CN107522587B - A method of 1,3- butadiene is recycled in alkynes selective hydrogenation in mixing carbon four - Google Patents
A method of 1,3- butadiene is recycled in alkynes selective hydrogenation in mixing carbon four Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0005—Catalytic processes under superatmospheric pressure
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/085—Feeding reactive fluids
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/883—Molybdenum and nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
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Abstract
The invention discloses a kind of methods of alkynes selective hydrogenation recycling 1,3-butadiene in mixing carbon four, include the following steps: to select supergravity reactor；It is efficiently mixed gas-liquid two-phase is carried out in hydrogen and mixing C 4 materials input feed cavity, is dispersed into slightly solubility hydrogen in mixing carbon four and largely receives micron bubble, solubility of the hydrogen in mixing carbon four reaches supersaturation, forms gas-liquid mixture；Gas-liquid mixture is delivered into supergravity reactor by liquid distribution trough, gas-liquid-solid catalytic hydrogenation reaction process is carried out in the rotor containing catalyst and filler；Reaction product and unreacted hydrogen leave reactor, and product is down to room temperature by condenser, enter knockout drum afterwards, and hydrogen is produced from top, and liquid product is produced from knockout drum lower part；The reactor that this method uses can make slightly solubility hydrogen reach supersaturation in liquid phase dissolved degree, efficiently utilize hydrogen, strengthen gas-liquid-solid phase mass transfer, butadiene production rate≤80%.
Description
Technical field
The invention belongs to fine chemistry industry catalytic hydrogenation reaction fields, more particularly, to alkynes selectivity in a kind of mixing carbon four
Add the method for hydrogen retrieval 1,3- butadiene.
Background technique
Butadiene plays an important role in national economy, is synthetic rubber such as butadiene rubber, fourth fat rubber, butylbenzene rubber
The primary raw materials such as glue, ABS engineering plastics, nylon, own dicyan.
In recent years, with the promotion of crude oil in China working depth and stepping up for ethylene production capacity, by-product carbon four is got over
Come abundanter.Utilization rate of China's carbon four in terms of chemical industry only has 16% or so at present, is mainly methyl by isobutene conversion
Tert-butyl (MTBE), there are also part 1- butylene to be used to prepare methyl ethyl ketone, and the carbon four of most of oil refining process is taken as fuel and liquid
Change gas to use, and the utilization rate of the industrially developed country such as the U.S., Japan and West Europe is up to 60%.In addition, with China's tire work
The fast development of industry, the consumption figure rapid increase of fourth rubber increase the demand of high purity butylene alkene monomer year by year, but high
Purity butene monomers rely primarily on import.
The fourth two of mass fraction 40%-60% is usually contained in the cracking c_4 fraction of hydrocarbons pyrolysis ethylene by-product
Alkene, butadiene are the important monomers of China Synthetic Rubber Industry.Butadiene is extracted from cracking c_4 fraction generallys use solvent extraction
Method, such as acetonitrile method, N methylpyrrolidone process and dimethylformamide method, currently, these methods substantially meet it is pure to butadiene
The requirement of degree.
Due to the influence of the factors such as cracking severity and cracking technique, alkynes content is in and gradually increases in cracking c_4 fraction
Gesture causes the loss increase of butadiene in extractive process and energy consumption to increase.Meanwhile with the development of organic synthesis industrial technology,
Stringenter to the limitation of alkynes content in butadiene, these factors cause the economy of butadiene extraction device to be deteriorated.?
When extracting butadiene, by recovery section butadiene after alkynes selective hydrogenation, the purpose to turn waste into wealth not only can achieve, but also
Important function is also functioned to reducing alkynes discharge and preventing the pollution of the environment.
High-gravity technology obtains more impressive progress, CN103102942A in the application study of field of chemical engineering in recent years
Feedstock oil is successfully passed through the supergravity reactor equipped with non-precious metal catalyst, desulfurization is carried out with hydrogen counter current contacting, takes off
Nitrogen and part aromatic hydrocarbons saturated reaction, but by the way of loading catalyst, operating process is difficult, and reaction process pressure drop is larger, urges
Agent is easy inactivation；Metal-polymer catalyst is fixed on the rotor of rotating packed bed reactor by CN104419454A,
Drippolene and hydrogen pass through the catalyst bed being rotating and carry out selective hydrogenation reaction, but propose that monoblock type is urged there is no specific
The raw material proportioning and fixing means of agent fixation procedure.It is the most outstanding in mixing carbon four in alkynes selective hydrogenation process
Disadvantage is exactly that raw material proportioning, type of feed and fixation of the solubility and catalyst being difficult to improve hydrogen in the liquid phase etc. are asked
Topic.Therefore the method that the present invention proposes to realize alkynes selective hydrogenation recycling butadiene in mixing carbon four using high-gravity technology.
