CN106673946B - A kind of method that MTBE and TBA mixture prepares isobutene - Google Patents
A kind of method that MTBE and TBA mixture prepares isobutene Download PDFInfo
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Abstract
The invention discloses a kind of methods that MTBE and TBA mixture prepares isobutene.This method comprises: MTBE and TBA mixture is contacted with catalyst and is reacted, catalyst used in it is hud typed amorphous silica-alumina, using the amorphous silica-alumina with or without adjuvant component M as core, using the amorphous silica-alumina of N containing adjuvant component and halogen as shell, the two organically cooperates, it realizes MTBE cracking and TBA is dehydrated two kinds of reactions while carrying out generation isobutene, the conversion ratio of the conversion ratio and MTBE that make TBA is higher, and the selectivity for generating isobutene is also higher.
Description
Technical field
The present invention relates to a kind of MTBE(methyl tertiary butyl ether(MTBE)s) and the TBA(tert-butyl alcohol) mixture simultaneously cracking prepare isobutene
Method.
Background technique
Isobutene is important Organic Chemicals, using its as raw material mainly for the production of methyl methacrylate (MMA),
Butyl rubber, polyisobutene, tertiary butyl phenol, tert-butylamine, methylallyl chloride, trimethylace tonitric, isoprene, p-tert-octyl phenol,
The fine chemical products such as antioxidant, agriculture medicine intermediate, tert-butyl acetate, silane.The raw material of production isobutene is mainly derived from
The by-product C-4-fraction of naphtha steam cracking ethylene unit, the by-product carbon four of refinery fluid catalytic cracking (FCC) device
The by-product tert-butyl alcohol etc. in fraction and the synthesis of Halcon method propylene oxide, wherein industrial process mainly have sulfuric acid extraction,
Adsorption separation method, tert-butyl alcohol dehydration method, methyl tertiary butyl ether(MTBE) cracking and n-butene isomerization process etc..
MTBE cracking is many to prepare a kind of technologically advanced, better economy method in isobutene method.It is split in MTBE
It solves in preparing isobutene reaction process, main reaction is under the effect of catalyst, and MTBE is cracked into isobutene and methanol, is most passed through afterwards
The processes such as rectifying obtain isobutene or high-purity isobutene.The catalyst type that MTBE cracks preparing isobutene is more, including aluminium oxide,
Silica, amorphous silica-alumina, ion exchange resin, molecular sieve, solid phosphoric acid and other acidic resin catalyst systems.Such as
The cracking of MTBE disclosed in CN1853772A, CN102451674A, JP2004115407, JP2004091443, JP3220136 etc.
Preparing isobutene catalyst is amorphous silicon aluminum-based catalyst, for another example DE 3509292, DE 3210435, US 4447668, GB
1482883, US 4570026, US 4551567 etc. then use ion-exchange resin catalyst, and patent CN for another example
96123535.7, EP 0118085, JP 7626401, JP 7494602 etc. are using solid phosphoric acid, sulfate, active carbon as MTBE
Catalyst for cracking.
Another the more universal method for producing isobutene is TBA dehydration.The reaction of TBA dehydration preparing isobutene has
The features such as by-product is few, separation and purification is easy, with low investment.Common catalyst includes aluminium oxide, molecular sieve, azochlorosulfonate acid ion exchange
Resin etc..The isobutene dehydration catalyst as disclosed in US3665048, CN101300211A, CN102516030A etc. is oxidation
Aluminum-based catalyst.It for another example is using sulfonate resin as catalyst in US4423271, US2005/0014985A1 etc..
The catalyst for tert-butyl alcohol cracking reaction that CN103611572A and CN103506158A is provided, is prepared by following methods
To: melt pelletization method is first passed through by polystyrene, chliorinated polyvinyl chloride, polytrifluorochloroethylene and Kynoar or poly- tribromo
Styrene is blended, is granulated after melting, then granulated to obtain the catalyst with sulfur trioxide progress sulfonating reaction.
In production process, MTBE and TBA mixture is more often met.There are two types of its main sources.The first source is with different
Butylene and methanol are that can produce the TBA of more amount the driving initial stage of waste MTBE.This is because when going into operation, catalyst
Or (and) install pipes in may adulterate a certain amount of water, excessive isobutene is reacted with water is readily generated TBA.To industry
For device, also imply that having considerable amount of MTBE and TBA product mix at the initial stage of going into operation generates.MTBE and TBA mixing produces
Product are separated as waste disposal, or using MTBE/TBA knockout tower, respectively obtain target product MTBE and TBA.
