CN109265308A - A kind of production method of the normal butane isomerization using solid acid bifunctional catalyst - Google Patents

A kind of production method of the normal butane isomerization using solid acid bifunctional catalyst Download PDF

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CN109265308A
CN109265308A CN201811317074.2A CN201811317074A CN109265308A CN 109265308 A CN109265308 A CN 109265308A CN 201811317074 A CN201811317074 A CN 201811317074A CN 109265308 A CN109265308 A CN 109265308A
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normal butane
isomerization
hydrogen
rectifying
catalyst
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连奕新
赖声松
韩保平
冯光平
赖伟坤
张�杰
霍秀春
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SHANGHAI NEW-UNITY ENERGY TECHNOLOGY Co Ltd
Xiamen University
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SHANGHAI NEW-UNITY ENERGY TECHNOLOGY Co Ltd
Xiamen University
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    • 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
    • C07C5/2778—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C5/2781—Acids of sulfur; Salts thereof; Sulfur oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
    • C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
    • C07C2527/055—Sulfates or other compounds comprising the anion (SnO3n+1)2- with alkali metals, copper, gold or silver
    • 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
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

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Abstract

A kind of production method of the normal butane isomerization using solid acid bifunctional catalyst, is related to the production method of normal butane isomerization.Raw material normal butane is pressurized mixing dry gas by normal butane booster pump and hydrogen circulator, and mixed material enters heat exchanger, then heats through middle pressure steam or electric heater, is sent into isomerization reactor；Hydrogeneous normal butane material carries out isomerization reaction in isomerization reactor, and isomerization reactor is provided with solid super acid catalyst；Materials at bottom of tower is by Steam reboiler temperature control, using low pressure steam heat supply；Material flows into rectifying pans after cooling, is re-fed into separation stabilizer by rectifying intercycle pump；The iso-butane of rectifying tundish bottom enters subsequent processing, separates and stablizes return normal butane basin after materials at bottom of tower normal butane directly returns to raw material system or the cooler cooling that discharged.

Description

A kind of production method of the normal butane isomerization using solid acid bifunctional catalyst
Technical field
The present invention relates to the production methods of normal butane isomerization, use solid acid bifunctional catalyst more particularly, to a kind of Normal butane isomerization production method.
Background technique
With the continuous development of combustion gas deep processing, the refinement of each component of liquefied petroleum gas using always constantly into Change, it is former to be successfully transformed into important industry all substantially departing from traditional fuel applications for alkene, propane, iso-butane component Material.The most important chemical use of normal butane is n butane oxidation legal system cis-butenedioic anhydride, is isomerization there are also a kind of faster purposes of development To carry out deep processing after iso-butane.Country's dehydrogenation of isobutane is equipped with corresponding scale normal butane isomerization device at present.
Different light hydrocarbon isomerization processes are because the catalyst that uses is different and operating condition is different, and the technique of isomerization is also not to the utmost It is identical.It is divided into following three kinds by the catalyst used: (1) with F-Al2O3For the high temperature isomerization mistake of catalyst (360~440 DEG C) Journey；(2) using molecular sieve as the medium temperature isomerization process of catalyst (250~300 DEG C)；(3) with chlorinated aluminas (120~180 DEG C) and (180~250 DEG C) of sulfate metal oxide be catalyst low temperature isomerization process, at present catalyst research towards Middle low temperature direction is developed.Common heterogeneous catalyst is that the bifunctional catalyst that solid acid carries platinum has molecular sieve doped platinum (Pt/ Zeolite), chlorinated aluminas carries platinum (Pt/Cl-Al2O3), solid super-strong acid carry platinum (Pt/SO4 2--ZrO2), first two by Applied to the various light hydrocarbon isomerizations reaction including normal butane, the third is the isomerization catalyst having recently been developed, It yet there are no it and industrially apply to butane isomerization reaction.Using molecular sieve as isomerization catalyst (Pt/zeolite) stability of carrier It is good, regenerating easily, and to the tolerance of water and sulphur also it is very strong compare with other catalyst it is maximum the disadvantage is that operation temperature compared with Height, this temperature are thermodynamically unfavorable for the formation of isomerized products.Chloride oxidation aluminium profiles catalyst (Pt/Cl-Al2O3) behaviour Make temperature usually at lower range (130~170 DEG C), so catalytic isomerization reacts no thermodynamic (al) limitation.Due to catalyst It is very sensitive to the pollutant in raw material, these impurity are removed by some purifying steps.Adding in isomerization process also needs to mend Chlorine removes the hydrogen chloride of generation to maintain catalyst activity, this just needs base extraction and therewith bring treatment fluid essence Refining problem.Sulfated zirconia catalyst (Pt/SO4 2--ZrO2) have both the major advantage of first two catalyst, this catalyst It is active high, it resists toxic impurities ability by force and can regenerate, raw material can even not have in some C5/C6 isomerization processes Pretreatment.The butane isomerization technique of the solid acid catalyst of supporting Pt is industrially developed, but it is due to containing noble metal Cause expensive.
