CN209128343U

CN209128343U - A kind of experimental provision of carbon tetra-alkylation

Info

Publication number: CN209128343U
Application number: CN201821739672.4U
Authority: CN
Inventors: 胡玉峰; 蒋斯麒
Original assignee: China University of Petroleum Beijing
Current assignee: China University of Petroleum Beijing
Priority date: 2018-10-25
Filing date: 2018-10-25
Publication date: 2019-07-19
Anticipated expiration: 2028-10-25

Abstract

The utility model provides a kind of experimental provision of carbon tetra-alkylation.The experimental provision includes: apparatus for feeding, consersion unit, separation and reclaimer；Apparatus for feeding includes C4 alkane steel cylinder, C4 alkene steel cylinder, C4 alkane head tank, C4 olefin feedstocks tank, raw material premix tank；C4 alkane steel cylinder is connected to C4 alkane head tank, and C4 alkene steel cylinder is connected to C4 olefin feedstocks tank, and C4 alkane head tank is connected to raw material premix tank, and C4 olefin feedstocks tank is connected to raw material premix tank；Consersion unit is connected to raw material premix tank；Separation and reclaimer include that gasoline alkylate knockout drum, tail gas condensing tank and spent acid collecting tank, consersion unit are connected to gasoline alkylate knockout drum, and gasoline alkylate knockout drum is connected to tail gas condensing tank, and gasoline alkylate knockout drum is connected to spent acid collecting tank.The metering of the experimental provision of the utility model is precisely, securely and reliably.

Description

Experimental device for four alkylation of carbon

Technical Field

The utility model relates to an experimental apparatus of carbon four alkylation especially relates to an experimental apparatus of sulfuric acid process carbon four alkylation is pressed in low temperature area, belongs to experimental apparatus technical field.

Background

At present, the alkylate oil technology in the oil refining industry of China is mainly a carbon four-alkylation technology taking sulfuric acid as a catalyst. The mainstream alkylation process in the world today employs liquid acid catalysts, including sulfuric acid and hydrofluoric acid. Hydrofluoric acid is volatile and extremely toxic, so that once leaked, the hydrofluoric acid can cause fatal harm to the surrounding environment and ecology, and the leakage accident is difficult to stop. The corrosivity and the environmental hazard of the sulfuric acid are less than those of hydrofluoric acid, and the sulfuric acid method has simple equipment, low requirement on raw materials and low production energy consumption. Therefore, the sulfuric acid process has higher technical maturity and safety, better meets the actual requirements of China, and is introduced and widely applied by the oil refining industry of China. Meanwhile, for the industrial application prospect of the technology, the theory and experimental research of laboratory scale have been developed successively.

Although the industrial technology and equipment of the sulfuric acid process C4 alkylation technology are relatively mature up to now, the technical research on the laboratory scale does not relate to the complete set of related technologies of the sulfuric acid process C4 alkylation experimental device. As is well known, the laboratory scale experimental apparatus is significantly different from the industrial apparatus, and the existing experimental apparatuses at home and abroad have the following problems:

the feeding quantity mode and the metering scheme cause the experimental precision to be low and can not meet the research requirements; the I/O value of the alkane-alkene ratio of the feeding is a fixed value and is difficult to adjust, and experimental research aiming at the influence of the I/O value on the alkylation reaction is influenced; the rotating speed of a stirrer arranged in the reactor is too low, so that acid and hydrocarbon phases in the reactor cannot be fully contacted, and the carrying out of the C4 alkylation reaction by the sulfuric acid method is seriously influenced; the acid hydrocarbon separation and sampling device and method have design defects, and the accuracy of sulfuric acid process C4 alkylation experimental research and the safety of the sampling process are seriously influenced; the tail gas evacuation design of flammable and explosive gases has obvious defects, and the health of experiment operators and the safety of laboratories are seriously harmed; the sulfuric acid method C4 alkylation experiment is inflammable and explosive (isobutane and isobutene), strong corrosivity (90-98 wt% sulfuric acid), and low-temperature and pressurized operation (reaction temperature 0 ℃ and 0.5MPa), and has strong danger.

SUMMERY OF THE UTILITY MODEL

In order to solve the technical problem, an object of the utility model is to provide an experimental apparatus of accurate, safe and reliable's carbon four alkylation of measurement.

In order to achieve the above technical object, the utility model provides an experimental apparatus for carbon four alkylation is provided at first, this experimental apparatus includes:

the device comprises feeding equipment, reaction equipment and separation and recovery equipment; wherein,

the feeding equipment comprises a C4 alkane steel cylinder and a C4 alkene steel cylinder; the C4 alkane steel bottle is communicated with the C4 alkane feeding tank, the C4 alkene steel bottle is communicated with the C4 alkene feeding tank, the C4 alkane feeding tank is communicated with the raw material premixing tank, and the C4 alkene feeding tank is communicated with the raw material premixing tank;

the reaction equipment is communicated with the raw material premixing tank;

the separation and recovery equipment comprises an alkylated gasoline separating tank, a tail gas condensing tank and a waste acid collecting tank, the reaction equipment is communicated with the alkylated gasoline separating tank, the alkylated gasoline separating tank is communicated with the tail gas condensing tank, and the alkylated gasoline separating tank is communicated with the waste acid collecting tank.

The utility model discloses an experimental apparatus of carbon four alkylation to safe and reliable, accurate measurement, economical and practical are the prerequisite, under laboratory scale and condition, can develop low temperature, area, the sulfuric acid process carbon four alkylation reaction of strong acid corrosion.

Drawings

Fig. 1 is a schematic structural diagram of an experimental apparatus for carbon tetra-alkylation according to an embodiment of the present invention.

