CN110003938A - Alkylation method of isobutane and C3-C5 olefin - Google Patents
Alkylation method of isobutane and C3-C5 olefin Download PDFInfo
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- CN110003938A CN110003938A CN201810006864.2A CN201810006864A CN110003938A CN 110003938 A CN110003938 A CN 110003938A CN 201810006864 A CN201810006864 A CN 201810006864A CN 110003938 A CN110003938 A CN 110003938A
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- hydrocarbon
- alkene
- liquid
- iso
- alkylation
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 50
- 239000001282 iso-butane Substances 0.000 title claims abstract description 50
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 40
- 230000029936 alkylation Effects 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 122
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 122
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 122
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000000839 emulsion Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 235000013847 iso-butane Nutrition 0.000 claims description 47
- 230000000694 effects Effects 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 3
- 238000003780 insertion Methods 0.000 claims description 3
- 230000037431 insertion Effects 0.000 claims description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 2
- -1 propylene, butylene Chemical group 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 28
- 238000004821 distillation Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 10
- 238000011160 research Methods 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 210000001190 lateral line system Anatomy 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000519996 Teucrium chamaedrys Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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 present invention relates to a kind of alkylated reaction, the alkane of especially a kind of iso-butane with sulfuric acid catalysis and C3~C5 alkene
Base method.
Background technique
Alkylate oil obtained by iso-butane and C3~C5 olefin alkylation has octane number height, and (research octane number (RON) is general
It is 90~96), the features such as steam forces down, and aromatic hydrocarbons and olefin(e) centent are low, and sensibility is good, be the high-knock rating gasoline tune of clean and environmental protection
It is combined point.As environmental regulation is to increasingly strict, the importance of alkylate oil of the limitations such as alkene, aromatic hydrocarbons, sulfur content in gasoline
It becomes increasingly conspicuous.
It is widely used in petroleum refining industry at present using sulfuric acid or hydrofluoric acid as the liquid acid alkylation processes of catalyst.Liquid acid
The characteristics of alkylation process be selectivity it is good, price is low, it is recyclable and continuously keep activity, to keep device long operation cycle.
Since hydrofluoric acid is volatile severe poisonous chemicals, once leakage hazard is very big, and sulfuric acid phase is smaller than hydrofluoric acid harm, therefore,
Alkyl plant is created in recent years based on sulfuric acid alkylation.
But sulfuric acid alkylation, since reaction temperature is lower (generally 4~10 DEG C between), sulfuric acid viscosity is higher, therefore,
There are the difficulties in dispersion between sulfuric acid and raw material hydrocarbon (iso-butane and C3~C5 alkene), and unfavorable to alkylate oil octane number asks
Topic.
In order to improve degree of scatter of the raw material hydrocarbon in sulfuric acid, novel liquid-liquid dispersal device is used for sulfuric acid alkylation, such as
The rotating packed-bed reactor of CN103861533A, the reactor at least two liquid materials of TW201429545A.On
Raw material hydrocarbon can be made preferably to disperse in sulfuric acid although stating liquid-liquid dispersion device, the residence time of sour hydrocarbon in the device is extremely short,
Cause the reaction time short, will cause and react insufficient, it is unfavorable to alkylated reaction.
CN101679143A disclose one kind overcome in liquid-liquid dispersion device sour hydrocarbon residence time it is short to alkylated reaction not
The method of benefit, is stirred reactor of connecting after liquid-liquid dispersion device, to increase the reaction time.Due to alkylate oil octane
Value is influenced by the reaction time, therefore need to be controlled residence time of the sour hydrocarbon in stirred reactor, i.e., anti-to stirring
Sour hydrocarbon liquid level in device is answered to be controlled.Common liquid level controlling method is that liquid level and disengaging stirred tank mass flow carry out interlocking control
System, this control mode are inevitably present level fluctuation, in addition stirring has disturbance to liquid level, Liquid level low precision is made
It is fluctuated at alkylate oil octane number, is unfavorable for the control of alkylate oil octane number.
