CN104710572A - Method for modifying C9/C5 petroleum resin through hydrogenation-desulfuration coupling and equipment thereof - Google Patents
Method for modifying C9/C5 petroleum resin through hydrogenation-desulfuration coupling and equipment thereof Download PDFInfo
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Abstract
The invention relates to a method for modifying C9/C5 petroleum resin through hydrogenation-desulfuration coupling. The method comprises the following steps: (1), mixing the C9/C5 petroleum resin and a solvent and adding a catalyst, heating, and dissolving; (2), introducing mixed gas of H2 and CO2 for carrying out a hydrogenation reaction, wherein the reaction temperature is 150-400 DEG C, and the reaction pressure is 3.0 MPa to 35.0 MPa; (3), separating H2S gas generated in the hydrogenation reaction process and the remaining mixed gas of H2 and CO2, removing H2S, H2 and CO2, pressurizing, and returning back for recycling of the hydrogenation reaction; (4), after carrying out a hydrogenation-desulfuration reaction for 1-10 h, obtaining the product. The method capable of effectively removing organic sulfur in the C9/C5 petroleum resin is provided while the quality of the modified C9/C5 petroleum resin is improved, and the reaction environment is optimized.
Description
Technical field
The invention belongs to technical field of petrochemical industry, relate to method and the equipment thereof of a kind of hydrogenation-desulfurization coupling modification C9/C5 petroleum resin.
Background technology
C9/C5 petroleum resin are that petroleum hydrocarbon Pintsch process prepares a kind of thermoplastic hydrocarbon resin of the by product-C_9 fraction of pyrolysis gasoline in ethylene process through pre-treatment, polymerization, distillation formation, softening temperature is at 60-160 DEG C, have and increase stickiness, agglutinating value(of coal) and easily and the feature that mixes of other resin, and low, water-fast, the resistance to ethanol of acid number and chemicals-resistant, chemical stability and Heat stability is good, and can viscosity be regulated, be widely used in paint, rubber, ink, thermosol, sticking tape and sizing agent industry.Add C9/C5 petroleum resin in paint, paint finishes degree can be increased, improve paint attachment degree, hardness, acidproof and alkali resistance; Add C9/C5 petroleum resin in rubber and can play thickening, reinforcement, softening effect; Add C9/C5 petroleum resin in sizing agent and can improve the bounding force of tackiness agent, acid resistance, alkali resistance and water tolerance; The effect that C9/C5 petroleum resin can play color development, quick-drying and blast is added in ink.All can there is a certain amount of double bond unsaturated compound in the C9/C5 petroleum resin obtained through thermopolymerization or catalyzed polymerization, color is darker, softening degree is low, stability is bad, easily react under ultraviolet, oxygen or other action of chemicals, resin thermostability and oxidation stability are deteriorated, also can reduce the consistency of resin and application.Therefore, can affect the Application Areas of C9/C5 petroleum resin, decreasing it can use range field.C9/C5 petroleum resin by shortening modification make the double bond that contains in resin and part phenyl ring saturated, remove the impurity such as sulfide, halogenide that C9/C5 petroleum resin are residual in polymerization, to reach the photo and thermal stability and mutual solubility that improve resin, reduce colourity, improve softening temperature and quality, thus expand the Application Areas of hydrogenation modification C9/C5 petroleum resin and increase use value.Such as at coating industry, use C9 hydrogenation modification petroleum resin to produce marking paint, its resistance to persistence and weathering resistance can be improved, make its life-span extend to 3 years by original 1 year.But the modification of C9/C5 hydrogenation of petroleum resin is a more thorny difficult problem, particularly C9/C5 petroleum resin contains micro-organosulfur, has both been easy to make poisoning of catalyst again limit its range of application.Although have a lot for the research of hydrogenation modification C9/C5 petroleum resin now, but, except affecting except the problems such as its use containing micro-organosulfur in modified C9/C5 petroleum resin described above, the C9/C5 petroleum resin quality of current modification is still unsatisfactory, and reaction is very high to the requirement of equipment, catalysis, thus cause the increase of cost.At present, the domestic demand to hydrogenation modification petroleum resin sharply increases in recent years, but the domestic C9/C5 hydrogenation of petroleum resin modified product manufacturer still not having an independent brand so far.
