CN103071544A - In-situ regeneration method of butylene oxy-dehydrogenation catalyst - Google Patents
In-situ regeneration method of butylene oxy-dehydrogenation catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title claims abstract description 94
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 42
- 238000011069 regeneration method Methods 0.000 title claims abstract description 42
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 66
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000008929 regeneration Effects 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
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- 238000010926 purge Methods 0.000 claims abstract description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 40
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 40
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052596 spinel Inorganic materials 0.000 claims description 2
- 239000011029 spinel Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 210000000689 upper leg Anatomy 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 3
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- 238000009776 industrial production Methods 0.000 abstract 1
- 210000000952 spleen Anatomy 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- 238000004939 coking Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000007664 blowing Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
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- 150000001336 alkenes Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910016287 MxOy Inorganic materials 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 239000005416 organic matter Substances 0.000 description 1
- -1 oxygen alkene Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 229920003051 synthetic elastomer Polymers 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an in-situ regeneration method of a butylene oxy-dehydrogenation catalyst, which mainly solves the problems that the in-situ regeneration effect of the butylene oxy-dehydrogenation catalyst is poor, so that the life of the catalyst is shortened, the conversion rate and yield of reaction are reduced, and the change of the catalyst results in long stopping time of a device and influences the output of the device in the prior art. The method comprises the following steps of: a) stopping feeding of oxygen-containing gas and then a butylene raw material, purging the catalyst with 300-500 DEG C superheated water vapor for 0.2-56h, b) gradually reducing the amount of the water vapor till the airspeed of the water vapor is 500-2000h<-1>, filling in air till the molar ratio of the air to the water vapor is 0.05-0.2, controlling the regeneration temperature at 360-450 DEG C, conducting regeneration of the oxy-dehydrogenation catalyst, and c) reducing the amount of the vapor, allowing the temperature rise of a bed to be reduced gradually till the temperature at an inlet and an outlet of the catalyst bed keeps constant, and accomplishing the technical scheme of catalyst regeneration. The method solves the problems better, and can be used for industrial production of preparing butadiene through butylene oxy-dehydrogenation.
Description
Technical field
The present invention relates to a kind of in situ regeneration method of butylene oxidation-dehydrogenation catalyst.
Background technology
Butadiene is the important monomer of synthetic rubber, synthetic resin, is mainly used in synthetic butadiene rubber, butadiene-styrene rubber, acrylonitrile-butadiene rubber and ABS resin etc.Butadiene also is multiple coating and Organic Chemicals.
At present the mode of production of butadiene mainly contains that C-4-fraction separates and two kinds of synthetic methods (comprising butane dehydrogenation, butylene dehydrogenation, butylene oxidation-dehydrogenation etc.).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 butadiene during almost all directly from hydrocarbon cracking ethene processed.The source of U.S.'s butadiene, only about half of from butane, butylene dehydrogenation, half is directly from the c4 cleavage cut.
Butylene oxidation-dehydrogenation is to produce at present the more competitive technology of butadiene, and Oxidative Dehydrogenation of Butene into Butadiene is in the presence of water vapour, utilizes the hydrogen of oxygen in the butylene molecule to be combined, and obtains butadiene and constitutionally stable water.This reaction is irreversible reaction substantially.The main reaction equation is as follows:
Other side reaction mainly contains:
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 sections axial restraint bed bioreactors, butene feedstock, water vapour and air segmenting enter, reactor outlet cools off by heating steam, enters next section reactor after reaching next section reactor inlet temperature.
Patent CN102675027A discloses a kind of preparing butadiene with butylene oxo-dehydrogenation technique, adopts thermal insulation radial fixed-bed by preparing butadiene with butylene oxo-dehydrogenation, and the radial adiabatic fixed bed forms by three sections.
Patent CN100494130C, its flow process is the reactor that the raw material normal butane enters non-oxidizable catalytic dehydrogenation, obtains containing the mixing logistics of normal butane, butylene, butadiene, hydrogen, low boiling secondary component and steam.This mixing logistics and oxygen-containing gas are mixed into the oxidative dehydrogenation zone, obtain containing the product gas flow of butadiene, normal butane, butylene, hydrogen, low boiling secondary component and steam, next isolate butadiene from this product gas flow.Similarly also has patent CN100447117C, different from patent CN100494130C is, after removing hydrogen, low boiling secondary species and steam, the product gas in autoxidation dehydrogenation zone is divided into two parts by extracting rectifying, the logistics that a part mainly comprises normal butane and butylene loops back non-oxide dehydrogenation zone, and another part mainly comprises butadiene stream.
