CN106673948A - Method for preparing isobutene from MTBE and TBA mixture - Google Patents
Method for preparing isobutene from MTBE and TBA mixture Download PDFInfo
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Abstract
The invention discloses a method for preparing isobutene from MTBE and TBA mixture. The method adopts a fixed bed technology which is carried out through at least two series-connected reactors. TBA is used as a raw material in one reactor and is subjected to a dehydration reaction in the presence of a TBA dehydration catalyst; and the dehydration reaction product and a MTBE and TBA mixture enter the other reactor and react in the presence of a core-shell amorphous silica-alumina catalyst so as to prepare isobutene. According to the core-shell amorphous silica-alumina catalyst, amorphous silica-alumina with or without an auxiliary component M is used as the core, and amorphous silica-alumina containing an auxiliary component N and halogen is used as the shell. By the method, MTBE cracking and TBA dehydration are simultaneously carried out to generate isobutene. Therefore, conversion rate of TBA and conversion rate of MTBE are both high; addition amount of water is avoided or reduced during MTBE cracking; reaction energy consumption is reduced; and selectivity for generation of isobutene is also high.
Description
Technical field
The present invention relates to a kind of method for preparing isobutene by cracking, is particularly well-suited to MTBE（Methyl tertiary butyl ether(MTBE)）And TBA（The tert-butyl alcohol）Compound prepares isobutene.
Background technology
Isobutene is important Organic Chemicals, is raw material with it mainly for the production of fine chemical products such as methyl methacrylate (MMA), butyl rubber, polyisobutene, tertiary butyl phenol, tert-butylamine, methylallyl chloride, trimethylace tonitric, isoprene, p-tert-octyl phenol, 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, refinery fluid catalytic cracking（FCC）By-product tert-butyl alcohol in the by-product C-4-fraction of device and the synthesis of Halcon methods expoxy propane etc., wherein industrial process mainly have sulfuric acid extraction, adsorption method of separation, tert-butyl alcohol dehydration method, methyl tertiary butyl ether(MTBE) cracking and n-butene isomerization process etc..
MTBE cracking is many to prepare advanced technology in isobutene method, a kind of method of better economy.In MTBE cracking preparing isobutene courses of reaction, main reaction is that under the effect of catalyst, MTBE is cracked into isobutene and methyl alcohol, most after the operation such as Jing rectifying obtain isobutene or high-purity isobutene.The catalyst type of MTBE cracking preparing isobutenes is more, including aluminum oxide, silica, amorphous silica-alumina, ion exchange resin, molecular sieve, solid phosphoric acid and other acidic resin catalyst systems.MTBE cracking preparing isobutene catalyst is amorphous silicon aluminum-based catalyst as disclosed in CN1853772A, CN102451674A, JP2004115407, JP2004091443, JP3220136 etc., for another example DE 3509292, DE 3210435, US 4447668, GB 1482883, US 4570026, US 4551567 etc. then adopt ion-exchange resin catalyst, and for another example patent CN 96123535.7, EP 0118085, JP 7626401, JP 7494602 etc. using solid phosphoric acid, sulfate, activated carbon as MTBE catalyst for cracking.When MTBE is cracked, water filling simultaneously is needed mostly, to prevent from generating the accessory substances such as Diisobutylene, dimethyl ether.
Another the more universal method for producing isobutene is TBA dehydrations.The reaction of TBA dehydration preparing isobutenes has that accessory substance is few, separation and purification easily, reduced investment the features such as.Conventional catalyst includes aluminum oxide, molecular sieve, sulfonic acid ion exchange resin etc..Isobutene dehydration catalyst is alumina series catalyst as disclosed in US3665048, CN101300211A, CN102516030A etc..For another example it is with 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:First pass through after polystyrene, chliorinated polyvinyl chloride, polytrifluorochloroethylene and Kynoar or poly- phenylstilbene bromide are blended, are melted by melt pelletization method and granulate, then granulated and sulfur trioxide carries out sulfonating reaction and obtains described catalyst.
In production process, MTBE and TBA compounds are more often met.Its main source has two kinds.The first source is the TBA that can produce more amount as the driving initial stage of waste MTBE with isobutene and methyl alcohol.This is because when going into operation, catalyst or（And）May adulterate a certain amount of water in installing pipes, and excessive isobutene is readily generated TBA with water reaction.For commercial plant, also imply that having considerable amount of MTBE and TBA product mix at the initial stage of going into operation generates.MTBE and TBA product mix is used as waste disposal, or is separated using MTBE/TBA knockout towers, respectively obtains target product MTBE and TBA.
