A kind of reaction system and method for producing ethylene with acetylene hydrogenation
Technical field
Present invention relates generally to the reaction systems and method of a kind of ethylene processed, and in particular to a kind of producing ethylene with acetylene hydrogenation
Reaction system and method.
Background technique
Ethylene is a kind of primary raw material of petro chemical industry, and process of preparing mainly passes through splitting for naphtha at present
Solution alkene and coal-to-olefin.Domestic ethylene aggregated capacity in 2015 reaches 22,000,000 t/a or so, the year two thousand twenty country ethylene production capacity into
One step will be added to 32,500,000 t/a, and expecting the year two thousand twenty country ethylene consumption figure is 48,000,000 tons/year, then demand will occurs
The phenomenon that greater than production capacity.This constitutes serious strategy for oil reserve China not abundant and threatens.Therefore, seek another
A kind of new source and process, can be largely so as to substitute petroleum in field of industrial production to prepare ethylene
Alleviate China for the dependence of petroleum.
In coal chemical technology, pass through Non-catalytic partial oxygen by calcium carbide technique or by raw material of natural gas by raw material of coal
Chemical industry skill produces acetylene, has been widely used.Using acetylene as raw material, under selective hydrocatalyst effect, by adding hydrogen to prepare
Ethylene product can further expand Development of Coal Chemical Industry approach.And the main downstream product polyvinyl chloride (PVC) of acetylene in recent years
Supply exceed demand, and PVC industrial profit is not high, is badly in need of expanding acetylene downstream product industrial chain;And polyethylene price is with petroleum valence
Lattice wave is dynamic very big, and other downstream product such as ethylene glycol, butanediol, acrylic acid, polyvinyl alcohol etc. also have good economic value.
Therefore, the novel technique for developing producing ethylene with acetylene hydrogenation can provide a kind of new raw material source for ethylene industry, and reduce second
Alkene has broad application prospects to the degree of dependence of petroleum resources and the production cost of ethylene.
Although acetylene selective hydrogenation is the current focus of attention, report both domestic and external also compares more, its research contents master
It concentrates on and removes cracking petroleum hydrocarbon and prepare micro acetylene (0.01-5 volume %) during ethylene process.Acetylene hydrogenation is
Strong exothermal reaction, high concentration acetylene hydrogenation release a large amount of reaction heat, and bed moves heat difficulty, easily causes catalyst inactivation, side reaction
Increase, yield of ethene decline, so for specially few using high concentration acetylene as the method for the catalysis selective hydrogenation ethylene of raw material
There is exploration, the corresponding large-scale application that industrializes is even more to have not been reported.
Therefore, in order to avoid in conventional method high purity acetylene add the fixed bed temperature runaway phenomenon of hydrogen ethylene, reaction heat move heat
The problem and green oil that difficult and bed pressure drop is big, slurry reactor pressure is low, production capacity is small are gathered, influence catalyst activity
Problem, it is necessary to propose the reaction system and method for a kind of new producing ethylene with acetylene hydrogenation.
Summary of the invention
The purpose of the present invention is to provide a kind of reaction system of producing ethylene with acetylene hydrogenation and methods, to solve conventional method
Middle high purity acetylene adds the fixed bed temperature runaway phenomenon of hydrogen ethylene, reaction heat to move, and heat is difficult and bed pressure drop is big, slurry reactor pressure
The problem and green oil that power is low, production capacity is small are gathered, influence the problem of catalyst activity.
The present invention provides a kind of reaction systems of producing ethylene with acetylene hydrogenation, and the system comprises hydrogen alkynes mixing pressure is single
Member, hydrogenation reaction unit, cryogenic separation unit, vacuum filter unit, revolving bed regeneration unit and vacuum low-pressure distillation unit;Institute
Stating hydrogenation reaction unit includes slurry bed system, slurry bed system temperature control device, gas-liquid condensation separating unit, wherein the slurry bed system is equipped with
Combi inlet port, gas products outlet, lime set import, serum outlet and heat transferring medium import, heat transferring medium outlet;It is described
Combi inlet port connects the hydrogen alkynes mixing pressure unit;The serum outlet connects the vacuum filter unit;The slurry
Temperature control device is exported bed by the heat transferring medium, heat transferring medium import is connected to the slurry bed system;The gas-liquid condenses and separates
The gas products import of device connects the gas products outlet of the slurry bed system, the condensate outlet of the gas-liquid condensation separating unit
The lime set import of the slurry bed system is connected, the gas vent of the gas-liquid condensation separating unit connects the cryogenic separation unit
Gas feed;The liquid phase material outlet of the vacuum filter unit connects the vacuum low-pressure distillation unit, the vacuum filter
The solid-phase material outlet of unit connects the revolving bed regeneration unit.