Common light hydrocarbon isomerization mature technology such as table 1, preceding two class portion due to reaction temperature is excessively high or pollution environment etc. Divide and has not used.For isomerization process mainly using UOP and Axens as representative, Praxair Technology, Inc (UOP) is isomerization skill at present The main developer of art possesses typical Penex (C5/C6) technique and Butamer (C4) technique.
1 light hydrocarbon isomerization technique of table
It is heated to reaction temperature after alkane and hydrogen mixing, is then sequentially entered in series reaction device.Material Enter in separator by the effluent of reactor and separates, the hydrogen for separating and recovering extra hydrogen from separator upper end and newly supplementing Into reactor, the substance of separator bottom end enters in stabilizer circulating reflux gas together.In stabilizer, tail gas is arranged from top Out, desmotropism oil product is obtained from bottom end.In order to maintain the acidity of carrier, a small amount of organochlorine can be with hydrogen and straight-chain hydrocarbons Together by injection reaction system.Unreacted normal butane is separated and recovered from iso-butane using fractionating process, raw material is entering instead Desulfurizer can be introduced into before answering device and drier carries out desulfurizing and drying processing.If butane isomery device is urged with the use of HF acid The alkyl plant of agent is used together, and recycling unreacted normal butane and entering also needs to be passed through in molecular sieve to remove before reactor HF.Uop Inc., British Petroleum Company (BP) and French Petroleum Institute (IFP) successively develop the Pt/Cl- using same type Al2O3The butane isomerization technique of catalyst.In the variant of early stage butane isomerization processes, two isomerizing reactor serial operations, And have hydrogen circulation device.In Butamer HOT new process, only one reactor and without hydrogen recycle.
In conclusion develop a kind of high conversion, high stability, environmental protection and cheap normal butane isomerization catalyst and Technique is particularly important.Chinese patent CN201710362941.3 discloses a kind of SO containing lanthanum salt4 2-/ZrO2Catalyst, positive definite alkane Isomerization rate can reach 39%.Chinese patent CN201611054059.4 discloses a kind of SO4 2-/ZrO2Catalyst, positive definite alkane Conversion ratio can reach 45%.Described above, the isomerization performance of solid acid catalyst has reached industrial requirements level.Therefore, In order to make it be able to achieve higher conversion ratio and stability in Butane isomerization, the applicant applies for one kind in early period Base metal Ga/M/SO4 2-/ZrO2On the basis of solid super acid catalyst patent (CN106732676A), a kind of use has been invented The method that solid superacid as catalyst normal butane isomerization produces iso-butane, or the positive fourth to use solid acid bifunctional catalyst Alkane isomerization produces iso-butane technique, one way n-butane conversion 50%~55%, iso-butane selectivity 80%~85%, There is the technical process raw material not need to pre-process, and process is not required to mend chlorine and post-processing, process is simple and environmentally-friendly, used catalyst is living Change the features such as easy to operate, long service life, operating cost are low and with low investment.