Summary of the invention
The present invention is directed to the deficiency existed in above-mentioned technology, invent method and the equipment thereof of a kind of hydrogenation-desulfurization coupling modification C9/C5 petroleum resin, while the quality improving modified C9/C5 petroleum resin, the method of organosulfur in a kind of energy effective elimination C9/C5 petroleum resin is provided, optimizes reaction environment.
For realizing object of the present invention, technical solution of the present invention is as follows:
The method of hydrogenation-desulfurization coupling modification C9/C5 petroleum resin, comprises following operation steps:
(1) by C9/C5 petroleum resin and solvent according to mass ratio 1:1 ~ 10:1, add catalyst mix, heating, dissolve;
(2) H is passed into
2and CO
2mol ratio is that the mixed gas of 1:1 ~ 20:1 carries out hydrogenation reaction, and temperature of reaction is 150 DEG C ~ 400 DEG C, and reaction pressure is 3.0MPa ~ 35.0MPa;
(3) the gas H produced in hydrogenation process
2s, remaining mixed gas H
2and CO
2be separated, removing H
2s, H
2and CO
2pressurization returns to be carried out hydrogenation reaction and recycles;
(4), after hydrogenation-desulphurization reaction 1 ~ 10h, after decompression, material is released and is blended hydrogenation modification rosin and C9/C5 petroleum resin products from hydrogenator.
Preferably, in described step (2), effluent air is after decompressor, and enter gas-liquid separator and be separated, the solvent liquid obtained is back in hydrogenator, and remaining gas is H
2s, H
2and CO
2,gas is passed in absorption tower, absorb H through absorption tower
2after S gas, residue H
2and CO
2pass into turbocompressor again.
Preferably, described step (3) takes out the flow of mixed gas from hydrogenator is 0 ~ 12000m
3/ h, by gas by decompressor, decompressor is connected with turbocompressor, in turbocompressor, supplement CO
2and H
2mixed gas, then mixed gas is passed in hydrogenator.
Preferably, 1 ~ 30% of the quality that the amount of the catalyzer added in step (1) is the C9/C5 petroleum resin that add and solvent total amount; Wherein said catalyzer is the catalyzer of nickel-loaded or palladium.
Preferably, in step (3), the temperature of gas-liquid separator is 0 ~ 50 DEG C, and pressure is 0.0 ~ 0.5MPa, and liquid flow rate is 0 ~ 100m
3/ h, gas flow is 0 ~ 10000m
3/ h.
Preferably.
Preferably, the solvent described in step (1) is the one in hexanaphthene, ethylcyclohexane, n-hexane, n-heptane, mineral essential oil, 200# solvent oil.
An equipment for hydrogenation-desulfurization coupling modification C9/C5 petroleum resin method, comprising:
Hydrogenator, it comprises: multiple heating tube, is located at hydrogenator inside; And gas distributor, it comprises inlet mouth and multiple shower nozzle for being vented; Decompressor, it is connected with described hydrogenator; And turbocompressor, it is connected with described decompressor, and drives described turbocompressor work by described decompressor, and the air outlet of described turbocompressor is connected with described hydrogenator.
Preferably, in technique scheme, described gas distributor is in " L " type, and its bottom is annulus tubulose, and this ring tube is evenly provided with multiple shower nozzle for being vented.
Preferably, in technique scheme, described heating tube is multiple, is distributed on described hydrogenator inside in parallel; Described gas distributor has multiple, and described multiple gas distributor is interconnected, and described each gas distributor is located between described heating tube.
Preferably, in technique scheme, the described device for rosin and the blended hydrogenation modification of C9/C5 petroleum resin, also comprise: dissolution kettle, it is connected with described hydrogenator, for dissolving the raw material needed for production; Gas-liquid separator, it is connected with described decompressor; Solvent pump, it is connected with described gas-liquid separator, for delivering in described hydrogenator by isolated liquid solvent; And absorption tower, its inlet mouth is connected with described gas-liquid separator, and air outlet is connected with described turbocompressor, for removing H
2s gas.