Above-mentioned system, the hydrogen alkynes mixing pressure unit are venturi mixer.
Above-mentioned system, the hydrogen inlet of the hydrogen outlet of the cryogenic separation unit and the hydrogen alkynes mixing pressure unit
It is connected.
Above-mentioned system, the slurry bed system temperature control device include electric heater, condenser and automatic temperature control system.
The solvent outlet of above-mentioned system, the vacuum low-pressure distillation unit connects the colvent inlet of the slurry bed system;Institute
The discharge port for stating revolving bed regeneration unit is connected with the catalyst inlet of the slurry bed system.
The present invention also provides a kind of methods for carrying out producing ethylene with acetylene hydrogenation using above system, and the method includes steps
It is rapid: acetylene and hydrogen are pressed into mixing by the hydrogen alkynes mixing pressure unit;Mixed acetylene and hydrogen are passed through described
Hydrogenation reaction unit is reacted;Deep cooling point is carried out by the cryogenic separation unit to the gas-phase product of acetylene hydrogenation solid/liquid/gas reactions
From obtaining product ethylene and hydrogen more than needed, the hydrogen more than needed is sent into the hydrogen alkynes mixing pressure unit;It will be in the slurry bed system
Slurries draw, pass through the isolated solid-phase material of the vacuum filter unit and liquid phase material;The solid-phase material is passed through
The revolving bed regeneration unit processing, obtains regenerated catalyst;The liquid phase material is passed through into the vacuum low-pressure distillation unit
Processing carries out solvent recovery.
Above-mentioned method, the acetylene pressure for being passed through the hydrogen alkynes mixing pressure unit is 5KPa-40KPa, temperature 5-80
℃;The Hydrogen Vapor Pressure being passed through is 0.44MPa-2.24MPa, and temperature is 5-40 DEG C;The molar ratio of the acetylene and hydrogen is 1:3-
15。
Above-mentioned method, the solid-phase material include catalyst and catalyst diluent.
Above-mentioned method, the catalyst diluent include perlite particle, alumina particle, silicon oxide particle, divide
One or more of son sieve and ceramic particle;The catalyst diluent partial size is the 80%- of the catalyst average grain diameter
120%;The mass ratio of the catalyst diluent and the catalyst is 0.1-10:1.
Above-mentioned method, the atmosphere of the revolving bed regeneration unit are hydrogen and nitrogen, molar ratio 1:3-6;It is described
Temperature range in revolving bed regeneration unit is 20-750 DEG C.
The method and system of producing ethylene with acetylene hydrogenation provided by the invention avoid high purity acetylene in conventional method and add hydrogen system
Ethylene fixed bed temperature runaway, reaction heat move the problem that heat is difficult and bed pressure drop is big, slurry reactor pressure is low, production capacity is small,
And the advantage that the present invention has operating flexibility big, adaptable to catalyst.
The present invention realizes the mixing of high pressure hydrogen and low pressure acetylene using venturi mixer, avoids gaseous mixture compressor
Use, thereby reduce the security risk of compression acetylene, while reducing the investment of equipment.
The present invention is filtered using continuous vacuum and low-pressure distillation technology, avoids green oil accumulation, influences catalyst activity
Defect, and realize solvent reclamation.
The present invention uses revolving bed regenerated catalyst technology, realizes catalyst on-line regeneration, reduces technique to catalysis
The requirement in agent service life, so that catalyst activity is high, in stable condition in slurry bed system.
Detailed description of the invention
Fig. 1 is the system schematic of the producing ethylene with acetylene hydrogenation of an embodiment of the present invention;
Fig. 2 is the work flow diagram of the producing ethylene with acetylene hydrogenation of an embodiment of the present invention.
In figure: 1- slurry bed system;2- condenser;3- gas-liquid condensation separating unit;4- cryogenic separation unit;The mixing of 5- hydrogen alkynes is equal
Press unit;6- revolving bed regeneration unit;7- vacuum filter unit;8- vacuum low-pressure distillation unit;9- slurry bed system temperature control device;
The outlet of 10- gas products;11- lime set import;12- heat transferring medium import;The outlet of 13- heat transferring medium;14- slurry inlet;15- slurry
Liquid outlet;16- combi inlet port;17- recombinates sub-export;The outlet of 18- ethylene.
