CN106540640A - A kind of hydrogenation of petroleum resin process desulfurization, the commercial run of dechlorination and device - Google Patents
A kind of hydrogenation of petroleum resin process desulfurization, the commercial run of dechlorination and device Download PDFInfo
- Publication number
- CN106540640A CN106540640A CN201610973726.2A CN201610973726A CN106540640A CN 106540640 A CN106540640 A CN 106540640A CN 201610973726 A CN201610973726 A CN 201610973726A CN 106540640 A CN106540640 A CN 106540640A
- Authority
- CN
- China
- Prior art keywords
- vapor
- liquid
- phase
- tank
- liquid separation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses a kind of hydrogenation of petroleum resin process desulfurization, the commercial run of dechlorination and device.For merging the water-oil phase emulsifying materials phenomenon that alkali washing process brings, vapor-liquid separation is carried out in vapor-liquid separation devices to the liquid-vapor mixture material of sulfide hydrogen after hydrogenation reactor and hydrogen chloride, the vapor phase stream of discharge carries out desulfurization, dechlorination in neutralization static mixer.Vapour method is washed using alkali liquor, the hydrogen sulfide and hydrogen chloride of hydrogenation process generation in recycle hydrogen and circulating solvent are removed effectively, eliminate the corrosion to the circulation of follow-up hydrogen, desolventizing and solvent recovering system equipment and instrument, particularly high-sulfur, the hydrogenation process of the Petropols of chlorinity；Due to being only neutralized dechlorination and desulfurization to vapour phase in material in whole hydrogenation-dechlorination and sweetening process, eliminate original resin vapour-liquid liquid knockout drum and resin liquid liquid knockout drum, the problem that the organic faciess and water for eliminating resinous material mutually coexist, emulsion is avoided, the separation process of water-oil phase liquid material is simplified.
Description
Technical field
The present invention relates to a kind of be applied to C5, C9 Petropols, cyclopentadiene resin or copolymerized petroleum resin hydrogenation process
Desulfurization, the commercial run of dechlorination.The method is applied to one section or two-stage nitration Petroleum Resin Hydrogenation Process, washes vapour method using alkali liquor,
The hydrogen sulfide (H2S) and hydrogen chloride (HCl) of hydrogenation process generation in recycle hydrogen and circulating solvent can be effectively removed, is disappeared
Except to hydrogen circulation and the corrosion of solvent circulation equipment and instrument, the reaction that improve hydrogenation of petroleum resin catalyst is lived
Property and stability, it is ensured that the safety of device is normal to be run.
Background technology
During with petroleum distillate producing ethylene by cracking, propylene, the substantial amounts of cracking c5 of meeting by-product, C9 fractions, Ke Yizuo
To produce the raw material of Petropols, using thermal polymerization or catalytic polymerization, through pretreatment, polymerization, desolventizing, sheeting molding
Etc. operation (catalytic polymerization also includes the operations such as denitrating catalyst, neutralization, washing), C5, C9 oil tree of various different sizes is produced
Fat or copolymerized petroleum resin (molecular weight is typically in 500-2000 or so), referred to as non-hydrogenated petroleum resin.Due to the raw material for adopting
Different from polymerization technique, non-hydrogenated petroleum resin is in light yellow to the various color and lusters of bronzing, generally existing color is deep, abnormal smells from the patient is smelly,
Thermo-oxidative stability is low, cohesive force and the defect such as the compatibility is poor, have impact on its application in high-end field, and main cause is polymerization
In thing chain, unsaturated double bond is high, and the not clear coloured groups for being formed in the course of the polymerization process.
Hydrogenated petroleum resin is aiming at the not enough above of non-hydrogenated petroleum resin, using Catalytic Hydrogenation Techniques, in catalysis
Unsaturated composition and coloured groups hydrogenation in the non-hydrogenated petroleum resin that will be obtained by cracking c5, C9 polymerizations in the presence of agent,
Double bond content is reduced, and the colourless or light colour petroleum resin obtained after removing the chlorine and sulfur for remaining in the course of the polymerization process.With not plus
Hydrogen Petropols are compared, and it is thermally-stabilised that hydrogenated petroleum resin further improves the colourity of Petropols, cohesive, weatherability, light
The performance such as property and the compatibility, has widened significantly the application of Petropols, can be widely used for coating, paint, ink, hot melt
On the fields such as glue, adhesive, pressure sensitive adhesive, especially hygienic article and traffic coating.
At present, the production technology of hydrogenated petroleum resin mainly has three kinds：Slurry hydrogenation technique, fountain hydrogenation technique and solid
Fixed bed hydrogenation technique.Slurry hydrogenation technique is usually batch tank reaction, it is adaptable to the production of small-scale, there is production technology
It is loaded down with trivial details, the drawback such as catalyst loss is big；Fountain hydrogenation technique realizes industrialization by Japanese Huang Chuan chemical companies, but there is also
Design requirement is high, equipment investment is big, it is wayward the shortcomings of：Petropols process units mainly adopts fixed bed hydrogenation work at present
Skill, the technique are produced suitable for large-scale hydrogenated petroleum resin.The fixed bed hydrogenation technique of Petropols is divided into one-stage hydrogenation
And two-stage hydrogenation, one-stage hydrogenation process characteristic be unsaturated bond hydrogenation, coloured groups and chlorine and sulfur removing in hydrogenation
In reactor, a step is completed；Petropols two-stage hydrogenation technique typically loads different adding in one section and second-stage hydrogenation reactor
Hydrogen catalysis add, and carry out the preliminary hydrogenation of unsaturated bond and carry out the de- of coloured groups and chlorine and sulfur in first paragraph reactor
Remove, hydrofinishing is carried out to Petropols in second segment hydrogenation reactor.Hydrogenation products Jing vapor-liquid separations, desolvation are laggard
Row pelletize obtains hydrogenated petroleum resin product.
Due to usually containing in the impurity such as sulfur, chlorine, and Petropols catalyzed polymerization process in Petropols polymer raw
Anhydrous AlCl is adopted generally3For catalyst, although carrying out the last handling processes such as alkali cleaning neutralization, washing to polymerization process product,
In hydrogenating materials resin, the chlorinity of remaining is still in 500～5000ppm, the hydrogenation activity of catalyst of substantially drawing up, while
Hydrogen sulfide (H2S) and hydrogen chloride (HCl) are converted into, heavy corrosion is caused to follow-up equipment and instrument.
It is mainly alkali wash currently used for the method for hydrogenation of petroleum resin process desulfurization, dechlorination, for example
ZL201010266085.X (a kind of industrially preparing process of hydrogenated petroleum resin) is disclosed to merge alkali washing process, and technological process is shown in
Fig. 1, the method are applied in two sections of fixed bed hydrogenation technique, are added into one section after resin, solvent and circulating hydrogen Hybrid Heating
Hydrogen reactor 1 carries out hydrogenation reaction, and reacting rear material carries out vapor-liquid separation into vapor-liquid separation tank 2, the liquid phase after separation and plus
Secondary hydrogenation reaction, second-stage hydrogenation reactor 3 are carried out into second-stage hydrogenation reactor 3 after hydrogen make-up, solvent mixing after heat
The vapour phase that product and vapor-liquid separation tank 2 are isolated is entered in high pressure and static mixer 5, is entered in the case where alkali liquor is pumped into
The hydrogen sulfide produced with elimination reaction in row alkali liquor and hydrogen chloride, the oil containing alkali liquor discharged with static mixer 5 in high pressure
Solvent, vapor and the condensation of dissolved hydrogen Jing high scores that aqueous mixtures gasify after entering one-level high pressure vapor-liquid separation tank 4, vapor-liquid separation
Device 7 enters two grades of high pressure vapor-liquid separation tanks after condensing；The liquid phase not gasified carries out vapour-liquid point into one-level low pressure vapor-liquid separation tank 9
Solvent, vapor and dissolved hydrogen from, gasification enters two grades of low pressure vapor-liquid separation tanks Jing after low point of condenser 12 is condensed；Do not gasify
Liquid phase enter the resin vapour-liquid liquid knockout drum 30 of normal pressure, material is divided into vapour phase, liquid phase, and liquid phase includes that alkali liquor water phase and resin have
Machine phase two parts, vapour phase therein enter solvent vapor-liquid separation tank 31, the solvent not gasified in solvent vapor-liquid separation tank 31 and water
Into thick solvent settling tank 20, here carries out solvent and water phase stratification, and the thick solvent on upper strata enters thick solvent refining tower 29
The water of dispensing, lower floor is gone to wash for resin as circulating solvent after dehydration.The liquid phase lower floor of resin vapour-liquid liquid knockout drum 30 is
Mutually become waste water discharge containing aqueous alkali, the organic faciess on upper strata mix laggard into blender 32 with the water from thick solvent settling tank 20
Enter lower floor's water after resin liquid liquid knockout drum 33 is layered mutually to configure for alkali liquor, the organic faciess of the resinous product in upper strata are dropped into one-level
After the removing partial solvent of film evaporator 14 into two grades of falling film evaporators 22 under conditions of steam stripping at reduced pressure desolvation and oligomeric
Melt after thing goes pelletizing unit sheeting pelletize to obtain qualified hydrogenated petroleum resin product.
