CN103553864A - Method for preparing butadiene through multi-stage oxidative dehydrogenation of butene - Google Patents
Method for preparing butadiene through multi-stage oxidative dehydrogenation of butene Download PDFInfo
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Abstract
The present invention relates to a method for preparing butadiene through multi-stage oxidative dehydrogenation of butene, wherein problems of non-uniform catalyst temperature in an isothermal reactor tube alignment, easy carbon deposition, short regeneration period and poor butadiene selectivity in the prior art are mainly solved. According to the present invention, the technical scheme comprises that: at least double stages of isothermal reactors are connected in series, all the steam is added from the first-stage reactor, the raw material butene and oxygen-containing gas are added to various stages of the reactors at sections, various stages of the reactors are tubular isothermal reactors, catalysts are filled inside the tube alignments, the shell side outside the tube alignment is separated into 1-M heat dissipating chambers by using separation plates perpendicular to the tube alignment direction, the heat dissipating chambers are not communicated, M is an integer of more than or equal to 2, the heat dissipating chambers are respectively communicated with external heat dissipating mediums, various heat dissipating chamber catalyst layers are provided with temperature measurement devices, and the temperatures of the catalyst layers in various heat dissipating chamber tube alignments are controlled through respectively adjusting the flow rates of the heat dissipating mediums communicated with various heat dissipating chambers. With the technical scheme, the problems are well solved, and the method can be used for industrial production of butadiene preparation through oxidative dehydrogenation of butene.
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 synthetic cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), paracril and ABS resin etc.Divinyl is also multiple coating and Organic Chemicals.
At present the mode of production of divinyl mainly contains two kinds of the separated and synthesis methods (comprising butane dehydrogenation, butylene dehydrogenation, butylene oxidation-dehydrogenation etc.) of C-4-fraction.At present except the U.S., the by-product C-4-fraction (again can be written as C-4-fraction) of countries in the world divinyl during almost all directly from hydrocarbon cracking ethene processed.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 is to produce at present the more competitive Technology of divinyl, and Oxidative Dehydrogenation of Butene into Butadiene is under water vapor exists, and utilizes the hydrogen of oxygen in butylene molecule to be combined, and obtains divinyl and constitutionally stable water.This reaction is irreversible reaction substantially.Main reaction equation is as follows:
Other side reaction mainly contains:
Butylene oxidation-dehydrogenation main reaction is that butylene and oxygen reaction generate divinyl, reacts for exothermic medium reaction, and 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, while adopting spinel Fe-series catalyst, the selectivity of butylene oxidation-dehydrogenation main reaction, 90 ~ 94%, generates CO
2selectivity 6% ~ 7%, generate the selectivity of CO 0.2% ~ 0.8%, in reaction process, except main reaction, a large amount of reaction heat is emitted in side reaction meeting.While adopting adiabatic reactor, for controlling reaction temperature rising and preventing catalyst carbon deposit, need to add a large amount of water vapors, even so, in the situation that water alkene is 16 than (mol ratio of water vapor and butylene), the thermal insulation warming of butylene oxidation-dehydrogenation reactor reaches more than 200 ℃, adiabatic reactor temperature in is in the time of 300 ~ 350 ℃, temperature out reaches 550 ℃ even higher, the rising of temperature brings the increase of side reaction, when more than 530 ℃, the rate of cleavage of the hydrocarbons such as butylene obviously increases, meeting is accelerator activator area carbon speed greatly, and can generate alkynes and propadiene, their content increases with the rising of temperature, these alkynes are increased to a certain degree as can not effectively remove, to polymerization be there is to serious impact.
The full scale plant of the divinyl of butylene oxidation-dehydrogenation method production at present 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 by heating steam and cooling, 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 amount 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, for controlling reaction thermal insulation warming, prevent hydrocarbon cracking and catalyst carbon deposit, in reaction process, must add a large amount of water vapors, cause plant energy consumption high, simultaneous reactions temperature raises and causes divinyl selectivity to decline, and product yield reduces.
