CN107304155A - The process units and method of a kind of iso-butane - Google Patents
The process units and method of a kind of iso-butane Download PDFInfo
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- CN107304155A CN107304155A CN201610258442.5A CN201610258442A CN107304155A CN 107304155 A CN107304155 A CN 107304155A CN 201610258442 A CN201610258442 A CN 201610258442A CN 107304155 A CN107304155 A CN 107304155A
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- hydrogenation
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- isobutane
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- isomerization
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 239000001282 iso-butane Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 28
- 235000013847 iso-butane Nutrition 0.000 title abstract 5
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 254
- 238000000926 separation method Methods 0.000 claims abstract description 130
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 81
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000047 product Substances 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 31
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003381 stabilizer Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000006227 byproduct Substances 0.000 claims abstract description 5
- 238000007599 discharging Methods 0.000 claims description 75
- 230000000087 stabilizing effect Effects 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000010992 reflux Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- 239000002918 waste heat Substances 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000001741 organic sulfur group Chemical group 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2791—Catalytic processes with metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of process units of iso-butane and method.Described device includes：Hydrogenation reactor, hydrogenation input and output material heat exchanger, hydrogenation feed heater, hydrogenation separator, dethanizer, depropanizing tower, stabilizer, iso-butane finishing column, isomerization input and output material heat exchanger, isomerization feed heater, isomerization reactor；Hydrogenation separator includes：It is hydrogenated with hot knock-out pot, hydrogenation aftercooler and is hydrogenated with cold knockout drum；Or including hydrogenation aftercooler and hydrogenation knockout drum.Methods described includes：The raw material of carbon four enters described device via the feeding line of carbon four, iso-butane and normal butane is made after hydrogenated, separation, iso-butane is made after isomerization reaction, separation in normal butane, while the product of by-product carbon three.The present invention can handle all rich in the lighter hydrocarbons of carbon four, while by waste heat recovery, improving the economic benefit of device.
Description
Technical Field
The invention relates to the field of light hydrocarbons with four carbon atoms, in particular to a device and a method for producing isobutane.
Background
Along with the continuous deepening of the processing depth of petrochemical industry, the by-product C of liquefied gas, oilfield associated gas, oil refining device and ethylene device4The rational utilization of the components in the fractions is increasingly being regarded. C41, 3-butadiene contained in the fraction can be separated by extractive distillation for producing synthetic rubber, C4Isobutene in the distillate reacts with methanol through an etherification device to generate MTBE and 1-butene with high purity can be obtained through further precise fractionation, and other four-carbon components are less utilized. Isobutane can produce methyl methacrylate, isobutylene, isobutanol, propylene oxide, and the like. In recent years, the demand of isobutene, isobutanol, propylene oxide and the like is increased year by year, so that the utilization of isobutane attracts more and more attention, and in addition, the large-scale expansion of an alkylation device driven by domestic oil upgrading causes isobutane in carbon four of a refinery to be rapidly changed from surplus to balance or even (possibly) insufficient. At the same time, the amount of butane associated with shale gas continues to increase due toThe high-content N-butane can cause the N-butane in the carbon four of the refinery to be more difficult to find, and the additional value is continuously reduced.
The refinery carbon four has wide sources and is mainly divided into two types, one type is saturated carbon four containing olefin less than or equal to 5 wt%, the other type is unsaturated carbon four containing olefin of 40-50 wt%, the carbon four after the ethylene device is etherified is mainly alkane and mono-olefin, and the olefin content is 30-60 wt%. Currently, most of the carbon-four mixture is burned as liquefied gas fuel, the chemical utilization rate is low, and the economic value of normal butane is limited due to the strong demand of isobutane, so that how to increase the yield of isobutane is very important.
Chinese patent document CN102294203A discloses a carbon four two-stage hydrogenation device and process in the preparation of ethylene by catalytic thermal cracking, which adopts two-stage selective hydrogenation to avoid the problems of coking of a reactor and reduction of the service life of a catalyst and the operation period of the device caused by deep hydrogenation of 1, 3-butadiene, and can directly hydrogenate mixed carbon four, thereby improving the utilization rate of raw materials. However, the carbon-carbon four mixture containing little or no diolefin is not related to a specific separation method, and is not related to a method for removing impurities such as organic sulfur nitrogen, and is not related to isomerization reaction and the like.
Chinese patent document CN102188985A discloses a selective hydrogenation catalyst for four carbon cuts and a preparation method thereof, the catalyst can selectively hydrogenate alkyne in the four carbon cuts, butadiene is not substantially lost, and the catalyst has high activity and high selectivity, and the preparation method is simple and has wide application. However, the invention mainly carries out selective hydrogenation on alkyne in the four-carbon fraction, does not have a method for hydrogenating mono-olefin in an alkane and alkene mixture, only prepares a catalyst, does not relate to a separation method, does not relate to a method for removing impurities such as organic sulfur nitrogen, and the like, and does not relate to isomerization reaction and the like.
