CN103553864B - The method of butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl - Google Patents
The method of butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl Download PDFInfo
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Abstract
The present invention relates to a kind of method of butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl, mainly solve that isothermal reactor tubulation inner catalyst temperature in prior art is uneven, easily carbon deposit, the regeneration period is short and butadiene selective is poor problem.The present invention adopts at least two-stage isothermal reactor series connection, and water vapor all adds from first step reactor, and raw material butylene and oxygen-containing gas segmentation add each stage reactor; Each stage reactor is shell and tube isothermal reactor, loading catalyst in tubulation, shell side outside tubulation is divided into 1 not connected ~ M with the dividing plate perpendicular to tubulation direction shell side and removes hot chamber, M be more than or equal to 2 integer, thermal medium is removed with ft connection respectively in described hot chamber of removing, respectively remove hot chamber catalyst layer and temperature measuring equipment is housed, by regulating respectively and the technical scheme of removing thermal medium flow to control the temperature of respectively removing hot chamber tubulation inner catalyst layer of respectively removing hot chamber and being communicated with, solve this problem preferably, can be used for the industrial production of Oxidative Dehydrogenation of Butene into Butadiene.
Description
Technical field
The present invention relates to a kind of method of butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl.
Background technology
Divinyl is the important monomer of synthetic rubber, synthetic resins, is mainly used in synthesis cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), paracril and ABS resin etc.Divinyl is also multiple coating and Organic Chemicals.
The mode of production of current divinyl mainly contains C-4-fraction and is separated and synthesis method (comprising butane dehydrogenation, butylene dehydrogenation, butylene oxidation-dehydrogenation etc.) two kinds.At present except the U.S., countries in the world divinyl is almost all direct from the by-product C-4-fraction (can be written as C-4-fraction again) during hydrocarbon cracking ethene.The source of U.S.'s divinyl, only about half of from butane, butylene dehydrogenation, half is directly from cracking c_4 cut.
Butylene oxidation-dehydrogenation produces the more competitive Technology of divinyl at present, and Oxidative Dehydrogenation of Butene into Butadiene is in the presence of water vapor, utilizes the hydrogen of oxygen in butylene molecule to be combined, obtain divinyl and constitutionally stable water.This reaction is irreversible reaction substantially.Main reaction equation is as follows:
2C
4H
8+O
2→2C
4H
6+2H
2O+128kJ/mol
Other side reaction mainly contains:
C
4H
8+6O
2→4CO
2+4H
2O+2532kJ/mol
C
4H
8+4O
2→4CO+4H
2O+1268kJ/mol
Butylene oxidation-dehydrogenation main reaction is that butylene and oxygen reaction generate divinyl, and react for exothermic medium reaction, side reaction is that butylene and oxygen generate CO and CO
2, and the oxygenatedchemicals such as aldehyde ketone, wherein generate CO and CO
2reaction be strong exothermal reaction, general, adopt spinel Fe-series catalyst time, the selectivity of butylene oxidation-dehydrogenation main reaction 90 ~ 94%, generate CO
2selectivity 6% ~ 7%, generate the selectivity of CO 0.2% ~ 0.8%, in reaction process except main reaction, side reaction can release a large amount of reaction heat.When adopting adiabatic reactor, for controlling reaction temperature rising and preventing catalyst carbon deposit, need to add a large amount of water vapors, even so, when water alkene ratio (mol ratio of water vapor and butylene) is 16, the thermal insulation warming of butylene oxidation-dehydrogenation reactor reaches more than 200 DEG C, adiabatic reactor temperature in is 300 ~ 350 DEG C time, temperature out reaches 550 DEG C even higher, the rising of temperature brings the increase of side reaction, time more than 530 DEG C, the rate of cleavage of the hydrocarbons such as butylene obviously increases, meeting accelerator activator area carbon speed greatly, and alkynes and propadiene can be generated, their content increases with the rising of temperature, these alkynes are increased to a certain degree as can not be effectively removed, serious impact is there is by polymerization.