Second source, be also most important source be artificial production, i.e., coproduction TBA while MTBE is prepared.First, it is that the technology for specially producing TBA has some problems.TBA production technologies are complex, and because C-4-fraction is poor with the intersolubility of water, therefore TBA product designs only have 45%-55%, and in addition TBA azeotrope with water is difficult to separate, and conventional distillation can only obtain 85% TBA.Being typically employed to multitple extraction rectifying can just obtain the TBA products of higher concentration, but equipment investment and operating cost will be increased substantially.Secondly, coproduction TBA has technical advantage while preparing MTBE:（1）Scheme simple and flexible.Process program can suitably be adjusted according to product demand commercially.Only need to simply be switched and be changed suitable catalyst to technological process, so that it may realize per unit area yield MTBE or TBA, and MTBE and TBA mixtures.（2）Flow process is convenient to carry out, and investment risk is little.Switch to joint production process by be transformed just can be easy to per unit area yield MTBE techniques, it is convenient to carry out.Again traditional per unit area yield technique can be easily returned to simultaneously, MTBE/TBA knockout towers more than needed can be used to carry out the separation of n-butene in C-4-fraction.Therefore, there is no investment risk in the technology.Finally, combined production device investment cost is low.If there be a special per unit area yield MTBE and special per unit area yield TBA devices in manufacturer, the two each architectonical, each other equipment can not be borrowed, therefore more than the equipment of joint production process, and investment is big.Combined production device can simultaneously produce MTBE and TBA, produce MTBE and TBA respectively with scale set than newly-built two sets and reduce investment outlay more than 40%, while also significantly reducing operating cost.Therefore, coproduction TBA technologies have obtained extensive attention while MTBE is prepared.In its Master's thesis " optimization of MTBE devices is analyzed and is related to pre-test with the coproduction of TBA ", coproduction TBA technologies have carried out serious analysis to the Lu Chunlong of Xi'an Petroleum University while with regard to preparing MTBE, have obtained answer certainly.CN200610104876.6 discloses the production method of the isobutene in a kind of use C-4-fraction and methanol-water coproducing methyl tertbutyl ether and the tert-butyl alcohol.But MTBE the and TBA compound products of coproduction, main whereabouts is separated using MTBE/TBA knockout towers, respectively obtains target product MTBE and TBA.
Whether the first source or second MTBE and TBA compound for obtaining of source, at this stage, compound is used as when producing isobutene, substantially using purer MTBE raw materials and TBA raw materials is obtained after compound is separated, then respectively on MTBE crackers and TBA dehydration devices distinguishing preparing isobutene.
Carry out cracking preparing isobutene technology about MTBE and TBA compounds, it is at this stage or blank.The reason for one of them is important is that the requirement of MTBE crackers and TBA dehydration devices to catalyst performance is inconsistent.It is generally believed that the active sites on MTBE catalyst for cracking surface are sour with Bronsted（B is sour）Based on center, and the catalyst of TBA dehydration preparing isobutenes is that Lewis is sour（L is sour）Catalytic reaction process.For single kind catalyst, or with B it is sour based on, or with L it is sour based on, it is impossible to both take into account.Another reason, using common catalyst, both reaction conditions are different, especially reaction temperature, and TBA dehydration temperaturres are lower compared with MTBE cracking temperatures.Therefore, how to process MTBE and TBA compounds simultaneously under same device same reaction conditions to produce isobutene, while being an important subject of this area with higher activity and selectivity.
The content of the invention
In order to realize preparing isobutene as raw material with MTBE and TBA compounds, the invention provides a kind of method that MTBE and TBA compounds prepare isobutene.The method can not only realize that MTBE and TBA simultaneous reactions generate isobutene, and MTBE and TBA are respectively provided with higher conversion ratio, and avoid or reduces the addition of water when MTBE is cracked, and reduction energy consumption of reaction, isobutene reaches higher selectivity.
