CN110003938B - Alkylation method of isobutane and C3-C5 olefin - Google Patents
Alkylation method of isobutane and C3-C5 olefin Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1088—Olefins
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Abstract
The invention discloses an alkylation method of isobutane and C3-C5 olefin, which comprises the following steps: raw material hydrocarbon containing isobutane and C3-C5 olefin and catalyst sulfuric acid enter a liquid-liquid dispersion device, alkylation reaction is started after the raw material hydrocarbon is contacted with the sulfuric acid, and acid hydrocarbon emulsion formed by mixing unreacted raw material hydrocarbon, reaction products and the sulfuric acid is formed at an outlet of the liquid-liquid dispersion device; the acid hydrocarbon emulsion enters a stirring reactor to continue alkylation reaction; and the acid hydrocarbon emulsion in the stirring reactor enters an acid hydrocarbon separator to be separated into sulfuric acid and liquid hydrocarbon, and the liquid hydrocarbon enters a distillation tower to be separated into alkylate oil. The invention can reduce the liquid level fluctuation of the reaction materials in the stirring reactor and stabilize the octane number of the alkylate oil product. Furthermore, the present invention is not subject to the volume requirements of the liquid level measurement and control instrumentation for a stirred reactor, and the alkylation process of the present invention can be carried out on a small scale.
Description
Technical Field
The invention relates to an alkylation reaction, in particular to an alkylation method of isobutane and C3-C5 olefin under the catalysis of sulfuric acid.
Background
The alkylate oil prepared by alkylating isobutane and C3-C5 olefin has the characteristics of high octane number (research octane number is generally 90-96), low vapor pressure, low content of aromatic hydrocarbon and olefin, good sensitivity and the like, and is a clean and environment-friendly high-octane number gasoline blending component. With the stricter environmental regulations on the content of olefin, aromatic hydrocarbon, sulfur and the like in gasoline, the importance of alkylate is highlighted.
Liquid acid alkylation processes using sulfuric or hydrofluoric acid as a catalyst are widely used in the oil refining industry. The liquid acid alkylation process has the characteristics of good selectivity, low price, recoverability and continuous activity maintenance, thereby ensuring that the device has long running period. Since hydrofluoric acid is a highly volatile and toxic chemical and is extremely harmful when leaked, and sulfuric acid is less harmful than hydrofluoric acid, in recent years, the main alkylation apparatus has been newly built.
However, sulfuric acid alkylation has a problem that the dispersion of sulfuric acid and raw material hydrocarbons (isobutane and C3 to C5 olefins) is difficult and the octane number of alkylate is unfavorable because the reaction temperature is low (generally between 4 and 10 ℃) and the viscosity of sulfuric acid is high.
To increase the degree of dispersion of the starting hydrocarbon in sulfuric acid, a novel liquid-liquid dispersion apparatus was used for the sulfuric acid alkylation, such as a rotating packed bed reactor of CN103861533A, a reactor for at least two liquid feeds of TW 201429545A. Although the above-mentioned liquid-liquid dispersion apparatus can achieve good dispersion of the raw material hydrocarbon in the sulfuric acid, the residence time of the acid hydrocarbon in the apparatus is extremely short, resulting in a short reaction time, which may result in insufficient reaction and be disadvantageous for the alkylation reaction.
CN101679143A discloses a method for overcoming the disadvantage of short residence time of acid hydrocarbon in liquid-liquid dispersion device for alkylation reaction, which is to connect a stirring reactor in series after the liquid-liquid dispersion device to increase the reaction time. Since alkylate octane number is affected by reaction time, the residence time of the acid hydrocarbon in the stirred reactor, i.e., the acid hydrocarbon liquid level in the stirred reactor, needs to be controlled. The common liquid level control method is that the liquid level and the material flow entering and exiting the stirring kettle are controlled in an interlocking manner, the control mode inevitably has liquid level fluctuation, and stirring disturbs the liquid level, so that the liquid level control precision is poor, the octane number of alkylate oil is fluctuated, and the octane number control of the alkylate oil is not facilitated.
In addition, when the volume of the stirred reactor is small, the relative accuracy of liquid level measurement and control is worse, and even when the volume of the stirred reactor is small to a certain extent (such as less than 5L or 3L), the existing liquid level measurement equipment cannot be used, and the traditional liquid level control method cannot be realized.
