A kind of imitative experimental appliance
Technical field
The present invention relates to a kind of experimental provision, in particular to a kind of imitative experimental appliance.
Background technique
In recent years, petroleum heavy in poor quality problem is all suffered from China or even world wide, but with economic hair
Exhibition, light-end products requirement but increasingly increase, and this requires us, and mink cell focus is more processed into light-end products, to meet warp
Needs of the Ji development to the high-quality oil product of lightweight.Currently, the main technological means of upgrading have it is conventional thermal cracking, face hydrogen and subtract
It glues cracking, hydrogen supply visbreaking and faces hydrogen hydrogen supply visbreaking.Modification oil stability that wherein conventional visbreaking obtains, 0API
Etc. poor, and other modification technologies are subjected to the limit that hydrogen source, Hydrogen activation and hydrogen supply agent develop the problems such as preferred difficulty is big
System.
Polycyclic aromatic hydrocarbon is rich in viscous crude, some of them can add hydrogen under the conditions of relatively mitigating, some are under the conditions of relatively mitigating
But it is difficult to add hydrogen.CO hydro-thermal converts the newborn hydrogen with high activity that can be generated, if viscous crude can be acted on newborn hydrogen in situ
In can add the polycyclic aromatic hydrocarbon of hydrogen under the conditions of relatively mitigating, on the one hand obtained hydrogenation products can carry out hydrogen turn inside viscous crude
It moves, plays the role of internal potential hydrogen supply agent, thus to being difficult under the conditions of mitigation plus the viscous crude molecule of hydrogen plays and adds hydrogen;
On the other hand, its own is changed into the polycyclic aromatic hydrocarbon of Yi Jiaqing again, to realize the effect that newborn hydrogen is efficiently transmitted into viscous crude.
The petroleum coke that raw material CO in CO hydro-thermal conversion process can be generated by delayed coking, which vaporizes, to be obtained, and can not only not had to H2
Further activation and significantly save the cost, can also more efficiently promote upgrading effect.Therefore, polycyclic aromatic hydrocarbon hydrogen migration
It is the project with huge practical value to upgrading with the transformation of CO hydro-thermal.
Summary of the invention
The purpose of the present invention is to drawbacks described above of the existing technology, provide a kind of imitative experimental appliance, this hair
It is bright to replace the polycyclic aromatic hydrocarbon in viscous crude in the case where CO hydro-thermal converts environment in experimental simulation device using polycyclic aromatic hydrocarbon model compound
Middle carry out hydrogenation reaction, and then polycyclic aromatic hydrocarbon is converted to the compound with virtue and cycloalkanes ring structure, to change as viscous crude
Potential hydrogen supply agent during matter reduces and generates oily viscosity, improves and generates oily stability, is finally reached the mesh that viscous crude efficiently modifies
's.
A kind of imitative experimental appliance that the present invention mentions, including CO air accumulator (1), high-pressure reaction pot, gas and liquid collecting system
It is most of with control system four, the high-pressure reaction pot by electromagnetic stirr device (12), finishing reactor (13), rupture disk (14),
First thermocouple (17), cover (15) and high pressure tank body (16) are constituted, and the high pressure tank body (16) is mounted in heating furnace (11)
The top of chamber, high pressure tank body (16) is equipped with cover (15), and electromagnetic stirr device (12), finishing reactor are installed on cover (15)
(13), rupture disk (14), the first thermocouple (17), rupture disk (14) are mounted on the side of the upside boss of cover (15), boss
Middle part be installed with electromagnetic stirr device (12) and the first thermocouple (17), the bottom of electromagnetic stirr device (12) is installed in high pressure tank body
(16) in, middle and upper part is cased with finishing reactor (13), and the top of electromagnetic stirr device (12) is connected to control system by control line;
The gas and liquid collecting system includes gas collection tank (9) and liquid collection tank (25) and the second thermocouple (23) group
At, wherein gas collection tank (9) by pipeline it is in parallel with CO air accumulator (1) after, then pass through cover (15) and be connected to high pressure tank body
(16), the liquid collection tank (25) is connected to high pressure tank body (16) by pipeline, cover (15);
The control system is by temperature and rotational speed governor (27), liquid collection tank temperature indicator (28), high pressure tank body
Temperature indicator (29) and speed display (30) are constituted.
Preferably, above-mentioned high-pressure reaction pot further includes the first needle-valve (3), the second needle-valve (20), air inlet (4), exhaust
Mouth (19), the CO air accumulator (1) are connected by pipeline with the air inlet (4) of high-pressure reaction pot, and in reaction under high pressure canister incoming gas
Mouth (4) installation the first needle-valve (3) controls air inlet aperture, in the connecting pipeline of the first needle-valve (3) and high-pressure reaction pot
Gas phase sampling system is installed.