The method that MTBE and TBA compounds of the present invention prepare isobutene, using fixed-bed process, carry out in the reactor of at least two series connection, previous reactor is with TBA as raw material, dehydration is carried out in the presence of TBA dehydration catalysts, product after dehydration enters latter reactor with MTBE and TBA compounds, is reacted in the presence of hud typed amorphous silicon Al catalysts, prepares isobutene；Wherein hud typed amorphous silicon Al catalysts, with A as core, with B as shell, A is the amorphous silica-alumina with or without adjuvant component M, and B is N containing adjuvant component and the amorphous silica-alumina of halogen.
In hud typed amorphous silicon Al catalysts used by the inventive method, in the A, SiO2Content is 65.0wt%～97.0wt%, preferably preferably 78.0wt%～93.0wt%, 85.0wt%～91.0wt%, the content that adjuvant component M is counted with element as 0～1.5wt%, preferred 0.2wt%～1.0wt%；In B, SiO2Content is 24.0wt%～60.0wt%, preferably 28.0wt%～54.0wt%, preferably 33.0wt%～50.0wt%, the content that adjuvant component N is counted with element as 0.2wt%～0.8wt%, it is preferred that 0.3wt%～0.5wt%, the content that halogen is counted with element as 0.05wt%～0.20wt%, preferred 0.08wt%～0.15wt%；The weight ratio of A and B is 40：1～4：1, preferably 30：1～6：1.
In hud typed amorphous silicon Al catalysts used by the present invention, one or more in the A containing adjuvant component M in group iia and group VIII metal, wherein group iia metal is preferably one or more in Be, Mg and Ca, and group VIII metal is preferably one or more in Ni, Pd and Pt.The adjuvant component N contained in the B is one or more in zinc, iron, niobium；Halogen is selected from one or more in fluorine, chlorine, bromine, preferred chlorine.
The property of the hud typed amorphous silicon Al catalysts used by the present invention is as follows：Specific surface area is 180m2/ g～450m2/ g, pore volume is 0.3mL/g～1.2 mL/g；Preferably specific surface area is 200m2/ g～410m2/ g, pore volume is 0.4mL/g～1.0mL/g.
The preparation method of the hud typed amorphous silicon Al catalysts used by the present invention, including：A is first prepared i.e. with or without the amorphous silica-alumina of adjuvant component M, then B is carried on the outer surface of A, form hud typed amorphous silicon Al catalysts.
The preparation method of A is as follows in hud typed amorphous silicon Al catalysts used by the present invention：After sial dry glue powder is molded, drying and roasting, then with saturated vapor process, temperature is 100 DEG C～600 DEG C, and the time is 1h～10h.Sial dry glue powder can be prepared using in conventional method such as sial with plastic method, it is also possible to buy finished product.When described A is molded, its shape is preferably spherical, 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 by the present invention.Adjuvant component M can adopt conventional method（Such as blending method, infusion process）In being introduced into A, such as introducing can be blended during sial plastic, it is also possible to introduce in sial plastic post blend；Introducing can be impregnated before steam treatment, it is also possible to which dipping is introduced after steam treatment.
In hud typed amorphous silica-alumina catalyst method used by the present invention, the adjuvant component N and halogen in the B can adopt conventional method（Such as blending method）In being introduced into B, such as introduce during sial plastic, it is also possible to introduce after sial plastic.
In hud typed amorphous silica-alumina catalyst method used by the present invention, B is carried on the method that the outer surface of A can adopt conventional formation core shell structure, such as dip coating, spray method etc..
The preferably specific preparation process of hud typed amorphous silicon Al catalysts used by the present invention is as follows：Shaping A, drying and roasting are first prepared, after then spraying the amorphous silica-alumina B slurries of N containing adjuvant component and halogen, drying and roasting obtain final catalyst.Wherein, A shapings are general using conventional forming method, can as needed make suitable size and shape, such as spherical, bar shaped etc..Spheric catalyst can be using oil drop method, rotary type comminution granulation, marumerizer method of forming etc., and its geometric diameter is preferably chosen as 2.0mm-3.0mm between 1.0mm-5.0mm.In the inventive method, in the forming process of A, can also add binding agent and shaping assistant, binding agent that conventional binding agent, generally little porous aluminum oxide can be adopted to account for the 2.0wt%～20.0wt% of final catalyst weight.Shaping assistant such as sesbania powder or methylcellulose, account for the 1.5wt%～3.0wt% of final catalyst weight.In the inventive method, involved drying and roasting in catalyst preparation process is typically carried out using normal condition, such as drying condition：1h ~ 24h, roasting condition are dried at 80 DEG C ~ 150 DEG C:At 400 DEG C～700 DEG C, roasting 1h ~ 24h at preferably 450 DEG C～600 DEG C.
