CN106631674A - System and method for preparing ethylene through acetylene hydrogenation - Google Patents
System and method for preparing ethylene through acetylene hydrogenation Download PDFInfo
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- CN106631674A CN106631674A CN201710034785.8A CN201710034785A CN106631674A CN 106631674 A CN106631674 A CN 106631674A CN 201710034785 A CN201710034785 A CN 201710034785A CN 106631674 A CN106631674 A CN 106631674A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/04—Ethylene
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to a system and a method for preparing ethylene through acetylene hydrogenation. The system comprises a mixed pressure increasing unit, a catalyst protection unit, a hydrogenation reaction unit, a cryogenic separation unit, a vacuum filtration unit, a revolving bed generation unit and a vacuum low-pressure distillation unit. The method comprises steps as follows: acetylene and hydrogen are mixed under increased pressure; feed gases obtained after mixing are sequentially introduced into the catalyst protection unit and the hydrogenation reaction unit for a reaction; gaseous products obtained after the reaction are separated, a product ethylene, byproducts and surplus hydrogen are obtained, and the surplus hydrogen is sent to the reaction unit; slurry in a slurry reactor is led out and separated by the vacuum filtration unit, and a solid-phase material and a liquid-phase material are obtained; the solid-phase material is treated by the revolving bed generation unit, and a regenerated catalyst is obtained; the liquid-phase material is treated by the vacuum low-pressure distillation unit, and a solvent is recovered. The system and the method have the advantages as follows: operating flexibility is high, energy consumption of a compressor is low, the service life of the catalyst is long and the adaptive capacity is high.
Description
Technical field
The invention belongs to chemical technology field, more particularly to a kind of system and method for producing ethylene with acetylene hydrogenation.
Background technology
Ethene is a kind of primary raw material of petro chemical industry, and current process of preparing mainly passes through splitting for naphtha
Solution alkene processed and olefin hydrocarbon making by coal.Domestic ethene aggregated capacity in 2015 reaches 22,000,000 t/a or so, and the year two thousand twenty country ethene production capacity is entered
One step will be added to 32,500,000 t/a, and it is 48,000,000 tons/year to expect the year two thousand twenty country ethene consumption figure, then will appear from demand
More than the phenomenon of production capacity.Serious strategy threat is constituted for this China not enriched to oil reserve.Therefore, seek another
A kind of new source and process to prepare ethene, so as to can be in field of industrial production petroleum replacing, can be largely
Alleviate China for the dependence of petroleum.
In coal chemical technology, Non-catalytic partial oxygen is passed through 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.It is standby by Hydrogenation under selective hydrocatalyst effect with acetylene as raw material
Ethylene product, can further expand Development of Coal Chemical Industry approach.And the main downstream product polyvinyl chloride (PVC) of acetylene in the last few years
Supply exceed demand, and PVC industrial profits are not high, is badly in need of expanding acetylene downstream product industrial chain；And polyethylene price is with oil valency
Lattice wave is dynamic very big, and other downstream product such as ethylene glycol, and butanediol, acrylic acid, polyvinyl alcohol etc. also have good economic worth.
Therefore, developing the novel technique of 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 ethene.
Although acetylene selective hydrogenation is the current focus of attention, report both domestic and external also compares many, its research contents master
Concentrate on removing cracking petroleum hydrocarbon and prepare acetylene (0.01-5 volume %) micro during ethylene process.Acetylene hydrogenation is
Strong exothermal reaction, high concentration acetylene hydrogenation releases a large amount of reaction heat, and bed moves heat difficulty, easily causes catalyst inactivation, side reaction
Increase, yield of ethene declines.
Prior art discloses a kind of system and method for high purity acetylene Hydrogenation ethene.Researcher has found that high purity acetylene adds
Noble metal catalyst activity and life-span used by hydrogen are easily affected by acetylene purification technique, need to be removed to sulphur phosphorus arsenic content
Below 10ppb, and unreacted hydrogen is recycled to suction port of compressor, significantly increases compressor and takes up an area, invests and run
Energy consumption.
The acetylene that calcium carbide is generated often is mixed with the impurity such as hydrogen sulfide, hydrogen phosphide and arsenic hydride, therefore needs in commercial Application
Thick acetylene gas is purified, to obtain pure acetylene gas industrial production is applied to.In prior art, thick acetylene gas is entered
The technique of row purification mainly has two kinds：Sodium hypochlorite purifies technique and concentrated sulfuric acid purification technique, however industrial sodium hypochlorite and
Objectionable impurities in thick acetylene (sulphur, phosphorus, arsenic) can only be removed to ＞ 50ppb by concentrated sulfuric acid purification technique.Continue to adopt conventional purge
Technique, is significantly greatly increased cleaning equipment investment and operation energy consumption.
The content of the invention
It is an object of the invention to provide a kind of system and method for producing ethylene with acetylene hydrogenation, to avoid green oil accumulation from causing
Catalyst activity reduction, while also avoiding existing acetylene purification craft precision not high, the noble metal catalyst of high dispersive is easily by micro-
Amount impurity effect and inactivate, and high hydrogen alkynes is than defect that unstripped gas compresses.
