CN106928003B - A kind of two back end hydrogenation technique of carbon removes alkynes method - Google Patents
A kind of two back end hydrogenation technique of carbon removes alkynes method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/745—Iron
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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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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A kind of two back end hydrogenation technique of carbon removes alkynes method, and hydrogenation catalyst is Fe-Cu selective hydrogenation catalyst, and carrier is high-temperature inorganic oxide, and in terms of catalyst quality 100%, catalyst contains Fe 2~12%, contains Cu 0.05~0.3%.Hydrogenating materials form (volume ratio): acetylene 0.98~2.2%, ethane 11.2~30.3%, ethylene 65.0~85.0%.Reaction condition: 40~100 DEG C of adiabatic reactor reactor inlet temperature, 1.5~2.5MPa of pressure, 2000~10000h of gas space velocity‑1.The specific surface of catalyst is 10~200m20.2~0.63ml/g of/g, Kong Rongwei, wherein Fe is to be loaded with by impregnation method on carrier.Alkynes method is removed using the present invention, catalyst reaction activity is moderate, and operating flexibility is good, and ethylene selectivity is good, and " green oil " production quantity is far below noble metal catalyst.
Description
Technical field
The present invention relates to a kind of two back end hydrogenations of carbon to add except alkynes method, especially a kind of Fe-Cu catalyst and its after carbon two
The method of acetylene hydrogenation in hydrogen technique.
Background technique
Polymer grade ethylene production is the faucet of petrochemical industry, and polymer grade ethylene and propylene are the most bases of downstream polymerisation device
This raw material.Wherein the selection of acetylene adds hydrogen to have extremely important influence to ethylene processing industry, in addition to guaranteeing going out for hydrogenator
Mouth acetylene content is up to standard outer, and the selectivity of catalyst is excellent, can make the generation ethane that ethylene is as few as possible, to the entire work of raising
It is significant to improve device economic benefit for the yield of ethene of skill process.
Cracking C-2-fraction contains the acetylene that molar fraction is 0.5%~2.5%, when producing polyethylene, in ethylene
A small amount of acetylene can reduce the activity of polymerization catalyst, and make the deterioration in physical properties of polymer, so must be by the second in ethylene
Alkynes content drops to certain limit, could be as the monomer of synthetic high polymer.Therefore acetylene separation and conversion are ethylene unit processes
In important one of process.
Catalysis selective hydrogenation includes being divided into front-end hydrogenation and back end hydrogenation in ethylene unit, and ethylene front-end hydrogenation and back end hydrogenation refer to second
For alkynes hydrogenator for domethanizing column position, it is before front-end hydrogenation that hydrogenator, which is located at domethanizing column, adds hydrogen anti-
It is back end hydrogenation after answering device to be located at domethanizing column.The advantages of back end hydrogenation is sequence separation process, technique is hydrogenation process control
Means are more, are not easy temperature runaway, easy to operate, but the disadvantage is that the easy coking of catalyst, the regeneration of catalyst are more frequent.The reason is that
In hydrogenation process, since the amount of allocating of hydrogen is few, be easy to happen acetylene adds hydrogen dimerization reaction, generates 1,3-butadiene, goes forward side by side
One step generates the wider oligomer of molecular weight, is commonly called as " green oil ".Green oil is adsorbed on catalyst surface, and is further formed coking,
Block catalyst duct, makes catalyst activity and selectivity decline.
Two back end hydrogenation of carbon mainly uses two sections or three sections of reactor tandem process, the dress that air speed is lower or alkynes content is low at present
It sets, can be connected using two reactor.Commercial plant at present, mainly based on three sections of reactor tandem process.
Back end hydrogenation material generally forms are as follows: 1.0~2.2% (v) acetylene, 65~85% ethylene, remaining is ethane, hydrogen
Gas after metering by being incorporated.
The reaction is exothermic reaction, but temperature rise is relatively low, and according to air speed size, single reactor maximum temperature rise is from 30~60
It DEG C differs, so using adiabatic reactor substantially.
To two reactor, first segment reactor requires the acetylene of 70% or more conversion, and second segment reactor will be remaining
Acetylene is converted to its content less than 1 μ L/L.
Or acetylene content higher device higher to air speed generally uses three sections of reactor process, first segment conversion 50%
Left and right, remaining the two sections remaining acetylene of conversion, three sections of reactor outlet acetylene contents are less than 1 μ L/L.
The amount of allocating of hydrogen is related with acetylene content and using technique.To three sections of reactor process, general first segment reaction
Device hydrogen/acetylene is 0.8~1.2, and second segment reactor hydrogen/acetylene is 1~1.5, and third section reactor hydrogen/acetylene is
1.5~3.
To two reactor technique, general first segment reactor hydrogen/acetylene is 1~1.5, second segment reactor hydrogen/
Acetylene is 2~4.
The reaction mechanism is as follows for this:
Main reaction
C2H2+H2→C2H4△ H=-175.7kJ/mol (1)
Side reaction
C2H4+H2→C2H6△ H=-138.1kJ/mol (2)
C2H2+2H2→C2H6 (3)
2C2H2+H2→C4H6 (4)
C2H2+nC2H2+H2→C2n+2H2n+4 (5)
In these are answered, reaction (1) is acetylene hydrogenation, and reaction (2) and (3) is ethylene hydrogenation.Reaction (4) is that acetylene adds
Hydrogen dimerization has important contribution to green oil is generated, and reaction (5) is to generate the General reactions formula of green oil.