Description of the main figures

1C 4 paraffin cylinder 2C 4 olefin cylinder 3 paraffin dryer 4 olefin dryer 5C 4 paraffin feed tank 6C 4 olefin feed tank 7 paraffin feed tank electronic scale 8 olefin feed tank electronic scale 9 raw material premix tank 10 low temperature pressure reactor 11 alkylated gasoline knockout tank 12 tail gas condensate tank 13 waste acid collection tank 14 refrigerator 15 nitrogen cylinder group 16 super high speed magnetic stirrer 17 first stop valve 18 second stop valve 19 third stop valve 20 fourth stop valve 21 first ball valve 22 second ball valve 23 first pressure reducing valve 24 fifth stop valve 25 sixth stop valve 26 third pressure reducing valve 27 first three way ball valve 28 second three way ball valve 29 first needle valve 30 fourth pressure reducing valve 31 seventh stop valve 32 eighth stop valve 33 third three way ball valve 34 second needle valve 35 first float flowmeter 36 second float flowmeter 37 third float flowmeter 38 ninth stop valve flowmeter 39 tenth stop valve 40 eleventh stop valve 41 third needle valve 42 twelfth stop valve 43 thirteenth stop valve

Detailed Description

In order to clearly understand the technical features, objects and advantages of the present invention, the following detailed description is given to the technical solution of the present invention, but the technical solution of the present invention is not limited to the limit of the implementable range of the present invention.

Carbon four alkylation technology: isobutane is used as an alkylation raw material and is subjected to alkylation reaction with C4 olefin to generate a high-octane gasoline blending component 2,2, 4-Trimethylpentane (TMP).

External alkane-alkene ratio (I/O): the ratio of the isobutane to the isobutylene volume fraction of the feed stream.

Acid-hydrocarbon ratio: volume ratio of sulfuric acid phase to hydrocarbon phase in the reaction kettle.

As shown in fig. 1, in one embodiment of the present invention, a carbon four alkylation experimental apparatus is provided, which may include a feeding device, a reaction device, a separation and recovery device; wherein,

the feeding equipment comprises a C4 alkane steel cylinder 1 and a C4 alkene steel cylinder 2; the C4 alkane steel bottle 1 is communicated with a C4 alkane feeding tank 5, the C4 alkene steel bottle 2 is communicated with a C4 alkene feeding tank 6, the C4 alkane feeding tank 5 is communicated with a raw material premixing tank 9, and the C4 alkene feeding tank 6 is communicated with the raw material premixing tank 9;

the reaction equipment is communicated with a raw material premixing tank 9;

the separation and recovery equipment comprises an alkylated gasoline separating tank 11, a tail gas condensing tank 12 and a waste acid collecting tank 13, the reaction equipment is communicated with the alkylated gasoline separating tank 11, the alkylated gasoline separating tank 11 is communicated with the tail gas condensing tank 12, and the alkylated gasoline separating tank 11 is communicated with the waste acid collecting tank 13.

Specifically, as shown in fig. 1, the feeding apparatus includes a C4 alkane cylinder 1, a C4 alkene cylinder 2; the C4 alkane steel bottle 1 is communicated with an alkane dryer 3 through an eighth stop valve 32 and a fourth reducing valve 30, the C4 alkene steel bottle 2 is communicated with an alkene dryer 4 through a sixth stop valve 25 and a third reducing valve 26, the alkane dryer 3 is communicated with a C4 alkane feeding tank 5 through a third three-way valve 33, the alkene dryer 4 is communicated with a C4 alkene feeding tank 6 through a first three-way valve 27, an alkane feeding tank electronic scale 7 is arranged at the bottom of the C4 alkane feeding tank 5, and an alkene feeding tank electronic scale 8 is arranged at the bottom of the C4 alkene feeding tank 6; the C4 alkane feed tank 5 is communicated with the raw material premixing tank 9 through the second needle valve 34, and the C4 alkene feed tank 6 is communicated with the raw material premixing tank 9 through the first needle valve 29. Wherein the C4 olefin feed tank 6 and the C4 paraffin feed tank 5 are both provided with a visual window.

Wherein, the C4 alkane steel cylinder 1 and the C4 alkene steel cylinder 2 are specially designed insertion-bottom steel cylinders, a metal conduit is arranged in the insertion-bottom steel cylinders, a liquid phase pressure reducing valve is arranged at the outlet of each steel cylinder, and the liquid phase pressure reducing valves are connected with corresponding interfaces of equipment through high-pressure metal hoses.

The alkane feeding tank and the alkene feeding tank are arranged on connecting pipelines of the alkane steel cylinder, the alkene steel cylinder and the raw material mixing tank, so that the I/O value of feeding can be adjusted according to experimental requirements. The bottom of the C4 paraffin feed tank 5 is provided with an paraffin feed tank electronic scale 7, the bottom of the C4 olefin feed tank 6 is provided with an olefin feed tank electronic scale 8, and the C4 olefin feed tank 6 and the C4 paraffin feed tank 5 are both provided with visible windows, which can achieve accurate metering of feed volume mass and volume.

Specifically, the reaction equipment comprises a low-temperature pressure reaction kettle 10 and an ultrahigh-speed magnetic stirrer 16; the low-temperature pressurized reaction kettle 10 is communicated with the raw material premixing tank 9, and a first stop valve 17 is arranged on a connecting conduit of the low-temperature pressurized reaction kettle 10 and the raw material premixing tank 9; the stirring speed of the ultra-high speed magnetic stirrer 16 is adjustable within 2000r/min-4000r/min, and the high-speed stirring requirement of the carbon four-alkylation reaction can be realized.

The low-temperature pressurized reaction kettle 10 and the ultrahigh-speed magnetic stirrer 16 in the reaction equipment can realize the carbon four alkylation reaction under the conditions of low temperature, pressure and strong stirring, provide a reaction environment and a reaction site for the sulfuric acid method C4 alkylation reaction, and ensure the safety of experimenters in the reaction process and the stability of the reaction.