The inventive method adds heating in melting still C9/C5 petroleum resin and solvent and is pressed in hydrogenator after melting, and is filled with H
2and CO
2mixed gas carries out hydrogenation reaction.Due to the organosulfur containing trace in C9/C5 petroleum resin, very easily make hydrogenation catalyst poisoning and deactivation, and hydrogenation byproduct H
2the accumulation of S not only inhibits chemical equilibrium towards the movement in hydrogenating desulfurization direction, and H
2s also has certain corrosive nature to hydrogenator, so the present invention adopts hydrogenator constantly to flow out the method for gas phase, makes the H that hydrogenation generates
2s gas constantly leaves hydrogenator, thus eliminates by product H
2the feedback inhibition that S accumulates and causes, has broken the chemical equilibrium of C9/C5 hydrogenation of petroleum resin-desulfurization, has improve hydrogenation reaction speed and equilibrium conversion, achieved the coupling of hydrogenation reaction-desulfurization.
The gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out are after expander step-down, and solvent vapo(u)r is condensed into liquid state from gas-liquid separator separates out, and H
2s is removed by absorption tower, and therefore pressurized circulation is only noncondensable gas H back into the gas of row hydrogenation reaction
2and CO
2.Therefore drive the gas flow of decompressor to be greater than the flow of turbocompressor pressurized recirculating gas, also that is to say that work of expansion that decompressor is made is greater than the compression work needed for turbocompressor, and the reaction heat that the required energy increased of system is released by hydrogenation in hydrogenator and heating coil heat supply are to improve solvent vapo(u)r flow; The reaction heat that the required energy increased of system is released by hydrogenation in hydrogenator and heating coil heat supply are to improve solvent vapo(u)r flow.H is passed in turbocompressor
2and CO
2mixed gas, decompressor directly promote turbocompressor pressurization H
2and CO
2circulating involuting system, and then pass in hydrogenator.Again due to H
2with CO
2in hydrogenator, constantly circulation and bubbling flowing, enhance stirring and the Mass and heat transfer of material in hydrogenator, and H
2with CO
2also produce " supercavitation " effect, not only can install but also decrease the transmission resistance of C9/C5 petroleum resin high viscosity storeroom and the sterically hindered of hydrogenation double bond to greatest extent by the agitator in economization hydrogenator, greatly increasing the reaction effect of C9/C5 hydrogenation of petroleum resin-desulfurization coupling.
Working cycle of the present invention is compression → reaction → separation → Trans-critical cycle expansion → gas-liquid separation → compression (steam power), from the gas phase that hydrogenator flows out, is wherein specially the CO flowed out by hydrogenator
2, from super/subcritical state transition is that namely low-temp low-pressure normality is called Trans-critical cycle state, this change makes expander do work and drives turbocompressor, to reach expansion-compression self-circulation.The steam of the reaction heat of being released by reactive system or the vaporization of coil pipe endogenous pyrogen indirect heating directly does power, and heat to power output efficiency is about 100%.
Compared with prior art, the invention has the beneficial effects as follows:
1, the present invention adopts hydrogenation-desulfurization coupling Trans-critical cycle CO
2reactive system modification C9/C5 petroleum resin, effectively can remove the organosulfur of the trace contained in C9/C5 petroleum resin, improve the quality of modified C9/C5 petroleum resin, expand its use field; Improve the stability, color and luster etc. of modified C9/C5 petroleum resin simultaneously.The by product H of generation effectively can be removed in further hydrogenation process of the present invention
2s, makes reaction constantly carry out towards the direction of hydrogenation-desulfurization, improves hydrogenation-desulphurization reaction speed and equilibrium conversion.
2, Trans-critical cycle CO is adopted
2expansion-compression self-circulation technology, makes the high pressure vapor flowed out from hydrogenator directly promote turbocompressor pressurization H through expander
2and CO
2circulating involuting system, decreases heat to power output process: the exergy loss of heat energy → mechanical energy → electric energy → mechanical energy, improves the heat power efficiency of thermal power transfer.
3, overcritical H
2and CO
2in hydrogenator, constantly bubbling circulates stirring and produces " supercavitation " effect, not only the transmission resistance of high viscosity C9/C5 petroleum resin storeroom and sterically hindered was installed but also decreased to greatest extent to the stirrer of economization hydrogenator, greatly increases heat and mass speed and the hydrogenation-desulphurization reaction effect of hydrogenator.
