CN106467445B - A kind of method of coproduction isobutene and high-knock rating gasoline - Google Patents
A kind of method of coproduction isobutene and high-knock rating gasoline Download PDFInfo
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Abstract
The present invention provides the methods of a kind of coproduction isobutene and high-knock rating gasoline, including step a, the logistics (such as waste gas of butadiene extraction unit) of butadiene and alkynes be will be enriched under the action of palladium series catalyst, selective hydrogenation reaction is carried out under conditions of low-temp low-pressure, obtains butene product；Step b, the butene product that step a is obtained carry out isomerization reaction under the action of HZSM-35 molecular sieve catalyst, obtain isobutene and high-knock rating gasoline product.Method and process provided by the invention is simple, reaction condition is mild, low energy consumption, strong operability, and the exhaust gas of Butadiene extraction process can be become to the isobutene and high-knock rating gasoline of great economic value, has environmental benefit and economic benefit.
Description
Technical field
The present invention relates to petrochemical industries, and in particular to a kind of method of coproduction isobutene and high-knock rating gasoline.
Background technique
Isobutene is a kind of important industrial chemicals, can be used for producing butyl rubber, polyisobutene, diisobutylene, three
Isobutene, methacrylate, 2,4- tert-butyl cresols, tert-butyl mercaptan, the tert-butyl alcohol, tert-butylamine, methylallyl chloride, methyl
The deep processed products such as acrylic acid, metering system be fine, neovaleraldehyde and isoprene.
With increasing sharply to the demand of isobutene in recent years, what traditional petroleum catalytic cracking and hot-working obtained
Isobutene yield far from can satisfy the market demand, and also when the river rises the boat goes up for the price of isobutene.
Octane number is that quick-fried index is shaken in the resistance of gasoline.Common gasoline label has No. 90, No. 93,95 currently on the market
Number, No. 97, No. 98 unleaded gases (motor method), these labels be indicate gasoline octane number index.Octane number is higher to indicate anti-
Shake ability is stronger.Therefore, it is known as the important hand protected automobile engine, improve car steering performance using high-knock rating gasoline
Section.However, the demand to gasoline, especially high-knock rating gasoline is also being constantly increasing with the increase of automobile usage amount.It is high
Effect, production high-knock rating gasoline will be with great economic significance and social effect at low cost.
Cracking petroleum hydrocarbon ethylene unit by-product largely mixes C-4-fraction, wherein 1 containing 40wt%~60wt%,
3- butadiene, the vinylacetylene (VA) and ethyl acetylene (EA) of 0.5~2.0wt%, rest part are butane, butylene and a small amount of
1,2- butadiene, carbon three and light dydrocarbon component.It is industrial generally to utilize the methods of extracting from carbon four by 1,3- separate butadiene
Out.Cracking c_4 will usually discharge four alkynes of carbon of about 10% butadiene production capacity, such as: fourth when carrying out Butadiene Extraction
Diene production capacity is 1,000,000 tons/year, and about 100,000 tons of four alkynes of carbon discharged every year can lose about in four alkynes of emission of carbon
The butadiene of 40~45 (wt) %.Moreover, the explosion accident easy to cause fire of carbon four, also can bring shadow for the safety in production of enterprise
It rings.Due to four alkynes of carbon using technology there is many problems, many butadiene production producers can only be by four alkynes of carbon first with containing
Flare system can be just discharged into after the dilution of raffinating oil for having butane, butylene to burn.Not only economic loss is huge for this, but also band
Biggish environmental pollution is carried out.With the increase of butadiene production scale, the four alkynes amount of carbon of discharge is consequently increased, and how to be closed
It manages using this four alkynes resource of part carbon, turn waste into wealth, become numerous butadiene plants problem in the urgent need to address.