The full scale plant that current butylene oxidation-dehydrogenation method produces divinyl generally adopts insulation fix bed reactor or fluidized-bed reactor, as patent CN101367702 discloses a kind of method of preparing butadiene with butylene oxo-dehydrogenation of axially-located bed, its flow process is for adopting two-stage axial restraint bed bioreactor, butene feedstock, water vapor and air segmenting enter, reactor outlet is cooled by heating steam, enters next stage reactor after reaching next stage reactor inlet temperature; Patent CN102675027A discloses a kind of preparing butadiene with butylene oxo-dehydrogenation technique, adopt adiabatic radial fixed-bed by preparing butadiene with butylene oxo-dehydrogenation, radial adiabatic fixed bed forms by three grades, but this patent adopts water vapor segmentation to add membership causes total water consumption to increase, and inter-stage adds liquid water also can make reactor inlet temperature local overcooling cause carbon distribution to increase.
Above patent all adopts adiabatic reactor technique, preventing hydrocarbon cracking and catalyst carbon deposit for controlling reaction thermal insulation warming, a large amount of water vapors must be added in reaction process, causing plant energy consumption high, simultaneous reactions temperature raises and causes butadiene selective to decline, and product yield reduces.
Research shows, on Fe-series catalyst, the reaction velocity constant of 480 DEG C is 1.7 times of 450 DEG C, that is, when other conditions are constant, 1.7 times when when 480 DEG C, the transformation efficiency of butylene is 450 DEG C, but consider the existence of side reaction, temperature raises same increase side reaction speed, due to different to both influence degrees, exists competitive.Concerning Fe-series catalyst, within the scope of 450 DEG C ~ 480 DEG C, butadiene selective change is little, when temperature is more than 480 DEG C, butylene deep oxidation increases, and selectivity declines, therefore 450 DEG C ~ 480 DEG C scopes, the over-all propertieies such as the transformation efficiency of butylene and selectivity are optimum.
For this reason, thermal isothermal reactor is removed as adopted, to greatly improve production capacity and the product yield of device, as patent CN102442874A discloses a kind of method of constant temperature fixed bed preparing butadiene with butylene oxo-dehydrogenation, mixed butylene, air, water vapor are added in static mixer in proportion, mixed raw material is heated to certain temperature by front interchanger, enter the oxydehydrogenation of constant temperature fixed-bed reactor, but the problem that this patent unresolved constant temperature fixed bed tubulation temperature is uneven, local temperature is too high.
Isothermal shell and tube reactor is similar to shell and tube heat exchanger, catalyzer is put in tubulation, the salt of logical melting between pipe or water vapor, heat conduction wet goods are as removing thermal medium, reaction gas reacts through pipe inner catalyst layer, reaction heat through tube wall with remove thermal medium and exchange and taken out of, temperature is difficult to control evenly to adopt the maximum difficult point of this reactor to be, because butylene oxidation-dehydrogenation main side effect causes local temperature in reactor too high at catalyzer regional area vigorous reaction, cause that hydrocarbon cracking, catalyzer are coking, pipe blocking.Good solution is not provided to this patent CN102442874A and other documents, seriously limits the industrial application of butylene oxidation-dehydrogenation isothermal process technology.
Summary of the invention
The problem that the technical problem that the present invention mainly solves is uneven, the easy carbon deposit of isothermal reactor tubulation inner catalyst temperature in the prior art existed in prior art, the regeneration period is short and butadiene selective is poor, provide a kind of method of new butylene isothermal oxidation Oxidative Dehydrogenation divinyl, the method has isothermal reactor tubulation inner catalyst homogeneous temperature, not easily carbon deposit, the regeneration period is long and butadiene selective is high advantage.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl, adopts N level isothermal reactor cascade reaction, wherein N be more than or equal to 2 positive integer; Each stage reactor is shell and tube isothermal reactor, loading catalyst in tubulation, the dividing plate of shell side outside tubulation perpendicular to tubulation direction, shell side is divided into 1 not connected ~ M and removes hot chamber, wherein M be more than or equal to 2 positive integer, described respectively remove hot chamber and remove thermal medium with outside respectively and be communicated with, the tubulation inner catalyst layer respectively removing hot chamber is equipped with temperature measuring equipment, and reaction process comprises following step:
A) butene feedstock is divided into N stock;
B) first step reactor is entered in butylene, oxygen, steam molar than the ratio for 1:0.4 ~ 1.5:0 ~ 18 through the water vapor of metering and first burst of butene feedstock and oxygen-containing gas, temperature of reaction controls to be 300 ~ 550 DEG C by removing thermal medium, and pressure is 0.02 ~ 1.0MPa;
C) monitor butene concentration in reacted material, according to upper level reaction conversion ratio determination next stage butylene sendout, by the mol ratio in step b), reacted material and required butene feedstock and oxygen-containing gas mixing, enter next stage reactor; Wherein, first strand of butylene is 1:0.4 ~ 1.0 with the allocation proportion scope of each stock butylene afterwards;
D) when N equals 2, step e) is entered; When N is greater than 2, reacted material repeating step c) mode, enter lower stage reactor successively, until reacted material enters N stage reactor;
E) N stage reactor outlets products enters follow-up workshop section and reclaims divinyl.
