CN103102235B - Method for isobutene production and co-production of gasoline with high octane value by n-butene isomerization - Google Patents
Method for isobutene production and co-production of gasoline with high octane value by n-butene isomerization Download PDFInfo
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- CN103102235B CN103102235B CN201110351797.6A CN201110351797A CN103102235B CN 103102235 B CN103102235 B CN 103102235B CN 201110351797 A CN201110351797 A CN 201110351797A CN 103102235 B CN103102235 B CN 103102235B
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Abstract
The invention provides a method for isobutene production and co-production of gasoline with high octane value by n-butene isomerization. Double temperature stage control and a catalyst surface carbon deposition process are combined organically, so that the catalyst realizes double functions in the reaction process, and can effectively adjust the distribution of isomeric olefine and a gasoline fraction with high octane value, and realize n-butene conversion rate higher than 40%, isobutene yield higher than 20%, yield of gasoline with high octane higher than 20% and octane value of the gasoline fraction with high octane value greater than 95. The invention uses one process to product two products, improves operation flexibility of the process, and fully utilizes n-butene in C4.
Description
Technical field
The present invention relates to a kind of method that iso-butylene co-production of gasoline with high octane is prepared in n-butene isomerization.
Background technology
Because methyl tertiary butyl ether (MTBE), Ethyl Tertisry Butyl Ether (ETBE) demonstrate higher octane value, low-steam pressure and the good solubility in gasoline fraction hydro carbons and become excellent gasoline addO-on therapy in reformulated gasoline and oxygenated gasoline, demand increases sharply in the whole world, causes many ether-based devices all to be expanded production.In the outlet material of ether-based device producing MTBE, after separating methyl alcohol and ether, normal olefine accounts for 40-100 % by weight, and the n-butene resource that will produce after a large amount of ether of expanding production of device, burns mainly as liquefied gas at present, is badly in need of finding new purposes.
Expanding production of ether-based device makes the iso-butylene output obtained by traditional petroleum catalytic cracking and hot-work far can not meet the needs of production.And the material being rich in n-butene after ether is carried out skeletal isomerization to produce the object that iso-butylene can reach volume increase iso-butylene, be the effective way that n-butene is recycled.
CN1068320A provides and a kind ofly adopts two-dimentional central hole zeolite catalyst that C4 ~ C10 normal olefine is converted into the method for iso-butylene, and used catalyst is by SiO
2/ Al
2o
3mol ratio be 5: 1 ~ 500: 1 H-ferrierite powder mix a kind of two-dimentional mesopore H-magnesium alkali zeolite catalyst or similar catalyst S APO, MEAPO that (H-ferrierite powder/binder wt ratio is 1: 9.5 ~ 9: 1) make with tackiness agent, at 340 ~ 650 DEG C, olefin partial pressures is higher than 0.5 normal atmosphere, stagnation pressure is 0.5 ~ 10 normal atmosphere, hydrogen/hydrocarbon mol ratio is 0 ~ 30, and air speed is 1 ~ 50h
-1under condition, the selectivity of iso-butylene is 50 ~ 99%, and isoolefine yield is 25 ~ 40%.The C5+ heavy hydrocarbon (aromatic hydrocarbons, heavy paraffin hydrocarbon and alkene) of the method by-product 0.01 ~ 58%, in reaction process can there is coking in catalyzer, needs to carry out regeneration activating more than 500 DEG C.
US5449851 discloses a kind of n-butene is converted into iso-butylene by the ZSM-35 of utilization catalyzer method by skeletal isomerization, and catalyzer used is by SiO
2/ Al2O
3mol ratio is HZSM-35 and the SiO of 20.3
2be mixed containing 65%HZSM-35 and 35%SiO
2mixed type HZSM-35/SiO2 catalyzer or SiO
2solid-carrying type HZSM-35 catalyzer, or rare-earth cation is introduced above-mentioned HZSM-35/SiO
2the catalyzer made, 325 ~ 500 DEG C, have N
2under existence, 156 ~ 177KPa total pressure, the transformation efficiency of n-butene is 10 ~ 35%, and the selectivity of iso-butylene is 75 ~ 99%, and the yield of iso-butylene is 25 ~ 40%, C5 ~ C6+ heavy hydrocarbon of the method by-product 0.1 ~ 0.7%, in reaction process can there is coking in catalyzer.