Second of source and most important source are artificially to produce, i.e. coproduction TBA while preparing MTBE.Firstly,
It is that there are some problems for the special technology for producing TBA.TBA production technology is complex, due to the intersolubility of C-4-fraction and water
It is poor, therefore TBA product design only has 45%-55%, TBA azeotrope with water is difficult to separate in addition, and conventional distillation can only obtain 85%
TBA.The TBA product of higher concentration can be obtained by being typically employed to multitple extraction rectifying, but equipment investment and operating cost will be big
Amplitude improves.Secondly, coproduction TBA has technical advantage: (1) scheme simple and flexible while preparation MTBE.It can be according to production
Demand carries out appropriate adjustment to process program to product in the market.Only process flow need to simply be switched and be replaced suitably
Catalyst, so that it may realize per unit area yield MTBE or TBA and MTBE and TBA mixture.(2) process is convenient to carry out, and investment risk is small.
It can be easy to switch to joint production process by being transformed per unit area yield MTBE technique, it is convenient to carry out.It simultaneously again can be easily extensive
Traditional per unit area yield technique is arrived again, and MTBE/TBA knockout tower more than needed can be used to carry out the separation of n-butene in C-4-fraction.Cause
This, which is not present investment risk.Finally, combined production device investment cost is low.If there is special per unit area yield MTBE and special in manufacturer
Per unit area yield TBA device, each architectonical of the two, mutual equipment cannot borrow, therefore more than the equipment of joint production process, investment
Greatly.Combined production device can produce MTBE and TBA simultaneously, produce MTBE respectively with scale set than newly-built two sets and TBA reduces investment outlay
40% or more, while also significantly reducing operating cost.Therefore, coproduction TBA technology has obtained extensively while preparing MTBE
General attention.The Lu Chunlong of Xi'an Petroleum University in its Master's thesis, " analyze and be related to just with the coproduction of TBA by the optimization of MTBE device
Visit " in, coproduction TBA technology has carried out serious analysis while with regard to preparation MTBE, has obtained answer certainly.
CN200610104876.6 discloses a kind of isobutene in C-4-fraction and methanol-water coproducing methyl tertbutyl ether and tertiary fourth
The production method of alcohol.But MTBE the and TBA mixture product of coproduction, main whereabouts are divided using MTBE/TBA knockout tower
From respectively obtaining target product MTBE and TBA.
Whether MTBE the and TBA mixture that the first source or second of source obtain at this stage uses mixture
When producing isobutene, substantially it is all made of and obtains purer MTBE raw material and TBA raw material after separating mixture, then distinguish
Preparing isobutene is distinguished on MTBE cracker and TBA dehydration device.
Cracking preparing isobutene technology is carried out in relation to MTBE and TBA mixture, at this stage or blank.One of them is important
The reason is that the requirement of MTBE cracker and TBA dehydration device to catalyst performance is inconsistent.It is generally believed that MTBE cracking and catalyzing
The active sites on agent surface are based on the center Bronsted acid (B acid), and the catalyst of TBA dehydration preparing isobutene is Lewis acid
(L acid) catalytic reaction process.Both for single kind catalyst, perhaps based on B acid or based on L acid, cannot
It takes into account.Another reason, using common catalyst, the reaction condition of the two is different, especially reaction temperature, TBA dehydration temperature
It spends lower compared with MTBE cracking temperature.Therefore, how MTBE and TBA is handled simultaneously under same device same reaction conditions to mix
Material is closed to produce isobutene, while activity and selectivity with higher, is an important subject of this field.
Summary of the invention
Isobutene is prepared in order to realize using MTBE and TBA mixture as raw material, it is mixed that the present invention provides a kind of MTBE and TBA
Close the method that material prepares isobutene.This method is not only able to achieve MTBE and TBA simultaneous reactions and generates isobutene, and MTBE and
TBA all has higher conversion ratio, and isobutene reaches higher selectivity.
The method that MTBE and TBA mixture of the present invention prepares isobutene, including MTBE and TBA mixture are contacted with catalyst
Reacted, used in catalyst be hud typed amorphous silicon Al catalysts, using A as core, using B as shell, A be with or without
The amorphous silica-alumina of adjuvant component M, B are the amorphous silica-alumina of N containing adjuvant component and halogen.