For achieving the above object, the present invention proposes a kind of system of producing ethylene with acetylene hydrogenation, and the system includes hydrogenation
Reaction member, vacuum filter unit, revolving bed regeneration unit, vacuum low-pressure distillation unit and separative element；Wherein,
The hydrogenation reaction unit is provided with recovery injection point, purified gas entrance, serum outlet and gas vent；
The vacuum filter unit is provided with injection point, liquid phase material outlet and solid-phase material outlet, the injection point
It is connected with the serum outlet；
The revolving bed regeneration unit be provided with charging aperture, discharging opening, atmosphere gas entrance, atmosphere gas outlet, it is described enter
Material mouth is connected with solid-phase material outlet, and the discharging opening is connected with the recovery injection point, the atmosphere gas entrance
Regenerate catalyst for being input into atmosphere gas hydrogen and nitrogen, the atmosphere gas export for will output atmosphere gas again
Circulation output is to the atmosphere gas entrance；
The vacuum low-pressure distillation unit is provided with liquid phase material entrance, solvent outlet and restructuring sub-export, the liquid phase thing
Material entrance connects the liquid phase material outlet, and the solvent outlet is connected with the recovery injection point；
The separative element includes that gas access and circulating hydrogen are exported, and the gas access connects the gas vent,
The circulating hydrogen outlet is connected with the purified gas entrance.
Specifically, the hydrogenation reaction unit includes that the gentle liquid condensing of slurry bed system, the first attemperating unit, condenser separates dress
Put.
The slurry bed system be provided with the purified gas entrance, lime set entrance, the recovery injection point, heat transferring medium entrance,
Gas products outlet, the outlet of the serum outlet, heat transferring medium.
First attemperating unit is connected by the heat transferring medium entrance, heat transferring medium outlet with the slurry bed system
It is logical.
The condenser include gas products entrance and condensation gas-liquid mixture outlet, the gas products entrance with it is described
Gas products outlet is connected.
The gas-liquid condensation separating unit includes condensation gas-liquid mixture entrance, condensate outlet and gas vent, described
Condensation gas-liquid mixture entrance is connected with the condensation gas-liquid mixture outlet, the condensate outlet and the lime set entrance phase
Even.
Further, the system also includes mixing pressure-raising unit and catalyst protection unit.Wherein,
The mixing pressure-raising unit includes acetylene entrance, hydrogen inlet and the unitary gas outlet of mixing pressure-raising.
The catalyst protection unit includes unstripped gas heat exchanger, the second attemperating unit and shell and tube catalyst protection device.
The unstripped gas heat exchanger includes heat exchanger gas access and heat exchanger gas vent, the heat exchanger gas access
It is connected with the mixing pressure-raising unitary gas outlet.
The shell and tube catalyst protection device is provided with unstripped gas entrance, clean gas outlet, heat transferring medium entrance, heat transferring medium
The outlet of outlet, regenerant inlet and regenerative agent；The unstripped gas entrance is connected with the heat exchanger gas vent；The shell and tube
Catalyst protection device inside includes tubulation, and the protective agent and its carrier are filled with the tubulation, is heat exchange outside the tubulation
Medium；The protective agent in the shell and tube catalyst protection device can remove the impurity of unstripped gas, so as to guard catalyst.
Second attemperating unit is connected with the heat transferring medium entrance, heat transferring medium outlet, the temperature control dress
Putting can control protectant temperature using the heat transferring medium.
Specifically, the mixing pressure-raising unit is linked in sequence including front surge tank, reciprocating compressor and rear surge tank, institute
Front surge tank is stated including the acetylene entrance and the hydrogen inlet, the rear surge tank includes being provided with the mixing pressure-raising unit
Gas vent；Or,
The mixing pressure-raising unit includes that front surge tank, liquid piston compressor, rear surge tank and eliminating water drying device are suitable
Sequence connects, and the front surge tank includes the acetylene entrance and the hydrogen inlet, and now, the mixing pressure-raising unitary gas goes out
Mouth is arranged on the eliminating water drying device；
The mixing pressure-raising unit is used to carry out mixing compression to unstripped gas.
Preferably, the shell and tube catalyst protection device is 2 or more than 2.
The present invention also provides a kind of method of producing ethylene with acetylene hydrogenation, it is characterised in that including step：
A. by acetylene and hydrogen by the mixing pressure-raising unit pressure-raising mixing；
B. the acetylene and hydrogen after mixing pressurization is passed through after the catalyst protection unit removing objectionable impurities, is delivered to
The hydrogenation reaction unit is reacted；
C. the gas-phase product after acetylene hydrogenation solid/liquid/gas reactions is separated by the separative element, obtain product ethylene with
Hydrogen more than needed, the hydrogen more than needed sends into the hydrogenation reaction unit；
D. the slurries in the hydrogenation reaction unit are drawn, by the isolated solid-phase material of the vacuum filter unit
And liquid phase material；
E. the solid-phase material is processed through the revolving bed regeneration unit, obtains regenerated catalyst and transport to the hydrogenation
Reaction member；
F. the liquid phase material is processed by the vacuum low-pressure distillation unit, carries out solvent recovery.
Further, when the shell and tube catalyst protection device more than one, multiple shell and tube catalyst are protected
Shield device is used in mode in parallel or series, or is used in turn.