Summary of the invention
The purpose of the present invention is to provide a kind of producers of normal butane isomerization using solid acid bifunctional catalyst Method.
The present invention the following steps are included:
1) after raw material normal butane mentions 1.5~3.0MPa by normal butane booster pump, it is pressurized mixing dry gas with hydrogen circulator, Mixed material enters heat exchanger, then is heated to 200~250 DEG C through middle pressure steam or electric heater, is sent into isomerization reactor；
In step 1), the raw material normal butane can be provided by normal butane basin；The purity of the raw material normal butane can be big In 90%；It is described to supplement fresh hydrogen, the supplement tolerance of the supplement fresh hydrogen with hydrogen circulator pressurization mixing dry gas It is suitable with the flow for being discharged into gas burning system, it can be the 5%~10% of system circulation amount by percent by volume；The hydrogen circulator The composition for being pressurized mixing dry gas can by percent by volume are as follows: hydrogen 90%~95%, methane 1%~3%, and ethane 2%~5%, Propane 1%~3%.
2) hydrogeneous normal butane material carries out isomerization reaction in isomerization reactor, and it is super that isomerization reactor is provided with solid Strong acid catalyst；
In step 2), the isomerization reactor can be fixed bed reactors, and upper and lower two are divided into isomerization reactor A reaction bed；The operating condition of the isomerization reactor can are as follows: 1.5~3.0MPa of pressure, 200~250 DEG C of inlet temperature, Hydrogen hydrocarbon volume ratio 1~5, normal butane mass space velocity 0.2~1.0.
3) solid super acid catalyst is Solid superacid bifunctional catalyst: CuGa-SO4 2-/ZrO2、NiGa-SO4 2-/ ZrO2、PtGa-SO4 2-/ZrO2、PbGa-SO4 2-/ZrO2At least one of；Solid super acid catalyst is before coming into operation using normal Force down hydrogen activation: activated gas is the nitrogen of percent by volume hydrogeneous 5%~10%, and air speed is 500~1000M3/h(G, ATM), temperature programming is to 230~260 DEG C；Isomerization reactor terminates in 230~260 DEG C of 3~6h of maintenance, activation；
4) 200~300 DEG C of isomerization reactor outlet mass temperatures, reacting rear material is cooled to through heat exchanger secondary heat exchange Decompression enters separation stabilizer after 100~120 DEG C；
5) the pressure control of stabilizer is separated in 1.5~2.5MPa, column bottom temperature control is at 100~120 DEG C, materials at bottom of tower By Steam reboiler temperature control, using low pressure steam heat supply；Tower top temperature is controlled at 90~110 DEG C, and tower top material is through overhead water Cooler temperature control is at 20~40 DEG C, and material flows into rectifying pans after cooling, is re-fed into separation by rectifying intercycle pump and stablizes Tower, 0~10, the number of plates for separating stabilizer is 100~200 for reflux ratio control；
6) iso-butane of rectifying tundish bottom enters subsequent processing, separates stable materials at bottom of tower normal butane and directly returns to original Material system returns to normal butane basin after discharging cooler is cooling, and the not solidifying dry gas composition of tank deck presses percent by volume among rectifying Are as follows: hydrogen 90%~95%, methane 1%~3%, ethane 2%~5%, propane 1%~3%, most of not solidifying mixing dry gas is about 85%~95% through hydrogen circulator reactor, and not solidifying mixing dry gas 5%~15% is discharged into gas burning system or recycles through UF membrane Hydrogen.