Summary of the invention
The technical problem to be solved in the present invention is to provide alkynes selective hydrogenations in a kind of mixing carbon four to recycle 1,3- fourth two
The method of alkene.The reactor that this method uses can make slightly solubility hydrogen reach supersaturation in liquid phase dissolved degree, efficiently utilize reduction
Property hydrogen, strengthen gas-liquid-solid phase mass transfer, butadiene production rate≤80%.
Term used in the present invention " mixing carbon four " refers to that the C-4-fraction rich in alkynes or the carbon rich in alkynes four evaporate
Divide the mixture with dilution material.Wherein the mixing carbon four rich in alkynes comes from butadiene extraction device, is residual after Butadiene Extraction
The remaining higher C-4-fraction of alkynes content, usually contains the components such as butylene, butane, butadiene, vinylacetylene, butine.
In order to solve the above technical problems, invention adopts the following technical scheme that:
A method of 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four, includes the following steps:
S1, selection supergravity reactor
Supergravity reactor, including motor, main shaft, rotor, shell and liquid distribution trough；The main shaft of the motor output end
It is extend into shell across housing bottom, the rotor is fixed on main shaft portion；The super-gravity device further includes secondary axes, speedup
Device, output shaft of the speed increaser and feed cavity；The top of shell is arranged in the feed cavity, and the lower part of feed cavity connects liquid distribution
Device；The main shaft is fixedly connected by secondary axes with speed increaser, and the output shaft of the speed increaser passes through feed cavity bottom and extend into charging
It is intracavitary；The feed cavity inner part of the output shaft of the speed increaser is equipped with stirring wing；The feed cavity be equipped with first gas inlet,
Liquid inlet and catalyst inlet, the lower part of the housing are equipped with gas liquid outlet；The upper part of the housing is equipped with gas inlet-outlet, described
Housing side is equipped with second gas inlet；
S2, supergravity reactor motor is started, speed increaser rotation is driven, to drive the stirring wing ultrahigh speed in feed cavity
Rotation；It is efficiently mixed gas-liquid two-phase is carried out in hydrogen and mixing C 4 materials input feed cavity, is mixing slightly solubility hydrogen
It is dispersed into carbon four and largely receives micron bubble, solubility of the hydrogen in mixing carbon four reaches supersaturation, forms gas-liquid mixed
Object；
S3, gas-liquid mixture is delivered into supergravity reactor by liquid distribution trough, contains catalyst and filler
Rotor in carry out gas-liquid-solid catalytic hydrogenation reaction process；
S4, reaction product and unreacted hydrogen pass through gas liquid outlet respectively and gas inlet-outlet leaves reactor, product
It is down to room temperature by condenser, enters knockout drum afterwards, hydrogen is produced from top, and liquid product is produced from knockout drum lower part.
As the further improvement of technical solution, in step S2, mixing four medium vinyl acetylene mass content of carbon is 20-
30wt%, butadiene mass content are usually 8-16%.
As the further improvement of technical solution, the speed increasing ratio of the speed increaser is 1:5-1:10000.
As the further improvement of technical solution, the material of the stirring wing include titanium alloy, chromium-base alloy, dual phase steel or
Ceramics etc..
As the further improvement of technical solution, in step S2, hydrogen is with the molar ratio for mixing alkynes total amount in carbon four
1.0-2.5；Preferably, hydrogen is 1.2-2 with the molar ratio for mixing alkynes total amount in carbon four.
As the further improvement of technical solution, in step S2, the micron bubble size Control of receiving is at 30nm-300 μm.
As the further improvement of technical solution, in step S3, the catalyst and filler are the catalysis of Integral-structure type
Agent filler；Preferably, catalyst includes active component and carrier.
Preferably, the active component includes one of palladium, rhodium, platinum, nickel, molybdenum simple substance or its compound or a variety of.
Preferably, the carrier includes Al2O3, silica, zinc oxide, one of molecular sieve or a variety of.
It is highly preferred that the catalyst is the nickel molybdenum catalyst using aluminium oxide as carrier；Most preferably, in the catalyst
It is with γ-Al2O3For carrier, using nickel and molybdenum as active component；Wherein nickel content is 0.3-0.8%, molybdenum content 3-8%.
