CN103964998B - The method improving n-butene oxidative dehydrogenation butadiene yield - Google Patents
The method improving n-butene oxidative dehydrogenation butadiene yield Download PDFInfo
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Abstract
The present invention relates to a kind of method improving n-butene oxidative dehydrogenation butadiene yield, mainly due to 1 butylene in n-butene raw material present in solution prior art, along 2 butylene, anti-three kinds of isomers of 2 butylene problem that conversion ratio is the highest under using same catalysts conditions.The present invention uses the multistage connection in series-parallel fixed bed reactors reaction of at least two-stage, water vapour all enters from first order reactor, raw material and oxygen-containing gas containing butylene respectively enter every stage reactor by a certain percentage with parallel form, every reacted material of stage reactor enters after mixing with dispensing butene feedstock and air and enters next stage reactor, every stage reactor beds segmentation is filled with catalyst I and catalyst II, wherein catalyst I is the catalyst having higher conversion to butylene 1 and maleic 2, catalyst II is the technical scheme of the catalyst having higher conversion to anti-butylene 2, preferably resolve this problem, can be used for the industrial production of n-butene oxidative dehydrogenation butadiene.
Description
Technical field
The present invention relates to a kind of method improving n-butene oxidative dehydrogenation butadiene yield.
Background technology
Butadiene is the important monomer of synthetic rubber, synthetic resin, is mainly used in synthesizing butadiene rubber, butadiene-styrene rubber, fourth
Nitrile rubber and ABS resin etc..Butadiene is also multiple coating and Organic Chemicals.
At present the mode of production of butadiene mainly have C-4-fraction to separate and synthetic method (include butane dehydrogenation, butylene dehydrogenation,
Butylene oxidation-dehydrogenation etc.) two kinds.At present in addition to the U.S., countries in the world butadiene almost all is directly from hydrocarbon cracking ethene
Time by-product C-4-fraction (C-4-fraction can be written as again).The source of U.S.'s butadiene, only about half of from butane, butylene take off
Hydrogen, half is directly from cracking c_4 cut.
Butylene oxidation-dehydrogenation is to produce the more competitive technology of butadiene, Oxidative Dehydrogenation of Butene into Butadiene at present
It is in the presence of water vapor, utilizes oxygen hydrogen in butylene molecule to be combined, obtain butadiene and constitutionally stable water.This reactive group
This is irreversible reaction.Main reaction equation is as follows:
Other side reaction mainly has:
Patent CN100494130C discloses a kind of butadiene preparation method, and its flow process is that the entrance of raw material normal butane is non-oxide
The reactor of property catalytic dehydrogenation, obtains containing normal butane, butylene, butadiene, hydrogen, low boiling secondary component and the mixing of steam
Logistics.This mixing logistics and oxygen-containing gas are mixed into oxidative dehydrogenation region, obtain containing butadiene, normal butane, butylene, hydrogen
Gas, low boiling secondary component and the product gas flow of steam, next isolate butadiene from this product gas flow.Similar also has
Patent CN100447117C, unlike patent CN100494130C, the product gas of autoxidation dehydrogenation zone removes hydrogen, low
Being divided into two parts by extracting rectifying after boiling point secondary species and steam, a part mainly comprises the logistics of normal butane and butylene and follows
Loopback Non-oxidative dehydrogenation region, another part mainly comprises butadiene stream.
Similar with the first two patent described in patent CN100387557C, the except for the difference that product gas of autoxidation dehydrogenation zone
It is divided into two parts by extracting rectifying after removing hydrogen, low boiling secondary species and steam, mainly comprises normal butane and butylene
Logistics is divided into three parts by rectification area: other purposes are made in the logistics rich in 1-butylene.Logistics rich in 2-butylene is passed through different
Structure changes into 1-butylene and loops back rectification area.Logistics rich in 2-butylene and normal butane loops back Non-oxidative dehydrogenation region.
Patent CN101367702 discloses a kind of method of preparing butadiene with butylene oxo-dehydrogenation of axially-located bed, its stream
Journey is for using the axially-located bed reactor of two-stage, and butene feedstock, water vapour and air segmenting enter, and reactor outlet is by heating
Water vapour and cool down, reach to enter after next stage reactor inlet temperature next stage reactor.