In these reactions, only reaction (1) is desirable to the reaction occurred, remaining is undesirable reaction.
US5856262 is reported using potassium hydroxide (or hydroxide of barium, strontium, rubidium etc.) modified silica as carrier,
The method for preparing low in acidity palladium catalyst, in air speed 3000h-1, 35 DEG C of inlet temperature, entrance acetylene molar fraction 0.71%, hydrogen
Under conditions of alkynes molar ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity is up to 56%.Patent
Using aluminium oxide as carrier, addition co-catalyst silver and palladium act on US4404124, are prepared for the C2 hydrogenation catalysis of function admirable
Agent.The catalyst, which has, reduces ethane production quantity, inhibits the acetylene being adsorbed on catalyst surface to carry out partial hydrogenation dimerization anti-
It answers, 1,3-butadiene is inhibited to generate, reduce the characteristics of green oil generates, improves ethylene selectivity, reduce oxygenatedchemicals production quantity,
It is applied widely in ethylene industry.However, above-mentioned catalyst is using prepared by infusion process, by the limit of preparation method
System, metal dispersity is only 30% or so, and there is also many deficiencies for catalyst performance, still there is further improved necessity.
Traditional Pd-Ag bimetallic selective hydrogenation catalyst is prepared using aqueous solution infusion process.Using sub-dip method
When, a kind of group of branch it is more be enriched in carrier surface, and another component is enriched in outer surface, only part metals atom phase
Mutually infiltration, forms alloy structure.Meanwhile using total immersion method, due to two metal ion species presoma and carrier it is mutual
Effect difference and surface tension and solvation, are hardly formed the uniform load of two kinds of components, also can only partially form alloy
Structure.It is often selectively preferable in initial reaction stage when this catalyst is applied to C 2 fraction selective hydrogenation, with runing time
Extend, selectivity constantly decline generally runs 3~6 months and just needs to regenerate, economic loss is larger.
CN201110086174.0 on carrier by adsorbing specific high-molecular compound, in carrier surface certain thickness
Macromolecule wrapped layer is formed, with compound and high molecular weight reactive with functional base, with can be complexed with active component
Function base, complex reaction is occurred on carrier surface function base by active component, guarantees active component orderly and height point
It dissipates.Using the patented method, the specific high-molecular compound of carrier adsorption carries out chemistry by the hydroxyl and macromolecule of aluminium oxide
Absorption, the amount of carrier adsorption high-molecular compound are limited the hydroxyl quantity by aluminium oxide；By the macromolecule of functionalization
Not strong with the complexing of Pd, activity component load quantity does not reach requirement sometimes, and residual fraction active component is gone back in maceration extract, is made
It is improved at catalyst cost；Preparing C2 hydrogenation catalyst using this method, there is also the disadvantages of process flow complexity.
CN2005800220708.2 discloses the selection hydrogenation catalyst of acetylene and alkadienes in a kind of light olefin raw material
Agent, the catalyst is by being selected from the first component of copper, gold, silver and selecting second group of grouping of nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium
At in addition catalyst further includes at least one inorganic salts and oxide selected from zirconium, lanthanide series and alkaline earth metal compound.It urges
Fluorite structure is formed after agent calcining, use or regeneration.Catalyst oxide total content 0.01~50%, preferably maturing temperature
700~850 DEG C.By adding the third oxide, modified aluminas or silica support, help to increase catalyst choice
With activity, the selectivity after regeneration.The technology is still with copper, gold, silver, palladium etc. for active component, nickel, platinum, palladium, iron, cobalt,
Ruthenium, rhodium etc., by the oxide modifying to carrier, improve the regenerability of catalyst as component is helped.
CN102218323A discloses a kind of hydrogenation catalyst of unsaturated hydrocarbons, the nickel oxide that active component is 5~15%
With the mixture of 1~10% other metal oxides, other metal oxides can be in molybdenum oxide, cobalt oxide and iron oxide
One or several kinds, additionally include 1~10% auxiliary agent.The inventive technique is mainly used for second in coal-to-oil industry tail gas
The hydro-conversions such as alkene, propylene, butylene are saturated hydrocarbons, have good deep hydrogenation ability.The technology be mainly used for rich in CO and
The complete plus hydrogen of ethylene, propylene, butylene etc., is not suitable for alkynes, the selection of alkadienes adds hydrogen in the various industrial tail gas of hydrogen.
ZL201080011940.0 discloses between a kind of ordered cobalt-aluminium and iron-aluminium compound as acetylene hydrogenation catalyst,
The intermetallic compound is selected from by CoAl, CoAl3、Co2Al5、Co2Al9、o-Co4Al13、h-Co4Al13、m-Co4Al13、
FeAl、FeAl2、Fe3Al、Fe2Al5、Fe4Al13The group of composition.Wherein preferred Fe4Al13And o-Co4Al13.Change between the metal
Object is closed to be prepared using the heat melting method in solid state chemistry.Catalyst hydrogenation performance test is carried out in quartz tube furnace, instead
Temperature 473K is answered, after stablizing reaction 20h, o-Co4Al13Catalyst conversion of alkyne reaches 62%, and ethylene selectivity reaches 71%,
Fe4Al13Conversion of alkyne reaches 40% on catalyst, and ethylene selectivity reaches 75%.The technology is to prepare under the high temperature conditions
Intermetallic compound, for the selective hydrogenation of acetylene, conversion of alkyne is low, and reaction temperature is high, is unfavorable for industrial applications.And
And catalyst is prepared using heat melting method, condition is harsh.