In the inventive method, in previous reactor and the charging of latter reactor, the weight ratio of TBA is 1：10~10：1, preferably 1：8~1：2.
The charging of the latter reactor of the present invention, the weight ratio of MTBE and TBA is 1 in MTBE and TBA compounds:1~50:1, preferably 2:1~30:1.The reaction condition of latter reactor is：Temperature is 120 DEG C～300 DEG C, preferably 150 DEG C～250 DEG C；Pressure is normal pressure～0.6MPa, preferably normal pressure～0.3MPa；Volume space velocity is 0.5h during total liquid-1～10.0h-1, preferably 2.0h-1～5.0h-1。
The inventive method can adopt conventional reactor, such as crack preparing isobutene device or TBA dehydration preparing isobutene devices using original MTBE.
The inventive method, the weight ratio for being particularly suitable for processing MTBE and TBA is 1:1~50:1 compound, the weight ratio of preferred MTBE and TBA is 2:1~30:1.Impurity in compound be equal to or less than routine MTBE for raw material prepare isobutene and TBA for raw material dehydration preparing isobutene when raw material in the impurity that contains, such as methyl sec-butyl ether≤0.2wt%, methyl alcohol≤0.05wt%, isobutylene oligomer≤0.05 wt%, carbon four and carbon hydro carbons≤0.1wt% below four.
The inventive method is using at least two reactors connected, previous reactor carries out TBA dehydrations, its product enters latter reactor with MTBE and TBA compounds, the cracking simultaneously of MTBE and TBA compounds is carried out in the presence of a kind of special catalyst and prepares isobutene, not only realize MTBE cracking and TBA is dehydrated two kinds of reactions while carrying out generation isobutene, make TBA conversion ratio and MTBE conversion ratio it is higher, and also save the process that adds water in conventional MTBE cracking reactions, energy consumption of reaction is reduced, the selectivity for generating isobutene is also higher.
The present invention is by a kind of raw catelyst of synthesis, for generating in the reaction of isobutene by raw material of MTBE and TBA compounds, TBA dehydrations are made to crack two kinds of reactions while being prepared isobutene with MTBE, avoid the separation process of MTBE and TBA compounds, and avoid building MTBE crackers respectively and TBA dehydration devices produce isobutene, save operating procedure, reduce cost of investment, make TBA conversion ratio and MTBE conversion ratio it is higher, and the step that adds water when saving MTBE cracking, energy consumption of reaction is reduced, the selectivity for generating isobutene is also higher.
Specific embodiment
In the inventive method, TBA dehydration catalysts can adopt conventional catalyst, can adopt sulfonic acid ion exchange resin catalyst, it would however also be possible to employ aluminium oxide catalyst.Sulfonic acid ion exchange resin catalyst used, is the polystyrene with sulfonic acid group, crosslinking, and after being processed with the concentrated sulfuric acid or chlorosulfonic acid after polymerisation sulfonic acid group is introduced.The exchange capacity of sulfonic acid ion exchange resin catalyst is 3.0mmol/g～6.0mmol/g.Aluminium oxide catalyst used can adopt conventional aluminium oxide catalyst.
In the inventive method, previous reactor TBA dehydrations can adopt conventional process conditions, general as follows：Temperature is 80 DEG C～300 DEG C, and pressure is normal pressure～0.6MPa, preferably normal pressure～0.3MPa；Volume space velocity is 0.3h during liquid-1～10.0h-1, preferably 0.8h-1～5.0h-1.Specific process conditions those skilled in the art can constitute according to selected catalyst and raw material and the requirement to product is determining.In the inventive method, for previous reactor TBA dehydrations, the conversion ratio of TBA will be at least more than 20wt%, preferably more than 50wt%.
In the present invention, material purity and product form adopt gas chromatography analysis.Specific surface area and pore volume are using low temperature liquid nitrogen determination of adsorption method.Constituent content is determined using inorganic analysis method.In the present invention, wt% is mass fraction.
