CN108069815A - A kind of method for preparing high-purity butane - Google Patents
A kind of method for preparing high-purity butane Download PDFInfo
- Publication number
- CN108069815A CN108069815A CN201610991238.4A CN201610991238A CN108069815A CN 108069815 A CN108069815 A CN 108069815A CN 201610991238 A CN201610991238 A CN 201610991238A CN 108069815 A CN108069815 A CN 108069815A
- Authority
- CN
- China
- Prior art keywords
- reaction
- temperature
- liquefied gas
- heat
- hydrogenation catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/888—Tungsten
Abstract
The invention discloses a kind of methods for preparing high-purity butane.Including herein below：A kind of shell and tube reactor is provided：Reactor tube side loads hydrogenation catalyst, and reactor shell side includes heat conduction carrier decane, and heat is taken for cycling；The temperature for controlling cycle decane in shell side is 205 ± 20 DEG C, and pressure is the MPa of 0.13MPa~0.21；Raw material liquefied gas and hydrogen are preheated to feeding temperature, into reactor tube side, with hydrogenation catalyst haptoreaction；Reaction effluent obtains butane product after separation and fractionation.The characteristics of present invention is much larger than sensible heat using the heat of vaporization of heat-conducting medium at the same temperature, can quickly absorbing reaction heat, and to carry out the temperature for reacting hot spot effective quantitative accurate control with this.The characteristics of reaction equilibrium constant is big at low temperature using this reaction, the present invention can produce the butane of high-purity, and product quality is stablized, and ensure the safety and steady operation of liquefied gas hydrogenation process.
Description
Technical field
The present invention relates to a kind of butylene to be hydrogenated with production technology, particularly a kind of side of butylene hydrogenation production high-purity butane
Method.
Background technology
Iso-butane is a basic chemical raw materials, its dehydrogenation can be produced isobutene；It is anti-with propylene progress cooxidation
It should can produce propylene oxide（PO）The co-production tert-butyl alcohol（TBA）Deng.
The ethylene unit in chemical plant, the coking plant of oil plant, the mixing C4 of the equal by-product of catalytic cracking unit, wherein containing
Iso-butane.The obtained iso-butane of separation is more or less containing a certain amount of alkene from mixing C4, thus also need to its into
One step hydrofinishing, just may be used as industrial chemicals afterwards.
CN1160701A describes a kind of C3The method of the hydrogenation of fraction, but this method purpose is to make C3Alkynes in fraction
Hydrocarbon selection hydrogenation, not to entire fraction（Including monoolefine）Hydrogenation.CN1145891A describes a kind of method of hydrotreating, but this
Method is only applicable to C5Cut fraction hydrogenation pentane.During using non-noble metal hydrogenation catalyst, the conversion ratio of monoolefine is relatively low.
CN01114163.8 describes a kind of method that hydrogenation of liquefied petroleum gas prepares Vehicular liquefied petroleum gas, but this method shortcoming is hydrogenation
Product index is alkene afterwards<5.0%.
CN102311760A, CN102311783A patent disclose a kind of preparing ethylene cracking material by hydrogenising liquefied petroleum gas
Method.This method is applicable in C4Cut fraction hydrogenation process, but the product index after being hydrogenated with is relatively low, and alkene contains in product after hydrogenation
It measures as ≯ 1.0%.
Iso-butane carries out cooxidation reaction with propylene can produce propylene oxide（PO）The co-production tert-butyl alcohol（TBA）, the skill
Art one of raw materials used is iso-butane, it is desirable that olefin(e) centent is less than 50 mg.m in iso-butane-3, this technical requirement height.
And conventional method of hydrotreating is used, olefin(e) centent reaches 0.1% in products obtained therefrom（That is 1000 mg.m-3）It is just quite difficult.So
Conventional method of hydrotreating is difficult to the requirement for meeting production high-purity butane.
C4Olefin hydrogenation is a balanced reaction, and when reaction temperature is low, reaction speed is too small, and technology is without practical valency
Value；When reaction temperature is high, reaction speed increases, but at this time the equilibrium constant but it is too small.Since the reaction under high temperature is put down
The limitation of weighing apparatus so that alkene content is higher in product after hydrogenation, is the C that impossible obtain high-purity4Alkane；In addition this is anti-in addition
Should or a strong exothermal reaction, this this factor cause to react effective use temperature range relatively narrow.It it can be seen that will reaction temperature
It is the difficult point for realizing the technology that how degree, which is controlled within an effective use scope,.Also just because of above-mentioned reason, to current
Until, without ripe Hydrogenation for the method for high-purity butane.
In the prior art, in order to improve the effect of hydrogenation of liquefied petroleum gas, it has to be hydrogenated at higher temperatures
Reaction.Since olefin hydrogenation heat release is violent, improves reaction temperature and be very easy to cause to react overtemperature, once control is bad,
Irreversible damage in performance will be brought to catalyst.Therefore, in the prior art for production high-purity（It is different）Butane is simultaneously
There is no good method.
The content of the invention
In view of the deficiencies of the prior art, the present invention is innovated in terms of production technology, provides a kind of production high purity butylene
The method of alkane.This method can make reaction temperature control stabilization and overtemperature, process units do not operate steadily, and product quality is stablized.
Present inventor, by C4Fraction（Liquefied gas）Hydrogenation reaction carries out system experimentation and further investigation, obtains
Obtain following experimental studies results and understanding：
（1）The characteristics of raw material liquefied gas：One is sulfur content is higher, content 0.02%；The second is alkenes content is 5.212%.
1 liquefied gas of table forms
| Sequence number | Component | Composition, wt% |
| 1 | Methane | 0.113 |
| 2 | Ethane | 0.356 |
| 3 | Propane | 9.674 |
| 4 | 1- butylene | 3.652 |
| 5 | Isobutene | 1.267 |
| 6 | Cis-2-butene | 0.042 |
| 7 | Trans-2-butene | 0.251 |
| 8 | Normal butane | 24.523 |
| 9 | Iso-butane | 58.998 |
| 10 | Isopentane | 1.104 |
| 11 | Sulfur content | 0.02 |
| It is total | 100 | |
| Alkene subtotal | 5.212 |
（2）Reaction characteristics：Olefin hydrogenation is a strong exothermal reaction；Using liquefied gas in table 1 as raw material be hydrogenated with anti-
Should, reaction heat when by its whole hydrogenation of olefins is 26.13KJ/mol；Adiabatic reaction Wen Sheng is up to 29 DEG C.
（3）Dynamics research result：This reaction is a fast reaction, thus in reaction bed heat release is non-homogeneous
's.When passing through catalyst bed reaction, at the 1/3 of entire residence time, exothermic heat of reaction amount has just reached reaction time
To 80% or so of entire reaction heat.Therefore cause in reaction bed entrance away from there are one " thermometer bulb " or having been said at entrance 1/3
One hot spot can only also reduce thermometer bulb, and effect even if the conventional mutil-stage adiabatic reactor of selection or shell and tube reactor
Less significantly.
In addition Reaction kinetics research result is also shown that excessive amounts of hydrogen（Hydrogen/volume of liquefied gas is than excessive）, can improve
The rate of gasification of liquefied gas can also improve the linear velocity of reaction feed, so excessive amounts of hydrogen is unfavorable to this reaction.
（4）Thermodynamic study result：As can be known from Table 1, it is isobutene that contained C4 alkene is highest in liquefied gas, to this
Reaction equilibrium constant calculating is carried out, result of calculation is listed in table 2.
2 reaction temperature of table and equilibrium constant relation
| Sequence number | Reaction temperature/DEG C | Reaction equilibrium constant/K |
| 1 | 160 | 1.96E+10 |
| 2 | 170 | 9.43E+09 |
| 3 | 180 | 4.67E+09 |
| 4 | 190 | 2.38E+09 |
| 5 | 200 | 1.25E+09 |
| 6 | 210 | 6.73E+08 |
| 7 | 220 | 3.71E+08 |
| 8 | 230 | 2.10E+08 |
| 9 | 240 | 1.21E+08 |
| 10 | 250 | 7.14E+07 |
| 11 | 260 | 4.29E+07 |
| 12 | 270 | 2.62E+07 |
| 13 | 280 | 1.63E+07 |
| 14 | 290 | 1.03E+07 |
| 15 | 300 | 6.65E+06 |
| 16 | 310 | 4.34E+06 |
| 17 | 320 | 2.88E+06 |
| 18 | 330 | 1.93E+06 |
| 19 | 340 | 1.31E+06 |
From data in table 2, with the rise of reaction temperature, the equilibrium constant quickly reduces therewith.For example, reaction temperature from
210 DEG C, 220 DEG C are increased to, temperature only improves 10 DEG C, and the equilibrium constant but has dropped nearly 50%.
Within the temperature range of calculating, the Δ G θ m of olefin hydrogenation are respectively less than 0, i.e., under corresponding temperature conditionss,
Olefin hydrogenation can spontaneous progress；The K θ eq values respectively reacted are very big, show that reaction is easy to carry out, and
With the rise of temperature, K θ eq reduce therewith, also illustrate that the rise of reaction temperature is unfavorable for the progress of each reaction.
An important factor for temperature is influence low-carbon alkene hydrogenation reaction, when subsequent olefin hydrogenation condition selects,
First, to improve reaction pressure, reaction temperature is reduced, to reduce influence of the temperature to reaction balance；Second, by reaction temperature
It controls as far as possible within an effective use scope, olefin hydrogenation is made with this to reach certain depth.
In terms of thermodynamics, low temperature reacts favourable to this, if reaction temperature is relatively low, although reaction is flat
The constant that weighs is larger, but reaction speed is slower；, whereas if reaction temperature is higher, although reaction speed is larger, reaction is flat
The constant that weighs is smaller.And the product purity that this is reacted after requiring hydrogenation is higher（Product index is less than 50 mg.m-3）, so right
For this reacts, if the diffusion of reaction heat cannot control well（Reaction temperature rising cannot be controlled effectively in other words）, just
Reaction controlling can be switched to balance controlled, make the conversion ratio of reaction reduce.
（5）Reaction process condition investigates result：Will this reaction in we have selected FH-10B catalyst, which is
The low-carbon alkene Hydrobon catalyst of the high activity of the newest development and production of Fushun Petrochemical Research Institute, physical property are listed in table 3
In.
The physicochemical property of 3 LH-10B catalyst of table
| Detection project | Quality index | Analysis method |
| Active metal | W-Mo-Co | Colorimetric method |
| Tenor, wt% | 15~23 | |
| Pore volume/(mLg-1) | ≮0.42 | Nitrogen absorption under low temperature |
| Specific surface area/(m2·g-1) | ≮220 | Nitrogen absorption under low temperature |
| Side pressure strength/(Ncm-1) | ≮150 | Gradual intensity meter |
| Shape | Trifolium-shaped | Range estimation |
| Bulk density/(gmL-1) | 0.75~0.85 | Graduated cylinder method |
We investigate reaction condition after catalyst determines, combined reaction condition investigates experiment and heating power is ground
The result studied carefully has obtained being suitable for the reaction condition of this reaction and the results are shown in Table 4.
4 reaction condition of table and result
| Reaction condition | |
| Reaction pressure/MPa | 8.0 |
| Liquefied gas feed volume air speed/h-1 | 0.2~1.5 |
| Hydrogen/liquefied gas, v/v | 200~300 |
| Inlet temperature/DEG C | 180~190 |
| Bed maximum temperature point（Hot spot）/℃ | ≯210 |
| Average reaction temperature/DEG C | 140~340 |
| Reaction result | |
| Olefin(e) centent in reaction product, mg.m-3 | ≯50 |
Above-mentioned result of study is to our enlightenment：
（1）It should be high pressure low temperature under suitable reaction condition.With raising reaction pressure, the method for reducing reaction temperature, to use up
Amount reduces influence of the temperature to reaction balance.
（2）The product purity reacted because of this after requirement hydrogenation is higher（Product index is less than 50ppm）, so in pressure
After selection, reaction temperature control is exactly main control condition, i.e. the taking-up problem of reaction heat be one to be solved it is main
Problem.
（3）Reduce " thermometer bulb " of reaction bed, it is possible to improve reaction equilibrium constant, improve conversion ratio.
Based on above-mentioned discovery, present inventor proposes a kind of method of liquefied gas Hydrogenation for high-purity butane,
Including herein below：
（1）A kind of shell and tube reactor is provided：Reactor tube side loads hydrogenation catalyst, and reactor shell side includes the heat conduction carrier last of the ten Heavenly stems
Alkane takes heat for cycling；The temperature for controlling cycle decane in shell side is 205 ± 20 DEG C, and pressure is the MPa of 0.13MPa~0.21；
（2）Raw material liquefied gas is preheated to feeding temperature with hydrogen, into reactor tube side, is contacted with hydrogenation catalyst instead
It should；Reaction effluent obtains butane product after separation and fractionation.
Step of the present invention（1）In, the shell and tube reactor is the conventional reactor of the art.It generally includes pipe
Journey and shell side.The pressure of control loop decane is the MPa of 0.13MPa~0.21.Wherein, the purity of heat-conducting medium decane generally will
Ask more than 90wt%, preferably more than 95wt%.
In the present invention, when pressure is set as 0.207MP, decane is liquid phase when temperature is less than 205 DEG C of gasification temperature；Temperature
Decane is vapour phase during higher than 205 DEG C of gasification temperature.And under set pressure limit and circulating temperature, the present invention is selected
Heat conduction carrier decane, under the conditions of reaction tube internal catalyst bed layer is well-defined reaction temp（It reacts hot spot and is less than 195 DEG C）For liquid
Body, the interior reaction heat released of reaction tube, passes through shell（Journey）The heat carrier for cycling takes out, and what is utilized at this time is thermal cyclic carrier
Sensible heat（Sensible heat of the decane at 195 DEG C is 0.403KJ/mol, and sensible heat at 205 DEG C is 0.411KJ/mol）.When in reaction tube
Catalyst bed is in overtemperature（A certain section of catalyst bed or hot localised points overtemperature, more than or equal to 205 DEG C）When, and temperature at this time
Degree is right up to the vapourizing temperature of reactor shell decane, and then the decane fast vaporizing in shell, becomes steam by liquid,
It is the latent heat using heat carrier decane to take thermal process at this time.
The present invention produces the further investigation of butane technical process by being hydrogenated with to liquefied gas, it is proposed that above-mentioned technical proposal.
The method of the present invention has the characteristics that：（1）Thermal process is taken to be more than the principle of sensible heat using the latent heat of same substance, is quickly inhaled
Reaction heat is received, makes the hot spot of its elimination reaction bed as early as possible.Because sensible heat of the decane at 205 DEG C is 0.411KJ/mol, vaporization
For heat for 39.397 KJ/mol, heat of vaporization at this temperature is 88.55 times of sensible heat.（2）Utilize a kind of vapourizing temperature of substance
The characteristics of being under a certain pressure certain, once reaching its vapourizing temperature can vaporize, the temperature to reacting hot spot was carried out with this
Carry out effective quantitative control.（3）Gas after vaporization is condensed, cooling Posterior circle uses.
The preheating temperature of hydrogen, liquefied gas described in the method for the present invention is generally 140 DEG C~240 DEG C, is preferably 180 DEG C
~190 DEG C；The maximum temperature point of tube side internal catalyst bed layer（That is hot spot）It is general 190 DEG C~240 DEG C reachable, it is preferably 200 DEG C
~210 DEG C；Reaction pressure is generally 4 MPa~10MPa, is preferably 7 MPa~9MPa；Hydrogen/volume of liquefied gas ratio for 200~
1000, it is preferably 200~300；Liquefied gas is fed（Liquid）Volume space velocity is 0.3~2.0 h-1, it is preferably 0.6~0.8 h-1。
Hydrogenation catalyst used in the method for the present invention can select conventional hydrogenation catalyst in the art.
The hydrogenation catalyst can be load hydrogenation catalyst or body phase hydrogenation catalyst.Load hydrogenation catalyst includes carrying
Body and the active metal component of load.The carrier is generally porous refractory inorganic oxide or activated carbon.Specifically, carrier
It is generally selected from Al2O3, containing SiO2Al2O3、TiO2, Al containing molecular sieve2O3With activated carbon form one group of substance in one kind or
It is several.Active metal component is selected from noble metal or base metal.Noble metal generally includes the one or more of Pt, Pd and Re, non-
Noble metal is generally selected from one or more of W, Mo, Ni and Co.In the present invention, base metal preferably includes W and/or Ni.With
Metal oxide meter, the content of noble metal are generally 0.1~2.0 wt%；The content of non-noble metal components is generally 5 wt%~35
wt%。
Body phase hydrogenation catalyst contains tri- kinds of metal components of Mo, W, Ni, and wherein W, Ni exists in the form of composite oxides：
NixWyOz, z=x+3y, Mo exist with oxide form：MoO3.Composite oxides NixWyOzRatio (the atomic molar of middle x and y
Than) it is 1: 8~8: 1, it is preferably 1: 4~4: 1.Composite oxides NixWyOzWith oxide M oO3Weight ratio be 1: 10~10:
1, it is preferably 1: 5~5: 1.Composite oxides Ni in bulk phase catalystxWyOzWith oxide M oO3Total weight content for 40%~
100%, it is preferably 50%~80%.（Composition when above-mentioned catalyst composition is oxidation state, catalyst are needed when in use by this field
Method known to technical staff carries out vulcanizing treatment）.
Compared with prior art, method of the invention has technique effect following prominent：
1st, using vulcanization type catalyst, solves in raw material Determination of Trace Sulfur to conventional precious metal catalyst in hydrogenation process
Intoxication, both reduced the use cost of catalyst, and also extended the cycle of operation of catalyst.
2nd, the vaporization using heat-conducting medium decane at the same temperature（Phase transformation）Heat is much larger than the characteristics of sensible heat, can be quick
Absorbing reaction heat, the hot spot of elimination reaction bed, has ensured the safety and steady operation of liquefied gas hydrogenation process as early as possible.
3rd, the characteristics of being under a certain pressure certain using the vapourizing temperature of heat-conducting medium decane, once reach its vaporization
Temperature can fast vaporizing, come to carry out effective quantitative accurate control to the temperature for reacting hot spot with this.
4th, the heat of vaporization of heat-conducting medium decane is made full use of, to make reaction bed temperature-controllable, not overtemperature, so as to fulfill adding
Hydrogen reacts quiet run at a lower temperature, and then reacts the characteristics of reaction equilibrium constant is big at low temperature using this, realizes
The butane of high-purity is produced, and product quality is stablized.
Description of the drawings
Fig. 1 is the process flow diagram of liquefied gas hydrogenation production high-purity butane.
Wherein：1- hydrogen, 2- hydrogen feed heaters, 3- liquefied gas, 4- liquefied gas feed heaters, the reaction of 5- tubulations
Device, 6- reactor shell circulating liquid liquid levels, 7- reactor tube side catalyst beds, 8- reactor shells gas phase extraction mouth, 9-
Reactor shell liquid phase produces mouth, 10- reactor shells gas phase extraction material condenser, 11- condensation liquid storage tanks, 12- reactors
Shell gas phase produces line；13- condensate liquids produce line, 14- reactor shell circulation fluid basins, and 15- reactor shell circulation fluids are adopted
Outlet, 16- reactor shell circulation fluid coolers, 17- reactor shell circulation fluids basin extraction line, 18- recycle liquid pumps, 19-
Circulation fluid entrance, 20- reactors extraction line.
Specific embodiment
The method of the present invention is described in more detail below in conjunction with attached drawing.
As shown in Figure 1, the technological process of the method for the present invention includes：
（1）Raw material heats
Reaction raw materials hydrogen 1, liquefied gas 2 are heated to a constant temperature through hydrogen feed heater 3 and liquefied gas feed heater 4 respectively
It is entered after degree in shell-and-tube reactor 5.
（2）It carries out hydrogenation reaction and takes heat
Hydrogen 1, liquefied gas 2 are entered in shell-and-tube reactor 5, are contacted and are reacted with hydrogenation catalyst, and release reaction heat；Instead
Device shell is answered to be heat conduction carrier, heat is taken for cycling equipped with decane.
Reactor shell Xun Huan decane temperature is generally set in 190 DEG C, and pressure is set in 0.207MPa, in this pressure
Under, when temperature is less than 205 DEG C, decane is liquid phase, and decane is vapour phase during higher than 205 DEG C.Selected heat conduction carrier, in reaction tube
Internal catalyst bed layer is under the conditions of well-defined reaction temp（Hot spot is less than 195 DEG C）For liquid, the interior reaction heat released of reaction tube is used
The heat carrier of shell Xun Huan takes out, and what is utilized at this time is the sensible heat of thermal cyclic carrier.When reaction tube internal catalyst bed layer is in super
Temperature（A certain section of catalyst bed or hot localised points overtemperature, more than 205 DEG C）When, and temperature at this time is right up to reactor shell
The vapourizing temperature of decane, then the decane fast vaporizing in shell, becomes steam by liquid, and it is to utilize heat to take thermal process at this time
The latent heat of carrier.The temperature of the vaporization thermal control reaction bed of Selection utilization decane be because：1）The latent heat of same substance is big
More than sensible heat, can quick absorbing reaction heat, make the hot spot of its elimination reaction bed as early as possible.2）Utilize a kind of vaporization temperature of substance
Once reaching its vapourizing temperature can vaporize, the temperature to reacting hot spot is carried out with this for the characteristics of degree is under a certain pressure certain
Degree carries out effective quantitative control.
The method of the present invention is described in further detail below by specific embodiment.
Comparative example 1-2
Using LH-10B catalyst, reaction raw materials are the raw material in table 1, the same Fig. 1 of reaction process flow, shell and tube reactor, only
Be the shell heat medium in shell and tube reactor for conduction oil, the technical specification of conduction oil is shown in Table 5, comparative example 1,2 it is anti-
It answers and is shown in Table 6 under condition and result.
5 Great Wall L-QB300 conduction oil technical specifications of table
| Project name | |
| Initial boiling point/DEG C | 348 |
| Flash-point/DEG C | 226 |
| Boiling range, DEG C | |
| HK/2%/97% | 348/376/473 |
| Pour point/DEG C | -12 |
| Corrosion | 1 |
| Density, kg/m3 | 868.5 |
| Appearance | Transparent, no suspended substance and precipitation |
| Deterioration rate, %（M/m) it is not more than | 5.5 |
Note：1st, L-QB300 conduction oils in Great Wall select refined narrow fraction mineral base oil, add in peace and quiet, scattered, anti-high oxidation etc.
Multiple additives refine；2nd, L-QB300 conduction oils in Great Wall are suitable for the pressure or optional that maximum temperature is no more than 300 DEG C
The enclosed heat transfer system for cycling；3rd, technical specification, product meet following specification：SH / T0677-1999；4th, application range is long
City L-QB300 conduction oils are suitable for forcing or the enclosed heat transfer system of optional cycling, available for heating, the processes such as drying, such as
The industries such as timber processing, textile dyeing and finishing, food processing, chemical industry.
6 reaction condition of table and result
| Comparative example 1 | Comparative example 2 | |
| Reaction condition | ||
| Reaction pressure/MPa | 8.0 | 9.0 |
| Liquefied gas feed volume air speed/h-1 | 0.6 | 0.6 |
| Hydrogen/liquefied gas, v/v | 300 | 200 |
| Reaction inlet temperature/DEG C | 185 | 195 |
| Bed Wen Sheng/DEG C | 27 | 28 |
| Bed maximum temperature point（Hot spot）/℃ | 212 | 228 |
| Average reaction temperature/DEG C | 198.5 | 214 |
| Reaction result | ||
| Olefin(e) centent in reaction product, mg.m-3 | 200 | 320 |
Note：1st, it is L-QB300 conduction oils in reactor shell, pressure 1.0MPa；2nd, reaction product analysis sample is gas phase.
From the data in table 6, using conventional conduction oil come controlling reaction temperature, the alkene in product after being hydrogenated with
Content is significantly larger than 50mg.m-3, the requirement of high-purity butane technology is not achieved.
Embodiment 1-3
Reaction is using LH-10B catalyst, and reaction raw materials are the raw material in table 1, the same Fig. 1 of reaction process flow, tubular reaction
Device is decane in the shell heat-conducting medium of shell and tube reactor（Purity 98wt%）, under the reaction condition and result of embodiment 1 ~ 3
It is shown in Table 7.
7 liquefied gas hydrogenation reactor prevailing operating conditions of table and result
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Reaction condition | |||
| Reactor pressure/MPa | 7.0 | 8.0 | 9.0 |
| React hydrogen/oil mol ratio | 300 | 200 | 350 |
| Volume of liquefied gas air speed/the h not being hydrogenated with-1 | 0.6 | 0.7 | 0.8 |
| Reactor inlet temperature/DEG C | 180 | 185 | 190 |
| Reactor hot(test)-spot temperature/DEG C | 184 | 190 | 194 |
| Reactor Wen Sheng/DEG C | 4 | 5 | 4 |
| Average reaction temperature/DEG C | 182 | 187.5 | 192 |
| Reactor shell control temperature/DEG C | 180 | 185 | 190 |
| Reactor shell control pressure/MPa | 0.15 | 0.17 | 0.20 |
| Reaction result | |||
| Olefin(e) centent in reaction product, mg.m-3 | 42 | 36 | 34 |
Note：1st, reaction product analysis sample is gas phase.
From the data in table 7, when the shell heat-conducting medium of shell and tube reactor is decane, reaction bed temperature compared with
Uniformly, bed Wen Sheng is smaller, and reaction bed not overtemperature, illustrates that the reaction temperature control program of the present invention reacts this item
The control of temperature is rationally effective, and the alkene content in product after hydrogenation is respectively less than 501.0mg.m-3, reached high-purity
The technology requirement of butane.
Claims (11)
1. a kind of liquefied gas Hydrogenation is for the method for high-purity butane, including herein below：
（1）A kind of shell and tube reactor is provided：Reactor tube side loads hydrogenation catalyst, and reactor shell side includes the heat conduction carrier last of the ten Heavenly stems
Alkane takes heat for cycling；The temperature for controlling cycle decane in shell side is 205 ± 20 DEG C, and pressure is the MPa of 0.13MPa~0.21；
（2）Raw material liquefied gas is preheated to feeding temperature with hydrogen, into reactor tube side, is contacted with hydrogenation catalyst instead
It should；Reaction effluent obtains butane product after separation and fractionation.
2. according to the method for claim 1, which is characterized in that the preheating temperature of liquefied gas and hydrogen is 140 DEG C~240
℃。
3. according to the method for claim 2, which is characterized in that the preheating temperature of liquefied gas and hydrogen is 180 DEG C~190
℃。
4. according to the method for claim 1, which is characterized in that step（2）The condition of the reaction is：Reaction pressure is 4
MPa~10MPa, hydrogen/volume of liquefied gas ratio are 200~1000, and liquefied gas feed volume air speed is 0.3~2.0 h-1。
5. according to the method for claim 4, which is characterized in that step（2）The condition of the reaction is：Reaction pressure is 7
MPa~9MPa, hydrogen/volume of liquefied gas ratio are 200~300, and liquefied gas feed volume air speed is 0.6~0.8 h-1。
6. according to the method for claim 1, which is characterized in that the hydrogenation catalyst for load hydrogenation catalyst or
Body phase hydrogenation catalyst.
7. according to the method for claim 6, which is characterized in that the load hydrogenation catalyst includes carrier and load
Active metal component, the carrier be selected from Al2O3, containing SiO2Al2O3、TiO2, Al containing molecular sieve2O3It is formed with activated carbon
One or more of one group of substance, active metal component is selected from noble metal or base metal, and noble metal includes Pt, Pd and Re
One or more, base metal is selected from one or more of W, Mo, Ni and Co.
8. according to the method for claim 7, which is characterized in that on the basis of the weight of catalyst, the content of noble metal is
0.1~2.0 wt%；Base metal is using the content that metal oxide is counted as the wt% of 5 wt%~35.
9. according to the method for claim 6, which is characterized in that the body phase hydrogenation catalyst contains tri- kinds of Mo, W, Ni
Metal component, wherein W, Ni exist in the form of composite oxides：NixWyOz, there are MoO with oxide form by z=x+3y, Mo3；
Composite oxides NixWyOzThe atomic molar ratio of middle x and y is 1: 8~8: 1, composite oxides NixWyOzWith oxide M oO3Weight
Amount is than being 1: 10~10: 1；Composite oxides Ni in body phase hydrogenation catalystxWyOzWith oxide M oO3Total weight content be
40%~100%.
10. according to the method for claim 9, which is characterized in that composite oxides NixWyOzThe atomic molar ratio of middle x and y
For 1: 4~4: 1；Composite oxides NixWyOzWith oxide M oO3Weight ratio be 1: 5~5: 1；It is multiple in body phase hydrogenation catalyst
Close oxide NixWyOzWith oxide M oO3Total weight content be 50%~80%.
11. according to the method for claim 1, which is characterized in that the purity of the heat-conducting medium decane is more than 90wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610991238.4A CN108069815B (en) | 2016-11-11 | 2016-11-11 | Method for preparing high-purity butane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610991238.4A CN108069815B (en) | 2016-11-11 | 2016-11-11 | Method for preparing high-purity butane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108069815A true CN108069815A (en) | 2018-05-25 |
| CN108069815B CN108069815B (en) | 2020-10-16 |
Family
ID=62154749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610991238.4A Active CN108069815B (en) | 2016-11-11 | 2016-11-11 | Method for preparing high-purity butane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108069815B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3918041A4 (en) * | 2019-01-29 | 2023-05-10 | Lanzatech, Inc. | Production of bio-based liquefied petroleum gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081998A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Hydrogenation method for C4 distillation cut |
| CN101113126A (en) * | 2006-07-26 | 2008-01-30 | 李莉 | Olefin-containing lighter hydrocarbons catalytic hydrogenation method |
| CN102311783A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Liquefied petroleum gas-coke gasoline hydrogenation combined process method |
| CN102452879A (en) * | 2010-10-14 | 2012-05-16 | 中国石油化工股份有限公司 | Method for producing ethylene cracking material through hydrogenation of liquefied petroleum gas |
-
2016
- 2016-11-11 CN CN201610991238.4A patent/CN108069815B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081998A (en) * | 2006-05-31 | 2007-12-05 | 中国石油化工股份有限公司 | Hydrogenation method for C4 distillation cut |
| CN101113126A (en) * | 2006-07-26 | 2008-01-30 | 李莉 | Olefin-containing lighter hydrocarbons catalytic hydrogenation method |
| CN102311783A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Liquefied petroleum gas-coke gasoline hydrogenation combined process method |
| CN102452879A (en) * | 2010-10-14 | 2012-05-16 | 中国石油化工股份有限公司 | Method for producing ethylene cracking material through hydrogenation of liquefied petroleum gas |
Non-Patent Citations (3)
| Title |
|---|
| 方向晨等: "《液化气加氢反应动力学研究》", 《石油化工》 * |
| 肖建良等: "《列管式反应器温度控制方法》", 《广州化工》 * |
| 艾抚宾等: "液化气加氢热力学的研究》", 《石油化工高等学校学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3918041A4 (en) * | 2019-01-29 | 2023-05-10 | Lanzatech, Inc. | Production of bio-based liquefied petroleum gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108069815B (en) | 2020-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ying et al. | Kinetic modeling of C2–C7 olefins interconversion over ZSM-5 catalyst | |
| Maia et al. | Isobutane and n-butane cracking on Ni-ZSM-5 catalyst: Effect on light olefin formation | |
| Pachulski et al. | Kinetics and reactor modeling of a Pd-Ag/Al2O3 catalyst during selective hydrogenation of ethyne | |
| Banzaraktsaeva et al. | Ethanol-to-ethylene dehydration on acid-modified ring-shaped alumina catalyst in a tubular reactor | |
| CN103908931B (en) | A kind of liquefied gas through aromatization prepares fluidized bed reaction and the using method of aromatic hydrocarbons | |
| Wu et al. | ZSM-5 crystals grown on the wall of a long tubular reactor as a structured catalyst for cracking of endothermic fuels | |
| JP2017521242A (en) | Improved homogeneous catalytic reactor system | |
| Savost’yanov et al. | Enhancement of the Fischer–Tropsch process for producing long-chain hydrocarbons on a cobalt–alumina–silica gel catalyst | |
| CN108069815A (en) | A kind of method for preparing high-purity butane | |
| CN102443430A (en) | Method for preparing ethylene cracking material by hydrogenising liquefied petroleum gas | |
| Liu et al. | Synthesis of 1, 3-butadiene from ethanol/acetaldehyde over ZrO2-MgO-SiO2 catalyst: The thermodynamics and reaction kinetics analysis | |
| CN106187662A (en) | A kind of fixed bed system of Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane | |
| TW201002422A (en) | Fluidized bed reactor and gas-phase exothermic reaction method with the same | |
| Ouni et al. | Isobutene dimerisation in a miniplant-scale reactor | |
| CN104549321B (en) | Catalyst for dehydrogenation of low-carbon paraffin and application thereof | |
| CN106883091A (en) | A kind of method by 4- methyl -3- hexamethylene cyclohexene carboxaldehyde selectivity synthesis paraxylene | |
| Banzaraktsaeva et al. | Catalytic dehydration of ethanol into ethylene in a tubular reactor of the pilot installation on alumina catalysts with varied grain size | |
| CN106883089B (en) | A kind of method of 4- methyl -3- cyclohexene formaldehyde synthesis toluene | |
| Derevich et al. | Heat and mass transfer in Fischer–Tropsch catalytic granule with localized cobalt microparticles | |
| Liu et al. | Aromatization of methane by using propane as co-reactant over cobalt and zinc-impregnated HZSM-5 catalysts | |
| Tong et al. | Kinetic studies on the dimerization of isobutene with Ni/Al2O3 as a catalyst for reactive distillation process | |
| Hammond et al. | Performance comparison of WO3/SiO2 to ZSM-5 and γ-Al2O3 in the catalytic dehydration of methanol | |
| CN107721791A (en) | The preparation system and preparation method of a kind of preparing propylene from methanol | |
| CN109529811A (en) | Alumina support, salic carried catalyst preparation method and catalyst application | |
| Liu et al. | Analysis of thermodynamic equilibrium yield and process simulation for catalytic pyrolysis of light hydrocarbons based on one set of independent reactions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |