CN106928003A - A kind of back end hydrogenation technique of carbon two except alkynes method - Google Patents
A kind of back end hydrogenation technique of carbon two except alkynes method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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
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Abstract
A kind of back end hydrogenation technique of carbon two except alkynes method, hydrogenation catalyst is Fe-Cu selective hydrogenation catalysts, and carrier is high-temperature inorganic oxide, and in terms of catalyst quality 100%, catalyst contains Fe 2~12%, containing Cu 0.05~0.3%.Hydrogenating materials constitute (volume ratio)：Acetylene 0.98~2.2%, ethane 11.2~30.3%, ethene 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 10~200m2/ g, pore volume is 0.2~0.63ml/g, and wherein Fe is loaded with carrier by impregnation method.Alkynes method is removed using the present invention, catalyst reaction activity is moderate, and operating flexibility is good, and ethylene selectivity is good, " green oil " growing amount is far below noble metal catalyst.
Description
Technical field
Add except alkynes method, particularly a kind of Fe-Cu catalyst and its after carbon two the present invention relates to a kind of back end hydrogenation of carbon two
The method of acetylene hydrogenation in hydrogen technique.
Background technology
Polymer grade ethylene production is the tap of petrochemical industry, and polymer grade ethylene and propylene are the most bases of downstream polymerisation device
This raw material.The selection hydrogenation of wherein acetylene has extremely important influence to ethene processing industry, except ensureing going out for hydrogenation reactor
Mouth acetylene content is up to standard outer, and the selectivity of catalyst is excellent, can make the generation ethane that ethene is as few as possible, to improving whole work
The yield of ethene of skill process, improves device economic benefit significant.
Cracking C-2-fraction contains the acetylene that molar fraction is 0.5%~2.5%, when polyethylene is produced, in ethene
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 ethene
Alkynes content drops to certain limit, could be used as the monomer of synthetic high polymer.Therefore acetylene is separated and conversion is ethylene unit flow
In one of important 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 domethanizing column position, hydrogenation reactor was front-end hydrogenation before domethanizing column to alkynes hydrogenation reactor, and hydrogenation is anti-
Device is answered to be located at after domethanizing column as back end hydrogenation.Back end hydrogenation is order separation process, and the advantage of technique is hydrogenation process control
Means are more, are difficult temperature runaway, easy to operate, but have the disadvantage the easy coking of catalyst, and the reproduction ratio of catalyst is more frequent.Its reason be
In hydrogenation process, because the amount of allocating of hydrogen is few, the hydrogenation dimerization reaction of acetylene is susceptible to, generates 1,3-butadiene, gone forward side by side
One step generation molecular weight oligomer wider, is commonly called as " green oil ".Green oil is adsorbed in catalyst surface, and further forms coking,
Obstruction catalyst duct, declines catalyst activity and selectivity.
The current back end hydrogenation of carbon two mainly uses two sections or three sections of reactor tandem process, the dress that air speed is relatively low or alkynes content is low
Put, can be connected using two reactor.Current commercial plant, mainly based on three sections of reactor tandem process.
Back end hydrogenation material is typically constituted：The acetylene of 1.0~2.2% (v), 65~85% ethene, remaining is ethane, hydrogen
Gas is allocated into by after metering.
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
DEG C, so using adiabatic reactor substantially.
To two reactor, the acetylene of first paragraph reactor requirement conversion more than 70%, second segment reactor will be remaining
Acetylene is converted to its content and is less than 1 μ L/L.
Or acetylene content higher device higher to air speed, typically uses three sections of reactor process, first paragraph 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 relevant with acetylene content and using technique.To three sections of reactor process, general first paragraph reaction
Device hydrogen/acetylene is 0.8~1.2, and second segment reactor hydrogen/acetylene is 1~1.5, and the 3rd section of reactor hydrogen/acetylene is
1.5~3.
To two reactor technique, general first paragraph reactor hydrogen/acetylene is 1~1.5, second segment reactor hydrogen/
Acetylene is 2~4.
The reaction mechanism is as follows：
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, there is important contribution to generation green oil, and reaction (5) is the General reactions formula for generating green oil.