In hud typed amorphous silicon Al catalysts used in the method for the present invention, in the A, SiO2Content be 65.0wt%~
97.0wt%, preferably 78.0wt%~93.0wt%, preferably 85.0wt%~91.0wt%, adjuvant component M containing based on the element
Amount is 0~1.5wt%, preferably 0.2wt%~1.0wt%；In B, SiO2Content is 24.0wt%~60.0wt%, preferably
28.0wt%~54.0wt%, preferably 33.0wt%~50.0wt%, the content of adjuvant component N based on the element be 0.2wt%~
0.8wt%, preferably 0.3wt%~0.5wt%, the content of halogen based on the element are 0.05wt%~0.20wt%, preferably
0.08wt%~0.15wt%；The weight ratio of A and B is 40:1~4:1, preferably 30:1~6:1.
The method of MTBE and TBA mixture preparing isobutene of the present invention can use fixed-bed process, can also use slurry
Bed process, it is preferred to use fixed-bed process.When using fixed-bed process, used reaction condition are as follows: volume space velocity when total liquid
For 0.5h-1~10.0h-1, preferably 2.0h-1~5.0h-1；Temperature is 120 DEG C~300 DEG C, preferably 150 DEG C~250 DEG C；Pressure
Power is normal pressure~0.6MPa, preferably normal pressure~0.3MPa.When using slurry bed process, used reaction condition are as follows: total liquid
When volume space velocity be 0.5h-1~10.0h-1, preferably 1.0h-1~5.0h-1；Temperature be 150 DEG C~300 DEG C, preferably 180
DEG C~250 DEG C；Pressure is normal pressure~0.6MPa, preferably normal pressure~0.3MPa.When using slurry bed process, inertia is generally required
Solvent, hydro carbons liquid phase medium can be the generally acknowledged atent solvent for slurry reactor, such as inert mineral oil, be hydrocracked tail
Oil, liquid paraffin hydrocarbon etc., atent solvent are usually after mixed serum is made with catalyst, to be added in paste state bed reactor, are mixed
The content of catalyst is generally 5.0wt%~30.0wt% in slurries.
In reaction process of the invention, water purification can be added into mixture, water purification additional amount accounts for the 1.0 of mixture weight
The wt% of wt% ~ 15.0.
Hud typed amorphous silicon Al catalysts used in the present invention can be preformed catalyst, be also possible to without molding
Catalyst, those skilled in the art select according to the technique of practical application.It, can be according to practical feelings when preparing preformed catalyst
Suitable size and shape, such as spherical shape, bar shaped etc. is made in condition.
In hud typed amorphous silicon Al catalysts used in the present invention, group iia is selected from containing adjuvant component M in the A
With one of group VIII metal or a variety of, wherein group iia metal is preferably one of Be, Mg and Ca or a variety of, and
Group VIII metal is preferably one of Ni, Pd and Pt or a variety of.The adjuvant component N contained in the B is zinc, in iron, niobium
It is one or more；Halogen is selected from one of fluorine, chlorine, bromine or a variety of, preferably chlorine.
The property of hud typed amorphous silicon Al catalysts used in the present invention is as follows: specific surface area 180m2/ g~450m2/
The mL/g of g, Kong Rongwei 0.3mL/g~1.2；Preferably specific surface area is 200m2/ g~410m2/ g, Kong Rongwei 0.4mL/g~
1.0mL/g。
The preparation method of hud typed amorphous silicon Al catalysts used in the present invention, comprising: first prepare A i.e. with or without helping
B, is then carried on the outer surface of A by the amorphous silica-alumina of agent component M, forms hud typed amorphous silicon Al catalysts.
A's the preparation method is as follows: sial dry glue powder is formed in hud typed amorphous silicon Al catalysts used in the present invention
Or do not form, then handled with saturated vapor, temperature is 100 DEG C~600 DEG C, and the time is 1h~10h.Sial dry glue powder can be used
It is prepared in conventional method such as sial with plastic method, finished product can also be bought.When the A is formed, shape is preferably spherical shape,
Pelletizing method, such as oil drop method, rotary type comminution granulation, the marumerizer method of forming, thermopnore comminution granulation etc..
Preferably M containing adjuvant component in A described in hud typed amorphous silicon Al catalysts used in the present invention.Adjuvant component M can
To be introduced into A using conventional method (such as blending method, infusion process), for example introducing can be blended during sial plastic,
It can be introduced in sial plastic post blend；Introducing can be impregnated before steam treatment, can also be impregnated after steam treatment
It introduces.
In hud typed amorphous silica-alumina catalyst method used in the present invention, adjuvant component N and halogen in the B can
It introduces, can also draw after sial plastic to be introduced into B using conventional method (such as blending method), such as during sial plastic
Enter.
In hud typed amorphous silica-alumina catalyst method used in the present invention, the outer surface that B is carried on A can be using conventional
Formation core-shell structure method, for example dip coating, spray method etc..