Further, methods described also includes making the process of the protective agent regeneration, i.e.,：When the protective agent fails,
The unstripped gas entrance and the clean gas outlet are closed, the regenerant inlet and regenerative agent outlet is opened, nitrogen is passed through
Air-blowing is swept, as fuel gas fraction ＜ 0.1% in nitrogen using the steam purging 0.5-4h of temperature 120-150 DEG C, most
Purged to dew point≤- 42 DEG C using the gaseous mixture of nitrogen or nitrogen and hydrogen afterwards, close the regenerant inlet and the regeneration
Agent is exported, and opens the unstripped gas entrance and the clean gas outlet, and the protective agent can be reused.
Preferably, unstripped gas acetylene and hydrogen mol ratio are controlled into 1:1.Mixing boosting after the unstripped gas dew point≤-
42℃.Pressure≤0.22MPa.Temperature≤90 DEG C.Using the attemperating unit by the shell and tube catalyst protection device temperature control
System controls 200～3200h of air speed in 30 DEG C of ＜-1, pressure drop≤100KPa.
Hydrogen and acetylene molar ratio are 2.5-9.5 in the hydrogenation reaction unit:1.
The atmosphere of the revolving bed regeneration unit is hydrogen and nitrogen, and its mol ratio is 1:3-6.The revolving bed regeneration is single
Temperature range in unit is 20-750 DEG C.
Reaction mass includes catalyst and catalyst diluent in the reaction member.
Described catalyst diluent includes perlite particle, alumina particle, silicon oxide particle, molecular sieve and ceramics
One or more in grain.The catalyst diluent particle diameter is the 80%-120% of the catalyst average grain diameter.It is described to urge
Agent diluent is 0.1-10 with the mass ratio of the catalyst:1.
Specifically, the protective agent active component includes Ag, Cu, Zn, Co, Ni, Fe, Mn of oxidation state and/or metallic state.
The carrier includes silica, aluminum oxide, ceramics, diatomite and molecular sieve.
The method and system of the producing ethylene with acetylene hydrogenation that the present invention is provided, solve fixed bed high purity acetylene Hydrogenation ethene
Temperature runaway phenomenon, reaction heat move that heat is difficult and bed pressure drop is big, the problem that slurry reactor pressure is low, production capacity is little and green oil
Accumulation, the problem for affecting catalyst activity.Existing acetylene purification craft precision is avoided simultaneously not high, be hydrogenated with noble metal catalyst
Easy in inactivation, and high hydrogen alkynes is than defect that unstripped gas compresses.
The present invention is using acetylene and hydrogen 1:1 mixing compression, greatly reduces gaseous mixture volume flow, reduces compressor
Take up an area and invest, reduce compressor operating energy consumption.The present invention is filtered and low-pressure distillation technology using continuous vacuum, it is to avoid green
The defect of oil accumulation, impact catalyst activity, and realize solvent reclamation.
The present invention adopts revolving bed regenerated catalyst technology, realizes catalyst on-line regeneration, reduces technique to catalysis
The requirement in agent life-span so that catalyst activity is high, in stable condition in slurry bed system.
The additional aspect and advantage of the present invention will be set forth in part in the description, and partly will become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Description of the drawings
Fig. 1 is the workflow diagram of the producing ethylene with acetylene hydrogenation of the present invention.
Fig. 2 is the system schematic of the producing ethylene with acetylene hydrogenation of the present invention；Wherein,
2- vacuum filter units, 3- revolving bed regeneration units, 4- vacuum low-pressure distillation units, 5- separative elements, 6- first
Attemperating unit, 7- condensers, 8- gas-liquid condensation separating units, 9- mixing pressure-raising units, 10- catalyst protection units；
11- reclaims injection point, 12- purified gas entrances, 13- serum outlets, 14- lime set entrances, 15- heat transferring mediums and enters
Mouth, the outlet of 16- gas products, the outlet of 17- heat transferring mediums；
21- injection points, the outlet of 22- liquid phase materials, the outlet of 23- solid-phase materials；
31- charging apertures, 32- discharging openings, 33- atmosphere gas entrances, the outlet of 34- atmosphere gas；
41- liquid phase material entrances, 42- solvent outlets, 43- restructuring sub-exports；
51- gas accesses, the outlet of 52- circulating hydrogens, the outlet of 53- ethene, the outlet of 54- byproducts；
71- gas products entrances, 72- condensation gas-liquid mixture outlets；
81 gas vents, 82- condensation gas-liquid mixture entrances, 83- condensate outlets；
91- acetylene entrances, 92- hydrogen inlets, the outlet of 93- mixing pressure-raisings unitary gas；Surge tank, 9b- are reciprocating before 9a-
Surge tank after compressor, 9c-；
101- heat exchangers gas access；10a- unstripped gas heat exchangers, the attemperating units of 10b- second, 10c1/10c2- shell and tubes
Catalyst protection device.