The method has higher requirement to adding hydrogen into resin depth, in resin vapour-liquid liquid knockout drum 30 and resin liquid liquid knockout drum
There is the possibility of water-oil phase emulsifying materials in 33, the separation method and equipment, desolventizing system to water-oil phase liquid material
Design and operation have higher requirement.
The present invention is improved to caustic wash desulfuration, dechlorination process, overcomes the shortcoming of the above, it is ensured that device is stablized
Operation.
The content of the invention
The invention provides one kind adds suitable for C5, C9 Petropols, cyclopentadiene resin or C5/C9 copolymerized petroleum resins
Hydrogen process desulfurization, the commercial run of dechlorination and device, concrete technical scheme are as follows：
A kind of hydrogenation of petroleum resin process desulfurization, the commercial run of dechlorination, is characterized in that：Suitable for one section of Petropols or
During two-stage hydrogenation, one after Petropols, solvent and hydrogen are mixed and heated during Petropols one-stage hydrogenation, is entered
Section hydrogenation reactor carries out hydrogenation reaction, and after reaction, the liquid-vapor mixture of sulfide hydrogen and hydrogen chloride is directly entered one-level high pressure vapour
Liquid knockout drum carries out vapor-liquid separation, and liquid phase enters one-level low pressure vapor-liquid separation tank, vapour phase enter in high pressure and static mixer and
The alkali liquor for pumping into is mixed into horizontal high voltage alkali cleaning, removing hydrogen sulfide and hydrogen chloride, and Jing after high pressure alkali cleaning, product is into two grades of high pressure point
Vapor-liquid separation is carried out from tank, detached vapour phase carries out hydrogen recovery and solvent recovery, liquid phase and Jing after high pressure condenser condensation
The detached vapour phase of level low pressure separation pot is in low pressure and static mixer carries out low pressure alkaline cleaning procedure, the material after low pressure alkali cleaning
Into two grades of low pressure vapor-liquid separation tanks, after the detached vapour phase condensation of two grades of low pressure vapor-liquid separation tanks, carry out that hydrogen is reclaimed and solvent is returned
Receive, liquid phase is entered in normal pressure and static mixer, the detached liquid phase of one-level low pressure vapor-liquid separation tank enters stage falling-film evaporators,
In the detached vapour phase of stage falling-film evaporators enters normal pressure and static mixer liquid detached with two grades of low pressure vapor-liquid separation tanks
Mixing carries out normal pressure alkali cleaning, and the detached liquid phase of stage falling-film evaporators enters two grades of falling film evaporators, and vapour phase Jing of removing is low
Polymers knockout tower enters decompression neutralization static mixer and carries out decompression alkali cleaning, normal pressure alkali cleaning, decompression alkali cleaning after isolating oligomer
Oil water mixture afterwards realizes the recycling of solvent and water, the melt that two grades of falling film evaporators are excluded Jing after sedimentation oil-water separation
Hydrogenated petroleum resin product is obtained Jing after prilling；
During Petropols two-stage hydrogenation；Petropols, solvent and hydrogen enter vapour Jing after one-stage hydrogenation reactor
Liquid knockout drum carries out vapor-liquid separation, and the liquid phase after separation is mixed into secondary hydrogenation with the solvent and hydrogen that supplement the heating come in
Reactor carries out the liquid-vapor mixture of hydrogenation reaction, sulfide hydrogen and hydrogen chloride and enters one-level high pressure knockout drum, in one-level high pressure
Knockout drum carries out vapor-liquid separation, and liquid phase enters one-level low pressure vapor-liquid separation tank, the sulfide hydrogen that one-level high pressure knockout drum is isolated
Merge the vapour phase that vapor-liquid separation tank is isolated after one-stage hydrogenation reactor with the vapour phase of hydrogen chloride to enter in high pressure and static mixing
Device is mixed into horizontal high voltage alkali cleaning with the alkali liquor for pumping into, low pressure below, normal pressure and decompression same section of hydrogenation technique phase of caustic wash process
Together；
The high-pressure is 4～15MPa, and low pressure is 0.4～4MPa.
The present invention is C5, C9 Petropols obtained by cracking c5, the polymerization of C9 fractions for the raw material Petropols of hydrogenation,
Cyclopentadiene resin or C5/C9 copolymerized petroleum resins.
For sodium hydroxide or calcium hydroxide aqueous solution, concentration is 1%～10% to the alkali liquor for adopting.
The hydrogenation solvent includes many alkyl naphthenes of saturated alkane class, saturation or aromatic hydrocarbon solvent.