The hud typed preferably specific preparation process of amorphous silicon Al catalysts used in the present invention is as follows: first preparing A, then
After the amorphous silica-alumina B slurries for spraying N containing adjuvant component and halogen, final catalyst is obtained through dry and roasting.Wherein, A can
With molding, needs dry after molding and roast, then spray B again, it is general using conventional forming method, it can according to need system
At suitable size and shape, such as spherical shape, bar shaped etc..Spheric catalyst can be used oil drop method, rotary type comminution granulation, spherical shape and make
Grain method of forming etc., geometric diameter is preferably chosen as 2.0mm-3.0mm between 1.0mm-5.0mm.In the method for the present invention, A's
In forming process, binder and shaping assistant can also be added, binder can be using conventional binder, generally aperture oxygen
Change aluminium, accounts for 2.0wt%~20.0wt% of final catalyst weight.Shaping assistant such as sesbania powder or methylcellulose account for final
1.5wt%~3.0wt% of catalyst weight.In the method for the present invention, in catalyst preparation process involved drying and
Roasting is generally carried out using normal condition, such as drying condition: the dry 1h ~ for 24 hours at 80 DEG C ~ 150 DEG C, roasting condition: 400
DEG C~700 DEG C, preferably 450 DEG C~600 DEG C at roast 1h ~ for 24 hours.
The method of the present invention is particularly suitable for completing to prepare isobutene reaction by raw material of MTBE and TBA mixture, i.e. MTBE is split
Solution preparing isobutene is reacted and can be carried out simultaneously with TBA dehydration preparing isobutene.
The method of the present invention can use conventional reactor, such as using original MTBE cracking preparing isobutene device or TBA
It is dehydrated preparing isobutene device.
The method of the present invention, the weight ratio for being particularly suitable for processing MTBE and TBA is the mixture of 0.5:1 ~ 40:1, preferably MTBE
Weight ratio with TBA is 1:1 ~ 20:1.It is that raw material prepares isobutene and TBA that impurity in mixture, which is equal to or less than routine MTBE,
The impurity contained in raw material when for raw material dehydration preparing isobutene, such as methyl sec-butyl ether≤0.2wt%, methanol≤
0.05wt%, isobutylene oligomer≤0.05 wt%, carbon four and carbon four or less hydro carbons≤0.1wt%.
Hud typed amorphous silicon Al catalysts are used in the method for the present invention with the amorphous silica-alumina with or without adjuvant component M
That is A is core, and using amorphous silica-alumina, that is, B of N containing adjuvant component and halogen as shell, the two organically cooperates, and realizes MTBE cracking
Two kinds of reactions are dehydrated with TBA while carrying out generation isobutene, and the conversion ratio of the conversion ratio and MTBE that make TBA is higher, generates different
The selectivity of butylene is also higher, avoids the separation process of MTBE and TBA mixture, and avoids building MTBE cracker respectively
Isobutene is produced with TBA dehydration device.
Specific embodiment
In the present invention, material purity and product form use gas chromatography analysis.Specific surface area and Kong Rong are using low
Warm liquid nitrogen determination of adsorption method.Constituent content is measured using inorganic analysis method.In the present invention, wt% is mass fraction.
Comparative example 1
Amorphous silica-alumina bead XQ1(particle size 2.2mm-2.5mm) is immersed into Ni (NO3)2In aqueous solution, passed through after dipping
400 DEG C of roasting 6h must contain the amorphous silica-alumina bead XQ1-1 of nickel oxide, then after 300 DEG C, the processing of 6h saturated vapor, obtain
Amorphous silica-alumina bead XQ1-2 containing nickel oxide.In XQ1-2, nickel content 0.40wt%, SiO2Content 86.90wt%, Al2O3Contain
Amount is 12.70wt%.
By Alusil GLJ1(in terms of butt, SiO2Content 35.00wt%, Al2O3Content is 65.00wt%) spray XQ1-
On 2,4h being dried at 120 DEG C, 6h is roasted at 500 DEG C, obtains catalyst DB-1, wherein the weight ratio of stratum nucleare and shell is 7:1.
It is specific that evaluation results are shown in Table 1.
Comparative example 2
XQ1-2 is prepared according to the method for comparative example 1.
By the Alusil GLJ1(containing zinc in terms of butt, SiO2Content 34.90wt%, Al2O3Content is 64.80wt%, and zinc contains
0.30%) amount is sprays on XQ1-2, the dry 4h at 120 DEG C, roasts 6h at 500 DEG C, obtains catalyst DB-2, wherein stratum nucleare
Weight ratio with shell is 7:1.It is specific that evaluation results are shown in Table 1.