Patent application CN101492334A discloses a kind of method for improving mixing four chemical utilization of carbon value, using steam
Cracker by-product mixing carbon four and FCC apparatus by-product mixing carbon four are raw material, realize its technical solution by following steps:
(1) using selection hydrogen addition technology, make to mix butadiene, alkynes in carbon four and be hydrogenated to monoolefine；(2) hydroisomerization skill is used
Art makes the butene-1 in first step product be isomerized to butene-2；(3) by distillation technology, second step product is separated, and is obtained
Product isobutene；(4) by olefin(e) disproportionation technology, make the butene-2 and ethylene disproportionation production third in third step residue mixing carbon four
Alkene；(5) the 4th step residues mix the circulation of carbon four and are used as cracking stock.The defect of technical solution provided by the patent application exists
In, (1) mixing carbon four carry out selection plus hydrogen and isomerization reaction, gained purpose product be butene-2, then again by butene-2 with
Ethylene carries out disproportionated reaction and obtains final product propylene, which uses two distillation processes and three reaction members, stream
Journey is long, and process is complicated, and practical control difficulty is big；It is to build that residue described in (2) the 5th steps, which mixes the circulation of carbon four as cracking stock,
Standing reacts butene-2 completely with ethylene by disproportionation, almost without ethylene and other alkene ability in remaining mixing carbon four
Meet the requirement as cracking stock, this is an ideal response, and practical operation is difficult to realize；(3) in the technical scheme, make
It is recovered to obtain only by distillation for the higher isobutene of application value, and it is more to generate to be not through isomerization process
Isobutene.
Patent CN102050695A discloses a kind of utilization method of Butadiene Extraction exhaust gas, includes butylene 0 using composition
~5 (wt) %, butadiene 30~70 (wt) %, vinylacetylene are that the waste gas of butadiene extraction unit of 20~50 (wt) % is former
Material, by one section or multi-stek hydrogenation, generates alkynes, diolefin and monoolefin hydrogenation in exhaust gas using palladium series catalyst
Alkane.The shortcoming of this method is that the alkene in (1) mixing carbon four does not efficiently use；(2) alkene and alkynes complete hydrogenation
Keep hydrogen consumption big, energy consumption is higher；(3) mix carbon four alkene be hydrogenated into entirely for the economy of alkane it is poor.
Summary of the invention
The purpose of the present invention is to provide the method for a kind of Joint Production isobutene and high-knock rating gasoline, in particular by
The method that butadiene extraction device tail gas produces isobutene and high-knock rating gasoline as raw material.Coproduction isobutene is not only provided
With the method for high-knock rating gasoline, while the mixing carbon four existing in the prior art complicated, practical operation using process is also solved
Difficulty is big, energy consumption is high and less economical problem, especially provides a kind of utilization method of new butadiene extraction device tail gas.
According to the present invention, the method for a kind of coproduction isobutene and high-knock rating gasoline is provided, which comprises step
A, the logistics that will be enriched in butadiene and alkynes carry out selective hydrogenation reaction under the action of palladium series catalyst, obtain butene product；
Step b, the butene product that step a is obtained carry out isomerization reaction under the action of HZSM-35 molecular sieve catalyst, are wrapped
Product containing isobutene and high-knock rating gasoline.The present invention also optionally further comprises by isobutene and high-knock rating gasoline point
It is not separated from product.Separating step can be realized by the conventionally known separation method in this field.
In the present invention, so-called " high-octane rating " refers to research octane number (RON) index 95 or more.
In some embodiments, the above-mentioned logistics rich in butadiene and alkynes is from butadiene extraction device tail gas.
As one of advantage of the invention, using butadiene extraction device tail gas as reaction raw materials, by selection plus hydrogen and isomerization
Step, while isobutene and high-knock rating gasoline is prepared.Exhaust gas is not only taken full advantage of, discharge is reduced, has saved the energy,
Exhaust gas is also become to simple technique the isobutene for having high utility value again, while obtaining the high-octane rating vapour of high value
Oil.Additional description, the mixing carbon four that the raw material sources of butadiene extraction device can be cracking petroleum hydrocarbon device by-product evaporate
Point.