Comparative example 1
With the macroporous cross-linked polystyrene-divinylbenzene Archon being polymerized（Diameter 2.6mm）It is solvent after 50 DEG C of swelling 1.5h with dichloroethanes, with sulfur trioxide as sulfonating agent for sulphonated supports, 3.0h is reacted at 80 DEG C, 120 DEG C of reaction 1.0h are warming up to, dichloroethanes is then removed, sulfonic acid ion exchange resin catalyst SZ-1 is obtained Jing after being washed to neutrality and drying.Its TBA cracking evaluation result is shown in Table 1.
Comparative example 2
By amorphous silica-alumina bead XQ1（Grain size 2.2mm-2.5mm）Immersion Ni (NO3)2In the aqueous solution, 400 DEG C of roasting 6h of Jing must contain the amorphous silica-alumina bead XQ1-1 of nickel oxide after dipping, then Jing after 300 DEG C, the process of 6h saturated vapors, obtain the amorphous silica-alumina bead XQ1-2 containing nickel oxide.In XQ1-2, nickel content is 0.40wt%, SiO2Content 86.90wt%, Al2O3Content is 12.70wt%.
By Alusil GLJ1（In terms of butt, SiO2Content 35.00wt%, Al2O3Content is 65.00wt%）Spray on XQ1-2,4h is dried at 120 DEG C, roasting 6h at 500 DEG C obtains catalyst DB-2, and wherein stratum nucleare and the weight ratio of shell are 7：1.Concrete evaluation result is shown in Table 2.
Comparative example 3
XQ1-2 grindings in comparative example 2 are become into the powder of the mesh of 250 mesh -300, XQ1-3 is made.
Under agitation, appropriate zinc carbonate is slowly added in the Alusil GLJ1 in comparative example 2 and ammonium chloride solution is mixed, 4 h are dried at 120 DEG C of Jing, GLJ1-1 powder is obtained after 450 DEG C of roastings, wherein the content of zinc is calculated as 0.30wt% with element, and chlorinity is 0.10wt%）.
XQ1-3 and GLJ1-1 are compared into 7 with weight:1 uniform mixing, be subsequently adding weight accounting be 10wt% little porous aluminum oxide as adhesive, grain size catalyst pellet between 2.2mm-2.5 mm is shaped to the marumerizer method of forming, be dried 4h at 120 DEG C, 450 DEG C of roasting 12h of Jing, obtain catalyst DB-3.Concrete evaluation result is shown in Table 2.
Comparative example 4
By the Alusil GLJ1 in comparative example 2,4 h are dried at 120 DEG C of Jing, the little porous aluminum oxide that weight accounting is 15wt% is added in the powder obtained after 450 DEG C of roastings as adhesive, grain size catalyst pellet between 2.2mm-2.5mm is shaped to the marumerizer method of forming, 4h is dried at 120 DEG C, 400 DEG C of roasting 16h of Jing, obtain catalyst DB-4.Concrete evaluation result is shown in Table 1.
Comparative example 5
The little porous aluminum oxide that weight accounting is 15wt% will be added in GLJ1-1 powder in comparative example 3 as adhesive, grain size catalyst pellet between 2.2mm-2.5 mm is shaped to the marumerizer method of forming, 4h, 400 DEG C of roasting 16h of Jing are dried at 120 DEG C, catalyst DB-5 is obtained.Concrete evaluation result is shown in Table 1.
Comparative example 6
By the amorphous silica-alumina bead XQ1-2 obtained in comparative example 2, in MTBE cracking reactions, its evaluation result to be shown in Table 3.
Comparative example 7
Using comparative example 2 and comparative example 3 and the catalyst of embodiment 1, its MTBE and TBA cracking evaluation result in the case of without preposition TBA dehydration catalysts is shown in Table 4.
Embodiment 1
Amorphous silica-alumina bead XQ1 is obtained XQ1-2 by the method according to comparative example 2.In XQ1-2, the content of nickel is 0.40wt%, SiO2Content 86.90wt%, Al2O3Content is 12.70wt%.
Zinc carbonate will be added in Alusil GLJ1 in comparative example 2 and ammonium chloride solution is mixed, sprayed on XQ1-2,4 h, roasting 6h at 500 DEG C are dried at 120 DEG C, obtain core shell structure SL-1 catalyst.The weight ratio of stratum nucleare A and shell B is 7：1, in shell B, SiO2Content is 34.80wt%, and alumina content is 64.80wt%, and Zn content is 0.30wt%, and chlorinity is 0.10wt%.Concrete evaluation result is shown in Table 2.