4, hydrogenator adopts super/subcritical H
2and CO
2carry out bubbling stirring, do not need mechanical stirrer is installed, be more conducive to the manufacture of high-tension apparatus, operation, maintenance and leakproof.
Accompanying drawing explanation
Fig. 1 is hydrogenation-desulfurization coupling modification C9/C5 petroleum resin method flow diagram, and wherein 1 is dissolution kettle, and 2 is hydrogenators, and 3 is decompressors, and 4 is gas-liquid separators, and 5 is absorption towers, and 6 is turbocompressors, and 7 is solvent pumps.
Fig. 2 is the structural representation according to hydrogenator of the present invention, and wherein 21 is opening for feeds, and 22 is air outlets, and 23 is discharge ports, and 24 is heating coils, and 25 is gas distributor, and 251 is inlet mouths, and 252 is shower nozzles.
Fig. 3 is the structural representation according to gas distributor single in hydrogenator of the present invention.
Fig. 4 is the vertical view according to gas distributor single in hydrogenator of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail, but is to be understood that protection scope of the present invention not by the restriction of embodiment.
Clearly represent unless otherwise other, otherwise in whole specification sheets and claims, term " comprise " or its conversion as " comprising " or " including " etc. by be understood to include the element of stating or integral part, and do not get rid of other element or other integral part.
Embodiment 1
As Figure 1-4, for the device of rosin and the blended hydrogenation modification of C9/C5 petroleum resin, comprising: dissolution kettle 1, hydrogenator 2, decompressor 3, gas-liquid separator 4, absorption tower 5, turbocompressor 6, solvent pump 7.
The discharge port of dissolution kettle 1 is connected with the opening for feed of described hydrogenator 2, and dissolution kettle 1 is for dissolving the raw material needed for production.Hydrogenator 2, cylindrical, the top of hydrogenator is provided with opening for feed 21, air outlet 22, and bottom is provided with discharge port 23, and hydrogenator 2 comprises heating tube 24, and be heating coil, it is located at hydrogenator inside; Gas distributor 25, it comprises inlet mouth 251 and multiple shower nozzle 252 for being vented; Decompressor 3 is connected with the air outlet of described hydrogenator 2.Turbocompressor 6 is connected with described decompressor 3, and drives described turbocompressor 6 to work by described decompressor 3, and the air outlet of described turbocompressor 6 is connected with described hydrogenator 2.Gas-liquid separator 4 is connected with described decompressor 3, for separating of the mixed gas produced after reaction, isolates gas and liquid.Solvent pump 7 is connected with gas-liquid separator 2, for being delivered to by isolated liquid solvent in described hydrogenator 2; The inlet mouth on absorption tower 5 is connected with described gas-liquid separator 4, and air outlet is connected with described turbocompressor 6, for removing the gas needing to remove.
Preferably, described gas distributor 25 is in " L " type, and its bottom is annulus tubulose, and this ring tube is evenly provided with multiple shower nozzle 252 for being vented, and described shower nozzle is " L " type, becomes same direction to be obliquely installed.Pipe is in the form of a ring evenly equipped with multiple exhaust shower nozzle, makes gaseous emission more even, make fully to contact with gas as the material in hydrogenator, accelerate speed of reaction.The gas of the shower nozzle ejection be inclined to set tilts to spray gas toward same direction, makes bubble be contorted motion in hydrogenator 2, the material reacted fully is contacted with gas, fast reaction speed.
Preferably, described heating tube 24 is multiple, is distributed on described hydrogenator 2 inside in parallel; Described gas distributor 25 has multiple, and described multiple gas distributor 25 is interconnected, and the ring tube of described each gas distributor 25 is located between described heating tube 24.