In some embodiments, the logistics rich in butadiene and alkynes include the butylene of 0~40wt%, 20~
The butadiene and total amount of 65wt% is the butine and vinylacetylene of 10~30wt%.The logistics can also optionally include
A small amount of normal butane, iso-butane, C5Component etc..
In some preferred embodiments of the invention, used palladium series catalyst uses TiO2-Al2O3Compound load
Body, and wherein the content of Metal Palladium is based on the total catalyst weight and is calculated as 0.1~0.3wt%, preferably 0.28~
0.3wt%, TiO2Content be based on the total catalyst weight be calculated as 8~20wt%.
It may further be preferable that the TiO2-Al2O3The specific surface area of complex carrier is 80~180m2/ g, Kong Rongwei 0.4
~1.0ml/g, most probable pore size are 110~140 angstroms.Under the action of such palladium series catalyst, better choosing can be obtained
Select hydrogenation effect.
In the present invention, specific surface area refers both to the specific surface area obtained by BET nitrogen adsorption methods measurement.
In some embodiments of the present invention, in step a, the inlet temperature of reactor is 20~80 DEG C；Reaction pressure
Power is 1.0~3.0MPa；Hydrogen is 0.7~4.0 to the molar ratio of butadiene and alkynes total amount；Liquid phase volume air speed be 1~
20h-1.In a further preferred embodiment, in step a, the inlet temperature of reactor is 30~70 DEG C；Hydrogen is to fourth two
The molar ratio of alkene and alkynes total amount is 0.8~3.0；Liquid phase volume air speed is 3~15h-1.As it can be seen that method provided by the present invention
Selection plus hydrogen can be carried out under low temperature and the Conditions Condition of low pressure, no matter this mild selection hydroconversion condition is from energy conservation
Aspect, or from the requirement to equipment, or be all obvious beneficial in terms of operation requires with production security.
In some embodiments of the present invention, in stepb, using being filled with consolidating for HZSM-35 molecular sieve catalyst
Fixed bed reactor；Reaction temperature is 200~350 DEG C；Reaction pressure is 0.1~1.0MPa；The volume space velocity of butene product is 0.5
~1.0h-1。
Preferably, the SiO of used HZSM-35 molecular sieve catalyst2/Al2O3Molar ratio is 10~80:1；Specific surface
Product is 200~400m2/g.HZSM-35 molecular sieve catalyst can be by baking mixed by HZSM-35 molecular sieve and inert component
And it is made, and the weight ratio of HZSM-35 molecular sieve and inert component is 1~4:1；The inert component preferably intends thin water aluminium
Stone.
The method of coproduction isobutene and high-knock rating gasoline as described above provided by the invention, can obtain good selection
Add hydrogen effect and isomerization effect, such as passes through selection hydrogenation process (step a), alkynes and butadiene group in gained hydrogenation products
Divide content less than 0.1 (wt) %；By isomerization reaction, (step b) keeps butene conversion in isomerization product reachable
50% or more, isobutene yield is up to 22% or more, and selective isobutene can reach 43% or more, and high-knock rating gasoline yield can
Up to 24.9% or more.For the recycling of waste gas of butadiene extraction unit, result above is enough to show the present invention
With beneficial effect outstanding.
In addition, the method for coproduction isobutene of the present invention and high-knock rating gasoline has further the advantage that and effect:
Simple process, reaction condition are mild, low energy consumption, strong operability, the exhaust gas of Butadiene extraction process can be become great warp
The isobutene and high-knock rating gasoline for value of helping, have environmental benefit and economic benefit.
Specific embodiment
Below by specific embodiment, the present invention will be further elaborated, it should be understood that specific reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
In the examples below, the n-butene yield of selective hydrogenation reaction, Trans-2-butene yield and cis-2-butene yield
It calculates as follows.