The production method of normal butane isomerization of the present invention using solid acid bifunctional catalyst can be used using solid The normal butane isomerization process units of body acid bifunctional catalyst, described device are equipped with normal butane basin (feed pump), normal butane Booster pump, hydrogen circulator, heat exchanger, auxiliary heater (middle pressure steam or electric heater), isomerization reactor, discharging cooling Device separates stabilizer, tower top water cooler, Steam reboiler, rectifying pans and rectifying intercycle pump.The normal butane storage Tank (feed pump) connects booster pump, and booster pump outlet connect mixing dry gas with hydrogen circulator, mixed material be sequentially connected again into Enter heat exchanger, auxiliary heater and isomerization reactor；Isomerization reactor outlet be sequentially connected heat exchanger, discharging cooler and Separate stabilizer；Separating stable tower bottom has normal butane discharge port and is hinged with Steam reboiler, is hinged with tower at the top of separation stabilizer Cooler is pushed up, discharging cooler reconnects rectifying pans；Rectifying pans top gas outlet connection gas burning system and hydrogen Circulator, rectifying tundish bottom outlet connection rectifying circulating pump and iso-butane discharge port.
The most important chemical use of normal butane is n butane oxidation legal system cis-butenedioic anhydride, is different there are also a kind of faster purposes of development Structure turns to the subsequent carry out deep processing of iso-butane, and country's dehydrogenation of isobutane is largely all equipped with corresponding scale normal butane isomerization at present Device.The present invention is mainly to provide a kind of method using solid superacid as catalyst normal butane isomerization production iso-butane, or To use the normal butane isomerization of solid acid bifunctional catalyst to produce iso-butane new process, industrial use chlorination at present relatively Carrying alumina platinum (Pt/Cl-Al2O3) technique, there is the present invention raw material not need pretreatment, process is not required to mend chlorine and post-processing, anti- Answer condition mitigate, technical process environmental protection, process is simple, operating cost is low and it is with low investment the features such as.
It is an object of the invention to optimization designs to go out a kind of normal butane isomerization life using solid acid bifunctional catalyst Iso-butane new process and combination unit are produced, excellent catalyst preconditioning process and isomerization reaction process conditions are provided, according to Higher normal butane conversion ratio and iso-butane selectivity may be implemented in method of the invention, while it is higher that catalyst can also be made to reach Stability.
Detailed description of the invention
Fig. 1 is the structure of the normal butane isomerization process units using solid acid bifunctional catalyst of the embodiment of the present invention Schematic diagram.
Fig. 2 is n-butane conversion of the embodiment 13 under the conditions of preferred isomerization process with reaction time variation diagram.
Fig. 3 is iso-butane selectivity of the embodiment 13 under the conditions of preferred isomerization process with reaction time variation diagram.
Specific embodiment
Following embodiment will the present invention is further illustrated in conjunction with attached drawing.
The embodiment of the present invention includes following steps:
1) after raw material normal butane mentions 1.5~3.0MPa by normal butane booster pump, it is pressurized mixing dry gas with hydrogen circulator, Mixed material enters heat exchanger, then is heated to 200~250 DEG C through middle pressure steam or electric heater, is sent into isomerization reactor；Institute Stating raw material normal butane can be provided by normal butane basin；The purity of the raw material normal butane can be greater than 90%；It is described to be recycled with hydrogen Machine pressurization mixing dry gas can supplement fresh hydrogen, the supplement tolerance of the supplement fresh hydrogen and the flow phase for being discharged into gas burning system When, by percent by volume can be system circulation amount 5%~10%；The composition of the hydrogen circulator pressurization mixing dry gas presses body Product percentage can are as follows: hydrogen 90%~95%, methane 1%~3%, ethane 2%~5%, propane 1%~3%.
2) hydrogeneous normal butane material carries out isomerization reaction in isomerization reactor, and it is super that isomerization reactor is provided with solid Strong acid catalyst；The isomerization reactor can be fixed bed reactors, and two reaction beds up and down are divided into isomerization reactor Layer；The operating condition of the isomerization reactor can are as follows: 1.5~3.0MPa of pressure, 200~250 DEG C of inlet temperature, and hydrogen hydrocarbon volume Than 1~5, normal butane mass space velocity 0.2~1.0.