Utilize above-mentioned device as reaction unit, a kind of method of rosin and the blended hydrogenation modification of C9/C5 petroleum resin, comprise the following steps: by raw material C9/C5 petroleum resin and ethylcyclohexane in mass ratio 1:1 add and melt still 1, add the catalyst mix of the supported palladium of the massfraction 1% of raw material total amount, heating, melt, form mixture, by H
2and CO
2mol ratio is that 10:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 7.0MPa to hydrogenator 2 internal pressure, continues to be heated to 250 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas discharge is 12000m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator 2 contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter gas-liquid separator 4, temperature≤50 DEG C of gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h.Solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting, and the flow that mixed gas flows out is about 10000m
3/ h, and the pressure maintaining hydrogenator is 7.0MPa, after reaction 1.5h, hydrogenator 2 is heated to 350 DEG C, control temperature of reaction to remain within the scope of 345 DEG C ~ 355 DEG C, reaction pressure is 14.0MPa ~ 15.0MPa, reacts 5.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2.Be modification C9/C5 hydrogenated petroleum resin through products obtained therefrom, bromine number is 1.0.
Embodiment 2
The reaction unit used is identical with embodiment 1, by raw material C9/C5 petroleum resin and hexanaphthene in mass ratio 3:1 add and melt still 1, add the catalyst mix of the nickel-loaded of the massfraction 30% of raw material total amount, heating, melt, formation mixture, by H
2and CO
2mol ratio is that 1:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 3.0MPa to hydrogenator 2 internal pressure, continues to be heated to 250 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas inflow amount is 7000m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter gas-liquid separator 4, temperature≤50 DEG C of gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h.Solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting.The flow that mixed gas flows out is about 5000m
3/ h, and the pressure maintaining hydrogenator is 3.0MPa, after reaction 3.0h, hydrogenator 2 is heated to 250 DEG C, and control temperature of reaction and remain within the scope of 250 DEG C ~ 255 DEG C, reaction pressure is 7.0MPa ~ 8.0MPa, react 5.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2, and bromine number is 4.0.
Embodiment 3
The reaction unit used is identical with embodiment 1, by C9/C5 petroleum resin and 200# solvent oil in mass ratio 5:1 add and melt still 1, add the catalyst mix of the nickel-loaded of the massfraction 20% of raw material total amount, heating, melt, formation mixture, by H
2and CO
2mol ratio is that 10:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 7.0MPa to hydrogenator 2 internal pressure, continues to be heated to 250 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas inflow amount is 5000m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter gas-liquid separator 4, temperature≤50 DEG C of gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h.Solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting.The flow that mixed gas flows out is about 3000m
3/ h, and the pressure maintaining hydrogenator is 7.0MPa, after reaction 1.5h, hydrogenator 2 is heated to 300 DEG C, and control temperature of reaction and remain within the scope of 300 DEG C ~ 310 DEG C, reaction pressure is 14.0MPa ~ 15.0MPa, react 7.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2, and bromine number is < 1.0.
Embodiment 4
The reaction unit used is identical with embodiment 1, by C9/C5 petroleum resin and n-heptane in mass ratio 4:1 add and melt still 1, add the catalyst mix of the supported palladium of the massfraction 5% of raw material total amount, heating, melt, formation mixture, by H
2and CO
2mol ratio is that 15:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 7.0MPa to hydrogenator 2 internal pressure, continues to be heated to 250 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas inflow amount is 3000m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter temperature≤50 DEG C of gas-liquid separator 4 gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h.Solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting.The flow that mixed gas flows out is about 1000m
3/ h, and the pressure maintaining hydrogenator is 7.0MPa, after reaction 1.5h, hydrogenator 2 is heated to 350 DEG C, and control temperature of reaction and remain within the scope of 345 DEG C ~ 355 DEG C, reaction pressure is 14.0MPa ~ 15.0MPa, react 3.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2, and bromine number is < 1.0.
Embodiment 5
The reaction unit used is identical with embodiment 1, by C9/C5 petroleum resin and n-hexane in mass ratio 7:1 add and melt still 1, add the catalyst mix of the supported palladium of the massfraction 10% of raw material total amount, heating, melt, formation mixture, by H
2and CO
2mol ratio is that 12:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 8.0MPa to hydrogenator 2 internal pressure, continues to be heated to 270 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas inflow amount is 1000m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter gas-liquid separator 4, temperature≤50 DEG C of gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h., solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting.The flow that mixed gas flows out is about 500m
3/ h, and the pressure maintaining hydrogenator is 8.0MPa, after reaction 1.5h, hydrogenator 2 is heated to 390 DEG C, and control temperature of reaction and remain within the scope of 380 DEG C ~ 400 DEG C, reaction pressure is 9.0MPa ~ 10.0MPa, react 9.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2, and bromine number is < 1.0.