Fig. 3 is the catalyst protection cellular system sketch of the present invention；Wherein,
10- catalyst protection units；10a- unstripped gas heat exchangers, the attemperating units of 10b- second, 10c1/10c2- shell and tubes
Catalyst protection device；
101- heat exchangers gas access, 10a2- heat exchanger gas vents；
Unstripped gas entrance 10c11/10c21, clean gas outlet 10c12/10c22, heat transferring medium entrance 10c13/10c23,
Heat transferring medium outlet 10c14/10c24, regenerant inlet 10c15/10c25 and regenerative agent outlet 10c16/10c26.
Specific embodiment
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in more details, so as to energy
Enough more fully understand the advantage of the solution of the present invention and its various aspects.However, specific embodiments described below and enforcement
Example is only descriptive purpose, rather than limitation of the present invention.
Such as Fig. 2, the present invention proposes a kind of system of producing ethylene with acetylene hydrogenation, the system include hydrogenation reaction unit,
Vacuum filter unit 2, revolving bed regeneration unit 3, vacuum low-pressure distillation unit 4 and separative element 5.
The hydrogenation reaction unit is provided with recovery injection point 11, purified gas entrance 12, serum outlet 13 and gas vent
81；Reaction mass includes catalyst and catalyst diluent in reaction member.Described catalyst diluent includes perlite
One or more in grain, alumina particle, silicon oxide particle, molecular sieve and ceramic particle.The catalyst diluent particle diameter
For the 80%-120% of the catalyst average grain diameter.The catalyst diluent is 0.1- with the mass ratio of the catalyst
10:1。
The vacuum filter unit 2 is provided with injection point 21, liquid phase material outlet 22 and solid-phase material outlet 23, the slurry
Liquid entrance 21 is connected with the serum outlet 13.
The revolving bed regeneration unit 3 is provided with charging aperture 31, discharging opening 32, the outlet of atmosphere gas entrance 33, atmosphere gas
34, the percutaneous band conveyer (not shown) of the charging aperture 31 is connected with solid-phase material outlet 23, the discharging opening 32
It is connected with the recovery injection point 11, the atmosphere gas entrance 33 makes catalyst for being input into atmosphere gas hydrogen and nitrogen
Regeneration, the atmosphere gas outlet 34 is used for the atmosphere gas recycling output of output to the atmosphere gas entrance 33.
The vacuum low-pressure distillation unit 4 is provided with liquid phase material entrance 41, solvent outlet 42 and restructuring sub-export 43, described
Liquid phase material entrance 41 connects the liquid phase material outlet 22, and the solvent outlet 42 is connected with the recovery injection point 11,
Achievable solvent is recycled, and restructuring sub-export 43 is used to export byproduct green oil.
The separative element 5 includes that the outlet 52, ethene of gas access 51, circulating hydrogen exports 53 and byproduct outlet 54,
The gas access 51 connects the gas vent 81, and the circulating hydrogen outlet 52 is connected with the purified gas entrance 12.
Specifically, the hydrogenation reaction unit includes slurry bed system 1, the first attemperating unit 6, the gentle liquid condensing of condenser 7 point
From device 8.
The slurry bed system 1 is provided with the purified gas entrance 12, lime set entrance 14, the recovery injection point 11, heat exchange Jie
Matter entrance 15, the gas products outlet 16, serum outlet 13, heat transferring medium outlet 17.
First attemperating unit 6 is by the heat transferring medium entrance 15, heat transferring medium outlet 16 and the slurry
Bed 1 is connected.
The condenser 7 includes gas products entrance 71 and condensation gas-liquid mixture outlet 72, the gas products entrance
71 are connected with gas products outlet 16.
The gas-liquid condensation separating unit 8 includes condensation gas-liquid mixture entrance 82, condensate outlet 83 and gas vent
81, the condensation gas-liquid mixture entrance 82 is connected with condensation gas-liquid mixture outlet 72, the condensate outlet 83 and institute
State lime set entrance 14 to be connected.
Further, the system also includes mixing pressure-raising unit 9 and catalyst protection unit 10.Wherein,
The mixing pressure-raising unit 9 includes acetylene entrance 91, hydrogen inlet 92 and mixing pressure-raising unitary gas outlet 93.Institute
Stating mixing pressure-raising unit is used to carry out mixing compression to unstripped gas.
Such as Fig. 3, the catalyst protection unit 10 includes unstripped gas heat exchanger 10a, the second attemperating unit 10b and shell and tube
Catalyst protection device 10c1/10c2.