Further improvement as technical solution, it is preferable that the catalyst may also include co-catalyst, the co-catalysis
Agent includes one of potassium, sodium, lithium, magnesium, copper, vanadium, arsenic or a variety of.
As the further improvement of technical solution, in step S3, supergravity reactor reaction temperature is 30-79 DEG C, reaction
Pressure is 1-2.5MPa, and liquid volume air speed is 8-30h-1；Preferably, supergravity reactor reaction temperature is 30-70 DEG C, reaction
Pressure is 1-2.0MPa, and liquid volume air speed is 10-25h-1；It is highly preferred that supergravity reactor reaction temperature is 40-60 DEG C,
Reaction pressure is 1.2-1.8MPa, and liquid volume air speed is 15-25h-1。
As the further improvement of technical solution, in step S3, the control of gas-liquid-solid catalytic hydrogenation reaction residence time is
It is realized by regulation supergravity reactor revolving speed, the revolving speed of supergravity reactor can be controlled in 200-2700rpm, and liquid phase exists
The residence time can be controlled in 50-2000ms in rotor.Preferably, when rotor speed is in 200rpm, the residence time is about
2000ms；The residence time is about 1500ms when 600rpm；When 1000rpm, the residence time is about 800ms；When 1500rpm, stop
Time is about 400ms；When 2000rpm, the residence time is about 100ms；When 2700rpm, the residence time is about 50ms.
In the case where the one way reaction process residence time is shorter, catalytic hydroconversion rate is lower, can be by material outside
The mode of portion's circulation improves reaction conversion ratio.Revolving speed by regulating and controlling supergravity reactor is realized to molecular mixing efficiency and material
The selectivity of mixing carbon four plus hydrogen retrieval butadiene can be improved in the control of residence time, reduces side reaction.
Any range documented by the present invention includes any numerical value between end value and end value and end value or end value
Between any subrange for being constituted of any number.
Unless otherwise specified, each raw material in the present invention can be obtained by commercially available purchase, equipment used in the present invention
The conventional equipment in fields can be used or carried out referring to the prior art of fields.
Compared with prior art, the invention has the following beneficial effects:
1) it is long to have the time in the liquid phase for bubble: common gas-liquid is simply mixed after bubble generates in the liquid phase in device, meeting
It rapidly rises to liquid phase surface and ruptures disappearance, it is very short there are the time；And the micro-nano generated by gas liquid high-efficiency pre-mixing apparatus
For rice bubble once generation, the rate of climb in water is slower, and the course from generating rupture generally reaches tens seconds even rather
Clock, and volume is constantly shunk in uphill process and finally dissolution disappears in water, and the smaller bubble of volume is in water
The rate of climb is slower；
2) gas-liquid mass transfer is high-efficient, and when bubble diameter is smaller, the surface tension of microbubble interface is to Bubble Characteristics
The more significant of performance is influenced, surface tension at this moment generates compression to internal gas, so that micron bubble was rising
It is constantly shunk in journey and shows itself pressurization.With the unlimited diminution of bubble diameter, the specific surface area of bubble interface is also therewith
It is unlimited to increase, finally since itself pressurized effect causes air pressure inside to increase to infinity.Therefore, it has so that more gases
It is dissolved into water across gas-liquid interface, may make that mass-transfer efficiency persistently enhances at gas-liquid interface, and micro- gas that this characteristic makes
Even if the gas content of bubble in the liquid phase reaches supersaturated condition, it may continue to the mass transport process for carrying out gas and keep efficient
Mass-transfer efficiency.Reaction and the dissolution of gas be it is simultaneous, while vapor-phase reactant is consumed, micron bubble of receiving is broken
Dissolution and macroscopical gas phase mass transfer into liquid phase are dissolved while being carried out, and gas can be supplemented within first time；
3) in terms of the selectivity of supergravity reactor of the invention during catalytic hydrogenation reaction, different types of mixing
Four catalytic hydroconversion of carbon is mixed in four compound of carbon can be by the revolving speed of change supergravity reactor for the selectivity of butadiene
Regulate and control the gas-liquid renewal rate of catalyst surface, select different loads catalyst type, to there is purpose selective catalysis, quantifies
Reaction process；
4) in terms of reducing reaction pressure: as mostly used the method for improving pressure to improve hydrogen greatly in hydrogenation plant at this stage
The dissolution of gas in the solution, such as uses gas liquid high-efficiency mixing arrangement of the invention, and liquid phase has reached before entering the reactor
Supersaturation, and since high efficient gas and liquid mixing arrangement can make Gas content in liquid phase be up to 90%, micron even nano bubble exists
The redissolution for carrying out gas phase is crushed in liquid phase, therefore the partial pressure of hydrogen can be reduced suitably in actual reactor, reduce investment at
This；
5) in terms of equipment investment: reactor of the invention is revolving bed, and revolving bed itself can be achieved with high efficient gas and liquid mixing,
It is combined with gas-liquid pre-mixing apparatus, mixed effect can be made to be further strengthened.And two parts are combined together can be reduced and set
Standby occupied area reduces the investment of equipment aspect without connecting again with other large size gas-liquid premixing devices.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing
Fig. 1 shows supergravity reactor schematic diagram of the invention；
Fig. 2 shows the flow diagrams that supergravity reactor of the invention is used to mix carbon four plus hydrogen retrieval butadiene；
Wherein: the extraction of 101- liquid phase；102- pump；103- head tank；104- valve；105- fluid flowmeter；
106- supergravity reactor；Valve；109- receives a micron catalyst inlet；110- valve；
111- condenser；The extraction of 112- gas；113- knockout drum；114- hydrogen；115- nitrogen；
116- valve；117- gas flowmeter.