Embodiment 6
The reaction unit used is identical with embodiment 1, by C9/C5 petroleum resin and ethylcyclohexane in mass ratio 6:1 add and melt still 1, add the catalyst mix of the nickel-loaded of the massfraction 15% of raw material total amount, heating, melt, formation mixture, by H
2and CO
2mol ratio is that 13:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 8.0MPa to hydrogenator 2 internal pressure, continues to be heated to 250 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas inflow amount is 500m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter gas-liquid separator 4, temperature≤50 DEG C of gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h.Solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting.The flow that mixed gas flows out is about 300m
3/ h, and the pressure maintaining hydrogenator is 8.0MPa, after reaction 1.5h, hydrogenator 2 is heated to 300 DEG C, and control temperature of reaction and remain within the scope of 300 DEG C ~ 305 DEG C, reaction pressure is 23.0MPa ~ 25.0MPa, react 5.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2, bromine number < 1.0.
Embodiment 7
The reaction unit used is identical with embodiment 1, by C9/C5 petroleum resin and 200# solvent oil in mass ratio 6:1 add and melt still 1, add the catalyst mix of the nickel-loaded of the massfraction 25% of raw material total amount, heating, melt, formation mixture, by H
2and CO
2mol ratio is that 10:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 7.0MPa to hydrogenator 2 internal pressure, continues to be heated to 250 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas inflow amount is 300m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter gas-liquid separator 4, temperature≤50 DEG C of gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h.Solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting.The flow that mixed gas flows out is about 100m
3/ h, and the pressure maintaining hydrogenator is 7.0MPa, after reaction 1.5h, hydrogenator 2 is heated to 200 DEG C, and control temperature of reaction and remain within the scope of 200 DEG C ~ 210 DEG C, reaction pressure is 14.0MPa ~ 15.0MPa, react 8.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2, and bromine number is 3.0.
Embodiment 8
The reaction unit used is identical with embodiment 1, by C9/C5 petroleum resin and hexanaphthene in mass ratio 4:1 add and melt still 1, add the catalyst mix of the supported palladium of the massfraction 8% of raw material total amount, heating, melt, formation mixture, by H
2and CO
2mol ratio is that 6:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 5.0MPa to hydrogenator 2 internal pressure, continues to be heated to 250 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas inflow amount is 50m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter gas-liquid separator 4, temperature≤50 DEG C of gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h.Solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting.The flow that mixed gas flows out is about 20m
3/ h, and the pressure maintaining hydrogenator is 5.0MPa, after reaction 1.5h, hydrogenator 2 is heated to 280 DEG C, and control temperature of reaction and remain within the scope of 280 DEG C ~ 290 DEG C, reaction pressure is 10.0MPa ~ 11.0MPa, react 3.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2, and bromine number is 2.0.
Embodiment 9
The reaction unit used is identical with embodiment 1, by C9/C5 petroleum resin and hexanaphthene in mass ratio 2:1 add and melt still 1, add the catalyst mix of the supported palladium of the massfraction 1% of raw material total amount, heating, melt, formation mixture, by H
2and CO
2mol ratio is that 3:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 5.0MPa to hydrogenator 2 internal pressure, continues to be heated to 250 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas inflow amount is 9m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter gas-liquid separator 4, temperature≤50 DEG C of gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h.Solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting.The flow that mixed gas flows out is about 5m
3/ h, and the pressure maintaining hydrogenator is 5.0MPa, after reaction 1.5h, hydrogenator 2 is heated to 250 DEG C, and control temperature of reaction and remain within the scope of 245 DEG C ~ 255 DEG C, reaction pressure is 16.0MPa ~ 17.0MPa, react 10.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2, and bromine number is 1.0.