Research shows, on Fe-series catalyst, the reaction velocity constant of 480 ℃ is 450 ℃ 1.7 times, that is to say, when other conditions are constant, when the transformation efficiency of butylene is 450 ℃ in the time of 480 ℃ 1.7 times, but consider the existence of side reaction, temperature raises increases side reaction speed equally, due to different to both influence degrees, exists competitive.Concerning Fe-series catalyst, within the scope of 450 ℃ ~ 480 ℃, divinyl selectivity changes little, when temperature surpasses 480 ℃, butylene deep oxidation increases, and selectivity declines, therefore 450 ℃ ~ 480 ℃ scopes, the over-all propertieies such as the transformation efficiency of butylene and selectivity are optimum.
For this reason, as adopted, remove hot charging and put isothermal reactor, production capacity and the product yield of device will greatly be improved, 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 unresolved constant temperature fixed bed of this patent tubulation temperature is uneven, the too high problem of local temperature.
Isothermal shell and tube reactor is similar to shell and tube heat exchanger, in tubulation, put catalyzer, between pipe, the salt of logical melting or water vapor, heat conduction wet goods are as removing thermal medium, reaction gas is through the reaction of pipe inner catalyst layer, reaction heat through tube wall with remove thermal medium exchange and taken out of, adopt the maximum difficult point of this reactor to be that temperature is difficult to control evenly, because butylene oxidation-dehydrogenation main side effect causes in reactor local temperature too high at catalyzer regional area vigorous reaction, cause that hydrocarbon cracking, catalyzer are coking, pipe stops up.This patent CN102442874A and other documents are not provided to good solution, seriously limited the industrial application of butylene oxidation-dehydrogenation isothermal process technology.
Summary of the invention
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 existing in prior art, the regeneration period is short and the problem of divinyl poor selectivity, a kind of method of new butylene isothermal oxidation Oxidative Dehydrogenation divinyl is provided, the method have advantages of isothermal reactor tubulation inner catalyst temperature evenly, be difficult for carbon deposit, the regeneration period is long and divinyl selectivity is high.
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, adopt N level isothermal reactor cascade reaction, and wherein N is 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 is 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 of respectively removing hot chamber is equipped with temperature measuring equipment, and reaction process comprises following step:
A) butene feedstock is divided into N thigh;
B) ratio that is 1:0.4～1.5:0～18 through the water vapor of metering and first burst of butene feedstock and oxygen-containing gas in butylene, oxygen, water vapor mol ratio enters first step reactor, temperature of reaction is 300～550 ℃ by removing thermal medium control, and pressure is 0.02～1.0MPa;
C) monitor butylene concentration in reacted material, according to upper level reaction conversion ratio, determine next stage butylene sendout, by the mol ratio in step b), reacted material and required butene feedstock and oxygen-containing gas are mixed, enter next stage reactor; Wherein, first strand of butylene is 1:0.4～1.0 with the allocation proportion scope of each strand of butylene afterwards;
D), when N equals 2, enter step e); When N is greater than 2, reacted material repeating step c) mode, enters lower stage reactor, successively until reacted material enters N stage reactor;
E) N stage reactor outlet product 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, between tubulation for water, water vapor, fused salt, heat conduction wet goods are removed thermal medium; 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.Being arranged in reactor respectively removes the tubulation in hot chamber and at least establishes 1 temperature measuring equipment; Preferred technical scheme is, entering the thermal medium of removing of respectively removing hot chamber can be same material or different substances, and temperature can be identical or different; Preferred technical scheme is that oxygen-containing gas is air or pure oxygen, or the mixture of air and oxygen; Preferably technical scheme is, catalyzer is a kind of ferrous oxide catalyzer with spinel structure, chief component iron, and zinc, the molar ratio of magnesium is: Fe:Zn:Mg=10:1～5:2～6, adopt coprecipitation method preparation; Preferred technical scheme is: the temperature of reaction of each stage reactor is 380～500 ℃, 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 used the dividing plate perpendicular to tubulation direction that shell side is divided into 1 not connected～M and removed hot chamber, 2≤M≤10, and M is integer, dividing plate is fixing or slide construction.