Specifically, as shown in fig. 1, the separation and recovery apparatus includes an alkylate gasoline separation tank 11, a tail gas condensation tank 12, and a waste acid collection tank 13. The alkylated gasoline separating tank 11 is communicated with the low-temperature pressure reaction kettle 10, wherein the alkylated gasoline separating tank 11 and the low-temperature pressure reaction kettle 10 are provided with two connecting guide pipes, one of the two connecting guide pipes flows out from the bottom of the alkylated gasoline separating tank 11 and enters the inlet of the low-temperature pressure reaction kettle 10 through a third stop valve 19, and the third stop valve is used for recovering concentrated sulfuric acid separated from the alkylated gasoline separating tank 11 into the low-temperature pressure reaction kettle 10 to perform the next four-carbon alkylation reaction; the other conduit is led out from the bottom of the low-temperature pressure reaction kettle 10 and enters the middle lower part of the alkylated gasoline separating tank 11 through a fourth stop valve 20, and is used for conveying the reaction product of carbon tetra-alkylation to the alkylated gasoline separating tank 11 for separation. The alkylated gasoline separating tank 11 is communicated with the tail gas condensing tank 12 through a ninth stop valve 38, and the alkylated gasoline separating tank 11 is communicated with the waste acid collecting tank 13 through a tenth stop valve 39. Wherein, the tail gas condensing tank 12 is used for recovering unreacted alkane in gas phase, and the waste acid collecting tank 13 is used for collecting the other part of concentrated sulfuric acid catalyst.

The separation and recovery equipment comprises an alkylate gasoline separating tank 11, a tail gas condensing tank 12 and a waste acid collecting tank 13. The separation of the sulfuric acid phase and the alkylate oil, the safe sampling of the alkylate gasoline and the waste acid, the volatilization of the excessive C4 alkane and the condensation, collection and discharge of the tail gas can be completed under the normal pressure condition, and the safety and the accuracy of the separation process, the sampling process and the tail gas discharge process are ensured.

Specifically, as shown in fig. 1, the experimental apparatus further includes a nitrogen steel cylinder group 15, and the nitrogen steel cylinder group 15 is respectively communicated with the C4 alkane feeding tank 5, the C4 alkene feeding tank 6, the raw material premixing tank 9, the reaction equipment, the alkylated gasoline separating tank 11, and the tail gas condensing tank 12. The nitrogen cylinder group 15 is used for providing a gas source, and purging substances in the whole flow path of the device when the experiment is completed, and provides pressure for the C4 alkane feeding tank 5, the C4 alkene feeding tank 6, the raw material premixing tank 9, the reaction equipment, the alkylated gasoline separating tank 11 and the tail gas condensing tank 12, so that the C4 alkane and the C4 alkene can exist in a gaseous state.

More specifically, the nitrogen cylinder group 15 is communicated with the C4 alkane feed tank 5 through the seventh cut-off valve 31, and the nitrogen cylinder group 15 is communicated with the C4 alkene feed tank 6 through the fifth cut-off valve 24, so that the C4 alkane and the C4 alkene can be fed in a gaseous form. The nitrogen gas cylinder group 15 is communicated with the raw material premixing tank 9 through a second three-way valve 28. The nitrogen gas steel cylinder group 15 is communicated with the low-temperature pressurized reaction kettle 10 through a second stop valve 18, wherein the second stop valve 18 is a branch of a second three-way valve 28, and a thirteenth stop valve 43 is arranged on a communication pipeline between the second stop valve 18 and the second three-way valve 28; the other branch of the second three-way valve 28 is communicated with the nitrogen cylinder group 15 through a second ball valve 22 and a first pressure reducing valve 23; the other branch of the second three-way valve 28 is communicated with the alkylate gasoline separator tank 11 through a third needle valve 41 and an eleventh stop valve 40. The nitrogen cylinder group 15 is communicated with the tail gas condensation tank 12 through a third needle valve 41 and a twelfth stop valve 42.

Specifically, as shown in fig. 1, the experimental apparatus further includes a refrigerator 14, and the refrigerator 14 is respectively communicated with the reaction device, the raw material premixing tank 9, and the tail gas condensing tank 12. The refrigerator 14 is used for providing a cold source for the whole experimental device.

More specifically, the refrigerator 14 is communicated with the low-temperature autoclave 10 through a second float flowmeter 36 and communicated with the raw material premixing tank 9 through a third float flowmeter 37, respectively. The raw material premixing tank 9 and the refrigerating machine 14 form a circulation loop.

Specifically, the method for the carbon tetraalkylation by the low-temperature pressure sulfuric acid process, which is carried out by adopting the experimental device for the carbon tetraalkylation shown in fig. 1, specifically comprises the following steps:

the method comprises the following steps: static air-tight test before experiment

Because the concentrated sulfuric acid is used in the device, the concentrated sulfuric acid has stronger oxidability and corrosivity, and the device can have good sealing performance in the experimental operation process, so that after the experiment is completed each time, an independent pressure test is carried out on the reaction kettle part before the next experiment. The airtight test pressure at this time was the highest operating pressure of the test of the apparatus itself.

First, the first stop valve 17, the second stop valve 18, the third stop valve 19, the fourth stop valve 20, and the first ball valve 21 are all in the closed state. And then opening a second stop valve 18 to fill nitrogen into the low-temperature pressurized reaction kettle 10, wherein the pressure is 0.5MPa, closing the first stop valve 18 to observe the numerical value of a pressure gauge, keeping the pressure for 15min, indicating that the air tightness is good if the pressure does not drop, and detecting the leakage if the pressure drops. And if the pressure is stable for not less than 30min, the airtight test is finished.

Step two: feeding process

And checking whether each valve is in a closed state and checking whether the thermocouple is inserted well. Starting the refrigerator 14 to set the temperature of the cooling water to-20 ℃; the second ball valve 22 is opened, and the first pressure reducing valve 23 is adjusted to a reduced pressure of 0.5 MPa.

C4 olefin feed

Opening the fifth stop valve 24, filling nitrogen into the C4 olefin feed tank 2 to 0.5MPa, and then closing the fifth stop valve 24; opening the sixth stop valve 25 and the third pressure reducing valve 26 to set the feeding pressure to 0.8MPa, opening the first three-way ball valve 27 to allow the C4 olefin to enter the C4 olefin feeding tank 6, and closing the first three-way ball valve 27 to stop feeding when the value of the pressure gauge is 1 MPa; opening a second three-way ball valve 28, filling nitrogen into the raw material premixing tank 9, and closing the second three-way ball valve 28 after maintaining the pressure at 0.4 MPa; the first needle valve 29 is slowly opened, and when the liquid level display of the visual window or the display value of the electronic scale reaches the required value, the first needle valve 29 is closed, and the feeding of the C4 olefin is completed.