Disclosure of Invention
In order to solve the problems, the invention provides a method for alkylating isobutane and C3-C5 olefin. The method is not limited by the volume of the reactor, can be flexibly applied to a large-volume alkylation reactor or a small-volume alkylation reactor, and can solve the problems of large liquid level measurement error, low control precision and the like when the existing liquid level automatic control is applied to the method.
In order to achieve the purpose, the invention provides an alkylation method of isobutane and C3-C5 olefin, which comprises the following steps:
s1: raw material hydrocarbon containing isobutane and C3-C5 olefin and catalyst sulfuric acid enter a liquid-liquid dispersion device, alkylation reaction is started after the raw material hydrocarbon is contacted with the sulfuric acid, and acid hydrocarbon emulsion formed by mixing unreacted raw material hydrocarbon, reaction products and the sulfuric acid is formed at an outlet of the liquid-liquid dispersion device;
s2: the acid hydrocarbon emulsion enters a stirring reactor to continue alkylation reaction;
s3: the acid hydrocarbon emulsion in the stirring reactor enters an acid hydrocarbon separator to be separated into sulfuric acid and liquid hydrocarbon, and the liquid hydrocarbon enters a distillation tower to be separated into alkylate oil;
the acid hydrocarbon separator is a gas-liquid three-phase separator, an overflow pipe is arranged in the stirring reactor, and the acid hydrocarbon emulsion in the stirring reactor enters the acid hydrocarbon separator under the action of gravity through the overflow pipe.
In the method for alkylating isobutane and C3-C5 olefins, in step S1, the liquid-liquid dispersion device is preferably a rotating packed bed or a stator-rotor reactor.
In the method for alkylating isobutane and C3-C5 olefins, the gas phase in the acid-hydrocarbon separator is preferably communicated with the gas phase in the stirred reactor.
In the method for alkylating isobutane and C3-C5 olefins, preferably, the gas phase in the acid-hydrocarbon separator is communicated with the gas phase in the stirred reactor through a gas-phase communicating pipe.
In the method for alkylating isobutane and C3-C5 olefins according to the present invention, preferably, the overflow pipe is inserted into the inner wall of the stirred reactor from the bottom inside the stirred reactor, and then the bottom of the overflow pipe is fixed and sealed in the inner wall of the stirred reactor.
In the method for alkylating isobutane and C3-C5 olefins, the bottom of the overflow pipe is preferably fixed and sealed in the inner wall of the stirring reactor through a clamping sleeve.
In the method for alkylating isobutane and C3-C5 olefins, an inflation pipe is preferably arranged at the upper part of the stirring reactor.
The invention relates to a method for alkylating isobutane and C3-C5 olefins, wherein the C3-C5 olefins are preferably selected from at least one of propylene, butylene and pentene.
The method for alkylating isobutane and C3-C5 olefins, disclosed by the invention, is characterized in that the molar ratio of isobutane to C3-C5 olefins in the raw material hydrocarbon is preferably 5-200: 1.
The alkylation method of isobutane and C3-C5 olefins, disclosed by the invention, wherein in the step S1, the reaction temperature is preferably-5-4 ℃, and the pressure is preferably 0.1-1 MPa.
The alkylation method of isobutane and C3-C5 olefins, disclosed by the invention, wherein in the step S2, the reaction temperature is preferably 5-20 ℃, the pressure is preferably 0.1-1 MPa, and the time is preferably 1-60 min.
The method for alkylating isobutane and C3-C5 olefins, disclosed by the invention, can be used for ensuring that the volume of the stirring reactor is less than 5L, and further less than 3L.
The alkylation method of isobutane and C3-C5 olefin specifically comprises the following steps:
(1) raw material hydrocarbon containing isobutane and C3-C5 olefin and catalyst sulfuric acid enter a liquid-liquid dispersion device, the raw material hydrocarbon is contacted with the sulfuric acid to start reaction, and an acid hydrocarbon emulsion formed by mixing unreacted raw material hydrocarbon, reaction products and the sulfuric acid is formed at an outlet of the liquid-liquid dispersion device (a rotary packed bed or a stator-rotor reactor);
(2) the acid hydrocarbon emulsion in the step (1) enters a stirring reactor for continuous reaction;
(3) the acid hydrocarbon emulsion in the stirring reactor in the step (2) enters an acid hydrocarbon separator (a gas-liquid three-phase separator) to be separated into sulfuric acid and liquid hydrocarbon, and the liquid hydrocarbon enters a distillation tower to be separated into alkylate oil;
in the step (3), the acid hydrocarbon emulsion in the stirring reactor enters the acid hydrocarbon separator through an overflow pipe arranged in the stirring reactor under the action of gravity.