In technique scheme, preferred technical scheme is, reactor is shell and tube isothermal fixed-bed reactor, loading catalyst in tubulation, for water, water vapor, fused salt, heat conduction wet goods remove thermal medium between tubulation; By regulate respectively with respectively remove that hot chamber is communicated with remove thermal medium flow, control the temperature of respectively removing hot chamber tubulation inner catalyst layer.Be arranged in the tubulation that reactor respectively removes hot chamber and at least establish 1 temperature measuring equipment; Preferred technical scheme is, entering the thermal medium of removing respectively removing hot chamber can be same material or different substances, and temperature can be identical or different; Preferred technical scheme is, oxygen-containing gas is air or pure oxygen, or the mixture of air and oxygen; Preferred technical scheme is, catalyzer is a kind of ferrous oxide catalyzer with spinel structure, mainly forms iron, zinc, and the molar ratio of magnesium is: Fe:Zn:Mg=10:1 ~ 5:2 ~ 6, adopts coprecipitation method preparation; Preferred technical scheme is: the temperature of reaction of each stage reactor is 380 ~ 500 DEG C, and pressure is 0.05 ~ 0.5M; Preferred technical scheme is: the mol ratio of every stage reactor entrance butylene, oxygen and water vapor is 1:0.45 ~ 0.9:2 ~ 10.Preferred technical scheme is: the shell side outside reactor tubulation is divided into 1 not connected ~ M with the dividing plate perpendicular to tubulation direction shell side and removes hot chamber, 2≤M≤10, and M is integer, and dividing plate is fixing or slide construction.
Preferred technical scheme is: the temperature of reaction of each stage reactor is 420 ~ 480 DEG C, and pressure is 0.1 ~ 0.3MPa.Preferred technical scheme is: catalyzer is a kind of carbon dioxide catalyzer with spinel structure, is Fe by its general formula of chemical constitution
2o
3mgOZnOP
2o
5m
xo
y, Fe
2o
3be 10 ~ 25%, P of catalyst weight for 52 ~ 76%, MgO of catalyst weight is 12 ~ 28%, ZnO of catalyst weight
2o
5being selected from least one in period 4 Sc, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn for 0.01 ~ 5.0%, M of catalyst weight, take oxide basis as 0.01 ~ 3.0% of catalyst weight, adopts coprecipitation method preparation.
The present invention adopts at least two-stage reactor series connection, the method of butylene and oxygen-containing gas sectional feeding, water vapor is all added from first step reactor, raw material butylene and oxygen-containing gas are divided at least two portions and enter every A reactor by a certain percentage, because water vapor all enters first step reactor, every stage reactor generation butylene oxidation-dehydrogenation water generation reaction, reacting rear material enters next stage reactor again, the water yield progressively increases, and butylene is segmentation enters every A reactor, like this at lower total water alkene than under condition, every stage reactor can maintain higher water alkene ratio, be conducive to preventing catalyzer coking and improve single-stage reactor transformation efficiency, and the raising of reaction order also improves reaction total conversion rate simultaneously.