Embodiment 2
By the amorphous silica-alumina bead XQ1 immersion Ca (NO in comparative example 23)2In the aqueous solution, 600 DEG C of roasting 3h of Jing obtain the amorphous silica-alumina bead XQ1-4 of calcic after dipping, then Jing after 500 DEG C, the process of 1.5h saturated vapors, obtain 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 2 and ammonium bromide mixed solution is mixed, sprayed（XQ1-5）On, 4 h, roasting 5h at 500 DEG C are dried at 110 DEG C, obtain core shell structure SL-2 catalyst.The weight ratio of stratum nucleare A and shell B is 10：1；In shell B, silica content is 34.82wt%, and alumina content is 64.66wt%, and iron content is 0.40wt%, and bromine content is 0.12wt%.Concrete evaluation result is shown in Table 2.
Embodiment 3
By a certain amount of amorphous silica-alumina bead XQ2（Grain size 2.6mm-2.9mm）Immersion Be (NO3)2In the aqueous solution, 500 DEG C of roasting 5h of Jing must contain the amorphous silica-alumina XQ2-1 of beryllium after dipping, then Jing after 200 DEG C, the process of 4h saturated vapors, obtain XQ2-2.In XQ2-2, the content of beryllium is 0.95wt%, SiO2Content 81.22wt%, Al2O3Content is 17.83wt%.
Add proper amount of acetic acid zinc, ammonium bromide mixed solution in Alusil GLJ2 to mix, spray on XQ2-2,2h is dried at 120 DEG C, roasting 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, in shell B, silica content is 44.84wt%, and alumina content is 54.74wt%, and Zn content is 0.34wt%, and bromine content is 0.08wt%.Concrete evaluation result is shown in Table 2.
Embodiment 4
By the amorphous silica-alumina bead XQ2 immersion Ni (NO in embodiment 33)2In the aqueous solution, 400 DEG C of roasting 3h of Jing obtain nickeliferous amorphous silica-alumina bead XQ2-3 after dipping, then Jing after 300 DEG C, the process of 4.5h saturated vapors, obtain 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 is mixed, sprayed on XQ2-4,3 h, roasting 3h at 500 DEG C are dried at 100 DEG C, obtain core shell structure SL-4 catalyst.The weight ratio of stratum nucleare A and shell B is 10：1；In shell B, silica content is 44.61wt%, and alumina content is 54.51wt%, and content of niobium is 0.78wt%, and Oil repellent is 0.10wt%.Concrete evaluation result is shown in Table 2.
Table
1
Comparative example
1
、
4
With
5
's
TBA
Cracking fixed bed appreciation condition and result
| Comparative example 1 | Comparative example 4 | Comparative example 4 | Comparative example 5 | Comparative example 5 | |
| Catalyst | SZ-1 | DB-4 | DB-4 | DB-5 | DB-5 |
| Volume space velocity during TBA liquid, h-1 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Reaction temperature, DEG C | 95 | 265 | 210 | 265 | 210 |
| Reaction pressure, MPa | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
| TBA conversion ratios, wt% | 83.5 | 93.1 | 90.8 | 96.5 | 94.4 |
| The selectivity of isobutene, wt% | 99.6 | 94.5 | 93.6 | 87.3 | 86.8 |
When for TBA being cracked from table 1, the amorphous silicon Al catalysts DB-4 without auxiliary agent and with the modified amorphous silicon Al catalysts DB-5 of zinc, chlorine, catalytic performance when catalytic performance when reaction temperature is 265 DEG C is 210 DEG C significantly better than reaction temperature.Further, when the modified amorphous silicon Al catalysts of zinc, chlorine are used for TBA cracking reactions, the conversion ratio of TBA is improved, but selective undesirable.