In conclusion, the beneficial effects of the invention are as follows:
1. the acid hydrocarbon separator adopts a gas-liquid three-phase separator, so that materials in the stirring reactor can enter the acid hydrocarbon separator under the action of gravity through an overflow pipe arranged between the stirring reactor and the separator, and the octane value fluctuation of alkylate oil caused by the material liquid level fluctuation in the stirring reactor can be reduced. In addition, the invention overcomes the problems of large liquid level measurement error, low control precision and the like when the existing liquid level automatic control is applied to the method.
2. The present invention is not subject to the volume requirements of level measurement and control instrumentation for stirred reactors, and therefore, the present invention can achieve the above alkylation process on a small scale unit (which may have a volume of less than 5L, and further may be less than 3L).
3. The octane number of the alkylate produced in the reaction process can be made more stable by communicating the gas phase in the acid-hydrocarbon separator with the gas phase in the stirred reactor.
4. Through inserting the overflow pipe in stirred tank reactor's inner wall from stirred tank reactor's bottom, sealed fixed and sealed in stirred tank reactor's inner wall through the cutting ferrule, can conveniently adjust stirred tank reactor liquid level through adjusting the overflow pipe height, realize alkylate oil quality regulation and control.
Drawings
FIG. 1 is a flow chart of an apparatus according to example 1 of the present invention.
FIG. 2 is a flow chart of an apparatus of embodiment 3 of the present invention.
FIG. 3 is a flow chart of an apparatus of embodiment 4 of the present invention.
Fig. 4 is a flow chart of the apparatus of comparative example 1 of the present invention.
Wherein:
1. rotating the packed bed; 2. stirring the reactor; 3. a distillation column; 4. a feedstock hydrocarbon feed conduit; 5. a sulfuric acid feeding pipe; 6. a stirred reactor motor; 7. a rotating packed bed outlet; 8. a sulfuric acid discharge pipe; 9. a liquid hydrocarbon discharge pipe; 10. a distillation column bottom tube; 11. a distillation column side line tube; 12. jacking a distillation tower; 13. an acid hydrocarbon separator; 14. a baffle plate; 15. rotating the packed bed packing; 16. an inflation tube; 17. an overflow pipe; 18. a gas phase communicating pipe; 19. a reaction material outflow pipe; 20. adjusting a valve; 21. a liquid level controller; 22. a liquid level meter.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
Referring to fig. 1, a raw material hydrocarbon containing isobutane and C3-C5 olefins and a catalyst sulfuric acid are fed into a rotating packed bed 1 through a raw material hydrocarbon feed pipe 4 and a sulfuric acid feed pipe 5, respectively, are mixed in a rotating packed bed packing 15, and then the reaction is started, and an acid hydrocarbon emulsion in which unreacted raw material hydrocarbon, a reaction product and sulfuric acid are mixed is formed at an outlet 7 of the rotating packed bed, wherein the rotating packed bed is a liquid-liquid dispersion device.
The acid hydrocarbon emulsion enters the stirred reactor 2 from the outlet 7 of the rotating packed bed to continue the alkylation reaction. The stirring reactor 2 is driven by a stirring reactor motor 6, and the pressure of the stirring reactor 2 can be adjusted by charging gas such as nitrogen, methane, ethane and the like into the gas charging pipe 16.
The acid hydrocarbon emulsion in the stirring reactor enters the acid hydrocarbon separator 13 through an overflow pipe 17 for separation. The acid hydrocarbon separator 13 is a gas-liquid three-phase separator, the acid hydrocarbon emulsion is separated into sulfuric acid and liquid hydrocarbon in the acid hydrocarbon separator 13, the liquid hydrocarbon enters the liquid hydrocarbon side of the acid hydrocarbon separator 13 from the top of the baffle plate 14, then enters the distillation tower 3 through the liquid hydrocarbon discharge pipe 9 for distillation separation, alkylate oil is distilled out of the bottom of the tower, and the alkylate oil is discharged from the bottom pipe 10 of the distillation tower. If the feed contains n-butane, it is removed in the distillation column via the side conduit 11 of the distillation column. The distillate at the top of the tower is discharged through a distillation tower top pipe 12 and is mainly unreacted isobutane. The sulfuric acid separated in the acid hydrocarbon separator 13 is discharged through the sulfuric acid discharge pipe 8.