In addition, when stirred reactor volume is smaller, the relative accuracy of level gauging and control can be worse, or even when stirring
Reactor volume it is small to a certain extent when (such as less than 5L or 3L), existing fluid level measuring device is not available, traditional liquid level control
Method processed cannot achieve.
Summary of the invention
To solve the above problems, the present invention provides the alkylation of a kind of iso-butane and C3~C5 alkene.This method is not
It is limited, can be flexibly applied on big volume alkylation reactor or small volume alkylation reactor by reactor volume, and
It is able to solve existing use liquid automatic control and is applied to the problems such as level gauging error when the above method is big low with control precision.
In order to achieve the above objectives, the present invention provides the alkylation of a kind of iso-butane and C3~C5 alkene, including as follows
Step:
S1: raw material hydrocarbon and catalyst sulfuric acid containing iso-butane and C3~C5 alkene enter liquid-liquid dispersion device, make raw material
Start alkylated reaction after hydrocarbon and sulfuric acid contact, liquid-liquid dispersion device export to be formed by unreacting material hydrocarbon, reaction product and
The sour hydrocarbon emulsion that sulfuric acid is mixed to form；
S2: the acid hydrocarbon emulsion enters stirred reactor and continues alkylated reaction；
S3: the sour hydrocarbon emulsion in the stirred reactor enters sour hydrocarbon separator and is separated into sulfuric acid and liquid hydrocarbon, the liquid
Body hydrocarbon enters destilling tower and isolates alkylate oil；
The acid hydrocarbon separator is solution-air-liquid three phase separator, is provided with overflow pipe in the stirred reactor, described
Sour hydrocarbon emulsion in stirred reactor enters sour hydrocarbon separator by overflow pipe under the effect of gravity.
The alkylation of iso-butane of the present invention and C3~C5 alkene, in step S1, the liquid-liquid dispersion device
Preferably rotary packed bed or rotor-stator reactor.
The alkylation of iso-butane of the present invention and C3~C5 alkene, wherein preferably, the acid hydrocarbon separation
Gas phase in device is connected with the gas phase in the stirred reactor.
The alkylation of iso-butane of the present invention and C3~C5 alkene, wherein preferably, the acid hydrocarbon separation
Gas phase in device is connected with the gas phase in the stirred reactor by gas phase communicating pipe.
The alkylation of iso-butane of the present invention and C3~C5 alkene, wherein preferably, the overflow pipe from
After the inner wall of bottom insertion stirred reactor inside stirred reactor, the bottom of the overflow pipe is fixed and is sealed in stirring
In the inner wall of reactor.
The alkylation of iso-butane of the present invention and C3~C5 alkene, wherein preferably, the overflow pipe
It fixes and is sealed in by cutting ferrule in the inner wall of stirred reactor in bottom.
The alkylation of iso-butane of the present invention and C3~C5 alkene, wherein preferably, described to be stirred to react
The top of device is provided with gas tube.
The alkylation of iso-butane of the present invention and C3~C5 alkene, wherein C3~C5 alkene preferably selects
From at least one of propylene, butylene and amylene.
The alkylation of iso-butane of the present invention and C3~C5 alkene, wherein in the raw material hydrocarbon iso-butane with
The ratio between mole of C3~C5 alkene is preferably 5~200:1.
The alkylation of iso-butane of the present invention and C3~C5 alkene, wherein in step S1, the temperature of the reaction
Preferably -5~4 DEG C of degree, pressure is preferably 0.1~1MPa.
The alkylation of iso-butane of the present invention and C3~C5 alkene, wherein in step S2, the temperature of the reaction
Preferably 5-20 DEG C of degree, pressure is preferably 0.1~1MPa, and the time is preferably 1~60min.
The alkylation of iso-butane of the present invention and C3~C5 alkene, wherein the volume of the stirred reactor
5L can be less than, 3L may further be less than.
