A kind of response system preparing ethylene removing green oil and method
Technical field
Present invention relates generally to the preparation field of ethylene, be specifically related to a kind of preparation second removing green oil
The response system of alkene and method.
Background technology
Ethylene is a kind of important basic material in modern industry, is also the chemistry of world wide production maximum
One of product, its product is widely used in the fields such as national economy, people's lives, national defence, is " to have
The mother of machine synthesis ".In the face of the shortage of petroleum resources and riseing of international oil price, raw material sources become
The bottleneck of development ethylene industry, is also to put the problem that must solve in face of people.Therefore, research
Develop a kind of new Technology to prepare ethylene, to be allowed to petroleum replacing as industrial raw materials,
The modern industry dependency to oil can be alleviated.
In coal chemical technology, with coal for raw material by carbide technique, or lead to natural gas for raw material
Cross non-catalytic partial oxidation technique and produce acetylene, it has also become maturation process.Again with acetylene as raw material,
Under the effect of selective hydrocatalyst, obtain ethylene product by hydrogenation process, can be further
Expand Coal Chemical Industry Route.Therefore, the novel technique of exploitation producing ethylene with acetylene hydrogenation, have wide
Application prospect.
Low concentration acetylene gas solid catalysis hydrogen addition technology is the most highly developed, mainly uses
Removing acetylene impurities in ethylene, the reactor of use is fixed bed reactors, fills in the reactor
Fill out solid-phase catalyst and carry out gas-solid phase reaction.But owing to ethyne reactive is high, hydrogenation reaction thermal discharge is big,
Even there is a small amount of acetylene in cracking gas, traditional gas-solid fixes bed hydroprocessing reactor and still suffers from
The serious problems such as green oil generating amount is big, catalyst cycle period is short, reactor easily " temperature runaway ".
Prior art one is fluidized-bed process and the device of a kind of producing ethylene with acetylene hydrogenation.This technique bag
Include following steps: in fluidized-bed reactor, add catalyst and diluent;Catalyst is risen
Temperature reduction;Acetylene and hydrogen mixture are passed through fluidized-bed reactor;Selective hydrogenation of acetylene generates
Ethylene;Cooling medium is passed through reactor heat exchange component to remove reaction heat;Isolated ethylene produces
Product.This Technology has the disadvantage in that
Preparing ethylene by selective hydrogenation of acetylene is strong exothermal reaction, although cooling medium is used in the process
The substantial amounts of heat released during to remove reaction, but still it is difficult to be completely eliminated local when reacting
The hidden danger that gas temperature is too high;
The fluid bed used because of this technique, is just difficult to avoid that the mutual sharp impacts of catalyst particles intergranular,
This can bring the loss of catalyst, increase the difficulty of dedusting, increase heat exchange component and the mill of reactor
The problems such as damage.
Prior art two is continuously separated production line, including oxygen hydrogenation reactor, cracking for a kind of ethylene
Gas the second exsiccator, removal of mercaptans/cos reactor, dearsenization reactor, acetylene hydrogenation reactor.
The reactor that its acetylene hydrogenation reactor used is used is fixed bed reactors.It is merely able to process
The acetylene of low concentration, and treating capacity is smaller;If acetylene content increase, can generate a large amount of green oil,
Cause the problem that catalyst cycle period shortens, even there will be reactor " temperature runaway ".
Therefore, so that reactor adapts to larger amount of reaction acetylene gas, do not result in and urge
Agent utilization rate is low, the problem of reactor " temperature runaway ", can remove green oil in time, fundamentally change
Kind gas-liquid flow field distribution, the quality fluidized in improving reactor, it is necessary to propose a kind of new preparation second
The response system of alkene and method.
Summary of the invention
It is an object of the invention to provide a kind of response system preparing ethylene removing green oil and side
Method, prepares that ethylene makes internal heat be difficult to spread out of, green oil is many, catalyst solving prior art
The problem that utilization rate is low.
The present invention provides a kind of response system preparing ethylene removing green oil, comprising: slurry bed system is anti-
Device, condenser, condensation separator, condensate tank, solvent pump, filter plant, green oil is answered to remove
System and solvent heater;Wherein said paste state bed reactor includes housing and sieve plate;Described housing
Bottom is provided with reaction gas inlet, solvent vapo(u)r entrance, liquid outlet;The top of described housing is provided with
Gas outlet and liquid inlet;Described sieve plate is positioned at described housing, is fixed in described inner walls,
It is positioned under described liquid inlet, on described reaction gas inlet, described solvent vapo(u)r entrance;Institute
State solvent heater to be connected with described paste state bed reactor by described solvent vapo(u)r entrance, described filtration
Equipment is connected with described paste state bed reactor by described liquid outlet, and described condenser passes through described gas
Body outlet connects with described paste state bed reactor, and described solvent pump is by described liquid inlet and described slurry
State bed reactor connects;Described condenser, described condensation separator, described condensate tank and described
Solvent pump is sequentially communicated;Described filter plant, described high-temperature heating equipment, described catalyst reduction dress
Put and described condensate tank is sequentially communicated;Described filter plant, described green oil removing system and described
Solvent heater is sequentially communicated.