Chinese patent documents CN201410444683.X and CN1170632A disclose a catalyst for preparing isobutane by isomerizing normal butane and application thereof, but mainly comprise a catalyst system and process operation parameters, and do not relate to flow development.
Disclosure of Invention
In order to solve the problems that a large amount of low-value n-butane is abundant and high-value isobutane is insufficient in the prior art, the invention provides a device and a method for producing isobutane. By combining hydrogenation and isomerization processes, the invention can treat all the light hydrocarbons rich in carbon four, including liquefied gas, oilfield associated gas, refinery carbon four, ethylene plant ether carbon four and the like, and simultaneously, by adopting a heat exchange network optimization technology, the waste heat is recovered, and the economic benefit of the device is improved.
An object of the present invention is to provide an apparatus for producing isobutane, which comprises: the system comprises a hydrogenation reactor, a hydrogenation feeding and discharging heat exchanger, a hydrogenation feeding heater, a hydrogenation separation device, a deethanizer, a depropanizer, a stabilizer, an isobutane finished product tower, an isomerization feeding and discharging heat exchanger, an isomerization feeding heater and an isomerization reactor; wherein,
the four-carbon feeding pipeline is connected with the hydrogenation feeding and discharging heat exchanger and the hydrogenation feeding heater and then is connected with the upper part of the hydrogenation reactor;
the bottom of the hydrogenation reactor is connected with a hydrogenation charging and discharging heat exchanger and then connected with a hydrogenation separation device, the hydrogenation separation device is sequentially connected with a compressor suction tank and a compressor and then combined with a four-carbon feeding pipeline, and then connected with the hydrogenation charging and discharging heat exchanger;
the bottom of the hydrogenation separation device is connected with a deethanizer, the bottom of the deethanizer is connected with a depropanizer, and the bottom of the depropanizer is connected with a stabilizing tower feeding and discharging heat exchanger and then is combined with a carbon four discharging pipeline after isomerization reaction and connected with the stabilizing tower;
the bottom of the stabilizer is connected with a stabilizer feeding and discharging heat exchanger and then connected with an isobutane finished product tower, and the side line of the isobutane finished product tower is sequentially connected with an isomerization feeding and discharging heat exchanger and an isomerization heater and then connected with an inlet of an isomerization reactor;
the outlet of the isomerization reactor is connected with an isomerization feeding and discharging heat exchanger and then connected with a stabilizing tower.
The hydrogenation charging and discharging heat exchanger can be directly connected to the top of the second-stage hydrogenation reactor through a pipeline.
The hydrogenation separation device is used for separating hydrogen and light hydrocarbon, and the hydrogenation separation device can adopt one of the following two compositions:
A) the hydrogenation separation device comprises a hydrogenation thermal separation tank, a hydrogenation aftercooler and a hydrogenation cold separation tank;
the bottom of the hydrogenation reactor is connected with a hydrogenation charging and discharging heat exchanger and then connected with a hydrogenation heat separation tank, the top of the hydrogenation heat separation tank is sequentially connected with a hydrogenation aftercooler and a hydrogenation cold separation tank, and the top of the hydrogenation cold separation tank is connected with a compressor suction tank; the bottom of the hydrogenation cold separation tank is connected with a hydrogenation hot separation tank; the bottom of the hydrogenation thermal separation tank is connected with a deethanizer.
B) The hydrogenation separation device can also comprise a hydrogenation aftercooler and a hydrogenation separation tank;
the bottom of the hydrogenation reactor is connected with a hydrogenation charging and discharging heat exchanger and then sequentially connected with a hydrogenation aftercooler and a hydrogenation separation tank, the top of the hydrogenation separation tank is connected with a compressor suction tank, and the bottom of the hydrogenation separation tank is connected with a deethanizer.
According to two hydrogenation separation devices, after reaction discharge is subjected to heat exchange through a hydrogenation feed and discharge heat exchanger, two modes can be provided, wherein one mode is that the reaction discharge is firstly fed into a hydrogenation heat separation tank for gas-liquid separation, a top gas phase is cooled through a hydrogenation aftercooler and then fed into a hydrogenation cold separation tank, the top of the hydrogenation cold separation tank is connected with a compressor suction tank, the bottom of the hydrogenation cold separation tank is connected with the hydrogenation heat separation tank, and a liquid phase at the bottom of the hydrogenation heat separation tank is connected with a deethanizer (as shown in figure 1); the other mode is that the mixture is cooled by a cooler after hydrogenation and then enters a hydrogenation separation tank for gas-liquid separation, the top gas phase is connected with a compressor suction tank, and the bottom liquid phase is connected with a deethanizer (as shown in figure 2).