Patent CN101757930A discloses a kind of for 1-Oxidative Dehydrogenation of Butene standby 1, Bi/Mo/Fe composite oxide catalysts and the method for making thereof of 3-butadiene, relate to a kind of Bi/Mo/Fe composite oxide catalysts, and the oxidative dehydrogenation of the 1-butylene that in the presence of this catalyst, carries out.
Patent CN102716754A discloses a kind of butadiene catalyst made by butylene oxidation dehydrogen for fluidized-bed reactor and its production and use, relates to a kind of butadiene catalyst made by butylene oxidation dehydrogen for fluidized-bed reactor and its production and use.
The method of the Oxidative Dehydrogenation of Butene into Butadiene that above patent provides, butene feedstock all need to be carried out oxidative dehydrogenation under the catalyst existence condition, the catalyst that generally adopts is Bi/Mo system, Fe system, or Bi/Mo/Fe composite oxide catalysts, reaction temperature is at 300 ~ 600 ℃, under this temperature, more subcarbide and coke can occur to be cracked on a small quantity in hydrocarbon compound, coke is enriched in the catalyst granules surface, make the activated centre lose adsorption capacity, as long as dehydrogenation reaction is carried out, cokingly just can not stop, although there is certain oxygen to exist, so that combustion reaction-make charcoal constantly occurs again in the charcoal layer of catalyst surface, but because oxygen alkene is than little, air-flow is uneven in the reactor, reaction temperature is crossed high reason, the coking meeting of catalyst surface progressively increases, and shows that reaction conversion ratio descends, and generates CO in the gas
2Content increases, and at this moment the aspects such as reactor pressure decrease increase need catalyst is regenerated, improving the service life of catalyst, but to the renovation process of butylene oxidation-dehydrogenation catalyst there are no bibliographical information.
Summary of the invention
The technical problem that the present invention mainly solves is the butylene oxidation-dehydrogenation catalyst in-situ regeneration poor effect that exists in the prior art, thereby affect the prolongation of catalyst life and reaction conversion ratio, reaction yield, and catalyst changes agent and causes device long down time, affects the problem of device output.A kind of in situ regeneration method of new butylene oxidation-dehydrogenation catalyst is provided, and the method has the catalyst performance of recovery, extending catalyst service life, shorten catalyst changes the agent device advantage of down time.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of in situ regeneration method of butylene oxidation-dehydrogenation catalyst may further comprise the steps successively:
A) in the butylene oxidation-dehydrogenation reaction unit, stop first the oxygen-containing gas charging, stop again butene feedstock, keep 300～550 ℃ superheated vapour to purge catalyst 0.2 ~ 56 hour;
B) in 1 ~ 10 hour, the water vapour air speed is by 3000 ~ 6000h
-1Be reduced to 800 ~ 2000h
-1, pass into simultaneously air, to air/water steam mol ratio be 0.05～0.5, control reactor catalyst bed outlet temperature is no more than 360 ~ 450 ℃, in reactor to the Oxydehydrogenation catalyst 0.1-100h that regenerates;
C) keep air capacity constant, take the speed of 10 ~ 20wt% per hour reduce the water vapour amount to the water vapour air speed as 400 ~ 600h
-1, the beds temperature rise descends gradually, until the beds out temperature when substantially constant, is finished catalyst regeneration.