Embodiment 10
The reaction unit used is identical with embodiment 1, by C9/C5 petroleum resin and ethylcyclohexane in mass ratio 10:1 add and melt still 1, add the catalyst mix of the supported palladium of the massfraction 12% of raw material total amount, heating, melt, formation mixture, by H
2and CO
2mol ratio is that 20:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 9.0MPa to hydrogenator 2 internal pressure, continues to be heated to 250 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas inflow amount is 8000m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter gas-liquid separator 4, temperature≤50 DEG C of gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h.Solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting.The flow that mixed gas flows out is about 5000m
3/ h, and the pressure maintaining hydrogenator is 9.0MPa, after reaction 1.5h, hydrogenator 2 is heated to 280 DEG C, and control temperature of reaction and remain within the scope of 275 DEG C ~ 285 DEG C, reaction pressure is 10.0MPa ~ 11.0MPa, react 6.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2, bromine number < 1.0.
Embodiment 11
The reaction unit used is identical with embodiment 1, by C9/C5 petroleum resin and ethylcyclohexane in mass ratio 4:1 add and melt still 1, add the catalyst mix of the nickel-loaded of the massfraction 28% of raw material total amount, heating, melt, formation mixture, by H
2and CO
2mol ratio is that 6:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 28.0MPa to hydrogenator 2 internal pressure, continues to be heated to 250 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas inflow amount is 4000m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter gas-liquid separator 4, temperature≤50 DEG C of gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h.Solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting.The flow that mixed gas flows out is about 3000m
3/ h, and the pressure maintaining hydrogenator is 28.0MPa, after reaction 3.0h, hydrogenator 2 is heated to 330 DEG C, and control temperature of reaction and remain within the scope of 325 DEG C ~ 335 DEG C, reaction pressure is 34MPa ~ 35MPa, react 1.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2, and bromine number is 3.0.
Embodiment 12
The reaction unit used is identical with embodiment 1, by C9/C5 petroleum resin and ethylcyclohexane in mass ratio 2:1 add and melt still 1, add the catalyst mix of the supported palladium of the massfraction 9% of raw material total amount, heating, melt, formation mixture, by H
2and CO
2mol ratio is that 6:1 mixed gas to pass in hydrogenator 2, is then heated to 150 DEG C, and is constantly filled with H
2and CO
2mixed gas is 5.0MPa to hydrogenator 2 internal pressure, continues to be heated to 250 DEG C, then opens hydrogenator 2 air outlet valve, makes the H produced in hydrogenation process
2s, reacts remaining gas H
2with CO
2mixed gas constantly flows out, and controlling mixed gas inflow amount is 6000m
3/ h, enters gas-liquid separator 4 after decompressor 3 throttling expansion, and the gas phase flowed out from hydrogenator contains H
2, CO
2, H
2s and solvent vapo(u)r, but these materials flowed out enter gas-liquid separator 4, temperature≤50 DEG C of gas-liquid separator 4, pressure≤0.5MPa, liquid flow rate≤100m through decompressor 3 step-down of expanding
3/ h, gas flow≤10000m
3/ h.Solvent vapo(u)r is condensed into liquid state and separates from gas-liquid separator 4, enters in solvent pump 7, returns systemic circulation and uses.And H
2, CO
2, H
2the mixing gas phase of these remainders of S enters in absorption tower 5, wherein H
2s is removed by absorption tower 5, remaining gas phase H
2, CO
2with the new H supplemented
2, CO
2together enter turbocompressor 6 pressurized circulation to return hydrogenator 2 and carry out hydrogenation reaction, it is that above-mentioned decompressor 3 expansion work promotes turbocompressor 6 and pressurizes that turbine 6 carries out acting.The flow that mixed gas flows out is about 5000m
3/ h, and the pressure maintaining hydrogenator is 5.0MPa, after reaction 1.5h, hydrogenator 2 is heated to 370 DEG C, and control temperature of reaction and remain within the scope of 375 DEG C ~ 385 DEG C, reaction pressure is 10.0MPa ~ 11.0MPa, react 3.0h at this point in the reaction, obtain product, modified C9/C5 petroleum resin flow out from the discharge port of hydrogenator 2, bromine number < 1.0.