In n-butene yield %=(n-butene in n-butene-raw material in product)/raw material (1,2- butadiene+1,
3- butadiene+vinylacetylene+1- butine) × 100%；
(1,2- in Trans-2-butene yield %=(Trans-2-butene in Trans-2-butene-raw material in product)/raw material
Butadiene+1,3- butadiene+vinylacetylene+1- butine) × 100%；
(1,2- in cis-2-butene yield %=(cis-2-butene in cis-2-butene-raw material in product)/raw material
Butadiene+1,3- butadiene+vinylacetylene+1- butine) × 100%.
Butene conversion, selective isobutene, isobutene yield and the high-knock rating gasoline yield of isomerization reaction press with
Lower formula calculates, and wherein " butylene " in following equation does not include isobutene, and butene conversion refers to n-butene, Trans-2-butene
With the total conversion of cis-2-butene.
Butylene × 100% before butene conversion %=(butylene in butylene-product before reaction)/reaction；
Selective isobutene %=(isobutene before isobutene-reaction in product)/(butylene-product before reaction
In butylene) × 100%；
Butylene × 100% before isobutene yield %=(isobutene before isobutene-reaction in product)/reaction；
Butylene × 100% before the high-knock rating gasoline/reaction generated after high-knock rating gasoline yield %=reaction.
Each amount in above-mentioned calculation formula is with weight.
Embodiment 1
The present embodiment is to illustrate that the selection of butadiene extraction device tail gas raw material A (composition is shown in Table 1) adds hydrogen and isomerization anti-
The example answered.
Take titanium oxide content 15.2 (wt) %, metal palladium content 0.3 (wt) %, specific surface area 89m2/ g, Kong Rong
0.51ml/g, the Pd/TiO that most probable pore size is 130 angstroms2-Al2O350 milliliters of catalyst are loaded in the reactor, in reaction pressure
1.5MPa, is restored 8 hours under conditions of 40 ml/min of hydrogen flowing quantity by 110 DEG C of temperature.
It is 30 DEG C, reaction pressure 1.2MPa in reactor inlet temperature, mole of the hydrogen to butadiene and alkynes total amount
Than being 1.0, liquid phase volume air speed is 10h-1, to be passed through raw material A under conditions of 9:1 (product 9), obtain plus hydrogen produces recycle ratio
The analysis of object A the results are shown in Table 1.
Take 100 milliliters of HZSM-35 acid molecular sieve catalyst fillings in the reactor, at 260 DEG C of reaction temperature, volume is empty
Speed is 0.5h-1Be passed through hydrogenation products A under the conditions of normal pressure (0.1MPa), carry out isomerization reaction, point of obtained isomerized products A
Analysis the results are shown in Table 1.
1 raw material A of table and its content composition (wt%) for selecting each component in hydrogenation products A and isomerization product A
| Ingredient names | Raw material A | Select hydrogenation products A | Isomerization product A |
| Iso-butane | 1.23 | 2.63 | 2.68 |
| Normal butane | 1.84 | 3.81 | 3.85 |
| Trans-2-butene | 2.30 | 17.38 | 11.33 |
| N-butene | 5.71 | 25.31 | 4.26 |
| Isobutene | 21.27 | 21.23 | 37.51 |
| Cis-2-butene | 24.18 | 29.56 | 20.13 |
| 1,2- butadiene | 5.18 | 0.03 | 0.01 |
| 1,3- butadiene | 21.81 | 0.05 | 0.01 |
| Vinylacetylene | 12.90 | 0 | 0 |
| 1- butine | 3.58 | 0 | 0 |
| High octane gasoline component* | - | - | 18.20 |
| Other | 0 | 0 | 2.01 |
Note:*Octane number (similarly hereinafter) is measured using organon.
It is computed, the reaction result parameter of selective hydrogenation reaction step and isomerization reaction step is as shown in table 2.