Preferred technical scheme is: the temperature of reaction of each stage reactor is 420～480 ℃, and pressure is 0.1～0.3MPa.Preferred technical scheme is: catalyzer is a kind of carbon dioxide catalyzer with spinel structure, by its general formula of chemical constitution, is Fe
2o
3mgOZnOP
2o
5m
xo
y, Fe
2o
3for 52～76% of catalyst weight, MgO is catalyst weight 12 ~ 28%, and ZnO is catalyst weight 10 ~ 25%, P
2o
5for 0.01 ~ 5.0% of catalyst weight, M is selected from least one in period 4 Sc, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, with oxide compound, counts 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 by a certain percentage every A reactor, 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 being segmentation, butylene 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 prevent catalyzer coking and improve single-stage reactor transformation efficiency, and the raising of reaction order has also improved 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, thereby a large amount of water vapor consumptions of originally controlling reaction temperature rising as thinner that reduce, the average reaction temperature of isothermal reactor, higher than adiabatic reactor, can improve single-stage reaction conversion ratio and selectivity simultaneously.Therefore, employing is removed hot charging and is put isothermal reactor, will greatly improve production capacity, product yield and the energy efficient of device.
Isothermal shell and tube reactor is similar to shell and tube heat exchanger, in tubulation, put catalyzer, salt or the water vapor of logical melting between pipe, heat conduction wet goods is as removing thermal medium, reaction gas is through the reaction of pipe inner catalyst layer, reaction heat through tube wall with remove thermal medium exchange and taken out of, adopt the maximum technological difficulties of this reactor to be that temperature is difficult to control evenly, especially true for butylene oxidation-dehydrogenation reaction, butylene and oxygen are produced the side reaction thermal discharge of CO2 and CO and are concentrated greatly, as do not removed effectively fast heat, in reactor, local temperature can be too high, cause hydrocarbon cracking, the coking even pipe of catalyzer stops up.
For this reason, the present invention uses the dividing plate perpendicular to tubulation direction that shell side is divided into the individual hot chamber (M >=2) of removing of 1 not connected～M at reactor shell side, remove hot chamber and be communicated with and remove thermal medium with outside respectively for 1～M, respectively remove hot chamber catalyst layer temperature measuring equipment is housed, by regulating respectively and respectively removing the thermal medium flow of removing that hot chamber is communicated with and control the temperature of respectively removing hot chamber tubulation inner catalyst layer.At catalyzer, use the initial stage, main side effect mainly occurs in the beds near opening for feed, thermal discharge also concentrates on this part, and other parts of tubulation do not have reaction substantially, there is no heat yet, as adopted, conventionally remove thermal means, although most of tubulation temperature can be controlled, but in the temperature rise of vigorous reaction section, be difficult to control, cause a large amount of cracking of hydro carbons, the serious carbon deposit of catalyzer; As strengthened, remove thermal cycling amount or thermal medium inlet temperature is removed in reduction, when reducing hot(test)-spot temperature, also can reduce the temperature of other tubulation sections, to 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 1 not connected～M method of removing hot chamber (M >=2), at the catalyzer application initial stage, only need to strengthen and correspondingly remove hot chamber and remove the internal circulating load of thermal medium or the temperature that thermal medium is removed in reduction, just can control this section of tubulation temperature of reaction, and other remove hot chamber because corresponding tubulation thermal discharge is very little, that can reduce that this removes hot chamber removes thermal medium internal circulating load, passing along with catalyzer Applicative time, hot(test)-spot temperature also can move down, what hot chamber was removed in the corresponding adjustment of tubulation temperature of reaction that now only need show according to temperature measuring equipment removes thermal medium flow or temperature, can control flexibly reactor tubulation temperature of reaction like this, effectively prevented temperature of reaction local superheating, catalyst carbon deposit inactivation, extend catalyzer and used the regeneration period, improved product divinyl yield.By adopting the inventive method, compared with prior art, the catalyst regeneration cycle can extend 3 months to 1 year, and divinyl yield improves 2% ~ 10%, has obtained good technique effect and significantly 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 the import of hot chamber for one section of A reactor removes thermal medium, 13 remove the outlet of hot chamber for one section of A reactor removes thermal medium, 14 remove the import of hot chamber for two sections of A reactors removes thermal medium, 15 remove the outlet of hot chamber for one section of second reactor removes thermal medium, 16 remove the import of hot chamber for one section of second reactor removes thermal medium, 17 remove the outlet of hot chamber for two sections of second reactors removes thermal medium, 18 remove the import of hot chamber for two sections of second reactors removes thermal medium.
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 the mixed A reactor entrance of water vapor 3 material 8 enter A reactor, tubulation loading catalyst in A reactor, by A reactor dividing plate, shell side is divided into two portions, in tubulation, establish temperature measuring equipment, by variable valve, regulate and enter the thermal medium amount of the removing control temperature of reaction of removing hot chamber, A reactor outlet logistics 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 logistics 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 oxidative dehydrogenation occurs, reactor tubulation apparatus with catalyst inside, in tubulation, establish temperature measuring equipment II, by variable valve III, regulate to enter and remove the hot 6 quality control temperature of reaction that are situated between of removing of hot chamber, reaction outlet logistics 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, chief component comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:Mg=10:3:5, the preparation of employing coprecipitation method, main 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, 4000 of tubulation radicals, heat interchanging area 3900m
2, A reactor and second reactor shell side are used the dividing plate perpendicular to tubulation to be divided into upper and lower two and are removed hot chamber, remove thermal medium and be thermal oil, heat conductive oil inlet temperature is 300 ℃, raw material butylene total amount 40000kg/h, air total amount 72000 kg/h, butene feedstock is divided into two portions, one section of butylene flow 26000 kg/h, two sections of butylene flow 14000 kg/h, water vapor 42000 kg/h and one section of butylene, air is in butylene: oxygen: the ratio that water (mol) is 1:0.52:5 is 420 ℃ of temperature, under pressure 0.15MPa condition, enter A reactor, A reactor reflects implication and two sections of butylene, two sections of air are by butylene: oxygen: water (mol) enters 430 ℃ for the molar ratio of 1:0.65:5.2 is blended in temperature, under pressure 0.13MPa condition, enter second reactor, second order reaction outlet logistics enters follow-up workshop section and carries out rectifying.
This device reaction device running condition is in Table 1, and the 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, chief component comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:Mg=10:3:5, the preparation of employing coprecipitation method, main 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, 4000 of tubulation radicals, heat interchanging area 3900m
2, A reactor and second reactor shell side are used the dividing plate perpendicular to tubulation to be divided into 4 and are removed hot chamber, remove thermal medium and be thermal oil, heat conductive oil inlet temperature is 300 ℃, raw material butylene total amount 40000kg/h, air total amount 72000 kg/h, butene feedstock is divided into two portions, one section of butylene flow 26000 kg/h, two sections of butylene flow 14000 kg/h, water vapor 42000 kg/h and one section of butylene, air is in butylene: oxygen: the ratio that water (mol) is 1:0.52:5 is 420 ℃ of temperature, under pressure 0.15MPa condition, enter A reactor, A reactor reflects implication and two sections of butylene, two sections of air are by butylene: oxygen: water (mol) enters 430 ℃ for the molar ratio of 1:0.65:5.2 is blended in temperature, under pressure 0.13MPa condition, enter second reactor, second order reaction outlet logistics enters follow-up workshop section and carries out rectifying.
This device reaction device running condition is in Table 2, and the 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, chief component comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:Mg=10:4:6, the preparation of employing coprecipitation method, main 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, 4000 of tubulation radicals, heat interchanging area 3900m
2, A reactor and second reactor shell side are used the dividing plate perpendicular to tubulation to be divided into 2 and are removed hot chamber, remove thermal medium and be fused salt, fused salt inlet temperature is 350 ℃, raw material butylene total amount 40000kg/h, air total amount 72000 kg/h, butene feedstock is divided into two portions, one section of butylene flow 26000 kg/h, two sections of butylene flow 14000 kg/h, water vapor 42000 kg/h and one section of butylene, air is in butylene: oxygen: the ratio that water (mol) is 1:0.52:5 is 420 ℃ of temperature, under pressure 0.15MPa condition, enter A reactor, A reactor reflects implication and two sections of butylene, two sections of air are by butylene: oxygen: water (mol) enters 430 ℃ for the molar ratio of 1:0.65:5.2 is blended in temperature, under pressure 0.13MPa condition, enter second reactor, second order reaction outlet logistics enters follow-up workshop section and carries out rectifying.
This device reaction device running condition is in Table 3, and the 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, the Technology that adopts Fig. 1, reactor is two-stage, two-stage reactor is isothermal calandria type fixed bed reactor, in two-stage reactor tubulation, all loading carbon dioxide catalyzer, is Fe by its general formula of chemical constitution
2o
3mgOZnOP
2o
5cuO, Cr
2o
3for 66% of catalyst weight, MgO is catalyst weight 20%, and ZnO is catalyst weight 10%, P
2o
5for 2% of catalyst weight, CuO is catalyst weight 2%, adopts coprecipitation method preparation, and A reactor is identical with second reactor structure, is of a size of Φ 4500 * 6000mm, and tubulation is Φ 50 * 6000mm, 4000 of tubulation radicals, heat interchanging area 3900m
2, A reactor and second reactor shell side are used the dividing plate perpendicular to tubulation to be divided into 3 and are removed hot chamber, remove thermal medium and be superheated vapour, superheated vapour inlet temperature is 280 ℃, raw material butylene total amount 40000kg/h, air total amount 72000 kg/h, butene feedstock is divided into two portions, one section of butylene flow 26000 kg/h, two sections of butylene flow 14000 kg/h, water vapor 42000 kg/h and one section of butylene, air is in butylene: oxygen: the ratio that water (mol) is 1:0.52:5 is 420 ℃ of temperature, under pressure 0.15MPa condition, enter A reactor, A reactor reflects implication and two sections of butylene, two sections of air are by butylene: oxygen: water (mol) enters 430 ℃ for the molar ratio of 1:0.65:5.2 is blended in temperature, under pressure 0.13MPa condition, enter second reactor, second order reaction outlet logistics enters follow-up workshop section and carries out rectifying.
This device reaction device running condition is in Table 4, and the 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, chief component comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:Mg=10:3:5, the preparation of employing coprecipitation method, main 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, 4000 of tubulation radicals, heat interchanging area 3900m
2, A reactor and second reactor shell side are used the dividing plate perpendicular to tubulation to be divided into upper and lower two and are removed hot chamber, remove thermal medium and be superheated vapour, superheated vapour inlet temperature is 280 ℃, raw material butylene total amount 40000kg/h, air total amount 72000 kg/h, butene feedstock is divided into two portions, one section of butylene flow 26000 kg/h, two sections of butylene flow 14000 kg/h, water vapor 16800 kg/h and one section of butylene, air is in butylene: oxygen: the ratio that water (mol) is 1:0.52:2 is 420 ℃ of temperature, under pressure 0.14MPa condition, enter A reactor, A reactor reflects implication and two sections of butylene, two sections of air are by butylene: oxygen: water (mol) enters 430 ℃ for the molar ratio of 1:0.65:2.2 is blended in temperature, under pressure 0.12MPa condition, enter second reactor, second order reaction outlet logistics enters follow-up workshop section and carries out rectifying.
This device reaction device running condition is in Table 5, and the 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, chief component comprises iron, zinc, magnesium component, molar ratio is: Fe:Zn:Mg=10:2:6, the preparation of employing coprecipitation method, main 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, 2900 of tubulation radicals, heat interchanging area 2700m
2, each stage reactor is used the dividing plate perpendicular to tubulation to be divided into three and is removed hot chamber, remove thermal medium and be superheated vapour, superheated vapour inlet temperature is 280 ℃, adopting pure oxygen and butylene is raw material, one section of butylene flow 20000 kg/h, two sections of butylene flow 10000 kg/h, three sections of butylene flow 10000 kg/h, water vapor 32000 kg/h, one section of butylene, oxygen, water vapor mol ratio is 1:0.52:5, two sections of butylene, oxygen, water vapor mol ratio is 1:0.6:5.1, three sections of butylene, oxygen, water vapor mol ratio is 1:0.65:5.2, 420 ℃ of first order reaction actuator temperatures, 425 ℃ of second order reaction actuator temperatures, 430 ℃ of third order reaction actuator temperatures.
This device reaction device running condition is in Table 6, and the 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 67000 kg/h, water vapor total amount 163000 kg/h, butene feedstock is according to butylene: oxygen: after the ratio that water (mol) is 1:0.6:12 is mixed with air, water vapor, in temperature, be under the condition of 340 ℃, enter oxidative dehydrogenation reactor, adopt fused salt for removing thermal medium, fused salt inlet temperature is 350 ℃; This device catalyst regeneration cycle is 3 months, divinyl average yield 65wt%.
Claims (10)
1. a method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl, adopts N level isothermal reactor cascade reaction, and wherein N is 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 is 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 of respectively removing hot chamber is equipped with temperature measuring equipment, and reaction process comprises following step:
A) butene feedstock is divided into N thigh;
B) ratio that is 1:0.4～1.5:0～18 through the water vapor of metering and first burst of butene feedstock and oxygen-containing gas in butylene, oxygen, water vapor mol ratio enters first step reactor, temperature of reaction is 300～550 ℃ by removing thermal medium control, and pressure is 0.02～1.0MPa;
C) monitor butylene concentration in reacted material, according to upper level reaction conversion ratio, determine next stage butylene sendout, by the mol ratio in step b), reacted material and required butene feedstock and oxygen-containing gas are mixed, enter next stage reactor; Wherein, first strand of butylene is 1:0.4～1.0 with the allocation proportion scope of each strand of butylene afterwards;
D), when N equals 2, enter step e); When N is greater than 2, reacted material repeating step c) mode, enters lower stage reactor, successively until reacted material enters N stage reactor;
E) N stage reactor outlet product enters follow-up workshop section and reclaims divinyl.
2. the method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl according to claim 1, is characterized in that reactor is shell and tube isothermal fixed-bed reactor, and loading catalyst in tubulation is a kind of 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, it is characterized in that shell side outside reactor tubulation uses dividing plate perpendicular to tubulation direction that shell side is divided into 1 not connected～M and remove hot chamber, 2≤M≤10, M is integer, 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 reactor and respectively removes the tubulation in hot chamber and at least establish 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 of respectively removing hot chamber is same material, temperature is identical or different.
7. the method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl according to claim 6, is characterized in that oxygen-containing gas is air or pure oxygen, or the mixture of air and oxygen; The thermal medium of removing of respectively removing hot chamber is different substances, and temperature is identical or different.
8. the method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl according to claim 1, it is characterized in that catalyzer is the ferrous oxide catalyzer with spinel structure, chief component iron, zinc, magnesium molar ratio is: Fe:Zn:Mg=10:1～5:2～6, adopt coprecipitation method preparation.
9. the method for butylene multi-stage oxidizing Oxidative Dehydrogenation divinyl according to claim 1, is characterized in that catalyzer is the carbon dioxide catalyzer with spinel structure, by its general formula of chemical constitution, is Fe
2o
3mgOZnOP
2o
5m
xo
y, Fe
2o
3for 52～76% of catalyst weight, MgO is catalyst weight 12 ~ 28%, and ZnO is catalyst weight 10 ~ 25%, P
2o
5for 0.01 ~ 5.0% of catalyst weight, M is selected from least one in periodic table of elements period 4 Sc, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, Zn, with oxide compound, counts 0.01～3.0% of catalyst weight, adopts coprecipitation method preparation.
10. 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 ℃, and pressure is 0.05～0.5MPa.
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