Comparative example 3
XQ1-2 is prepared according to the method for comparative example 1.
By the Alusil GLJ1(containing chlorine in terms of butt, SiO2Content 35.00wt%, Al2O3Content is 64.90wt%, and chlorine contains
Amount is 0.10wt%) it sprays on XQ1-2, the dry 4h at 120 DEG C, 6h is roasted at 500 DEG C, obtains catalyst DB-3, center
The weight ratio of layer and shell is 7:1.It is specific that evaluation results are shown in Table 1.
Comparative example 4
XQ1-2 grinding in comparative example 1 is become into -300 mesh powder of 250 mesh, XQ1-3 is made.
Under agitation, appropriate zinc carbonate and ammonium chloride solution are slowly added in the Alusil GLJ1 into comparative example 1
It mixes, through 4 h dry at 120 DEG C, obtains GLJ1-1 powder after 450 DEG C of roastings, wherein the content of zinc is based on the element
0.30wt%, chlorinity 0.10wt%).
XQ1-3 is uniformly mixed with GLJ1-1 with weight ratio 7:1, the aperture that weight accounting is 10wt% is then added and aoxidizes
Aluminium is shaped to particle size catalyst pellet between 2.2mm-2.5 mm as adhesive, with the marumerizer method of forming, 120
Dry 4h obtains catalyst DB-4 through 450 DEG C of roasting 12h at DEG C.It is specific that evaluation results are shown in Table 1.
Comparative example 5
By the Alusil GLJ1 in comparative example 1, through 4 h dry at 120 DEG C, add in the powder obtained after 450 DEG C of roastings
Entering weight accounting is the small porous aluminum oxide of 15wt% as adhesive, is shaped to particle size with the marumerizer method of forming and exists
Catalyst pellet between 2.2mm-2.5mm, dry 4h obtains catalyst DB-5 through 400 DEG C of roasting 16h at 120 DEG C.Its TBA
Cracking evaluation result is shown in Table 2.
Comparative example 6
Small porous aluminum oxide that weight accounting is 15wt% will be added in GLJ1-1 powder in comparative example 4 as adhesive, with
The marumerizer method of forming is shaped to particle size catalyst pellet between 2.2mm-2.5 mm, dry 4h, warp at 120 DEG C
400 DEG C of roasting 16h, obtain catalyst DB-6.Its TBA cracking evaluation result is shown in Table 2.
Comparative example 7
By amorphous silica-alumina bead XQ1-2 obtained in comparative example 1, in MTBE cracking reaction, evaluation result to be shown in
Table 3.
Embodiment 1
XQ1-2 is made in amorphous silica-alumina bead XQ1 according to the method for comparative example 1.In XQ1-2, the content of nickel is
0.40wt%, SiO2Content 86.90wt%, Al2O3Content is 12.70wt%.
Appropriate zinc carbonate will be added in Alusil GLJ1 in comparative example 1 and ammonium chloride solution mixes, and sprays XQ1-2
On, 4 h are dried at 120 DEG C, are roasted 6h at 500 DEG C, are obtained core-shell structure SL-1 catalyst.The weight ratio of stratum nucleare A and shell B
For 7:1, in shell B, SiO2Content is 34.80wt%, alumina content 64.80wt%, Zn content 0.30wt%, chlorinity
For 0.10wt%.It is specific that evaluation results are shown in Table 1.
Embodiment 2
Amorphous silica-alumina bead XQ1 in comparative example 1 is immersed into Ca (NO3)2In aqueous solution, through 600 DEG C of roasting 3h after dipping
The amorphous silica-alumina bead XQ1-4 of calcic is obtained, then after 500 DEG C, the processing of 1.5h saturated vapor, obtains XQ1-5.In XQ1-5,
The content of calcium is 0.80wt%, SiO2Content 86.50wt%, Al2O3Content is 12.70wt%.
Appropriate ferric nitrate will be added in Alusil GLJ1 in comparative example 1 and ammonium bromide mixed solution mixes, and is sprayed
(XQ1-5) on, 4 h are dried at 110 DEG C, 5h is roasted at 500 DEG C, obtains core-shell structure SL-2 catalyst.Stratum nucleare A and shell B
Weight ratio be 10:1；In shell B, silica content 34.82wt%, alumina content 64.66wt%, iron content is
0.40wt%, bromine content 0.12wt%.It is specific that evaluation results are shown in Table 1.