3) solid super acid catalyst is Solid superacid bifunctional catalyst: CuGa-SO4 2-/ZrO2、NiGa-SO4 2-/ ZrO2、PtGa-SO4 2-/ZrO2、PbGa-SO4 2-/ZrO2At least one of；Solid super acid catalyst is before coming into operation using normal Force down hydrogen activation: activated gas is the nitrogen of percent by volume hydrogeneous 5%~10%, and air speed is 500~1000M3/h(G, ATM), temperature programming is to 230~260 DEG C；Isomerization reactor terminates in 230~260 DEG C of 3~6h of maintenance, activation；
4) 200~300 DEG C of isomerization reactor outlet mass temperatures, reacting rear material is cooled to through heat exchanger secondary heat exchange Decompression enters separation stabilizer after 100~120 DEG C；
5) the pressure control of stabilizer is separated in 1.5~2.5MPa, column bottom temperature control is at 100~120 DEG C, materials at bottom of tower By Steam reboiler temperature control, using low pressure steam heat supply；Tower top temperature is controlled at 90~110 DEG C, and tower top material is through overhead water Cooler temperature control is at 20~40 DEG C, and material flows into rectifying pans after cooling, is re-fed into separation by rectifying intercycle pump and stablizes Tower, 0~10, the number of plates for separating stabilizer is 100~200 for reflux ratio control；
6) iso-butane of rectifying tundish bottom enters subsequent processing, separates stable materials at bottom of tower normal butane and directly returns to original Material system returns to normal butane basin after discharging cooler is cooling, and the not solidifying dry gas composition of tank deck presses percent by volume among rectifying Are as follows: hydrogen 90%~95%, methane 1%~3%, ethane 2%~5%, propane 1%~3%, most of not solidifying mixing dry gas is about 85%~95% through hydrogen circulator reactor, and not solidifying mixing dry gas 5%~15% is discharged into gas burning system or recycles through UF membrane Hydrogen.
Referring to Fig. 1, the production method of the normal butane isomerization of the present invention using solid acid bifunctional catalyst can be adopted With the normal butane isomerization process units for using solid acid bifunctional catalyst, described device is equipped with normal butane basin (feed pump) 1, normal butane booster pump, hydrogen circulator 11, heat exchanger 2, auxiliary heater 3 (middle pressure steam or electric heater), isomerization are anti- It answers in device 4, discharging cooler 5, separation stabilizer 6, tower top water cooler 7, Steam reboiler 10, rectifying pans 8 and rectifying Between circulating pump 9.The normal butane basin (feed pump) 1 connects booster pump, and booster pump outlet connect mixing with hydrogen circulator 11 Dry gas, mixed material are sequentially connected again into heat exchanger 2, auxiliary heater 3 and isomerization reactor 4；Isomerization reactor 4 goes out Mouth is sequentially connected heat exchanger 2, discharging cooler 5 and separation stabilizer 6；There is normal butane discharge port C in separation 6 bottom of stabilizer and connects Steam reboiler 10 is filled, separates and is hinged with tower top cooler 7 at the top of stabilizer 6, discharging cooler 5 reconnects rectifying pans 8；Essence 8 top gas of pans outlet connection gas burning system and hydrogen circulator 11 are evaporated, the connection rectifying of 8 outlet at bottom of rectifying pans follows Ring pumps 9 and iso-butane discharge port D.In Fig. 3, label A indicates n-butane feed, and B indicates that supplement hydrogen, E indicate that on-condensible gas is gone Gas burning system.
Specific embodiment is given below.
Embodiment 1
By catalyst filling in fixed bed reactors, it is passed through nitrogen, is warming up to 350 DEG C with 2 DEG C/min heating rate.So The nitrogen in reactor is changed to hydrogen afterwards, reactor pressure maintains 2MPa, keeps 2h.The rate of temperature fall of last 2 DEG C/min 250 DEG C are cooled to, reaction gas normal butane is passed through, feedstock quality air speed is 4h-1, reactor pressure 2MPa, hydrogen-hydrocarbon ratio is 3 ︰ 1.