In conclusion the selective hydrogenation of low-carbon alkynes and alkadienes, mainly uses noble metal catalyst, for non-at present
Extensive work is carried out in the research and development of noble metal catalyst, but still has far distance apart from industrial applications.In order to solve this
Problem, the present invention provide a kind of novel Fe-Cu hydrogenation catalyst and preparation method thereof.
Summary of the invention
The purpose of the present invention is to provide a kind of two back end hydrogenations of carbon to remove alkynes method.Particularly relate to a kind of Fe-Cu selection plus hydrogen
Catalyst goes out selective hydrogenation of acetylene contained in object that will come from deethanizer overhead stream, is fully converted to ethylene, while second
Alkene does not lose.
Two back end hydrogenation technique of carbon of the present invention removes alkynes method, and using Fe-Cu selective hydrogenation catalyst, carrier is resistance to
High temperature inorganic oxide, active component at least contain Fe, Cu, and in terms of catalyst quality 100%, catalyst contains Fe 2~12%,
Preferred content is 4~10%, contains Cu 0.05~0.3%, and preferred content is 0.08~0.2%；The specific surface of catalyst be 10~
200m2/ g, preferably 30~100m2/ g, Kong Rongwei 0.2~0.63ml/g, preferably 0.35~0.49ml/g；Wherein Fe is to pass through leaching
Stain mode is loaded on carrier, is roasted through 250 DEG C~600 DEG C, then is made with 200~400 DEG C of hydrogen atmosphere reduction；Catalyst
Middle Fe is mainly with α-Fe2O3Form exists；Selective hydrogenation reaction condition: 40~100 DEG C of reactor inlet temperature, reaction pressure 1.5
~2.5MPa, 2000~10000h of gas volume air speed-1, H2/C2H2Volume ratio is 1~20.Preferred hydroconversion condition are as follows: reaction
45~55 DEG C of device inlet temperature, 1.8~2.2MPa of reaction pressure, 5000~8000h of gas volume air speed-1, H2/C2H2Volume ratio
It is 1.2~5.
Of the present invention to remove alkynes method, used hydrogenation catalyst, carrier is high-temperature inorganic oxide, of the invention
Key problem in technology is in catalyst containing Fe, and have passed through roasting and reduction process, to carrier and has no special requirements, such as can be
One or more of aluminium oxide, silica, zirconium oxide, magnesia etc..But most common is also most preferably aluminium oxide or oxygen
Change aluminium system carrier, alumina series carrier refers to the complex carrier of aluminium oxide Yu other oxides, and wherein aluminium oxide accounts for complex carrier
50% or more of quality, such as can be the compound of aluminium oxide and silica, zirconium oxide, magnesia oxide, preferably oxygen
Change aluminium-zirconia composite carrier, wherein alumina content is 60% or more.Aluminium oxide can be θ, α, γ type or its a variety of crystal form
Mixture, preferably α-Al2O3Or-the Al containing α2O3Mixing crystal form aluminium oxide.
The present invention remove alkynes method, used Fe-Cu selective hydrogenation catalyst the preparation method comprises the following steps:
Catalyst is aged respectively by preparation Fe predecessor aqueous solution, Cu predecessor aqueous solution, difference impregnated carrier, is dry
Dry, roasting or with its mixed solution impregnated carrier, rear ageing, dry, roasting, finally reduction obtains.Maturing temperature is preferably 250
DEG C~600 DEG C；It is restored at 260~330 DEG C.
Preferred condition in preparation method of the present invention are as follows:
30~60 DEG C of dipping temperature, 10~60min of load time, maceration extract pH value 1.5~5.0, Aging Temperature 30~60
DEG C, 30~120min of digestion time, 300 DEG C~400 DEG C of maturing temperature, 240~300min of calcining time.
Dry in the present invention is preferably that temperature programming is dry, drying temperature program setting are as follows:
Roasting is activation process, preferably temperature-programmed calcination, maturing temperature program setting in the present invention are as follows:
Heretofore described catalyst can spray using incipient impregnation, excessive dipping, surface, vacuum impregnation and repeatedly
Any one impregnation method preparation in infusion process.
Specific step is as follows:
(1) carrier is weighed after measuring carrier water absorption rate.
(2) the Fe predecessor (recommending soluble nitrate, chloride or sulfate) accurately weighed by load capacity, according to load
Body water absorption rate and dipping method prepare dipping solution, and adjust maceration extract pH value 1.5~5.0 as required, and solution is heated to
30~60 DEG C spare.
(3) using incipient impregnation or when spraying method, weighed carrier can be put into rotary drum, adjusts rotary drum revolving speed
25~30 turns/min, it is totally turned over carrier, prepared 30~60 DEG C of maceration extract is poured into or sprayed with given pace
It is spread across on carrier, loads 5~10min.
When using excessive infusion process, weighed carrier is placed in container, 30~60 DEG C of dipping of preparation is then added
Solution, the visibly moved device of Quick shaking, discharges rapidly the heat released in adsorption process, and makes active component uniform load to carrier
On, standing 5~10min balances active component competitive Adsorption in surface active composition and solution.