Patent CN102675027A discloses a kind of preparing butadiene with butylene oxo-dehydrogenation technique, uses adiabatic radially fixed
Bed is by preparing butadiene with butylene oxo-dehydrogenation, and radial adiabatic fixed bed is formed by three grades
At present butylene oxidation-dehydrogenation method produces the commercial plant of butadiene, raw material commonly used steam cracking ethylene unit or
Butene component in refinery catalytic cracking by-product mixing carbon four, in mixing carbon four, butylene has three kinds of isomers, is butene-1 respectively,
Along 2-butylene and anti-2-butylene, the physical property such as three kinds of isomers boiling points is close, is difficult to separate, can aoxidize with oxygen
Dehydrogenation reaction generates butadiene, but owing to structure is different, on same catalyst surface, butylene absorption and butadiene are desorbed
Performance has difference, causes three kinds of isomers conversion ratios different, wherein close, at same along 2-butylene and butene-1 space structure
Having close reactivity worth on catalyst, anti-2-butylene then has bigger difference with other two kinds of isomers, such as certain butylene oxygen
Fluidized dehydrogenation device uses a kind of Fe-series catalyst, and three kinds of isomers conversion ratios of butylene are: suitable 2-butylene 75%, butene-1 74%, instead
2-butylene 60%, the difference of anti-2-butylene and other two kinds of isomers conversion ratios reaches 15%, causes device butylene total conversion low,
Product butadiene yields poorly.
Disclosed patent and document, the most all without reference to three kinds of isomers for butene feedstock different content, are taked not
Same catalyst or technological process improve the total conversion of butylene, cause butylene total conversion on the low side, butylene isomery in raw material
The body burden change fashionable dress amount of buying property is unstable, seriously limits the commercial Application of Oxidative Dehydrogenation of Butene into Butadiene technology.
Summary of the invention
Present invention mainly solves technical problem is that present in prior art due to three kinds of isomers in n-butene raw material
(1-butylene, along 2-butylene, anti-2-butylene) conversion ratio under using a kind of catalysts conditions is different and causes butadiene yield not
High problem, it is provided that a kind of new method improving n-butene oxidative dehydrogenation butadiene yield, the method has just can be made
In butene feedstock, three kinds of isomers have higher conversion, the advantage that butadiene yield is high, energy consumption is low.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of raising n-butene oxidative dehydrogenation system
The method of butadiene yield, uses N level fixed bed reactors cascade reaction, and butene feedstock is divided into N stock, respectively enters N order reaction
Device, wherein N is the integer more than or equal to 2；Every stage reactor beds segmentation is filled with catalyst I and catalyst II, instead
Process is answered to include following step:
A) through water vapour and first burst of butene feedstock and the oxygen-containing gas of metering, by butylene, oxygen, steam molar ratio it is
The ratio of 1:0.4～1.5:0～18 enters first order reactor, and reaction temperature is 280～600 DEG C, reaction pressure be 0.02～
1.5MPa；
B) next stage butylene sendout, first order butylene and butylene the most at different levels are determined according to upper level reaction conversion ratio
Allocation proportion scope is 1:0.4～1.0；The reacted material of upper level, then after mixing with butene feedstock and oxygen-containing gas, by step
Identical mol ratio in a), enters next stage reactor；
C) when N equal to 2 time, should after material enter step d)；When N is more than 2, reacted material is according to step c)
Mode, sequentially enters next stage reactor, until reacted material enters N stage reactor；
D) N stage reactor outlets products enters follow-up workshop section and reclaims butadiene.