In these reactions, the reaction that (1) is desirable to occur only is reacted, remaining is undesirable reaction.
US5856262 is reported with the modified silica of potassium hydroxide (or barium, strontium, rubidium etc. hydroxide) 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 mol ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity is up to 56%.Patent
With aluminum oxide as carrier, addition co-catalyst silver is acted on US4404124 with palladium, is prepared for the C2 hydrogenation catalysis of function admirable
Agent.The catalyst has reduction ethane growing amount, and it is anti-that acetylene of the suppression absorption on catalyst surface carries out partial hydrogenation dimerization
Should, suppress 1,3-butadiene generation, reduce green oil generation, improve ethylene selectivity, reduce oxygenatedchemicals growing amount the characteristics of,
It is applied widely in ethylene industry.However, above-mentioned catalyst is prepared using infusion process, limited by preparation method
System, metal dispersity is only 30% or so, and catalyst performance there is also many deficiencies, still there is further improved necessity.
Traditional Pd-Ag bimetallics selective hydrogenation catalyst is prepared using aqueous impregnation method.Using sub-dip method
When, what a kind of component can be more is 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, because the presoma of two metal ion species is mutual with carrier
Effect is different, and surface tension and solvation, is hardly formed two kinds of uniform loads of component, also can only partly form alloy
Structure.When this catalyst is applied to C 2 fraction selective hydrogenation, often in initial reaction stage selectivity preferably, with run time
Extension, selectivity constantly declines, and typically operation is accomplished by regeneration for 3~6 months, and economic loss is larger.
CN201110086174.0 by adsorbing specific macromolecular compound on carrier, in carrier surface certain thickness
Macromolecule wrapped layer is formed, with the compound and high molecular weight reactive of the functional base of band, being allowed to have can be complexed with active component
Function base, there is complex reaction on carrier surface function base by active component, it is ensured that active component in order and height point
Dissipate.Using the patented method, the specific macromolecular compound of carrier adsorption carries out chemistry by the hydroxyl of aluminum oxide with macromolecule
Absorption, the amount of carrier adsorption macromolecular compound will be limited by the hydroxyl quantity of aluminum oxide；By the macromolecule of functionalization
Complexing with Pd is not strong, and activity component load quantity does not reach requirement sometimes, and residual fraction active component is gone back in maceration extract, makes
Improved into catalyst cost；C2 hydrogenation catalyst is prepared using the method and also haves the shortcomings that technological process is complicated.
CN2005800220708.2 discloses the selection hydrogenation catalyst of acetylene and alkadienes in a kind of light olefin raw material
Agent, the catalyst by selected from copper, the first component of gold, silver and selection nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium second component group
Into catalyst also includes at least one inorganic salts and oxide selected from zirconium, lanthanide series and alkaline earth metal compound in addition.Urge
Agent calcining, using or regeneration after form fluorite structure.Catalyst oxide total content 0.01~50%, preferably sintering temperature
700~850 DEG C.By adding the third oxide, modified aluminas or silica support, help to increase catalyst choice
With active, the selectivity after regeneration.The technology be still with copper, gold, silver, palladium etc. as 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, and active component is 5~15% nickel oxide
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, additionally include 1~10% auxiliary agent.The inventive technique is mainly used in second in coal-to-oil industry tail gas
The hydro-conversions such as alkene, propylene, butylene are saturated hydrocarbons, with good deep hydrogenation ability.The technology be mainly used in rich in CO and
The full hydrogenation of ethene, propylene, butylene etc. in the various industrial tail gas of hydrogen, is not suitable for the selection hydrogenation of alkynes, alkadienes.
ZL201080011940.0 discloses between a kind of ordered cobalt-aluminium and iron-aluminium compound as acetylene hydrogenation catalyst,
Described 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 described metal
Compound is 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 stabilization 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 sum, the selective hydrogenation of low-carbon (LC) alkynes and alkadienes, mainly uses noble metal catalyst at present, for non-
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 provides a kind of new Fe-Cu hydrogenation catalysts and preparation method thereof.