Embodiment 3
A certain amount of amorphous silica-alumina bead XQ2(particle size 2.6mm-2.9mm) is immersed into Be (NO3)2In aqueous solution, leaching
The amorphous silica-alumina XQ2-1 of beryllium must be contained by roasting 5h through 500 DEG C after stain, then after 200 DEG C, the processing of 4h saturated vapor, be obtained
XQ2-2.In XQ2-2, the content of beryllium is 0.95wt%, SiO2Content 81.22wt%, Al2O3Content is 17.83wt%.
Proper amount of acetic acid zinc, the mixing of ammonium bromide mixed solution are added in Alusil GLJ2, are sprayed on XQ2-2, at 120 DEG C
Lower dry 2h roasts 5h at 450 DEG C, obtains core-shell structure SL-3 catalyst.The weight ratio of stratum nucleare A and shell B is 6:1, shell B
In, silica content 44.84wt%, alumina content 54.74wt%, Zn content 0.34wt%, bromine content 0.08wt%.
It is specific that evaluation results are shown in Table 1.
Embodiment 4
Amorphous silica-alumina bead XQ2 in embodiment 3 is immersed into Ni (NO3)2In aqueous solution, through 400 DEG C of roasting 3h after dipping
Nickeliferous amorphous silica-alumina bead XQ2-3 is obtained, then after 300 DEG C, the processing of 4.5h saturated vapor, obtains XQ2-4.In XQ2-4,
The content of nickel is 0.36wt%, SiO2Content 81.70wt%, Al2O3Content is 17.94wt%.
Appropriate niobium oxalate will be added in Alusil GLJ2 in embodiment 3 and ammonium fluoride solution mixes, and sprays XQ2-4
On, 3 h are dried at 100 DEG C, are roasted 3h at 500 DEG C, are obtained core-shell structure SL-4 catalyst.The weight ratio of stratum nucleare A and shell B
For 10:1；In shell B, silica content 44.61wt%, alumina content 54.51wt%, content of niobium 0.78wt%, fluorine contains
Amount is 0.10wt%.It is specific that evaluation results are shown in Table 1.
Slurry bed process can also be used in catalyst SL-1, SL-2, SL-3, SL-4 in embodiment 1-4, and specific evaluation result is shown in
Table 4.
The evaluation result of 1 comparative example 1-4 of table and embodiment 1-4 prepared catalyst
| Evaluation condition and result | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Catalyst | DB-1 | DB-2 | DB-3 | DB-4 |
| Volume space velocity when total liquid, h-1 | 3 | 3 | 3 | 3 |
| Volume space velocity when MTBE liquid, h-1 | 2 | 2 | 2 | 2 |
| Volume space velocity when TBA liquid, h-1 | 1 | 1 | 1 | 1 |
| Reaction temperature, DEG C | 210 | 210 | 210 | 210 |
| Reaction pressure, MPa | 0.2 | 0.2 | 0.2 | 0.2 |
| MTBE conversion ratio, wt% | 92.0 | 93.8 | 97.5 | 98.6 |
| TBA conversion ratio, wt% | 93.1 | 95.0 | 96.6 | 97.5 |
| Selective isobutene, wt% | 94.4 | 96.2 | 98.3 | 99.5 |
Continued 1
| Evaluation condition and result | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Catalyst | SL-1 | SL-2 | SL-3 | SL-4 |
| Volume space velocity when total liquid, h-1 | 5 | 3 | 2 | 1 |
| Volume space velocity when MTBE liquid, h-1 | 4.6 | 2 | 1.5 | 0.5 |
| Volume space velocity when TBA liquid, h-1 | 0.4 | 1 | 0.5 | 0.9 |
| Reaction temperature, DEG C | 250 | 210 | 150 | 130 |
| Reaction pressure, MPa | 0.3 | 0.1 | 0.1 | Normal pressure |
| MTBE conversion ratio, wt% | 99.6 | 99.7 | 99.7 | 99.3 |
| TBA conversion ratio, wt% | 99.9 | 99.8 | 99.5 | 99.6 |
| Selective isobutene, wt% | 99.8 | 99.9 | 99.8 | 99.7 |
As can be seen from Table 1, catalyst of the present invention is using the amorphous silica-alumina A of the M containing adjuvant component as core, to contain adjuvant component
The amorphous silica-alumina B of N and halogen is the catalyst of shell, is organically cooperated by the two, it can be achieved that MTBE cracking and TBA dehydration two
Kind reacts while carrying out generating isobutene reaction process.It is only modified in comparative example 1-3 with unmodified or single element amorphous
Sial is shell, MTBE and TBA conversion ratio is not high, and the selectivity of isobutene is also poor.Even if using the kneading method of comparative example 4
The catalyst of preparation, although the conversion ratio of MTBE and TBA, selective isobutene increase, but still it is undesirable.