Preferably, nitrogen protection valve (6) is installed on gas collection tank (9) top, takes air valve (7), first pressure gauge
(8), lower part is equipped with the blow valve (10) of liquid.
Preferably, the right end of cover (15) is provided with second pressure gauge (18), exhaust outlet (19) and the second needle-valve (20),
Second needle-valve (20) controls the aperture of exhaust outlet (19).
Preferably, the lower end of above-mentioned gas collection tank (9) is equipped with blow valve (10), and upper end side is equipped with and takes air valve (7)
With first pressure gauge (8), upper center is connected to the pipe between the first needle-valve (3) and cover (15) by pipeline and valve (5)
On line.
Preferably, nitrogen protection valve (6) are connected on the pipeline on the downside of valve (5).
Preferably, above-mentioned liquid collection tank (25) top is equipped with third pressure gauge (24) and the second thermocouple (23), under
Portion is equipped with liquid taking valve (26).
Preferably, the first thermocouple (17) and the second thermocouple (23) and electromagnetic stirr device (12) by route and temperature and
Revolving speed control cabinet (27) is connected.
Preferably, the finishing reactor (13) uses quickly cooling coil pipe.
A kind of application method for imitative experimental appliance that the present invention mentions, including following operating procedure:
(1) checkout facility device airtightness, by water and as the anthracene of polycyclic aromatic hydrocarbon model compound if airtightness is intact
It is dissolved in toluene with naphthalene to be placed in pressure pan body, with CO pressurising, purging is pressurized to reaction initial pressure afterwards three times;
(2) heat up heating after pressure needed for being pressurized to reaction in kettle, is warming up to 100oStart to stir when C, and continues to heat up
Until reaction required temperature, and maintain at the reaction temperatures until reaching the defined reaction time;
(3) after reaching the time required to reaction, the valve that liquid phase sampling system is connected with high-pressure reaction pot, Partial Liquid Phase are opened
Enter in liquid-phase collection tank under high pressure, liquid taking valve is opened after the temperature in liquid-phase collection tank reaches requirement with pressure and is taken
Liquid product out, then be dissolved in toluene after wherein condensed water is distilled off and carry out chromatography, liquid-phase collection tank is clear using solvent
Wash clean, and the continuous sampling of liquid product is used for after being purged with nitrogen;
(4) after liquid product taking-up, the valve that gas phase sampling system is connected with high-pressure reaction pot, taking-up portion are opened immediately
Point gas phase enters in gas collection tank, stablizes to pressure in gas collection tank, stablizes and is cooled to room temperature opening and takes air valve, collects gas
Phase product carries out chromatography;The liquid phase in blow valve emptying tank is opened, for gas after cleaning using solvent and being purged with nitrogen
The continuous sampling of phase product;
(5) according to the gas-phase product gas chromatographic analysis obtained under the differential responses time as a result, showing that CO hydro-thermal converts
Kinetics, and compared with pure CO hydro-thermal conversion reaction;Liquid product show that anthracene and naphthalene face CO through chromatography respectively
Hydro-thermal converts dynamics, and compares with the dynamics under hydro condition;
(6) in using anthracene and naphthalene as viscous crude under the conditions of relatively mitigating easily plus hydrogen and difficult plus hydrogen polycyclic aromatic hydrocarbon modelling
Object is closed, anthracene and naphthalene are subjected to above-mentioned test in high pressure tank body simultaneously, by the continuous sampling to liquid-phase product and analysis obtains naphthalene
Conversion ratio and with its only face CO hydro-thermal transformation in conversion ratio compare;
(7) finishing reactor is opened after the reaction was completed to terminate reaction.
The beneficial effects of the present invention are: replacing the polycyclic aromatic hydrocarbon in viscous crude in CO hydro-thermal using polycyclic aromatic hydrocarbon model compound
Hydrogenation reaction is carried out under transformation environment in simulator, and then polycyclic aromatic hydrocarbon is converted to the change with virtue and cycloalkanes ring structure
Object is closed, to become the potential hydrogen supply agent during upgrading, reduces and generates oily viscosity, improve and generate oily stability, finally
Achieve the purpose that viscous crude efficiently modifies;
In addition, the present invention reaches requirement of experiment by imitative experimental appliance, and can letter by setting gas-liquid sampling system
List rapidly realizes that viscous crude faces the continuous sampling of CO hydro-thermal modification, more fast, accurately measures polycyclic aromatic hydrocarbon hydrogen migration and CO
Hydro-thermal converts the effect to upgrading.