In technique scheme, preferred technical scheme is: raw material butylene contains 1-butylene, cis-2-butene, trans-2-fourth
At least two in alkene；Preferably technical scheme is: the mol ratio of every stage reactor entrance butylene, oxygen and water vapour is 1:
0.45～1.0:2～12, the reaction inlet temperature of every stage reactor is 300～500 DEG C, and pressure is 0.05～1.0MPa；Preferably
Technical scheme be: oxygen-containing gas is air or pure oxygen, or air and the mixture of oxygen；Preferably technical scheme is: urge
Agent I is to have the ferrous oxide catalyst of spinel structure, mainly comprises iron, zinc, and magnesium molar ratio is: Fe:Zn:Mg=
10:1～5:2～6, uses coprecipitation to prepare；Catalyst II is a kind of molybdenum-bismuth series catalysts, mainly comprises molybdenum, bismuth, iron, cobalt
Ratio (weight) is: Mo:Bi:Fe:Co=10:1～4:1～3:2～8, and auxiliary agent is in Sn, Re, W, Pb, Ti, Zn, La or Ce
One or more, carrier is SiO2、Al2O3Or silicate molecular sieve；Preferably technical scheme is: described fixed bed reactors
Including Adiabatic Axial Fixed-Bed reactor, adiabatic radial fixed-bed reactor, shell and tube isothermal fixed bed reactors；Preferably skill
Art scheme is: the filling ratio of catalyst I and II is 1:0.1～10；Preferably technical scheme is: use Adiabatic Axial Fixed-Bed
During reactor, catalyst I and II is the filling of upper and lower segmentation；When using adiabatic radial fixed-bed reactor, catalyst I and II is
Internal and external cycle separately filling；When using isothermal calandria type fixed bed reactor, catalyst I and II is tubulation upper and lower segmentation filling.
Preferred technical scheme is: the mol ratio of every stage reactor entrance butylene, oxygen and water vapour be 1:0.50～
0.9:4～10.Preferred technical scheme is: for insulation fix bed reactor, the reaction inlet temperature of every stage reactor is
300～400 DEG C.Preferred technical scheme is: for isothermal fixed bed reactors, and the reaction temperature of every stage reactor is 400
～500 DEG C.Preferred technical scheme is: the filling ratio of catalyst I and II is 1:0.5～2.
Water vapour, by using at least series-parallel method of two-stage reactor, is all entered by the present invention with cascade
First order insulation fix bed reactor, containing the raw material of one or more in 1-butylene, cis-2-butene, Trans-2-butene and sky
Gas is divided at least two parts and is mixed into every A reactor by a certain percentage with parallel form and water vapour, owing to water vapour is complete
Portion enters first order reactor, and every stage reactor generation butylene oxidation-dehydrogenation water generation reaction, reacting rear material enters back into next
Stage reactor, the water yield is stepped up, and butylene is the segmentation every A reactor of entrance, so under the conditions of relatively low total water alkene ratio,
Every stage reactor can maintain higher water alkene ratio, desirably prevents catalyst coking, and the raising reacting hop count is the most permissible
Obtain higher conversion per pass.
The present invention is filled with two kinds of different catalyst I and catalyst II in every stage reactor, and catalyst I is a kind of tool
Having the ferrous oxide catalyst of spinel structure, mainly comprise iron, zinc, magnesium ratio (mole) is: Fe:Zn:Mg=10:1～5:
2～6, the close suitable 2-butylene of space structure and butene-1 can be made to have higher conversion ratio, and catalyst II is a kind of molybdenum-bismuth system
Catalyst, mainly comprises as molybdenum, bismuth, iron, cobalt, and auxiliary agent is one or more in Sn, Re, W, Pb, Ti, Zn, La or Ce, carrier
For SiO2、Al2O3Or silicate molecular sieve, can improve the absorption property to anti-2-butylene, the most in the reactor, containing butylene-
1, when the raw material along 2-butylene and anti-2-butylene leads to reactor catalyst I bed, butene-1 and suitable 2-butylene are more converted into
Butadiene, during by catalyst II bed, remains unconverted anti-2-butylene and then can be converted into butadiene more, compare use
A kind of catalyst, this method can make three kinds of isomers of butylene all obtain higher conversion ratio, thus improve product butadiene
Yield.By using the inventive method, compared with prior art, the butene feedstock total conversion containing three kinds of isomers can carry
High 5%～30%, achieve preferable technique effect and obvious technological progress.
Accompanying drawing explanation
Fig. 1 is that the present invention improves the process flow diagram of the method for n-butene oxidative dehydrogenation butadiene yield (with two
As a example by order reaction).