When using vacuum impregnation technology, weighed carrier is placed in cyclonic evaporator, is vacuumized, is added 30~60 DEG C
Maceration extract impregnates 5~10min, and heating water bath to carrier surface moisture is completely dried.
(4) impregnated catalyst moves into container, and catalyst aging 30~120min is carried out at 25~60 DEG C.
(5) solution extra after dipping is filtered out, is then dried in an oven using the method for temperature programming, it is dry
Temperature program(me):
(6) dried catalyst is roasted using temperature programming method, roasts temperature program:
Catalyst Cu component is loaded using above-mentioned same steps, and 250~600 DEG C of maturing temperature, preferably 300~
400 DEG C, two kinds of components can also be configured to mixed solution, disposably impregnate according to above-mentioned steps to carrier surface.
Catalyst of the invention is before use, the catalyst after roasting is restored with hydrogen-containing gas, H2Content is preferably
10~50%, reduction temperature is preferably 200~400 DEG C, 100~500h of volume space velocity-1, restore 0.1~0.8MPa of pressure；Recommend
Condition be using N2+H2Gaseous mixture is restored for 260~330 DEG C under the conditions of micro-positive pressure, and the recovery time is preferably 240~
360min, the best 200~400h of volume space velocity-1, reduction pressure is preferably 0.1~0.5MPa.The process is usually in selection plus hydrogen
It is carried out before reaction, carries out carrying out outside i.e. selective hydrogenation reaction device preferably outside device.
The active component of catalyst is mainly Fe in the present invention, can be non-precious metal catalyst, it might even be possible to without cobalt,
Nickel, molybdenum, tungsten, greatly reduce cost, and catalyst cost is far below precious metals pd catalyst.
Activity composition, content and carrier related, the activated mistake of the activation temperature of catalyst and catalyst in the present invention
α-Fe is formd after journey2O3The Fe of form, and it is relatively stable, and activation temperature can not be excessively high；On the other hand, activation degree is again
It determines the reducing condition of catalyst, provides in the catalyst used in the present invention still with α-Fe2O3The Fe of form be mainly at
Point, the effect that will affect catalyst instead is excessively restored, selectivity, easy coking are influenced.
Fe element can be with Fe, Fe in catalyst of the invention2O3、Fe3O4, the variforms such as FeO exist, but wherein α-
Fe2O3The Fe of form is higher than the content of other forms, preferably accounts for 50% or more of Fe gross mass.
Recommend to add Cu in iron-containing activity composition in the present invention, is more advantageous to reduction activation temperature, is conducive to urge
Agent activates the formation of phase, dispersion, improves catalyst choice.The addition of Cu simultaneously facilitates the absorption of alkynes, activation, favorably
In the activity for improving catalyst.
Two back end hydrogenation of carbon of the present invention removes alkynes method, refers in two sections or three sections of series connection adiabatic reactors, will
Deethanizer overhead stream goes out contained acetylene in material and carries out selective hydrogenation, is converted into ethylene.
Reactor refers to adiabatic reactor reactor in the present invention.It can be single hop or multi-stage series, preferably 2~3 sections series connection
It uses.When adiabatic reactor reactor reaction bed number is three sections, 40~50 DEG C of first segment reactor inlet temperature, hydrogen/acetylene body
Product is than being 0.8~1.2, and 5~55 DEG C of second segment reactor inlet temperature, hydrogen/acetylene volume ratio is 1~1.5, three sections of reactors
50~60 DEG C of inlet temperature, hydrogen/acetylene volume ratio is 1.5~3.0.
When reactor is two sections of adiabatic reactor reactor series connection in the present invention, 40~50 DEG C of first segment reactor inlet temperature,
Hydrogen/acetylene volume ratio is 1~1.5, and 50~60 DEG C of second segment reactor inlet temperature, hydrogen/acetylene volume ratio is 2~4.
In the present invention, hydrogenation material is selected to go out object, raw material group from deethanizer overhead stream in two back end hydrogenation technique of carbon
It is best are as follows: acetylene 0.98~2.2%, ethane 11.2~30.3%, ethylene 65.0~85.0% at volume basis.
Alkynes method is removed using the present invention, catalyst reaction activity is moderate, and operating flexibility is good, and ethylene selectivity is good, and green oil is raw
Noble metal catalyst is far below at amount.
Detailed description of the invention
Fig. 1 is to select hydrogenation technique flow chart using the carbon two of sequence separation process.1-oil scrubber；2-water scrubbers；3—
Caustic wash tower；4-driers；5-domethanizing columns；6-dethanizers；7-Acetylene converters；8-heat exchangers.
Fig. 2 is XRD spectra after the catalyst reduction of the embodiment of the present invention 3 (deducting vector background).
Fig. 3 is XRD spectra (deducting vector background) after 2 high-temperature roasting catalyst reduction of comparative example.
Fig. 4 is XRD spectra after the catalyst high temperature reduction of comparative example 5 (deducting vector background).