Preferably in the first way.
The above-described heater for the hydrogenation feed may be a heating device generally used in the art, such as: an electric heater, a steam heater, or a furnace.
The following technical scheme can be specifically adopted:
the isobutane production apparatus includes: the system comprises a hydrogenation reactor, a hydrogenation feeding and discharging heat exchanger, a hydrogenation feeding heater, a hydrogenation separation device, a deethanizer, a depropanizer, a stabilizer, an isobutane finished product tower, an isomerization feeding and discharging heat exchanger, an isomerization feeding heater and an isomerization reactor; wherein,
the four-carbon feeding pipeline is connected with the hydrogenation feeding and discharging heat exchanger and the hydrogenation feeding heater and then is connected with the upper part of the hydrogenation reactor;
the bottom of the hydrogenation reactor is connected with a hydrogenation charging and discharging heat exchanger and then connected with a hydrogenation heat separation tank; the top of the hydrogenation thermal separation tank is sequentially connected with a hydrogenation aftercooler and a hydrogenation cold separation tank, the top of the hydrogenation cold separation tank is sequentially connected with a compressor suction tank and a compressor, then is combined with a four-carbon feeding pipeline, and then is connected with a hydrogenation feeding and discharging heat exchanger; the bottom of the hydrogenation cold separation tank is connected with a hydrogenation hot separation tank;
the bottom of the hydrogenation thermal separation tank is connected with a deethanizer, the bottom of the deethanizer is connected with a depropanizer, and the bottom of the depropanizer is connected with a stabilizing tower feeding and discharging heat exchanger and then is combined with a carbon four discharging pipeline after isomerization reaction and connected with the stabilizing tower;
the bottom of the stabilizer is connected with a stabilizer feeding and discharging heat exchanger and then connected with an isobutane finished product tower, and the side line of the isobutane finished product tower is sequentially connected with an isomerization feeding and discharging heat exchanger and an isomerization heater and then connected with an inlet of an isomerization reactor;
the outlet of the isomerization reactor is connected with an isomerization feeding and discharging heat exchanger and then connected with a stabilizing tower.
It is a second object of the present invention to provide a method for producing isobutane using said apparatus, said method comprising:
and the carbon four raw material enters the device through a carbon four feeding pipeline, isobutane and normal butane are prepared after hydrogenation and separation, wherein the normal butane is subjected to isomerization reaction and separation to prepare isobutane, and a carbon three product is byproduct.
The method specifically comprises the following steps:
(a) the method comprises the following steps of (1) exchanging heat of a carbon four raw material outside the boundary through a hydrogenation feeding and discharging heat exchanger, then feeding the carbon four raw material into a hydrogenation reactor to hydrogenate and saturate olefins and remove impurities; the impurities comprise trace organic sulfur, nitrogen and the like;
(b) the bottom discharge of the hydrogenation reactor enters a hydrogenation separation device after passing through a hydrogenation feeding and discharging heat exchanger, the separated hydrogen returns to the hydrogenation reactor, the bottom material of the hydrogenation separation device enters a deethanizer, and the top of the deethanizer is separated by rectification to obtain carbon-II light components;
(c) the material at the bottom of the deethanizer enters a depropanizer, a carbon-three liquid phase product is separated from the top of the deethanizer, and the material at the bottom is subjected to heat exchange by a stabilizing tower feeding and discharging heat exchanger, then is combined with carbon-four after isomerization reaction, and enters the stabilizing tower;
(d) the material at the bottom of the stabilizer enters an isobutane finished product tower after heat exchange through a stabilizer feeding and discharging heat exchanger; obtaining an isobutane product from the top of the tower through rectification separation, obtaining a carbon five-component from the bottom of the tower, and extracting a mixture containing normal butane and isobutane from a side line of the tower;
(e) the mixture containing the normal butane and the isobutane enters an isomerization reactor after heat exchange through an isomerization feeding and discharging heat exchanger and an isomerization heater, isomerization reaction is carried out, and the normal butane is converted into the isobutane;
(f) the material discharged from the bottom of the isomerization reactor is subjected to heat exchange by an isomerization feeding and discharging heat exchanger and then is merged with the material at the bottom of the depropanizing tower to enter a stabilizing tower.