Above-mentioned system, is provided with agitating device in described condensate tank.
Above-mentioned system, described condensation separator connection ethylene collection device.
Above-mentioned system, is dispersed with the sieve plate that multilamellar is parallel to each other, phase inside described paste state bed reactor
Between the sieve plate of adjacent bed spaced, the interval of each layer sieve plate is equal.
Above-mentioned system, every layer of described sieve plate includes seal pot, bubbling area, downflow weir and downspout;
Wherein, the part edge of described sieve plate is fixed with described inner walls;Described fixing part edge with
The part that described downflow weir fences up is seal pot;For holding the liquid flowed down from downspout described in upper strata
Body;The centre of described seal pot is distributed sieve aperture, forms bubbling area, and described bubbling area is gas-liquid
The main region of reaction;Described downflow weir is located at revocable edge of described sieve plate, described downflow weir
Higher than the seal pot of place layer, for keeping the height of liquid on every layer of described sieve plate;Described downspout
For making liquid flow to the seal pot of sieve plate described in lower floor from the downflow weir of sieve plate described in upper strata, it is positioned at institute
State the side of downflow weir.
Above-mentioned system, described sieve aperture is equally distributed circular aperture, and the centre-to-centre spacing of described aperture is
1-5 times of aperture, a diameter of 5-20mm of described aperture.
Above-mentioned system, the sieve aperture of described sieve plate is provided with float valve or bubble-cap.
Above-mentioned system, the bottom of the downspout of sieve plate described in upper strata is not higher than sieve plate overflow described in lower floor
The height on weir.
The present invention provides a kind of method utilizing said system to prepare ethylene, and described method includes:
The gaseous mixture of acetylene and hydrogen is sent in described paste state bed reactor;Described solvent pump is utilized to incite somebody to action
Liquid flux and catalyst in described condensate tank are sent in described paste state bed reactor;Make described
Liquid flux and catalyst flow to described slurry reactor through described sieve plate in described paste state bed reactor
The bottom of device;Described solvent heater is utilized to be passed through described slurry after liquid flux is evaporated to solvent vapo(u)r
In state bed reactor;The gaseous mixture making described acetylene and hydrogen is reacted by catalyst;Make described
Acetylene and the reacted gas of hydrogen circulate into described condenser from described paste state bed reactor, then pass through
Described condensation separator, condenses out the solvent in described reacted gas;Make to condense out
Solvent enters into described condensate tank, by the most cooled for condensed gas isolated ethylene;Make
Partially liq solvent and catalyst bottom described paste state bed reactor enter described filter plant;Incited somebody to action
The described partially liq solvent that filter obtains returns the heating of described solvent after sending into described green oil removing system
Device;The described partial catalyst being filtrated to get is sequentially sent to described high-temperature heating equipment, described catalysis
Agent reduction apparatus and described condensate tank.
Above-mentioned method, by the agitating device in described condensate tank by catalyst and liquid flux
After mix homogeneously, then by described solvent pump, described mixed catalyst and liquid flux are sent into institute
State in paste state bed reactor.
The beneficial effects of the present invention is, what the present invention proposed a kind of new removing green oil prepares ethylene
Response system and method, this response system and method are simple to operation, and course of reaction is easily achieved
Move heat, it is possible to remove green oil, catalyst reusable edible so that utilize paste state bed reactor in time
Carry out high concentration selective hydrogenation of acetylene and become the production ways of a kind of important alkene processed.
Accompanying drawing explanation
Fig. 1 is the structural representation that technical solution of the present invention prepares the paste state bed reactor of ethylene;
Fig. 2 is the plan structure schematic diagram of sieve plate in technical solution of the present invention;And
Fig. 3 is the system structure schematic flow sheet that technical solution of the present invention embodiment prepares ethylene.
Detailed description of the invention
Below in conjunction with drawings and Examples, the detailed description of the invention of the present invention is carried out more detailed
Explanation, so as to the advantage being more fully understood that the solution of the present invention and its various aspects.But,
Specific embodiments described below and embodiment are only descriptive purposes rather than to the present invention
Limit.