The TBA cracking evaluation condition and result of 2 comparative example 5,6 of table
| Comparative example 5 | Comparative example 5 | Comparative example 6 | Comparative example 6 | |
| Catalyst | DB-5 | DB-5 | DB-6 | DB-6 |
| Volume space velocity when TBA liquid, h-1 | 1 | 1 | 1 | 1 |
| Reaction temperature, DEG C | 250 | 150 | 250 | 150 |
| Reaction pressure, MPa | 0.1 | 0.1 | 0.1 | 0.1 |
| TBA conversion ratio, wt% | 92.2 | 86.8 | 99.5 | 90.4 |
| The selectivity of isobutene, wt% | 93.9 | 92.9 | 95.8 | 93.8 |
As can be seen from Table 2, catalytic when DB-5 and DB-6 is as TBA catalyst for cracking, when reaction temperature is 250 DEG C
Catalytic performance when can be 150 DEG C significantly better than reaction temperature.Further more, being used for by zinc and the modified amorphous silica-alumina of chlorine
When TBA cracking reaction, the conversion ratio of TBA has more apparent raising, but selectivity is undesirable.
The MTBE cracking evaluation condition and result of 3 comparative example 7 of table
| Catalyst | DB-7 | DB-7 |
| Volume space velocity when MTBE liquid, h-1 | 2.5 | 2.5 |
| Volume space velocity when aqueous, h-1 | 0.08 | 0.08 |
| Reaction temperature, DEG C | 230 | 180 |
| Reaction pressure, MPa | Normal pressure | 0.05 |
| MTBE conversion ratio, wt% | 99.7 | 96.3 |
| The selectivity of isobutene, wt% | 99.6 | 98.1 |
As can be seen from Table 3, when DB-7 is cracked for MTBE, catalytic performance when reaction temperature is 230 DEG C is significantly better than
Catalytic performance when reaction temperature is 180 DEG C.
The slurry bed process evaluation result of 4 embodiment 1-4 prepared catalyst of table
| Catalyst | SL-1 | SL-2 | SL-3 | SL-4 |
| Atent solvent | Hydrocracking tail oil | Liquid paraffin hydrocarbon | Hydrocracking tail oil | Liquid paraffin hydrocarbon |
| The weight ratio of catalyst and atent solvent | 1:3 | 1:8 | 1:12 | 1:15 |
| Volume space velocity when total liquid, h-1 | 4.5 | 3.0 | 2.0 | 1.0 |
| Volume space velocity when MTBE liquid, h-1 | 1.5 | 2.0 | 3.5 | 2.0 |
| Volume space velocity when TBA liquid, h-1 | 2.0 | 1.0 | 0.5 | 0.1 |
| Reaction temperature, DEG C | 170 | 205 | 230 | 270 |
| Reaction pressure, MPa | 0.05 | 0.10 | 0.20 | 0.05 |
| MTBE conversion ratio, wt% | 99.7 | 99.6 | 99.7 | 99.6 |
| TBA conversion ratio, wt% | 99.6 | 99.6 | 99.9 | 99.7 |
| Selective isobutene, wt% | 99.8 | 99.7 | 99.8 | 99.6 |
As can be seen from Table 4, it uses using the amorphous silica-alumina A of the M containing adjuvant component as core, with N containing adjuvant component and halogen
Amorphous silica-alumina B be shell catalyst, organically cooperated by the two, under the conditions of slurry bed process can be achieved MTBE cracking
Two kinds of reactions are dehydrated with TBA while carrying out generating isobutene reaction process.
Claims (16)
1. a kind of method that MTBE and TBA mixture prepares isobutene, including MTBE and TBA mixture contact progress with catalyst
Reaction, used in catalyst be hud typed amorphous silicon Al catalysts, using A as core, using B as shell, wherein A be group containing auxiliary agent
Divide the amorphous silica-alumina of M, SiO in A2Content be 65.0wt%~97.0wt%, the content of adjuvant component M based on the element be 0~
1.5wt% and not be 0；B is the amorphous silica-alumina of N containing adjuvant component and halogen, SiO in B2Content is 24.0wt%~60.0wt%,
The content of adjuvant component N based on the element be 0.2wt%~0.8wt%, the content of halogen based on the element be 0.05wt%~
0.20wt%；The weight ratio of A and B is 40:1~4:1；Adjuvant component M be selected from one of group iia and group VIII metal or
It is a variety of；The adjuvant component N contained is one of zinc, iron, niobium or a variety of.