C4 alkane feed

Opening the seventh stop valve 31, filling nitrogen into the C4 alkane feed tank 5 to 0.5MPa, and then closing the seventh stop valve 31; opening the eighth cut-off valve 32, the fourth pressure reducing valve 30, setting the feeding pressure to 0.8MPa, opening the third three-way ball valve 33 to allow the C4 paraffin to enter the C4 paraffin feeding tank 5, closing the third three-way ball valve 33 when the display value of the pressure gauge (PG-1104) is 1.0MPa, and stopping feeding; the second needle valve 34 is slowly opened and when the level display of the visual window or the value displayed by the electronic scale 7 reaches the desired value, the second needle valve 34 is closed. At this point the C4 alkane feed is complete. Note that the amount of alkane present in the line volume is taken into account for the first addition of C4 alkane, and no further consideration is given to the line volume for the second addition.

Cooling of raw materials

The first float flowmeter 35 is opened, the flow is set to be 20L/min, when the display value of the thermometer is the required temperature, the flow of the float flowmeter is properly reduced, and the temperature is kept stable; in the process of waiting for cooling the material in the raw material premixing tank 9, adding required concentrated sulfuric acid into the first ball valve 21 on the low-temperature pressure reaction kettle 10, and closing the first ball valve 21; and opening a second stop valve 18 to introduce nitrogen, maintaining the pressure of the reaction kettle at 0.5MPa, opening a second floater flow meter 36, setting the flow rate at 80L/min, cooling the concentrated sulfuric acid in the kettle to the required temperature, introducing cooling air into a bearing of a stirring motor, setting the initial value at 500NL/h, slowly starting the stirring motor, setting the rotating speed at 1000rmp, and waiting for the concentrated sulfuric acid to be cooled.

Step three: alkylation reaction

After the concentrated sulfuric acid, the mixture of the alkane and the alkene are all cooled to the required temperature, opening the first stop valve 17, and adding the mixture of the alkane and the alkene into the low-temperature pressure reaction kettle 10; after alkane and olefin all flow into the reaction kettle, immediately adjusting the rotating speed of the stirring motor to a required value, closing the first float flowmeter 35, and simultaneously adjusting the opening degree of the second float flowmeter 36 in time to maintain the reaction temperature of the low-temperature pressure reaction kettle 10 at the required value; after the reaction time is reached, the stirring motor is stopped, the second stop valve 18 is closed, and the second float flowmeter 36 may not be closed, so as to maintain the temperature in the low-temperature pressurized reaction kettle 10 stable, and prepare for the next experiment.

Step four: alkylated gasoline separation and sampling operations

Opening the third float flowmeter 37, setting an initial value of 20L/min, cooling the tail gas condensation tank 12, and performing subsequent operation when the display value of the thermometer is-20 ℃; the ninth stop valve 38 is opened, and the valve is fully opened; slowly opening the fourth stop valve 20, and observing the value of the pressure gauge without exceeding 0.1 MPa; until the materials in the low-temperature pressure reaction kettle 10 completely enter the alkylated gasoline separation tank 11, and then the fourth stop valve 20 is closed. If the residual nitrogen exists, the fourth stop valve 20 can be opened, the low-temperature pressure reaction kettle 10 is closed after 0.1MPa of nitrogen is injected into the low-temperature pressure reaction kettle, then the fourth stop valve 20 is opened, the discharging operation is repeated until the discharging is complete, the kettle internal pressure of the low-temperature pressure reaction kettle 10 is zero, and then the fourth stop valve 20 is closed; the raw material is placed in an alkylate gasoline separating tank 11 and then stands still, the alkylate gasoline and concentrated sulfuric acid are layered, and sampling operation of the alkylate gasoline and the concentrated sulfuric acid can be carried out after layering.

Sample point 1: 13 sampling points of waste acid collecting tank

During sampling, the indication of the pressure gauge is observed, the pressure display value is 0MPa, and if the pressure exists, nitrogen in the alkylated gasoline separating tank can be slowly discharged through the ninth stop valve 38 to reduce the pressure. After the PFA pipe at the outlet of the tenth stop valve 39 is firmly connected with the acid inlet of the waste acid collecting tank 13 by using the polytetrafluoroethylene ferrule, the tenth stop valve 39 is slowly opened, the vent of the waste acid collecting tank 13 is forbidden to face the human side in the sampling process, the sampling operation is slowly performed, and the concentrated sulfuric acid is prevented from splashing to damage operators. When the sample amount required by analysis is obtained, the tenth stop valve 39 is closed and is kept still for a period of time, so that the wall-hung concentrated sulfuric acid fully flows into the waste acid collecting tank 13. And then removing the polytetrafluoroethylene clamping sleeve, taking down the waste acid collecting tank 13, and entering an analysis chamber for sample analysis.

Sampling point 2: alkylated gasoline sampling port of alkylated gasoline separating tank 11

The reacted materials enter an alkylated gasoline separation tank 11 and are subjected to sampling operation after stable layering. During sampling, the pressure display of the pressure gauge is observed, and only when the pressure display is zero, the sampling port of the alkylate gasoline can be opened for operation. The sampling operation is carried out by using a sampler through an alkylated gasoline sampling port, and the operation process is carried out slowly. And closing the sampling port of the alkylated gasoline after sampling.

Step five: recycling of sulfuric acid

Closing the ninth stop valve 38, slowly opening the eleventh stop valve 40, filling nitrogen gas of 0.1MPa into the alkylate gasoline separating tank 11, and closing the eleventh stop valve 40; slowly opening the third stop valve 19, pressing the concentrated sulfuric acid back into the low-temperature pressurized reaction kettle 10 by using nitrogen, and closing the third stop valve 19 after the concentrated sulfuric acid is completely returned into the low-temperature pressurized reaction kettle 10. If the concentrated sulfuric acid cannot be completely returned to the low-temperature pressure reaction kettle 10 through one-time discharging, the step is repeated until the concentrated sulfuric acid is completely returned to the low-temperature pressure reaction kettle 10.