Fig. 2 is conventional Oxidative Dehydrogenation of Butene into Butadiene process flow diagram.
In Fig. 1,1 is butene feedstock, and 2 is oxygen-containing gas, and 3 is water vapour, and 4 is one section of butylene, and 5 is two sections of butylene, and 6 is one
Section oxygen-containing gas, 7 is two sections of oxygen-containing gas, and 8 is A reactor entrance material, and 9 is second reactor entrance material, and 10 is one
Stage reactor outlet material, 11 is second reactor outlet material, and 101 is A reactor, and 102 is second reactor, 103
Exporting heat exchanger for A reactor, I is catalyst I, and II is catalyst II.
In Fig. 1, raw material butylene 1 and oxygen-containing gas 2 divide two parts, 4, one section of oxygen-containing gas 6 of one section of butylene and water to steam respectively
The mixed logistics of vapour 38 enters A reactor 101, filling two kinds of catalyst, respectively catalyst I in A reactor 101
With II, reaction outlet streams 10 is after A reactor outlet heat exchanger 103 heat exchange, with two sections of butylene 5 and two sections of oxygen-containing gas 7
After mixing, second reactor entrance material 9 enters second reactor 102, two kinds of catalyst of filling in second reactor 102, point
Not Wei catalyst I and II, reaction outlet streams 11 enters follow-up workshop section and carries out butadiene rectifying.
In Fig. 2,1 is butene feedstock, and 2 is oxygen-containing gas, and 3 is water vapour, and 4 is reactor inlet material, and 5 go out for reactor
Mouth material, 101 is reactor.
In Fig. 2, raw material butylene 1, oxygen-containing gas 2 and the mixed logistics of water vapour 34 enter reactor 101 and aoxidize
Dehydrogenation reaction, the built-in a kind of catalyst of reactor 101, reaction outlet streams 5 enters follow-up workshop section and carries out butadiene rectifying.
Below by specific embodiment, invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, raw material butylene composition is shown in Table 1, uses the technique skill of Fig. 1
Art, reactor is two-stage, and two-stage reactor is Adiabatic Axial Fixed-Bed reactor, reactor internal upper part loading catalyst I, urges
Agent I is ferrous oxide catalyst, mainly comprises iron, zinc, and magnesium ratio (mole) is: Fe:Zn:Mg=10:3:6, and bottom is loaded
Catalyst II, catalyst II is molybdenum-bismuth series catalysts, mainly comprises molybdenum, bismuth, iron, and cobalt ratio (weight) is: Mo:Bi:Fe:Co=
10:4:3:6, auxiliary agent is Sn, W, and carrier is Al2O3, the loadings of catalyst I and catalyst II is than for 1:0.5(weight), raw material
Butylene total amount 19670kg/h, air total amount 36000 kg/h, water vapour total amount 66000 kg/h, butene feedstock is divided into two parts,
One section of butylene flow 9400 kg/h, according to butylene: oxygen: water (mol) is that the ratio of 1:0.52:15 mixes with air, water vapour
After, it being 320 DEG C in temperature, under the conditions of pressure 0.12MPaG, enter first order oxidative dehydrogenation reactor, A reactor is worked off one's feeling vent one's spleen
Temperature 485 DEG C, after heat exchanger heat exchange, is mixed into second reactor with two sections of butylene and two sections of air, two sections of butylene flows
10270 kg/h, second reactor entrance butylene: oxygen: water (mol) ratio is 1:0.65:16, reaction temperature is 330 DEG C, pressure
Power 0.11MPaG, second reactor is worked off one's feeling vent one's spleen temperature 512 DEG C.
This device reaction part water vapour consumption 66000kg/h, device total energy consumption 1200kg marks oil/t butadiene, and butylene is total
Conversion ratio 82%, overall selectivity 91.5%.