2. according to the method for claim 1, it is characterised in that: the weight ratio of A and B is 30:1~6:1.
3. according to the method for claim 1, it is characterised in that: in the A of the hud typed amorphous silicon Al catalysts, SiO2
Content is 78.0wt%~93.0wt%, and the content of adjuvant component M based on the element is 0.2wt%~1.0wt%；In B, SiO2Contain
Amount is 28.0wt%~54.0wt%, and the content of adjuvant component N based on the element is 0.3wt%~0.5wt%, and halogen is based on the element
Content be 0.08wt%~0.15wt%.
4. according to the method for claim 1, it is characterised in that: in A, SiO2Content is 85.0wt%~91.0wt%, auxiliary agent
The content of component M based on the element is 0.2wt%~1.0wt%；In B, SiO2Content is 33.0wt%~50.0wt%, auxiliary agent group
Dividing the content of N based on the element is 0.3wt%~0.5wt%, and the content of halogen based on the element is 0.08wt%~0.15wt%.
5. according to the method for claim 1, it is characterised in that: in the A of the hud typed amorphous silicon Al catalysts, the
Group IIA metal is one of Be, Mg and Ca or a variety of, and group VIII metal is one of Ni, Pd and Pt or a variety of；It is described
In the B of catalyst, halogen is selected from one of fluorine, chlorine, bromine or a variety of.
6. according to the method for claim 1, it is characterised in that the property of the hud typed amorphous silicon Al catalysts is such as
Under: specific surface area 180m2/ g~450m2/ g, Kong Rongwei 0.3mL/g~1.2 mL/g.
7. according to the method for claim 1, it is characterised in that the property of the hud typed amorphous silicon Al catalysts is such as
Under: specific surface area 200m2/ g~410m2/ g, Kong Rongwei 0.4mL/g~1.0mL/g.
8. according to the method for claim 1, it is characterised in that: use fixed-bed process, used reaction condition are as follows: total
Volume space velocity is 0.5h when liquid-1~10.0h-1, temperature is 120 DEG C~300 DEG C, and pressure is normal pressure~0.6MPa.
9. according to the method for claim 1, it is characterised in that: use fixed-bed process, used reaction condition are as follows: total
Volume space velocity is 2.0h when liquid-1~5.0h-1, temperature is 150 DEG C~250 DEG C, and pressure is normal pressure~0.3MPa.
10. according to the method for claim 8, it is characterised in that: the hud typed amorphous silicon Al catalysts are spherical shape,
Diameter is in 1.0mm-5.0mm.
11. according to the method for claim 1, it is characterised in that: when using slurry bed process, used reaction condition
Are as follows: volume space velocity is 0.5h when total liquid-1~10.0h-1, temperature is 150 DEG C~300 DEG C, and pressure is normal pressure~0.6MPa；Using
When slurry bed process, used atent solvent is one of inert mineral oil, hydrocracking tail oil, liquid paraffin hydrocarbon or more
Kind, atent solvent is after mixed serum is made with catalyst, to be added in paste state bed reactor, the content of catalyst in mixed serum
For 5.0wt%~30.0wt%.
12. according to the method for claim 11, it is characterised in that: when using slurry bed process, used reaction condition
Are as follows: volume space velocity is 1.0h when total liquid-1~5.0h-1, temperature is 180 DEG C~250 DEG C, and pressure is normal pressure~0.3MPa.
13. according to method described in claim 1,10 or 11, it is characterised in that: in the mixture of MTBE and TBA, MTBE with
The weight ratio of TBA is 0.5:1 ~ 40:1.
14. according to the method for claim 13, it is characterised in that: in the mixture of MTBE and TBA, the weight of MTBE and TBA
Amount is than being 1:1 ~ 20:1.
15. according to method described in claim 1,10 or 11, it is characterised in that: in the mixture of MTBE and TBA, methyl Zhong Ding
Base ether≤0.2wt%, methanol≤0.05wt%, isobutylene oligomer≤0.05 wt%, four or less hydro carbons of carbon four and carbon≤
0.1wt%.
16. according to method described in claim 1,10 or 11, it is characterised in that: add water purification into mixture, water purification is added
Amount accounts for the wt% of 1.0 wt% ~ 15.0 of mixture weight.
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| JP2858281B2 (en) * | 1992-02-19 | 1999-02-17 | 三菱レイヨン株式会社 | Method for producing tertiary olefin |
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