In the experimental device for the carbon tetra-alkylation of the utility model, C4 alkane and alkene are fed in liquid phase, and the feeding volume and the quality of the alkane and the alkene can be accurately measured by using an electronic scale and a feeding tank with a glass visual window; the I/O value of the feed can be adjusted according to the required proportion in the experimental process, and the adjustment can be 1:20-20: 1; the material in the whole device is conveyed by adopting a pressure difference conveying mode, the pressure range is 4-8atm, and the intermittent alkylation reaction is ensured to be carried out under the harsh operating conditions of keeping a continuous liquid phase in the conveying process, keeping the constant temperature at-10-20 ℃, keeping the constant pressure at 3-15atm, keeping the high stirring speed at 2000-4000r/min, using sulfuric acid with the concentration of 85-98 wt% and the like; the alkylate gasoline separating tank can directly recycle waste acid back to the reaction kettle to continue to participate in the reaction, and the design scheme of the device can complete the multiple circulation of the sulfuric acid catalyst in the alkylate gasoline separating tank and the reaction kettle only in the device, so that the safety and the reliability of the device are improved; the tail gas collecting tank with the refrigeration jacket can condense and liquefy excessive C4 alkane under normal pressure, solves the problems of collection and discharge of excessive C4 alkane tail gas, can effectively control the concentration of C4 isobutane in a laboratory, and ensures the safety of experiment operators and the reliability of equipment operation. The waste acid collecting tank can be specially used for collecting the alkylated gasoline and the waste sulfuric acid, and the device has the characteristics that the splashing problem in the waste acid sampling process can be effectively prevented, and the safety of experiment operators and the reliability of device operation are ensured.

Example 1

This example provides a carbon four alkylation method, specifically an apparatus shown in fig. 1, comprising the following steps:

the feeding conditions are as follows: the volume of 98% sulfuric acid is 275mL, and the use times of the sulfuric acid are 1 time; the isobutene feed amount was 29.33mL, the isobutane feed amount was 121.79mL, the alkane-olefin ratio I/O value was 9.59, and the acid-hydrocarbon ratio A/H value was 1.0.

Reaction conditions are as follows: the reaction temperature is 0-9 ℃, the reaction pressure is 0.5MPa, the stirring speed is 3000r/min, the reaction time is 10min, and the feeding speed is 15.11 mL/min.

The experimental method comprises the following steps: 157.6g of isobutane and 17.6g of isobutene were taken from an isobutane cylinder and an isobutene cylinder, respectively, placed in a feed tank, and weighed by an electronic scale. And (3) pressing isobutane and isobutene into a raw material premixing tank, and refrigerating to 0 ℃. In addition, 275mL of concentrated sulfuric acid was weighed into the reaction kettle and cooled to 0 ℃. After the stirrer is started, the hydrocarbon raw material is slowly fed into the reaction kettle at a feeding rate of 15.11mL/min, and then the reaction is carried out for 10min, thus finishing the alkylation reaction experiment. And after the reaction is finished, introducing the mixed solution into an alkylated gasoline separation tank, standing for 12 hours, taking out an alkylated gasoline product from an alkylated gasoline sampling port, sampling and analyzing, and analyzing the composition of the alkylated gasoline product by using gas chromatography.

The measurement result shows that: the alkylate product has composition C₄Content 4.57%, C₅Content 2.61%, C₆Content 4.60%, C₇Content 5.50%, C₈Content 56.77% (TMP content 46.05% and DMH content 10.51%) and C₉₊The alkylate product octane number RON was calculated to be 89.12 by simulation at a content of 25.30%.

Example 2

the feeding conditions are as follows: the volume of 98% sulfuric acid is 275mL, and the use times of the sulfuric acid are 1 time; isobutene feed rate was 18.50mL, isobutane feed rate was 175.71mL, alkane-olefin ratio I/O value was 13.91, and acid-hydrocarbon ratio A/H value was 1.0.

Reaction conditions are as follows: the reaction temperature is 0-8 ℃, the reaction pressure is 0.5MPa, the stirring speed is 2999r/min, the reaction time is 10min, and the feeding speed is 17.66 mL/min.

The experimental method comprises the following steps: 144.1g of isobutane and 11.1g of isobutene are respectively removed from an isobutane steel cylinder and an isobutene steel cylinder, placed in a raw material tank, and weighed by an electronic scale. And (3) pressing isobutane and isobutene into a raw material premixing tank, and refrigerating to 0 ℃. In addition, 275mL of concentrated sulfuric acid was weighed into the reaction kettle and cooled to 0 ℃. After the stirrer was started, the hydrocarbon feedstock was slowly fed into the reactor at a feed rate of 17.66mL/min and reacted for 10min to complete the alkylation reaction experiment. And after the reaction is finished, introducing the mixed solution into an alkylated gasoline separation tank, standing for 12 hours, taking out an alkylated gasoline product from an alkylated gasoline sampling port, sampling and analyzing, and analyzing the composition of the alkylated gasoline product by using gas chromatography.

The measurement result shows that: the alkylate product has composition C₄Content 14.32%, C₅Content 3.60%, C₆Content 5.38%, C₇Content 6.37%, C₈55.96% (TMP content 46.78% and DMH content 8.76%) and C₉₊The alkylate product octane number RON was calculated to be 93.0 by simulation at a level of 14.24%.

Example 3

the feeding conditions are as follows: the volume of 98% sulfuric acid is 275mL, and the use times of the sulfuric acid are 1 time; isobutene feed rate was 32.17mL, isobutane feed rate was 291.96mL, alkane-olefin ratio I/O value was 13.25, and acid-hydrocarbon ratio A/H value was 0.60.

Reaction conditions are as follows: the reaction temperature is 0-7 ℃, the reaction pressure is 0.5MPa, the stirring speed is 3000r/min, the reaction time is 10min, and the feeding speed is 41.67 mL/min.