Table 1
| Component | Content (weight %) |
| Butene-1 | 35 |
| Along 2-butylene | 31 |
| Anti-2-butylene | 34 |
[embodiment 2]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, raw material butylene composition is shown in Table 2, uses the technique skill of Fig. 1
Art, reactor is three grades, and three reactor is adiabatic radial fixed-bed reactor, the filling catalysis of reactor catalyst cylinder outer ring
Agent I, catalyst I are ferrous oxide catalyst, mainly comprise iron, zinc, and magnesium ratio (mole) is: Fe:Zn:Mg=10:4:5, interior
Circle loading catalyst II, catalyst II is molybdenum-bismuth series catalysts, mainly comprises molybdenum, bismuth, iron, and cobalt ratio (weight) is: Mo:Bi:
Fe:Co=10:2:5:7, auxiliary agent is Zn, and carrier is Al2O3, the loadings of catalyst I and catalyst II is than for 1:1(weight), former
Material butylene total amount 18920kg/h, air total amount 36000 kg/h, water vapour total amount 47500 kg/h, butene feedstock is divided into three
Point, one section of butylene flow 9200 kg/h, according to butylene: oxygen: water (mol) is that the ratio of 1:0.5:15 is mixed with air, water vapour
After conjunction, being 320 DEG C in temperature, under the conditions of pressure 0.12MPaG, enter first order oxidative dehydrogenation reactor, A reactor exports
Temperature 490 DEG C, after heat exchanger heat exchange, is mixed into second reactor with two sections of butylene and two sections of air, two sections of butene stream
Measuring 4800 kg/h, second reactor entrance butylene: oxygen: water (mol) ratio is 1:0.6:15, reaction temperature is 330 DEG C, pressure
Power 0.11MPaG, second reactor is worked off one's feeling vent one's spleen temperature 506 DEG C, after heat exchanger heat exchange, mixes with three sections of butylene and three sections of air
Enter three reactor, three sections of butylene flow 4920 kg/h, three reactor entrance butylene: oxygen: water (mol) ratio is 1:
0.66:16, three reactor inlet temperature is 340 DEG C, temperature of working off one's feeling vent one's spleen 520 DEG C, pressure 0.0951MPaG.
This device reaction part water vapour consumption 47500kg/h, device total energy consumption 900kg marks oil/t butadiene, and butylene is total
Conversion ratio 84%, overall selectivity 92%.
Table 2
| Component | Content (weight %) |
| Butene-1 | 25 |
| Along 2-butylene | 26 |
| Anti-2-butylene | 51 |
.[embodiment 3]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, raw material butylene composition is shown in Table 1, uses the technique skill of Fig. 1
Art, reactor is two-stage, and two-stage reactor is Adiabatic Axial Fixed-Bed reactor, reactor internal upper part loading catalyst II,
Catalyst II is molybdenum-bismuth series catalysts, mainly comprises molybdenum, bismuth, iron, and cobalt ratio (weight) is: Mo:Bi:Fe:Co=10:4:3:6
, auxiliary agent is Sn, W, and carrier is Al2O3, bottom loading catalyst I, catalyst I are ferrous oxide catalyst, mainly comprise iron,
Zinc, magnesium ratio (mole) is: Fe:Zn:Mg=10:3:6, and the loadings of catalyst I and catalyst II is than for 1:0.5(weight), former
Material butylene total amount 19670kg/h, air total amount 36000 kg/h, water vapour total amount 55000 kg/h, butene feedstock is divided into two
Point, one section of butylene flow 9400 kg/h, according to butylene: oxygen: water (mol) is ratio and air, the water vapour of 1:0.52:13
After mixing, being 320 DEG C in temperature, under the conditions of pressure 0.12MPaG, enter first order oxidative dehydrogenation reactor, A reactor goes out
Implication temperature 505 DEG C, after heat exchanger heat exchange, is mixed into second reactor with two sections of butylene and two sections of air, two sections of butylene
Flow 10270 kg/h, second reactor entrance butylene: oxygen: water (mol) ratio is 1:0.65:14, reaction temperature is 330
DEG C, pressure 0.11MPaG, second reactor is worked off one's feeling vent one's spleen temperature 520 DEG C.
This device reaction part water vapour consumption 55000kg/h, device total energy consumption 1100kg marks oil/t butadiene, and butylene is total
Conversion ratio 80%, overall selectivity 91%.