The hydrogenation of petroleum resin process desulfurization of the present invention, the device of the industry of dechlorination：In Petropols one-stage hydrogenation technique
In device, hydrogenation reactor outlet connection one-level high pressure vapor-liquid separation tank material inlet, one-level high pressure vapor-liquid separation tank top vapour
Mutually outlet is pumped into during pipeline is connected to high pressure and at the top of static mixer with static mixer material inlet, alkali liquor in being connected to high pressure
Lye import, is connected with two grades of high pressure vapor-liquid separation tank material inlets with the outlet of static mixer bottom liquid phases in high pressure, two grades
High pressure vapor-liquid separation tank top vapor phase exit is connected with high score condenser, high score condensator outlet connection three-level high pressure knockout drum,
The outlet of three-level high pressure knockout drum top gas phase is connected to and follows light machine import surge tank, and three-level high pressure knockout drum bottom liquid-phase outlet connects
Three-level low pressure separation pot is connected to, is entered in two grades of high pressure vapor-liquid separation tank bottom liquid phases outlet connection low pressure and at the top of static mixer
Mouthful, the outlet of one-level high pressure vapor-liquid separation tank bottom liquid phases is connected to one-level low pressure vapor-liquid separation tank material inlet, one-level low-pressure steam
The connection stage falling-film evaporators import of liquid knockout drum bottom liquid-phase outlet, at the top of one-level low pressure vapor-liquid separation tank vapor phase exit with it is low
Pressure neutralization static mixer vapour phase entrance is connected, in low pressure and static mixer outlet at bottom and two grades of low pressure vapor-liquid separation tank things
Material import connection, two grades of low pressure vapor-liquid separation tank vapor phase exits are connected to low point of condenser, low point of condenser material outlet and three
The import connection of level low pressure separation pot, the outlet of three-level low pressure separation pot top gas phase are connected to new hydrogen machine import surge tank, and three-level is low
Pressure knockout drum liquid-phase outlet is connected with normal pressure vapor-liquid separation tank material inlet, two grades of low pressure vapor-liquid separation bottom liquid phases outlet connections
With static mixer top entry in normal pressure, the outlet of stage falling-film evaporators bottom liquid phases is connected to two grades of falling film evaporator materials
Import, at the top of stage falling-film evaporators, vapor phase exit is connected with static mixer vapour phase entrance with normal pressure, in normal pressure and static
The outlet of blender bottom liquid phases is connected to normal pressure alkali liquor settling tank, normal pressure alkali liquor settling tank vapor phase exit and atmospheric condenser phase
Even, atmospheric condenser outlet connection normal pressure vapor-liquid separation tank material inlet, normal pressure vapor-liquid separation tank outlet at bottom is connected to thick molten
Agent settling tank, the outlet of normal pressure alkali liquor settling tank oil phase are connected to static mixer, and normal pressure alkali liquor settling tank water is mutually exported and is connected to
Decompression neutralization static mixer material inlet, two grades of falling film evaporator outlet at bottoms connect sheeting granulating system device, two grades of drops
At the top of film evaporator, vapor phase exit is connected with oligomer knockout tower charging aperture, and oligomer separation column vapor phase exit is connected to and subtracts
Pressure neutralization static mixer top entry, decompression neutralization static mixer outlet are connected to decompression alkali liquor settling tank, and reduce pressure alkali liquor
The outlet of settling tank oil phase is connected to static mixer, and decompression alkali liquor settling tank vapor phase exit is connected to decompression condensation implements material and enters
Mouthful, decompression condensation device material outlet is connected to slightly with the entrance connection of decompression vapor-liquid separation tank, decompression vapor-liquid separation tank liquid-phase outlet
Solvent settling tank, vapor phase exit are connected with liquid-ring vacuum pump, and liquid ring vacuum pump discharge is connected to thick solvent settling tank, static mixing
Device outlet is connected to cleaning mixture settling tank, and cleaning mixture settling tank water is mutually exported and is connected to normal pressure alkali liquor settling tank, cleaning mixture sedimentation
The outlet of tank oil phase is connected to thick solvent settling tank, and thick solvent settling tank water is mutually exported and is connected with static mixer, thick solvent sedimentation
The outlet of tank oil phase is connected with thick solvent refining tower；
In Petropols two-stage hydrogenation process unit, one-stage hydrogenation reactor outlet is connected with vapor-liquid separation tank material inlet
Connect, the outlet connection second-stage hydrogenation reactor import of vapor-liquid separation tank bottom liquid phases, second-stage hydrogenation reactor outlet connection one-level are high
Pressure vapor-liquid separation tank material inlet, vapour-liquid after one-level high pressure vapor-liquid separation tank top vapor phase exit pipeline and one-stage hydrogenation reactor
Vapor phase exit pipeline merging at the top of knockout drum pumps into pipeline and is connected to height with static mixer material inlet, alkali liquor in being followed by high pressure
Lye import at the top of pressure neutralization static mixer, other device methods of attachment also desulfurization of Petropols one-stage hydrogenation, dechlorination process
It is identical.
In high pressure, low pressure desulfurization, dechlorination process, after neutralization static mixer, vapor-liquid separation tank is configured；Normal pressure and decompression
In desulfurization, dechlorination process, alkali liquor settling tank after neutralization static mixer, is configured, the alkali liquor that normal pressure alkali liquor settling tank is discharged is used as subtracting
The alkali liquor of pressure-off sulfur, dechlorination process, the alkali liquor discharger that the alkali liquor settling tank that reduces pressure is discharged.
Alkali liquor or water-oil phase mixture after the neutralization is static mixed to the neutralization of low first class pressure by system pressure difference
Clutch flows, and realizes alkali liquor by high pressure, low pressure, normal pressure and decompression desulfurization, the multiplexing of the alkali liquor of dechlorination process.
It is vapor-liquid separation tank or alkali liquor settling tank are discharged after static mixer the condensed device of vapour phase, vapor-liquid separation tank row
Go out oil water mixture；The thick solvent settling tanks of oil water mixture Jing of discharge realize oil-water separation, and oil phase goes thick solvent refining tower to take off
As hydrogenation circulating solvent after crystal's system；Water phase and supplementary fresh deionized water are together as washings, heavy to normal pressure alkali liquor
The oil phase that drop tank and decompression settling tank are discharged carries out being sufficiently mixed washing by static mixer, and enters cleaning mixture settling tank,
The oil phase discharged from cleaning mixture settling tank goes thick solvent settling tank molten as hydrogenation circulation Jing after the dehydration of thick solvent refining tower is refined
Agent, mutually a part removes dilution decompression alkaline cleaning procedure alkali liquor to water, and for its cooling, to reduce depressurized system vapour phase load, water phase its
Remaining part point deallocation alkaline soda liquid.
It is described as follows：
The method is applied to Petroleum Resin Hydrogenation Process, and the water-oil phase emulsifying materials brought for merging alkali washing process are existing
As carrying out in vapor-liquid separation devices to the liquid-vapor mixture material of sulfide hydrogen after hydrogenation reactor (H2S) and hydrogen chloride (HCl)
Vapor-liquid separation, the vapor phase stream of discharge carry out desulfurization, dechlorination in neutralization static mixer (neutralization reactor).The present invention is adopted
Alkali liquor washes vapour method, effectively can remove hydrogenation process is produced in recycle hydrogen and circulating solvent hydrogen sulfide (H2S) and
Hydrogen chloride (HCl), eliminates the corrosion to the circulation of follow-up hydrogen, desolventizing and solvent recovering system equipment and instrument, particularly
The hydrogenation process of high-sulfur, the Petropols of chlorinity.As in whole hydrogenation-dechlorination and sweetening process to the vapour phase in material
Dechlorination and desulfurization are neutralized, original resin vapour-liquid liquid knockout drum 30 and resin liquid liquid knockout drum 33 are eliminated, is eliminated containing tree
The problem that the organic faciess of fat material are mutually coexisted with water, it is to avoid emulsion, simplifies the separation of water-oil phase liquid material
Journey.
The method is applied to the hydrogenation technique of one section and two sections fixed bed Petropols, due to one section and two-stage hydrogenation technique
It is different, therefore the technological process of dechlorination and desulfurization also has difference in response system in one section of two step process.
Hydrogenation reactor is entered after Petropols, solvent and hydrogen are mixed and heated during Petropols one-stage hydrogenation
1 carries out hydrogenation reaction, and after reaction, the liquid-vapor mixture of sulfide hydrogen (H2S) and hydrogen chloride (HCl) is directly entered one-level high pressure vapour
Liquid knockout drum 4 carries out vapor-liquid separation, and liquid phase enters one-level low pressure vapor-liquid separation tank 9, and vapour phase is entered in high pressure and static mixer 5
Horizontal high voltage alkali cleaning, removing hydrogen sulfide and hydrogen chloride are mixed into the alkali liquor for pumping into, product enters two grades of high pressure Jing after high pressure alkali cleaning
Knockout drum 6 carries out vapor-liquid separation, and detached vapour phase Jing after the condensation of high pressure condenser 7 carries out hydrogen recovery and solvent recovery, separates
Liquid phase afterwards with 9 detached vapour phase of one-level low pressure separation pot is in low pressure and static mixer 10 carries out low pressure alkaline cleaning procedure,
Material after low pressure alkali cleaning enters two grades of low pressure vapor-liquid separation tanks 11, two grades of 11 detached vapour phase Jing low pressure of low pressure vapor-liquid separation tank
Condenser 12 carries out hydrogen recovery and solvent recovery after condensing, liquid phase is entered in normal pressure and static mixer 15, in normal pressure and quiet
Into normal pressure alkali liquor settling tank 16,9 detached liquid phase of one-level low pressure vapor-liquid separation tank enters stage falling-film to the discharging of state blender 15
Vaporizer 14, divides with static mixer 15 and two grades of low pressure vapour-liquids in 14 detached vapour phase of stage falling-film evaporators enters normal pressure
Normal pressure alkali cleaning is carried out from 11 detached liquid-phase mixing of tank, 14 detached liquid phase of stage falling-film evaporators enters two grades of falling film evaporators
22, the vapour phase of removing enters decompression neutralization static mixer 24 Jing after oligomer knockout tower 23 isolates oligomer carries out decompression alkali
Wash, the decompression neutralization discharging of static mixer 24 enters decompression alkali liquor settling tank 25, and decompression alkali liquor settling tank 25 and normal pressure alkali liquor are heavy
Drop tank 16 enters cleaning mixture settling tank 21, the melt Jing pelletizes that two grades of falling film evaporators 22 are discharged after the washing of static mixer 19
Hydrogenated petroleum resin product is obtained after technique.