The alkylation of iso-butane and C3~C5 alkene of the invention, specifically comprises the following steps:
(1) raw material hydrocarbon and catalyst sulfuric acid containing iso-butane and C3~C5 alkene enter liquid-liquid dispersion device, raw material hydrocarbon
And sulfuric acid contact, start to react, be formed in the outlet of liquid-liquid dispersion device (rotary packed bed or rotor-stator reactor) not anti-
Answer the sour hydrocarbon emulsion of raw material hydrocarbon, reaction product and sulfuric acid mixing；
(2) step (1) the sour hydrocarbon emulsion enters stirred reactor the reaction was continued；
(3) the sour hydrocarbon emulsion in step (2) described stirred reactor enters sour hydrocarbon separator (solution-air-liquid three phase separation
Device) it is separated into sulfuric acid and liquid hydrocarbon, the liquid hydrocarbon enters destilling tower and isolates alkylate oil；
In step (3), sour hydrocarbon emulsion in the stirred reactor is by being set to the overflow pipe of stirred reactor, by weight
Power effect enters sour hydrocarbon separator.
In conclusion the invention has the benefit that
1, sour hydrocarbon separator uses solution-air-liquid three phase separator, stirs the material of stirred reactor by being set to
The overflow pipe between reactor and separator is mixed, enters sour hydrocarbon separator under the effect of gravity, object in stirred reactor can be reduced
Expect that alkylate oil octane number caused by level fluctuation fluctuates.Also, liquid automatic control application is used the present invention overcomes existing
The problems such as level gauging error is big low with control precision when the above method.
2, the not requirement by level gauging and control instrument to stirred reactor volume of the invention, therefore, the present invention can be
The abovementioned alkyl method that midget plant is realized on (its volume can be less than 5L, may further be less than 3L).
3, by communicating the gas phase in sour hydrocarbon separator with the gas phase in stirred reactor, can make raw in reaction process
At alkylate oil octane number it is more stable.
4, it by the way that overflow pipe to be inserted into the inner wall of stirred reactor from the bottom of stirred reactor, is sealed and is fixed by cutting ferrule
And be sealed in the inner wall of stirred reactor, stirred reactor liquid level is adjusted by adjusting overflow pipe height with can be convenient,
Realize alkylate oil controlling of quality.
Detailed description of the invention
Fig. 1 is the device flow chart of the embodiment of the present invention 1.
Fig. 2 is the device flow chart of the embodiment of the present invention 3.
Fig. 3 is the device flow chart of the embodiment of the present invention 4.
Fig. 4 is the device flow chart of comparative example 1 of the invention.
Wherein:
1, rotary packed bed；2, stirred reactor；3, destilling tower；4, raw material hydrocarbon feed pipe；5, sulfuric acid feed pipe；6, it stirs
Reactor motor；7, rotary packed bed exports；8, sulfuric acid discharge pipe；9, liquid hydrocarbon discharge pipe；10, destilling tower bottom tube；11, it distills
Tower lateral line canal；12, destilling tower push pipe；13, sour hydrocarbon separator；14, baffle；15, rotary packed bed filler；16, gas tube；17,
Overflow pipe；18, gas phase communicating pipe；19, reaction mass effuser；20, regulating valve；21, fluid level controller；22, liquidometer.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The present invention is described in further detail with reference to the accompanying drawings and examples.
Embodiment 1
It is shown in Figure 1, raw material hydrocarbon and catalyst sulfuric acid containing iso-butane and C3~C5 alkene respectively through raw material hydrocarbon into
Expects pipe 4 and sulfuric acid feed pipe 5 enter rotary packed bed 1, are mixed in rotary packed bed filler 15, then start to react,
The sour hydrocarbon emulsion of unreacting material hydrocarbon, reaction product and sulfuric acid mixing is formed in rotary packed bed outlet 7, wherein rotary packed bed
That is liquid-liquid dispersion device.