The content of the invention
Alkynes method is removed it is an object of the invention to provide a kind of back end hydrogenation of carbon two.Particularly relate to a kind of Fe-Cu selections hydrogenation
Catalyst, contained selective hydrogenation of acetylene, is fully converted to ethene in it will go out thing from deethanizer overhead stream, while second
Alkene does not lose.
The back end hydrogenation technique of carbon of the present invention two except alkynes method, using Fe-Cu selective hydrogenation catalysts, carrier is resistance to
High temperature inorganic oxide, active component at least contains Fe, Cu, and in terms of catalyst quality 100%, catalyst contains Fe 2~12%,
Preferred content is 4~10%, and containing Cu 0.05~0.3%, preferred content is 0.08~0.2%；The specific surface of catalyst be 10~
200m2/ g, preferably 30~100m2/ g, pore volume is 0.2~0.63ml/g, preferably 0.35~0.49ml/g；Wherein Fe is by leaching
Stain mode is loaded with carrier, through 250 DEG C~600 DEG C roastings, then is obtained with 200~400 DEG C of reduction of hydrogen atmosphere；Catalyst
Middle Fe is main with α-Fe2O3Form is present；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 is：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 use hydrogenation catalyst except alkynes method, carrier is high-temperature inorganic oxide, of the invention
Key problem in technology is that, containing Fe in catalyst, and have passed through roasting and reduction process, to carrier and is had no special requirements, and such as can be
One or more in aluminum oxide, silica, zirconium oxide, magnesia etc..But most common is also most preferably aluminum oxide or oxygen
Change aluminium system carrier, alumina series carrier refers to the complex carrier of aluminum oxide and other oxides, and wherein aluminum oxide accounts for complex carrier
More than the 50% of quality, such as can be aluminum oxide and silica, zirconium oxide, the preferably compound of magnesia oxide, oxygen
Change aluminium-zirconia composite carrier, wherein alumina content is more than 60%.Aluminum oxide can be θ, α, γ type or its various crystal formation
Mixture, preferably α-Al2O3Or-the Al containing α2O3Mixing crystal formation aluminum oxide.
The present invention removes alkynes method, the preparation method of the Fe-Cu selective hydrogenation catalysts that use for：
Catalyst distinguishes impregnated carrier, is aged respectively, does by preparing the Fe predecessors aqueous solution, the Cu predecessor aqueous solution
Dry, roasting or with its mixed solution impregnated carrier, is aged, dries, roasting afterwards, and finally reduction is obtained.Sintering temperature is preferably 250
DEG C~600 DEG C；Reduced at 260~330 DEG C.
Preferred condition is in preparation method of the present invention：
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 sintering temperature, 240~300min of roasting time.
Dried in the present invention and be preferably temperature programming drying, drying temperature program setting is：
Roasting is activation process in the present invention, preferably temperature-programmed calcination, and sintering temperature program setting is：
Heretofore described catalyst can be sprayed using incipient impregnation, excessive dipping, surface, vacuum impregnation and repeatedly
It is prepared by any one impregnation method in infusion process.
Comprise the following steps that：
(1) carrier is weighed after measurement carrier water absorption rate.
(2) the Fe predecessors (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 regulation maceration extract pH value 1.5~5.0 on request, and solution is heated to
30~60 DEG C standby.
(3) using incipient impregnation or when spraying method, the carrier that will can be weighed is put into rotary drum, adjusts rotary drum rotating speed
25~30 turns/min, it is totally turned over carrier, the maceration extract of 30~60 for preparing DEG C is poured into or sprayed with given pace
It is spread across on carrier, loads 5~10min.
During using excessive infusion process, the carrier that will be weighed is placed in container, is subsequently adding 30~60 DEG C of preparation of dipping
Solution, the visibly moved device of Quick shaking, liberated heat discharges rapidly in making adsorption process, and makes active component uniform load to carrier
On, standing 5~10min makes surface active composition be balanced with active component competitive Adsorption in solution.
During using vacuum impregnation technology, the carrier that will be weighed is placed in cyclonic evaporator, is vacuumized, and adds 30~60 DEG C
Maceration extract impregnates 5~10min, and heating water bath to carrier surface moisture is completely dried.
(4) catalyst for having impregnated is moved into container, and catalyst aging 30~120min is carried out at 25~60 DEG C.