During Petropols two-stage hydrogenation, Petropols, solvent and hydrogen enter high pressure Jing after one-stage hydrogenation reactor 1
Vapor-liquid separation tank 2 carries out vapor-liquid separation, and the liquid phase after separation is mixed into two-stage nitration with the solvent and hydrogen that supplement the heating come in
Hydrogenation reactor 3 carries out the liquid-vapor mixture of sulfide hydrogen and hydrogen chloride after hydrogenation reaction and enters one-level high pressure knockout drum 4, one
Level high pressure knockout drum 4 carries out vapor-liquid separation, and liquid phase enters one-level low pressure vapor-liquid separation tank 9, what one-level high pressure knockout drum 4 was isolated
The vapour phase that high pressure vapor-liquid separation tank 2 is isolated after the vapour phase merging one-stage hydrogenation reactor of sulfide hydrogen and hydrogen chloride enters high pressure
Neutralization static mixer 5 is mixed into horizontal high voltage alkali cleaning with the alkali liquor for pumping into, and low pressure below, normal pressure and decompression caustic wash process are same
Section hydrogenation technique is identical.
During vapor-phase material during whole hydrogenation-dechlorination (sulfur) for sulfide hydrogen (H2S) and hydrogen chloride (HCl) is carried out
With dechlorination and desulfurization, increased in low pressure and static mixer, normal pressure in and static mixer and decompression neutralization static mixer
Equipment component, eliminates original resin vapour-liquid liquid knockout drum 30 and resin liquid liquid knockout drum 33, so as to avoid emulsion.
For aqueous solutions such as sodium hydroxide (NaOH), calcium hydroxide (Ca (OH) 2), concentration is 1% to the alkali liquor that the present invention is adopted
～10%, alkali liquor is sufficiently mixed in neutralization static mixer and neutralization occurs with hydrogen sulfide (H2S) and hydrogen chloride (HCl) gas
Reaction, the hydrogen sulfide (H2S) produced in hydrogenation reaction in removing vapour phase and hydrogen chloride (HCl), while neutralized reaction product enters static
After blender, vapor-liquid separation tank (alkali liquor settling tank), realizes vapor-liquid separation and oil-water separation.
In the present invention, neutralization desulfurization, dechlorination process are carried out under high pressure, low pressure, normal pressure and decompression respectively, and alkali liquor is washed in vapour
The method of sum, removes the hydrogen sulfide (H2S) and hydrogen chloride (HCl) in the gas that blood pressure lowering is flashed off successively, so as to substantially reduce liquid
Hydrogen sulfide (H2S) and hydrogen chloride (HCl) concentration in phase, reduces the hydrogen sulfide (H2S) and hydrogen chloride (HCl) in liquid phase to follow-up
The corrosion of equipment and instrument；Alkali liquor or water-oil phase mixture after neutralization relies on neutralization of the system pressure difference to low first class pressure
Static mixer, realizes alkali liquor by high pressure, low pressure, normal pressure and decompression desulfurization, the multiplexing of the alkali liquor of dechlorination process.
In high pressure, low pressure desulfurization, dechlorination process, after neutralization static mixer, vapor-liquid separation tank is configured；Normal pressure and decompression
In desulfurization, dechlorination process, alkali liquor settling tank after neutralization static mixer, is configured, the alkali liquor that normal pressure alkali liquor settling tank is discharged is used as subtracting
The alkali liquor of pressure-off sulfur, dechlorination process, the alkali liquor discharger that the alkali liquor settling tank of reducing pressure is discharged, and carry out at the recovery of alkali and salt
Reason.
Vapor-liquid separation tank (alkali liquor settling tank) is discharged after static mixer the condensed device of vapour phase, vapour liquid separator tank are discharged
Oil water mixture；The thick solvent settling tanks of oil water mixture Jing of discharge realize oil-water separation, and oil phase goes thick solvent refining tower (tank)
As hydrogenation circulating solvent after dehydration is refined；Water phase and supplement fresh deionized water together as washings, to normal pressure alkali liquor
The oil phase that settling tank and decompression settling tank are discharged carries out being sufficiently mixed washing by static mixer, and settles into cleaning mixture
Tank, the oil phase discharged from cleaning mixture settling tank go thick solvent settling tank or thick solvent refining tower (tank) dehydration refined rear as hydrogenation
Circulating solvent, mutually a part removes dilution decompression alkaline cleaning procedure alkali liquor to water, and lowers the temperature for which, to reduce depressurized system vapour phase load,
Water phase remainder deallocation alkaline soda liquid.
The hydrogenation solvent that the present invention is suitable for includes many alkyl naphthenes of saturated alkane class, saturation, aromatic hydrocarbon solvent etc., such as ring
Hexane, alkyl cyclohexane, heptane, octane, nonane, decane, hydrogenation Aromatic raffinate, the saturation distillate being hydrocracked, with
And heavy aromatics and heavy aromatics many alkyl cyclohexanes for obtaining of hydrogenation etc..
Petropols two-stage hydrogenation technique desulfurization, dechlorination process schematic flow sheet are as shown in Figure 3：
The sulfide hydrogen (H2S) discharged from one section of hydrogenation of petroleum resin reactor 1 and the liquid-vapor mixture of hydrogen chloride (HCl)
Knockout drum 2 is directly entered, liquid phase and the supplementing solvent and hydrogen of vapor-liquid separation tank 2 are carried out into second-stage hydrogenation reactor 3
Secondary hydrogenation reacts, and the sulfide hydrogen (H2S) discharged from second-stage hydrogenation reactor 3 and the liquid-vapor mixture of hydrogen chloride (HCl) enter
Enter one-level high pressure vapor-liquid separation tank 4, sulfide hydrogen (H2S) and chlorine that one-level high pressure vapor-liquid separation tank 4 is discharged with vapor-liquid separation tank 2
The vapor-phase material and alkali liquor for changing hydrogen (HCl) enters two grades of high pressure vapour-liquids point with static mixer 5 together with after in high pressure
From tank 6.
9 flash distillation of liquid phase Jing one-level low pressure vapor-liquid separation tank that one-level high pressure vapor-liquid separation tank 4 is discharged, one-level low pressure vapour-liquid point
The sulfide hydrogen (H2S) and the vapour phase of hydrogen chloride (HCl) discharged from tank 9 is mixed with the liquid phase that two grades of vapour-liquid high pressure knockout drums 6 are discharged
Close in low pressure and static mixer 10, after neutralization, enter two grades of low pressure vapor-liquid separation tanks 11.
14 flash distillation of liquid phase Jing stage falling-film evaporators that one-level low pressure vapor-liquid separation tank 9 is discharged, stage falling-film evaporators 14
The vapour phase of the sulfide hydrogen (H2S) and hydrogen chloride (HCl) of discharge enters normal with the liquid-phase mixing that two grades of low pressure separation pots 11 are discharged
Pressure neutralization static mixer 15, enters normal pressure alkali liquor settling tank 16 after neutralization.
The liquid phase decompression that stage falling-film evaporators 14 are discharged strips falling film evaporator 22, second depressurized vapour into second depressurized
The melt (liquid phase) for carrying falling film evaporator 22 goes pelletize, vapour phase to remove oligomer knockout tower 23, the liquid that oligomer knockout tower 23 is discharged
Discharge as by-product, vapour phase enters decompression neutralization static mixer 24 with the alkali liquor that normal pressure alkali liquor settling tank 16 is discharged, in
Decompression alkali liquor settling tank 25 is entered with rear, the alkali liquor discharger that the alkali liquor settling tank 25 that reduces pressure is discharged, and carry out returning for alkali and salt
Receipts process, vapour phase Jing decompression condensation device 26, decompression knockout drum 27, liquid-ring vacuum pump 28 enter thick solvent settling tank 20.