The experimental method comprises the following steps: 238.7g of isobutane and 19.3g of isobutene were removed from isobutane and isobutene cylinders, placed in feed tanks, and weighed by electronic scales. And (3) pressing isobutane and isobutene into a raw material premixing tank, and refrigerating to 0 ℃. In addition, 275mL of concentrated sulfuric acid was weighed into the reaction kettle and cooled to 0 ℃. After the stirrer is started, the hydrocarbon raw material is slowly introduced into the reaction kettle at a feeding rate of 41.67mL/min, and then the reaction is carried out for 10min, thus completing the alkylation reaction experiment. And after the reaction is finished, introducing the mixed solution into an alkylated gasoline separation tank, standing for 12 hours, taking out an alkylated gasoline product from an alkylated gasoline sampling port, sampling and analyzing, and analyzing the composition of the alkylated gasoline product by using gas chromatography.

The measurement result shows that: the alkylate product has composition C₄Content 0.16%, C₅Content 1.15%, C₆Content 4.47%, C₇Content 6.88%, C₈65.69% (TMP content 54.65% and DMH content 10.97%) and C₉₊Content 21.64%, the alkylate product octane number RON was calculated by simulation to be 90.20.

Example 4

the feeding conditions are as follows: the volume of 98% sulfuric acid is 275mL, and the use times of the sulfuric acid are 1 time; isobutene feed rate was 15.50mL, isobutane feed rate was 144.11mL, alkane-olefin ratio I/O value was 13.82, and acid-hydrocarbon ratio A/H value was 1.20.

Reaction conditions are as follows: the reaction temperature is 0-3 ℃, the reaction pressure is 0.5MPa, the stirring speed is 3006r/min, the reaction time is 10min, and the feeding speed is 12.28 mL/min.

The experimental method comprises the following steps: 120g of isobutane and 9.3g of isobutene are respectively taken from an isobutane steel cylinder and an isobutene steel cylinder and placed in a raw material tank, and the mass is weighed by an electronic scale. And (3) pressing isobutane and isobutene into a raw material premixing tank, and refrigerating to 0 ℃. In addition, 275mL of concentrated sulfuric acid was weighed into the reaction kettle and cooled to 0 ℃. After the stirrer is started, the hydrocarbon raw material is slowly fed into the reaction kettle at the feeding rate of 12.28mL/min, and then the reaction is carried out for 10min, thus finishing the alkylation reaction experiment. And after the reaction is finished, introducing the mixed solution into an alkylated gasoline separation tank, standing for 12 hours, taking out an alkylated gasoline product from an alkylated gasoline sampling port, sampling and analyzing, and analyzing the composition of the alkylated gasoline product by using gas chromatography.

The measurement result shows that: the alkylate product has composition C₄Content 7.07%, C₅Content 2.33%, C₆Content 4.34%, C₇Content 5.86%, C₈64.62% (TMP content 55.52% and DMH content 9.29%) and C₉₊Content 15.78%, the alkylate product octane number RON was calculated by simulation to be 92.68.

Example 5

the feeding conditions are as follows: the volume of 98% sulfuric acid is 275mL, and the use times of the sulfuric acid are 1 time; isobutene feed rate was 14.33mL, isobutane feed rate was 133.57mL, alkane-olefin ratio I/O value was 13.33, and acid-hydrocarbon ratio A/H value was 1.34.

Reaction conditions are as follows: the reaction temperature is 0-3 ℃, the reaction pressure is 0.5MPa, the stirring speed is 3004r/min, the reaction time is 10min, and the feeding speed is 7.71 mL/min.

The experimental method comprises the following steps: 107g of isobutane and 8.6g of isobutene were taken from isobutane and isobutene cylinders and placed in a feed tank, and the mass was measured by an electronic scale. And (3) pressing isobutane and isobutene into a raw material premixing tank, and refrigerating to 0 ℃. In addition, 275mL of concentrated sulfuric acid was weighed into the reaction kettle and cooled to 0 ℃. After the stirrer is started, the hydrocarbon raw material is slowly fed into the reaction kettle at the feeding rate of 7.71mL/min, and then the reaction is carried out for 10min, thus finishing the alkylation reaction experiment. And after the reaction is finished, introducing the mixed solution into an alkylated gasoline separation tank, standing for 12 hours, taking out an alkylated gasoline product from an alkylated gasoline sampling port, sampling and analyzing, and analyzing the composition of the alkylated gasoline product by using gas chromatography.

The measurement result shows that: the alkylate product has composition C₄Content 3.47%, C₅Content 1.72%, C₆Content 3.82%, C₇Content 5.82%, C₈67.55% (TMP content 57.60% and DMH content 9.88%) and C₉₊Content 17.62%, the alkylate product octane number RON was calculated by simulation to be 92.02.

Example 6

the feeding conditions are as follows: the volume of 98% sulfuric acid is 275mL, and the use times of the sulfuric acid are 1 time; the isobutene feed rate was 11.83mL, the isobutane feed rate was 110.00mL, the alkane/olefin ratio I/O value was 13.57, and the acid-hydrocarbon ratio A/H value was 1.60.

Reaction conditions are as follows: the reaction temperature is 0-3 ℃, the reaction pressure is 0.5MPa, the stirring speed is 3000r/min, the reaction time is 10min, and the feeding speed is 10.23 mL/min.

The experimental method comprises the following steps: 89.9g of isobutane and 7.1g of isobutene are respectively removed from an isobutane steel cylinder and an isobutene steel cylinder, placed in a raw material tank, and weighed by an electronic scale. And (3) pressing isobutane and isobutene into a raw material premixing tank, and refrigerating to 0 ℃. In addition, 275mL of concentrated sulfuric acid was weighed into the reaction kettle and cooled to 0 ℃. After the stirrer is started, the hydrocarbon raw material is slowly fed into the reaction kettle at a feeding rate of 10.23mL/min, and then the reaction is carried out for 10min, thus finishing the alkylation reaction experiment. And after the reaction is finished, introducing the mixed solution into an alkylated gasoline separation tank, standing for 12 hours, taking out an alkylated gasoline product from an alkylated gasoline sampling port, sampling and analyzing, and analyzing the composition of the alkylated gasoline product by using gas chromatography.

The measurement result shows that: the alkylate product has composition C₄Content 4.40%, C₅Content 2.17%, C₆Content 4.39%, C₇Content 5.64%, C₈61.08% (TMP content 51.29% and DMH content 9.71%) and C₉₊The alkylate product octane number RON was calculated to be 90.48 by simulation at a level of 21.75%.