Above-mentioned acid hydrocarbon emulsion enters stirred reactor 2 by rotary packed bed outlet 7 and continues alkylated reaction.This is stirred to react
Device 2 is driven by stirred reactor motor 6, and the pressure of stirred reactor 2 can be filled with nitrogen, methane, ethane by gas tube 16
Equal gases are adjusted.
Sour hydrocarbon emulsion in above-mentioned stirred reactor enters sour hydrocarbon separator 13 through overflow pipe 17 and is separated.Sour hydrocarbon separation
Device 13 is solution-air-liquid three phase separator, and sour hydrocarbon emulsion is separated into sulfuric acid and liquid hydrocarbon in sour hydrocarbon separator 13, liquid hydrocarbon from
The top of baffle 14 enters the liquid hydrocarbon side of sour hydrocarbon separator 13, then carries out distillation point into destilling tower 3 through liquid hydrocarbon discharge pipe 9
From distillating alkylate oil in tower bottom, and be discharged by destilling tower bottom tube 10.If containing normal butane in charging, in a distillation column
It is removed through destilling tower lateral line canal 11.Overhead is discharged through destilling tower push pipe 12, predominantly unreacted iso-butane.Sour hydrocarbon point
It is discharged from the sulfuric acid isolated in device 13 through sulfuric acid discharge pipe 8.
In above-mentioned apparatus, first with the air in nitrogen replaceable equipment, then start rotary packed bed 1, to rotary filling
It filling in bed 1 and is passed through raw material hydrocarbon and sulfuric acid, iso-butane and C3~C5 alkene quality sum account for the 90% of raw material hydrocarbon quality in raw material hydrocarbon,
Remaining is normal butane, and the molar ratio of isobutane and olefins is 150:1, wherein alkene by propylene that molar ratio is 2.8:100:0.8,
2- butylene and 1- amylene composition, the volume flow rate of raw material hydrocarbon are 1m3/h.Rotary packed bed revolving speed is 1000rpm, and reaction temperature is
3℃.Stirred reactor speed of agitator is 550rpm, and pressure 0.6MPa, reaction temperature is 6 DEG C, and agitating paddle is straight oar, paddle diameter with
Stirred reactor diameter ratio is 1/3, and mean residence time of the reaction mass in stirred reactor is 30min.In stirred tank
Material be separated into sulfuric acid and liquid hydrocarbon two-phase in sour hydrocarbon separator.Liquid hydrocarbon enters destilling tower, obtains product-alkane in tower bottom
Base carburetion.
After device is stable, starts timing, take alkylate oil sample every 1h, continuously take 10 samples, measures alkyl
Carburetion RON (research octane number (RON)).Alkylate oil RON changes with time as shown in table 1.
The standard deviation of 1 measured value of table is 0.02625.
1 embodiment of table, 1 alkylate oil RON changes with time situation
| 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 |
Embodiment 2
Liquid-liquid dispersion device uses the rotor-stator reactor of CN1704155A, and the gas phase and stirring in sour hydrocarbon separator are anti-
The gas phase in device is answered to be connected, remaining is same as Example 1.
After device is stable, starts timing, take alkylate oil sample every 1h, continuously take 10 samples, measures alkyl
Carburetion RON (research octane number (RON)).Alkylate oil RON changes with time as shown in table 2.
The standard deviation of 2 measured value of table is 0.02582.
2 embodiment of table, 2 alkylate oil RON changes with time situation
| 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 |
Embodiment 3
It is shown in Figure 2, it is distinguished with embodiment 1 are as follows: the gas phase of gas phase and stirred reactor in sour hydrocarbon separator passes through
Gas phase communicating pipe 18 communicates, other same as Example 1.
After device is stable, starts timing, take alkylate oil sample every 1h, continuously take 10 samples, measures alkyl
Carburetion RON (research octane number (RON)).Alkylate oil RON is as shown in table 3 with the variation of sample time.The standard deviation of 3 measured value of table
Difference is 0.01826.