Specific embodiment
Below in conjunction with drawings and examples, a specific embodiment of the invention is described in more details, so as to energy
The advantages of enough more fully understanding the solution of the present invention and its various aspects.However, specific embodiments described below and reality
It applies example to be for illustrative purposes only, rather than limiting the invention.
As shown in Figure 1, a kind of high purity acetylene adds the system of hydrogen ethylene, including hydrogen alkynes mixing pressure unit, hydrogenation reaction
Unit, cryogenic separation unit, vacuum filter unit, revolving bed regeneration unit and vacuum low-pressure distillation unit.
Venturi mixer can be used instead of gaseous mixture compressor in hydrogen alkynes mixing pressure unit, reduces the peace of compression acetylene
Full hidden danger, while reducing the investment of equipment.When venturi mixer is for using static mixer, two strands or two strands or more
Fluid enter static mixer before, each fluid streams smooth delivery of power and design.Fluid during transportation, often due to
Each fluid streams discharge pressure imbalance influences mixing ratio, selects venturi shaped distributor, venturi shaped distribution in this case
Device has the performance of injection booster, under conditions of guaranteeing secondary stream flow, the outlet pressure of material is made to reach required pressure
Power.
The hydrogenation reaction unit includes slurry bed system, slurry bed system temperature control device, gas-liquid condensation separating unit, the slurry bed system
Equipped with combi inlet port, gas products outlet, lime set import, serum outlet and heat transferring medium import and export, the gaseous mixture into
Mouth connection hydrogen alkynes mixing pressure unit mixed gas outlet, the serum outlet connect vacuum filter unit, the slurry bed system temperature control
Device is imported and exported equipped with heat transferring medium, is connect respectively with slurry bed system heat transferring medium exit port.The gas-liquid condensation separating unit is set
There are gas products import, condensate outlet and gas vent, condensate outlet connects the import of slurry bed system lime set, and the gas vent connects
Connect cryogenic separation unitary gas import.
Further, the slurry bed system temperature control device may include conduction oil temperature control device, high pressure soft water temperature control device, steam
Temperature control device and flue gas temperature control device.
The vacuum filter unit includes continuous vacuum filter device, is equipped with slurry inlet, liquid phase material and solid-phase material
Outlet, the liquid phase material outlet connection vacuum low-pressure distillation unit, solid-phase material are exported through belt conveyer and revolving bed
The feed inlet of regeneration unit connects.
Further, the vacuum filter may include rotary drum vacuum filter, belt vacuum filter or tipping bucket type
Vacuum filter.
The present invention is filtered using continuous vacuum and low-pressure distillation technology, avoids green oil accumulation, influences catalyst activity
Defect, and realize solvent reclamation.
Further, the revolving bed regeneration unit includes revolving bed, is equipped with feed inlet and outlet and gas inlet and outlet.Revolving bed
It is a kind of reactor of bottom rotation.The revolving bed includes input and output material area, preheating zone, dry section, roast area and reducing zone;
Temperature range is 20-750 DEG C in revolving bed.
Further, the revolving bed gas vent is connected with slurry bed system flue gas temperature control device, for recycling fluidized bed
Heat in exit gas.
The vacuum low-pressure distilling apparatus includes low-pressure distillation column, is equipped with liquid phase material import, solvent outlet and heavy constituent
Outlet.
The present invention uses revolving bed regenerated catalyst technology, realizes catalyst on-line regeneration, reduces technique to catalysis
The requirement in agent service life, so that catalyst activity is high, in stable condition in slurry bed system.
The method of producing ethylene with acetylene hydrogenation of the invention, includes the following steps:
1) hydrogen alkynes mixing is pressed
Low pressure acetylene and high pressure hydrogen are mixed by venturi mixer, while realizing that hydrogen alkynes is pressed.
2) hydrogenation reaction
Gaseous mixture obtained by step 1) is passed through the slurry bed system in hydrogenation reaction process, carries out acetylene selective hydrogenation reaction.
3) cryogenic separation
Cryogenic separation is carried out to the gas-phase product of acetylene hydrogenation reaction, separate using compression and depth cooling means
To product ethylene, hydrogen of having more than needed is sent into hydrogen alkynes mixing pressure process.
4) vacuum filter
Slurries in slurry bed system are continuously drawn, the isolated solid-phase material of vacuum filter and liquid phase material are passed through.
5) revolving bed regenerates
The solid-phase material is handled by revolving bed, obtains regenerated catalyst.
6) vacuum low-pressure distills
The liquid phase material is distilled by vacuum low-pressure, recycling design.