Table
2
Comparative example
2
、
3
And embodiment
1-4
The fixed-bed process evaluation result of prepared catalyst
| Appreciation condition and result | Comparative example 2 | Comparative example 3 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| First paragraph TBA dehydration reactors | ||||||
| Catalyst | DB-4 | DB-4 | DB-4 | SZ-1 | SZ-1 | DB-4 |
| Volume space velocity during TBA liquid, h-1 | 1.0 | 1.0 | 2.0 | 1.0 | 1.0 | 2.0 |
| Reaction temperature, DEG C | 210 | 210 | 210 | 105 | 95 | 155 |
| Reaction pressure, MPa | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | Normal pressure |
| Second segment MTBE and TBA compound is cracked | ||||||
| Catalyst | DB-2 | DB-3 | SL-1 | SL-2 | SL-3 | SL-4 |
| Volume space velocity during MTBE liquid, h-1 | 4.0 | 4.0 | 4.0 | 3.5 | 2.3 | 3.0 |
| Volume space velocity during TBA liquid, h-1（Fresh feed） | 0.5 | 0.5 | 0.5 | 0.5 | 1.0 | 2.0 |
| Reaction temperature, DEG C | 210 | 210 | 210 | 210 | 210 | 155 |
| Reaction pressure, MPa | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | Normal pressure |
| MTBE conversion ratios, wt% | 97.7 | 97.4 | 99.9 | 99.9 | 99.7 | 98.0 |
| TBA conversion ratios, wt% | 91.7 | 93.5 | 99.7 | 99.7 | 99.9 | 99.3 |
| Selective isobutene, wt% | 98.3 | 98.9 | 99.9 | 99.8 | 99.7 | 99.7 |
As can be seen from Table 2, using the technical process of the present invention, and the new catalyst provided using the present invention（Catalyst i.e. with the amorphous silica-alumina B of additive modification as shell, with the amorphous silica-alumina A of additive modification as core）, can not only realize that MTBE cracking and TBA are dehydrated two kinds of reactions while carrying out generating isobutene reaction process, and with the conversion ratio of higher MTBE and TBA, the selectivity of isobutene is higher, illustrates that the inventive method can efficiently control the generation of side reaction.
Meanwhile, the nucleocapsid catalyst for only being prepared as shell with unmodified amorphous silica-alumina B, itself MTBE and TBA conversion ratio is not high, and the selectivity of isobutene is also poor；Even if modified amorphous silica-alumina A and modified amorphous silica-alumina B is mixed to prepare into catalyst, although the conversion ratio of MTBE and TBA, selective isobutene increase, but still undesirable.
Table
3
Comparative example
6
's
MTBE
Cracking fixed bed appreciation condition and result
| Comparative example 6 | Comparative example 6 | |
| Catalyst | XQ1-2 | XQ1-2 |
| Volume space velocity during MTBE liquid, h-1 | 2.5 | 2.0 |
| Volume space velocity during aqueous, h-1 | 0.1 | 0.1 |
| Reaction temperature, DEG C | 230 | 210 |
| Reaction pressure, MPa | Normal pressure | 0.05 |
| MTBE conversion ratios, wt% | 99.8 | 98.6 |
| The selectivity of isobutene, wt% | 99.4 | 99.3 |
As can be seen from Table 3, the catalytic performance when amorphous silica-alumina pellet catalyst containing nickel oxide is cracked for MTBE, when catalytic performance when reaction temperature is 230 DEG C is 210 DEG C significantly better than reaction temperature.
Table
4
Comparative example
7
's
MTBE
With
TBA
Compound cracks fixed bed appreciation condition and result
| Catalyst | DB-2 | DB-3 | SL-1 |
| Volume space velocity during total liquid, h-1 | 4.5 | 4.5 | 4.5 |
| Volume space velocity during MTBE liquid, h-1 | 4.0 | 4.0 | 4.0 |
| Volume space velocity during TBA liquid, h-1 | 0.5 | 0.5 | 0.5 |
| Reaction temperature, DEG C | 230 | 230 | 230 |
| Reaction pressure, MPa | 0.05 | 0.05 | 0.05 |
| MTBE conversion ratios, wt% | 97.6 | 96.3 | 99.1 |
| TBA conversion ratios, wt% | 92.5 | 91.9 | 99.0 |
| Selective isobutene, wt% | 98.3 | 99.3 | 99.5 |
As can be seen from Table 4, the nucleocapsid catalyst that prepared as shell with unmodified amorphous silica-alumina B, modified amorphous silica-alumina A and modified amorphous silica-alumina B are mixed to prepare catalyst, are exclusively used in the catalyst of MTBE and TBA compounds cracking, if not preposition TBA dehydrations, its conversion ratio and selective isobutene do not reach the embodiment level of table 2.