In the above-mentioned apparatus, firstly, replacing the air in the apparatus with nitrogen gas, then starting the rotating packed bed 1, feeding raw material hydrocarbon and sulfuric acid into the rotating packed bed 1, the sum of the mass of isobutane and C3-C5 olefin in the raw material hydrocarbon is 90% of the mass of the raw material hydrocarbon, the rest is n-butane, the molar ratio of isobutane to olefin is 150:1, in which the olefin is formed from propylene, 2-butene and 1-pentene in the molar ratio of 2.8:100:0.8, and the volume flow rate of the raw material hydrocarbon is 1m3H is used as the reference value. The rotating packed bed speed was 1000rpm and the reaction temperature was 3 ℃. The stirring speed of the stirring reactor is 550rpm, the pressure is 0.6MPa, the reaction temperature is 6 ℃, the stirring paddle is a straight-blade paddle, the ratio of the paddle diameter to the stirring reactor diameter is 1/3, and the average residence time of the reaction materials in the stirring reactor is 30 min. The material in the stirring kettle is separated into two phases of sulfuric acid and liquid hydrocarbon in an acid-hydrocarbon separator. The liquid hydrocarbon enters a distillation tower, and the alkylate is obtained at the bottom of the tower.
After the device runs stably, timing is started, samples of the alkylate oil are taken every 1 hour, 10 samples are continuously taken, and the RON (research octane number) of the alkylate oil is determined. The change of alkylate RON with time is shown in Table 1.
Table 1 the standard deviation of the measurements is 0.02625.
Table 1 example 1 change over time of alkylate RON
| Time | 0 | 1h | 2h | 3h | 4h |
| Octane number | 97.51 | 97.54 | 97.47 | 97.52 | 97.46 |
| Time | 5h | 6h | 7h | 8h | 9h |
| Octane number | 97.49 | 97.51 | 97.49 | 97.53 | 97.48 |
Example 2
The liquid-liquid dispersion apparatus used a stator-rotor reactor of CN1704155A, and the gas phase in the acid-hydrocarbon separator was connected to the gas phase in the stirred reactor, and the rest was the same as in example 1.
After the device runs stably, timing is started, samples of the alkylate oil are taken every 1 hour, 10 samples are continuously taken, and the RON (research octane number) of the alkylate oil is determined. The change of alkylate RON over time is shown in table 2.
Table 2 the standard deviation of the measurements is 0.02582.
Table 2 example 2 change over time of alkylate RON
| Time | 0 | 1h | 2h | 3h | 4h |
| Octane number | 98.48 | 98.47 | 98.52 | 98.48 | 98.53 |
| Time | 5h | 6h | 7h | 8h | 9h |
| Octane number | 98.47 | 98.48 | 98.52 | 98.53 | 98.52 |
Example 3
Referring to fig. 2, the difference from the embodiment 1 is: the gas phase in the acid hydrocarbon separator and the gas phase in the stirred reactor were communicated through the gas communicating tube 18, and the rest was the same as in example 1.
After the device runs stably, timing is started, samples of the alkylate oil are taken every 1 hour, 10 samples are continuously taken, and the RON (research octane number) of the alkylate oil is determined. The change of alkylate RON with sampling time is shown in table 3. Table 3 the standard deviation of the measurements is 0.01826.
Table 3 example 3 change over time of alkylate RON
| Time | 0 | 1h | 2h | 3h | 4h |
| Octane number | 97.50 | 97.47 | 97.52 | 97.49 | 97.50 |
| Time | 5h | 6h | 7h | 8h | 9h |
| Octane number | 97.51 | 97.49 | 97.53 | 97.48 | 97.51 |
Example 4
Referring to fig. 3, the difference from example 3 is: the overflow pipe 17 is inserted into the inner wall of the stirred reactor from the bottom of the stirred reactor, fixed and sealed in the inner wall of the stirred reactor.