[embodiment 4]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, raw material butylene composition is shown in Table 3, uses the technique skill of Fig. 1
Art, reactor is two-stage, and two-stage is isothermal calandria type fixed bed reactor, every tubulation top loading catalyst in reactor
I, catalyst I are ferrous oxide catalyst, mainly comprise iron, zinc, and magnesium ratio (mole) is: Fe:Zn:Mg=10:3:5, bottom
Loading catalyst II, catalyst II is molybdenum-bismuth series catalysts, mainly comprises molybdenum, bismuth, iron, and cobalt ratio (weight) is: Mo:Bi:
Fe:Co=10:4:2:6, auxiliary agent is Sn, W, and carrier is SiO2, the loadings of catalyst I and catalyst II is than for 1:2(weight),
Raw material butylene total amount 19670kg/h, air total amount 36000 kg/h, water vapour total amount 6300 kg/h, butene feedstock is divided into two
Point, one section of butylene flow 9400 kg/h, according to butylene: oxygen: water (mol) is that the ratio of 1:0.52:2 is mixed with air, water vapour
After conjunction, being 450 DEG C in temperature, under the conditions of pressure 0.13MPaG, enter first order oxidative dehydrogenation reactor, A reactor exports
Gas, after heat exchanger heat exchange, is mixed into second reactor with two sections of butylene and two sections of air, two sections of butylene flow 10270 kg/
H, second reactor entrance butylene: oxygen: water (mol) ratio is 1:0.65:2.1, reaction temperature is 460 DEG C, pressure
0.10MPaG。
This device reaction part water vapour consumption 6300kg/h, device total energy consumption 600kg marks oil/t butadiene, and butylene always turns
Rate 85%, overall selectivity 90.5%.
Table 3
| Component | Content (weight %) |
| Butene-1 | 25 |
| Along 2-butylene | 10 |
| Anti-2-butylene | 65 |
[embodiment 5]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, raw material butylene composition is shown in Table 4, uses the technique skill of Fig. 1
Art, reactor is two-stage, and two-stage reactor is Adiabatic Axial Fixed-Bed reactor, reactor internal upper part loading catalyst I, urges
Agent I is ferrous oxide catalyst, mainly comprises iron, zinc, and magnesium ratio (mole) is: Fe:Zn:Mg=10:2:4, and bottom is loaded
Catalyst II, catalyst II is molybdenum-bismuth series catalysts, mainly comprises molybdenum, bismuth, iron, and cobalt ratio (weight) is: Mo:Bi:Fe:Co=
10:3:2:5, auxiliary agent is Sn, and carrier is Al2O3, the loadings of catalyst I and catalyst II is than for 1:0.1(weight), raw material fourth
Alkene total amount 19670kg/h, air total amount 36000 kg/h, water vapour total amount 50000 kg/h, butene feedstock is divided into two parts, and one
Section butylene flow 9400 kg/h, according to butylene: oxygen: water (mol) is that the ratio of 1:0.52:12 mixes with air, water vapour
After, it being 320 DEG C in temperature, under the conditions of pressure 0.12MPaG, enter first order oxidative dehydrogenation reactor, A reactor is worked off one's feeling vent one's spleen
Temperature 505 DEG C, after heat exchanger heat exchange, is mixed into second reactor with two sections of butylene and two sections of air, two sections of butylene flows
10270 kg/h, second reactor entrance butylene: oxygen: water (mol) ratio is 1:0.65:12, reaction temperature is 320 DEG C, pressure
Power 0.11MPaG, second reactor is worked off one's feeling vent one's spleen temperature 525 DEG C.
This device reaction part water vapour consumption 50000kg/h, device total energy consumption 1050kg marks oil/t butadiene, and butylene is total
Conversion ratio 84%, overall selectivity 92%.