Wherein, low pressure acetylene pressure is 5KPa-40KPa, and temperature is 5-80 DEG C.The high pressure hydrogen pressure is
0.44MPa-2.24MPa, temperature are 5-40 DEG C.The molar ratio of acetylene and hydrogen is 1:3-15.
Wherein, the solid-phase material includes catalyst and catalyst diluent.
Wherein, it (is crystalline state that catalyst diluent, which includes perlite particle, alumina particle, silicon oxide particle, molecular sieve,
Silicate or alumino-silicate, be connected by oxygen-octahedron or aluminum-oxygen tetrahedron by oxygen bridge key and formed.) and ceramic particle in
One or more;Catalyst diluent partial size is the 80%-120% of catalyst average grain diameter;Catalyst diluent and catalysis
The mass ratio of agent is 0.1-10:1.
Wherein, revolving bed includes input and output material area, preheating zone, dry section, roast area and reducing zone;Temperature range is 20-750
℃.Atmosphere in revolving bed is hydrogen and nitrogen, molar ratio 1:3-6.
The method and system of producing ethylene with acetylene hydrogenation provided by the invention avoid high purity acetylene in conventional method and add hydrogen system
Ethylene fixed bed temperature runaway, reaction heat move the problem that heat is difficult and bed pressure drop is big, slurry reactor pressure is low, production capacity is small,
And the advantage that the present invention has operating flexibility big, adaptable to catalyst.
The present invention is now illustrated with following most preferred embodiment.Technique numerical value in following embodiment is illustrative explanation,
Specific range is subject to the value in description.
Embodiment 1
As shown in Fig. 2, a kind of high purity acetylene adds the system of hydrogen ethylene, which is characterized in that the system includes the mixing of hydrogen alkynes
Pressure unit 5, hydrogenation reaction unit, cryogenic separation unit 4, vacuum filter unit 7, revolving bed regeneration unit 6 and vacuum low-pressure
Distillation unit 8.
The hydrogenation reaction unit includes slurry bed system 1, slurry bed system temperature control device 9, gas-liquid condensation separating unit 3, the slurry
State bed is equipped with combi inlet port 16, gas products outlet 10, lime set import 11, serum outlet 15 and heat transferring medium import and export
12,13, the combi inlet port 16 connects hydrogen alkynes mixing pressure unit mixed gas outlet, and the serum outlet 15 connects vacuum mistake
Unit 7 is filtered, the temperature control device 9 is equipped with heat transferring medium import and export, goes out respectively with slurry bed system heat transferring medium, import 13,12 connects
It connects, the gas-liquid condensation separating unit 3 is equipped with gas products import, condensate outlet and gas vent, condensate outlet connection slurry
The 1 lime set import of state bed, the gas vent connect 4 gas feed of cryogenic separation unit.Cryogenic separation unit 4 goes out equipped with ethylene
Mouth 18.
The vacuum filter unit 7 includes continuous vacuum filter device, is equipped with slurry inlet 14, liquid phase material and solid formation
Material outlet, the liquid phase material outlet connection vacuum low-pressure distillation unit, solid-phase material outlet is through belt conveyer and rotation
Bed feed inlet connection.
The revolving bed regeneration unit 6 includes revolving bed, is equipped with feed inlet and outlet and gas inlet and outlet.Its middle charging aperture and true
The solid-phase material of empty filter element 7 exports connection.Gas feed is for inputting atmosphere hydrogen and nitrogen.Discharge port is used for and adds hydrogen
The catalyst inlet of reaction member is connected.Gas vent is used to the atmosphere recycling of output be output to atmosphere entrance.
The vacuum low-pressure distilling apparatus includes low-pressure distillation column, is equipped with liquid phase material import, solvent outlet and heavy constituent
Outlet 17.Liquid phase material import is used to connect the liquid phase material outlet of vacuum filter unit 7.Solvent outlet can be with hydrogenation reaction list
The lime set import connection of member is, it can be achieved that solvent recycles.Recombination sub-export 17 is for exporting byproduct green oil.
In the present embodiment, slurry bed system temperature control device 9 is heat-conducting oil system, is equipped with electric heater, condenser 2 and temp autocontrolled
System.