Will containing carbon four after alkene (as n-butene) ether under special-purpose catalyst effect, there is the reactions such as superimposed, cyclisation, isomerization, hydrogen transference, alkylation, dehydrogenation, producing the gasoline fraction being rich in isomeric hydrocarbon, aromatic hydrocarbons, is also an effective utilization ways.CN1597867A discloses a kind of catalyzer generating high-octane rating clean gasoline for the alkene aromizing in refinery's liquefied gas and alkylated reaction, and this catalyzer is by SiO
2/ Al
2o
3mol ratio be 20 ~ 80 ZSM-5, ZSM-11, MCM-22, one or more mixed molecular sieves of ZSM-35 molecular sieve and inert fraction introduce rare earth element again after being mixed and made into hydrogen type molecular sieve and make, wherein molecular sieve content is 15 ~ 70wt%, ree content is 0 ~ 5wt%, and all the other are inert component.Under 250 ~ 450 DEG C of conditions, the gasoline octane rating of gained is high, non-benzene aromaticity content high (being greater than 50%), and benzene content very low (being less than 1%), olefin(e) centent low (being less than 15%).
The skeletal isomerization just carrying out alkene had in above-mentioned prior art generates iso-butylene, generates with C5+ heavy hydrocarbon (aromatic hydrocarbons, heavy paraffin hydrocarbon and alkene) component, and easily generation coking makes catalyst deactivation; What have only can only be converted into liquid gasoline cut by liquefied gas.Above-mentioned technology all can not make positive structure butylene generation skeletal isomerization in liquefied gas generate iso-butylene and the high octane gasoline component of coproduction simultaneously in one apparatus.Therefore, be necessary that aligning isomerization of butene preparing isobutene production technique improves, make it both to generate iso-butylene by the skeletal isomerization of alkene, simultaneously coproduction high octane gasoline products again, and coking reduction rate of catalyst deactivation can be reduced, thus n-butene in C4 is utilized more fully.
Summary of the invention
Technical problem to be solved by this invention provides a kind of n-butene isomerization to prepare the method for iso-butylene co-production of gasoline with high octane for above-mentioned the deficiencies in the prior art.Adopt the inventive method while n-butene skeletal isomerization prepares iso-butylene, adjustable produces high octane gasoline products.
In order to achieve the above object, the invention provides a kind of method preparing iso-butylene co-production of gasoline with high octane for n-butene isomerization, comprising:
Steps A, there is superimposed, cyclisation, isomerization, hydrogen transference, alkylation and dehydrogenation reaction in the carbon Four composition being rich in positive structure butylene, produce the high octane gasoline component containing C8 isomeric olefine and aromatic hydrocarbons under an acidic catalyst effect;
Step B, under an acidic catalyst effect, there is selectivity skeletal isomerization generate iso-butylene in the carbon Four composition being rich in positive structure butylene;
Wherein, the temperature of reaction of steps A is 200 ~ 300 DEG C, and the temperature of reaction of step B is 300 ~ 350 DEG C.
According to the present invention, steps A and step B all carry out in fixed-bed reactor, and react for gas-solid phase reaction, reaction pressure is normal pressure.The reaction times of steps A is 36 ~ 72h, and reaction velocity is 0.5 ~ 1.0h
-1.The reaction times of step B is 144 ~ 192h, and reaction velocity is 0.5 ~ 1.0h
-1.
An acidic catalyst described in the present invention is acid molecular sieve catalyst, and wherein molecular sieve is Si-Al molecular sieve or sial phosphorus molecular sieve.
According to the inventive method, described molecular sieve is HZSM-35 molecular sieve, wherein SiO
2/ Al
2o
3mol ratio is 10 ~ 80: 1.Described HZSM-35 molecular sieve and inert component baking mixed after make HZSM-35 acid molecular sieve catalyst, wherein HZSM-35/ inert component weight ratio is 1: 1 ~ 4: 1, and catalyst surface area is greater than 200m
2/ g.Described inert component is preferably pseudo-boehmite.