Table 4
| Component | Content (weight %) |
| Butene-1 | 80 |
| Along 2-butylene | 12 |
| Anti-2-butylene | 8 |
[embodiment 6]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, raw material butylene composition is shown in Table 5, uses the technique skill of Fig. 1
Art, reactor is two-stage, and two-stage is isothermal calandria type fixed bed reactor, every tubulation top loading catalyst in reactor
I, catalyst I are ferrous oxide catalyst, mainly comprise iron, zinc, and magnesium ratio (mole) is: Fe:Zn:Mg=10:3:5, bottom
Loading catalyst II, catalyst II is molybdenum-bismuth series catalysts, mainly comprises molybdenum, bismuth, iron, and cobalt ratio (weight) is: Mo:Bi:
Fe:Co=10:4:2:6, auxiliary agent is Sn, W, and carrier is SiO2, the loadings of catalyst I and catalyst II is heavier than for 1:0.3(
Amount), raw material butylene total amount 19670kg/h, air total amount 42000 kg/h, water vapour total amount 30000 kg/h, butene feedstock is divided
For two parts, one section of butylene flow 9400 kg/h, according to butylene: oxygen: water (mol) is the ratio of 1:0.6:10 and empty gas and water
After steam, it is 480 DEG C in temperature, under the conditions of pressure 0.13MPaG, enters first order oxidative dehydrogenation reactor, first order reaction
Device is worked off one's feeling vent one's spleen after heat exchanger heat exchange, is mixed into second reactor with two sections of butylene and two sections of air, two sections of butylene flows
10270 kg/h, second reactor entrance butylene: oxygen: water (mol) ratio is 1:0.65:11, reaction temperature is 460 DEG C, pressure
Power 0.10MPaG.
This device reaction part water vapour consumption 30000kg/h, device total energy consumption 800kg marks oil/t butadiene, and butylene is total
Conversion ratio 86%, overall selectivity 91%.
Table 5
| Component | Content (weight %) |
| Butene-1 | 70 |
| Along 2-butylene | 8 |
| Anti-2-butylene | 22 |
[comparative example 1]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, raw material butylene composition is shown in Table 1, uses the technique skill of Fig. 2
Art, reactor is the axial insulation fix bed reactor of single-stage, filling ferrous oxide catalyst, raw material butylene flow in reactor
22700kg/h, air capacity 34000 kg/h, water vapour amount 160500 kg/h, butene feedstock is according to butylene: oxygen: water (mol)
After mixing with air, water vapour for the ratio of 1:0.6:22, it is 330 DEG C in temperature, under the conditions of pressure 0.12MPaG, enters oxidation
Dehydrogenation reactor, oxidative dehydrogenation is worked off one's feeling vent one's spleen temperature 520 DEG C.
This device reaction part water vapour consumption 160500kg/h, device total energy consumption 1600kg marks oil/t butadiene, butylene
Total conversion 70%, overall selectivity 90%.
Claims (8)
1. the method improving n-butene oxidative dehydrogenation butadiene yield, uses N level fixed bed reactors cascade reaction, fourth
Alkene raw material is divided into N stock, respectively enters N stage reactor, and wherein N is the integer more than or equal to 2；Every stage reactor beds divides
Section is filled with catalyst I and catalyst II, and course of reaction includes following step:
A) through water vapour and first burst of butene feedstock and the oxygen-containing gas of metering, it is 1 by butylene, oxygen, steam molar ratio:
The ratio of 0.4～1.5:0～18 enters first order reactor, and reaction temperature is 280～600 DEG C, reaction pressure be 0.02～
1.5MPa；
B) distribution of next stage butylene sendout, first order butylene and butylene the most at different levels is determined according to upper level reaction conversion ratio
Proportion is 1:0.4～1.0；The reacted material of upper level, then after mixing with butene feedstock and oxygen-containing gas, by step a)
In identical mol ratio, enter next stage reactor；
C) when N is equal to 2, reacted material enters step d)；When N is more than 2, reacted material is according to the side of step b)
Formula, sequentially enters next stage reactor, until reacted material enters N stage reactor；
D) N stage reactor outlets products enters follow-up workshop section and reclaims butadiene；
Described catalyst I is the ferrous oxide catalyst with spinel structure, mainly comprises iron, zinc, and magnesium molar ratio is:
Fe:Zn:Mg=10:1～5:2～6；Catalyst II is molybdenum-bismuth series catalysts, mainly comprises molybdenum, bismuth, iron, and weight of cobalt ratio is:
Mo:Bi:Fe:Co=10:1～4:1～3:2～8, auxiliary agent is at least one in Sn, Re, W, Pb, Ti, Zn, La or Ce, carrier
For SiO2、Al2O3Or silicate molecular sieve.
The method of raising n-butene oxidative dehydrogenation butadiene yield the most according to claim 1, it is characterised in that raw material
Butylene contains at least two in 1-butylene, cis-2-butene, Trans-2-butene；Oxygen-containing gas is air or pure oxygen, or air
Mixture with oxygen；Catalyst I is the catalyst having higher conversion to butene-1 and maleic-2, and catalyst II is to instead
Butene-2 has the catalyst of higher conversion.
The method of raising n-butene oxidative dehydrogenation butadiene yield the most according to claim 1, it is characterised in that every grade
The mol ratio of reactor inlet butylene, oxygen and water vapour is 1:0.45～1.0:2～12；The reaction entrance temperature of every stage reactor
Degree is 300～550 DEG C, and pressure is 0.05～1.0MPa.
The method of raising n-butene oxidative dehydrogenation butadiene yield the most according to claim 1, it is characterised in that catalysis
The charge weitght ratio of agent I and II is 1:0.1～10.
The method of raising n-butene oxidative dehydrogenation butadiene yield the most according to claim 1, it is characterised in that described
Fixed bed reactors include Adiabatic Axial Fixed-Bed reactor, adiabatic radial fixed-bed reactor, shell and tube isothermal fixed bed
Reactor.
The method of raising n-butene oxidative dehydrogenation butadiene yield the most according to claim 4, it is characterised in that catalysis
The charge weitght ratio of agent I and II is 1:0.2～8.
The method of raising n-butene oxidative dehydrogenation butadiene yield the most according to claim 5, it is characterised in that use
During Adiabatic Axial Fixed-Bed reactor, catalyst I and II is the filling of upper and lower segmentation；When using adiabatic radial fixed-bed reactor
Catalyst I and II is Internal and external cycle separately filling；When using isothermal calandria type fixed bed reactor, catalyst I and II is on tubulation
Lower segmentation is loaded.
The method of raising n-butene oxidative dehydrogenation butadiene yield the most according to claim 3, it is characterised in that every grade
The mol ratio of reactor inlet butylene, oxygen and water vapour is 1:0.50～0.9:4～10；The reaction entrance temperature of every stage reactor
Degree is 300～500 DEG C, and pressure is 0.1～0.5MPa.
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| CN105152837B (en) * | 2015-10-16 | 2017-04-05 | 安徽工业大学 | The method for synthesizing 1,3 butadiene with five component composite oxide catalysts moving beds of Bi/Mo/Co/Ce/Fe |
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| CN107081144A (en) * | 2017-06-17 | 2017-08-22 | 安徽海德石油化工有限公司 | A kind of method that n-butene prepares butadiene in utilization C-4-fraction |
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| CN101367702A (en) * | 2008-09-26 | 2009-02-18 | 淄博齐翔腾达化工股份有限公司 | Method for preparing butadiene with butylene oxo-dehydrogenation of axially-located bed |
| CN101980992A (en) * | 2008-03-28 | 2011-02-23 | Sk能源株式会社 | Method for preparing 1,3-butadiene from normal butene by using continuous-flow dual-bed reactor |
| WO2013002459A1 (en) * | 2011-06-30 | 2013-01-03 | (주) 엘지화학 | High yield production method for 1,3-butadiene |
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| CN101980992A (en) * | 2008-03-28 | 2011-02-23 | Sk能源株式会社 | Method for preparing 1,3-butadiene from normal butene by using continuous-flow dual-bed reactor |
| CN101367702A (en) * | 2008-09-26 | 2009-02-18 | 淄博齐翔腾达化工股份有限公司 | Method for preparing butadiene with butylene oxo-dehydrogenation of axially-located bed |
| WO2013002459A1 (en) * | 2011-06-30 | 2013-01-03 | (주) 엘지화학 | High yield production method for 1,3-butadiene |
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