Example 7

the feeding conditions are as follows: the volume of 98% sulfuric acid is 275mL, and the use times of the sulfuric acid are 1 time; isobutene feed rate was 15.83mL, isobutane feed rate was 145.36mL, alkane-olefin ratio I/O value was 13.64, and acid-hydrocarbon ratio A/H value was 1.19.

Reaction conditions are as follows: the reaction temperature is 0-3 ℃, the reaction pressure is 0.5MPa, the stirring speed is 3004r/min, the reaction time is 10min, and the feeding speed is 4.03 mL/min.

The experimental method comprises the following steps: 120.9g of isobutane and 9.5g of isobutene are respectively removed from an isobutane steel cylinder and an isobutene steel cylinder, placed in a raw material tank, and weighed by an electronic scale. And (3) pressing isobutane and isobutene into a raw material premixing tank, and refrigerating to 0 ℃. In addition, 275mL of concentrated sulfuric acid was weighed into the reaction kettle and cooled to 0 ℃. After the stirrer is started, the hydrocarbon raw material is slowly fed into the reaction kettle at the feeding rate of 4.03mL/min, and then the reaction is carried out for 10min, thus finishing the alkylation reaction experiment. And after the reaction is finished, introducing the mixed solution into an alkylated gasoline separation tank, standing for 12 hours, taking out an alkylated gasoline product from an alkylated gasoline sampling port, sampling and analyzing, and analyzing the composition of the alkylated gasoline product by using gas chromatography.

The measurement result shows that: the alkylate product has composition C₄Content 5.77%, C₅Content 1.79%, C₆Content 3.56%, C₇Content 5.07%, C₈68.51% (TMP content 59.14% and DMH content 9.31%) and C₉₊The alkylate product octane number RON was calculated to be 93.15 by simulation at 15.17%.

Example 8

the feeding conditions are as follows: the volume of 98% sulfuric acid is 275mL, and the use times of the sulfuric acid are 1 time; isobutene feed rate was 16.83mL, isobutane feed rate was 144.11mL, alkane-olefin ratio I/O value was 12.73, and acid-hydrocarbon ratio A/H value was 1.19.

Reaction conditions are as follows: the reaction temperature is 0-4 ℃, the reaction pressure is 0.5MPa, the stirring speed is 3001r/min, the reaction time is 10min, and the feeding speed is 32.64 mL/min.

The experimental method comprises the following steps: 120.0g of isobutane and 10.1g of isobutene are respectively removed from an isobutane steel cylinder and an isobutene steel cylinder, placed in a raw material tank, and weighed by an electronic scale. And (3) pressing isobutane and isobutene into a raw material premixing tank, and refrigerating to 0 ℃. In addition, 275mL of concentrated sulfuric acid was weighed into the reaction kettle and cooled to 0 ℃. After the stirrer is started, the hydrocarbon raw material is slowly fed into the reaction kettle at the feeding rate of 32.64mL/min, and then the reaction is carried out for 10min, thus finishing the alkylation reaction experiment. And after the reaction is finished, introducing the mixed solution into an alkylated gasoline separation tank, standing for 12 hours, taking out an alkylated gasoline product from an alkylated gasoline sampling port, sampling and analyzing, and analyzing the composition of the alkylated gasoline product by using gas chromatography.

The measurement result shows that: the alkylate product has composition C₄Content 7.92%, C₅Content 2.57%, C₆Content 4.39%, C₇Content 5.61%, C₈60.45% (TMP content 51.44% and DMH content 8.76%) and C₉₊The alkylate product has a 19.07% content, and the octane number RON of the alkylate product is calculated by simulation to be 91.85.

Example 9

the feeding conditions are as follows: the volume of 98% sulfuric acid is 275mL, and the use times of the sulfuric acid are 1 time; isobutene feed rate was 15.17mL, isobutane feed rate was 146.07mL, alkane-olefin ratio I/O value was 14.34, and acid-hydrocarbon ratio A/H value was 1.18.

Reaction conditions are as follows: the reaction temperature is 0-5 ℃, the reaction pressure is 0.5MPa, the stirring speed is 3001r/min, the reaction time is 10min, and the feeding speed is 53.46 mL/min.

The measurement result shows that: the alkylate product has composition C₄Content 7.84%, C₅Content 3.08%, C₆Content 5.24%, C₇Content 6.19%, C₈51.13% (TMP content 42.35% and DMH content 8.69%) and C₉₊The alkylate product octane number RON was calculated by simulation to be 89.68 at 26.48%.

TABLE 1 basegasolene product composition distribution

C_num	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7	Example 8	Example 9
										4	4.57	14.32	0.16	7.07	3.47	4.40	5.77	7.92	7.84
5	2.61	3.60	1.15	2.33	1.72	2.17	1.79	2.57	3.08
										6	4.60	5.38	4.47	4.34	3.82	4.39	3.56	4.39	5.24
7	5.50	6.37	6.88	5.86	5.82	5.64	5.07	5.61	6.19
										8	56.77	55.96	65.69	64.62	67.55	61.08	68.51	60.45	51.13
TMP	46.05	46.78	54.65	55.25	57.60	51.29	59.14	51.44	42.35
										DMH	10.51	8.76	10.97	9.29	9.88	9.71	9.31	8.76	8.69
C₉₊	25.30	14.24	21.64	15.78	17.62	21.75	15.17	19.07	26.48
										Total	99.3	99.9	100.0	100.0	100.0	99.4	99.9	100.0	100.0
RON	89.12	93.00	90.20	92.68	92.02	90.48	93.15	91.85	89.68