Table 2
Embodiment 2
Take titanium oxide content 16.5 (Wt) %, metal palladium content 0.2wt%, specific surface area 87m2/ g, Kong Rong 0.48ml/
G, the Pd/TiO that most probable pore size is 110 angstroms2-Al2O350 milliliters of catalyst fillings in the reactor, are replaced real with this catalyst
The catalyst in example 1 is applied, other steps are same as Example 1.The knot of selective hydrogenation reaction product B and isomerization reaction product B
Fruit is shown in Table 3.
3 raw material A of table and its content composition (wt%) for selecting each component in hydrogenation products B and isomerization product B
| Ingredient names | Raw material A | Select hydrogenation products B | Isomerization product B |
| Iso-butane | 1.23 | 3.3. | 3.31 |
| Normal butane | 1.84 | 4.22 | 4.68 |
| Trans-2-butene | 2.30 | 21.18 | 13.03 |
| N-butene | 5.71 | 22.49 | 4.13 |
| Isobutene | 21.27 | 22.33 | 38.07 |
| Cis-2-butene | 24.18 | 26.36 | 17.05 |
| 1,2- butadiene | 5.18 | 0.01 | 0.01 |
| 1,3- butadiene | 21.81 | 0.06 | 0.01 |
| Vinylacetylene | 12.90 | 0 | 0 |
| 1- butine | 3.58 | 0 | 0 |
| High octane gasoline component | - | - | 17.44 |
| Other | 0 | 0 | 2.27 |
It is computed, the reaction result parameter of selective hydrogenation reaction step and isomerization reaction step is as shown in table 4.
Table 4
Embodiment 3
The present embodiment is to illustrate that the selection of butadiene extraction device tail gas raw material B (composition is shown in Table 3) adds hydrogen and isomerization anti-
The example answered.
Take titanium oxide content 15.2 (wt) %, metal palladium content 0.3 (wt) %, specific surface area 89m2/ g, Kong Rong
0.51ml/g, the Pd/TiO that most probable pore size is 130 angstroms2-Al2O350 milliliters of catalyst are loaded in the reactor, in reaction pressure
1.5MPa, is restored 8 hours under conditions of 40 ml/min of hydrogen flowing quantity by 110 DEG C of temperature.
It is 43 DEG C, reaction pressure 1.8MPa in reactor inlet temperature, mole of the hydrogen to butadiene and alkynes total amount
Than being 1.2, liquid phase volume air speed is 11h-1, recycle ratio is is passed through raw material B under conditions of 10:1 (product 10), obtain plus hydrogen
The analysis of product C the results are shown in Table 5.
Take 100 milliliters of HZSM-35 acid molecular sieve catalyst fillings in the reactor, at 320 DEG C of reaction temperature, volume is empty
Speed is 0.9h-1Be passed through hydrogenation products C under 0.4MPa pressure condition, carry out isomerization reaction, the analysis of obtained isomerized products C
It the results are shown in Table 5.
The content of each component forms (wt%) in 5 raw material B of table and its selection hydrogenation products C and isomerization product C
| Ingredient names | Raw material B | Select hydrogenation products C | Isomerization product C |
| Iso-butane | 0.31 | 1.63 | 2.48 |
| Normal butane | 0.05 | 1.82 | 3.65 |
| Trans-2-butene | 0.23 | 32.01 | 21.65 |
| N-butene | 0.92 | 39.43 | 7.70 |
| Isobutene | 1.35 | 2.68 | 23.88 |
| Cis-2-butene | 7.41 | 22.01 | 15.58 |
| 1,2- butadiene | 6.54 | 0.01 | 0.01 |
| 1,3- butadiene | 55.47 | 0.07 | 0.01 |
| Vinylacetylene | 25.14 | 0 | 0 |
| 1- butine | 2.16 | 0 | 0 |
| C5Component | 0.42 | 0.34 | - |
| High octane gasoline component | - | - | 23.31 |
| Other | 0 | 0 | 1.73 |
It is computed, the reaction result parameter of selective hydrogenation reaction step and isomerization reaction step is as shown in table 6.