(5) solution unnecessary after dipping is leached, is then dried using the method for temperature programming in an oven, dried
Temperature program(me)：
(6) dried catalyst is calcined using temperature programming method, is calcined heating schedule：
Catalyst Cu components are loaded using above-mentioned same steps, 250~600 DEG C of sintering temperature, preferably 300~
400 DEG C, two kinds of components can also be configured to mixed solution, disposably be impregnated to carrier surface according to above-mentioned steps.
Catalyst of the invention is reduced the catalyst after roasting with hydrogen-containing gas, H using preceding2Content is preferably
10~50%, reduction temperature is preferably 200~400 DEG C, 100~500h of volume space velocity-1, 0.1~0.8MPa of reduction pressure；Recommend
Condition be to use N2+H2Gaseous mixture is reduced for 260~330 DEG C under the conditions of pressure-fired, and the recovery time is preferably 240~
360min, the best 200~400h of volume space velocity-1, reduce pressure and be preferably 0.1~0.5MPa.The process is generally hydrogenated with selection
Carried out before reaction, preferably carry out being carried out outside i.e. selective hydrogenation reaction device 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.
The activity composition of the activation temperature of catalyst and catalyst, content and carrier related, activated mistake in the present invention
α-Fe are formd after journey2O3The Fe of form, and it is relatively stable, and activation temperature can not be too high；On the other hand, its activation degree is again
Determine the reducing condition of catalyst, provided in the present invention in the catalyst for using still with α-Fe2O3The Fe of form for it is main into
Point, undue reduction can influence the effect of catalyst, influence selectivity, easy coking on the contrary.
Fe elements can be with Fe, Fe in catalyst of the invention2O3、Fe3O4, the variform such as FeO exist, but wherein α-
Fe2O3The Fe of form is higher than the content of other forms, preferably accounts for more than the 50% of Fe gross masses.
Recommend to add Cu in the activity composition of iron content in the present invention, be more beneficial for reducing activation temperature, be conducive to urging
Formation, the dispersion of agent activation phase, improve catalyst choice.The addition of Cu simultaneously contributes to the absorption of alkynes, activation, favorably
In the activity for improving catalyst.
The back end hydrogenation of carbon of the present invention two removes alkynes method, refers in two sections or three sections of series connection adiabatic reactors, to incite somebody to action
Deethanizer overhead stream goes out contained acetylene in material carries out selective hydrogenation, is converted into ethene.
Reactor refers to adiabatic reactor reactor in the present invention.Can be single hop or multi-stage series, preferably 2~3 sections series connection
Use.When adiabatic reactor reactor reaction bed number is three sections, 40~50 DEG C of first paragraph reactor inlet temperature, hydrogen/acetylene body
Than being 0.8~1.2,5~55 DEG C of second segment reactor inlet temperature, hydrogen/acetylene volume ratio is 1~1.5, three sections of reactors to product
50~60 DEG C of inlet temperature, hydrogen/acetylene volume ratio is 1.5~3.0.
When reactor is that two sections of adiabatic reactor reactors are connected in the present invention, 40~50 DEG C of first paragraph reactor inlet temperature,
Hydrogen/acetylene volume ratio is 1~1.5,50~60 DEG C of second segment reactor inlet temperature, and hydrogen/acetylene volume ratio is 2~4.
In the present invention, hydrogenation material is selected in the back end hydrogenation technique of carbon two, thing, raw material group to be gone out from deethanizer overhead stream
Into with volume basis, preferably：Acetylene 0.98~2.2%, ethane 11.2~30.3%, ethene 65.0~85.0%.
Alkynes method is removed using the present invention, catalyst reaction activity is moderate, and operating flexibility is good, and ethylene selectivity is good, green oil life
Noble metal catalyst is far below into amount.
Brief description of the drawings
Fig. 1 is to select hydrogenation technique flow chart using the carbon two of order separation process.1-oil scrubber；2-water scrubber；3—
Caustic wash tower；4-drier；5-domethanizing column；6-dethanizer；7-Acetylene converter；8-heat exchanger.
Fig. 2 is XRD spectra (deduction vector background) after the catalyst reduction of the embodiment of the present invention 3.