The unstripped gas heat exchanger 10a includes heat exchanger gas access 101 and heat exchanger gas vent 10a2, the heat exchange
Device gas access 101 is connected with mixing pressure-raising unitary gas outlet 93.
The shell and tube catalyst protection device 10c1/10c2 is provided with unstripped gas entrance 10c11/10c21, clean gas outlet
10c12/10c22, heat transferring medium entrance 10c13/10c23, heat transferring medium outlet 10c14/10c24, regenerant inlet 10c15/
10c25 and regenerative agent outlet 10c16/10c26；The unstripped gas entrance 10c11/10c21 and the heat exchanger gas vent
10a2 is connected；The shell and tube catalyst protection device inside includes tubulation, and the protective agent and its load are filled with the tubulation
Body, is heat transferring medium outside the tubulation；The protective agent in the shell and tube catalyst protection device can remove unstripped gas
Impurity, so as to guard catalyst.
The shell and tube catalyst protection device can be for 2 or more than 2.When the shell and tube catalyst protection device
During more than one, multiple shell and tube catalyst protection devices are used in mode in parallel or series, or used in turn.
The protective agent active component includes Ag, Cu, Zn, Co, Ni, Fe, Mn of oxidation state and/or metallic state.The load
Body includes silica, aluminum oxide, ceramics, diatomite and molecular sieve.
Above-mentioned protective agent can regenerate by the following method, i.e.,：When the protective agent fails, close the unstripped gas and enter
Mouthful 10c11/10c21 and clean gas outlet 10c12/10c22, opens the regenerant inlet 10c15/10c25 and described
Regenerative agent exports 10c16/10c26, is passed through nitrogen purging, and temperature is adopted as fuel gas fraction ＜ 0.1% in nitrogen
120-150 DEG C of steam purging 0.5-4h, is finally purged to dew point≤- 42 using the gaseous mixture of nitrogen or nitrogen and hydrogen
DEG C, the regenerant inlet 10c15/10c25 and regenerative agent outlet 10c16/10c26 is closed, open the unstripped gas and enter
The mouth 10c11/10c21 and clean gas outlet 10c12/10c22, the protective agent can be reused.
The second attemperating unit 10b and heat transferring medium entrance 10c13/10c23, heat transferring medium outlet
10c14/10c24 is connected, and the attemperating unit can control protectant temperature using the heat transferring medium.
Specifically, the mixing pressure-raising unit 9 includes front surge tank 9a, reciprocating compressor 9b and rear surge tank 9c orders
Connection, the front surge tank 9a includes the acetylene entrance 91 and the hydrogen inlet 92, and the rear surge tank 9c includes being provided with
Mixing pressure-raising unitary gas outlet 93；Or,
The mixing pressure-raising unit 9 includes that front surge tank, liquid piston compressor, rear surge tank and eliminating water drying device are suitable
Sequence connects (not shown), and the front surge tank includes the acetylene entrance and the hydrogen inlet, now, the mixing pressure-raising
Unitary gas outlet is arranged on the eliminating water drying device (not shown).
The present invention also provides a kind of method of producing ethylene with acetylene hydrogenation, it is characterised in that including step：
A. by acetylene and hydrogen by the mixing pressure-raising unit pressure-raising mixing；
B. the acetylene and hydrogen after mixing pressurization is passed through after the catalyst protection unit removing objectionable impurities, is delivered to
The hydrogenation reaction unit is reacted；
C. the gas-phase product after acetylene hydrogenation solid/liquid/gas reactions is separated by the separative element, obtain product ethylene with
Hydrogen more than needed, the hydrogen more than needed sends into the hydrogenation reaction unit；
D. the slurries in the hydrogenation reaction unit are drawn, by the isolated solid-phase material of the vacuum filter unit
And liquid phase material；
E. the solid-phase material is processed through the revolving bed regeneration unit, obtains regenerated catalyst and transport to the hydrogenation
Reaction member；
F. the liquid phase material is processed by the vacuum low-pressure distillation unit, carries out solvent recovery.
Preferably, unstripped gas acetylene and hydrogen mol ratio are controlled into 1:1.Mixing boosting after the unstripped gas dew point≤-
42℃.Pressure≤0.22MPa.Temperature≤90 DEG C.Using the attemperating unit by the shell and tube catalyst protection device temperature control
System controls 200～3200h of air speed in 30 DEG C of ＜-1, pressure drop≤100KPa.
Hydrogen and acetylene molar ratio are 2.5-9.5 in the hydrogenation reaction unit:1.
The atmosphere of the revolving bed regeneration unit is hydrogen and nitrogen, and its mol ratio is 1:3-6.The revolving bed regeneration is single
Temperature range in unit is 20-750 DEG C.
In present embodiment, the first attemperating unit 6 is heat-conducting oil system, is provided with electric heater, condensing unit and temperature certainly
Control system.Heat-conducting oil system carries out temperature control using conduction oil as heat transferring medium to slurry bed system.