XRD determining condition:
German Brooker company D8ADVANCE X diffractometer
Tube voltage: 40kV electric current 40mA
Scanning: 0.02 ° of step-length, 25 DEG C of temperature of 4 °~120 ° of frequency 0.5s scanning range
1 wavelength of Cu K α, abscissa is 2 θ of the angle of diffraction in figure, and ordinate is diffracted intensity
Symbol description in Fig. 2:
▲ it is α-Fe2O3, ◆ it is Cu, ■ Fe3O4。
Symbol description in Fig. 3:
▲ it is α-Fe2O3, ● it is CuFeO3, ■ Fe3O4。
Symbol description in Fig. 4:
★ is α-Fe, ■ Fe3O4, ◆ it is Cu.
α-Fe in Fig. 22O3Relative amount 11.20%.
Fe forms CuFe in conjunction with second of component in Fig. 32O4, help component and active component to be sintered, destroy active component
Distribution and structure.
α-Fe is free of in Fig. 42O3Phase, Fe mainly in the form of simple substance α-Fe occur, relative amount 8.92%, third component with
Simple substance Cu form occurs.
Specific embodiment
Analysis test method:
Specific surface: GB/T-5816
Kong Rong: GB/T-5816
Different crystal forms Fe oxide content: XRD
Catalyst activity component content: GB/T 1537-94
Conversion of alkyne (C)
It is hydrogenated to the selectivity (S) of ethylene
Embodiment 1
Weigh the trifolium-shaped alpha-alumina supports of 4.5 × 4.5mm of Φ.Ferric nitrate is taken, is dissolved by heating in 60ml deionization
In water, pH value 2.5 is adjusted, maceration extract temperature 50 C, incipient impregnation stirs rapidly carrier impregnation 6min in carrier surface, quiet
Only 30min is to adsorption equilibrium, 60 DEG C of ageing 30min, then in an oven according to program:Then it is living catalyst to be carried out using programmed temperature method
Change, activation procedure:
Copper nitrate is weighed, is impregnated according to above-mentioned preparation step.Carrier and catalyst physical index, catalyst components content are shown in Table
1。
Catalyst in reduction furnace with+60% nitrogen of 40% hydrogen before use, restored, 300 DEG C of reduction temperature, pressure
0.5MPa, recovery time 4h.Catalyst packing is in fixed-bed reactor.
Using back end hydrogenation technique, process flow chart is as shown in Fig. 1, raw material composition are as follows:
C2H2: 1.6% (Φ), C2H4: 75.3% (Φ), C2H6: 23.1% (Φ).
Reaction condition: two sections of adiabatic reactor reactor tandem reactions, i.e. first stage reactor outlet material enter second stage reactor.
Every section of reactor has independent air distribution system.
Material gas space velocity: 2000h-1, operating pressure: 2.5MPa.First stage reactor H2/C2H2=1.5:1 (molar ratio)；
Second stage reactor H2/C2H2=3:1 (molar ratio).
Appraisal result is as shown in table 2.
Embodiment 2
At 50 DEG C, by NaAlO2Solution and ZrCl4Solution is stirred, and is then neutralized with nitric acid solution, and 10h is stirred, coprecipitated
It forms sediment and generates uniform Al-Zr particle.Product is filtered, Na therein is washed with deionized+And Cl-Then matter is added in ion
Measuring concentration is 15% polyvinyl alcohol as pore creating material, kneaded and formed.It is multiple that 130 DEG C of dry 2h, 650 DEG C of roasting 4h obtain Zr-Al
Close carrier.Aluminium oxide and zirconium oxide mass ratio are 4:1 in carrier.
Catalyst is prepared with alumina-zirconia composite carrier.Iron chloride and copper chloride are taken, is dissolved by heating in deionized water
In, pH value 2.0 is adjusted, 80 DEG C of maceration extract temperature, is excessively impregnated on carrier, beaker is shaken and impregnates 10min, by extra maceration extract
It filters out, catalyst is aged 50min in 60 DEG C of water-baths, then in an oven according to program:Activation of catalyst is carried out using programmed temperature method,
Activation procedure: It carries
Body and catalyst physical index, catalyst components content are shown in Table 1.
Catalyst in reduction furnace with+60% nitrogen of 30% hydrogen before use, restored, 260 DEG C of reduction temperature, pressure
0.5MPa, recovery time 4h.Catalyst packing is in fixed-bed reactor.
Using back end hydrogenation technique, process flow chart is as shown in Fig. 1, raw material composition are as follows:
C2H2: 1.4% (Φ), C2H4: 80.0% (Φ), C2H6: 18.6% (Φ).
Reaction condition: two sections of adiabatic reactor reactor tandem reactions, i.e. first stage reactor outlet material enter second stage reactor.
Every section of reactor has independent air distribution system.
Material gas space velocity: 5000h-1, operating pressure: 2.2MPa.First stage reactor H2/C2H2=1.5:1 (molar ratio)；
Second stage reactor H2/C2H2=4:1 (molar ratio).
Appraisal result is as shown in table 2.
Embodiment 3
The ball-type aluminium oxide for weighing Φ 1.5mm prepares catalyst.It takes ferric nitrate to be dissolved in deionized water, adjusts pH value
3.0,40 DEG C of maceration extract temperature, watering can sprays on carrier, and load 10min uploads active component uniformly, then in an oven
According to program: It is urged using programmed temperature method
Agent activation, activation procedure:
Obtain a leaching catalyst.
Using first step same procedure, copper nitrate is taken, is sprayed after dissolution to a leaching catalyst surface, is then dried, roast,
Obtain final catalyst.Drying program:Calcination procedure:Carrier and catalysis
Agent physical index, catalyst components content are shown in Table 1.