3 embodiment of table, 3 alkylate oil RON changes with time situation
| 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 |
Embodiment 4
Difference shown in Figure 3, with embodiment 3 are as follows: overflow pipe 17 is stirred to react from the insertion of the bottom of stirred reactor
The inner wall of device is fixed and is sealed in the inner wall of stirred reactor.
In above-mentioned apparatus, first with the air in nitrogen replaceable equipment, then start rotary packed bed 1, to rotary filling
It fills in bed 1 and is passed through raw material hydrocarbon and sulfuric acid, raw material hydrocarbon is the mixed raw material of iso-butane and 1- butylene, mole of iso-butane and 1- butylene
Than being 1m for the volume flow rate of 200:1, raw material hydrocarbon3/h.Rotary packed bed revolving speed is 2000rpm, and reaction temperature is -5 DEG C.Stirring
Reactor speed of agitator is 750rpm, and pressure 0.1MPa, reaction temperature is 4 DEG C, and agitating paddle is straight oar, paddle diameter be stirred to react
Device diameter ratio is 1/3, adjusts 17 height of overflow pipe, makes mean residence time of the reaction mass in stirred reactor
60min.Material in stirred tank is separated into sulfuric acid and liquid hydrocarbon two-phase in sour hydrocarbon separator.Liquid hydrocarbon enters destilling tower, in tower
Bottom obtains product-alkylate oil.
After device is stable, starts timing, take alkylate oil sample every 1h, continuously take 10 samples, measures alkyl
Carburetion RON (research octane number (RON)).Alkylate oil RON is as shown in table 4 with the variation of sample time.The standard deviation of 4 measured value of table
Difference is 0.01955.
4 embodiment of table, 4 alkylate oil RON changes with time situation
| 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 |
Embodiment 5
With the difference of embodiment 4 are as follows: overflow pipe is sealed fixed and is sealed in the inner wall of stirred reactor by cutting ferrule, this
Sample, can be convenient by adjusting overflow pipe height, adjust stirred reactor in liquid level, regulation product alkylate oil it is pungent
Alkane value.
In above-mentioned apparatus, first with the air in nitrogen replaceable equipment, then start rotary packed bed 1, to rotary filling
It fills in bed 1 and is passed through raw material hydrocarbon and sulfuric acid, raw material hydrocarbon is the mixture of iso-butane and 2- butylene, the molar ratio of iso-butane and 2- butylene
For 5:1, the volume flow rate of raw material hydrocarbon is 1m3/h.Rotary packed bed revolving speed is 3000rpm, and reaction temperature is 4.1 DEG C.Stirring is anti-
Answering device speed of agitator is 850rpm, and pressure 1MPa, reaction temperature is 20 DEG C, and agitating paddle is straight oar, paddle diameter and stirred reactor
Diameter ratio is 1/3, adjusts 17 height of overflow pipe, makes mean residence time 1min of the reaction mass in stirred reactor.
Material in stirred tank is separated into sulfuric acid and liquid hydrocarbon two-phase in sour hydrocarbon separator.Liquid hydrocarbon enters destilling tower, obtains in tower bottom
Product-alkylate oil.
After device is stable, starts timing, take alkylate oil sample every 1h, continuously take 10 samples, measures alkyl
Carburetion RON (research octane number (RON)).Alkylate oil RON is as shown in table 5 with the variation of sample time.The standard deviation of 5 measured value of table
Difference is 0.02183.
5 embodiment of table, 5 alkylate oil RON changes with time situation
| 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 |
Embodiment 6
Difference shown in Figure 1, with embodiment 1 are as follows: the volume flow rate of raw material hydrocarbon is 1L/h, and stirred reactor volume is
2L。
After device is stable, starts timing, take alkylate oil sample every 1h, continuously take 10 samples, measures alkyl
Carburetion RON (research octane number (RON)).Alkylate oil RON changes with time as shown in table 6.The standard deviation of 6 measured value of table is
0.02749。
6 embodiment of table, 6 alkylate oil RON changes with time situation
Comparative example 1
It is shown in Figure 4, it is distinguished with embodiment 1 are as follows: stirred tank Liquid level uses common automatic control mode, stirring
Reactor content passes through the reaction mass effuser 19 of stirred reactor bottom, and stirred reactor liquid level passes through liquidometer 22, liquid
Level controller 21 and regulating valve 20 carry out interlocked control.