In the device, firstly, nitrogen is used for replacing air in the device, then the rotating packed bed 1 is started, raw material hydrocarbon and sulfuric acid are fed into the rotating packed bed 1, the raw material hydrocarbon is a mixed raw material of isobutane and 1-butene, the molar ratio of the isobutane to the 1-butene is 200:1, and the volume flow rate of the raw material hydrocarbon is 1m3H is used as the reference value. The rotating speed of the rotating packed bed is 2000rpm, and the reaction temperature is-5 ℃. The stirring speed of the stirring reactor is 750rpm, the pressure is 0.1MPa, the reaction temperature is 4 ℃, the stirring paddle is a straight-blade paddle, the ratio of the paddle diameter to the stirring reactor diameter is 1/3, and the height of the overflow pipe 17 is adjusted to ensure that the average residence time of the reaction materials in the stirring reactor is 60 min. The material in the stirring kettle is separated into two phases of sulfuric acid and liquid hydrocarbon in an acid-hydrocarbon separator. The liquid hydrocarbon enters a distillation tower and is obtained at the bottom of the towerThe product is alkylate.
After the device runs stably, timing is started, samples of the alkylate oil are taken every 1 hour, 10 samples are continuously taken, and the RON (research octane number) of the alkylate oil is determined. The change of alkylate RON with sampling time is shown in table 4. Table 4 the standard deviation of the measurements is 0.01955.
Table 4 example 4 change over time of alkylate RON
| Time | 0 | 1h | 2h | 3h | 4h |
| Octane number | 99.51 | 99.49 | 99.50 | 99.49 | 99.52 |
| Time | 5h | 6h | 7h | 8h | 9h |
| Octane number | 99.49 | 99.51 | 99.54 | 99.48 | 99.53 |
Example 5
The differences from example 4 are: the overflow pipe is fixed and sealed in the inner wall of the stirring reactor through the cutting ferrule in a sealing way, so that the liquid level height in the stirring reactor can be adjusted and the octane number of the alkylate oil can be regulated and controlled conveniently by adjusting the height of the overflow pipe.
In the above-mentioned apparatus, firstly, the air in the apparatus is replaced by nitrogen gas, then the rotating packed bed 1 is started, and the raw material hydrocarbon and sulfuric acid are fed into the rotating packed bed 1, the raw material hydrocarbon is a mixture of isobutane and 2-butene, the mole ratio of isobutane to 2-butene is 5:1, and the volume flow rate of the raw material hydrocarbon is 1m3H is used as the reference value. The rotating speed of the rotating packed bed was 3000rpm, and the reaction temperature was 4.1 ℃. The stirring speed of the stirring reactor is 850rpm, the pressure is 1MPa, the reaction temperature is 20 ℃, the stirring paddle is a straight blade paddle, the ratio of the diameter of the paddle to the diameter of the stirring reactor is 1/3, and the height of the overflow pipe 17 is adjusted to ensure that the average residence time of the reaction materials in the stirring reactor is 1 min. The material in the stirring kettle is separated into two phases of sulfuric acid and liquid hydrocarbon in an acid-hydrocarbon separator. The liquid hydrocarbon enters a distillation tower, and the alkylate is obtained at the bottom of the tower.
After the device runs stably, timing is started, samples of the alkylate oil are taken every 1 hour, 10 samples are continuously taken, and the RON (research octane number) of the alkylate oil is determined. The change of alkylate RON with sampling time is shown in table 5. Table 5 the standard deviation of the measurements is 0.02183.
Table 5 example 5 change over time of alkylate RON
| Time | 0 | 1h | 2h | 3h | 4h |
| Octane number | 96.52 | 96.51 | 96.50 | 96.49 | 96.46 |
| Time | 5h | 6h | 7h | 8h | 9h |
| Octane number | 96.51 | 96.47 | 96.51 | 96.53 | 96.49 |
Example 6
Referring to fig. 1, the difference from embodiment 1 is: the volumetric flow rate of the feed hydrocarbon was 1L/h, and the volume of the stirred reactor was 2L.
After the device runs stably, timing is started, samples of the alkylate oil are taken every 1 hour, 10 samples are continuously taken, and the RON (research octane number) of the alkylate oil is determined. The change of alkylate RON over time is shown in table 6. Table 6 the standard deviation of the measurements is 0.02749.
TABLE 6 example 6 variation of alkylate RON with time
Comparative example 1
Referring to fig. 4, the difference from the embodiment 1 is: the liquid level control of the stirring kettle adopts a common automatic control mode, the material of the stirring reactor passes through a reactant outflow pipe 19 at the bottom of the stirring reactor, and the liquid level of the stirring reactor is controlled in an interlocking way through a liquid level meter 22, a liquid level controller 21 and a regulating valve 20.