Table 6
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that various aspects, different specific embodiment that the present invention records
Each section and the various features enumerated can be combined or all or part of exchange.In above-mentioned each specific embodiment, that
A little embodiments with reference to another embodiment can be combined suitably with other embodiment, this is will be by this field skill
Art personnel are to understand.In addition, it will be understood to those of skill in the art that the description of front is only exemplary mode, not purport
In the limitation present invention.
Claims (9)
1. a kind of method of coproduction isobutene and high-knock rating gasoline, which comprises
Step a, the logistics that will be enriched in butadiene and alkynes carry out selective hydrogenation reaction under the action of palladium series catalyst, obtain fourth
Ene product；
Step b, the butene product that step a is obtained carry out isomerization reaction under the action of HZSM-35 molecular sieve catalyst, obtain
To the product comprising isobutene and high-knock rating gasoline；
Wherein, the logistics rich in butadiene and alkynes include the butylene of 0~40 wt%, 20~65 wt% butadiene and
Total amount is the butine and vinylacetylene of 10~30 wt%；
The palladium series catalyst uses TiO2-Al2O3Complex carrier, and wherein the content of Metal Palladium is total based on the catalyst
Weight is calculated as 0.1~0.3 wt%, TiO2Content be based on the total catalyst weight be calculated as 8~20 wt%.
2. the method according to claim 1, wherein the logistics rich in butadiene and alkynes is from fourth two
Alkene extraction device tail gas.
3. the method according to claim 1, wherein the TiO2-Al2O3The specific surface area of complex carrier is 80
~180m20.4~1.0ml/g of/g, Kong Rongwei, most probable pore size are 110~140 angstroms.
4. the method according to claim 1, wherein the inlet temperature of reactor is 20~80 in step a
℃；Reaction pressure is 1.0~3.0MPa；Hydrogen is 0.7~4.0 to the molar ratio of butadiene and alkynes total amount；Liquid phase volume is empty
Speed is 1~20h-1。
5. according to the method described in claim 4, it is characterized in that, the inlet temperature of reactor is 30~70 in step a
℃；Hydrogen is 0.8~3.0 to the molar ratio of butadiene and alkynes total amount；Liquid phase volume air speed is 3~15h-1。
6. the method according to claim 1, wherein in stepb, being urged using HZSM-35 molecular sieve is filled with
The fixed bed reactors of agent；Reaction temperature is 200~350 DEG C；Reaction pressure is 0.1 ~ 1.0MPa；The volume of butene product is empty
Speed is 0.5~1.0 h-1。
7. the method according to claim 1, wherein the SiO of the HZSM-35 molecular sieve catalyst2/Al2O3It rubs
You are than being 10 ~ 80:1；Specific surface area is 200~400m2/g。
8. the method according to claim 1, wherein the HZSM-35 molecular sieve catalyst is by by HZSM-35
Molecular sieve is baking mixed with inert component and is made, and the weight ratio of HZSM-35 molecular sieve and inert component is 1~4:1.
9. according to the method described in claim 8, it is characterized in that, the inert component is boehmite.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101434508A (en) * | 2008-12-11 | 2009-05-20 | 中国石油天然气股份有限公司 | Selective hydrogenation method for alkyne |
| CN101492334A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Method for improving mixed C4 chemical industry exploitation value |
| CN102050695A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for recycling waste gas of butadiene extracting device |
| CN103102235A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Method for isobutene production and co-production of gasoline with high octane value by n-butene isomerization |
-
2015
- 2015-08-19 CN CN201510512283.2A patent/CN106467445B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492334A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Method for improving mixed C4 chemical industry exploitation value |
| CN101434508A (en) * | 2008-12-11 | 2009-05-20 | 中国石油天然气股份有限公司 | Selective hydrogenation method for alkyne |
| CN102050695A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for recycling waste gas of butadiene extracting device |
| CN103102235A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Method for isobutene production and co-production of gasoline with high octane value by n-butene isomerization |
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