Catalyst in reduction furnace with 20% hydrogen before use, restored, 280 DEG C of reduction temperature, pressure 0.5MPa, also
Former time 4h.It is as shown in Fig. 2 to restore rear catalyst XRD analysis.Catalyst packing is in fixed-bed reactor.
Using back end hydrogenation technique, reaction raw materials are as follows:
C2H2: 2.2 (v%) C2H4: 79.3 (v%), C2H6: 18.5 (v%).
Reaction condition: three sections of bed adiabatic reactor reactor tandem process, i.e. first stage reactor outlet material enter second-stage reaction
Device, second stage reactor outlet material enter three sections of reactors, and every section of reactor has independent air distribution system.
Material gas space velocity: 7000h-1, operating pressure: 1.8MPa.First stage reactor H2/C2H2=1:1 (molar ratio)；Two
Section reactor H2/C2H2=1.5:1 (molar ratio)；Three sections of reactor H2/C2H2=3:1 (molar ratio).
Appraisal result is as shown in table 2.
Embodiment 4
The spherical tio2 carrier of weighed Φ 2.0mm is placed in vacuum impregnation plant.Take ferric nitrate be dissolved in from
In sub- water, it is spare to adjust pH value 3.5.Vacuum impregnation plant vacuum pumping pump is opened, until vacuum degree 0.1mmHg, then from feed opening
It is slowly added to prepared maceration extract, 5min is added, and catalyst surface mobile moisture is evaporated at 60 DEG C and is completely disappeared, and is completed
Load, the catalyst that will have been loaded, in an oven according to program:In Muffle furnace according to: A leaching is obtained to urge
Agent.
Copper nitrate is taken, is impregnated according to above-mentioned same procedure, is then dried, roasts, obtains final catalyst.Dry journey
Sequence:Calcination procedure: Obtain final catalyst.Carrier and catalyst
Physical index, catalyst components content are shown in Table 1.
Catalyst is urged before use, being restored in reduction furnace with 15% hydrogen, 300 DEG C of reduction temperature, pressure 0.5MPa,
Recovery time 4h.Catalyst packing is in fixed-bed reactor.
Using back end hydrogenation technique, reaction raw materials are as follows:
C2H2: 2.2 (v%) C2H4: 79.3 (v%), C2H6: 18.5 (v%).
Reaction condition: three sections of bed adiabatic reactor tandem process, i.e. first stage reactor outlet material enter second stage reactor,
Second stage reactor outlet material enters three sections of reactors, and every section of reactor has independent air distribution system.
Material gas space velocity: 10000h-1, operating pressure: 1.5MPa.First stage reactor H2/C2H2=1:1 (molar ratio)；Two
Section reactor H2/C2H2=1.5:1 (molar ratio)；Three sections of reactor H2/C2H2=3:1 (molar ratio).
Appraisal result is as shown in table 2.
Embodiment 5
The alpha-alumina supports for weighing 100ml Φ 4.0mm prepare catalyst using 3 same procedure of embodiment.Activation temperature
400℃.Carrier and catalyst physical index, catalyst components content are shown in Table 1.
Catalyst in reduction furnace with 25% hydrogen before use, restored, 320 DEG C of temperature, pressure 0.5MPa, when reduction
Between 4h.Catalyst packing is in fixed-bed reactor.
Using back end hydrogenation technique, reaction raw materials are as follows:
C2H2: 1.2 (v%) C2H4: 80.3 (v%), C2H6: 18.5 (v%).
Reaction condition: three sections of bed adiabatic reactor tandem process, i.e. first stage reactor outlet material enter second stage reactor,
Second stage reactor outlet material enters three sections of reactors, and every section of reactor has independent air distribution system.
Material gas space velocity: 10000h-1, operating pressure: 1.5MPa.First stage reactor H2/C2H2=1:1 (molar ratio)；Two
Section reactor H2/C2H2=1.5:1 (molar ratio)；Three sections of reactor H2/C2H2=3:1 (molar ratio).
Appraisal result is as shown in table 2.
Embodiment 6
Commercially available boehmite, silica gel, zirconium oxychloride powder and extrusion aid are pressed according to aluminium oxide: silica: zirconium oxide
=8:1:3 ratio is uniformly mixed, then the extruded moulding on banded extruder, and 120 DEG C of dryings, 550 DEG C of roasting 3h, obtain in Muffle furnace
To Zr-Si-Al composite oxide carrier.Catalyst is prepared using 4 same procedure of embodiment.Carrier and catalyst physical index,
Catalyst components content is shown in Table 1.
Catalyst 360 DEG C of temperature, pressure 0.5MPa, activates before use, with+55% nitrogen of 45% hydrogen in reduction furnace
Time 4h.Catalyst packing is in fixed-bed reactor.
Using back end hydrogenation technique, reaction raw materials are as follows:
C2H2: 2.2 (v%) C2H4: 79.3 (v%), C2H6: 18.5 (v%).
Reaction condition: three sections of bed adiabatic reactor tandem process, i.e. first stage reactor outlet material enter second stage reactor,
Second stage reactor outlet material enters three sections of reactors, and every section of reactor has independent air distribution system.