In the present invention's specific embodiment, reactant silicon sol, Tai-Ace S 150 or pseudo-boehmite, sodium hydroxide and water are mixed, add tetrahydrofuran (THF) or quadrol or hexahydroaniline and do template and crystal seed, proceed in the high pressure crystallizing kettle of polytetrafluoro liner after stirring, under 150 ~ 220 DEG C and autogenous pressure, hydro-thermal static crystallization 20 ~ 80h, preferable reaction temperature is 160 ~ 180 DEG C, and crystallization time is 40 ~ 60h.Purified product, after washing, filtering, at 120 DEG C of drying 2 ~ 4h, obtains molecular screen primary powder, then obtains white NaZSM-35 molecular screen primary powder through 450 DEG C ~ 550 DEG C roasting 4 ~ 8h.In above-mentioned reaction process, each material molar ratio is: SiO
2/ Al
2o
3=10 ~ 80: 1; R/SiO
2=0.2 ~ 2.0: 1 (R represents template agent); OH-/SiO
2=0 ~ 1.0: 1; Na
+/ SiO
2=0 ~ 1.0: 1; H
2o/SiO
2=10 ~ 100: 1.
The NaZSM-35 molecular screen primary powder NH that said process is obtained
3nO
3solution is exchanged into NH three times
3type, dry 2h at 120 DEG C, 450 DEG C ~ 550 DEG C roasting 4h, obtain HZSM-35 molecular sieve.Gained HZSM-35 molecular sieve and pseudo-boehmite are dry mixed, then dripping that aqueous nitric acid makes can the material of extrusion, HZSM-35 molecular sieve/pseudo-boehmite weight ratio 1: 1, be extruded into the bar that diameter is 2mm, 120 DEG C of dry 2h, 540 DEG C of roasting 3h, obtained HZSM-35 molecular sieve catalyst.
According to the present invention, steps A is carried out under the effect of described HZSM-35 acid molecular sieve catalyst.The catalytic activity that this catalyzer possesses makes the carbon Four composition being rich in positive structure butylene that superimposed, cyclisation, isomerization, hydrogen transference, alkylation and dehydrogenation reaction occur under this acidic catalyst effect, produces the high octane gasoline component being rich in C8 isomeric olefine and a small amount of aromatic hydrocarbons.
Meanwhile, steps A also comprises the carbon to described HZSM-35 acid molecular sieve catalyst surface deposition 0.5 ~ 10wt%.Catalyst surface changes its pore structure and acid distribution, thus makes it possess good n-butene skeletal isomerization selectivity and catalytic activity after forming carbon laydown.
According to the present invention, step B carries out under the HZSM-35 acid molecular sieve catalyst effect of the carbon of described surface deposition 0.5 ~ 10wt%.The good n-butene skeletal isomerization selectivity that this catalyzer possesses and catalytic activity make the carbon Four composition being rich in positive structure butylene that selectivity skeletal isomerization occur under an acidic catalyst effect and generate iso-butylene.
The present invention is organically combined by the process to catalyst surface deposit carbon in warm section control two time two and low-temperature zone reaction process, catalyzer is made to achieve bi-functional in reaction process, in 200 ~ 300 DEG C and 300 ~ 350 DEG C of two temperature of reaction segment limits, effectively can adjust isomeric olefine and stop bracket gasoline is fractional distribution, n-butene conversion is made to be greater than 40%, iso-butylene yield is greater than 20%, and stop bracket gasoline yield is greater than 20%, and the octane value of high octane gasoline component is greater than 95.
The present invention aligns isomerization of butene production iso-butylene production technique and improves, and warm sections two time two is controlled to organically combine with catalyst surface carbon laydown process, makes catalyzer achieve bi-functional in reaction process.Adopt the inventive method, in same reactive system, both the skeletal isomerization by alkene generates iso-butylene, simultaneously coproduction high octane gasoline products again, a set of technique achieves two kinds of product outputs, improve the flexibility of operation of this technique, n-butene in carbon four is utilized more fully.
Embodiment
Below by embodiment, the invention will be further described, but described embodiment does not form any restriction to the scope of the invention.