In the technique scheme, preferred technical scheme is: the series connection of N stage reactor is adopted in the Oxidative Dehydrogenation of Butene into Butadiene reaction, and wherein N is the integer more than or equal to 2; Course of reaction comprises following step:
A) butene feedstock is divided into the N thigh;
B) water vapour, the raw material that contains butylene and oxygen-containing gas are take butylene: oxygen: the water vapour mol ratio enters first order reactor as the proportioning of 1:0.4～1.5:0.5～20;
C) reacted material after mixing with butene feedstock and oxygen-containing gas, by identical mol ratio in the step b), enters the next stage reactor again; Wherein, the butene conversion of pressing the upper level reactor determines next stage butene feedstock sendout, and first order butylene is 1:0.4～1.0 with the allocation proportion scope of butylene at different levels afterwards;
D) when N equals 2, enter step e); When N greater than 2 the time, reacted material enters subsequent reactor successively according to the method for step c), until reacted material enters the N stage reactor;
E) N stage reactor outlet product enters follow-up workshop section and reclaims butadiene;
Wherein, the reaction inlet temperature of each stage reactor is 300～400 ℃, and pressure is 0.0～0.5MPaG.
Preferred technical scheme is: butylene in the step b): the oxygen mol ratio is 1:0.3～2.0; First burst of butene feedstock is 1:0.3～0.7 with the allocation proportion scope of butene feedstock at different levels afterwards; The molar ratio of first strand of butene feedstock, oxygen-containing gas and water vapour is 1:0.3～2.0:2～18.
Preferred technical scheme is: the series connection of N stage reactor is adopted in the Oxidative Dehydrogenation of Butene into Butadiene reaction, wherein N is the integer more than or equal to 3, course of reaction comprises following step: a) butene feedstock is divided into the N stock and does not enter the N stage reactor, press the upper level reaction conversion ratio and determine next stage butylene sendout, first order butylene is 1:0.4～1.0 with the allocation proportion scope of butylene at different levels afterwards; B) water vapour, the raw material that contains butylene and oxygen-containing gas are take butylene: oxygen: the water vapour mol ratio enters first order reactor as the proportioning of 1:0.4～1.5:4～18; C) reacted material, again with step b) in mix by the butene feedstock of identical mol ratio and oxygen-containing gas after, enter the next stage reactor; Reacted material repeating step c), until reacted material enters the N stage reactor; E) N stage reactor outlet product enters follow-up workshop section and reclaims butadiene, and wherein, the reaction inlet temperature of each stage reactor is 300～400 ℃, and pressure is 0.01～0.5MPaG.
Preferred technical scheme is: the required catalyst of oxidative dehydrogenation is Fe-series catalyst, and chief component comprises iron, zinc, and magnesium component, the molar ratio of each component is: Fe:Zn:Mg=10:1 ~ 5:2 ~ 6, adopt the coprecipitation preparation, main crystalline phase is ZnFe
2O
4Spinelle.Preferred technical scheme is: the required catalyst of oxidative dehydrogenation is the preparing butadiene with butylene oxo-dehydrogenation carbon dioxide catalyst with spinel structure, is Fe by its general formula of chemical composition
2O
3MgOZnOP
2O
5MxOy, M are selected from least a among period 4 Sc, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, the Zn.
Preferred technical scheme is: keep 450～500 ℃ superheated vapour to purge catalyst 2 ~ 48 hours in the step a); In 1 ~ 10 hour, the water vapour air speed is by 4000 ~ 5000h in the step b)
-1Be reduced to 1000 ~ 1600h
-1, pass into simultaneously air, to air/water steam mol ratio be 0.1～0.3, control reactor catalyst bed outlet temperature is no more than 400 ~ 420 ℃, in reactor to the Oxydehydrogenation catalyst 2-24h that regenerates; The basic invariant time of beds out temperature described in the step c) is 0.5 ~ 2 hour.
Preferred technical scheme is: the butylene oxidation-dehydrogenation reaction unit adopts at least two sections insulation fix bed reactors, and reactor types is axial insulation fix bed reactor or radial adiabatic fixed bed reactors.
Preferred technical scheme is: the butylene oxidation-dehydrogenation reaction unit adopts at least two sections isothermal fixed bed reactors, and reactor types is the shell and tube isothermal reactor.
The present invention is at least the series-parallel method of two-stage reactor by employing, water vapour is all entered first order insulation fix bed reactor with the series connection form, raw material butylene and air are divided at least, and two parts are mixed into every A reactor by a certain percentage with parallel form and water vapour, because water vapour all enters first order reactor, every stage reactor generation butylene oxidation-dehydrogenation water generation reaction, reacting rear material enters the next stage reactor again, the water yield progressively increases, and being segmentation, butylene enters every A reactor, hanging down total water alkene than under the condition like this, every section reactor can be kept higher water alkene ratio, be conducive to prevent that catalyst is coking, the extending catalyst regeneration period, and obtain higher butene conversion.