Specific embodiment
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Narration is intended merely to conveniently using the noun of locality " upper and lower, left and right " etc. in the present invention, and those skilled in the art can
Know, these orientation be it is opposite, may by rotation etc. modes change.
A method of carbon four plus hydrogen retrieval butadiene being mixed in supergravity reactor, included the following steps:
S1, selection supergravity reactor
Supergravity reactor 106, including motor 1, main shaft 2, rotor 3, shell 4 and liquid distribution trough 14；The motor is defeated
The main shaft 2 of outlet passes through housing bottom and extend into shell 4, and the rotor 3 is fixed on 2 top of main shaft；The hypergravity reaction
Device further includes secondary axes 17, speed increaser 15, output shaft of the speed increaser 6 and feed cavity 7；The top of shell 4 is arranged in the feed cavity 7,
The lower part of feed cavity 7 connects liquid distribution trough 14；The main shaft 2 is fixedly connected by secondary axes 17 with speed increaser 15, the speedup
Device output shaft 6 passes through 7 bottom of feed cavity and extend into feed cavity 7；The feed cavity inner part of the output shaft of the speed increaser 6 is equipped with
Stirring wing 11；The feed cavity 7 is equipped with first gas inlet 10, liquid inlet 8 and catalyst inlet 9,4 lower part of shell
Equipped with gas liquid outlet 16；4 top of shell is equipped with gas inlet-outlet 12, and the housing side is equipped with second gas inlet 13；
Sealing 5 is equipped between rotor 3 and shell 4；
S2, supergravity reactor motor 1 is started, drives speed increaser 15 to rotate, to drive the stirring wing 11 in feed cavity 7
Ultrahigh speed rotation；It is efficiently mixed gas-liquid two-phase is carried out in hydrogen and mixing C 4 materials input feed cavity 7, makes slightly solubility hydrogen
It is dispersed into mixing carbon four and largely receives micron bubble, solubility of the hydrogen in mixing carbon four reaches supersaturation, forms gas
Liquid mixture；
S3, gas-liquid mixture is delivered into supergravity reactor by liquid distribution trough 14, is containing catalyst and is filling out
Gas-liquid-solid catalytic hydrogenation reaction process is carried out in the rotor of material；
S4, reaction product and unreacted hydrogen pass through gas liquid outlet 16 respectively and gas inlet-outlet 12 leaves reactor,
Product is down to room temperature by condenser 111, enters knockout drum 113 afterwards, and hydrogen is produced from top, and liquid product divides from gas-liquid
113 extraction lower from tank.
In certain embodiments of the present invention, in step S2, mixing four medium vinyl acetylene mass content of carbon is 20-
30wt%, butadiene mass content are usually 8-16%.
In certain embodiments of the present invention, the speed increasing ratio of the speed increaser is 1:5-1:10000 or 1:5-1:9500,
Or 1:5-1:9000 or 1:5-1:8500 or 1:5-1:8000 or 1:5-1:7500 or 1:5-1:7000 or 1:5-1:
6500 or 1:5-1:6000 or 1:5-1:5500 or 1:5-1:5000 or 1:5-1:4500 or 1:5-1:4000 or 1:5-
1:3500 or 1:5-1:3000 or 1:5-1:2500 or 1:5-1:2000 or 1:5-1:1500 or 1:5-1:1000 or 1:
5-1:500,1:100-1:10000 or 1:100-1:9500 or 1:100-1:9000 or 1:100-1:8500 or 1:100-1:
8000 or 1:100-1:7500 or 1:100-1:7000 or 1:100-1:6500 or 1:100-1:6000 or 1:100-1:
5500 or 1:100-1:5000 or 1:100-1:4500 or 1:100-1:4000 or 1:100-1:3500 or 1:100-1:
3000 or 1:100-1:2500 or 1:100-1:2000 or 1:100-1:1500 or 1:100-1:1000.