Below with reference to specific embodiment, present invention is described, it should be noted that embodiment is only descriptive
, and the present invention is limited never in any form.
Embodiment 1
The invention provides a kind of method of high purity acetylene Hydrogenation ethene, its technique is：
By catalyst diluent aluminum oxide that particle diameter is the mesh of 100 mesh -150 with acetylene hydrogenation catalyst according to 1:1 quality
Ratio is well mixed, and adds slurry bed system inside to be mixed to form slurries with solvent N- first class pyrrolidones afterwards.
Reaction gas is entered into slurries by slurry bed system internal gas distributor, hydrogen and acetylene molar ratio are 5 in slurry bed system:
1, react under the conditions of 170 DEG C.Reacted gaseous phase materials obtain target product ethene through cryogenic separation, the hydrogen of recovery with
Raw hydrogen mixing returns hydrogenation reaction unit.Liquid phase material Jing rotary drum vacuum filters obtain solid-phase material and liquid phase material.
The percutaneous band of solid-phase material delivers to revolving bed, and revolving bed atmosphere is hydrogen and nitrogen, and its mol ratio is 1:4, preheated, drying, roasting
The catalyst for obtaining regenerating is burnt and reduces, regeneration temperature is 300 DEG C, and catalyst returns slurry bed system and is continuing with.Liquid phase material pump
Enter vacuum low-pressure destilling tower, pressure 5KPa (A) collects the cut (N- first class pyrrolidones) that boiling range is 130 DEG C -150 DEG C, reclaims
N- first class pyrrolidones return slurry bed system, heavy constituent is green oil.
Embodiment 2
Using the system of the present invention, the technique of high purity acetylene Hydrogenation ethene of the present invention is：
By catalyst diluent aluminum oxide that particle diameter is the mesh of 100 mesh -150 with acetylene hydrogenation catalyst according to 2:1 quality
Ratio is well mixed, and adds slurry bed system inside to be mixed to form slurries with solvent N- first class pyrrolidones afterwards.Acetylene is pressed with hydrogen
1:1 mol ratio forms gaseous mixture, pressure-raising to 0.18MPa by compressor mixing pressure-raising, and temperature is 60 DEG C, and dew point is -44
℃.Unstripped gas after compression is cooled to 28 DEG C into unstripped gas heat exchanger, through shell and tube catalyst protection device, is purified
Gas；Protective agent bed temperature is 28 DEG C, and protective agent active component is cupric oxide and zinc oxide, and carrier is ceramics；Air speed 1500h-1、
Pressure drop 100KPa.
When shell and tube catalyst protection device 10c1 outlet purified gas sulphur phosphorus arsenic contents are more than 15ppb, close shell and tube and urge
The raw material gas inlet and clean gas outlet of agent protector 10c1, opens the raw material gas inlet of shell and tube catalyst protection device 10c2
And clean gas outlet, shell and tube protector 10c2 comes into operation.Open the regenerative agent import and again of shell and tube catalyst protection device 10c1
Raw agent outlet, is passed through nitrogen purging；As fuel gas fraction ＜ 0.1% in nitrogen, blown using 150 DEG C of vapor of temperature
Sweep 4h；Finally using the purging of nitrogen to dew point≤- 42 DEG C, the regeneration of the shell and tube catalyst protection device 10c1 closed after regeneration
Agent import and regenerative agent are exported, and catalyst protection device 10c1 is standby for shell and tube.
Purified gas enter slurries by slurry bed system internal gas distributor, and hydrogen and acetylene molar ratio are 6 in slurry bed system:1,
React under the conditions of 200 DEG C.Reacted gaseous phase materials obtain target product ethene, hydrogen and the original of recovery through cryogenic separation
Material hydrogen mixing returns hydrogenation reaction unit.Liquid phase material Jing rotary drum vacuum filters obtain solid-phase material and liquid phase material.Gu
The percutaneous band of phase materials delivers to revolving bed, and revolving bed atmosphere is hydrogen and nitrogen, and its mol ratio is 1:4, preheated, drying, roasting
And reduction obtains the catalyst of regeneration, regeneration temperature is 400 DEG C, and catalyst returns slurry bed system and is continuing with.Liquid phase material is pumped into
Vacuum low-pressure destilling tower, pressure 5KPa (A) collects the cut (N- first class pyrrolidones) that boiling range is 130 DEG C -150 DEG C, recovery
N- first class pyrrolidones returns slurry bed system, and heavy constituent is green oil.
Embodiment 3
The technique of high purity acetylene Hydrogenation ethene of the present invention is：
By catalyst diluent perlite particle that particle diameter is the mesh of 100 mesh -150 with acetylene hydrogenation catalyst according to 10:1
Mass ratio is well mixed to form solid-phase material, adds slurry bed system inside to be mixed to form slurry with solvent N- first class pyrrolidones afterwards
Liquid.Acetylene and hydrogen are pressed into 1:1 mol ratio forms gaseous mixture, material pressure after compression by compressor mixing pressure-raising unit
Power is 0.22MPa, and temperature is 70 DEG C, and dew point is -46 DEG C, and the unstripped gas after compression is cooled to 30 DEG C into unstripped gas heat exchanger,
Through shell and tube catalyst protection device, gas is purified, protective agent active component is silver oxide and zinc oxide, and carrier is spherical oxygen
Change aluminium, bed temperature is 30 DEG C, air speed 3200h-1, pressure drop 50KPa.By Valve controlling, multiple shell and tube protectors can be simultaneously
Connection is used.