The present invention stops first the oxygen-containing gas charging, stop again butene feedstock, keep 300～550 ℃ superheated vapour to purge catalyst 0.2 ~ 56 hour, remove organic matter and partially catalyzed agent surface carbon deposit in the system, gradually reducing water vapour amount to water vapour air speed is 800 ~ 2000h again
-1, increasing simultaneously air capacity to air/water steam mol ratio is 0.05～0.5, coking the reacting with oxygen of catalyst surface this moment generates CO
2, water vapour is used for the control temperature, and regeneration temperature is controlled at 360 ~ 450 ℃ of scopes, at device Oxydehydrogenation catalyst is regenerated, along with coking burn off, reduce again quantity of steam, the bed temperature rise descends gradually, until the beds out temperature is substantially constant, this moment, catalyst regeneration was finished.
Adopt the inventive method, because substep passes into water vapour and air, control simultaneously temperature, so that coking elimination in catalyst surface and the duct, and impelling catalyst crystalline phases to change, the catalyst appearance after the regeneration is identical with fresh catalyst, activation recovering, catalyst prolongs 0.5 to 1 year overall service life, and catalyst changes shortening down time of agent device, has obtained preferably technique effect.
Description of drawings
Fig. 1 is the multistage adiabatic oxidative dehydrogenation of butylene of the present invention Butadiene Extraction Process schematic flow sheet processed (take two-stage reaction as example).
Among Fig. 1,1 is butene feedstock, and 2 is air, 3 is water vapour, and 4 is one section butylene, and 5 is two sections butylene, 6 is one section air, and 7 is two sections air, and 8 is A reactor entrance material, 9 is second reactor entrance material, 10 is second reactor entrance material, and 11 is the second reactor outlet material, and 101 is A reactor, 102 is second reactor, and 103 are A reactor outlet heat exchanger.
Among Fig. 1, raw material butylene 1 and air divided respectively three parts in 2 minutes, one section butylene 4, one section air 5 and water vapour 3 mixed logistics 8 enter A reactor 101 oxidative dehydrogenations occur, reaction outlet logistics 11 is after 103 heat exchange of A reactor outlet heat exchanger, after two sections butylene 5 and two sections air 7 mix, second reactor entrance material 10 enters second reactor 102, and the reaction outlet is logistics 11.
Below by embodiment invention is further elaborated.
The specific embodiment
[embodiment 1]
Certain 100,000 ton/years of Oxidative Dehydrogenation of Butene into Butadiene device, the technology of employing Fig. 1 adopts a kind of Fe-series catalyst, its chief component comprises iron, zinc, magnesium component, the molar ratio of each component is: Fe:Zn:Mg=10:2:5, adopt the coprecipitation preparation, and main crystalline phase is ZnFe
2O
4Spinelle, reactor is two-stage, two-stage reactor is adiabatic radial fixed-bed reactor, 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 butylene flow 9400 kg/h, according to butylene: oxygen: water (mol) is ratio and the air of 1:0.52:15, after water vapour mixes, it is 320 ℃ in temperature, under the pressure 0.12MPaG condition, enter first order oxidative dehydrogenation reactor, work off one's feeling vent one's spleen 485 ℃ of temperature of A reactor, after the heat exchanger heat exchange, be mixed into second reactor with two sections butylene and two sections air, two sections butylene flow 10270 kg/h, second reactor entrance butylene: oxygen: water (mol) ratio is 1:0.65:15.5, reaction temperature is 330 ℃, work off one's feeling vent one's spleen 512 ℃ of temperature of pressure 0.10MPaG, second reactor, move continuously 1 year after, the butylene total conversion drops to 70% by 82% of the initial stage, overall selectivity drops to 81% by 92%, and the reaction system pressure drop rises to 0.1MPa by 0.02MPa, judges catalysqt deactivation, carry out subsequently the regeneration of catalyst original position, at first stop air feed, stop again butene feedstock, keep 450 ℃ superheated vapour to purge catalyst 36 hours, the reactor outlet temperature is substantially constant, progressively with the steam air speed by 5000 h
-1Be reduced to 1600h
-1, pass into simultaneously air, progressively increasing air capacity to air/water steam mol ratio is 0.5, the control regeneration temperature is at 450 ℃ in the regenerative process, 1.5 the bed temperature rise begins to descend after hour, keeps air capacity constant, take the speed of 30 wt% per hour reduce the water vapour amount to the water vapour air speed as 400h
-1, rear catalyst bed out temperature was substantially constant in 3 hours, continued blowing air after 1 hour, and catalyst regeneration is finished.