By the adjusting to speed increaser, the bubble in feed cavity 7 can be made to there is the time in the liquid phase long: common gas-liquid
It is simply mixed after bubble generates in the liquid phase in device, liquid phase surface can be rapidly risen to and rupture disappearance, it is very short there are the time；
And the micro-nano bubble generated by gas liquid high-efficiency pre-mixing apparatus, once generation, the rate of climb in water is slower, from generation
To rupture course generally reach tens seconds even a few minutes, and in uphill process volume constantly shrinks and in water finally
Dissolution disappears, and the rate of climb of the smaller bubble of volume in water is slower；
When bubble diameter is smaller, influence performance of the surface tension of microbubble interface to Bubble Characteristics is more shown
It writes, surface tension at this moment generates compression to internal gas, so that micron bubble is constantly shunk in uphill process and table
Reveal itself pressurization；With the unlimited diminution of bubble diameter, the specific surface area of bubble interface is also unlimited therewith to be increased, finally due to
Itself pressurized effect causes air pressure inside to increase to infinity；Therefore, it has so that more gases are dissolved across gas-liquid interface
Into water, may make that mass-transfer efficiency persistently enhances at gas-liquid interface, even and if this characteristic microbubble that makes in the liquid phase
When gas content reaches supersaturated condition, it may continue to carry out the mass transport process of gas and keep efficient mass-transfer efficiency.Reaction
Dissolution with gas be it is simultaneous, while vapor-phase reactant is consumed, the broken dissolution of micron bubble of receiving and macroscopical gas phase
Into liquid phase, mass transfer is dissolved while being carried out, and gas can be supplemented within first time；
It mostly uses the method for improving pressure to improve the dissolution of hydrogen in the solution in hydrogenation plant at this stage greatly, and adopts
With gas liquid high-efficiency mixing arrangement (motor 1, main shaft 2, secondary axes 17, speed increaser 15, output shaft of the speed increaser 6, stirring wing of the invention
11, feed cavity 7 etc. is collectively referred to as), liquid phase has had reached supersaturation before entering rotor, and due to gas liquid high-efficiency mixing arrangement
The Gas content in liquid phase can be made to be up to 90%, micron even nano bubble is crushed the redissolution for carrying out gas phase in the liquid phase, therefore
The partial pressure of hydrogen can be reduced suitably in actual reactor, reduce cost of investment.
In certain embodiments of the present invention, the material of the stirring wing 11 include titanium alloy, chromium-base alloy, dual phase steel or
Ceramics etc..
In certain embodiments of the present invention, in step S2, hydrogen is with the molar ratio for mixing alkynes total amount in carbon four
1.0-2.5；Preferably, hydrogen is 1.2-2 with the molar ratio for mixing alkynes total amount in carbon four.
In certain preferred embodiments of the invention, in step S2, the micron bubble size Control of receiving is in 30nm-300 μ
M or 30nm-250 μm or 30nm-200 μm or 30nm-150 μm or 30nm-100 μm or 30nm-50 μm or 30nm-10 μ
M or 30nm-1 μm or 100nm-300 μm or 100nm-250 μm or 100nm-200 μm or 100nm-100 μm or 100nm-
1μm。
In certain embodiments of the present invention, in step S3, the catalyst and filler are the catalyst of Integral-structure type
Filler；Preferably, catalyst includes active component and carrier.
In certain preferred embodiments of the invention, the active component includes palladium, rhodium, platinum, nickel, molybdenum simple substance or its change
Close one of object or a variety of.
In certain preferred embodiments of the invention, the carrier includes Al2O3, silica, zinc oxide, in molecular sieve
It is one or more.
In certain preferred embodiments of the invention, the catalyst is the nickel molybdenum catalyst using aluminium oxide as carrier；Most
It preferably, is with γ-Al in the catalyst2O3For carrier, using nickel and molybdenum as active component；Wherein nickel content is 0.3-
0.8%, molybdenum content 3-8%.
In certain preferred embodiments of the invention, it is preferable that the catalyst may also include co-catalyst, and described help is urged
Agent includes one of potassium, sodium, lithium, magnesium, copper, vanadium, arsenic or a variety of.