The reactor that the present invention adopts is isothermal reactor, compare adiabatic reaction technique, although this process reactor structure is slightly complicated, but for this strong exothermal reaction of butylene oxidation-dehydrogenation, thermal medium is removed in employing can effectively control reactor outlet temperature, thus a large amount of minimizing controls the amount of steam of reaction temperature rising originally as thinner, the average reaction temperature of isothermal reactor is higher than adiabatic reactor simultaneously, can improve single-stage reaction conversion ratio and selectivity.Therefore, adopt and remove thermal isothermal reactor, will greatly improve the production capacity of device, product yield and energy efficient.
Isothermal shell and tube reactor is similar to shell and tube heat exchanger, catalyzer is put in tubulation, the salt of logical melting between pipe or water vapor, heat conduction wet goods is as removing thermal medium, reaction gas reacts through pipe inner catalyst layer, reaction heat through tube wall with remove thermal medium and exchange and taken out of, temperature is difficult to control evenly to adopt the maximum technological difficulties of this reactor to be, especially true for butylene oxidation-dehydrogenation reaction, the side reaction thermal discharge that butylene and oxygen produce CO2 and CO is concentrated greatly, as heat can not be removed effectively fast, in reactor, local temperature can be too high, cause hydrocarbon cracking, the coking even pipe blocking of catalyzer.
For this reason, the present invention is divided into not connected 1 ~ M with the dividing plate perpendicular to tubulation direction shell side at reactor shell side and removes hot chamber (M >=2), remove hot chamber and remove thermal medium with ft connection respectively for 1 ~ M, respectively remove hot chamber catalyst layer and temperature measuring equipment be housed, by regulate respectively with respectively remove that hot chamber is communicated with remove thermal medium flow to control the temperature of respectively removing hot chamber tubulation inner catalyst layer.The initial stage is used at catalyzer, main side effect mainly occurs in the beds near opening for feed, thermal discharge also concentrates on this part, and other parts of tubulation are not reacted substantially, there is no heat yet, usually removing thermal means as adopted, although most of tubulation temperature can control, but be difficult to control in the temperature rise of vigorous reaction section, cause a large amount of cracking of hydro carbons, the serious carbon deposit of catalyzer; Removing thermal cycling amount or thermal medium inlet temperature is removed in reduction as strengthened, while reducing hot(test)-spot temperature, also can reduce the temperature of other tubulation sections, bring the adverse consequences that total conversion rate is not high, energy consumption is large.And adopt dividing plate that shell side is divided into the method that 1 not connected ~ M is removed hot chamber (M >=2), at the catalyst application initial stage, only need strengthen and correspondingly remove hot chamber and remove the temperature that thermal medium is removed in the internal circulating load of thermal medium or reduction, just can control this section of tubulation temperature of reaction, and other remove hot chamber due to corresponding tubulation thermal discharge very little, that can reduce that this removes hot chamber removes thermal medium internal circulating load, along with the passing of catalyst application time, hot(test)-spot temperature also can move down, that now only need remove hot chamber according to the corresponding adjustment of tubulation temperature of reaction of temperature measuring equipment display removes thermal medium flow or temperature, reactor tubulation temperature of reaction can be controlled flexibly like this, effectively prevent temperature of reaction local superheating, catalyst carbon deposit inactivation, extend catalyzer and use the regeneration period, improve product butadiene yield.By adopting the inventive method, compared with prior art, catalyst regeneration cycle can extend 3 months to 1 year, and butadiene yield improves 2% ~ 10%, achieves good technique effect and obvious technical progress.
Accompanying drawing explanation
Fig. 1 is butylene isothermal oxidation Oxidative Dehydrogenation Butadiene Extraction Process schematic flow sheet of the present invention (with two-stage reaction, being divided into two in every stage reactor, to remove hot chamber is example).
Fig. 2 is butylene isothermal oxidation Oxidative Dehydrogenation Butadiene Extraction Process schematic flow sheet in the past.
In Fig. 1, 1 is butene feedstock, 2 is oxygen-containing gas, 3 is water vapor, 4 is one section of butylene, 5 is two sections of butylene, 6 is one section of oxygen-containing gas, 7 is two sections of oxygen-containing gass, 8 is A reactor entrance material, 9 is A reactor outlet material, 10 is second reactor entrance material, 11 is second reactor outlet material, 12 remove thermal medium for A reactor one section removes the import of hot chamber, 13 remove the outlet of hot chamber for A reactor one section removes thermal medium, 14 remove thermal medium for A reactor two sections removes the import of hot chamber, 15 remove the outlet of hot chamber for second reactor one section removes thermal medium, 16 remove thermal medium for second reactor one section removes the import of hot chamber, 17 remove the outlet of hot chamber for second reactor two sections removes thermal medium, 18 remove thermal medium for second reactor two sections removes the import of hot chamber.
In Fig. 1, butene feedstock 1 is divided into 2 strands, be respectively one section of butylene 4 and two sections of butylene 5, oxygen-containing gas 2 is divided into 2 strands, be respectively one section of oxygen-containing gas, 6 and two sections of oxygen-containing gass 7, one section of butylene 4, one section of oxygen-containing gas 6 and water vapor 3 mixed A reactor entrance material 8 enter A reactor, tubulation loading catalyst in A reactor, by A reactor dividing plate, shell side is divided into two portions, temperature measuring equipment is established in tubulation, thermal medium amount of the removing control temperature of reaction entering and remove hot chamber is regulated by variable valve, A reactor outlet streams 9 is through A reactor and two sections of butylene 5, after two sections of oxygen-containing gass 7 mix, second reactor entrance material 10 enters second reactor, second reactor inner structure is identical with A reactor with temperature-controlled process, second reactor outlet streams 11 enters follow-up workshop section and carries out divinyl rectifying.
In Fig. 2,1 is butene feedstock, and 2 is oxygen-containing gas, and 3 is water vapor, and 4 is reactor inlet material, and 5 is reactor outlet material, and 6 remove thermal medium for import, and 7 remove thermal medium for outlet, and I is reactor, and II is temperature measuring equipment, and III is variable valve.
In Fig. 2, the mixed logistics 4 of raw material butylene 1, oxygen-containing gas 2 and water vapor 3 enters reactor I and oxidative dehydrogenation occurs, reactor tubulation apparatus with catalyst inside, temperature measuring equipment II is established in tubulation, regulated by variable valve III and enter the heat of removing of removing hot chamber and to be situated between 6 quality control temperature of reaction, reaction outlet streams 5 enters follow-up workshop section and carries out divinyl rectifying.
Below by specific embodiment, invention is further elaborated.
Embodiment
[embodiment 1]
Certain 200,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, reactor is two-stage, and two-stage reactor is isothermal calandria type fixed bed reactor, all loads ferrous oxide catalyzer in two-stage reactor tubulation, main composition comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:Mg=10:3:5, prepared by employing coprecipitation method, principal crystalline phase is ZnFe
2o
4spinel, A reactor is identical with second reactor structure, is of a size of Φ 4500 × 6000mm, and tubulation is Φ 50 × 6000mm, tubulation radical 4000, heat interchanging area 3900m
2, A reactor and second reactor shell side are divided into upper and lower two with the dividing plate perpendicular to tubulation and remove hot chamber, remove thermal medium and be thermal oil, heat conductive oil inlet temperature is 300 DEG C, raw material butylene total amount 40000kg/h, air total amount 72000kg/h, butene feedstock is divided into two portions, one section of butylene flow 26000kg/h, two sections of butylene flow 14000kg/h, water vapor 42000kg/h and one section butylene, air is in butylene: oxygen: the ratio that water (mol) is 1:0.52:5 is temperature 420 DEG C, A reactor is entered under pressure 0.15MPa condition, A reactor reflects implication and two sections of butylene, two sections of air are by butylene: oxygen: the molar ratio that water (mol) is 1:0.65:5.2 is blended in temperature and enters 430 DEG C, second reactor is entered under pressure 0.13MPa condition, second order reaction outlet streams enters follow-up workshop section and carries out rectifying.
This device reaction device running condition is in table 1, and catalyst regeneration cycle is 9 months, divinyl average yield 72wt%.
Table 1
[embodiment 2]
Certain 200,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, reactor is two-stage, and two-stage reactor is isothermal calandria type fixed bed reactor, all loads ferrous oxide catalyzer in two-stage reactor tubulation, main composition comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:Mg=10:3:5, prepared by employing coprecipitation method, principal crystalline phase is ZnFe
2o
4spinel, A reactor is identical with second reactor structure, is of a size of Φ 4500 × 6000mm, and tubulation is Φ 50 × 6000mm, tubulation radical 4000, heat interchanging area 3900m
2, A reactor and second reactor shell side are divided into 4 with the dividing plate perpendicular to tubulation and remove hot chamber, remove thermal medium and be thermal oil, heat conductive oil inlet temperature is 300 DEG C, raw material butylene total amount 40000kg/h, air total amount 72000kg/h, butene feedstock is divided into two portions, one section of butylene flow 26000kg/h, two sections of butylene flow 14000kg/h, water vapor 42000kg/h and one section butylene, air is in butylene: oxygen: the ratio that water (mol) is 1:0.52:5 is temperature 420 DEG C, A reactor is entered under pressure 0.15MPa condition, A reactor reflects implication and two sections of butylene, two sections of air are by butylene: oxygen: the molar ratio that water (mol) is 1:0.65:5.2 is blended in temperature and enters 430 DEG C, second reactor is entered under pressure 0.13MPa condition, second order reaction outlet streams enters follow-up workshop section and carries out rectifying.
This device reaction device running condition is in table 2, and catalyst regeneration cycle is 1 year, divinyl average yield 74wt%.
Table 2
[embodiment 3]
Certain 200,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, reactor is two-stage, and two-stage reactor is isothermal calandria type fixed bed reactor, all loads ferrous oxide catalyzer in two-stage reactor tubulation, main composition comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:Mg=10:4:6, prepared by employing coprecipitation method, principal crystalline phase is ZnFe
2o
4spinel, A reactor is identical with second reactor structure, is of a size of Φ 4500 × 6000mm, and tubulation is Φ 50 × 6000mm, tubulation radical 4000, heat interchanging area 3900m
2, A reactor and second reactor shell side are divided into 2 with the dividing plate perpendicular to tubulation and remove hot chamber, remove thermal medium and be fused salt, fused salt inlet temperature is 350 DEG C, raw material butylene total amount 40000kg/h, air total amount 72000kg/h, butene feedstock is divided into two portions, one section of butylene flow 26000kg/h, two sections of butylene flow 14000kg/h, water vapor 42000kg/h and one section butylene, air is in butylene: oxygen: the ratio that water (mol) is 1:0.52:5 is temperature 420 DEG C, A reactor is entered under pressure 0.15MPa condition, A reactor reflects implication and two sections of butylene, two sections of air are by butylene: oxygen: the molar ratio that water (mol) is 1:0.65:5.2 is blended in temperature and enters 430 DEG C, second reactor is entered under pressure 0.13MPa condition, second order reaction outlet streams enters follow-up workshop section and carries out rectifying.
This device reaction device running condition is in table 3, and catalyst regeneration cycle is 10 months, divinyl average yield 75wt%.
Table 3
[embodiment 4]
Certain 200,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, reactor is two-stage, and two-stage reactor is isothermal calandria type fixed bed reactor, all loading carbon dioxide catalyzer in two-stage reactor tubulation, is Fe by its general formula of chemical constitution
2o
3mgOZnOP
2o
5cuO, Cr
2o
3be 10%, P of catalyst weight for 66%, MgO of catalyst weight is 20%, ZnO of catalyst weight
2o
5for 2%, CuO of catalyst weight is 2% of catalyst weight, adopt coprecipitation method preparation, A reactor is identical with second reactor structure, is of a size of Φ 4500 × 6000mm, and tubulation is Φ 50 × 6000mm, tubulation radical 4000, heat interchanging area 3900m
2, A reactor and second reactor shell side are divided into 3 with the dividing plate perpendicular to tubulation and remove hot chamber, remove thermal medium and be superheated vapour, superheated vapour inlet temperature is 280 DEG C, raw material butylene total amount 40000kg/h, air total amount 72000kg/h, butene feedstock is divided into two portions, one section of butylene flow 26000kg/h, two sections of butylene flow 14000kg/h, water vapor 42000kg/h and one section butylene, air is in butylene: oxygen: the ratio that water (mol) is 1:0.52:5 is temperature 420 DEG C, A reactor is entered under pressure 0.15MPa condition, A reactor reflects implication and two sections of butylene, two sections of air are by butylene: oxygen: the molar ratio that water (mol) is 1:0.65:5.2 is blended in temperature and enters 430 DEG C, second reactor is entered under pressure 0.13MPa condition, second order reaction outlet streams enters follow-up workshop section and carries out rectifying.
This device reaction device running condition is in table 4, and catalyst regeneration cycle is 9 months, divinyl average yield 75wt%.
Table 4
[embodiment 5]
Certain 200,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, reactor is two-stage, and two-stage reactor is isothermal calandria type fixed bed reactor, all loads ferrous oxide catalyzer in two-stage reactor tubulation, main composition comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:Mg=10:3:5, prepared by employing coprecipitation method, principal crystalline phase is ZnFe
2o
4spinel, A reactor is identical with second reactor structure, is of a size of Φ 4500 × 6000mm, and tubulation is Φ 50 × 6000mm, tubulation radical 4000, heat interchanging area 3900m
2, A reactor and second reactor shell side are divided into upper and lower two with the dividing plate perpendicular to tubulation and remove hot chamber, remove thermal medium and be superheated vapour, superheated vapour inlet temperature is 280 DEG C, raw material butylene total amount 40000kg/h, air total amount 72000kg/h, butene feedstock is divided into two portions, one section of butylene flow 26000kg/h, two sections of butylene flow 14000kg/h, water vapor 16800kg/h and one section butylene, air is in butylene: oxygen: the ratio that water (mol) is 1:0.52:2 is temperature 420 DEG C, A reactor is entered under pressure 0.14MPa condition, A reactor reflects implication and two sections of butylene, two sections of air are by butylene: oxygen: the molar ratio that water (mol) is 1:0.65:2.2 is blended in temperature and enters 430 DEG C, second reactor is entered under pressure 0.12MPa condition, second order reaction outlet streams enters follow-up workshop section and carries out rectifying.
This device reaction device running condition is in table 5, and catalyst regeneration cycle is 6 months, divinyl average yield 70wt%.
Table 5
[embodiment 6]
Certain 200,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, reactor is three grades, and three reactor is isothermal calandria type fixed bed reactor, all loads ferrous oxide catalyzer in three reactor tubulation, main composition comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:Mg=10:2:6, prepared by employing coprecipitation method, principal crystalline phase is ZnFe
2o
4spinel, one-level preheater is identical with secondary preheater, is of a size of Φ 1800 × 3000mm, tubulation specification Φ 38 × 3000mm, heat interchanging area 410m
2, A reactor is identical with second reactor, is of a size of Φ 3800 × 5000mm, and tubulation is Φ 50 × 5000mm, tubulation radical 2900, heat interchanging area 2700m
2, each stage reactor is divided into three with the dividing plate perpendicular to tubulation and removes hot chamber, remove thermal medium and be superheated vapour, superheated vapour inlet temperature is 280 DEG C, pure oxygen and butylene is adopted to be raw material, one section of butylene flow 20000kg/h, two sections of butylene flow 10000kg/h, three sections of butylene flow 10000kg/h, water vapor 32000kg/h, one section of butylene, oxygen, steam molar is than being 1:0.52:5, two sections of butylene, oxygen, steam molar is than being 1:0.6:5.1, three sections of butylene, oxygen, steam molar is than being 1:0.65:5.2, first order reaction actuator temperature 420 DEG C, second order reaction actuator temperature 425 DEG C, third order reaction actuator temperature 430 DEG C.
This device reaction device running condition is in table 6, and catalyst regeneration cycle is 12 months, divinyl average yield 81wt%.
Table 6
[comparative example 1]
Certain 200,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 2, reactor is single-stage constant temperature fixed-bed reactor, raw material butylene total amount 42300kg/h, air total amount 67000kg/h, water vapor total amount 163000kg/h, butene feedstock is according to butylene: oxygen: after the ratio that water (mol) is 1:0.6:12 mixes with air, water vapor, be under the condition of 340 DEG C in temperature, enter oxidative dehydrogenation reactor, adopt fused salt for removing thermal medium, fused salt inlet temperature is 350 DEG C; This device catalyst regeneration cycle is 3 months, divinyl average yield 65wt%.
Claims (8)
1. a method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl, adopts N level isothermal reactor cascade reaction, wherein N be more than or equal to 2 positive integer; Each stage reactor is shell and tube isothermal reactor, loading catalyst in tubulation, the dividing plate of shell side outside tubulation perpendicular to tubulation direction, shell side is divided into 1 not connected ~ M and removes hot chamber, wherein M be more than or equal to 2 positive integer, described respectively remove hot chamber and remove thermal medium with outside respectively and be communicated with, the tubulation inner catalyst layer respectively removing hot chamber is equipped with temperature measuring equipment, and reaction process comprises following step:
A) butene feedstock is divided into N stock;
B) first step reactor is entered in butylene, oxygen, steam molar than the ratio for 1:0.4 ~ 1.5:0 ~ 18 through the water vapor of metering and first burst of butene feedstock and oxygen-containing gas, temperature of reaction controls to be 300 ~ 550 DEG C by removing thermal medium, and pressure is 0.02 ~ 1.0MPa;
C) butene concentration in reacted material is monitored, according to upper level reaction conversion ratio determination next stage butylene sendout, by step b) in mol ratio, reacted material and required butene feedstock and oxygen-containing gas mixing, enter next stage reactor; Wherein, first strand of butylene is 1:0.4 ~ 1.0 with the allocation proportion scope of each stock butylene afterwards;
D) when N equals 2, step e is entered); When N is greater than 2, reacted material repeating step c) mode, enter lower stage reactor successively, until reacted material enters N stage reactor;
E) N stage reactor outlets products enters follow-up workshop section and reclaims divinyl;
Described catalyzer is the carbon dioxide catalyzer with spinel structure, is Fe by its general formula of chemical constitution
2o
3mgOZnOP
2o
5m
xo
y, Fe
2o
3be 10 ~ 25%, P of catalyst weight for 52 ~ 76%, MgO of catalyst weight is 12 ~ 28%, ZnO of catalyst weight
2o
5for 0.01 ~ 5.0%, M of catalyst weight is selected from least one in periodic table of elements period 4 Sc, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, take oxide basis as 0.01 ~ 3.0% of catalyst weight, adopt coprecipitation method preparation.
2. the method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl according to claim 1, it is characterized in that reactor is shell and tube isothermal fixed-bed reactor, loading catalyst in tubulation, is the one in water, water vapor, fused salt, thermal oil between tubulation.
3. the method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl according to claim 1, it is characterized in that by regulate respectively with respectively remove that hot chamber is communicated with remove thermal medium flow, control the temperature of respectively removing hot chamber tubulation inner catalyst layer.
4. the method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl according to claim 1, the shell side that it is characterized in that outside reactor tubulation is divided into 1 not connected ~ M with the dividing plate perpendicular to tubulation direction shell side and removes hot chamber, 2≤M≤10, M is integer, and dividing plate is fixing or slide construction.
5. the method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl according to claim 1, is characterized in that being arranged in the tubulation that reactor respectively removes hot chamber and at least establishes 1 temperature measuring equipment.
6. the method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl according to claim 1, it is characterized in that entering the thermal medium of removing respectively removing hot chamber is same material, and temperature is identical or different.
7. the method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl according to claim 1, is characterized in that oxygen-containing gas is air or pure oxygen, or the mixture of air and oxygen.
8. the method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl according to claim 1, is characterized in that the mol ratio of every stage reactor entrance butylene, oxygen and water vapor is 1:0.45 ~ 0.9:2 ~ 10; The temperature of reaction of each stage reactor is 380 ~ 500 DEG C, and pressure is 0.05 ~ 0.5MPa.
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| CA2996532C (en) * | 2015-08-29 | 2020-07-14 | Uop Llc | Staged pressure for butadiene reactors to enhance energy recovery |
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| CN113856569A (en) * | 2021-09-28 | 2021-12-31 | 联化新瑞(北京)科技有限公司 | Reactor for preparing succinic anhydride through maleic anhydride hydrogenation and control method thereof |
| WO2024148999A1 (en) * | 2023-01-10 | 2024-07-18 | 中国石油化工股份有限公司 | Low-energy method and apparatus for preparing ethylene via oxidative dehydrogenation of ethane |
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