Purified gas enter slurries by slurry bed system internal gas distributor, and hydrogen and acetylene molar ratio are 9.5 in slurry bed system:
1, react under the conditions of 180 DEG C.Reacted gaseous phase materials obtain target product ethene through cryogenic separation, the hydrogen of recovery with
Raw hydrogen mixing returns hydrogenation reaction unit.Liquid phase material Jing belt vacuum filters obtain solid-phase material and liquid phase material.
The percutaneous band of solid-phase material delivers to revolving bed, and revolving bed atmosphere is hydrogen and nitrogen, and its mol ratio is 1:6, preheated, drying, roasting
The catalyst for obtaining regenerating is burnt and reduces, regeneration temperature is 50 DEG C, and catalyst returns slurry bed system and is continuing with.Liquid phase material is pumped into
Vacuum low-pressure destilling tower, pressure 5KPa (A) collects the cut (N- first class pyrrolidones) that boiling range is 130 DEG C -150 DEG C, recovery
N- first class pyrrolidones returns slurry bed system, and heavy constituent is green oil.
Embodiment 4
The technique of high purity acetylene Hydrogenation ethene of the present invention is：
By catalyst diluent silicon oxide particle, molecular sieve and ceramic mixture and second that particle diameter is the mesh of 100 mesh -150
Alkynes hydrogenation catalyst is according to 0.1:1 mass ratio is well mixed to form solid-phase material, and slurry bed system inside and solvent N- are added afterwards
First class pyrrolidones is mixed to form slurries.Acetylene and hydrogen are pressed into 1:1 mol ratio forms mixing by compressor mixing pressure-raising
Gas, it is 0.15MPa to mix the raw gas pressure after pressure-raising, and temperature is 90 DEG C, and dew point is -43 DEG C.Unstripped gas after compression is entered
Unstripped gas heat exchanger is cooled to 25 DEG C, through tubular type catalyst protection device, is purified gas.Protective agent active component is silver oxide
And zinc oxide, carrier is ball-aluminium oxide, and bed temperature is 25 DEG C, air speed 200h-1, pressure drop 20KPa.It is many by Valve controlling
Individual shell and tube protector can be used in series, that is, the unstripped gas after compressing sequentially passes through two or more shell and tube protections
Device removal of impurities.
Purification enters slurries by slurry bed system internal gas distributor, and hydrogen and acetylene molar ratio are 2.5 in slurry bed system:1,
React under the conditions of 160 DEG C.Reacted gaseous phase materials obtain target product ethene, hydrogen and the original of recovery through cryogenic separation
Material hydrogen mixing returns hydrogenation reaction unit.Liquid phase material Jing belt vacuum filters obtain solid-phase material and liquid phase material.Gu
The percutaneous band of phase materials delivers to revolving bed, and revolving bed atmosphere is hydrogen and nitrogen, and its mol ratio is 1:3, preheated, drying, roasting
And reduction obtains the catalyst of regeneration, regeneration temperature is 700 DEG C, and catalyst returns slurry bed system and is continuing with.Liquid phase material is pumped into
Vacuum low-pressure destilling tower, pressure 5KPa (A) collects the cut (N- first class pyrrolidones) that boiling range is 130 DEG C -150 DEG C, recovery
N- first class pyrrolidones returns slurry bed system, and heavy constituent is green oil.
Embodiment 5
Producing ethylene with acetylene hydrogenation reaction is carried out using the system of the present invention, except shell and tube catalyst protection device does not come into operation
Outward, remaining condition is consistent with embodiment 2.
Embodiment 6
Producing ethylene with acetylene hydrogenation reaction is carried out using the system of the present invention, except shell and tube catalyst protection device does not come into operation
Outward, remaining condition is consistent with embodiment 3.
Waste gas content in the purified gas of each embodiment and catalyst life are analyzed, it is as a result as follows：
Table 1
Finally it should be noted that：Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and and
The non-restriction to embodiment.For those of ordinary skill in the field, can also do on the basis of the above description
Go out the change or variation of other multi-forms.There is no need to be exhaustive to all of embodiment.And thus drawn
Obvious change that Shen goes out or among changing still in protection scope of the present invention.