Material gas space velocity: 10000h-1, operating pressure: 1.5MPa.First stage reactor H2/C2H2=1:1 (molar ratio)；Two
Section reactor H2/C2H2=1.5:1 (molar ratio)；Three sections of reactor H2/C2H2=3:1 (molar ratio).
Appraisal result is as shown in table 2.
Comparative example 1
Take Φ 4.0mm alumina support, specific surface 22.3m2/ g, Kong Rongwei 0.31ml/g.Using equi-volume impregnating,
By silver nitrate solution incipient impregnation to carrier on, ageing-drying-roasting obtains a leaching catalyst, then by palladium chloride
Dissolution, incipient impregnation, ageing-drying-roasting obtain final catalyst (petrochemical industry research institute LY-C2-02 hydrogenation catalyst).
Catalyst Pd content is that 0.040%, Ag content is 0.12%.
Catalyst is at 100 DEG C with hydrogen reducing 160min, pressure 0.5MPa, hydrogen gas space velocity 100h-1.Catalyst packing is in exhausted
In hott bed reaction unit.
Using 1 same process of embodiment, reaction condition: air speed 6000h-1, operating pressure: 2.0MPa.
Reaction result is as shown in table 2.
Comparative example 2
Make carrier with Φ 4.0mm aluminium oxide, catalyst, catalyst activation temperature are prepared using the identical method of embodiment 1
850℃.Carrier and catalyst physical index, catalyst components content are shown in Table 1.
Catalyst in reduction furnace with 25% hydrogen before use, restored, 300 DEG C of temperature, pressure 0.5MPa, when activation
Between 4h.Catalyst packing is in insulation bed reaction device.The XRD diffraction spectrogram for restoring rear catalyst is as shown in Figure 3.
Using 1 same process of embodiment.Raw material composition are as follows:
C2H2: 1.4% (Φ), C2H4: 80.0% (Φ), C2H6: 18.6% (Φ).
Reaction condition: air speed 2000h-1, operating pressure: 2.5MPa.
Reaction result is as shown in table 2.
Comparative example 3
The aluminium oxide for weighing Φ 4.0mm makees carrier, prepares catalyst using 1 same procedure of embodiment, lives at 350 DEG C
Change.Carrier and catalyst physical index, catalyst components content are shown in Table 1.
Catalyst in reduction furnace with 45% hydrogen before use, restored, 300 DEG C of temperature, pressure 0.5MPa, when activation
Between 4h.Add hydrogen process shown in attached drawing 1, Catalyst packing is in fixed-bed reactor.
Reaction condition: three sections of bed adiabatic reactor reactor tandem process, i.e. first stage reactor outlet material enter second-stage reaction
Device, second stage reactor outlet material enter three sections of reactors, and every section of reactor has independent air distribution system.
Material gas space velocity: 8000h-1, operating pressure: 1.5MPa.First stage reactor H2/C2H2=1:1 (molar ratio)；Two
Section reactor H2/C2H2=1.5:1 (molar ratio)；Three sections of reactor H2/C2H2=3:1 (molar ratio).
Reaction result is as shown in table 2.
Comparative example 4
1 same catalyst of Example is directly driven after 350 DEG C of activation, is restored without hydrogen.With 1 institute of attached drawing
Show and add hydrogen process, Catalyst packing is in fixed-bed reactor.
Using three sections of series connection adiabatic reactor techniques, raw material forms same as Example 1, reaction condition: air speed 3000h-1,
Operating pressure: 2.0MPa.
Using three sections of series connection adiabatic reactor techniques, raw material forms same as Example 1, reaction condition: air speed 3000h-1,
Operating pressure: 2.0MPa.
Reaction result is as shown in table 2.
Comparative example 5
1 same catalyst of Example is activated at 350 DEG C.
Catalyst is restored in tube furnace, atmosphere be+55% nitrogen of 30% hydrogen, 500 DEG C of temperature, pressure
0.5MPa, activation time 4h.Add hydrogen process shown in attached drawing 1, Catalyst packing is in fixed-bed reactor.It is catalyzed after reduction
The XRD diffraction spectrogram of agent is as shown in Figure 4.
Hydrogenating materials form same as Example 7, two sections of serial hydrogenations, reaction condition: air speed 15000h-1, pressure
2.0MPa。
Reaction result is as shown in table 2.
Carrier and catalyst physical index, catalyst components content are shown in Table 1.
1 carrier of table, catalyst physical property and catalyst components content
Reaction result is as shown in table 2.
2 process conditions of table and catalyst performance
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (17)
1. a kind of two back end hydrogenation technique of carbon removes alkynes method, will go out in two back end hydrogenation ethylene unit of carbon from deethanizer overhead stream
Object enters adiabatic reactor and carries out selection plus hydrogen, to remove acetylene therein, it is characterised in that selects in reactor equipped with Fe-Cu
Hydrogenation catalyst, carrier are high-temperature inorganic oxide, and active component at least contains Fe, Cu, and catalyst contains Fe2~12%, contains
Cu0.05~0.3%；The specific surface of catalyst is 10~200m20.2~0.63mL/g of/g, Kong Rongwei；Wherein Fe is to pass through leaching
Stain mode is loaded on carrier, is roasted through 250 DEG C~600 DEG C, then is made with 200~400 DEG C of hydrogen atmosphere reduction；Catalyst
Middle Fe is mainly with α-Fe2O3Form exists；Selective hydrogenation reaction condition: 40~100 DEG C of reactor inlet temperature, reaction pressure 1.5
~2.5MPa, 2000~10000h of gas volume air speed-1, H2/C2H2Volume ratio is 1~20.