In embodiment, the catalyzer of isomerization reactor filling is SiO
2/ Al
2o
3mol ratio is the HZSM-35 acid molecular sieve catalyst of 10 ~ 80, and its concrete preparation method is as follows:
By 20 parts of water and the Tai-Ace S 150 of 0.05 part and the silicon sol of 1 part, be uniformly mixed, add 0.5 part of sodium hydroxide, then add the crystal seed of 0.5 part of hexahydroaniline and 0.36 part, be uniformly mixed, reaction mixture proceeds to reactor, crystallization 48h under 200 DEG C and pressure itself.Crystallization product through washing, filter, at 120 DEG C of dry 2h, 550 DEG C of roasting 4h, obtain NaZSM-35 molecular screen primary powder.Use NH
3nO
3solution is exchanged into NH three times
3type, dry 2h at 120 DEG C, 450 DEG C ~ 550 DEG C roasting 4h, obtain HZSM-35 molecular sieve.Gained HZSM-35 molecular sieve and pseudo-boehmite are dry mixed, then dripping that aqueous nitric acid makes can the material of extrusion, HZSM-35 molecular sieve/pseudo-boehmite weight ratio 1: 1, be extruded into the bar that diameter is 2mm, 120 DEG C of dry 2h, 540 DEG C of roasting 3h, obtained HZSM-35 acid molecular sieve catalyst.
Catalyzer obtained for said process is loaded in fixed bed isomerization reactor, the carbon Four composition being rich in positive structure butylene after by MTBE synthesizer is reacted under this catalyst action, adopt Agilent 6890N gas chromatograph to carry out online total composition analysis to reaction product, wherein chromatographic column is the PLOT/Al through KCl process of 50m
2o
3packed column, carrier gas is nitrogen.Reaction terminate rear n-butene conversion, selective isobutene, iso-butylene yield, heavy constituent oil yield calculate by formula (1), (2) and (3).
Embodiment
Embodiment 1:
In the fixed-bed reactor that HZSM-35 acid molecular sieve catalyst is housed, the reaction of first stage is carried out by the carbon Four composition being rich in positive structure butylene after MTBE synthesizer, after ether, carbon four raw material composition is in table 1, temperature of reaction 260 DEG C, reaction pressure is normal pressure, and air speed is 0.5h
-1, the reaction times is 60h.Now, catalyst surface carbon distribution reaches 6.0%, and products distribution is in 1-I routine in table 1, and n-butene conversion is 53.59%, and iso-butylene yield is 22.52%, and stop bracket gasoline yield is 24.89%, gasoline octane rating 95.
After the first stage, reaction terminated, under the condition of not more catalyst changeout, temperature of reaction is increased to 340 DEG C, continues by the carbon Four composition being rich in positive structure butylene after MTBE synthesizer the reaction carrying out subordinate phase at former reactive system, reaction pressure is normal pressure, air speed 1.0h
-1, the reaction times is 190h, and products distribution is in 1-II routine in table 1, and n-butene conversion is 44.95%, and iso-butylene yield is 35.45%, and oily yield is 2.01%.
Embodiment 2:
As different from Example 1, temperature of reaction 200 DEG C, the reaction times is 36h, and other reaction conditionss are identical with embodiment 1 in the reaction of first stage.Now, catalyst surface carbon distribution reaches 2.5%, and products distribution is in 2-I routine in table 1, and its n-butene conversion is 47.58%, and iso-butylene yield is 26.00%, and stop bracket gasoline yield is 20.95%, and gasoline octane rating is 96.
As different from Example 1, temperature of reaction is 300 DEG C in the reaction of subordinate phase, and air speed is 0.5h-1, and the reaction times is 185h, and other reaction conditionss are identical with embodiment 1.Products distribution is in 2-II routine in table 1, and its n-butene conversion is 44.03%, and iso-butylene yield is 30.48%, and oily yield is 6.04%.
Embodiment 3:
As different from Example 1, temperature of reaction 300 DEG C, air speed is 1.0h-1, and the reaction times is 70h, and other reaction conditionss are identical with embodiment 1 in the reaction of first stage.Now, catalyst surface carbon distribution reaches 7.5%, and products distribution is in 3-I routine in table 1, and n-butene conversion is 44.60%, and iso-butylene yield is 26.22%, and stop bracket gasoline yield is 13.23%, and gasoline octane rating is 95.