In the step (a), the raw material of the carbon four is heated to 160-300 ℃ and then enters a hydrogenation reactor. When the temperature rise of the hydrogenation reaction is very high, the temperature rise of a hydrogenation feeding heater is not needed during normal production, the reaction temperature can be reached through the heat exchange of feeding and discharging materials, the hydrogenation feeding heater is needed only during starting, and at the moment, the materials subjected to the heat exchange of the hydrogenation feeding and discharging heat exchanger can directly enter the second-stage hydrogenation reactor through a pipeline. When the temperature rise of the hydrogenation reaction is not high, a hydrogenation feeding heater is required for heating in addition to feeding and discharging heat exchange during normal production.
In the step (b), when the hydrogenation separation device comprises a hydrogenation heat separation tank, a hydrogenation after-cooler and a hydrogenation cold separation tank, the discharge material at the bottom of the hydrogenation reactor is cooled to 50-100 ℃ through a hydrogenation feeding and discharging heat exchanger and then enters the hydrogenation heat separation tank, and the gas phase at the top of the hydrogenation heat separation tank is cooled to 20-50 ℃ through the hydrogenation after-cooler and then enters the hydrogenation cold separation tank.
In the step (b), when the hydrogenation separation device comprises a hydrogenation aftercooler and a hydrogenation separation tank, the material at the bottom of the hydrogenation reactor is subjected to heat exchange through a hydrogenation feeding and discharging heat exchanger, then is cooled to 20-50 ℃ through the hydrogenation aftercooler, and then enters the hydrogenation separation tank.
Specifically, the following technical scheme can be adopted:
(a) mixing carbon four raw materials from outside with circulating hydrogen returned by a compressor, feeding the mixture into a hydrogenation feeding and discharging heat exchanger, heating the mixture to 160-300 ℃ by a hydrogenation feeding heater, and finally feeding the mixture into a hydrogenation reactor to hydrogenate and saturate olefins and convert trace organic sulfur nitrogen into H2S and NH3；
(b) The bottom discharge of the hydrogenation reactor is cooled to 50-100 ℃ after heat exchange with the hydrogenation feed in two ways, one way is that the bottom discharge is cooled to 20-50 ℃ through a cooler after hydrogenation, then enters a hydrogenation separation tank for gas-liquid separation, the top gas phase is connected with a compressor suction tank, and the bottom liquid phase is connected with a deethanizer; the other mode is that the gas-liquid separation is carried out in a hydrogenation heat separation tank, the gas phase at the top is cooled to 20-50 ℃ through a cooler after hydrogenation, and then the gas phase enters a hydrogenation cold separation tank, the top of the cold separation tank is connected with a compressor suction tank, the bottom of the cold separation tank is connected with the hydrogenation heat separation tank, and the liquid phase at the bottom of the hydrogenation heat separation tank is connected with a deethanizer.
Most of the gas phase at the top of the hydrogenation separation tank or the hydrogenation cold separation tank is used as circulating hydrogen to return to the hydrogenation reaction feed, and the non-hydrogen gas content in the circulating hydrogen system is maintained to be stable through a discharge pipeline.
(c) Fresh hydrogen is combined with gas sucked from the tank top by a compressor from the outside and enters the compressor, and the mixture enters a hydrogenation charging and discharging heat exchanger together with the carbon four raw material after being pressurized by the compressor;
(d) feeding the material at the bottom of the hydrogenation thermal separation tank into a deethanizer, and separating the carbon two light components at the top by rectification;
(e) the material at the bottom of the deethanizer enters a depropanizer, a carbon-three liquid phase product is separated from the top of the deethanizer, and the material at the bottom is subjected to heat exchange by a stabilizing tower feeding and discharging heat exchanger, then is combined with carbon-four after isomerization reaction, and enters the stabilizing tower;
(f) and (3) exchanging heat of the material at the bottom of the stabilizing tower by a stabilizing tower feeding and discharging heat exchanger, then feeding the material into an isobutane finished product tower, rectifying and separating to obtain an isobutane product from the top of the isobutane finished product tower, and obtaining the carbon pentagon component at the tower bottom.
(g) Mixing a mixture containing normal butane and isobutane extracted from the side line of an isobutane finished product tower with fresh hydrogen outside, heating the mixture to 100-250 ℃ through an isomerization feeding and discharging heat exchanger and an isomerization feeding heater, and then feeding the mixture into an isomerization reactor, wherein normal butane is converted into isobutane;
(h) the material after isomerization reaction is circulated into a stabilizing tower after heat exchange by an isomerization feed-discharge heat exchanger, and H is removed from the tower top through rectification separation2、H2S and other light components, and obtaining a normal isobutane mixture at the tower bottom.
The hydrogenation catalyst adopted by the invention is a nickel-based or palladium-based hydrogenation catalyst; the isomerization catalyst is a catalyst composed of one or two of Pt, Pd and Ir.