Fig. 3 is XRD spectra (deduction vector background) after the high-temperature roasting catalyst reduction of comparative example 2.
Fig. 4 is XRD spectra (deduction vector background) after the catalyst high temperature reduction of comparative example 5.
XRD determining condition：
German Brooker company D8ADVANCE X diffractometers
Tube voltage：40kV electric currents 40mA
Scanning：0.02 ° of step-length, 4 °~120 ° of frequency 0.5s sweep limits, 25 DEG C of temperature
The wavelength of Cu K α 1, abscissa is the θ of the angle of diffraction 2 in figure, and ordinate is diffracted intensity
Symbol description in Fig. 2：
▲ it is α-Fe2O3, ◆ it is Cu, ■ is Fe3O4。
Symbol description in Fig. 3：
▲ it is α-Fe2O3, ● it is CuFeO3, ■ is Fe3O4。
Symbol description in Fig. 4：
★ is Fe for α-Fe, ■3O4, ◆ it is Cu.
α-Fe in Fig. 22O3Relative amount 11.20%.
Fe and second component combine to form CuFe in Fig. 32O4, help component to be sintered with active component, destroy active component
Distribution and structure.
α-Fe are free of in Fig. 42O3Phase, Fe mainly with simple substance α-Fe forms occur, relative amount 8.92%, third component with
Simple substance Cu forms occur.
Specific embodiment
Analysis test method：
Specific surface：GB/T-5816
Pore volume：GB/T-5816
Different crystal forms Fe oxide contents：XRD
Catalyst activity component content：GB/T 1537-94
Conversion of alkyne (C)
It is hydrogenated to the selectivity (S) of ethene
Embodiment 1
Weigh the trifolium-shaped alpha-alumina supports of 4.5 × 4.5mm of Φ.Ferric nitrate is taken, heating for dissolving is in 60ml deionizations
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 to adsorption equilibrium, 60 DEG C are aged 30min to 30min, then in an oven according to program：Then activation of catalyst is carried out using programmed temperature method,
Activation procedure： Claim
Copper nitrate is taken, is impregnated according to above-mentioned preparation process.Carrier and catalyst physical index, catalyst components content are shown in Table 1.
Catalyst is reduced, 300 DEG C of reduction temperature, pressure in reduction furnace using preceding with the nitrogen of 40% hydrogen+60%
0.5MPa, recovery time 4h.Catalyst packing is in fixed-bed reactor.
Using back end hydrogenation technique, as shown in Figure 1, raw material composition is its process chart：
C2H2：1.6% (Φ), C2H4：75.3% (Φ), C2H6：23.1% (Φ).
Reaction condition：Two sections of adiabatic reactor reactor cascade reactions, i.e. first stage reactor outlet material enters 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 (mol ratio)；
Second stage reactor H2/C2H2=3：1 (mol ratio).
Appraisal result is as shown in table 2.
Embodiment 2
At 50 DEG C, by NaAlO2Solution and ZrCl4Solution stirring mixing, is then neutralized with salpeter solution, stirs 10h, coprecipitated
Form sediment the uniform Al-Zr particles of generation.Product is filtered, Na therein is washed with deionized+And Cl-Ion, is subsequently adding matter
Amount concentration be 15% polyvinyl alcohol as pore creating material, it is kneaded and formed.130 DEG C dry 2h, and 650 DEG C of roasting 4h obtain Zr-Al and answer
Close carrier.Aluminum oxide and zirconium oxide mass ratio are 4 in carrier:1.
Catalyst is prepared with alumina-zirconia composite carrier.Iron chloride and copper chloride are taken, heating for dissolving is in deionized water
In, pH value 2.0 is adjusted, 80 DEG C of maceration extract temperature is excessively impregnated on carrier, shake beaker dipping 10min, by unnecessary maceration extract
Filter, 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： Carry
Body and catalyst physical index, catalyst components content are shown in Table 1.
Catalyst is reduced, 260 DEG C of reduction temperature, pressure in reduction furnace using preceding with the nitrogen of 30% hydrogen+60%
0.5MPa, recovery time 4h.Catalyst packing is in fixed-bed reactor.