2. according to claim 1 remove alkynes method, it is characterised in that in catalyst, α-Fe2O3The Fe of form will account for the total matter of Fe
50% or more of amount.
3. according to claim 1 remove alkynes method, it is characterised in that the carrier of catalyst is aluminium oxide or aluminium oxide and its
The complex carrier of his oxide, aluminium oxide account for 50% or more of complex carrier quality, other oxides be silica, zirconium oxide,
Magnesia or titanium oxide；Aluminium oxide is θ, α, γ type.
4. according to claim 1 remove alkynes method, it is characterised in that before catalyst is by preparation Fe predecessor aqueous solution, Cu
Drive object aqueous solution, respectively impregnated carrier, be aged respectively, be dry, roasting or to be aged after its mixed solution impregnated carrier, it is dry,
Roasting obtains after finally restoring；Maturing temperature is 250 DEG C~600 DEG C；It is restored at 260~330 DEG C.
5. according to claim 4 remove alkynes method, it is characterised in that: 30~60 DEG C of dipping temperature when catalyst preparation are born
10~60min of time is carried, maceration extract pH value 1.5~5.0,30~60 DEG C of Aging Temperature, 30~120min of digestion time, roasting is warm
250 DEG C~600 DEG C of degree；240~300min of calcining time.
6. according to claim 4 remove alkynes method, it is characterised in that drying condition are as follows:
7. according to claim 4 remove alkynes method, it is characterised in that be roasted to temperature-programmed calcination, maturing temperature program is set
It is set to:
8. according to claim 1 or 4 remove alkynes method, it is characterised in that the impregnation method is incipient impregnation, excess
Dipping, surface spray, vacuum impregnation or repeatedly dipping.
9. according to claim 1 or 4 remove alkynes method, it is characterised in that reduction refers to catalyst before use, with hydrogeneous
Gas restores the catalyst after roasting, H2Content be 10~50%, 200~400 DEG C of reduction temperature, the recovery time 240
~360min, 100~500h of volume space velocity-1, restore 0.1~0.8MPa of pressure.
10. according to claim 1 remove alkynes method, it is characterised in that carry out adding hydrogen using two sections or three sections of adiabatic reactors
Reaction, hydrogen are added by the way of distribution.
11. according to claim 10 remove alkynes method, it is characterised in that when adiabatic reactor reactor is three sections of series connection, one section anti-
Answer 40~50 DEG C of device inlet temperature, hydrogen/acetylene volume ratio is 0.8~1.2,45~55 DEG C of second stage reactor inlet temperature, hydrogen
Gas/acetylene volume ratio is 1~1.5, and three sections 50~60 DEG C of reactor inlet temperature, hydrogen/acetylene volume ratio is 1.5~3.0.
12. according to claim 10 remove alkynes method, it is characterised in that adiabatic reactor reactor is anti-when being two sections of series connection, and first
40~50 DEG C of reactor inlet temperature of section, hydrogen/acetylene volume ratio are 1~1.5, second segment reactor inlet temperature 50~60
DEG C, hydrogen/acetylene volume ratio is 2~4.
13. according to claim 1 remove alkynes method, it is characterised in that select hydrogenation material in two back end hydrogenation technique of carbon,
Going out object from deethanizer overhead stream, raw material is formed with volume basis, are as follows: acetylene 0.98~2.2%, ethane 11.2~
30.3%, ethylene 65.0~85.0%.
14. according to claim 1 remove alkynes method, which is characterized in that catalyst is 4~10% containing Fe, is 0.08 containing Cu
~0.2%；The specific surface of catalyst is 30~100m20.35~0.49mL/g of/g, Kong Rongwei；Hydroconversion condition are as follows: reactor enters
45~55 DEG C of temperature, 1.8~2.2MPa of reaction pressure, 5000~8000h of gas volume air speed of mouth-1, H2/C2H2Volume ratio is 1.2
~5.
15. according to claim 3 remove alkynes method, which is characterized in that the complex carrier of aluminium oxide and other oxides is
Alumina-zirconia composite carrier, aluminium oxide are α-Al2O3。
16. according to claim 5 remove alkynes method, which is characterized in that maturing temperature is 300~400 DEG C.
17. according to claim 9 remove alkynes method, which is characterized in that reducing condition is to use N2+H2Gaseous mixture 260~
It is restored at 330 DEG C, 200~400h of volume space velocity-1, reduction pressure is 0.1~0.5MPa.
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| CN101434508A (en) * | 2008-12-11 | 2009-05-20 | 中国石油天然气股份有限公司 | Acetylene hydrocarbon selective hydrogenation method |
| CN101913975A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 distillate |
| CN102206131A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 fraction |
| CN104383923A (en) * | 2013-07-18 | 2015-03-04 | 中国石油大学(北京) | Gasoline and diesel hydrogenation iron-based catalyst and application thereof |
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| CN101428228A (en) * | 2008-09-11 | 2009-05-13 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and method of producing the same |
| CN101434508A (en) * | 2008-12-11 | 2009-05-20 | 中国石油天然气股份有限公司 | Acetylene hydrocarbon selective hydrogenation method |
| CN101913975A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 distillate |
| CN102206131A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 fraction |
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