Claims (12)
1. a kind of method that MTBE and TBA compounds prepare isobutene, using fixed-bed process, carry out in the reactor of at least two series connection, previous reactor is with TBA as raw material, dehydration is carried out in the presence of TBA dehydration catalysts, product after dehydration enters latter reactor with MTBE and TBA compounds, is reacted in the presence of hud typed amorphous silicon Al catalysts, prepares isobutene；Wherein hud typed amorphous silicon Al catalysts, with A as core, with B as shell, wherein A is the amorphous silica-alumina with or without adjuvant component M, SiO in A2Content is 65.0wt%～97.0wt%, and the content that adjuvant component M is counted with element is as 0～1.5wt%；B is N containing adjuvant component and the amorphous silica-alumina of halogen, SiO in B2Content is 24.0wt%～60.0wt%, the content that adjuvant component N is counted with element as 0.2wt%～0.8wt%, the content that halogen is counted with element as 0.05wt%～0.20wt%；The weight ratio of A and B is 40：1～4：1, preferably 30：1～6：1.
2. in accordance with the method for claim 1, it is characterised in that：In the A of the hud typed amorphous silicon Al catalysts, SiO2Content is 78.0wt%～93.0wt%, the content that adjuvant component M is counted with element as 0.2wt%～1.0wt%；In B, SiO2Content is 28.0wt%～54.0wt%, the content that adjuvant component N is counted with element as 0.3wt%～0.5wt%, the content that halogen is counted with element as 0.08wt%～0.15wt%；It is preferably as follows：In A, SiO2Content is 85.0wt%～91.0wt%, the content that adjuvant component M is counted with element as 0.2wt%～1.0wt%；In B, SiO2Content is 33.0wt%～50.0wt%, the content that adjuvant component N is counted with element as 0.3wt%～0.5wt%, the content that halogen is counted with element as 0.08wt%～0.15wt%.
3. in accordance with the method for claim 1, it is characterised in that：In the A of the hud typed amorphous silicon Al catalysts, adjuvant component M is selected from one or more in group iia and group VIII metal, wherein group iia metal is preferably one or more in Be, Mg and Ca, and group VIII metal is preferably one or more in Ni, Pd and Pt；In B, the adjuvant component N for containing is one or more in zinc, iron, niobium, and halogen is selected from one or more in fluorine, chlorine, bromine.
4. in accordance with the method for claim 1, it is characterised in that the property of described hud typed amorphous silicon Al catalysts is as follows：Specific surface area is 180m2/ g～450m2/ g, pore volume is 0.3mL/g～1.2 mL/g；Preferably specific surface area is 200m2/ g～410m2/ g, pore volume is 0.4mL/g～1.0mL/g.
5. according to the arbitrary described method of Claims 1 to 4, it is characterised in that：The hud typed amorphous silicon Al catalysts are spherical, and its diameter is in 1.0mm-5.0mm.
6. in accordance with the method for claim 1, it is characterised in that：In the charging of latter reactor, the weight ratio of MTBE and TBA is 1:1~50:1, preferably 2:1~30:1.
7. in accordance with the method for claim 1, it is characterised in that：In previous reactor and the charging of latter reactor, the weight ratio of TBA is 1：10~10：1, preferably 1：8~1：2.
8. in accordance with the method for claim 1, it is characterised in that：The reaction condition of latter reactor is：Temperature is 120 DEG C～300 DEG C, and pressure is normal pressure～0.6MPa, and volume space velocity is 0.5h during total liquid-1～10.0h-1, preferably temperature is 150 DEG C～250 DEG C, and pressure is normal pressure～0.3MPa, and volume space velocity is 2.0h during total liquid-1～5.0h-1。
9. in accordance with the method for claim 1, it is characterised in that：In the compound of latter reactor, methyl sec-butyl ether≤0.2wt%, methyl alcohol≤0.05wt%, isobutylene oligomer≤0.05 wt%, carbon four and carbon hydro carbons≤0.1wt% below four.
10. in accordance with the method for claim 1, it is characterised in that：TBA dehydration catalysts are using sulfonic acid ion exchange resin catalyst or adopt aluminium oxide catalyst.
11. according to the method described in claim 1 or 10, it is characterised in that：The process conditions of previous reactor TBA dehydrations are as follows：Temperature is 80 DEG C～300 DEG C, and pressure is normal pressure～0.6MPa, and volume space velocity is 0.3h during liquid-1～10.0h-1。
12. in accordance with the method for claim 1, it is characterised in that：For previous reactor TBA dehydrations, the conversion ratio of TBA will be at least more than 20wt%, more preferably at least more than 50wt%.
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