Embodiment 2
Using the system of embodiment 1, technique that high purity acetylene adds hydrogen ethylene are as follows:
By partial size be -150 mesh of 100 mesh catalyst diluent aluminium oxide and acetylene hydrogenation catalyst according to 2:1 quality
Ratio is uniformly mixed and forms solid-phase material, and rear be added inside slurry bed system is mixed to form slurries with solvent N- first class pyrrolidones.It will
20KPa, 40 DEG C of acetylene are mixed by the molar ratio of 1:6 by venturi mixer with 0.44MPa, 5 DEG C of hydrogen, form mixing
Gas.Gaseous mixture enters slurries by slurry bed system internal gas distributor, reacts under the conditions of 170 DEG C.Gaseous phase materials after reaction
Target product ethylene is obtained by cryogenic separation, the hydrogen of recycling is mixed with raw hydrogen.Liquid phase material is through rotating drum vacuum filtration
Machine obtains solid-phase material and liquid phase material.Solid-phase material is sent through belt to revolving bed, and revolving bed atmosphere is hydrogen and nitrogen, is rubbed
, than being 1:4, preheated, drying, roasting and reduction obtain regenerated catalyst for you, and catalyst returns to slurry bed system and continues to use.Liquid
Phase materials are pumped into vacuum low-pressure destilling tower, and pressure 5KPa (A) collects fraction (the N- first class pyrrolidines that boiling range is 130 DEG C -150 DEG C
Ketone), the N- first class pyrrolidones of recycling returns to slurry bed system, and heavy constituent is green oil.
Embodiment 3
Using the system of embodiment 1, technique that high purity acetylene adds hydrogen ethylene are as follows:
By partial size be -150 mesh of 100 mesh catalyst diluent perlite particle and acetylene hydrogenation catalyst according to 10:1's
Ratio is uniformly mixed and forms solid-phase material, and rear be added inside slurry bed system is mixed to form slurries with solvent N- first class pyrrolidones.It will
40KPa, 80 DEG C of acetylene are mixed by the molar ratio of 1:15 by venturi mixer with 2.2MPa, 10 DEG C of hydrogen, are formed mixed
Close gas.Gaseous mixture enters slurries by slurry bed system internal gas distributor, reacts under the conditions of 170 DEG C.Gas gas-phase objects after reaction
Material obtains target product ethylene by cryogenic separation, and the hydrogen of recycling is mixed with raw hydrogen.Liquid phase material is through belt vacuum mistake
Filter obtains solid-phase material and liquid phase material.Solid-phase material is sent through belt to revolving bed, and revolving bed atmosphere is hydrogen and nitrogen,
Molar ratio is 1:6, and preheated, drying, roasting and reduction obtain regenerated catalyst, and catalyst returns to slurry bed system and continues to use.
Liquid phase material is pumped into vacuum low-pressure destilling tower, and pressure 5KPa (A) collects fraction (the N- first class pyrroles that boiling range is 130 DEG C -150 DEG C
Alkanone), the N- first class pyrrolidones of recycling returns to slurry bed system, and heavy constituent is green oil.
Embodiment 4
Using the system of embodiment 1, technique that high purity acetylene adds hydrogen ethylene are as follows:
By the mixture and second of catalyst diluent silicon oxide particle, molecular sieve and ceramics that partial size is -150 mesh of 100 mesh
Alkynes hydrogenation catalyst is uniformly mixed according to the ratio of 0.1:1 and forms solid-phase material, rear to be added inside slurry bed system and solvent N- first class
Pyrrolidones is mixed to form slurries.5KPa, 5 DEG C of acetylene and 1.4MPa, 40 DEG C of hydrogen are passed through into literary mound by the molar ratio of 1:3
In mixer mix, formed gaseous mixture.Gaseous mixture enters slurries by slurry bed system internal gas distributor, under the conditions of 170 DEG C
Reaction.Gaseous phase materials after reaction obtain target product ethylene by cryogenic separation, and the hydrogen of recycling is mixed with raw hydrogen.Liquid
Phase materials obtain solid-phase material and liquid phase material through belt vacuum filter.Solid-phase material is sent through belt to revolving bed, revolving bed
Atmosphere is hydrogen and nitrogen, and molar ratio 1:3, preheated, drying, roasting and reduction obtain regenerated catalyst, catalyst
Slurry bed system is returned to continue to use.Liquid phase material is pumped into vacuum low-pressure destilling tower, and pressure 5KPa (A), collecting boiling range is 130 DEG C -150
DEG C fraction (N- first class pyrrolidones), the N- first class pyrrolidones of recycling returns to slurry bed system, and heavy constituent is green oil.
Finally, it should be noted that obviously, the above embodiment is merely an example for clearly illustrating the present invention, and simultaneously
The non-restriction to embodiment.For those of ordinary skill in the art, it can also do on the basis of the above description
Other various forms of variations or variation out.There is no necessity and possibility to exhaust all the enbodiments.And thus drawn
The obvious changes or variations that Shen goes out are still in the protection scope of this invention.