As different from Example 1, temperature of reaction is 350 DEG C in the reaction of subordinate phase, and the reaction times is 178h, and other reaction conditionss are identical with embodiment 1.Products distribution is in 3-II routine in table 1, and n-butene conversion is 44.95%, and iso-butylene yield is 35.45%, and oily yield is 2.01%.
Comparative example 1:
Not identical with embodiment 1 is, live catalyst is adopted directly to carry out the reaction of subordinate phase, other reaction conditionss are identical with embodiment 1, reaction times is 140h, its products distribution is in comparative example in table 11, n-butene conversion is 56.45%, and iso-butylene yield is 22.78%, and oily yield is 3.70%.
As can be seen from embodiment 1 and comparative example 1, catalyst surface can change pore structure and the acid distribution of catalyzer, make catalyzer possess good n-butene skeletal isomerization selectivity and catalytic activity after forming carbon laydown, extends the isomerization reaction time simultaneously.
The composition of table 1 C 4 mixture material and isomerization product
A: butene conversion refers to the total conversion rate of Trans-2-butene, 1-butylene and cis-2-butene.
I: the reaction result of first stage.
II: the reaction result of subordinate phase.
Claims (6)
1. prepare a method for iso-butylene co-production of gasoline with high octane for n-butene isomerization, comprising:
Steps A, there is superimposed, cyclisation, isomerization, hydrogen transference, alkylation and dehydrogenation reaction in the carbon Four composition being rich in positive structure butylene, produce the high octane gasoline component containing C8 isomeric olefine and aromatic hydrocarbons under an acidic catalyst effect;
Step B, there is selectivity skeletal isomerization in the carbon Four composition being rich in positive structure butylene, generate iso-butylene under an acidic catalyst effect;
Wherein, the temperature of reaction of steps A is 200 ~ 300 DEG C, and the temperature of reaction of step B is 300 ~ 350 DEG C;
Steps A is carried out under the effect of HZSM-35 acid molecular sieve catalyst;
Steps A also comprises the carbon to described HZSM-35 acid molecular sieve catalyst surface deposition 0.5 ~ 10wt%;
Step B carries out under the HZSM-35 acid molecular sieve catalyst effect of the carbon of described surface deposition 0.5 ~ 10wt%.
2. method according to claim 1, is characterized in that: the reaction times of steps A is 36 ~ 72h, and reaction velocity is 0.5 ~ 1.0h
-1.
3. method according to claim 1, is characterized in that: the reaction times of step B is 144 ~ 192h, and reaction velocity is 0.5 ~ 1.0h
-1.
4. method according to claim 1, is characterized in that: HZSM-35 acid molecular sieve catalyst by HZSM-35 molecular sieve and inert component baking mixed after make, wherein HZSM-35/ inert component weight ratio is 1:1 ~ 4:1, and catalyst surface area is greater than 200m
2/ g.
5. method according to claim 4, is characterized in that: in HZSM-35 molecular sieve, SiO
2/ Al
2o
3mol ratio is 10 ~ 80:1.
6. method according to claim 4, is characterized in that: described inert component is pseudo-boehmite.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106467451B (en) * | 2015-08-19 | 2019-06-28 | 中国石油化工股份有限公司 | A kind of method of coproduction isobutene and high-knock rating gasoline |
| CN106467445B (en) * | 2015-08-19 | 2019-03-26 | 中国石油化工股份有限公司 | A kind of method of coproduction isobutene and high-knock rating gasoline |
| CN106675639B (en) * | 2015-11-09 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of method that isobutene and high-knock rating gasoline are produced using n-butene as raw material |
| CN107286983B (en) * | 2016-04-12 | 2019-02-19 | 中国石油化工股份有限公司 | The method of C 4 olefin oligomerisation gasoline component |
| CN108017497B (en) * | 2016-11-03 | 2021-07-02 | 中国石油化工股份有限公司 | Method for producing isobutene and co-producing high-octane gasoline by isomerizing linear butene |
| CN112441865B (en) * | 2019-09-04 | 2022-08-09 | 中国石油化工股份有限公司 | Method for preparing butene-2 from isobutene |
| CN114456834B (en) * | 2020-10-21 | 2023-07-14 | 中国石油化工股份有限公司 | Method and device for producing gasoline component by olefin polymerization |
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