If Fig. 1 is the structure chart of the paste state bed reactor in the present invention.Wherein: 1, reacting gas
Entrance;2, liquid outlet;3, gas outlet;4, liquid inlet;5, sieve plate;6, descending liquid
Pipe;7, solvent vapo(u)r entrance.
The principle of paste state bed reactor is that gas (is starched by being suspended with the liquid of solid fine grain with bubbling form
Liquid) layer, to realize the reactor of gas-liquid-solid phase reaction process.This kind is used for selective hydrogenation of acetylene system
The paste state bed reactor of ethylene, described paste state bed reactor includes reactor shell and sieve plate 5.
Reactor shell bottom is provided with reaction gas inlet 1, solvent vapo(u)r entrance 7 and liquid discharge
Mouth 2, gas outlet 3 is arranged at reactor shell top.
Described sieve plate 5 is positioned at described housing, is fixed in described inner walls, is positioned at described liquid
Under entrance 4, on described reaction gas inlet 1, described solvent vapo(u)r entrance 7.
Middle part in reactor enclosure body, is evenly distributed sieve plate 5.Every layer of sieve plate 5 has
Seal pot, downflow weir, downspout 6 and bubbling area.The part edge of sieve plate is fixed with inner walls,
Revocable edge is provided with downflow weir.The part that fixing part edge and described downflow weir fence up is
Seal pot, for holding the liquid flowed down from upper strata downspout.
The top view of sieve plate 5 is as shown in Figure 2.Effect at the downflow weir of one end of sieve plate 5 is to protect
Hold the liquid having certain altitude on every layer of sieve plate.It is next to downspout 6 at downflow weir.Specifically,
Downspout can be formed by the gap of the downflow weir of described sieve plate Yu described reactor wall.Certainly downspout 6
May also be other structure is such as pipeline configuration.The effect of downspout 6 is to allow liquid from upper strata sieve plate
Downflow weir at flow to the seal pot of lower floor's sieve plate.The bottom of the downspout 6 of upper strata sieve plate 5 is the highest
Height in lower floor's sieve plate 5 downflow weir.So design be to realize fluid-tight, i.e. prevent gas from
Rising at downspout 6 causes each layer gas to connect and short-circuit.Central region on sieve plate 5 is bubbling
District, it is uniform-distribution with circular aperture.Aperture is the main thoroughfare that gas rises, it is possible to make
Gas and liquid uniform contact.
Described downspout 6 being projected on the direction being perpendicular to described seal pot of reactor adjacent layer
It is staggeredly arranged on circumferential angle.The most conveniently realize the liquid that upper strata sieve plate 5 flows down be stored in adjacent under
Layer sieve plate 5 upper certain time, until liquid exceeds the downflow weir of this lower floor and flows out to the sieve of lower floor again
Plate 5.
Aperture can keep pitching row's state with the flow direction of liquid, and the arrangement mode of aperture can be positive triangle
Formula.Small hole center is away from for 1-5 times of aperture, and the centre-to-centre spacing between preferred hole is 1.5 times;Hole
A diameter of 5-20mm, a diameter of 10mm in preferred hole.
The sieve aperture of sieve plate also can be provided with float valve or bubble-cap.Float valve can float on sieve plate, with
The change of gas flow and change its open degree.Riser is had, at bubble-cap and riser in bubble-cap
Between formed rotary space.Riser is fixed on sieve plate, and gas phase enters revolution sky by riser
Between, sprayed by slot with certain spouting velocity, form bubbling with the liquid on sieve plate and contact.
Being illustrated in figure 3 the response system preparing ethylene of removing green oil, it includes carrying in described above
The paste state bed reactor 10 that arrives, solvent heater 20, condenser 30, condensation separator 40, condensation
Liquid storage tank 50, solvent pump 60, filter plant 70 and green oil removing system 80, high-temperature heating equipment 90
With catalyst reduction device 100.Solvent heater 20 is by described solvent vapo(u)r entrance and described slurry
Bed reactor 10 connects, and described filter plant 70 is by described liquid outlet and described slurry reactor
Device 10 connects, and described condenser 30 is connected with described paste state bed reactor 10 by described gas outlet,
Described solvent pump 60 is connected with described paste state bed reactor 10 by described liquid inlet;Described condensation
Device 30, described condensation separator 40, described condensate tank 50 and described solvent pump 60 are sequentially communicated;
Described filter plant 70, described green oil removing system 80 and described solvent heater 20 are sequentially communicated;
Described filter plant 70, described high-temperature heating equipment 90, described catalyst reduction device 100 and described
Condensate tank 50 is also sequentially communicated.