The process conditions of each apparatus of the present invention may be those generally used in the prior art, and in the present invention, the following process conditions may be preferably used:
the hydrogenation reactor is a fixed bed reactor, the inlet temperature of the reactor is 160-300 ℃, the pressure is 1.5-4.5 MPaG (gauge pressure, the same applies below), the reaction temperature is increased to 5-100 ℃, the molar ratio of hydrogen to oil is 0.2-5, and the volume of liquid is emptyThe speed is 0.5 to 6 hours-1；
The operating conditions of the deethanizer column include: the pressure is 1-3 MPaG, the operation temperature at the top of the tower is 20-80 ℃, the number of tower plates is 30-100, and the reflux ratio is 1-20;
the operating conditions of the depropanizer column include: the pressure is 1-3 MPaG, the operation temperature at the top of the tower is 20-80 ℃, the number of tower plates is 30-100, and the reflux ratio is 1-20;
the operating conditions of the stabilizer column include: the pressure is 1-3 MPaG, the operation temperature at the top of the tower is 20-100 ℃, the number of tower plates is 30-100, and the reflux ratio is 1-100;
the operating conditions of the isobutane finishing column include: the pressure is 0.1-1 MPaG, the operation temperature at the top of the tower is 20-70 ℃, the number of tower plates is 80-150, and the reflux ratio is 1-20;
the isomerization reactor is a fixed bed reactor, the inlet temperature of the reactor is 100-250 ℃, the pressure is 1.0-4.0 MPaG, the reaction temperature is 5-50 ℃, and the liquid volume space velocity is 1-20 h-1。
The invention is characterized in that:
1) unsaturated olefin is completely converted into saturated hydrocarbon by hydrogenation, and impurities such as organic sulfur, nitrogen and the like in the raw material are converted into H2S and NH3The removal is carried out, so that the influence on the product is avoided;
2) energy is recovered to the maximum extent by reasonably setting a heat exchange sequence, the energy consumption of the system is reduced, the economic benefit of the device is improved, and the energy consumption is saved by more than 15% by optimizing a series of heat exchange networks;
3) the temperature of the tower kettle is lower than 150 ℃ and the temperature of the tower top is about 45 ℃ through proper operating parameters, heat exchange can be realized by adopting low-pressure steam and circulating cooling water with low price, and high-grade steam and high-quality chilled water do not need to be externally introduced;
4) according to the invention, all light hydrocarbons rich in carbon four can be treated for producing isobutane by combining hydrogenation and isomerization processes;
5) the invention can simultaneously produce the carbon three products as by-products.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
FIG. 1 is a schematic view of an apparatus for producing isobutane according to the present invention, wherein the hydrogenation separation apparatus includes a hydrogenation heat separation tank, a hydrogenation aftercooler, and a hydrogenation cold separation tank.
FIG. 2 is a schematic view of an apparatus for producing isobutane according to the present invention, wherein the hydrogenation separation apparatus comprises a hydrogenation aftercooler and a hydrogenation separation tank.
Description of reference numerals:
the device comprises a hydrogenation reactor 1, a hydrogenation feeding and discharging heat exchanger 2, a hydrogenation feeding heater 3, a hydrogenation aftercooler 4, a hydrogenation separation tank 5, a hydrogenation heat separation tank 6, a hydrogenation cold separation tank 7, a compressor suction tank 8, a compressor 9, a deethanizer 10, a deethanizer condenser 11, a deethanizer reboiler 12, a depropanizer 13, a depropanizer condenser 14, a depropanizer reboiler 15, a stabilizer feeding and discharging heat exchanger 16 and a stabilizer 17; a stabilizer condenser 18, a stabilizer reboiler 19, an isobutane finished product tower 20, an isobutane finished product tower condenser 21, an isobutane finished product tower reboiler 22, an isomerization feed and discharge heat exchanger 23, an isomerization feed heater 24, an isomerization reactor 25, a carbon four raw material 26, purge gas 27, hydrogenation make-up hydrogen 28, C2Products 29, C330 parts of product, 31 parts of non-condensable gas at the top of the stabilizing tower, 32 parts of isobutane product, 33 parts of five carbon heavy components and 34 parts of isomerization supplementary hydrogen.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below with reference to the accompanying drawings.
Isobutane was produced using the apparatus shown in fig. 1.