Claims (9)
1. a kind of system of producing ethylene with acetylene hydrogenation, the system includes hydrogenation reaction unit, vacuum filter unit, revolving bed again
Raw unit, vacuum low-pressure distillation unit, separative element, mixing pressure-raising unit and catalyst protection unit；Wherein,
The hydrogenation reaction unit is provided with recovery injection point, purified gas entrance, serum outlet and gas vent；
The vacuum filter unit is provided with injection point, liquid phase material outlet and solid-phase material outlet, the injection point and institute
State serum outlet to be connected；
The revolving bed regeneration unit is provided with charging aperture, discharging opening, atmosphere gas entrance, atmosphere gas outlet, the charging aperture
It is connected with solid-phase material outlet, the discharging opening is connected with the recovery injection point, and the atmosphere gas entrance is used for
Input atmosphere gas hydrogen and nitrogen regenerate catalyst, and the atmosphere gas are exported for the atmosphere gas of output to be recycled
Export to the atmosphere gas entrance；
The vacuum low-pressure distillation unit is provided with liquid phase material entrance, solvent outlet and restructuring sub-export, and the liquid phase material enters
The mouth connection liquid phase material outlet, the solvent outlet is connected with the recovery injection point；
The separative element includes that gas access and circulating hydrogen are exported, and the gas access connects the gas vent, described
Circulating hydrogen outlet is connected with the purified gas entrance；
The mixing pressure-raising unit includes acetylene entrance, hydrogen inlet and the unitary gas outlet of mixing pressure-raising；
The catalyst protection unit includes heat exchanger gas access and clean gas outlet, the heat exchanger gas access and described
The unitary gas outlet of mixing pressure-raising is connected；The catalyst protection unit includes shell and tube catalyst protection device, the shell and tube
Protective agent is filled with catalyst protection device, the protective agent is used to remove the impurity in thick acetylene gas.
2. system according to claim 1, it is characterised in that the hydrogenation reaction unit includes slurry bed system, the first temperature control
The gentle liquid condensing separating device of device, condenser；Wherein,
The slurry bed system is provided with the purified gas entrance, lime set entrance, the recovery injection point, heat transferring medium entrance, gas
Products export, the serum outlet, heat transferring medium outlet；
First attemperating unit is connected by the heat transferring medium entrance, heat transferring medium outlet with the slurry bed system；
The condenser includes gas products entrance and condensation gas-liquid mixture outlet, the gas products entrance and the gas
Products export is connected；
The gas-liquid condensation separating unit includes condensation gas-liquid mixture entrance, condensate outlet and the gas vent, described
Condensation gas-liquid mixture entrance is connected with the condensation gas-liquid mixture outlet, the condensate outlet and the lime set entrance phase
Even.
3. system according to claim 1 and 2, it is characterised in that
The mixing pressure-raising unit is linked in sequence including front surge tank, reciprocating compressor and rear surge tank, the front surge tank
Including the acetylene entrance and the hydrogen inlet, the rear surge tank includes being provided with the mixing pressure-raising unitary gas outlet.
4. system according to claim 1, it is characterised in that the shell and tube catalyst protection device be 2 or 2 with
On.
5. a kind of method of producing ethylene with acetylene hydrogenation, it is characterised in that including step：
A. by acetylene and hydrogen by the mixing pressure-raising unit pressure-raising mixing；
B. the acetylene and hydrogen after mixing pressurization is passed through after the catalyst protection unit removing objectionable impurities, is delivered to described
Hydrogenation reaction unit is reacted；
C. the gas-phase product after acetylene hydrogenation solid/liquid/gas reactions is separated by the separative element, obtains product ethylene and have more than needed
Hydrogen, the hydrogen more than needed sends into the hydrogenation reaction unit；
D. the slurries in the hydrogenation reaction unit are drawn, by the isolated solid-phase material of the vacuum filter unit and liquid
Phase materials；
E. the solid-phase material is processed through the revolving bed regeneration unit, obtains regenerated catalyst and transport to the hydrogenation reaction
Unit；
F. the liquid phase material is processed by the vacuum low-pressure distillation unit, carries out solvent recovery.
6. method according to claim 5, it is characterised in that
When the shell and tube catalyst protection device more than one, by multiple shell and tube catalyst protection devices with parallel or string
Connection mode is used.
7. the method according to claim 5 or 6, it is characterised in that
Unstripped gas acetylene and hydrogen mol ratio are controlled into 1:1.
8. the method according to claim 5 or 6, it is characterised in that
Reaction mass includes catalyst and catalyst diluent in the hydrogenation reaction unit.
9. the method according to claim 5 or 6, it is characterised in that
The protective agent active component includes Ag, Cu, Zn, Co, Ni, Fe, Mn of oxidation state and/or metallic state.
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| CN107335441A (en) * | 2017-06-08 | 2017-11-10 | 北京华福工程有限公司 | A kind of Ni Zn Co metal composite catalysts and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107335441A (en) * | 2017-06-08 | 2017-11-10 | 北京华福工程有限公司 | A kind of Ni Zn Co metal composite catalysts and preparation method thereof |
| CN107335441B (en) * | 2017-06-08 | 2020-06-19 | 北京华福工程有限公司 | Ni-Zn-Co metal composite catalyst and preparation method thereof |
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