The vapour phase difference Jing that two grades of high pressure vapor-liquid separation tanks, 6, two grades of low pressure separation pots 11, normal pressure alkali liquor settling tank 16 are discharged
High score condenser 7, low point of condenser 12, atmospheric condenser 17 are condensed, and respectively enter three-level high pressure vapor-liquid separation tank 8, three-level low
Pressure knockout drum 13, normal pressure vapor-liquid separation tank 18；The vapour phase that three-level high pressure vapor-liquid separation tank 8 is discharged goes to follow hydrogen machine import surge tank,
Liquid phase enters three-level low pressure separation pot 13 and reclaims dissolved hydrogen；The vapour phase that three-level low pressure separation pot 13 is discharged goes new hydrogen machine import buffering
Tank, liquid phase enter normal pressure vapor-liquid separation tank 18；Normal pressure vapor-liquid separation tank 18 discharges vapour phase as waste gas discharge or as stripping gas,
Liquid phase enters thick solvent settling tank 20；The oil phase that thick solvent settling tank 20 is discharged goes to be used for after the thick dehydration of solvent refining tank 29 is refined
Hydrogenation of petroleum resin dispensing, water phase and supplement fresh deionized water together as washings, to 16 He of normal pressure alkali liquor settling tank
The oil phase that decompression settling tank 25 is discharged carries out being sufficiently mixed washing by static mixer 19, and enters cleaning mixture settling tank 21,
The oil phase discharged from cleaning mixture settling tank 21 goes thick solvent settling tank 20 Jing after the dehydration of thick solvent refining tower 29 is refined as hydrogenation
Circulating solvent, the water discharged from cleaning mixture settling tank 21 mutually remove normal pressure alkali liquor settling tank 16, are neutralized dechlorination, and remainder goes
Prepare alkali cleaning alkali liquor.
Petropols one-stage hydrogenation technique desulfurization, dechlorination process schematic flow sheet are as shown in Figure 2：
The sulfide hydrogen (H2S) discharged from hydrogenation of petroleum resin reactor 1 and the liquid-vapor mixture of hydrogen chloride (HCl) are direct
Into one-level high pressure vapor-liquid separation tank 4, the sulfide hydrogen (H2S) and hydrogen chloride (HCl) of the discharge of one-level high pressure vapor-liquid separation tank 4
Vapor-phase material and alkali liquor to be entered together and enter two grades of high pressure vapor-liquid separation tanks 6 with after in high pressure and in static mixer 5, other steps
Suddenly as two-stage hydrogenation technique desulfurization, dechlorination method.
The method and device are applied to one section or two-stage nitration Petroleum Resin Hydrogenation Process, wash vapour method, Neng Gouyou using alkali liquor
Effect ground removing recycle hydrogen and circulating solvent in hydrogenation process produce hydrogen sulfide and hydrogen chloride, eliminate to hydrogen circulation and
The corrosion of solvent circulation equipment and instrument, improves the reactivity and stability of hydrogenation of petroleum resin catalyst, it is ensured that
The safety of device is normal to be run.
Description of the drawings
Fig. 1：The hydrogenation of petroleum resin vapour-liquid of prior art merges alkali washing process figure；
Fig. 2：Petropols one-stage hydrogenation desulfurization, dechlorination process schematic flow sheet；
Fig. 3：Petropols two-stage hydrogenation desulfurization, dechlorination process schematic flow sheet；
Wherein：1 one-stage hydrogenation reactor, 2 vapor-liquid separation tank, 3 second-stage hydrogenation reactor, 4 one-level high pressure knockout drum 5 is high
Pressure neutralization 6 two grades of 7 high score condenser of high pressure knockout drum, 8 three-level high pressure knockout drum, 9 one-level low pressure separation pots of static mixer
Drop with 13 three-level low pressure separation pot of static mixer 11 2 grades of low pressure separation pots, 12 low points of condensers, 14 one-level in 10 low pressure
With 16 17 atmospheric condenser of normal pressure alkali liquor settling tank of static mixer, 18 normal pressure vapor-liquid separation tank in 15 normal pressure of film evaporator
19 static mixer, 20 thick 21 cleaning mixture settling tank of solvent settling tank, 22 second depressurized strips 23 oligomer of falling film evaporator
26 decompression condensation device of the decompression neutralization decompression alkali liquor settling tank of static mixer 25 of knockout tower 24,27 decompression vapor-liquid separation tank 28
29 thick solvent refining tower of liquid-ring vacuum pump, 30 32 blender of resin vapour-liquid liquid 31 solvent vapor-liquid separation tank of knockout drum, 33 resin
Liquid liquid Separation tank.
Specific embodiment
Following instance and comparative example further illustrate the feature and details of this technique, but listed process and data are not intended to
Limitation of the scope of the invention.
Embodiment 1：
This example carries out hydropyrolysis experiment, the outlet of one-stage hydrogenation reactor 1 and vapour-liquid point according to the exemplary flow shown in accompanying drawing 3
Connect from 2 material inlet of tank, outlet connection 3 import of second-stage hydrogenation reactor of 2 bottom liquid phases of vapor-liquid separation tank, secondary hydrogenation reaction
4 material inlet of the outlet connection of device 3 one-level high pressure vapor-liquid separation tank, 4 top vapor phase exit pipeline of one-level high pressure vapor-liquid separation tank with
2 top vapor phase exit pipeline merging of vapor-liquid separation tank pumps into pipeline with 5 material inlet of static mixer, alkali liquor in being followed by high pressure
It is connected in high pressure and 5 top lye import of static mixer, exports and two grades of high pressure with 5 bottom liquid phases of static mixer in high pressure
6 material inlet of vapor-liquid separation tank is connected, and two grades of 6 top vapor phase exits of high pressure vapor-liquid separation tank are connected with high score condenser 7, high score
The outlet connection of condenser 7 three-level high pressure knockout drum 8, the outlet of 8 top gas phase of three-level high pressure knockout drum are connected to and follow light machine import and delay
Tank is rushed, the outlet of 8 bottom liquid phases of three-level high pressure knockout drum is connected to three-level low pressure separation pot 13, two grades of 6 bottoms of high pressure vapor-liquid separation tank
Connect with 10 top entry of static mixer, the outlet of 4 bottom liquid phases of one-level high pressure vapor-liquid separation tank in portion's liquid-phase outlet connection low pressure
9 material inlet of one-level low pressure vapor-liquid separation tank is connected to, 9 bottom liquid phases of one-level low pressure vapor-liquid separation tank outlet connection stage falling-film steams
14 import of device is sent out, 9 top vapor phase exit of one-level low pressure vapor-liquid separation tank is connected with 10 vapour phase entrance of static mixer with low pressure,
It is connected with two grades of 11 material inlets of low pressure vapor-liquid separation tank with 10 outlet at bottom of static mixer in low pressure, two grades of low pressure vapour-liquids point
Low point of condenser 12 is connected to from 11 vapor phase exit of tank, low point of 12 material outlet of condenser is connected with 13 import of three-level low pressure separation pot
Connect, the outlet of 13 top gas phase of three-level low pressure separation pot is connected to new hydrogen machine import surge tank, the outlet of three-level low pressure separation pot 13 with
Normal pressure vapor-liquid separation tank material inlet connects, and mixes with static state in two grades of 11 bottom liquid phases of low pressure vapor-liquid separation tank outlet connection normal pressures
15 top entry of clutch, 14 bottom liquid phases of stage falling-film evaporators are exported and are connected to two grades of 22 material inlets of falling film evaporator, and one