Raw material hydrocarbon containing isobutane and C3-C5 olefin and catalyst sulfuric acid respectively enter a rotary packed bed 1 through a raw material hydrocarbon feeding pipe 4 and a sulfuric acid feeding pipe 5, are mixed in a rotary packed bed filler 15, then start to react, and form an acid hydrocarbon emulsion formed by mixing unreacted raw material hydrocarbon, reaction products and sulfuric acid at a rotary packed bed outlet 7, wherein the rotary packed bed is a liquid-liquid dispersion device.
The acid hydrocarbon emulsion enters the stirred reactor 2 from the outlet 7 of the rotating packed bed to continue the alkylation reaction. The stirring reactor 2 is driven by a stirring reactor motor 6, and the pressure of the stirring reactor 2 is adjusted by charging gases such as nitrogen, methane, ethane and the like through a gas charging pipe 16.
The acid hydrocarbon emulsion in the stirred reactor enters the acid hydrocarbon separator 13 through a reactant outflow pipe 19 at the bottom of the stirred reactor for separation, and the liquid level of the stirred reactor is controlled in an interlocking manner through a liquid level meter 22, a liquid level controller 21 and a regulating valve 20. The acid hydrocarbon emulsion is separated into sulfuric acid and liquid hydrocarbon in an acid hydrocarbon separator 13, the liquid hydrocarbon enters a distillation tower 3 through a liquid hydrocarbon discharge pipe 9 for distillation separation, alkylate oil is distilled out of the bottom of the tower and is discharged from a distillation tower bottom pipe 10. If the feed contains n-butane, it is removed in the distillation column via the side conduit 11 of the distillation column. The distillate at the top of the tower is discharged through a distillation tower top pipe 12 and is mainly unreacted isobutane. The sulfuric acid separated in the acid hydrocarbon separator 13 is discharged through the sulfuric acid discharge pipe 8.
In the above-mentioned apparatus, firstly, replacing the air in the apparatus with nitrogen gas, then starting the rotating packed bed 1, feeding raw material hydrocarbon and sulfuric acid into the rotating packed bed 1, the sum of the mass of isobutane and C3-C5 olefin in the raw material hydrocarbon is 90% of the mass of the raw material hydrocarbon, the rest is n-butane, the molar ratio of isobutane to olefin is 150:1, in which the olefin is formed from propylene, 2-butene and 1-pentene in the molar ratio of 2.8:100:0.8, and the volume flow rate of the raw material hydrocarbon is 1m3H is used as the reference value. The rotating packed bed speed was 1000rpm and the reaction temperature was 3 ℃. The stirring speed of the stirring reactor is 550rpm, the pressure is 0.6MPa, the reaction temperature is 6 ℃, the stirring paddle is a straight blade paddle, and the ratio of the paddle diameter to the diameter of the stirring reactor is 1/3. The material in the stirring kettle is separated into two phases of sulfuric acid and liquid hydrocarbon in an acid-hydrocarbon separator. The liquid hydrocarbon enters a distillation tower, and the alkylate is obtained at the bottom of the tower.
After the device runs stably, timing is started, samples of the alkylate oil are taken every 1 hour, 10 samples are continuously taken, and the RON (research octane number) of the alkylate oil is determined. The change of alkylate RON over time is shown in table 5. Table 7 the standard deviation of the measurements is 0.09452.
TABLE 7 Change over time of comparative example 1 alkylate RON
| Time | 0 | 1h | 2h | 3h | 4h |
| Octane number | 97.41 | 97.39 | 97.40 | 97.61 | 97.59 |
| Time | 5h | 6h | 7h | 8h | 9h |
| Octane number | 97.44 | 97.42 | 97.60 | 97.56 | 97.58 |
As can be seen by comparing the results of examples 1-6 and comparative example 1, the standard deviation of the alkylate RON of examples 1-6 is smaller than that of comparative example 1, which shows that the fluctuation of the alkylate RON in the reaction process can be effectively reduced by adopting the method of the invention.