Using back end hydrogenation technique, as shown in Figure 1, raw material composition is its process chart：
C2H2：1.4% (Φ), C2H4：80.0% (Φ), C2H6：18.6% (Φ).
Reaction condition：Two sections of adiabatic reactor reactor cascade reactions, i.e. first stage reactor outlet material enters 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 (mol ratio)；
Second stage reactor H2/C2H2=4：1 (mol ratio).
Appraisal result is as shown in table 2.
Embodiment 3
The ball-type aluminum oxide for weighing Φ 1.5mm prepares catalyst.Take ferric nitrate to be dissolved in deionized water, adjust pH value 3.0,
40 DEG C of maceration extract temperature, watering can is sprayed on carrier, and load 10min makes active component upload uniformly, then in an oven according to journey
Sequence： Catalyst work is carried out using programmed temperature method
Change, activation procedure：
Obtain a leaching catalyst.
Using first step same procedure, copper nitrate is taken, is sprayed after dissolving to a leaching catalyst surface, then dried, be calcined,
Obtain final catalyst.Drying program：Calcination procedure：Carrier and catalysis
Agent physical index, catalyst components content is shown in Table 1.
Catalyst is reduced, 280 DEG C of reduction temperature, pressure 0.5MPa in reduction furnace using preceding with 20% hydrogen, also
Former time 4h.Reduction rear catalyst XRD analysis are as shown in Figure 2.Catalyst packing is in fixed-bed reactor.
Using back end hydrogenation technique, reaction raw materials are：
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 enters second-stage reaction
Device, second stage reactor outlet material enters 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 (mol ratio)；Two
Section reactor H2/C2H2=1.5：1 (mol ratio)；Three sections of reactor H2/C2H2=3：1 (mol ratio).
Appraisal result is as shown in table 2.
Embodiment 4
The spherical tio2 carrier of the Φ 2.0mm for weighing is placed in vacuum impregnation plant.Take ferric nitrate and be dissolved in deionized water
In, regulation pH value 3.5 is standby.Vacuum impregnation plant vacuum pumping pump is opened, to vacuum 0.1mmHg, is then slowly added to from charge door
The maceration extract for preparing, 5min is added, and catalyst surface mobile moisture is evaporated at 60 DEG C and is wholly absent, and completes load, will be loaded
Good catalyst, in an oven according to program：In Muffle furnace
According to：
Obtain a leaching catalyst.
Copper nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, be calcined, obtain final catalyst.Dry journey
Sequence：Calcination procedure： Obtain final catalyst.Carrier and catalyst
Physical index, catalyst components content is shown in Table 1.
Urge catalyst to use preceding, reduced with 15% hydrogen in reduction furnace, 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：
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 enters 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 (mol ratio)；Two
Section reactor H2/C2H2=1.5：1 (mol ratio)；Three sections of reactor H2/C2H2=3：1 (mol ratio).
Appraisal result is as shown in table 2.
Embodiment 5
The alpha-alumina supports of 100ml Φ 4.0mm are weighed, catalyst is prepared using the same procedure of embodiment 3.Activation temperature
400℃.Carrier and catalyst physical index, catalyst components content are shown in Table 1.
Catalyst is reduced, 320 DEG C of temperature, pressure 0.5MPa, during reduction in reduction furnace using preceding with 25% hydrogen
Between 4h.Catalyst packing is in fixed-bed reactor.
Using back end hydrogenation technique, reaction raw materials are：
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 enters 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 (mol ratio)；Two
Section reactor H2/C2H2=1.5：1 (mol ratio)；Three sections of reactor H2/C2H2=3：1 (mol 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 aluminum oxide：Silica：Zirconium oxide
=8:1:3 ratios are well mixed, then the extruded moulding on banded extruder, 120 DEG C of dryings, and 550 DEG C of roasting 3h, obtain in Muffle furnace
To Zr-Si-Al composite oxide carriers.Catalyst is prepared using the same procedure of embodiment 4.Carrier and catalyst physical index,
Catalyst components content is shown in Table 1.
