation reactor 12, and second-stage hydrogenation reactor 12 divides with high-pressure gas-liquid successively It is connected with low-pressure gas-liquid knockout drum 14 from tank 13, is connected with distillation system 15 and granulating system 18 subsequently.

New hydrogen is connected with circulating hydrogen compressor 16 after being pressurizeed by compressor, described circulating hydrogen compressor 16 respectively with one section Hydrogenation reactor 10 is connected with second-stage hydrogenation reactor 12, and respectively two-stage hydrogenation reaction provides hydrogen；Meanwhile, hydrogen cleaning system System 17 with whole device present in each gas-liquid separator (include one section of knockout drum 11, high-pressure gas-liquid knockout drum 13 and Low-pressure gas-liquid knockout drum 14) it is connected.

According to temperature and pressure condition, the high-temperature hydro-refining pipeline of hydrogenation process uses chrome-molybdenum steel high-temperature resistant pipeline, non-hydrogen In, cryogenic piping use ordinary carbon steel pipeline.

Embodiment 2

Present embodiments provide a kind of method using device described in embodiment 1 to produce low colourity carbon nine hydrogenation resin, its Process flow diagram refers to shown in the installation drawing of Fig. 1, specifically includes following steps:

(1) carbon nine raw material is under multicomponent skeleton nickel catalyst (content of Ni is 1%, the copper possibly together with 1%) acts on, 130 DEG C, carry out selective hydrogenation, removing alkynes and gel under conditions of 1.0MPa, hydrogen-oil ratio 200:1 and generate component, obtain pre- Process raw material；

(2) cold poly-reaction: described pretreated feedstock needs preferably to be properly added modifying agent according to component, is cooled to anti- After answering temperature, it is being continuously injected into BF₃Polyreaction, polyreaction is carried out under conditions of catalyst, temperature 30 DEG C, pressure 300Kpa Rear products therefrom is sufficiently mixed with the sig water that concentration is 1%, terminates polyreaction, after alkali cleaning under conditions of temperature 85 DEG C The hot water that resin liquid controls with temperature at 80 DEG C mixes, and water elution is except excessive alkali liquor and catalyst residue etc. repeatedly, after washing Resin liquid refine, removing unnecessary moisture to moisture is 200ppm, it is ensured that the activity of downstream catalyst and use Life-span；

(3) one-stage hydrogenation removing sulfur, dechlorination: the polymerizate after Jing Zhi mixes with volume ratio 700:1 with hydrogen, is pressurized to 12MPa, it is heated to 200 DEG C, in air speed 0.6h^-1Under the conditions of enter one section of fixed bed hydrogenation reactor carry out hydrogenation reaction, reaction Product enters gas-liquid separator removing part containing the light-component gas virose to secondary hydrogenation catalyst such as sulfur and chlorine, it is ensured that Secondary hydrogenation catalyst activity and service life；The height that one-stage hydrogenation catalyst uses Chinese Academy of Sciences's Shanxi coalification to be produced is lived Property nickel catalytic hydrogenation (Ni content 20%, refractory aluminium oxide and silica support), use Clover-shaped catalyzer, inertia Catalyst uses large-pore alumina active porcelain ball；

Secondary hydrogenation reacts: enter second-stage hydrogenation reactor from gas-liquid separator logistics out, 15MPa, 260 DEG C, Air speed 0.5h^-1Condition carry out hydrogenation reaction.Product sequentially enters high-low pressure separator again, flashes off unreacted hydrogen Gas；Secondary hydrogenation catalyst uses palladium metal Hydrobon catalyst (the Pt content that Chinese Academy of Sciences's Shanxi coalification is produced 3%, refractory aluminium oxide and silica support), using Clover-shaped catalyzer, inert catalyst uses large-pore alumina activity Porcelain ball；

(4) liquid phase sequentially enters decompression distillation system, isolates circulating solvent and oligomer, obtains carbon nine hydrogenation of high-quality Petropols.

Gained carbon nine hydrogenated petroleum resin, softening point is 104, and colourity is 1, and resin yield can reach 86%.

Although, used general explanation, detailed description of the invention and test, this utility model made detailed Describing, but on the basis of this utility model, can make some modifications or improvements it, this is aobvious to those skilled in the art And be clear to.Therefore, these modifications or improvements on the basis of without departing from this utility model spirit, belong to this practicality Novel claimed scope.

Claims (10)

1. the process units of one kind low colourity carbon nine hydrogenated petroleum resin, it is characterised in that include carbon nine raw material that order is connected Pretreatment system, cold poly-response system, two-part hydrogenation reaction system and distillation system；

Described carbon nine feedstock pre-processing system includes the fixed bed reactors loading nickel series hydrogenating catalyst.

Device the most according to claim 1, it is characterised in that described cold poly-response system includes that the raw material that order is connected is cold But device, cold poly-reactor, at least one caustic treater, at least one water washing tank and treatment tank.

Device the most according to claim 1 and 2, it is characterised in that described two-part hydrogenation reaction system includes order phase One-stage hydrogenation reactor even, one section of knockout drum, second-stage hydrogenation reactor and two-stage nitration knockout drum.

Device the most according to claim 3, it is characterised in that before described one-stage hydrogenation reactor, also sets up order phase Material mixer even and feed preheater；The outlet of described feed preheater is connected with the entrance of one-stage hydrogenation reactor.

Device the most according to claim 3, it is characterised in that described one-stage hydrogenation reactor includes that filling nickel series hydrogenating urges The fixed bed reactors of agent.

Device the most according to claim 5, it is characterised in that described second-stage hydrogenation reactor includes that filling palladium system hydrogenation urges The fixed bed reactors of agent.

Device the most according to claim 3, it is characterised in that described two-stage nitration knockout drum by high-pressure gas-liquid knockout drum with Low-pressure gas-liquid knockout drum is in series.

Device the most according to claim 3, it is characterised in that described one section of knockout drum, two-stage nitration high-pressure gas-liquid separate Tank and the respective gaseous phase outlet of two-stage nitration low-pressure gas-liquid knockout drum enter respectively through hydrogen purification system and circulating hydrogen compressor Mouth is connected；The outlet of described circulating hydrogen compressor is connected with one-stage hydrogenation reactor and second-stage hydrogenation reactor respectively.

Device the most according to claim 8, it is characterised in that the outlet of new hydrogen source compressor and described circulating hydrogen compressor Entrance be connected.

Device the most according to claim 1, it is characterised in that the outlet of described distillation system is connected with granulating system.