In certain embodiments of the present invention, in step S3, supergravity reactor reaction temperature is 30-79 DEG C, reaction pressure
Power is 1-2.5MPa, and liquid volume air speed is 8-30h-1；Preferably, supergravity reactor reaction temperature is 30-70 DEG C, reaction pressure
Power is 1-2.0MPa, and liquid volume air speed is 10-25h-1；It is highly preferred that supergravity reactor reaction temperature is 40-60 DEG C, instead
Answering pressure is 1.2-1.8MPa, and liquid volume air speed is 15-25h-1。
In certain embodiments of the present invention, in step S3, the control of gas-liquid-solid catalytic hydrogenation reaction residence time is logical
Cross what regulation supergravity reactor revolving speed was realized, the revolving speed of supergravity reactor can be controlled in 200-2700rpm, or or 200-
2500rpm or 200-2000rpm or 200-1500rpm or 200-1000rpm or 200-500rpm or 500-2500rpm,
Or 500-2000rpm or 500-1500rpm or 500-1000rpm.Liquid phase residence time in rotor can be controlled in 50-
2000ms.When rotor speed is in 200rpm, the residence time is about 2000ms；The residence time is about 1500ms when 600rpm；
When 1000rpm, the residence time is about 800ms；When 1500rpm, the residence time is about 400ms；When 2000rpm, the residence time is about
For 100ms；When 2700rpm, the residence time is about 50ms.
In the case where the one way reaction process residence time is shorter, catalytic hydroconversion rate is lower, can be by material outside
The mode of portion's circulation improves reaction conversion ratio.Revolving speed by regulating and controlling supergravity reactor is realized to molecular mixing efficiency and material
The selectivity for mixing carbon four plus hydrogen retrieval butadiene can be improved in the control of residence time, reduces side reaction.
Embodiment 1
As shown in Fig. 2, a kind of method that will mix carbon four plus hydrogen retrieval butadiene in supergravity reactor, including it is as follows
Step:
The mixing C-4-fraction of unsaturated hydrocarbons will be contained as raw material, hydrocarbons hydrogenation reaction uses nickel molybdenum catalyst, wherein
Nickel 0.3wt%, molybdenum 8wt%, catalyst carrier are γ-Al2O3, the reactor that this selective hydrogenation uses is carried out as rotation
Turn packed bed reactor, inlet temperature is 30 DEG C, pressure 2.0MPa, the mixing C 4 materials liquid volume containing unsaturated hydrocarbons
Air speed is 10h-1, the molar ratio 1.2:1 of hydrogen and alkynes.Influence of the different RPB revolving speeds to hydrogen degree is added is investigated, as a result such as table 1
It is shown；With the raising of RPB revolving speed, the unsaturated hydro carbons of height can remove completely substantially in raw material, but butadiene is also hydrogenated
Saturation, butene content dramatically increases, therefore need to select suitable RPB revolving speed.Table 1 is shadow of the different RPB revolving speeds to hydrogenation reaction
It rings.
Table 1: influence of the different RPB revolving speeds to the butadiene rate of recovery
| RPB revolving speed/rpm | W (butylene)/% | W (alkynes)/% | W (butadiene)/% |
| 400 | 4.97 | 2.91 | 82.10 |
| 800 | 5.07 | 2.43 | 84.15 |
| 1200 | 6.86 | 1.97 | 85.35 |
| 1600 | 6.98 | 0.53 | 88.52 |
| 2000 | 7.56 | 0.21 | 92.12 |
It is compared with existing published supergravity reactor, such as patent CN103102942A, material conveying is directly logical
It crosses liquid distribution trough and enters catalyst surface, carry out gas-liquid-solid three-phase haptoreaction, since the alternate mixed effect of gas-liquid is poor, hydrogen
Most of evolution, finally obtains Ding diene Shou Shuai≤70% under identical operating conditions.
Embodiment 2
As shown in Fig. 2, a kind of method that will mix carbon four plus hydrogen retrieval butadiene in supergravity reactor, including it is as follows
Step:
The mixing C-4-fraction of unsaturated hydrocarbons will be contained as raw material, hydrocarbons hydrogenation reaction uses nickel molybdenum catalyst, wherein
Nickel 0.8wt%, molybdenum 3wt%, catalyst carrier are γ-Al2O3, the reactor that this selective hydrogenation uses is carried out as rotation
Turn packed bed reactor, inlet temperature is 30 DEG C, pressure 2.0MPa, the mixing C 4 materials liquid volume containing unsaturated hydrocarbons
Air speed is 10h-1, the molar ratio 1.2:1 of hydrogen and alkynes；Influence of the different RPB revolving speeds to hydrogen degree is added is investigated, as a result such as table 2
It is shown；With the raising of RPB revolving speed, the unsaturated hydro carbons of height can remove completely substantially in raw material, but butadiene is also hydrogenated
Saturation, butene content dramatically increases, therefore need to select suitable RPB revolving speed.Table 2 is shadow of the different RPB revolving speeds to hydrogenation reaction
It rings.