Raw material hydrocarbon and catalyst sulfuric acid containing iso-butane and C3~C5 alkene respectively through raw material hydrocarbon feed pipe 4 and sulfuric acid into
Expects pipe 5 enters rotary packed bed 1, is mixed in rotary packed bed filler 15, then starts to react, gone out in rotary packed bed
Mouth 7 forms the sour hydrocarbon emulsion of unreacting material hydrocarbon, reaction product and sulfuric acid mixing, wherein rotary packed bed, that is, liquid-liquid dispersion dress
It sets.
Above-mentioned acid hydrocarbon emulsion enters stirred reactor 2 by rotary packed bed outlet 7 and continues alkylated reaction.This is stirred to react
Device 2 is driven by stirred reactor motor 6, and the pressure of stirred reactor 2 is filled with the gas such as nitrogen, methane, ethane by gas tube 16
Body is adjusted.
Sour hydrocarbon emulsion in above-mentioned stirred reactor enters acid by the reaction mass effuser 19 of stirred reactor bottom
Hydrocarbon separator 13 is separated, and stirred reactor liquid level is interlocked by liquidometer 22, fluid level controller 21 and regulating valve 20
Control.Sour hydrocarbon emulsion is separated into sulfuric acid and liquid hydrocarbon in sour hydrocarbon separator 13, and liquid hydrocarbon enters through liquid hydrocarbon discharge pipe 9 to be distilled
Tower 3 carries out distillation separation, distillates alkylate oil in tower bottom, and be discharged by destilling tower bottom tube 10.If containing normal butane in charging,
Then removed in a distillation column through destilling tower lateral line canal 11.Overhead is discharged through destilling tower push pipe 12, predominantly unreacted
Iso-butane.The sulfuric acid isolated in sour hydrocarbon separator 13 is discharged through sulfuric acid discharge pipe 8.
In above-mentioned apparatus, first with the air in nitrogen replaceable equipment, then start rotary packed bed 1, to rotary filling
It filling in bed 1 and is passed through raw material hydrocarbon and sulfuric acid, iso-butane and C3~C5 alkene quality sum account for the 90% of raw material hydrocarbon quality in raw material hydrocarbon,
Remaining is normal butane, and the molar ratio of isobutane and olefins is 150:1, wherein alkene by propylene that molar ratio is 2.8:100:0.8,
2- butylene and 1- amylene composition, the volume flow rate of raw material hydrocarbon are 1m3/h.Rotary packed bed revolving speed is 1000rpm, and reaction temperature is
3℃.Stirred reactor speed of agitator is 550rpm, and pressure 0.6MPa, reaction temperature is 6 DEG C, and agitating paddle is straight oar, paddle diameter with
Stirred reactor diameter ratio is 1/3.Material in stirred tank is separated into sulfuric acid and liquid hydrocarbon two-phase in sour hydrocarbon separator.Liquid
Hydrocarbon enters destilling tower, obtains product-alkylate oil in tower bottom.
After device is stable, starts timing, take alkylate oil sample every 1h, continuously take 10 samples, measures alkyl
Carburetion RON (research octane number (RON)).Alkylate oil RON changes with time as shown in table 5.The standard deviation of 7 measured value of table is
0.09452。
7 comparative example of table, 1 alkylate oil RON changes with time situation
| 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 |
It is compared by the result to Examples 1 to 6 and comparative example 1 as can be seen that the Examples 1 to 6 alkyl measured
The standard deviation of carburetion RON is less than comparative example 1, illustrates that using the method for the present invention that can effectively reduce in reaction process is alkylated
The fluctuation of oily RON.