The isobutane production apparatus includes: the device comprises a hydrogenation reactor 1, a hydrogenation feeding and discharging heat exchanger 2, a hydrogenation feeding heater 3, a hydrogenation separation device, a deethanizer 10, a depropanizer 13, a stabilizer 17, an isobutane finished product tower 20, an isomerization feeding and discharging heat exchanger 23, an isomerization feeding heater 24 and an isomerization reactor 25; wherein,
the four-carbon feeding pipeline is connected with the hydrogenation feeding and discharging heat exchanger 2 and the hydrogenation feeding heater 3 and then connected with the upper part of the hydrogenation reactor 1;
the bottom of the hydrogenation reactor 1 is connected with a hydrogenation charging and discharging heat exchanger 2 and then connected with a hydrogenation heat separation tank 6; the top of the hydrogenation thermal separation tank 6 is sequentially connected with a hydrogenation aftercooler 4 and a hydrogenation cold separation tank 7, the top of the hydrogenation cold separation tank 7 is sequentially connected with a compressor suction tank 8 and a compressor 9, then is combined with a four-carbon feeding pipeline, and then is connected with a hydrogenation feeding and discharging heat exchanger 2; the bottom of the hydrogenation cold separation tank 7 is connected with a hydrogenation hot separation tank 6;
the bottom of the hydrogenation heat separation tank 6 is connected with a deethanizer 10, the bottom of the deethanizer 10 is connected with a depropanizer 13, the bottom of the depropanizer 13 is connected with a stabilizing tower feeding and discharging heat exchanger 16 and then is combined with a carbon four discharging pipeline after isomerization reaction and connected with a stabilizing tower 17;
the bottom of the stabilizing tower 17 is connected with a stabilizing tower feeding and discharging heat exchanger 16 and then connected with an isobutane finished product tower 20, and the side line of the isobutane finished product tower 20 is connected with an isomerization feeding and discharging heat exchanger 23 and an isomerization heater 24 in sequence and then connected with an inlet of an isomerization reactor 25;
the outlet of the isomerization reactor 25 is connected with an isomerization feed-discharge heat exchanger 23 and then connected with a stabilizing tower 17.
The method for producing isobutane comprises:
(a) mixing carbon four raw material 26 from outside with circulating hydrogen returned by a compressor, feeding the mixture into a hydrogenation feeding and discharging heat exchanger 2, heating the mixture to 240 ℃ by a hydrogenation feeding heater 3, and finally feeding the mixture into a hydrogenation reactor 1 to hydrogenate and saturate olefins and convert trace organic sulfur nitrogen into H2S and NH3；
(b) The bottom discharge of the hydrogenation reactor 1 is cooled to 80 ℃ after heat exchange with hydrogenation feed, and then enters a hydrogenation heat separation tank 6 for gas-liquid separation, the top gas phase is cooled to 40 ℃ through a hydrogenation aftercooler 4 and then enters a hydrogenation cold separation tank 7, the top of the hydrogenation cold separation tank 7 is connected with a compressor suction tank 8, the bottom of the hydrogenation cold separation tank 7 is connected with the hydrogenation heat separation tank 6, and the bottom liquid phase of the hydrogenation heat separation tank 6 is connected with a deethanizer 10.
Most of the gas phase at the top of the hydrogenation cold separation tank 7 is used as recycle hydrogen to return to the hydrogenation reaction feed, and the purge gas 27 is released through a discharge pipeline to maintain the stable content of non-hydrogen gas in the recycle hydrogen system.
(c) Fresh hydrogen as hydrogenation supplementary hydrogen 28 is combined with gas at the top of a compressor suction tank 8 from the outside and enters a compressor 9, and the fresh hydrogen and the carbon four raw material enter a hydrogenation charging and discharging heat exchanger 2 together after being pressurized by the compressor 9;
(d) feeding the material at the bottom of the hydrogenation thermal separation tank 6 into a deethanizer 10, and separating the carbon-carbon light component from the top by rectification;
(e) the material at the bottom of the deethanizer 10 enters a depropanizer 13, the carbon-three liquid phase product is separated from the top, the material at the bottom is subjected to heat exchange by a stabilizing tower feeding and discharging heat exchanger 16, and then is combined with carbon-four after isomerization reaction and enters a stabilizing tower 17;
(f) the material at the bottom of the stabilizer 17 enters an isobutane finished product tower 20 after heat exchange through the stabilizer feeding and discharging heat exchanger 16, an isobutane product is obtained from the top of the isobutane finished product tower 20 through rectification separation, and the carbon five-component is obtained at the tower bottom.
(g) A mixture containing normal butane and isobutane is extracted from the side line of an isobutane finished product tower 20 and is mixed with fresh hydrogen outside, namely isomerization supplementary hydrogen 34, the mixture is heated to 180 ℃ through an isomerization feeding and discharging heat exchanger 23 and an isomerization feeding heater 24 and then enters an isomerization reactor 25, and normal butane is converted into isobutane;
(h) the material after isomerization reaction is circulated into the stabilizing tower 17 after heat exchange by an isomerization feed-discharge heat exchanger 23, and H is removed at the tower top through rectification separation2、H2S and other light components, and obtaining a normal isobutane mixture at the tower bottom.