TABLE 2 alkylation reaction Experimental operating conditions

As can be seen from tables 1 and 2, examples 1 and 2 examined the effect of the alkane to olefin ratio on the alkylation reaction product, and the experiment changed the feed ratio of alkane to olefin, the alkane to olefin ratio increased from 9.59 to 13.91, and C in the alkylation reaction product₉ ⁺The content is obviously reduced, and the RON value of the obtained alkylation product is improved from 89.12 to 93.0. According to analysis, C₉ ⁺Component (C) is mainly obtained by olefin polymerization₄The olefin is easy to generate a polymerization reaction in an acid environment, and the product quality is reduced. C₄Alkane and C₄The olefin is easy to generate alkylation reaction under the acidic environment to generate C₈Component C being the main product of the alkylation reaction₈The increase of the content can obviously improve the RON value of the product and improve the quality of the alkylated product. Therefore, an increase in the feed alkane-to-alkene ratio I/OEffectively improve C₄Alkane and C₄The collision probability of the olefin is improved, the selectivity of the alkylation reaction is improved, and the quality of the obtained alkylate oil is obviously improved. The test result shows that the I/O value of the alkane-alkene ratio has obvious influence on the alkylation reaction and the composition distribution of the product, the experimental research cannot be ignored, the I/O value of the alkane-alkene ratio in the feeding process is reasonably improved, and the product quality of the alkylation reaction can be effectively improved. At the same time, the accurate measurement C₄The feed amounts of alkane and alkene are a prerequisite for determining the alkane to alkene ratio I/O value.

As is clear from tables 1 and 2, examples 3, 4, 5 and 6 examined the effect of acid-to-hydrocarbon ratio on the alkylation reaction product, and the experiments were carried out to increase the feed rate of the hydrocarbon phase stepwise so that the acid-to-hydrocarbon ratio values at the alkylation reaction were 0.6, 1.2, 1.3 and 1.6, respectively, and the RON values at the alkylation reaction product were 90.20, 92.68, 92.02 and 90.48, respectively, and C was 90.20, 92.68, 92.02 and 90.48, respectively₉ ⁺The contents are respectively 21.62, 15.87, 17.62 and 21.75, the RON value of the alkylation reaction product is increased and then decreased, and conversely, C₉ ⁺The content tends to decrease and then increase. Analysis shows that the control step of the sulfuric acid alkylation reaction rate is the mass transfer step of isobutane to the sulfuric acid phase, and experiments prove that the dispersion degree of olefin in the acid hydrocarbon emulsion is an extremely important operation variable. In the acid hydrocarbon dispersion process, the viscosity of the sulfuric acid is high, and the solubility of the isobutane is low, so that C is caused₄The dispersion and mass transfer process of the raw material in the sulfuric acid phase is difficult. The increase of the acid-hydrocarbon ratio A/H is helpful for the dissolving process of isobutane in the sulfuric acid phase and promotes C₄The dispersion of the raw materials in the sulfuric acid phase improves the selectivity of the alkylation reaction, and the quality of the obtained alkylation reaction product is improved. However, too high a/H values result in a reduced probability of olefin-alkane collisions and a reaction towards C₄The olefin polymerization reaction shifts and the quality of the alkylate product decreases. The test result shows that the acid-hydrocarbon ratio A/H value has obvious influence on the alkylation reaction and the composition distribution of the product, the experimental research cannot be ignored, and the experiment proves that when the A/H value is 1.2, the distribution of the reaction product is better. At the same time, the accurate measurement C₄The feed amounts of alkane and alkene are a prerequisite for determining the acid to hydrocarbon ratio a/H value.

As can be seen from tables 1 and 2, examples 7, 8 and 9 examined the effect of the feed rate of the hydrocarbon phase on the alkylation reaction product, with experimental feed rates of 4.03mL/min, 32.64mL/min and 53.46mL/min, respectively, corresponding to C of the product of the alkylation reaction₈The contents of 68.51%, 60.45% and 51.13% respectively, C₉ ⁺The contents were 15.17%, 19.07% and 26.48%, respectively, and the RON values were 93.15, 91.85 and 89.68, respectively. With increasing feed rate, C of the product₈The content gradually decreases, C₉ ⁺The content is gradually increased, and the RON value shows a remarkable reduction trend. Analysis shows that the increase of the alkane feeding rate obviously reduces C₄The diffusion of hydrocarbons in the sulfuric acid phase causes the C4 olefin metathesis reaction to occur, decreasing the alkylation reaction selectivity. The experimental result shows that the alkane feeding rate has obvious influence on the alkylation reaction and the product composition distribution, experimental research cannot be ignored, and experiments prove that when the feeding rate value is 4.0mL/min, the reaction product distribution is better, and the RON value of the product can reach 93.15. At the same time, the accurate measurement C₄The amount of alkane and alkene fed is a prerequisite for determining the feed rate.

Claims

1. A carbon tetralkylation experimental facility, comprising:

the feeding equipment comprises a C4 alkane steel cylinder, a C4 alkene steel cylinder; the C4 alkane steel cylinder is communicated with a C4 alkane feeding tank, the C4 alkene steel cylinder is communicated with a C4 alkene feeding tank, the C4 alkane feeding tank is communicated with a raw material premixing tank, and the C4 alkene feeding tank is communicated with the raw material premixing tank;

the reaction equipment is communicated with the raw material premixing tank;

2. The experimental set up of claim 1, further comprising a nitrogen cylinder set.

3. The experimental facility as claimed in claim 2, wherein the nitrogen cylinder group is respectively communicated with a C4 alkane feeding tank, a C4 alkene feeding tank, a raw material premixing tank, a reaction device, an alkylate gasoline separating tank and a tail gas condensing tank.

4. The experimental device of claim 1 further comprising a refrigerator.

5. The experimental device according to claim 4, wherein the refrigerator is respectively communicated with the reaction equipment, the raw material premixing tank and the tail gas condensing tank.

6. The experimental facility as claimed in claim 1, wherein the bottom of the C4 paraffin feed tank is provided with paraffin feed tank electronic scales, and the bottom of the C4 olefin feed tank is provided with olefin feed tank electronic scales.

7. The experimental set-up of claim 1, wherein the C4 paraffin cylinder is in communication with an alkane dryer and the C4 olefin cylinder is in communication with an olefin dryer.

8. The experimental facility as claimed in claim 7, wherein the alkane dryer is in communication with the C4 alkane feed tank and the alkene dryer is in communication with the C4 alkene feed tank.

9. The experimental set-up of claim 1, characterized in that both the C4 paraffin feed tank and the C4 olefin feed tank are provided with a visual window.

10. The experimental device as claimed in claim 1, wherein the reaction equipment comprises a low-temperature autoclave and a high-speed stirrer.