Above-mentioned system, is provided with agitating device in described condensate tank 50, for condensate tank 50
Middle solvent and the stirring of catalyst.
Said system has solvent heater 20 in the outside of reactor, it is possible to make liquid flux evaporate,
The steam air-flow risen continuously is provided, provides thermal source for whole reactor simultaneously.
When preparing ethylene, anti-by bottom paste state bed reactor 10 of the gaseous mixture of acetylene and hydrogen
Gas access 1 is answered to enter in reactor.At the bottom solvent vapo(u)r entrance of reactor, steam is extremely
Lower and on pass through reactor, it is provided that the steam air-flow risen continuously, provide for whole reactor simultaneously
Thermal source.Reacting gas is entered by the aperture on the sieve plate of inside reactor together along with solvent vapo(u)r
Among liquid phase.Wherein solvent vapo(u)r is by 20 liquid fluxs of the solvent heater outside reactor
Heating evaporation and generate.The liquid inlet 4 on catalyst and carrier solvent autoreactor top is flowed
Enter.Because aperture is equally distributed on sieve plate 5, so reacting gas evenly spreads to the most therewith
In the middle of liquid.In a liquid, under the catalytic action of reacting gas catalyst in being suspended in liquid
React.Reacted gas departs from this layer of sieve plate 5, then is entered by the aperture of upper strata sieve plate 5
Enter in the middle of supernatant liquid.The most repeatedly until passing through reactor sieve plate 5 topmost, from reaction
The gas outlet 3 on device top goes out.
In the reactor, gas be to lower and on the flow direction, liquid is the flow direction from top to down, gas
Present the direction of adverse current mutually with liquid phase entirety, increase the effect of mass transfer and heat transfer.Due to reaction
Device has multiple sieve plate, namely means reactor also exists multiple little slurry reactor
Device, increases the area that gas-liquid-solid three-phase is fully contacted, and improves gas-liquid flow field distribution, it is to avoid short
Road, but also turbulence and gas-liquid mass transfer can be strengthened, the quality fluidized in improving reactor.
From reactor top reaction gas out, then by the cooling of condenser 30 by gas temperature
Cool down.Subsequently, then by condensation separator 40 solvent in gas is condensed out.Cold
Coagulate the solvent got off and enter into condensate tank 50.And gas is again through degree of depth refrigerated separation
Obtain product ethylene.Thus condensation separator 40 can connect ethylene collection device such as deep cooling further
Separator.
Solvent at reactor bottom enters in filter plant 70 by liquid outlet, will catalysis
Agent filters out from solvent.Solvent after filtration enters in green oil removing system 80, passes through
Green oil is separated by green oil removing system with solvent, and solvent enters back into solvent heater 20, green oil
Then enter green oil storage tank to preserve.After solvent heater 20 internal solvent is heated and becomes steam,
Enter in reactor from the steam inlet of reactor bottom.Filter out from filter plant 70
Catalyst is again after the calcining of high-temperature heating equipment 90, it is possible to effectively Removal of catalyst surface is attached
The impurity such as the green oil and solvent, it is achieved the regeneration of catalyst;But the catalyst after calcination is oxidation
State, therefore to realize the reduction of catalyst again through catalyst reduction device 100;After reducing/regenerating
Catalyst add again to condensate tank 50.
In condensate tank 50, by agitating device by after catalysts and solvents mix homogeneously,
By solvent pump 60, mixed liquid is sent in reactor again.This process can realize catalysis
Recycling of agent.
In the present embodiment, the solvent of use is distilled water (electrical conductivity < 5 μm/cm).From instead
Answering the steam of rising bottom device is the thermal source of whole reactor, keeps the most stable of system temperature.
When starting selective hydrogenation of acetylene reaction, the substantial amounts of heat of releasing, can be by the evaporation of solvent
Shift, it is to avoid in reactor the phenomenon that local temperature is too high occurs.
Solvent heater in the present invention can use electrical heating, steam heating, flue gas or lead
The mode of deep fat heating realizes.
High-temperature heating equipment in the present invention can use the heating such as electrical heating, revolving bed, fluid bed
Device realizes.
Compared with the technology of acetylene hydrogenation a small amount of with current ethylene, this technology can realize by high concentration
Preparing ethylene by selective hydrogenation of acetylene, has expanded the technology path of Coal Chemical Industry further.
Further, in technical solution of the present invention, gas be to lower and on the flow direction, liquid is
The flow direction from top to down, gas phase and liquid phase entirety present the direction of adverse current, increase mass transfer and biography
The effect of heat.