Particularly, after the gas phase in the acid-hydrocarbon separator is communicated with the gas phase in the stirring reactor in the examples 3 to 5, the standard deviation of the alkylate RON in the examples 3 to 5 is greatly smaller than that in the comparative example 1, which shows that the fluctuation of the alkylate RON in the reaction process can be greatly reduced by adopting the method.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (12)
1. A method for alkylating isobutane and C3-C5 olefins is characterized by comprising the following steps:
s1: raw material hydrocarbon containing isobutane and C3-C5 olefin and catalyst sulfuric acid enter a liquid-liquid dispersion device, alkylation reaction is started after the raw material hydrocarbon is contacted with the sulfuric acid, and acid hydrocarbon emulsion formed by mixing unreacted raw material hydrocarbon, reaction products and the sulfuric acid is formed at an outlet of the liquid-liquid dispersion device;
s2: the acid hydrocarbon emulsion enters a stirring reactor to continue alkylation reaction;
s3: the acid hydrocarbon emulsion in the stirring reactor enters an acid hydrocarbon separator to be separated into sulfuric acid and liquid hydrocarbon, and the liquid hydrocarbon enters a distillation tower to be separated into alkylate oil;
the acid hydrocarbon separator is a gas-liquid three-phase separator, an overflow pipe is arranged in the stirring reactor, and the acid hydrocarbon emulsion in the stirring reactor enters the acid hydrocarbon separator under the action of gravity through the overflow pipe.
2. The process for the alkylation of isobutane with C3-C5 olefins according to claim 1, wherein in step S1 said liquid-liquid dispersion device is a rotating packed bed or a stator-rotor reactor.
3. The process for the alkylation of isobutane with C3-C5 olefins according to claim 1, wherein the gas phase in the acid-hydrocarbon separator is in communication with the gas phase in the stirred reactor.
4. The process for the alkylation of isobutane with C3-C5 olefins according to claim 3, wherein the gas phase in the acid-hydrocarbon separator is in communication with the gas phase in the stirred reactor via a gas phase communicating tube.
5. The process for the alkylation of isobutane with C3-C5 olefins according to claim 1, wherein said overflow pipe is fixed and sealed inside the inner wall of the stirred reactor after it is inserted into the inner wall of the stirred reactor from the bottom thereof.
6. The process for the alkylation of isobutane with olefins C3-C5 according to claim 5, wherein said overflow pipe is fixed and sealed inside the inner wall of the stirred reactor by means of a ferrule.
7. The process for the alkylation of isobutane with C3-C5 olefins according to claim 1, wherein an aeration tube is provided in the upper part of the stirred reactor.
8. The process for the alkylation of isobutane with C3-C5 olefins according to claim 1, wherein said C3-C5 olefins are selected from at least one of propylene, butene and pentene.
9. The method for alkylating isobutane with C3-C5 olefins according to claim 1, wherein the molar ratio of isobutane to C3-C5 olefins in the feed hydrocarbon is 5-200: 1.
10. The method for alkylating isobutane with C3-C5 olefins according to claim 1, wherein in step S1, the reaction temperature is-5-4 ℃ and the pressure is 0.1-1 MPa.
11. The method for alkylating isobutane with C3-C5 olefins according to claim 1, wherein in step S2, the reaction temperature is 4.1-20 ℃, the pressure is 0.1-1 MPa, and the reaction time is 1-60 min.
12. The process for the alkylation of isobutane with C3-C5 olefins according to claim 1, wherein the volume of said stirred reactor is less than 5L.
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| GB763314A (en) * | 1953-10-20 | 1956-12-12 | Kellogg M W Co | Improvements in or relating to hydrocarbon conversion |
| CN1281839A (en) * | 1999-07-22 | 2001-01-31 | 中国石油化工集团公司 | Isoalkane and alkylation method of olefine |
| CN101679143A (en) * | 2007-06-27 | 2010-03-24 | Hrd有限公司 | System and process for alkylation |
| CN204952360U (en) * | 2015-06-18 | 2016-01-13 | 中石化洛阳工程有限公司 | Sour hydrocarbon separator |
| CN106929093A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | The alkylation and device of a kind of iso-butane and C3~C5 alkene |
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| GB763314A (en) * | 1953-10-20 | 1956-12-12 | Kellogg M W Co | Improvements in or relating to hydrocarbon conversion |
| CN1281839A (en) * | 1999-07-22 | 2001-01-31 | 中国石油化工集团公司 | Isoalkane and alkylation method of olefine |
| CN101679143A (en) * | 2007-06-27 | 2010-03-24 | Hrd有限公司 | System and process for alkylation |
| CN204952360U (en) * | 2015-06-18 | 2016-01-13 | 中石化洛阳工程有限公司 | Sour hydrocarbon separator |
| CN106929093A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | The alkylation and device of a kind of iso-butane and C3~C5 alkene |
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