The following process conditions were used:
the hydrogenation reactor is a fixed bed reactor, the inlet temperature of the reactor is 250 ℃, the pressure is 3MPaG, the reaction temperature rise is 25 ℃, the hydrogen-oil molar ratio is 1.1, and the liquid volume space velocity is 2h-1；
The operating conditions of the deethanizer column include: the pressure is 2.2MPaG, the operation temperature at the top of the tower is 60 ℃, the number of tower plates is 60, and the reflux ratio is 10;
the operating conditions of the depropanizer column include: the pressure is 1.5MPaG, the operation temperature at the top of the tower is 50 ℃, the number of tower plates is 80, and the reflux ratio is 20;
the operating conditions of the stabilizer column include: the pressure is 2.0MPaG, the operation temperature at the top of the tower is 85 ℃, the number of tower plates is 60, and the reflux ratio is 50;
the operating conditions of the isobutane finishing column include: the pressure is 0.5MPaG, the operation temperature at the top of the tower is 50 ℃, the number of tower plates is 130, and the reflux ratio is 7;
the isomerization reactor is a fixed bed reactor, the inlet temperature of the reactor is 160 ℃, the pressure is 3.3MPaG, the reaction temperature is 30 ℃, and the liquid volume space velocity is 10h-1。
The results of Table 1 were obtained using the system shown in FIG. 1.
The result shows that the isobutane yield is more than 97 percent when the system and the method are used for preparing the isobutane.
TABLE 1
By the device and the process method, the energy consumption is saved by more than 15%.
While various embodiments of the present invention have been described above, the above description is intended to be exemplary, and not exhaustive. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. An isobutane production device, characterized in that:
the device comprises: the system comprises a hydrogenation reactor, a hydrogenation feeding and discharging heat exchanger, a hydrogenation feeding heater, a hydrogenation separation device, a deethanizer, a depropanizer, a stabilizer, an isobutane finished product tower, an isomerization feeding and discharging heat exchanger, an isomerization feeding heater and an isomerization reactor; wherein,
the four-carbon feeding pipeline is connected with the hydrogenation feeding and discharging heat exchanger and the hydrogenation feeding heater and then is connected with the upper part of the hydrogenation reactor;
the bottom of the hydrogenation reactor is connected with a hydrogenation charging and discharging heat exchanger and then connected with a hydrogenation separation device, the hydrogenation separation device is sequentially connected with a compressor suction tank and a compressor and then combined with a four-carbon feeding pipeline, and then connected with the hydrogenation charging and discharging heat exchanger;
the bottom of the hydrogenation separation device is connected with a deethanizer, the bottom of the deethanizer is connected with a depropanizer, and the bottom of the depropanizer is connected with a stabilizing tower feeding and discharging heat exchanger and then is combined with a carbon four discharging pipeline after isomerization reaction and connected with the stabilizing tower;
the bottom of the stabilizer is connected with a stabilizer feeding and discharging heat exchanger and then connected with an isobutane finished product tower, and the side line of the isobutane finished product tower is sequentially connected with an isomerization feeding and discharging heat exchanger and an isomerization heater and then connected with an inlet of an isomerization reactor;
the outlet of the isomerization reactor is connected with an isomerization feeding and discharging heat exchanger and then connected with a stabilizing tower.
2. Isobutane production plant according to claim 1, characterized in that:
the hydrogenation separation device comprises a hydrogenation thermal separation tank, a hydrogenation aftercooler and a hydrogenation cold separation tank;
the bottom of the hydrogenation reactor is connected with a hydrogenation charging and discharging heat exchanger and then connected with a hydrogenation heat separation tank, the top of the hydrogenation heat separation tank is sequentially connected with a hydrogenation aftercooler and a hydrogenation cold separation tank, and the top of the hydrogenation cold separation tank is connected with a compressor suction tank; the bottom of the hydrogenation cold separation tank is connected with a hydrogenation hot separation tank; the bottom of the hydrogenation thermal separation tank is connected with a deethanizer.
3. Isobutane production plant according to claim 1, characterized in that:
the hydrogenation separation device comprises a hydrogenation aftercooler and a hydrogenation separation tank;
the bottom of the hydrogenation reactor is connected with a hydrogenation charging and discharging heat exchanger and then sequentially connected with a hydrogenation aftercooler and a hydrogenation separation tank, the top of the hydrogenation separation tank is connected with a compressor suction tank, and the bottom of the hydrogenation separation tank is connected with a deethanizer.
4. Isobutane production plant as claimed in any one of the claims 1-3, characterized in that: the hydrogenation feeding heater is an electric heater, a steam heater or a heating furnace.