Using preceding, with the nitrogen of 45% hydrogen+55% in reduction furnace, 360 DEG C of temperature, pressure 0.5MPa is activated catalyst
Time 4h.Catalyst packing is in fixed-bed reactor.
Using back end hydrogenation technique, reaction raw materials are：
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 enters 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 (mol ratio)；Two
Section reactor H2/C2H2=1.5：1 (mol ratio)；Three sections of reactor H2/C2H2=3：1 (mol ratio).
Appraisal result is as shown in table 2.
Comparative example 1
Φ 4.0mm alumina supports are taken, specific surface is 22.3m2/ g, pore volume is 0.31ml/g.Using equi-volume impregnating,
By silver nitrate solution incipient impregnation on carrier, ageing-dry-roasting obtains a leaching catalyst, then by palladium bichloride
Dissolving, incipient impregnation, ageing-dry-roasting obtains final catalyst (petrochemical industry research institute LY-C2-02 hydrogenation catalysts).
Catalyst Pd contents are that 0.040%, Ag contents are 0.12%.
Catalyst uses hydrogen reducing 160min, pressure 0.5MPa, hydrogen gas space velocity 100h at 100 DEG C-1.Catalyst packing is in exhausted
In hott bed reaction unit.
Using the same process of embodiment 1, reaction condition：Air speed 6000h-1, operating pressure：2.0MPa.
Reaction result is as shown in table 2.
Comparative example 2
Carrier is made with Φ 4.0mm aluminum 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 is reduced, 300 DEG C of temperature, pressure 0.5MPa, during activation in reduction furnace using preceding with 25% hydrogen
Between 4h.Catalyst packing is in adiabatic bed reaction device.The XRD diffraction spectrograms for reducing rear catalyst are as shown in Figure 3.
Using the same process of embodiment 1.Raw material is constituted：
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 aluminum oxide for weighing Φ 4.0mm makees carrier, and catalyst is prepared using the same procedure of embodiment 1, is lived at 350 DEG C
Change.Carrier and catalyst physical index, catalyst components content are shown in Table 1.
Catalyst is reduced, 300 DEG C of temperature, pressure 0.5MPa, during activation in reduction furnace using preceding with 45% hydrogen
Between 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, 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 enters second-stage reaction
Device, second stage reactor outlet material enters 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 (mol ratio)；Two
Section reactor H2/C2H2=1.5：1 (mol ratio)；Three sections of reactor H2/C2H2=3：1 (mol ratio).
Reaction result is as shown in table 2.
Comparative example 4
The same catalyst of Example 1, directly drives after being activated at 350 DEG C, is reduced without hydrogen.With the institute of accompanying drawing 1
Show hydrogenation flow, Catalyst packing is in fixed-bed reactor.
Using three sections of series connection adiabatic reactor techniques, raw material constitutes 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 constitutes 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
The same catalyst of Example 1, in 350 DEG C of activation.
Catalyst is reduced in tube furnace, and atmosphere is the nitrogen of 30% hydrogen+55%, 500 DEG C of temperature, pressure
0.5MPa, soak time 4h.With flow is hydrogenated with accompanying drawing 1 Suo Shi, Catalyst packing is in fixed-bed reactor.It is catalyzed after reduction
The XRD diffraction spectrograms of agent are as shown in Figure 4.
Hydrogenating materials constitute 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.
The carrier of table 1, catalyst physical property and catalyst components content
Reaction result is as shown in table 2.
The process conditions of table 2 and catalyst performance
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Knowing those skilled in the art can make various corresponding changes and deformation, but these corresponding changes and deformation according to the present invention
The protection domain of the claims in the present invention should all be belonged to.
Claims (13)
1. a kind of back end hydrogenation technique of carbon two except alkynes method, will go out from deethanizer overhead stream in the back end hydrogenation ethylene unit of carbon two
Thing carries out selection hydrogenation into adiabatic reactor, to remove acetylene therein, it is characterised in that selected equipped with Fe-Cu in reactor
Hydrogenation catalyst, carrier is high-temperature inorganic oxide, and active component at least contains Fe, Cu, and catalyst contains Fe 2~12%, excellent
It is 4~10% to select content, and containing Cu 0.05~0.3%, preferred content is 0.08~0.2%；The specific surface of catalyst be 10~
200m2/ g, preferably 30~100m2/ g, pore volume is 0.2~0.63ml/g, preferably 0.35~0.49ml/g；Wherein Fe is by leaching
Stain mode is loaded with carrier, through 250 DEG C~600 DEG C roastings, then is obtained with 200~400 DEG C of reduction of hydrogen atmosphere；Catalyst
Middle Fe is main with α-Fe2O3Form is present；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 is：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.