Detailed description of the invention
Attached drawing 1 is structural schematic diagram of the invention;
In upper figure: CO air accumulator 1, the first needle-valve 3, air inlet 4, valve 5, nitrogen protection valve 6, takes air valve 7, at valve 2
One pressure gauge 8, gas collection tank 9, blow valve 10, heating furnace 11, electromagnetic stirr device 12, finishing reactor 13, rupture disk 14, tank
Lid 15, high pressure tank body 16, thermocouple 17, second pressure gauge 18, exhaust outlet 19, the second needle-valve 20, common valve 21, solvent cleaning
Valve 22, the second thermocouple 23, third pressure gauge 24, liquid collection tank 25, liquid taking valve 26, temperature and rotational speed governor 27, liquid
Collecting tank temperature indicator 28, high pressure pot temperature display 29 and speed display 30, mobile base 31.
Specific embodiment
In conjunction with attached drawing 1, the invention will be further described:
A kind of imitative experimental appliance that the present invention mentions, including CO air accumulator 1, high-pressure reaction pot, gas and liquid collecting system and
Control system four is most of, and the high-pressure reaction pot is by electromagnetic stirr device 12, finishing reactor 13, rupture disk 14, the first thermoelectricity
Even 17, cover 15 and high pressure tank body 16 are constituted, and the high pressure tank body 16 is mounted on 11 inner cavity of heating furnace, the top of high pressure tank body 16
Equipped with cover 15, electromagnetic stirr device 12, finishing reactor 13, rupture disk 14, the first thermocouple 17, explosion are installed on cover 15
Piece 14 is mounted on the side of the upside boss of cover 15, and electromagnetic stirr device 12 and the first thermocouple 17 are installed in the middle part of boss, electricity
The bottom of magnetic stirring device 12 is installed in high pressure tank body 16, and middle and upper part is cased with finishing reactor 13, the top of electromagnetic stirr device 12
Control system is connected to by control line;
Wherein, gas and liquid collecting system includes that gas collection tank 9 and liquid collection tank 25 and the second thermocouple 23 form,
In, gas collection tank 9 by pipeline it is in parallel with CO air accumulator 1 after, then pass through cover 15 be connected to high pressure tank body 16, the liquid
Collecting tank 25 is connected to high pressure tank body 16 by pipeline, cover 15;
The control system is by temperature and rotational speed governor 27, liquid collection tank temperature indicator 28, high pressure pot temperature
Display 29 and speed display 30 are constituted.
In addition, above-mentioned high-pressure reaction pot further includes the first needle-valve 3, the second needle-valve 20, air inlet 4, exhaust outlet 19, it is described
CO air accumulator 1 is connected by pipeline with the air inlet 4 of high-pressure reaction pot, and installs the first needle-valve 3 in high-pressure reaction pot air inlet 4
Air inlet aperture is controlled, gas phase sampling system is installed in the first needle-valve 3 and the connecting pipeline of high-pressure reaction pot.
Preferably, nitrogen protection valve 6 is installed on 9 top of gas collection tank, takes air valve 7, first pressure gauge 8, lower part peace
There is the blow valve 10 of liquid.
Preferably, the right end of cover 15 is provided with second pressure gauge 18, exhaust outlet 19 and the second needle-valve 20, the second needle-valve
The aperture of 20 pairs of exhaust outlets 19 controls.
Preferably, the lower end of above-mentioned gas collection tank 9 is equipped with blow valve 10, and upper end side is equipped with and takes air valve 7 and first
Pressure gauge 8, upper center are connected on the pipeline between the first needle-valve 3 and cover 15 by pipeline and valve 5.
Preferably, it is connected with nitrogen protection valve 6 on the pipeline of 5 downside of valve, nitrogen is passed through when for needing and is protected
Shield.
Preferably, above-mentioned 25 top of liquid collection tank is equipped with third pressure gauge 24 and the second thermocouple 23, and lower part is equipped with
Liquid taking valve 26.
Preferably, the first thermocouple 17 and the second thermocouple 23 and electromagnetic stirr device 12 pass through route and temperature and revolving speed control
Case 27 processed is connected.In addition, finishing reactor (13) uses quickly cooling coil pipe, by coil winding in the outer of electromagnetic stirr device 12
Side, by being passed through refrigerant liquid, such as cold water, can quickly realize that temperature declines, and then terminate at the end of reacting needs
Reaction.
In addition, specifically heating furnace 11 is tubular construction, and top is equipped in the middle part of the inner cavity of high-pressure reaction pot installation heating furnace
Bell, bell center are equipped with circular hole, and high pressure tank body 16 passes through the inner cavity that circular hole is placed into heating furnace 11, the top of high pressure tank body 16
Equipped with cover 15, the cover 15 is fixedly connected with bell by multiple bolts, is equipped with boss in the upside of cover 15;Rupture disk
Superpressure is prevented for the confined space or excessive vacuum occurs, plays the role of safeguard protection.