Embodiment 2
By catalyst filling in fixed bed reactors, it is passed through hydrogen, is warming up to 250 DEG C with the heating rate of 2 DEG C/min. Reactor pressure maintains 2MPa, keeps 2h.It is passed through reaction gas normal butane, feedstock quality air speed is 4h-1, reactor pressure is 2MPa, hydrogen-hydrocarbon ratio are 3 ︰ 1.
Embodiment 3
By catalyst filling in fixed bed reactors, it is passed through hydrogen, is warming up to 300 DEG C with the heating rate of 2 DEG C/min. Reactor pressure maintains 2MPa, keeps 2h.It is passed through reaction gas normal butane, feedstock quality air speed is 4h-1, reactor pressure is 2MPa, hydrogen-hydrocarbon ratio are 3 ︰ 1.
Embodiment 4
By catalyst filling in fixed bed reactors, it is passed through hydrogen, is warming up to 400 DEG C with the heating rate of 2 DEG C/min. Reactor pressure maintains 2MPa, keeps 2h.It is passed through reaction gas normal butane, feedstock quality air speed is 4h-1, reactor pressure is 2MPa, hydrogen-hydrocarbon ratio are 3 ︰ 1.
Embodiment 5
By catalyst filling in fixed bed reactors, it is not passed through gas, is warming up to 250 with the heating rate of 2 DEG C/min ℃.Reactor pressure maintains 2MPa, keeps 2h.It is passed through reaction gas normal butane, feedstock quality air speed is 4h-1, reactor pressure For 2MPa, hydrogen-hydrocarbon ratio is 3 ︰ 1.
Reduction temperature, conversion ratio, selectivity and the yield of Examples 1 to 5 are referring to table 2.
Table 2
Embodiment 6: the preparation of catalyst, pretreatment and reaction process condition are same as Example 1, only catalyst Reaction temperature is changed to 230 DEG C.
Embodiment 7: the preparation of catalyst, pretreatment and reaction process condition are same as Example 1, only catalyst Reaction temperature is changed to 210 DEG C.
Embodiment 8: the preparation of catalyst, pretreatment and reaction process condition are same as Example 1, only catalyst Reaction temperature is changed to 270 DEG C.
Reduction temperature, conversion ratio, selectivity and the yield of embodiment 1,6~8 are referring to table 3.
Table 3
Embodiment 9: the preparation of catalyst, pretreatment and reaction process condition are same as Example 1, only catalyst Reaction hydrogen-hydrocarbon ratio is changed to 2 ︰ 1.
Embodiment 10: the preparation of catalyst, pretreatment and reaction process condition are same as Example 1, only catalyst Reaction hydrogen-hydrocarbon ratio be changed to 4 ︰ 1.
Reduction temperature, conversion ratio, selectivity and the yield of embodiment 1,9 and 10 are referring to table 4.
Table 4
Embodiment 11: the preparation of catalyst, pretreatment and reaction process condition are same as Example 1, only catalyst Reaction pressure be changed to 1.5MPa.
Embodiment 12: the preparation of catalyst, pretreatment and reaction process condition are same as Example 1, only catalyst Reaction pressure be changed to 2.5MPa.
Reduction temperature, conversion ratio, selectivity and the yield of embodiment 1,11 and 12 are referring to table 5.
Table 5
Embodiment 13: nitrogen is passed through by catalyst filling in fixed bed reactors according to preferred isomerization process condition After displacement apparatus system, the nitrogen being passed through then is changed to hydrogen, is warming up to 250 DEG C with the heating rate of 2 DEG C/min.Reactor Pressure maintains 2MPa, keeps 2h.It is passed through reaction gas normal butane (purity 98%), feedstock quality air speed is 4h-1, reactor pressure Power is 2MPa, and hydrogen-hydrocarbon ratio is 3 ︰ 1,250 DEG C of reaction temperature.Catalyst stablizes reaction in 200h, and n-butane conversion is stablized 55% or so, iso-butane selectivity is in 85% or so (as shown in Figures 2 and 3).