Further, the reactor of technical scheme there is multiple sieve plate, namely means
And reactor also exists multiple little paste state bed reactor, increase gas-liquid-solid three-phase and be fully contacted
Contact area, improve gas-liquid flow field distribution, short circuit can be avoided, but also turbulence can be strengthened
With gas-liquid mass transfer, the quality fluidized in improving reactor.
Further, the system of the present invention is provided with green oil removing system and catalyst regeneration is
System, greatly reduces green oil and catalyst activity reduces the impact on reaction, it is achieved that device
Smooth long term running;The solvent simultaneously used in solvent heater is the solvent after removing green oil, energy
Enough save heat, and local temperature is too high in avoiding reactor.
The system and method for the present invention makes catalyst to recycle, and improves the profit of catalyst
Use efficiency.
Technical scheme utilize liquid phase solvent sensible heat (sensible heat refer to when this heat add or
After removing, the change of mass temperature can be caused, and do not undergo phase transition), heat-sinking capability significantly improves,
The heat produced because selective hydrogenation of acetylene generates ethylene can be quickly moved out, reduce reaction bed
Temperature, improves conversion ratio and the selectivity of ethylene of acetylene.
It addition, the heating system of the technical program is simple, only rely on the solvent heating outside reactor
Device can be realized as heat supply.
In a word, the present invention provide response system and method, carry out selective hydrogenation of acetylene reaction
Time, can be effectively prevented from " temperature runaway " phenomenon, it is possible to remove green oil in time, can preferably press down
Focus in the beds caused because of exothermic reaction during preparation of ethylene through selective hydrogenation of acetylene processed
Appearance, and then avoid catalysqt deactivation, improve the stability of catalyst.What the present invention proposed sets
The standby mode using catalyst recycling solves the problem that catalyst use efficiency is low well.
Embodiment 1
Use the system for preparing ethylene by selective hydrogenation of acetylene in embodiment as shown in Figure 3.
System structure form as described in above-mentioned embodiment.The operation pressure of this system is
0.25MPa, temperature is 130 DEG C.Can first use nitrogen as in source of the gas, with paste state bed reactor
Solvent containing catalyst is set up gas-liquid and is flowed to;Subsequently, more gradually solvent heater (solvent is opened
Pressure in heater is 0.27MPa), set up steam ascending air.When steam rises to reaction
Device top cooling for reflux, and after temperature stabilization, nitrogen gradually can be converted to hydrogen and second
The gaseous mixture of alkynes gas is passed in the middle of reactor.In the reactor, acetylene and hydrogen are at catalyst
Ethylene is generated under catalytic action;Reacted gas passes through condenser 30 and condensation separator 40 again,
After being condensed out by solvent in gas, then send response system battery limit (BL).Gas can travel further into
Ethylene collection device carries out deep condensation and forms ethylene.It flow at the bottom of reactor with solvent from reactor top
The catalyst in portion, then filtered out by filter plant 70, then through high-temperature heating equipment 90
After calcining, it is possible to the impurity such as the green oil of effective Removal of catalyst surface attachment and solvent, it is achieved catalysis
The regeneration of agent;But the catalyst after calcination is oxidation state, therefore will be again through catalyst reduction device
100 reduction realizing catalyst;Catalyst after reducing/regenerating adds to condensate tank 50 again
In.
In condensate tank 50 after mix homogeneously solvent and catalyst, use the solvent pump will catalysis
Agent is transported to reactor head.Solvent after filtration enters in green oil removing system 80, passes through
Green oil is separated by green oil removing system 80 with solvent, and solvent enters back into solvent heater 20;?
Solvent heater 20 internal solvent is heated after becoming steam, from the solvent vapo(u)r entrance of reactor bottom
Enter in reactor.
In the present embodiment, the solvent of use is distilled water (electrical conductivity < 5 μm/cm), from molten
The steam of the rising entering reactor in agent heater is the thermal source of whole reactor, keeps system temperature
That spends is the most stable.When starting selective hydrogenation of acetylene reaction, the substantial amounts of heat of releasing is permissible
Shifted by the evaporation of solvent, it is to avoid local temperature is too high.The particle diameter of the catalyst used is
40-150 μm, the filtering accuracy of the filter plant of use is 1 μm.
Last it is noted that obvious, above-described embodiment is only for clearly demonstrating institute of the present invention
The citing made, and not restriction to embodiment.Those of ordinary skill in the field are come
Say, can also make other changes in different forms on the basis of the above description.Here
Without also cannot all of embodiment be given exhaustive.And thus amplified out obvious
Change or change among still in protection scope of the present invention.