A kind of application method for imitative experimental appliance that the present invention mentions, including following operating procedure:
(1) checkout facility device airtightness, by water and as the anthracene of polycyclic aromatic hydrocarbon model compound if airtightness is intact
It is dissolved in toluene with naphthalene to be placed in pressure pan body, with CO pressurising, purging is pressurized to reaction 2 ~ 6MPa of initial pressure afterwards three times;
(2) heat up heating after pressure needed for being pressurized to reaction in kettle, is warming up to 100oStart to stir when C, and continues to heat up
Until 380 ~ 420 DEG C of required temperature of reaction, and maintain at the reaction temperatures until reaction time 2-24h as defined in reaching;
(3) after reaching the time required to reaction, the valve that liquid phase sampling system is connected with high-pressure reaction pot, Partial Liquid Phase are opened
Enter in liquid-phase collection tank under high pressure, liquid taking valve is opened after the temperature in liquid-phase collection tank reaches requirement with pressure and is taken
Liquid product out, then be dissolved in toluene after wherein condensed water is distilled off and carry out chromatography, liquid-phase collection tank is clear using solvent
Wash clean, and the continuous sampling of liquid product is used for after being purged with nitrogen;
(4) after liquid product taking-up, the valve that gas phase sampling system is connected with high-pressure reaction pot, taking-up portion are opened immediately
Point gas phase enters in gas collection tank, stablizes to pressure in gas collection tank, stablizes and is cooled to room temperature opening and takes air valve, collects gas
Phase product carries out chromatography;The liquid phase in blow valve emptying tank is opened, for gas after cleaning using solvent and being purged with nitrogen
The continuous sampling of phase product;
(5) according to the gas-phase product gas chromatographic analysis obtained under the differential responses time as a result, showing that CO hydro-thermal converts
Kinetics, and compared with pure CO hydro-thermal conversion reaction;Liquid product show that anthracene and naphthalene face CO through chromatography respectively
Hydro-thermal converts dynamics, and compares with the dynamics under hydro condition;
(6) in using anthracene and naphthalene as viscous crude under the conditions of relatively mitigating easily plus hydrogen and difficult plus hydrogen polycyclic aromatic hydrocarbon modelling
Object is closed, anthracene and naphthalene are subjected to above-mentioned test in high pressure tank body simultaneously, by the continuous sampling to liquid-phase product and analysis obtains naphthalene
Conversion ratio and with its only face CO hydro-thermal transformation in conversion ratio compare;
(7) finishing reactor is opened after the reaction was completed to terminate reaction.
The high pressure tank volume of above-mentioned high-pressure reaction pot is 300mL, and gas collection tank volume is 100mL, liquid collection tank
Volume is 60mL, and reaction temperature is usually 380 ~ 420 DEG C, reacts 2 ~ 6MPa of initial pressure, the molar ratio of CO and water be 1:2 ~
1:6, anthracene and naphthalene are 0.1-10wt% in the accounting of toluene, and electromagnetic stirr device is made of resistant material, in addition, CO can lead to
The petroleum coke vaporization for crossing delayed coking generation obtains, and can not only not have to H2Further activation and significantly save the cost, also
Upgrading effect can more efficiently be promoted.
Embodiment 2, imitative experimental appliance of the invention are same as Example 1, wherein the imitative experimental appliance mentioned makes
With method, wherein parameter are as follows: the volume ratio of water and solvent toluene is 1:10, and anthracene/naphthalene of addition is organic solvent mass fraction
5.0wt%, reaction time 4h, every 0,30,60,90,120min sampling.
Embodiment 3, imitative experimental appliance of the invention are same as Example 1, wherein the imitative experimental appliance mentioned makes
With method, wherein parameter are as follows: the volume ratio of water and solvent toluene is 1:10, and anthracene/naphthalene of addition is organic solvent mass fraction
0.1wt%, reaction time for 24 hours, sample every 0,30,60,90,120min.
Embodiment 4, imitative experimental appliance of the invention is different from embodiment 1, increases a mobile base 31, will be each
Experiment accessory is mounted on mobile base, easy to remove, convenient in laboratory operation and movement, wherein the simulated experiment dress mentioned
The application method set, wherein parameter are as follows: the volume ratio of water and solvent toluene is 1:10, and anthracene/naphthalene of addition is organic solvent quality
The 10wt% of score, reaction time 2h, every 0,30,60,90,120min sampling.
The above, is only part preferred embodiment of the invention, and anyone skilled in the art may benefit
Equivalent technical solution is modified or is revised as with the technical solution of above-mentioned elaboration.Therefore, technology according to the present invention
Any simple modification or substitute equivalents that scheme is carried out, belong to the greatest extent the scope of protection of present invention.