Table 2: influence of the different RPB revolving speeds to the butadiene rate of recovery
| RPB revolving speed/rpm | W (butylene)/% | W (alkynes)/% | W (butadiene)/% |
| 400 | 2.86 | 3.98 | 80.26 |
| 800 | 5.26 | 2.95 | 86.23 |
| 1200 | 5.68 | 2.01 | 90.15 |
| 1600 | 6.98 | 1.56 | 91.12 |
| 2000 | 7.54 | 0.86 | 91.95 |
It is compared with existing published supergravity reactor, such as patent CN104419454A, under identical operating conditions
Finally obtain product Ding diene Shou Shuai≤70%.
Embodiment 3
As shown in Fig. 2, a kind of method that will mix carbon four plus hydrogen retrieval butadiene in supergravity reactor, including it is as follows
Step:
The mixing C-4-fraction of unsaturated hydrocarbons will be contained as raw material, hydrocarbons hydrogenation reaction uses nickel molybdenum catalyst, wherein
Nickel 0.56wt%, molybdenum 5.6wt%, catalyst carrier are γ-Al2O3, carrying out the reactor that this selective hydrogenation uses is
Rotating packed-bed reactor, inlet temperature are 30 DEG C, pressure 2.0MPa, the mixing C 4 materials liquid bulk containing unsaturated hydrocarbons
Product air speed is 10h-1, the molar ratio 1.2:1 of hydrogen and alkynes.Influence of the different RPB revolving speeds to hydrogen degree is added is investigated, as a result such as table
Shown in 3；With the raising of RPB revolving speed, the unsaturated hydro carbons of height can remove completely substantially in raw material, but butadiene is also hydrogenated
Saturation, butene content dramatically increases, therefore need to select suitable RPB revolving speed；Table 3 is shadow of the different RPB revolving speeds to hydrogenation reaction
It rings.
Table 3: influence of the different RPB revolving speeds to the butadiene rate of recovery
| RPB revolving speed/rpm | W (butylene)/% | W (alkynes)/% | W (butadiene)/% |
| 400 | 2.52 | 4.12 | 76.54 |
| 800 | 3.25 | 3.16 | 81.25 |
| 1200 | 5.24 | 2.65 | 85.69 |
| 1600 | 6.12 | 1.68 | 87.25 |
| 2000 | 8.02 | 0.95 | 91.01 |
It is compared with existing published supergravity reactor, such as patent CN104419454A, under identical operating conditions
Finally obtain Shou Shuai≤70% of product butadiene.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.Here all embodiments can not be exhaustive.It is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (14)
1. a kind of method of alkynes selective hydrogenation recycling 1,3-butadiene in mixing carbon four, which is characterized in that including walking as follows
It is rapid:
S1, selection supergravity reactor
Supergravity reactor, including motor, main shaft, rotor, shell and liquid distribution trough；The main shaft of the motor output end passes through
Housing bottom is extend into shell, and the rotor is fixed on main shaft portion；The supergravity reactor further includes secondary axes, speedup
Device, output shaft of the speed increaser and feed cavity；The top of shell is arranged in the feed cavity, and the lower part of feed cavity connects liquid distribution
Device；The main shaft is fixedly connected by secondary axes with speed increaser, and the output shaft of the speed increaser passes through feed cavity bottom and extend into charging
It is intracavitary；The feed cavity inner part of the output shaft of the speed increaser is equipped with stirring wing；The feed cavity be equipped with first gas inlet,
Liquid inlet and catalyst inlet, the lower part of the housing are equipped with gas liquid outlet；The upper part of the housing is equipped with gas inlet-outlet, described
Housing side is equipped with second gas inlet；
S2, supergravity reactor motor is started, speed increaser rotation is driven, so that the stirring wing ultrahigh speed in feed cavity be driven to revolve
Turn；It is efficiently mixed gas-liquid two-phase is carried out in hydrogen and mixing C 4 materials input feed cavity, makes slightly solubility hydrogen in mixing carbon
It is dispersed into four and largely receives micron bubble, solubility of the hydrogen in mixing carbon four reaches supersaturation, forms gas-liquid mixture；
S3, gas-liquid mixture is delivered into supergravity reactor by liquid distribution trough, in turn containing catalyst and filler
Gas-liquid-solid catalytic hydrogenation reaction process is carried out in son；
S4, reaction product and unreacted hydrogen pass through gas liquid outlet respectively and gas inlet-outlet leaves reactor, and product passes through
Condenser is down to room temperature, enters knockout drum afterwards, and hydrogen is produced from top, and liquid product is produced from knockout drum lower part；
In step S3, the catalyst and filler are the catalyst filling of Integral-structure type；Catalyst includes active component and load
Body；The active component includes one of palladium, rhodium, platinum, nickel, molybdenum simple substance or its compound or a variety of；The carrier includes
Al2O3, silica, zinc oxide, one of molecular sieve or a variety of.
2. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 1, special
Sign is: the speed increasing ratio of the speed increaser is 1:5-1:10000.
3. a kind of method that will mix carbon four plus hydrogen retrieval butadiene in supergravity reactor according to claim 1,
Be characterized in that: the material of the stirring wing includes titanium alloy, chromium-base alloy, dual phase steel or ceramics.
4. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 1, special
Sign is: in step S2, the four medium vinyl acetylene mass content of mixing carbon is 20-30wt%, and butadiene mass content is
8-16%.
5. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 1, special
Sign is: in step S2, hydrogen is 1.0-2.5 with the molar ratio for mixing alkynes total amount in carbon four.
6. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 5, special
Sign is: hydrogen is 1.2-2 with the molar ratio for mixing alkynes total amount in carbon four.
7. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 1, special
Sign is: in step S2, the micron bubble size Control of receiving is at 30nm-300 μm.
8. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 1, special
Sign is: the catalyst is the nickel molybdenum catalyst using aluminium oxide as carrier.
9. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 8, special
Sign is: being with γ-Al in the catalyst2O3For carrier, using nickel and molybdenum as active component；Wherein nickel content is 0.3-
0.8%, molybdenum content 3-8%.
10. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 7, special
Sign is: the catalyst may also include co-catalyst, and the co-catalyst includes potassium, sodium, lithium, magnesium, copper, vanadium, one in arsenic
Kind is a variety of.
11. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 1, special
Sign is: in step S3, supergravity reactor reaction temperature is 30-79 DEG C, reaction pressure 1-2.5MPa, liquid volume air speed
For 8-30h-1。
12. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 11,
Be characterized in that: supergravity reactor reaction temperature is 30-70 DEG C, reaction pressure 1-2.0MPa, and liquid volume air speed is 10-
25h-1。
13. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 11,
Be characterized in that: supergravity reactor reaction temperature is 40-60 DEG C, reaction pressure 1.2-1.8MPa, and liquid volume air speed is 15-
25h-1。
14. a kind of method that 1,3-butadiene is recycled in alkynes selective hydrogenation in mixing carbon four according to claim 1, special
Sign is: in step S3, the revolving speed of supergravity reactor is controlled in 200-2700rpm；Liquid phase residence time in rotor is controlled
System is in 50-2000ms.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0023745A2 (en) * | 1977-12-01 | 1981-02-11 | Imperial Chemical Industries Plc | Process and apparatus for effecting mass transfer |
| CN102311790A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Liquid phase circular hydrogenation treatment method capable of improving mixed amount of hydrogen |
| EP2486966A1 (en) * | 2011-02-09 | 2012-08-15 | Alstom Technology Ltd | Rotating packed bed |
| CN104419453A (en) * | 2013-09-05 | 2015-03-18 | 中国石油化工股份有限公司 | Method for selective hydrogenation of unsaturated polyhydrocarbon |
| CN104415715A (en) * | 2013-09-05 | 2015-03-18 | 中国石油化工股份有限公司 | Catalytic hydrogenation method |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0023745A2 (en) * | 1977-12-01 | 1981-02-11 | Imperial Chemical Industries Plc | Process and apparatus for effecting mass transfer |
| CN102311790A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Liquid phase circular hydrogenation treatment method capable of improving mixed amount of hydrogen |
| EP2486966A1 (en) * | 2011-02-09 | 2012-08-15 | Alstom Technology Ltd | Rotating packed bed |
| CN104419453A (en) * | 2013-09-05 | 2015-03-18 | 中国石油化工股份有限公司 | Method for selective hydrogenation of unsaturated polyhydrocarbon |
| CN104415715A (en) * | 2013-09-05 | 2015-03-18 | 中国石油化工股份有限公司 | Catalytic hydrogenation method |
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