Level 14 top vapor phase exit of falling film evaporator is connected with 15 vapour phase entrance of static mixer with normal pressure, in normal pressure and static mixing
The outlet of 15 bottom liquid phases of device is connected to normal pressure alkali liquor settling tank 16,16 vapor phase exit of normal pressure alkali liquor settling tank and atmospheric condenser 17
It is connected, 18 material inlet of the outlet connection normal pressure of atmospheric condenser 17 vapor-liquid separation tank, 18 outlet at bottom of normal pressure vapor-liquid separation tank connect
Thick solvent settling tank 20 is connected to, the outlet of 16 oil phase of normal pressure alkali liquor settling tank is connected to static mixer 19, normal pressure alkali liquor settling tank
16 water are mutually exported and are connected to decompression neutralization 24 material inlet of static mixer, and two grades of 22 outlet at bottoms of falling film evaporator connect sheeting
Granulating system device, two grades of 22 top vapor phase exits of falling film evaporator are connected with 23 charging aperture of oligomer knockout tower, oligomer point
Decompression neutralization 24 top entry of static mixer is connected to from 23 top vapor phase exit of tower, decompression neutralization static mixer 24 is exported
Decompression alkali liquor settling tank 25 is connected to, the 25 oil phase outlet of decompression alkali liquor settling tank is connected to static mixer 19, and decompression alkali liquor sinks
Drop 25 vapor phase exit of tank is connected to 26 material inlet of decompression condensation device, 26 material outlet of decompression condensation device and decompression vapor-liquid separation tank
27 entrances connect, the thick solvent settling tank 20 of decompression vapor-liquid separation tank 27 bottom liquid phases outlet connection, and reduce pressure 27 vapour of vapor-liquid separation tank
Mutually export and be connected with liquid-ring vacuum pump 28, the outlet of liquid-ring vacuum pump 28 is connected to thick solvent settling tank 20, and static mixer 19 goes out
Mouth is connected to cleaning mixture settling tank 21, and 21 water of cleaning mixture settling tank is mutually exported and is connected to normal pressure alkali liquor settling tank 16, and cleaning mixture sinks
The 21 oil phase outlet of drop tank is connected to thick solvent settling tank 20, and thick 20 water of solvent settling tank is mutually exported and is connected with static mixer 19,
The 20 oil phase outlet of thick solvent settling tank is connected with thick solvent refining tower 29.Experimental raw be C5 Petropols, one, secondary hydrogenation it is anti-
Device is answered to load homemade loading type Pd-Al2O3 hydrogenation catalysts, neutralization reactor filling inert ceramic balls respectively, hydrogenation solvent is
Hexamethylene, neutralization alkali liquor are 5%NaOH aqueous solutions, only carry out alkali cleaning neutralization to circulating hydrogen, hydrogenation products liquid phase is not washed,
Stabilizer is deoxidizer 1010, and removing process is using normal pressure, vacuum two-stage removing process, recycling design recycling.Work
Skill condition is shown in Table 1, and experimental result is shown in Table 3.
1 process conditions of table
Comparative example 1：
This comparative example carries out hydrogenation of petroleum resin vapour-liquid according to the exemplary flow shown in accompanying drawing 1 and merges caustic wash desulfuration dechlorination examination
Test, experimental raw is C5 Petropols, using two-stage hydrogenation reaction process, in high pressure and static mixer feed volume flow velocity/
Hydrogenation feed volume flow velocity is 0.25, and other are identical with example 1., experimental result is shown in Table 3.
Embodiment 2：
The present embodiment is one-stage hydrogenation reaction process, carries out hydropyrolysis experiment according to the exemplary flow shown in accompanying drawing 2, and hydrogenation is anti-
4 material inlet of device outlet connection one-level high pressure vapor-liquid separation tank, the outlet of 4 bottom liquid phases of one-level high pressure vapor-liquid separation tank is answered to be connected to
In 9 material inlet of one-level low pressure vapor-liquid separation tank, 4 top vapor phase exit of one-level high pressure vapor-liquid separation tank and high pressure and static mixing
5 material inlet of device is connected, and other devices connect as one-stage hydrogenation technique vapour phase desulfurization, dechlorination method, and experimental raw is C5
Petropols, hydrogenation reactor load homemade loading type Pd-Al2O3 hydrogenation catalysts, and only circulating hydrogen is carried out in alkali cleaning
With, hydrogenation products liquid phase not to be washed, other are identical with example 1.Process conditions are shown in Table 2, and experimental result is shown in Table 3.
2 process conditions of table
Embodiment 3：
This example hydrogenation solvent is trimethyl-cyclohexane, and other are identical with example 1, and experimental result is shown in Table 3.
Embodiment 4：
This example carries out hydropyrolysis experiment according to the exemplary flow shown in accompanying drawing 2, and experimental raw is produced for catalytic polymerization
C9 Petropols, normal pressure desolventizing temperature brings up to 200 DEG C, and decompression falling liquid film desolventizing brings up to 250 DEG C, and solvent is trimethyl
Hexamethylene, other are identical with example 1.Experimental result is shown in Table 3.
Embodiment 5：
C9 Petropols of this example laboratory raw material for high sulfur content, other are identical with example 4, and experimental result is shown in Table 3.
Embodiment 6：
This example carries out hydropyrolysis experiment according to exemplary flow shown in the drawings, and experimental raw is catalytic polymerization production
C5/C9 copolymerized petroleum resins, normal pressure desolventizing temperature bring up to 180 DEG C, and decompression falling liquid film desolventizing brings up to 230 DEG C, and solvent is
Trimethyl-cyclohexane, other are identical with example 1.Experimental result is shown in Table 3.
Embodiment 7：
This comparative example is one-stage hydrogenation reaction process, and experimental raw is the C5/C9 copolymerization oil of catalytic polymerization production
Resin, normal pressure desolventizing temperature bring up to 180 DEG C, and decompression falling liquid film desolventizing brings up to 230 DEG C, and solvent is trimethyl-cyclohexane,
Other are identical with comparative example 1.Experimental result is shown in Table 3.
Embodiment 8～12
Using 1 petrochina resin two-stage hydrogenation desulfurization of embodiment, dechlorination process condition and device connected mode, experimental raw
For C5, tested from different neutralization alkali liquor, neutralization alkali liquor condition and experimental result are shown in Table 4
Embodiment 13～17
Using 4 petrochina resin two-stage hydrogenation desulfurization of embodiment, dechlorination process conditions method, experimental raw is catalytic polymerization
The C9 Petropols of method production, are tested from different neutralization alkali liquor, and neutralization alkali liquor condition and experimental result are shown in Table 4
3 experimental result of table
Table 4
The technic index and computational methods of technical process：
Bromine valency：gBr/100g
The test instrunment and method (execution standard) of hydrogenated petroleum resin
Colour：U.S.'s HunterLab Colour Quest EX colorimetric analysiss instrument, ASTM E313
Bromine valency：U.S.'s METTLER TOLEDO T50 type automatical potentiometric titrimeters, ASTM D1159-98
Softening point：Domestic SYD-2806F types softening point apparatus, ring and ball method GB/T 12007.6-1989
Chlorinity：Domestic RPA -200A micro-coulometric titrations instrument, Shi Ke institutes RIPP64
Conclusion
Can draw to draw a conclusion from data in table 3：During hydrogenation of petroleum resin using this method can effectively dechlorination,
Desulfurization, the characteristics of obtained hydrogenated petroleum resin has low bromine valency, light colour, low chlorine, low-sulfur.