After especially the gas phase in sour hydrocarbon separator is connected to by embodiment 3~5 with the gas phase of stirred reactor, the reality of measurement
The standard deviation for applying 3~5 alkylate oil RON of example is significantly smaller than comparative example 1, illustrates that reaction can be greatly reduced using the above method
The fluctuation of alkylate oil RON in the process.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (12)
1. the alkylation of a kind of iso-butane and C3~C5 alkene, which comprises the steps of:
S1: raw material hydrocarbon and catalyst sulfuric acid containing iso-butane and C3~C5 alkene enter liquid-liquid dispersion device, make raw material hydrocarbon and
Start alkylated reaction after sulfuric acid contact, exports to be formed by unreacting material hydrocarbon, reaction product and sulfuric acid in liquid-liquid dispersion device
The sour hydrocarbon emulsion being mixed to form；
S2: the acid hydrocarbon emulsion enters stirred reactor and continues alkylated reaction；
S3: the sour hydrocarbon emulsion in the stirred reactor enters sour hydrocarbon separator and is separated into sulfuric acid and liquid hydrocarbon, the liquid hydrocarbon
Alkylate oil is isolated into destilling tower；
The acid hydrocarbon separator is solution-air-liquid three phase separator, is provided with overflow pipe, the stirring in the stirred reactor
Sour hydrocarbon emulsion in reactor enters sour hydrocarbon separator by overflow pipe under the effect of gravity.
2. the alkylation of iso-butane according to claim 1 and C3~C5 alkene, which is characterized in that in step S1,
The liquid-liquid dispersion device is rotary packed bed or rotor-stator reactor.
3. the alkylation of iso-butane according to claim 1 and C3~C5 alkene, which is characterized in that the acid hydrocarbon point
It is connected from the gas phase in device with the gas phase in the stirred reactor.
4. the alkylation of iso-butane according to claim 3 and C3~C5 alkene, which is characterized in that the acid hydrocarbon point
It is connected with the gas phase in the stirred reactor by gas phase communicating pipe from the gas phase in device.
5. the alkylation of iso-butane according to claim 1 and C3~C5 alkene, which is characterized in that the overflow pipe
After the inner wall of the bottom of stirred reactor insertion stirred reactor, the overflow pipe is fixed and is sealed in stirred reactor
In inner wall.
6. the alkylation of iso-butane according to claim 5 and C3~C5 alkene, which is characterized in that the overflow pipe
In the inner wall for fixing and being sealed in stirred reactor by cutting ferrule.
7. the alkylation of iso-butane according to claim 1 and C3~C5 alkene, which is characterized in that the stirring is anti-
The top of device is answered to be provided with gas tube.
8. the alkylation of iso-butane according to claim 1 and C3~C5 alkene, which is characterized in that the C3~C5
Alkene is selected from least one of propylene, butylene and amylene.
9. the alkylation of iso-butane according to claim 1 and C3~C5 alkene, which is characterized in that the raw material hydrocarbon
The ratio between mole of middle iso-butane and C3~C5 alkene is 5~200:1.
10. the alkylation of iso-butane according to claim 1 and C3~C5 alkene, which is characterized in that in step S1,
The temperature of the reaction is -5~4 DEG C, and pressure is 0.1~1MPa.
11. the alkylation of iso-butane according to claim 1 and C3~C5 alkene, which is characterized in that in step S2,
The temperature of the reaction is 4.1~20 DEG C, and pressure is 0.1~1MPa, and the time is 1~60min.
12. the alkylation of iso-butane according to claim 1 and C3~C5 alkene, which is characterized in that the stirring
The volume of reactor is less than 5L.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114432976A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Production device and method of alkylated gasoline |
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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 | Method and device for alkylating isobutane and C3-C5 olefins |
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Patent Citations (5)
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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 | Method and device for alkylating isobutane and C3-C5 olefins |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114432976A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Production device and method of alkylated gasoline |
| CN114432976B (en) * | 2020-10-31 | 2023-11-07 | 中国石油化工股份有限公司 | Alkylated gasoline production device and method |
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