2. it is according to claim 1 except alkynes method, it is characterised in that in catalyst, α-Fe2O3The Fe of form will account for the total matter of Fe
More than the 50% of amount.
3. according to claim 1 except alkynes method, it is characterised in that the carrier of catalyst be aluminum oxide, or aluminum oxide and its
The complex carrier of his oxide, best aluminum oxide accounts for more than the 50% of complex carrier quality, and other oxides are silica, oxidation
The preferred alumina-zirconia composite carrier of complex carrier of zirconium, magnesia or titanium oxide, aluminum oxide and other oxides；Oxidation
Aluminium is θ, α, γ type, preferably α-Al2O3。
4. it is according to claim 1 except alkynes method, it is characterised in that before catalyst is by preparing the Fe predecessors aqueous solution, Cu
Drive the thing aqueous solution, respectively impregnated carrier, respectively be aged, dry, roasting or with after its mixed solution impregnated carrier be aged, dry,
Roasting, obtains after finally reducing；Sintering temperature is preferably 250 DEG C~600 DEG C；Preferably reduced at 260~330 DEG C.
5. according to claim 4 except alkynes method, it is characterised in that：30~60 DEG C of dipping temperature during catalyst preparation, bear
10~60min of load time, maceration extract pH value 1.5~5.0,30~60 DEG C of Aging Temperature, 30~120min of digestion time, roasting temperature
250 DEG C~600 DEG C, preferably 300~400 DEG C of degree；240~300min of roasting time.
6. it is according to claim 4 except alkynes method, it is characterised in that to dry as temperature programming is dried, drying temperature program sets
It is set to：
7. according to claim 4 except alkynes method, it is characterised in that to be roasted to temperature-programmed calcination, sintering temperature program sets
It is set to：
8. according to claim 1 or 4 except alkynes method, it is characterised in that the impregnation method be incipient impregnation, excess
Dipping, surface spray, vacuum impregnation or repeatedly dipping.
9. according to claim 1 or 4 except alkynes method, it is characterised in that reduction refers to catalyst using preceding, with hydrogeneous
Gas is reduced to the catalyst after roasting, H2Content is preferably 10~50%, 200~400 DEG C of reduction temperature, recovery time
240~360min, 100~500h of volume space velocity-1, 0.1~0.8MPa of reduction pressure；Optimum condition is to use N2+H2Gaseous mixture
Reduced at 260~330 DEG C, 200~400h of volume space velocity-1, reduce pressure and be preferably 0.1~0.5MPa.
10. it is according to claim 1 except alkynes method, it is characterised in that to be hydrogenated with using two sections or three sections of adiabatic reactors
Reaction, hydrogen is added by the way of distribution.
11. is according to claim 10 except alkynes method, it is characterised in that when adiabatic reactor reactor is three sections of series connection, and one section anti-
40~50 DEG C of device inlet temperature is answered, 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, three sections of 50~60 DEG C of reactor inlet temperatures, and hydrogen/acetylene volume ratio is 1.5~3.0.
12. is according to claim 10 except alkynes method, it is characterised in that when adiabatic reactor reactor is instead for two sections of series connection, and first
40~50 DEG C of reactor inlet temperature of section, hydrogen/acetylene volume ratio is 1~1.5, second segment reactor inlet temperature 50~60
DEG C, hydrogen/acetylene volume ratio is 2~4.
13. is according to claim 1 except alkynes method, it is characterised in that selection hydrogenation material be the back end hydrogenation technique of carbon two in,
Go out thing from deethanizer overhead stream, raw material is constituted with volume basis, is：Acetylene 0.98~2.2%, ethane 11.2~
30.3%, ethene 65.0~85.0%.
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