Claims (8)
1. a kind of hydrogenation of petroleum resin process desulfurization, the commercial run of dechlorination, is characterized in that：Suitable for one section of Petropols or two
In section hydrogenation process, after Petropols, solvent and hydrogen are mixed and heated during Petropols one-stage hydrogenation, one section is entered
Hydrogenation reactor carries out hydrogenation reaction, and after reaction, the liquid-vapor mixture of sulfide hydrogen and hydrogen chloride is directly entered one-level high pressure vapour-liquid
Knockout drum carries out vapor-liquid separation, and liquid phase enters one-level low pressure vapor-liquid separation tank, and vapour phase is entered in high pressure and static mixer and pump
The alkali liquor for entering is mixed into horizontal high voltage alkali cleaning, removing hydrogen sulfide and hydrogen chloride, and Jing after high pressure alkali cleaning, product is separated into two grades of high pressure
Tank carries out vapor-liquid separation, and detached vapour phase carries out hydrogen recovery and solvent recovery, liquid phase and one-level Jing after high pressure condenser condensation
The detached vapour phase of low pressure separation pot is in low pressure and static mixer carries out low pressure alkaline cleaning procedure, and the material after low pressure alkali cleaning enters
Enter two grades of low pressure vapor-liquid separation tanks, after the detached vapour phase condensation of two grades of low pressure vapor-liquid separation tanks, carry out that hydrogen is reclaimed and solvent is returned
Receive, liquid phase is entered in normal pressure and static mixer, the detached liquid phase of one-level low pressure vapor-liquid separation tank enters stage falling-film evaporators,
In the detached vapour phase of stage falling-film evaporators enters normal pressure and static mixer liquid detached with two grades of low pressure vapor-liquid separation tanks
Mixing carries out normal pressure alkali cleaning, and the detached liquid phase of stage falling-film evaporators enters two grades of falling film evaporators, and vapour phase Jing of removing is low
Polymers knockout tower enters decompression neutralization static mixer and carries out decompression alkali cleaning, normal pressure alkali cleaning, decompression alkali cleaning after isolating oligomer
Oil water mixture afterwards realizes the recycling of solvent and water, the melt that two grades of falling film evaporators are excluded Jing after sedimentation oil-water separation
Hydrogenated petroleum resin product is obtained Jing after prilling；
During Petropols two-stage hydrogenation；Petropols, solvent and hydrogen are Jing after one-stage hydrogenation reactor into vapour-liquid point
Vapor-liquid separation is carried out from tank, the liquid phase after separation is mixed into secondary hydrogenation reaction with the solvent and hydrogen that supplement the heating come in
Device carries out the liquid-vapor mixture of hydrogenation reaction, sulfide hydrogen and hydrogen chloride and enters one-level high pressure knockout drum, separates in one-level high pressure
Tank carries out vapor-liquid separation, and liquid phase enters one-level low pressure vapor-liquid separation tank, sulfide hydrogen and chlorine that one-level high pressure knockout drum is isolated
Change hydrogen vapour phase merge one-stage hydrogenation reactor after the vapour phase isolated of vapor-liquid separation tank enter in high pressure and static mixer and
The alkali liquor for pumping into is mixed into horizontal high voltage alkali cleaning, and low pressure below, normal pressure are identical with decompression same section of hydrogenation technique of caustic wash process；
The high-pressure is 4～15MPa, and low pressure is 0.4～4MPa.
2. according to the desulfurization described in claims 1, dechlorination method, it is characterised in that for hydrogenation raw material Petropols be
C5, C9 Petropols obtained by cracking c5, the polymerization of C9 fractions, cyclopentadiene resin or C5/C9 copolymerized petroleum resins.
3. according to the desulfurization described in claims 1, dechlorination method, it is characterised in that the alkali liquor for adopting is sodium hydroxide or hydrogen
Calcium oxide aqueous solution, concentration are 1%～10%.
4. according to the desulfurization described in claims 1, dechlorination method, it is characterised in that hydrogenation solvent include saturated alkane class,
The many alkyl naphthenes of saturation or aromatic hydrocarbon solvent.
5. hydrogenation of petroleum resin process desulfurization according to claim 1, the device of the industry of dechlorination are realized, it is characterised in that：
In Petropols one-stage hydrogenation process unit, hydrogenation reactor outlet connection one-level high pressure vapor-liquid separation tank material inlet, one-level
High pressure vapor-liquid separation tank top vapor phase exit pumps into pipeline and is connected to height with static mixer material inlet, alkali liquor in being connected to high pressure
Lye import at the top of pressure neutralization static mixer, exports and two grades of high pressure vapor-liquid separations with static mixer bottom liquid phases in high pressure
Tank material inlet is connected, and two grades of high pressure vapor-liquid separation tank top vapor phase exits are connected with high score condenser, high score condensator outlet
Connection three-level high pressure knockout drum, the outlet of three-level high pressure knockout drum top gas phase are connected to and follow light machine import surge tank, three-level high pressure
Knockout drum bottom liquid-phase outlet is connected to three-level low pressure separation pot, two grades of high pressure vapor-liquid separation tank bottom liquid phases outlet connection low pressure
Neutralization static mixer top entry, the outlet of one-level high pressure vapor-liquid separation tank bottom liquid phases are connected to one-level low pressure vapor-liquid separation tank
Material inlet, the connection stage falling-film evaporators import of one-level low pressure vapour-liquid separation tank bottom portion liquid-phase outlet, one-level low pressure vapour-liquid point
Be connected with static mixer vapour phase entrance with low pressure from tank top vapor phase exit, in low pressure and static mixer outlet at bottom with
Two grades of low pressure vapor-liquid separation tank material inlet connections, two grades of low pressure vapor-liquid separation tank vapor phase exits are connected to low point of condenser, low
Condenser material outlet is divided to be connected with three-level low pressure separation pot import, the outlet of three-level low pressure separation pot top gas phase is connected to new hydrogen
Machine import surge tank, three-level low pressure separation pot liquid-phase outlet are connected with normal pressure vapor-liquid separation tank material inlet, two grades of low pressure vapour-liquids
Connection is exported with static mixer top entry, stage falling-film evaporators bottom liquid phases in separating bottom liquid phases outlet connection normal pressure
To two grades of falling film evaporator material inlets, enter with static mixer vapour phase in vapor phase exit and normal pressure at the top of stage falling-film evaporators
Mouth is connected, and exports and is connected to normal pressure alkali liquor settling tank, normal pressure alkali liquor settling tank vapour phase with static mixer bottom liquid phases in normal pressure
Outlet is connected with atmospheric condenser, atmospheric condenser outlet connection normal pressure vapor-liquid separation tank material inlet, normal pressure vapor-liquid separation tank
Outlet at bottom is connected to thick solvent settling tank, and the outlet of normal pressure alkali liquor settling tank oil phase is connected to static mixer, and normal pressure alkali liquor sinks
Drop tank water is mutually exported and is connected to decompression neutralization static mixer material inlet, and two grades of falling film evaporator outlet at bottom connection sheeting are made
Grain system and device, at the top of two grades of falling film evaporators, vapor phase exit is connected with oligomer knockout tower charging aperture, and oligomer separates tower top
Portion's vapor phase exit is connected to decompression neutralization static mixer top entry, and decompression neutralization static mixer outlet is connected to decompression alkali
Liquid settling tank, the oil phase outlet of decompression alkali liquor settling tank are connected to static mixer, and decompression alkali liquor settling tank vapor phase exit is connected to
Decompression condensation device material inlet, decompression condensation device material outlet and the entrance connection of decompression vapor-liquid separation tank, reduce pressure vapor-liquid separation tank
Liquid-phase outlet is connected to thick solvent settling tank, and vapor phase exit is connected with liquid-ring vacuum pump, and liquid ring vacuum pump discharge is connected to thick molten
Agent settling tank, static mixer outlet are connected to cleaning mixture settling tank, and cleaning mixture settling tank water is mutually exported and is connected to normal pressure alkali liquor
Settling tank, the outlet of cleaning mixture settling tank oil phase are connected to thick solvent settling tank, and thick solvent settling tank water is mutually exported and static mixing
Device connects, and thick solvent settling tank oil phase outlet is connected with thick solvent refining tower；
In Petropols two-stage hydrogenation process unit, one-stage hydrogenation reactor outlet is connected with vapor-liquid separation tank material inlet,
The outlet connection second-stage hydrogenation reactor import of vapor-liquid separation tank bottom liquid phases, second-stage hydrogenation reactor outlet connection one-level high pressure vapour
Vapor-liquid separation after liquid knockout drum material inlet, one-level high pressure vapor-liquid separation tank top vapor phase exit pipeline and one-stage hydrogenation reactor
Tank top vapor phase exit pipeline merging pumps into pipeline and is connected in high pressure with static mixer material inlet, alkali liquor in being followed by high pressure
With lye import at the top of static mixer, also the desulfurization of Petropols one-stage hydrogenation, dechlorination process are identical for other device methods of attachment.