5. A process for producing isobutane with the device according to any one of claims 1 to 4, characterized in that it comprises:
and the carbon four raw material enters the device through a carbon four feeding pipeline, isobutane and normal butane are prepared after hydrogenation and separation, wherein the normal butane is subjected to isomerization reaction and separation to prepare isobutane, and a carbon three product is byproduct.
6. The process for producing isobutane according to claim 5, characterized in that it comprises:
(a) the method comprises the following steps of (1) exchanging heat of a carbon four raw material outside the boundary through a hydrogenation feeding and discharging heat exchanger, then feeding the carbon four raw material into a hydrogenation reactor to hydrogenate and saturate olefins and remove impurities;
(b) the bottom discharge of the hydrogenation reactor enters a hydrogenation separation device after passing through a hydrogenation feeding and discharging heat exchanger, the separated hydrogen returns to the hydrogenation reactor, the bottom material of the hydrogenation separation device enters a deethanizer, and the top of the deethanizer is separated by rectification to obtain carbon-II light components;
(c) the material at the bottom of the deethanizer enters a depropanizer, a carbon-three liquid phase product is separated from the top of the deethanizer, and the material at the bottom is subjected to heat exchange by a stabilizing tower feeding and discharging heat exchanger, then is combined with carbon-four after isomerization reaction, and enters the stabilizing tower;
(d) the material at the bottom of the stabilizer enters an isobutane finished product tower after heat exchange through a stabilizer feeding and discharging heat exchanger; obtaining an isobutane product from the top of the tower through rectification separation, obtaining a carbon five-component from the bottom of the tower, and extracting a mixture containing normal butane and isobutane from a side line of the tower;
(e) the mixture containing the normal butane and the isobutane enters an isomerization reactor after heat exchange through an isomerization feeding and discharging heat exchanger and an isomerization heater, isomerization reaction is carried out, and the normal butane is converted into the isobutane;
(f) the material discharged from the bottom of the isomerization reactor is subjected to heat exchange by an isomerization feeding and discharging heat exchanger and then is merged with the material at the bottom of the depropanizing tower to enter a stabilizing tower.
7. Process for the production of isobutane according to claim 6, characterized in that:
in the step (a), the raw material of the carbon four is heated to 160-300 ℃ and then enters a hydrogenation reactor.
8. Process for the production of isobutane according to claim 6, characterized in that:
in the step (b), when the hydrogenation separation device comprises a hydrogenation heat separation tank, a hydrogenation after-cooler and a hydrogenation cold separation tank, the discharge material at the bottom of the hydrogenation reactor is cooled to 50-100 ℃ through a hydrogenation feeding and discharging heat exchanger and then enters the hydrogenation heat separation tank, and the gas phase at the top of the hydrogenation heat separation tank is cooled to 20-50 ℃ through the hydrogenation after-cooler and then enters the hydrogenation cold separation tank.
9. Process for the production of isobutane according to claim 6, characterized in that:
in the step (b), when the hydrogenation separation device comprises a hydrogenation aftercooler and a hydrogenation separation tank, the material at the bottom of the hydrogenation reactor is subjected to heat exchange through a hydrogenation feeding and discharging heat exchanger, then is cooled to 20-50 ℃ through the hydrogenation aftercooler, and then enters the hydrogenation separation tank.
10. Process for the production of isobutane according to any one of the claims 6 to 9, characterized in that:
the hydrogenation reactor is a fixed bed reactor, the inlet temperature of the reactor is 160-300 ℃, the pressure is 1.5-4.5 MPaG, the reaction temperature is increased to 5-100 ℃, the molar ratio of hydrogen to oil is 0.2-5, and the liquid volume space velocity is 0.5-6 h-1；
The operating conditions of the deethanizer column include: the pressure is 1-3 MPaG, the operation temperature at the top of the tower is 20-80 ℃, the number of tower plates is 30-100, and the reflux ratio is 1-20;
the operating conditions of the depropanizer column include: the pressure is 1-3 MPaG, the operation temperature at the top of the tower is 20-80 ℃, the number of tower plates is 30-100, and the reflux ratio is 1-20;
the operating conditions of the stabilizer column include: the pressure is 1-3 MPaG, the operation temperature at the top of the tower is 20-100 ℃, the number of tower plates is 30-100, and the reflux ratio is 1-100;
the operating conditions of the isobutane finishing column include: the pressure is 0.1-1 MPaG, the operation temperature at the top of the tower is 20-70 ℃, the number of tower plates is 80-150, and the reflux ratio is 1-20;
the isomerization reactor is a fixed bed reactor, the inlet temperature of the reactor is 100-250 ℃, the pressure is 1.0-4.0 MPaG, the reaction temperature is 5-50 ℃, and the liquid volume space velocity is 1-20 h-1。
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