Claims (10)
1. the method for hydrogenation-desulfurization coupling modification C9/C5 petroleum resin, is characterized in that, comprise following operation steps:
(1) by C9/C5 petroleum resin and solvent according to mass ratio 1:1 ~ 10:1, add catalyst mix, heating, dissolve;
(2) H is passed into
2and CO
2mol ratio is that the mixed gas of 1:1 ~ 20:1 carries out hydrogenation reaction, and temperature of reaction is 150 DEG C ~ 400 DEG C, and reaction pressure is 3.0MPa ~ 35.0MPa;
(3) the gas H produced in hydrogenation process
2s, remaining mixed gas H
2and CO
2be separated, removing H
2s, H
2and CO
2pressurization returns to be carried out hydrogenation reaction and recycles;
(4), after hydrogenation-desulphurization reaction 1 ~ 10h, after decompression, material is released and is blended hydrogenation modification rosin and C9/C5 petroleum resin products from hydrogenator.
2. the method for hydrogenation-desulfurization coupling modification C9/C5 petroleum resin according to claim 1, it is characterized in that: in described step (2), effluent air is after decompressor, enter gas-liquid separator to be separated, the solvent liquid obtained is back in hydrogenator, and remaining gas is H
2s, H
2and CO
2,gas is passed in absorption tower, absorb H through absorption tower
2after S gas, residue H
2and CO
2pass into turbocompressor again.
3. the method for hydrogenation-desulfurization coupling modification C9/C5 petroleum resin according to claim 1, is characterized in that: the flow that described step (3) takes out mixed gas from hydrogenator is 0 ~ 12000m
3/ h, by gas by decompressor, decompressor is connected with turbocompressor, in turbocompressor, supplement CO
2and H
2mixed gas, then mixed gas is passed in hydrogenator.
4. the method for hydrogenation-desulfurization coupling modification C9/C5 petroleum resin according to claim 1, it is characterized in that: the massfraction 1 ~ 30% that the amount of the catalyzer added in step (1) is the C9/C5 petroleum resin that add and solvent total amount, wherein said catalyzer is the catalyzer of nickel-loaded or palladium.
5. the method for hydrogenation-desulfurization coupling modification C9/C5 petroleum resin according to claim 1, is characterized in that: in step (3), the temperature of gas-liquid separator is 0 ~ 50 DEG C, and pressure is 0.0 ~ 0.5MPa, and liquid flow rate is 0 ~ 100m
3/ h, gas flow is 0 ~ 10000m
3/ h.
6. the method for hydrogenation-desulfurization coupling modification C9/C5 petroleum resin according to claim 1, is characterized in that: the solvent described in step (1) is the one in hexanaphthene, ethylcyclohexane, n-hexane, n-heptane, mineral essential oil, 200# solvent oil.
7. an equipment for hydrogenation-desulfurization coupling modification C9/C5 petroleum resin method as claimed in claim 1, is characterized in that, comprising:
Hydrogenator, it comprises: multiple heating tube, is located at hydrogenator inside; And gas distributor, it comprises inlet mouth and multiple shower nozzle for being vented; Decompressor, it is connected with described hydrogenator; And turbocompressor, it is connected with described decompressor, and drives described turbocompressor work by described decompressor, and the air outlet of described turbocompressor is connected with described hydrogenator.
8. equipment according to claim 8, is characterized in that: in technique scheme, and described gas distributor is in " L " type, and its bottom is annulus tubulose, and this ring tube is evenly provided with multiple shower nozzle for being vented.
9. equipment according to claim 8, it is characterized in that: in technique scheme, described heating tube is multiple, and to be distributed on described hydrogenator inner in parallel; Described gas distributor has multiple, and described multiple gas distributor is interconnected, and described each gas distributor is located between described heating tube.
10. equipment according to claim 8, it is characterized in that: in technique scheme, the described device for rosin and the blended hydrogenation modification of C9/C5 petroleum resin, also comprises: dissolution kettle, it is connected with described hydrogenator, for dissolving the raw material needed for production; Gas-liquid separator, it is connected with described decompressor; Solvent pump, it is connected with described gas-liquid separator, for delivering in described hydrogenator by isolated liquid solvent; And absorption tower, its inlet mouth is connected with described gas-liquid separator, and air outlet is connected with described turbocompressor, for removing H
2s gas.
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