6. according to the desulfurization described in claim 5, the commercial plant of dechlorination, it is characterised in that high pressure, low pressure desulfurization, dechlorination
Cheng Zhong, configures vapor-liquid separation tank after neutralization static mixer；In normal pressure and decompression desulfurization, dechlorination process, static mixer is neutralized
Alkali liquor settling tank is configured afterwards, and used as decompression desulfurization, the alkali liquor of dechlorination process, reduce pressure the alkali liquor that normal pressure alkali liquor settling tank is discharged alkali liquor
The alkali liquor discharger that settling tank is discharged.
7. according to the desulfurization described in claim 5, the commercial plant of dechlorination, it is characterised in that the alkali liquor or profit two after neutralization
Phase mixture relies on neutralization static mixer of the system pressure difference to low first class pressure, realizes alkali liquor by high pressure, low pressure, often
Pressure and reduce pressure desulfurization, the multiplexing of the alkali liquor of dechlorination process.
8. according to the desulfurization described in claim 5, the commercial plant of dechlorination, it is characterised in that vapor-liquid separation after static mixer
The condensed device of vapour phase of tank or the discharge of alkali liquor settling tank, vapor-liquid separation tank discharge oil water mixture；The oil water mixture Jing of discharge
Thick solvent settling tank realizes oil-water separation, oil phase after going thick solvent refining tower dehydration refined as hydrogenation circulating solvent；Water phase and
, together as washings, the oil phase discharged to normal pressure alkali liquor settling tank and decompression settling tank is by quiet for supplementary fresh deionized water
State blender carries out being sufficiently mixed washing, and enters cleaning mixture settling tank, and the oil phase discharged from cleaning mixture settling tank removes thick solvent
Jing after the dehydration of thick solvent refining tower is refined as hydrogenation circulating solvent, mutually a part removes dilution decompression alkaline cleaning procedure alkali to water to settling tank
Liquid, and lower the temperature for which, to reduce depressurized system vapour phase load, water phase remainder deallocation alkaline soda liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610973726.2A CN106540640B (en) | 2016-10-28 | 2016-10-28 | The commercial run and device of a kind of hydrogenation of petroleum resin process desulfurization, dechlorination |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610973726.2A CN106540640B (en) | 2016-10-28 | 2016-10-28 | The commercial run and device of a kind of hydrogenation of petroleum resin process desulfurization, dechlorination |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106540640A true CN106540640A (en) | 2017-03-29 |
| CN106540640B CN106540640B (en) | 2018-08-21 |
Family
ID=58394690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610973726.2A Active CN106540640B (en) | 2016-10-28 | 2016-10-28 | The commercial run and device of a kind of hydrogenation of petroleum resin process desulfurization, dechlorination |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106540640B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548450A (en) * | 2020-06-17 | 2020-08-18 | 武汉科林化工集团有限公司 | Hydrogenation method of high-chlorine C9 petroleum resin |
| CN113061202A (en) * | 2021-04-21 | 2021-07-02 | 武汉科林化工集团有限公司 | Defluorination method of high-fluorine-content petroleum resin |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004083679A (en) * | 2002-08-26 | 2004-03-18 | Idemitsu Petrochem Co Ltd | Method of producing hydrogenated petroleum resin |
| CN102382259A (en) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Industrial manufacture method for hydrogenated petroleum resin |
| CN102807900A (en) * | 2011-06-01 | 2012-12-05 | 中国科学院过程工程研究所 | High-value utilization method for oxygen-enriched coal tar |
| CN104312624A (en) * | 2014-10-21 | 2015-01-28 | 广西大学 | Liquid phase hydrogen desulfurization-separation and coupling refining method for petroleum refining coarse oil |
| CN106008819A (en) * | 2016-07-07 | 2016-10-12 | 朗盈科技（北京）有限公司 | Production device and method of low-chroma C9 hydrogenated petroleum resin |
| CN106047404A (en) * | 2016-07-08 | 2016-10-26 | 中海油天津化工研究设计院有限公司 | Combined technique for improving yield of high-octane gasoline by using inferior catalytic cracking diesel |
-
2016
- 2016-10-28 CN CN201610973726.2A patent/CN106540640B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004083679A (en) * | 2002-08-26 | 2004-03-18 | Idemitsu Petrochem Co Ltd | Method of producing hydrogenated petroleum resin |
| CN102382259A (en) * | 2010-08-30 | 2012-03-21 | 中国石油化工股份有限公司 | Industrial manufacture method for hydrogenated petroleum resin |
| CN102807900A (en) * | 2011-06-01 | 2012-12-05 | 中国科学院过程工程研究所 | High-value utilization method for oxygen-enriched coal tar |
| CN104312624A (en) * | 2014-10-21 | 2015-01-28 | 广西大学 | Liquid phase hydrogen desulfurization-separation and coupling refining method for petroleum refining coarse oil |
| CN106008819A (en) * | 2016-07-07 | 2016-10-12 | 朗盈科技（北京）有限公司 | Production device and method of low-chroma C9 hydrogenated petroleum resin |
| CN106047404A (en) * | 2016-07-08 | 2016-10-26 | 中海油天津化工研究设计院有限公司 | Combined technique for improving yield of high-octane gasoline by using inferior catalytic cracking diesel |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548450A (en) * | 2020-06-17 | 2020-08-18 | 武汉科林化工集团有限公司 | Hydrogenation method of high-chlorine C9 petroleum resin |
| CN111548450B (en) * | 2020-06-17 | 2022-09-09 | 武汉科林化工集团有限公司 | Hydrogenation method of high-chlorine C9 petroleum resin |
| CN113061202A (en) * | 2021-04-21 | 2021-07-02 | 武汉科林化工集团有限公司 | Defluorination method of high-fluorine-content petroleum resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106540640B (en) | 2018-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20230010199A (en) | Upgrading waste plastic-based oil to expensive chemicals through direct catalytic cracking | |
| CN102382259B (en) | Industrial manufacture method for hydrogenated petroleum resin | |
| CN101376842B (en) | Method for reducing sulfur content in gasoline | |
| US2734046A (en) | Steam or | |
| CN106540640B (en) | The commercial run and device of a kind of hydrogenation of petroleum resin process desulfurization, dechlorination | |
| CN1200082C (en) | Combined technologic process for manufacturing petroleum residue | |
| CN106008820A (en) | Production system of low-chromaticity C5/C9 copolymerization hydrogenation resin and method | |
| CN104277179B (en) | A kind of method that free radical hot polymerization produces m-pentadiene petro-resin | |
| CN106279539A (en) | Hydrogenation of petroleum resin process desulfurization, the commercial run of dechlorination | |
| CN105585412B (en) | A method of preparing polymer grade piperyene | |
| CN104395427B (en) | The manufacture of the polymer of thiophene, benzothiophene and their alkyl derivative | |
| CN101054332B (en) | Method of synthesizing poly alpha-olefin oil | |
| CN109704908B (en) | Method for preparing hexane from aromatic raffinate oil | |
| EA019489B1 (en) | System and process for producing high quality gasoline by hydrogenation and recombination of oil refining hydrocarbon component | |
| KR101945569B1 (en) | Selective single-stage hydroprocessing system and method | |
| CN1195822C (en) | Process for viscosity breaking of deoiled asphalt | |
| US11306262B2 (en) | Pretreatment method and system for fraction oil for production of alkylbenzene | |
| KR0154363B1 (en) | The process for the preparation of polybutene | |
| CN107137948B (en) | Method for removing dicyclopentadiene from ethylene cracking carbon nine fraction | |
| CN205907205U (en) | Production system of low nine copolymerization hydrogenation resins in five carbon in colourity carbon | |
| CN1219854C (en) | Method of crude oil and fraction oil deacidification and naphthenic acid refining method | |
| CN111589407B (en) | Sulfuric acid alkylation system and method for producing isooctane by using same | |
| US2845467A (en) | Process for treating polymers produced by alkali-metal catalyzed polymerizations with acidic cationic exchange resins | |
| CN105658290B (en) | The method and apparatus for preparing the diesel oil with high cetane number | |
| US11007456B2 (en) | Short-process separation system for separating ionic liquid from alkylation reaction effluent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |