CN104892339B - A kind of method that normal butane is prepared by iso-butane - Google Patents
A kind of method that normal butane is prepared by iso-butane Download PDFInfo
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Abstract
The present invention relates to a kind of method preparing normal butane by iso-butane, it comprises the steps of：A., feed stream a including at least mass percent 80% iso-butane is provided；B. feed stream a is fed at least one positive structure region, and make iso-butane positive structureization reaction occur, thus obtaining product gas flow b under catalyst action；C. product gas flow b is fed at least one hydrogenation zone of saturation and carry out hydrogenation catalyst reaction, obtain air-flow c；D. condensation separation air-flow c at 0 40 DEG C, obtains gas phase stream d1 and liquid phase stream d2；E. liquid phase stream d2 is fed the first distillation zone and separate the product stream e2 that the low boiling secondary component formation in liquid phase stream d2 comprises iso-butane and normal butane further；F. stream e2 is fed after-fractionating region, separate iso-butane and normal butane forms normal butane stream.Its method of the present invention is totally simply controlled, high conversion rate, and yield is high, and economic benefit is more preferable.
Description
Technical field
The present invention relates to a kind of method preparing normal butane, specially using metallic catalyst, positive for iso-butane structure is just turned to
The production method of butane.
Background technology
Normal butane is a kind of important Organic Chemicals, is mainly used in the preparation of maleic anhydride.Additionally, also can be through
Dehydrogenation butylene and butadiene；Extract acetic acid, acetaldehyde etc. through catalysis oxidation；Through halogenation butyl halide；Through nitrifying nitro fourth processed
Alkane.
At present, the production method of normal butane, typically with refinery's C-4-fraction as raw material, obtains normal butane using partition method.As
CN102690158A proposes a kind of component from refinery C four and separates the method obtaining high-purity normal butane, will be pretreated
Refinery C four component raw material hydrocarbon sends into extraction tower, water scrubber, using the mixed solution of acetonitrile and water as extractant, by raw material hydrocarbon
Alkene remove, obtain butane；Then butane enters deisobutanizer, removes iso-butane light component, obtains thick
Normal butane；Finally normal butane treating column sent into by thick normal butane, to remove heavy constituent, obtains highly purified normal butane.University Of Yantai
Patent CN102603454A propose a kind of whole method adding extractant separation iso-butane, normal butane and butylene, extraction
Agent can be using the mixed solvent of butanone and n-formylmorpholine, and from unlike patent CN102690158A, the method is being pressed
Extractant as under " light, weight " order separately obtain iso-butane, normal butane and butylene successively.This method is due to adding extraction
Agent, the separating degree between each component of C4 increases, but the whole of extractant adds the equipment that also results in increase, and operating cost increase etc. is asked
Topic.Patent 102351626A of TH Gases Co., Ltd. proposes the side that a kind of employing adsorbing separation purifies normal butane
Method, the method, to mix carbon four as raw material, is adsorbed using three steps, and adsorbent is respectively CaA, 13X molecular sieve, silica gel and 5A molecule
Sieve, is respectively used to except alkene, except iso-butane, normal butane refine, after process, highly purified normal butane is adsorbed staying absorption phase
Interior, then molecular sieve is heated or be aided with nitrogen purging, so that normal butane is desorbed, collect desorption gas and can obtain high-purity normal butane
Product, product purity is 99.5 ~ 99.8%.The said firm has also been proposed and a kind of combines purification normal butane using absorption-rectification afterwards
Method, few for volume of production, the higher normal butane of purity requirement produces.The core of both approaches is all adsorbing separation, energy
Obtain highly purified normal butane, but adsorbent cost is high, production procedure is complicated, is not suitable for large-scale production normal butane.
The method of above method and some other patent domestic offer is is divided using physics from mixing carbon packet point
Produce normal butane from method, its shortcoming is to be inevitably generated a large amount of side-product iso-butanes, butylene etc., and this will be significantly greatly increased
The storage of enterprise, cost of transportation, have a strong impact on the overall economic efficiency of enterprise.Liaoning is with the patent of benefit petrochemical industry company limited
CN203269811U propose a kind of with carbon four as raw material, overlap under conditions of non-hydrogen, dehydrocyclization, aromatization, cyclisation
The a series of complex reaction such as dehydrogenation, produces light aromatic hydrocarbons and heavy aromatics, the method for by-product normal butane simultaneously, but the emphasis of this method is not
It is normal butane product, the aromatic hydrocarbons gasifying device building bulky complex in order to produce normal butane is not appropriate under supporting normal butane
Trip device.United States Patent (USP) US4191845 provides a kind of method by unsaturated C_4 hydrocarbon Hydrogenation normal butane, first enters raw material
Row hydrogenation, be then peeled off obtaining normal butane, iso-butane then on the metallic catalyst of traditional platinum or palladium in 238 DEG C, 2.0MPa
Lower reaction generates normal butane.This method solve above-mentioned by-product iso-butane problem, but the method is under lower temperature and pressure
Operation, relatively low reaction temperature makes the conversion ratio of iso-butane low, and only 30%, which results in substantial amounts of iso-butane circulation, increased
Energy consumption, and relatively low reaction pressure makes product separate increase with hydrogen, increased the loss of butane, additionally,
If it is desired that reaction is carried out at higher temperatures and pressures it is necessary to adopt the more preferable catalyst of performance；In addition, the method generates
Normal butane purity be only 95mol%, be mainly used in refining art, cracking increasing output of ethylene and propylene, this normal butane is had no idea
The production meeting the normal butane downstream chemical product such as maleic anhydride, butylene, butadiene, acetic acid, butyl halide, nitrobutane is former
Material needs；Furthermore, the method is economically inappropriate using the higher C 4 olefin of added value as raw material production normal butane.
The concrete meaning that in the present invention, positive structure is related to is：
Positive structure：Refer to change the structure of isoparaffin and do not change its elementary composition and molecular weight, it is converted into positive structure
The process of alkane.
Content of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, provides a kind of iso-butane positive structure
The method that normal butane is prepared in change, the method income height, high conversion rate, does not have by-product.
For achieving the above object, the concrete scheme of the present invention is：
A kind of method preparing normal butane by iso-butane, it comprises the following steps：
A) feed stream a including at least mass percent 80% iso-butane is provided；
B) feed stream a is fed at least one positive structure region, and make iso-butane that positive structure occurs under catalyst action
Change reaction, thus obtaining comprising iso-butane, normal butane, methane, ethane, propane, propylene, isobutene., 1-butylene, 2-butylene, hydrogen
Product gas flow b of gas；
C) product gas flow b is fed at least one hydrogenation zone of saturation and carry out hydrogenation catalyst reaction, make isobutene., 1- fourth
Alkene, 2-butylene, propene are thus obtain the air-flow c comprising iso-butane, normal butane, methane, ethane, propane and hydrogen；
D) condensation separation air-flow c at 0-40 DEG C, obtains comprising the low boiling secondary component such as hydrogen, methane, ethane, propane
Gas phase stream d1 and comprise liquid phase stream d2 of methane, ethane, propane, normal butane, iso-butane；
E) liquid phase stream d2 being fed the first distillation zone, to separate methane in liquid phase stream d2, ethane, propane etc. further low
Boiling point secondary component simultaneously forms the product stream e1 comprising methane, ethane, propane and iso-butane and comprises iso-butane and normal butane
Product stream e2；
F) stream e2 is fed after-fractionating region, separate iso-butane and normal butane and formed and comprise iso-butane stream f1 and just
The circulation of iso-butane stream f1 is fed back to positive structure region by butane stream f2 simultaneously.
Step B of the present invention）Described in positive structureization react in condition specific as follows and carry out：1st, in positive structure region, just
Structureization reaction is carried out under limited amount hydrogen existence condition, to reduce the coking rate of catalyst, is simultaneously used for equilibrium reaction
Device catalyst bed in the layer temperature；The mol ratio of iso-butane content in the hydrogen total content providing in the present invention and feed stream a
For 1-3：1, preferably 1.2-2：1.The presentation mode of wherein hydrogen can be less than 20 % for pure hydrogen or containing light paraffins（Mole
Percentage ratio）Mixing hydrogen stream；2nd, in positive structure region, in 200 DEG C -700 DEG C of temperature, operating pressure is 2-5MPa for its reaction
Hydro condition under carry out；3rd, the catalyst used in the present invention positive structure region comprises carrier and live body component, wherein carries
Body is the mixing of one or more refractory oxides, and active constituent is the VIII transition of one or more periodic table of elements
Race is elementary composition；Its loading is mass percent 0.01 ~ 5%；The wherein preferred zirconium oxide of carrier, zinc oxide, aluminium oxide, dioxy
One or more of SiClx, titanium dioxide, magnesium oxide, lanthana, cerium oxide；The preferred platinum of active constituent and/or palladium.In order to carry
The performance of high catalyst, has been also added with acidic components and auxiliary agent in catalyst according to the present invention, the preferred chloride of acidic components
To keep acid, its loading is mass percent 0.01 ~ 5%.The preferred cerium oxide of auxiliary agent, stannum oxide, zinc oxide, vanadium oxide, oxygen
Change one of lanthanum, chromium oxide, ferrum oxide, zirconium oxide, manganese oxide, its loading is mass percent 0.01 ~ 5%.In the present invention
The geometry of catalyst can be for example spherical or cylindrical.
In the present invention, positive structureization reaction can be carried out using fixed bed, moving bed, fluid bed；Feed stream a can more than
Capable, the descending or mode of Radial Flow is contacted with the bed of catalyst granules.The reactor that positive structureization reaction adopts can be single
Platform, alternatively multiple stage.Bed number in reactor is 1-2 layer.
The present invention is further improved by, step C）Described in hydrogenation catalyst react in temperature 50-250 DEG C, reaction pressure
Carry out under the conditions of power 50-200 kPa, the hydrogen total content of described offer and iso-butane content in feed stream a are than for 1-3mol：
1mol, and the presentation mode of hydrogen can be less than 20 % for pure hydrogen or containing light paraffins（Molar percentage）Mixing hydrogen
Stream；In this course of reaction, catalyst is any suitable hydrogenation catalyst, and the preferably nickel-base catalyst of alumina support is urged
The geometry of agent can be spherical or cylindrical.In the present invention, hydrogenation catalyst reaction can adopt fixed bed, moving bed, stream
Change bed；Stream can be contacted with the bed of catalyst granules in the way of up, descending or Radial Flow.
In order to control the temperature of charge entering hydrogenation reaction region, the present invention also can arrange cooling before hydroconversion reaction zone
Device.
The present invention is further improved by, and is provided with step G）：By step E）In obtained stream e1 separate further,
Obtain containing 20-40%（Mass percent）The material stream g3 of iso-butane, and material stream g3 is recycled to the first distillation zone,
Improve the conversion ratio of the present invention further.
As the preferred embodiments of the present invention, the lock out operation of the first distillation zone is carried out using in lightness-removing column, takes off light
The tower top of tower adopts condensation at low temperature mode, and the temperature of condensation is 5 ~ 30 DEG C, is condensed using heat exchanger or segregation and fractionation system
Operation, lightness-removing column tower top pressure is 0.7 ~ 1.2MPa.
As the preferred embodiments of the present invention, the lock out operation in after-fractionating region is carried out in butane tower, and butane tower can
Think that double tower may also be employed single-tower operation.
As the preferred embodiments of the present invention one, the feed stream a in the present invention derives from liquefied petroleum gas, and it specifically walks
Suddenly as follows：
A11）Liquefied petroleum gas is provided（LPG）Stream；
A12）Remove propane and C4- hydrocarbon and C5+ hydrocarbon from above-mentioned LPG stream, obtain comprising normal butane and iso-butane
Stream；
A13）From comprise the stream of normal butane and iso-butane take out normal butane and obtain comprising feed stream a of iso-butane.
As the preferred embodiments of the present invention two, in the present invention, feed stream a contains butane by what carbon after ether four obtained
Raw material processing formed, concretely comprise the following steps：
A21）Raw material containing butane is provided；
A22）Using step E）In lightness-removing column remove isobutene. in above-mentioned material, 1-butylene, 2-butylene and other not
Saturated hydrocarbons, obtain the stream containing normal butane and iso-butane；
A23）Using step F）In butane tower separation normal butane thus forming iso-butane stream and formed and comprising 80%（Matter
Amount percentage ratio）The feed stream a of iso-butane.
Compared with prior art, the beneficial effect of technical scheme mainly has advantages below：
1. the direct material that can be produced using butane as normal butane, improves the economic value added of butane；
2. the high usage of butane raw material, does not have the iso-butane of by-product, factory need not arrange iso-butane products pot with
And huge head tank group, load and unload and traffic unit also can greatly reduce scale；
3. the normal butane of purity >=98.5 can be produced, can be used for producing maleic anhydride, butylene, butadiene, vinegar
The normal butane downstream chemical product such as acid, butyl halide, nitrobutane；
4. adopt new iso-butane positive structure catalyst, this catalyst can be carried out at higher temperatures and pressures
Positive structureization reaction；
5. positive structureization reaction is carried out at higher temperatures, is conducive to improving the conversion ratio of iso-butane, reduces iso-butane
Circulating load, reduces plant energy consumption；
6. positive structureization reaction is carried out at a higher pressure, is conducive to reacted separating property, improves butane-component
The response rate, reduces material consumption；
7. the high usage of raw material, does not have the iso-butane of by-product, and factory need not arrange iso-butane products pot and huge
Head tank group, handling and traffic unit also can greatly reduce scale.
Method according to the present invention makes iso-butane be converted into normal butane by iso-butane is fed positive structure step；By adding
Hydrogen step increases the yield of the positive structureization of iso-butane normal butane processed；By unconverted iso-butane is recycled to positive structure step
And so that the iso-butane in raw material is reacted completely, further increase the conversion ratio of iso-butane；Its method is totally simply controlled, conversion
Rate is high, and yield is high, and economic benefit is more preferable.
Figure of description
The flow chart that Fig. 1 is related to for embodiment one；
The flow chart that Fig. 2 is related to for embodiment two.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation description is it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of not making creative work
Embodiment, broadly falls into the scope of protection of the invention.
Embodiment one
The present embodiment is related to liquefied petroleum gas stream to be prepared feed stream a and prepares two portions of normal butane by feed stream a
Point.
Part I：Feed stream a is prepared using liquefied petroleum gas stream, comprises the following steps：
A11）Liquefied petroleum gas stream is provided；
A12）Using multiple conventional rectification towers, in first rectifying column, C4- hydrocarbon can be isolated from tower top；In the second rectification
In tower, isolate C5+ hydrocarbon thus obtaining comprising the stream of normal butane and iso-butane from bottom of towe；
A13）Normal butane is separated from above-mentioned stream using butane tower and obtains the feed stream a comprising iso-butane.
Second, as shown in figure 1, normal butane is prepared by the feed stream a comprising iso-butane:
1. provide the feed stream a comprising iso-butane, the iso-butane content comprising in feed stream a is by percent mass
Hundred count more than 80%, and preferably 95 more than % comprise 96% iso-butane in feed stream a in the present embodiment.
2. feed stream a is fed at least one positive structure region, and make iso-butane that positive structure occurs under catalyst action
Change reaction and be converted into normal butane, thus obtaining comprising iso-butane, normal butane, methane, ethane, propane, propylene, isobutene., 1- fourth
Alkene, 2-butylene, product gas flow b of hydrogen；
It is specially：In iso-butane positive structure reactor, iso-butane reacts on positive structure catalyst and obtains normal butane,
Generate isobutene., 1-butylene and 2-butylene simultaneously, and also form a small amount of methane, ethane, propane and propylene.Due in the present embodiment
Positive structureization reaction is to carry out under limited amount hydrogen existence condition, therefore also exists in reacted product gas flow b of positive structureization
Unconverted iso-butane and hydrogen.
In the present embodiment, positive structure catalyst comprises carrier, active constituent, acid composition and auxiliary agent.Carrier is by heat-resisting oxygen
Compound or mixed oxide composition, carrier be preferably zirconium oxide, zinc oxide, aluminium oxide, silicon dioxide, titanium dioxide, magnesium oxide,
One or more of lanthana, cerium oxide mix, and in the present embodiment, as carrier, loading is percent mass to selective oxidation aluminum
Ratio 91%；Described active constituent comprises one or more VIII transition element, and its loading is mass percent 2%；Preferably platinum
And/or palladium, select platinum in the present embodiment.It is chosen as chloride to keep acid, its loading in described acidic components embodiment
For mass percent 4%；Described auxiliary agent selective oxidation cerium, stannum oxide, zinc oxide, vanadium oxide, lanthana, chromium oxide, ferrum oxide,
One of zirconium oxide, manganese oxide, its loading is mass percent 3%；The geometry of positive structure catalyst is the centre of sphere.
In the present embodiment, positive structure reactor adopts fluidized-bed reactor, arranges beds 1-6 layer in reactor.Just
In structure reactor, at 200 DEG C -700 DEG C, operating pressure is carried out under the hydro condition for 2-5MPa internal temperature, weight (hourly) space velocity (WHSV)
（WHSV）For 0.5 ~ 2 h-1.
In the present embodiment, positive structureization reaction is carried out, to reduce the coking of catalyst under limited amount hydrogen existence condition
Speed, is simultaneously used for equalizing reactor catalyst bed in the layer temperature, hydrogen total content and charging in the hydrogen stream of described offer
In air-flow a, the mol ratio of iso-butane content is 1-3：1；, in the present embodiment, mol ratio is 1.5:1.The hydrogen being provided can be
Pure hydrogen or containing light paraffins be less than 20 %（Molar percentage）Mixing hydrogen stream, in the present embodiment be pure hydrogen；
In the present embodiment, the positive structureization carrying out under these conditions is reacted, and can make in the feed stream a comprising iso-butane
The 50% positive structure of iso-butane.
3. product gas flow b is fed at least one hydrogenation zone of saturation and carry out hydrogenation catalyst reaction, make isobutene., 1- fourth
Alkene, 2-butylene, propylene carry out hydrogenation reaction；
In hydrogenation saturating reactor, butylene is reacted with hydrogen on hydrogenation catalyst and obtains normal butane and different for this reaction
Butane.In above-mentioned reaction, alkene is converted into alkane, thus define comprising iso-butane, normal butane, methane, ethane, propane
Product gas flow c with hydrogen.
During hydrogenation catalyst, using general hydrogenation catalyst, such as zirconium oxide, zinc oxide, aluminium oxide, titanium dioxide
Silicon, titanium dioxide, magnesium oxide, lanthana, cerium oxide etc., active metal component can be the VIII of one or more periodic chart
Transition element, such as alumina support nickel-base catalyst.The geometry of catalyst is cylinder.
In the present embodiment, hydrogenation saturating reactor adopts separate unit fixed bed, and the catalyst bed number of plies in reactor is 1-2 layer.
Generally at 50-250 DEG C, preferably 50-150 DEG C, the present embodiment selects 120 DEG C to catalytic inner reaction temperature in hydrogenation zone.
In the present embodiment, the operating pressure of hydrogenation zone is less than positive structure region, is 50-200 kPa, preferably 60kPa, 80kPa, during gas
Air speed selects 0.5-2 h-1.In hydrogenation zone, hydrogen total content and iso-butane content in feed stream a in the hydrogen stream being provided
Than for 1-3mol：1mol, selects 1.5 mol/1mol in the present embodiment, identical with the hydrogen hydrocarbon in positive structure region.
In order to control air-flow b to enter the temperature of hydrogenation zone, the present embodiment arranges cooler in hydrogenation reactor.
In embodiments, in the feed stream b that can make to comprise C4 alkene, 99% alkene is converted into alkane.
4. condensation separation air-flow c at 0-40 DEG C, obtains comprising the low boiling secondary component such as hydrogen, methane, ethane, propane
Gas phase stream d1 and comprise liquid phase stream d2 of methane, ethane, propane, normal butane, iso-butane；
In embodiments, in order to save energy expenditure, in the present embodiment, condensing mode adopts multistage cooling, preferably 2-3
Level cooling.By condensing plant, air-flow c is cooled to 0 ~ 40 DEG C in this programme, in this example be 20 DEG C, normal butane, iso-butane,
The higher material of the boiling points such as propane is condensed into liquid, and the low boiling secondary component such as hydrogen, methane, ethane, propane is still then gas
Body, isolates above-mentioned gas and liquid forms gas phase stream d1 and liquid phase stream d2, and in wherein gas phase stream d1, hydrogen content reaches 70 ~ 90
%, based on mole very.The above-mentioned gas phase stream d1 isolating can be directly or anti-for positive structureization reaction or hydrogenation after purification
Should, also can be transported to other application, for example, be used in fuel cell producing electric energy.
5. liquid phase stream d2 being fed the first distillation zone, to separate methane in liquid phase stream d2, ethane, propane etc. further low
Boiling point secondary component simultaneously forms the product stream e1 comprising methane, ethane, propane and iso-butane and comprises iso-butane and normal butane
Product stream e2；
In the present embodiment, the first distillation zone is carried out in lightness-removing column, and lightness-removing column has 20 ~ 50 pieces of theoretical plates, and column plate pattern can
Think bubble cap tray, valve tray, sieve plate, structured packing or random packing may also be employed.
The tower top of lightness-removing column adopts condensation at low temperature mode, and condensation temperature is controlled to as 5 ~ 30 DEG C, to reclaim more isobutyls
Alkane, carries out condensation operation using heat exchanger or segregation and fractionation system, and lightness-removing column tower top pressure is 0.7 ~ 1.2MPaA, full tower pressure drop
For 20 ~ 50kPa, column bottom temperature is 80 ~ 90 DEG C, overhead reflux ratio >=3；Condensation at low temperature mode is directly condensed using salt cooler, takes off
The heating medium of light tower bottom reboiler can be low-pressure steam, hot water, conduction oil.
By aforesaid operations, discharge, in the bottom of towe of tower, stream e2 comprising iso-butane and normal butane, stream e2 contains 90-99
The normal butane of quality % and iso-butane.Discharge stream e1 comprising methane, ethane, propane and iso-butane in the tower top of tower.
In the present embodiment, using segregation fractionating column to stream e1 further carry out separate, overhead extraction substantially by
Liquid phase stream g1 of propane composition, gas phase stream g2 being substantially made up of ethane, methane.Stream g1 usually contains 40-70 mass %
Propane；Discharge, in the bottom of tower, valuable stream g3 comprising iso-butane, and stream g3 is recycled to the first distillation zone.
6. stream e2 is fed after-fractionating region, separate iso-butane and normal butane formed comprise iso-butane stream f1 and
The circulation of iso-butane stream f1 is fed back to positive structure region by normal butane stream f2 simultaneously.
It is specially：Future the light bottom of towe of autospasy iso-butane and the product stream e2 of normal butane send into butane tower.Butane column overhead
Obtain iso-butane stream f1 containing mass percent 95 ~ 99 %, bottom of towe obtains the normal butane containing mass percent 95 ~ 99 %
Stream f2, in normal butane stream f2, iso-butane content is 0.1 ~ 1%.Butane tower can adopt single-tower operation, higher in separation requirement
When, double tower can be adopted.Butane tower has 60 ~ 120 pieces of theoretical plates, and column plate pattern can be bubble cap tray, valve tray, sieve plate, also may be used
Using structured packing or random packing.Lightness-removing column tower top pressure is 0.5 ~ 0.8 MPa, and tower top temperature is 40 ~ 60 DEG C, full tower pressure
It is reduced to 80 ~ 120kPa, column bottom temperature is 60 ~ 75 DEG C, overhead reflux ratio >=7, preferential 9-12.The isobutyl of butane tower top in this example
Alkane stream f1 feedback is sent into positive structure unit and is used as charging.The heating medium of butane tower tower bottom reboiler can be that low pressure is steamed
Vapour, hot water, conduction oil or press factory scenario scheduling.
Embodiment two
The present embodiment, on the basis of embodiment one, prepares feed stream a and by feeding with the raw material comprising butane
Air-flow a prepares two parts of normal butane, wherein prepares normal butane part flow process by feed stream a identical with embodiment one.
The present embodiment is prepared feed stream a with the raw material comprising butane and is comprised the steps：
A21）Raw material containing butane is provided；
A22）Using step E）In lightness-removing column remove isobutene. in above-mentioned material, 1-butylene, 2-butylene and other not
Saturated hydrocarbons, obtain the stream containing normal butane and iso-butane；
A23）Using step F）In butane tower separation normal butane thus forming iso-butane stream and formed and comprising 80%（Matter
Amount percentage ratio）The feed stream a of iso-butane.
In A21）In step, provide the raw material containing butane can be somebody's turn to do using the refined alkane stream from refinery
Raw material comprise 90-99mol% butane,<1% butylene, the light component of 1-10mol%（Propane, ethane）, the weight of 0.1-10mol%
Component（Pentane）.
The whole technical process of the present embodiment is：As shown in Fig. 2
Raw material containing butane is removed after weight component through lightness-removing column 104, butane tower 106, acquisition will be more high-purity
The iso-butane air-flow of degree, and it is supplied to positive structure reactor 101 after mixing with hydrogen stream as feed stream a.
Iso-butane is converted into normal butane in positive structure reactor, and reaction temperature is 500 DEG C, and reaction pressure 3.0MPa is different
Conversion per pass >=40% of butane, representative value about 50%, selectivity >=85% of normal butane, representative value about 90%.Positive structureization catalysis
In agent carrier be silicon dioxide, two kinds of magnesium oxide mixing, loading is mass percent 90%；Active constituent is palladium loading
For mass percent 3%；Acidic components are chloride, and its loading is mass percent 3%；Described auxiliary agent is manganese oxide, and it is born
Lotus amount is mass percent 4%.The hydrogen stream of described offer is pure hydrogen, iso-butane content in its hydrogen total amount and feed stream a
Mol ratio be 2.2：1.
Enter hydrogenation saturating reactor 102 from the air-flow b of positive structure reactor.The alkene that positive structureization reaction produces is adding
It is converted into alkane, 150 DEG C of reaction temperature, reaction pressure 100 kPa, hydrogen total amount and feed stream a in hydrogen saturating reactor
Middle iso-butane content is than for 2.2mol：1mol, olefin conversion >=99%.
Air-flow c from hydrogenation saturating reactor enters condensing plant 103, and condensation temperature is 15 DEG C, obtains gas phase stream d1
With liquid phase stream d2.Remove in gas phase stream d1 and obtain high-purity hydrogen after C4 component, can be used as hydrogen after high-purity hydrogen is pressurized
A part in stream and pure hydrogen are mixed into positive structure reactor.
Liquid phase stream d2 from condensing plant 103 enters lightness-removing column 104.The extraction on lightness-removing column top contains methane, ethane, propane
And the product stream e1 of iso-butane, product stream e1 entrance segregation fractionating column 105.Product stream e1 separates in segregation fractionating column 105, main
Stream g3 of iso-butane to be contained is from the bottom of towe discharging of segregation fractionating column, and backs into lightness-removing column top；Mainly contain the material of propane
Stream g2 produces from the tower top liquid phase of segregation fractionating column；Stream g1 mainly containing methane, ethane is from the top gaseous phase of segregation fractionating column
Extraction.
Remove through lightness-removing column 104 after light component in the extraction of lightness-removing column bottom containing iso-butane and normal butane product stream e2, product
Stream e2 enters butane tower 106, and in butane tower 106, iso-butane separates with normal butane, the iso-butane stream f1 circulation of higher degree
Enter positive structure reactor, and normal butane stream f2 produces from the bottom of towe of butane tower, obtains normal butane product.
Raw material that is the present embodiment process is simple, controlled, being produced using butane as normal butane, improves butane
Economic value added；There is no the iso-butane of by-product, factory need not arrange iso-butane products pot and huge head tank group, dress simultaneously
Unload and traffic unit also can greatly reduce scale；And the normal butane of purity >=98.5 can be produced.
Claims (10)
1. a kind of method preparing normal butane by iso-butane, it comprises the following steps：
A) feed stream a including at least mass percent 80% iso-butane is provided；
B) feed stream a is fed at least one positive structure region, and make iso-butane that positive structure occurs under catalyst action
Reaction, thus obtain comprising iso-butane, normal butane, methane, ethane, propane, propylene, isobutene., 1-butylene, 2-butylene, hydrogen
Product gas flow b；
C) product gas flow b is fed at least one hydrogenation zone of saturation and carry out hydrogenation catalyst reaction, make isobutene., 1-butylene, 2-
Butylene, propene are thus obtain the air-flow c comprising iso-butane, normal butane, methane, ethane, propane and hydrogen；
D) condensation separation air-flow c at 0-40 DEG C, obtains comprising the low boiling secondary component such as hydrogen, methane, ethane, propane
Gas phase stream d1 and liquid phase stream d2 comprising methane, ethane, propane, normal butane, iso-butane；
E) liquid phase stream d2 is fed the first distillation zone and separate methane in liquid phase stream d2, ethane, the low boiling such as propane further
Point secondary component simultaneously forms the product stream e1 comprising methane, ethane, propane and iso-butane and the product comprising iso-butane and normal butane
Logistics e2；
F) stream e2 is fed after-fractionating region, separate iso-butane and normal butane and formed and comprise iso-butane stream f1 and just
The circulation of iso-butane stream f1 is fed back to positive structure region by butane stream f2 simultaneously；
Wherein, described positive structure refers to change the structure of isoparaffin and does not change its elementary composition and molecular weight, and it is converted into
The process of n-alkane.
2. the method according to claim 1 it is characterised in that：Step B）Described in positive structureization react in temperature
200 DEG C -700 DEG C, operating pressure is carried out under the hydro condition for 2-5MPa, and the hydrogen total content providing is different with feed stream a
The mol ratio of butane content is 1-3：1；Used catalyst comprises carrier and live body component, and wherein carrier is heat-resisting for one or more
The mixing of oxide, active constituent is made up of the VIII transition element of more than one periodic table of elements.
3. the method according to claim 2 it is characterised in that：Described carrier be zirconium oxide, zinc oxide, aluminium oxide, two
One or more of silicon oxide, titanium dioxide, magnesium oxide, lanthana, cerium oxide mix；Described active constituent be platinum and/or
Palladium, its loading is percent mass 0.01 ~ 5%.
4. method according to claim 2 it is characterised in that：Acidic components and auxiliary agent, institute is also included in used catalyst
Stating acidic components is chloride, and its loading is mass percent 0.01 ~ 5%；Described auxiliary agent is cerium oxide, stannum oxide, oxidation
One of zinc, vanadium oxide, lanthana, chromium oxide, ferrum oxide, zirconium oxide, manganese oxide, its loading is mass percent 0.01
~5%.
5. method according to claim 1 it is characterised in that：Step C）Described in hydrogenation catalyst react in temperature 50-
250 DEG C, carry out under the conditions of reaction pressure 50-200 kPa, the hydrogen total content providing and iso-butane content ratio in feed stream a
For 1-3mol：1mol.
6. the method according to claim 2 or 4 it is characterised in that：Step B）With step C）In involved hydrogen carry
For form for flow of pure hydrogen or/and containing light paraffins molar percentage be less than 20 % mixing hydrogen stream.
7. method according to claim 1 it is characterised in that：It is provided with step G）：By step E）In obtained stream
E1 separates further, obtains the material stream g3 containing mass percent 20-40% iso-butane, and material stream g3 is recycled to
First distillation zone.
8. method according to claim 1 it is characterised in that：Step E）Described in operate and carry out in lightness-removing column.
9. method according to claim 8 it is characterised in that：Step F）Described in operate and carry out in butane tower.
10. method according to claim 9 it is characterised in that：Described feed stream a is by the Raw material processing containing butane
Formed, concretely comprise the following steps：A21）Raw material containing butane is provided；A22）Using step E）In lightness-removing column remove above-mentioned thing
Isobutene. in material, 1-butylene, 2-butylene and other unsaturated hydrocarbons, obtain the stream containing normal butane and iso-butane；A23）Profit
Use step F）In butane tower separation normal butane thus formed iso-butane stream formed comprise mass percent be 80% iso-butane
Feed stream a.
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| CN107285978A (en) * | 2017-07-03 | 2017-10-24 | 无锡南理工科技发展有限公司 | The preparation method of normal butane |
| CN115505419B (en) * | 2021-06-23 | 2023-11-03 | 中国石化工程建设有限公司 | Light naphtha orthographic structuring method |
| CN116239438A (en) * | 2021-12-08 | 2023-06-09 | 中国科学院大连化学物理研究所 | Device and method for orthosteric reaction of carbon tetraalkylalkane |
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| US6140547A (en) * | 1998-12-01 | 2000-10-31 | Phillips Petroleum Company | Isomerization of hydrocarbons |
| CN102320911A (en) * | 2011-07-29 | 2012-01-18 | 天津市泰亨气体有限公司 | Method for purifying n-butane by rectifying |
| CN102633585A (en) * | 2012-02-03 | 2012-08-15 | 南京迈森科技发展有限公司 | Method for preparing high-purity propane, iso-butane and n-butane |
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