Behind this device catalyst regeneration, again drive in the normal order, the catalyst after the regeneration moves again 10 months, total conversion is between 76wt% ~ 82wt%, selectively between 86wt% ~ 92wt%, in 10 months extending catalyst life-spans, stop to be regenerated to and again produced totally 3 days.
[embodiment 2]
Certain 100,000 ton/years of Oxidative Dehydrogenation of Butene into Butadiene device, the technology of employing Fig. 1 adopts a kind of Fe-series catalyst, its chief component comprises iron, zinc, magnesium component, the molar ratio of each component is: Fe:Zn:Mg=10:2:6, adopt the coprecipitation preparation, and main crystalline phase is ZnFe
2O
4Spinelle, reactor is three grades, three reactor is adiabatic radial fixed-bed reactor, raw 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 parts, one section butylene flow 9200 kg/h, according to butylene: oxygen: water (mol) is ratio and the air of 1:0.5:15, after water vapour mixes, it is 320 ℃ in temperature, under the pressure 0.13MPaG condition, enter first order oxidative dehydrogenation reactor, work off one's feeling vent one's spleen 490 ℃ of temperature of A reactor, after the heat exchanger heat exchange, be mixed into second reactor with two sections butylene and two sections air, two sections butylene flow 4800 kg/h, second reactor entrance butylene: oxygen: water (mol) ratio is 1:0.6:15, reaction temperature is 330 ℃, pressure 0.11MPaG, work off one's feeling vent one's spleen 506 ℃ of temperature of second reactor, after the heat exchanger heat exchange, be mixed into three reactor with three sections butylene and three sections air, three sections butylene flow 4920 kg/h, three reactor entrance butylene: oxygen: water (mol) ratio is 1:0.66:16, and the three reactor inlet temperature is 340 ℃, 520 ℃ of the temperature of working off one's feeling vent one's spleen, pressure 0.01MPaG, move continuously 10 months years after, the butylene total conversion drops to 75% by 82% of the initial stage, overall selectivity drops to 85% by 92%, the reaction system pressure drop rises to 0.05MPa by 0.03MPa, carries out subsequently the regeneration of catalyst original position, at first stops air feed, stop again butene feedstock, keep 400 ℃ superheated vapour to purge catalyst 48 hours, the reactor outlet temperature is substantially constant, progressively with the steam air speed by 6000 h
-1Be reduced to 800h
-1, pass into simultaneously air, progressively increasing air capacity to air/water steam mol ratio is 0.1, the control regeneration temperature is at 420 ℃ in the regenerative process, the bed temperature rise begins to descend after 4 hours, keeps air capacity constant, take the speed of 20 wt% per hour reduce the water vapour amount to the water vapour air speed as 500h
-1, rear catalyst bed out temperature was substantially constant in 2 hours, continued blowing air after 1.5 hours, and catalyst regeneration is finished.
Behind this device catalyst regeneration, again drive in the normal order, the catalyst after the regeneration moves again 10 months, total conversion is between 75wt% ~ 82wt%, selectively between 85wt% ~ 92wt%, in 10 months extending catalyst life-spans, stop to be regenerated to and again produced totally 4 days.
[embodiment 3]
Certain 100,000 ton/years of Oxidative Dehydrogenation of Butene into Butadiene device, the technology of employing Fig. 1 adopts a kind of Fe-series catalyst, and its chief component is Fe
2O
3MgOZnOP
2O
5ZnxOy, reactor is two-stage, two-stage reactor is adiabatic radial fixed-bed reactor, raw material butylene total amount 19670kg/h, air total amount 36000 kg/h, water vapour total amount 30200 kg/h, butene feedstock is divided into two parts, one section butylene flow 9400 kg/h, according to butylene: oxygen: water (mol) is ratio and the air of 1:0.52:10, after water vapour mixes, it is 330 ℃ in temperature, under the pressure 0.12MPaG condition, enter first order oxidative dehydrogenation reactor, work off one's feeling vent one's spleen 495 ℃ of temperature of A reactor, after the heat exchanger heat exchange, be mixed into second reactor with two sections butylene and two sections air, two sections butylene flow 10270 kg/h, second reactor entrance butylene: oxygen: water (mol) ratio is 1:0.65:10.5, reaction temperature is 350 ℃, pressure 0.10MPaG, work off one's feeling vent one's spleen 520 ℃ of temperature of second reactor, move 9 months continuously after, the butylene total conversion drops to 74% by 82% of the initial stage, overall selectivity drops to 82% by 92%, the reaction system pressure drop rises to 0.06MPa by 0.02MPa, carries out subsequently the regeneration of catalyst original position, at first stops air feed, stop again butene feedstock, keep 380 ℃ superheated vapour to purge catalyst 48 hours, the reactor outlet temperature is substantially constant, progressively with the steam air speed by 4000 h
-1Be reduced to 1200h
-1, pass into simultaneously air, progressively increasing air capacity to air/water steam mol ratio is 0.3, the control regeneration temperature is at 400 ℃ in the regenerative process, the bed temperature rise begins to descend after 3 hours, keeps air capacity constant, take the speed of 15 wt% per hour reduce the water vapour amount to the water vapour air speed as 500h
-1, rear catalyst bed out temperature was substantially constant in 3 hours, continued blowing air after 1 hour, and catalyst regeneration is finished.
Behind this device catalyst regeneration, again drive in the normal order, the catalyst after the regeneration moves again 9 months, and total conversion selectively between 85wt% ~ 91wt%, in 9 months extending catalyst life-spans, stops to be regenerated to and again produced totally 3 days between 75wt% ~ 80wt%.
?
[comparative example 1]
Certain 100,000 ton/years of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the axial insulation fix bed reactor of single-stage, raw material butylene total amount 22700kg/h, air total amount 34000 kg/h, water vapour total amount 131330 kg/h, butene feedstock is according to butylene: oxygen: water (mol) is ratio and the air of 1:0.6:18, after water vapour mixes, it is 330 ℃ in temperature, under the pressure 0.15MPaG condition, enter oxidative dehydrogenation reactor, work off one's feeling vent one's spleen 520 ℃ of temperature of oxidative dehydrogenation, pressure 0.10MPaG, operation is after 6 months continuously, and the butylene total conversion drops to 55% by 75% of the initial stage, and overall selectivity drops to 75% by 91%, the reaction system pressure drop rises to 0.12MPa by 0.05MPa, judge catalysqt deactivation, carry out subsequently catalyst change, more catalyst changeout is to again producing totally 7 days.
Claims (10)
1. the in situ regeneration method of a butylene oxidation-dehydrogenation catalyst may further comprise the steps successively:
A) in the butylene oxidation-dehydrogenation reaction unit, stop first the oxygen-containing gas charging, stop again butene feedstock, keep 300～550 ℃ superheated vapour to purge catalyst 0.2 ~ 56 hour;
B) in 1 ~ 10 hour, the water vapour air speed is by 3000 ~ 6000h
-1Be reduced to 800 ~ 2000h
-1, pass into simultaneously air, to air/water steam mol ratio be 0.05～0.5, control reactor catalyst bed outlet temperature is no more than 360 ~ 450 ℃, in reactor to the Oxydehydrogenation catalyst 0.1-100h that regenerates;
C) keep air capacity constant, take the speed of 10 ~ 30wt% per hour reduce the water vapour amount to the water vapour air speed as 400 ~ 600h
-1, the beds temperature rise descends gradually, until the beds out temperature when substantially constant, is finished catalyst regeneration.
2. the in situ regeneration method of butylene oxidation-dehydrogenation catalyst according to claim 1 is characterized in that the series connection of Oxidative Dehydrogenation of Butene into Butadiene reaction employing N stage reactor, and wherein N is the integer more than or equal to 2; Course of reaction comprises following step:
A) butene feedstock is divided into the N thigh;
B) water vapour, the raw material that contains butylene and oxygen-containing gas are take butylene: oxygen: the water vapour mol ratio enters first order reactor as the proportioning of 1:0.4～1.5:0.5～20;
C) reacted material after mixing with butene feedstock and oxygen-containing gas, by identical mol ratio in the step b), enters the next stage reactor again; Wherein, the butene conversion of pressing the upper level reactor determines next stage butene feedstock sendout, and first order butylene is 1:0.4～1.0 with the allocation proportion scope of butylene at different levels afterwards;
D) when N equals 2, enter step e); When N greater than 2 the time, reacted material enters subsequent reactor successively according to the method for step c), until reacted material enters the N stage reactor;
E) N stage reactor outlet product enters follow-up workshop section and reclaims butadiene;
Wherein, the reaction inlet temperature of each stage reactor is 300～400 ℃, and pressure is 0.0～0.5MPaG.
3. the in situ regeneration method of butylene oxidation-dehydrogenation catalyst according to claim 1, it is characterized in that the required catalyst of oxidative dehydrogenation is Fe-series catalyst, chief component comprises iron, zinc, magnesium component, the molar ratio of each component is: Fe:Zn:Mg=10:1 ~ 5:2 ~ 6, adopt the coprecipitation preparation, and main crystalline phase is ZnFe
2O
4Spinelle.
4. the in situ regeneration method of butylene oxidation-dehydrogenation catalyst according to claim 1, it is characterized in that the required catalyst of oxidative dehydrogenation is the preparing butadiene with butylene oxo-dehydrogenation carbon dioxide catalyst with spinel structure, is Fe by its general formula of chemical composition
2O
3MgOZnOP
2O
5M
xO
y, M is selected from least a among period 4 Sc, Ti, V, Cr, Fe, Mn, Co, Ni, Cu, the Zn.
5. the in situ regeneration method of butylene oxidation-dehydrogenation catalyst according to claim 1 is characterized in that keeping in the step a) 450～500 ℃ superheated vapour to purge catalyst 2 ~ 48 hours.
6. the in situ regeneration method of butylene oxidation-dehydrogenation catalyst according to claim 1 is characterized in that in the step b) that in 1 ~ 10 hour, the water vapour air speed is by 4000 ~ 5000h
-1Be reduced to 1000 ~ 1600h
-1, pass into simultaneously air, to air/water steam mol ratio be 0.1～0.3, control reactor catalyst bed outlet temperature is no more than 400 ~ 420 ℃, in reactor to the Oxydehydrogenation catalyst 2-24h that regenerates.
7. the in situ regeneration method of butylene oxidation-dehydrogenation catalyst according to claim 1 is characterized in that the basic invariant time of beds out temperature described in the step c) is 0.5 ~ 2 hour.
8. the in situ regeneration method of butylene oxidation-dehydrogenation catalyst according to claim 2, it is characterized in that butylene in the step b): the oxygen mol ratio is 1:0.3～2.0; First burst of butene feedstock is 1:0.3～0.7 with the allocation proportion scope of butene feedstock at different levels afterwards; The molar ratio of first strand of butene feedstock, oxygen-containing gas and water vapour is 1:0.3～2.0:2～18.
9. the in situ regeneration method of butylene oxidation-dehydrogenation catalyst according to claim 1, it is characterized in that the butylene oxidation-dehydrogenation reaction unit adopts at least two sections insulation fix bed reactors, reactor types is axial insulation fix bed reactor or radial adiabatic fixed bed reactors.
10. the in situ regeneration method of butylene oxidation-dehydrogenation catalyst according to claim 1 is characterized in that the butylene oxidation-dehydrogenation reaction unit adopts at least two sections isothermal fixed bed reactors, and reactor types is the shell and tube isothermal reactor.
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| CN104226334A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Regeneration method of butene oxidative dehydrogenation catalyst |
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