Embodiment 14: this embodiment technical process as shown,
It is mixed with the pressurization of hydrogen circulator after the raw material normal butane (purity 98%) sent by basin mentions 2.0Mpa by booster pump Dry gas is closed, and suitably supplements fresh hydrogen, mixed material enters heat exchanger, then is heated to 250 DEG C through electric heater auxiliary, is sent into Isomerization reactor.Circulator comes mixing dry gas main ingredient (volume ratio) are as follows: hydrogen (90%~95%), methane (1%~ 3%), ethane (2%~5%), propane (1%~3%).Fresh hydrogen supplement tolerance is suitable with the flow for being discharged into gas burning system, about It is the 5%~10% of system circulation amount.
Hydrogeneous normal butane material carries out isomerization reaction in isomerization reactor, and isomerization reactor is provided with solid super strong Acid catalyst.Reactor can be fixed bed reactors, inside be divided into two reaction bed isomerization reaction operating conditions up and down are as follows: Feedstock quality air speed is 4h-1, reactor pressure 2MPa, hydrogen-hydrocarbon ratio is 3 ︰ 1.Used catalyst is the double function of solid super-strong acid Energy catalyst: CuGa-SO4 2-/ZrO2.Catalyst uses normal pressure low hydrogen to activate before coming into operation: activated gas is pure hydrogen, and air speed is about 500~1000M3/ h (G, ATM), temperature programming is to 250 DEG C.Reactor terminates in 250 DEG C of maintenance 4h, activation.
About 280 DEG C of reactor outlet material temperature.Reacting rear material depressurizes after heat exchanger secondary heat exchange cools to 100 DEG C Separated into separation stabilizer and stablize pressure tower control in 1.8MPa, column bottom temperature controls 110 DEG C, materials at bottom of tower by steam again Device temperature control is boiled, using low pressure steam heat supply.At 90 DEG C, tower top material is cooled by water device temperature control at 30 DEG C for tower top temperature control, Material flows into rectifying pans after cooling, is re-fed into separation stabilizer by rectifying intercycle pump.Rectifying tundish bottom it is different Butane enters subsequent processing.Stable materials at bottom of tower normal butane is separated directly to return to raw material system or return to raw material storage after cooling Tank.Tank deck does not coagulate dry gas main ingredient (volume ratio) among rectifying are as follows: hydrogen (90%~95%), methane (1%~3%), second Alkane (2%~5%), propane (1%~3%).Most of not solidifying mixing dry gas (about 90%) is not solidifying to mix through circulator reactor Dry gas (about 10%) is discharged into gas burning system.

Claims (9)

1. a kind of production method of the normal butane isomerization using solid acid bifunctional catalyst, it is characterised in that including following step It is rapid:
1) after raw material normal butane mentions 1.5~3.0MPa by normal butane booster pump, mixing dry gas, mixing are pressurized with hydrogen circulator Material enters heat exchanger, then is heated to 200~250 DEG C through middle pressure steam or electric heater, is sent into isomerization reactor；
2) hydrogeneous normal butane material carries out isomerization reaction in isomerization reactor, and isomerization reactor is provided with solid super-strong acid Catalyst；
3) solid super acid catalyst is Solid superacid bifunctional catalyst: CuGa-SO4 2-/ZrO2、NiGa-SO4 2-/ZrO2、 PtGa-SO4 2-/ZrO2、PbGa-SO4 2-/ZrO2At least one of；Solid super acid catalyst uses normal pressure low hydrogen before coming into operation Activation: activated gas is the nitrogen of percent by volume hydrogeneous 5%~10%, and air speed is 500~1000M3/ h, temperature programming are arrived 230~260 DEG C；Isomerization reactor terminates in 230~260 DEG C of 3~6h of maintenance, activation；
4) 200~300 DEG C of isomerization reactor outlet mass temperatures, reacting rear material cools to 100 through heat exchanger secondary heat exchange Decompression enters separation stabilizer after~120 DEG C；
5) the pressure control of stabilizer is separated in 1.5~2.5MPa, and column bottom temperature is controlled at 100~120 DEG C, and materials at bottom of tower is by steaming Vapour reboiler temperature control, using low pressure steam heat supply；At 90~110 DEG C, tower top material is cooling through overhead water for tower top temperature control Device temperature control is at 20~40 DEG C, and material flows into rectifying pans after cooling, is re-fed into separation stabilizer by rectifying intercycle pump, returns For stream than control 0~10, the number of plates for separating stabilizer is 100~200；
6) iso-butane of rectifying tundish bottom enters subsequent processing, separates stable materials at bottom of tower normal butane and directly returns to raw material system System returns to normal butane basin after discharging cooler is cooling, and the not solidifying dry gas composition of tank deck presses percent by volume among rectifying are as follows: Hydrogen 90%~95%, methane 1%~3%, ethane 2%~5%, propane 1%~3%, part solidifying mixing dry gas 85%~ 95% through hydrogen circulator reactor, and not solidifying mixing dry gas 5%~15% is discharged into gas burning system or recycles hydrogen through UF membrane.
2. a kind of production method of the normal butane isomerization using solid acid bifunctional catalyst as described in claim 1, special Sign is that in step 1), the raw material normal butane is provided by normal butane basin.
3. a kind of production method of the normal butane isomerization using solid acid bifunctional catalyst as described in claim 1, special Sign is that in step 1), the purity of the raw material normal butane is greater than 90%.
4. a kind of production method of the normal butane isomerization using solid acid bifunctional catalyst as described in claim 1, special Sign is in step 1), described to supplement fresh hydrogen with hydrogen circulator pressurization mixing dry gas, the supplement fresh hydrogen Supplement tolerance is suitable with the flow for being discharged into gas burning system, can be the 5%~10% of system circulation amount by percent by volume.
5. a kind of production method of the normal butane isomerization using solid acid bifunctional catalyst as described in claim 1, special Sign is that in step 1), the composition of the hydrogen circulator pressurization mixing dry gas presses percent by volume are as follows: hydrogen 90%~ 95%, methane 1%~3%, ethane 2%~5%, propane 1%~3%.
6. a kind of production method of the normal butane isomerization using solid acid bifunctional catalyst as described in claim 1, special Sign is that in step 2), the isomerization reactor is fixed bed reactors.
7. a kind of production method of the normal butane isomerization using solid acid bifunctional catalyst as described in claim 1, special Sign is in step 2), and 2 reaction beds up and down are divided into the isomerization reactor.
8. a kind of production method of the normal butane isomerization using solid acid bifunctional catalyst as described in claim 1, special It levies and is in step 2), the operating condition of the isomerization reactor are as follows: 1.5~3.0MPa of pressure, inlet temperature 200~ 250 DEG C, hydrogen hydrocarbon volume ratio 1~5, normal butane mass space velocity 0.2~1.0.
9. using the normal butane isomerization process units for using solid acid bifunctional catalyst, it is characterised in that be equipped with normal butane and store Tank, normal butane booster pump, hydrogen circulator, heat exchanger, auxiliary heater, isomerization reactor, discharging cooler, separation are stablized Tower, tower top water cooler, Steam reboiler, rectifying pans and rectifying intercycle pump；The normal butane basin connection pressurization Pump, booster pump outlet connect mixing dry gas with hydrogen circulator, and mixed material is sequentially connected again into heat exchanger, auxiliary heater And isomerization reactor；Isomerization reactor outlet is sequentially connected heat exchanger, discharging cooler and separation stabilizer；Separation is stablized Tower bottom has normal butane discharge port and is hinged with Steam reboiler, is hinged with tower top cooler at the top of separation stabilizer, and discharge cooler Reconnect rectifying pans；Rectifying pans top gas outlet connection gas burning system and hydrogen circulator, rectifying pans bottom Portion outlet connection rectifying circulating pump and iso-butane discharge port.
CN201811317074.2A 2018-11-07 2018-11-07 A kind of production method of the normal butane isomerization using solid acid bifunctional catalyst Pending CN109265308A (en)

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Application publication date: 20190125