CN108452852A - A kind of outer prereduction of the device of ethylene front-end hydrogenation catalyst and deactivating process for the treatment of - Google Patents
A kind of outer prereduction of the device of ethylene front-end hydrogenation catalyst and deactivating process for the treatment of Download PDFInfo
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- CN108452852A CN108452852A CN201710090795.3A CN201710090795A CN108452852A CN 108452852 A CN108452852 A CN 108452852A CN 201710090795 A CN201710090795 A CN 201710090795A CN 108452852 A CN108452852 A CN 108452852A
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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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
- 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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Abstract
The invention discloses prereduction and deactivating process for the treatment of outside a kind of device of ethylene front-end hydrogenation catalyst.This method includes：(1) pre-reduction treatment is carried out by the hydrogenation catalyst of active constituent of Pd and Ag to oxidation state；(2) processing is passivated to the hydrogenation catalyst after pre-reduction treatment, passivating process is as follows：30 50 DEG C of passivation temperature is cooled under normal pressure, nitrogen protection, the oxygen-containing gas for being passed through oxygen mole a concentration of 0.61% 5.0% is passivated, and passivation time is 2.5 5.5h, is passed through air later and is continued to be passivated 9 11h.The method of the present invention is easy to operate, mild condition, good passivation effect, stable in the air can exist, and convenient for storage and transport, is easy to when in use by the H in unstripped gas2Reduction, can promptly show higher activity and selectivity, substantially reduce on-stream time, good economic benefit is brought to enterprise.
Description
Technical field
The present invention relates to prereduction and deactivating process for the treatment of outside a kind of device of ethylene front-end hydrogenation catalyst, and in particular to
Pd-Ag is the outer prereduction of device and the deactivating process for the treatment of of the ethylene front-end hydrogenation catalyst of active constituent.
Background technology
Often contain a small amount of acetylene, propine (MA) and allene in the cracking gas generated during cracking petroleum hydrocarbon vapor
(PD) etc. impurity, their presence can influence in follow-up workshop section used in homogeneous polymerization and polymerization process efficiently to some extent
Polyethylene and polypropylene catalyst.By the requirement of the post-processings process such as polyethylene, EP rubbers, polypropylene, in polymer grade ethylene
The molar concentration of acetylene has to be lower than 5ppm, and the molar concentration of acetylene in ethylene is also required to be less than 10ppm in ethylene glycol production.
There are many method for removing acetylene in ethylene, have solvent absorption, selection hydrogenation method, cryogenic rectification method, Gestoral heavy
Shallow lake method, ammoniation process, Absorption via Chemical Complexation etc..Wherein selection hydrogenation method is a kind of industrial most widely used and most effective side
Method.Acetylene selective hydrogenation process is a very important workshop section in ethylene unit, the fine or not direct relation of acetylene converter operating
Normal table to whole system is run.It mostly uses catalysis selective hydrogenation method removing acetylene on commercial plant greatly at present, is used
Catalyst be mostly palladium-silver noble metal catalyst.According to position of the hydrogenation reactor before and after domethanizing column, add before being divided into
Hydrogen takes off acetylene technique and back end hydrogenation takes off acetylene technique, because there is separation process simplification, equipment investment is few, without adding H2With
The advantages that CO, Ethylene purity is good, and green oil generating amount is few, front-end hydrogenation technique is more and more applied to large-scale ethylene plant.
The main active component that the front-end hydrogenation industrially applied takes off acetylene catalyst is palladium (Pd), and the palladium on catalyst is
Existing for oxidation state, needs to be reduced to simple substance palladium with hydrogen in use, can just show hydrogenation activity.Industrial one
As catalyst is restored using two methods, one is oxidation state directly to drive, while hydrogenation reaction carries out, utilize
The advantages of hydrogen in cracking gas is restored, this method is omitted additional catalyst pre-reduction, simplifies stream
Journey, the disadvantage is that initial activity is low, the alkynes and CO in cracking gas can influence the reduction of palladium oxide, and border ring reduction in side be easy to cause winged
Temperature；Another kind is first to be passed through pure hydrogen to carry out in-situ reducing in device to catalyst, then be passed through unstripped gas and carry out hydrogenation reaction, advantage
It is that catalyst reduction is abundant, activity is high, the disadvantage is that needing to add reduction apparatus, the recovery time is longer, influences normally to drive.It is comprehensive
Both the above is to the advantage and disadvantage of catalyst reduction method, and the outer prereduction of device is a good selection, but simple substance palladium activity is very high,
It is oxidized easily in air, its activity is made to be greatly affected, for the ease of storing and transporting, the catalyst restored outside device needs
To pass through Passivation Treatment.
Passivating technique is generally divided into gas passivation, liquid passivating and solids passivation.Gas passivation mainly uses O2Deng oxidation
Property gas, under the conditions of certain temperature by the catalyst surface of reduction-state aoxidize, formed one layer of fine and close oxidation film, with protection urge
Not oxidation by air inside agent.Liquid passivating main organic hydrocarbon, by the methods of spraying, dipping, stirring, in catalyst
Surface forms protective layer.Solids passivation mainly melts passivator in catalyst surface to achieve the purpose that protection.
For same catalyst, the activity and selectivity that it reacts different with Passivation Treatment mode is restored
Influence it is also different.And for different catalyst, in order to reach preferable activity and selectivity, can generally also use not
Same reduction and Passivation Treatment mode.
Invention content
In order to overcome the shortcomings of to be restored in device, the present invention provides prereduction outside a kind of device of ethylene front-end hydrogenation catalyst and
Deactivating process for the treatment of.Catalyst obtained by this method stable in the air can exist, can be convenient convenient for storage and transport
It applies on commercial plant, shortens on-stream time, and be easy to during the reaction by the hydrogen reducing in unstripped gas, Neng Gouxun
Higher catalytic activity and selectivity are shown fastly.
The outer prereduction of the device of ethylene front-end hydrogenation catalyst in the present invention and deactivating process for the treatment of, including：
(1) pre-reduction treatment is carried out by the hydrogenation catalyst of active constituent of Pd and Ag to oxidation state；
(2) processing is passivated to the hydrogenation catalyst after pre-reduction treatment, passivating process is as follows：It is protected in normal pressure, nitrogen
30-50 DEG C of passivation temperature is cooled under shield, the oxygen-containing gas for being passed through a concentration of 0.61%-5.0% of oxygen mole is passivated, blunt
The change time is 2.5-5.5h, is passed through air later and continues to be passivated 9-11h.
In step (1), conventional vehicle group may be used as the hydrogenation catalyst of active constituent using Pd and Ag for oxidation state
Point, such as aluminium oxide, titanium oxide or aluminium oxide and titanium oxide complex carrier etc..On the basis of the weight of hydrogenation catalyst, Pd
Weight content be 0.01%-3.0%, the weight content of Ag is 0.01%-5.0%.
Pre-reduction described in step (1) is as follows：Under normal pressure, using pure hydrogen as reducing gas, with 0.5-2.0 DEG C/
The heating rate temperature programming of min keeps 2-4h to 125-135 DEG C.
The volume space velocity of the reducing gas (such as pure hydrogen) used when step (1) prereduction is 2500-3500h-1, heating is always
Time is 1-3h.
Protection gas nitrogen volume space velocity in step (2) is 2500-3500h-1。
30-50 DEG C of passivation temperature in step (2) can also use and become wherein the mode of constant temperature passivation may be used in passivation
The mode of temperature passivation.
The concentration of oxygen can be by adjusting N in oxygen-containing gas in step (2)2Flow and O2Flow controls.
The molar concentration of oxygen is stepped up by following eight gradients and is passivated in oxygen-containing gas in step (2),
Each concentration holding 20-40min, the molar concentration gradient of wherein oxygen are：0.61%-0.64%, 0.95%-0.98%,
1.25%-1.29%, 1.73%-1.77%, 2.11%-2.15%, 2.40%-2.44%, 3.24%-3.28%, 4.97%-
5.0%, the volume space velocity of the corresponding oxygen-containing gas of each concentration gradient is：3410-3440h-1、3710-3730h-1、4010-
4040h-1、4610-4630h-1、5210-5230h-1、5810-5830h-1、4310-4330h-1、2810-2830h-1。
It is blunt to be preferably stepped up progress by following eight gradients for the molar concentration of oxygen in oxygen-containing gas in step (2)
Change, each concentration holding 30min, the molar concentration gradient of wherein oxygen is：0.61%, 0.97%, 1.27%, 1.75%,
2.13%, 2.42%, 3.26%, 5.0%, the corresponding air speed of each concentration gradient is：3420h-1、3720h-1、4020h-1、
4620h-1、5220h-1、5820h-1、4320h-1、2820h-1。
The volume space velocity of air described in step (2) is 2500-3500h-1。
The present invention is suitable for prereduction and the Passivation Treatment process for the ethylene front-end hydrogenation catalyst that active constituent is Pd-Ag
In.
Compared with prereduction technology in existing device, the present invention has the following advantages：
The catalyst prereduction and Passivation Treatment process of the present invention is easy to operate, mild condition, good passivation effect.By this
Treated that catalyst coating is aoxidized for invention, forms fine and close oxidation film, air is prevented to go deep into oxygen to catalytic inner
Change, convenient for storage and transport, while directly going into operation when in use, oxidation film is easy to by the H in unstripped gas in the reaction2Also
Original can rapidly show higher catalytic activity and selectivity, suitable with the activity and selectivity of in-situ reducing catalyst,
On-stream time is substantially reduced, good economic benefit is brought to enterprise.
Description of the drawings
Fig. 1 is that the conversion of alkyne of embodiment 1-3 and comparative example 1-3 varies with temperature figure；
Fig. 2 is that the MAPD conversion ratios of embodiment 1-3 and comparative example 1-3 vary with temperature figure；
Fig. 3 is that the ethylene selectivity of embodiment 1-3 and comparative example 1-3 varies with temperature figure.
Specific implementation mode
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not limited by embodiment
System.Involved in the present invention to gas concentration be molar concentration, wt% is mass fraction.
The oxidized catalyst used in the following example and comparative example is Pd-Ag/Al2O3Catalyst (cat0), wherein Pd
Content 0.035wt%, Ag content 0.06wt%.
In following embodiment and comparative example, the SP3420 gas phases of Rayleigh analytical instrument Co., Ltd are divided using Beijing North
Chromatography carries out product on-line analysis, and chromatographic column is stationary phase HP-PLOT/Al2O3(50m × 0.53mm × 15 μm), FID detections, N2
For carrier gas.
The conversion of alkyne of reaction, the computational methods of MAPD conversion ratios (MA is propine, PD is allene), ethylene selectivity
Such as formula (1), (2), (3)：
Embodiment 1
Weigh the Pd-Ag/Al of 1g20-40 mesh2O3Catalyst (cat0) is fitted into reactor and carries out at prereduction and passivation
Reason.In normal pressure, volume space velocity 3000h-1Pure H2Under the conditions of with the rate program of 1 DEG C/min be warming up to 130 DEG C reduction 3h, will
H2It is switched to N2, close heating mantle power supply and be cooled to 50 DEG C of beginning Passivation Treatments, be passed through N2And 5%O2, 95%N2Gaseous mixture it is blunt
Change, by adjusting N2The concentration of passivating gas, O are adjusted with the flow of gaseous mixture2Molar concentration from 0.61% by eight gradients by
Step is increased to 5.0%, and each concentration keeps 30min.It is 3000h to be passed through volume space velocity later-1Air continue be passivated 10h, obtain
To catalyst cat1；
The molar concentration gradient of wherein oxygen is：0.61%, 0.97%, 1.27%, 1.75%, 2.13%, 2.42%,
3.26%, 5.0%, the volume space velocity of the corresponding passivating gas of each concentration gradient is：3420h-1、3720h-1、4020h-1、
4620h-1、5220h-1、5820h-1、4320h-1、2820h-1。
Embodiment 2
Specific implementation process is roughly the same with embodiment 1, difference place be passivation temperature it is constant be 50 DEG C, what is obtained is blunt
Catalyst after change is cat2.
Embodiment 3
Specific implementation process is roughly the same with embodiment 1, difference place be passivation temperature it is constant be 30 DEG C, what is obtained is blunt
Catalyst after change is cat3.
Embodiment 4
For the present embodiment with embodiment 1, difference place is that concentration gradient difference, the molar concentration gradient of oxygen are：
0.61%, 2.13%, 5.0%, passivation gas air speed is 3420h-1, the catalyst after obtained passivation is cat4.
Embodiment 5
After catalyst cat1 after above-mentioned passivation is placed for 24 hours in air, diluted with 1mL quartz sands, after mixing
It is packed into the flat-temperature zone that internal diameter is Ф 5mm fixed bed reaction pipes, quartz sand is filled up on catalyst.Wherein evaluating apparatus is KLCP-
3010 catalyst test apparatus, tube inner diameter are Ф 5mm, which is the miniature evaluating apparatus of catalyst, used raw material
Gas composition is shown in Table 1, and evaluation condition is：Reaction pressure 1.5MPa；Feed gas volume air speed 6000h-1.Evaluation result be shown in Table 2 and
Fig. 1-3.
Embodiment 6-8
The method that embodiment 5 evaluates cat1 is respectively adopted in catalyst cat2, cat3, cat4 after above-mentioned passivation
It is evaluated.Evaluation result is shown in Table 2 and Fig. 1-3.
1 unstripped gas of table forms
| Composition | Content |
| CO, % (V/V) | 0.0585 |
| C2H2, % (V/V) | 0.66 |
| CH4, % (V/V) | 21.70 |
| C2H4, % (V/V) | 39.60 |
| C2H6, % (V/V) | 7.0 |
| MA (propine), % (V/V) | 0.43 |
| PD (allene), % (V/V) | 0.32 |
| C3H6, % (V/V) | 8.98 |
| C3H3, % (V/V) | 1.10 |
| C4H8, % (V/V) | 0.12 |
| H2, % (V/V) | 20.0 |
1 oxidation state of comparative example is directly driven
Comparative example 1 uses the evaluating apparatus and unstripped gas of embodiment 5.
Weigh the oxidized catalyst Pd-Ag/Al of 1g20-40 mesh2O3(cat0), it is diluted, is uniformly mixed with 1mL quartz sands
It is packed into the flat-temperature zone that internal diameter is Ф 5mm fixed bed reaction pipes afterwards, quartz sand is filled up on catalyst.Volume space velocity 3000h-1N2It blows
After sweeping 1h, it is 6000h to be passed through volume space velocity-1Unstripped gas, and adjust pressure be 1.5MPa carry out hydrogenation reaction, product gas
Phase chromatography carries out on-line analysis, and the catalyst reaction result under such state is denoted as cat5.Evaluation result is shown in Table 2 and Fig. 1-3.
2 in-situ reducing of comparative example
Comparative example 2 uses the evaluating apparatus and unstripped gas of embodiment 5.
Weigh the oxidized catalyst Pd-Ag/Al of 1g20-40 mesh2O3(cat0), it is diluted, is uniformly mixed with 1mL quartz sands
It is packed into the flat-temperature zone that internal diameter is Ф 5mm fixed bed reaction pipes afterwards, quartz sand is filled up on catalyst.In normal pressure, volume space velocity is
3000h-1Pure H2Under the conditions of with the rate program of 1 DEG C/min be warming up to 130 DEG C reduction 3h.By H2It is switched to N2, close heating mantle
Power supply is cooled to room temperature, closes N2It is 6000h to be passed through volume space velocity-1Unstripped gas, and adjust pressure be 1.5MPa added
Hydrogen reacts, and product carries out on-line analysis with gas-chromatography, and the catalyst reaction result under such state is denoted as cat6.Evaluation result
It is shown in Table 2 and Fig. 1-3.
It is passed through air after 3 in-situ reducing of comparative example
Comparative example 3 uses the evaluating apparatus and unstripped gas of embodiment 5.
Weigh the oxidized catalyst Pd-Ag/Al of 1g20-40 mesh2O3(cat0), it is diluted, is uniformly mixed with 1mL quartz sands
It is packed into the flat-temperature zone that internal diameter is Ф 5mm fixed bed reaction pipes afterwards, quartz sand is filled up on catalyst.In normal pressure, volume space velocity is
3000h-1Pure H2Under the conditions of with the rate program of 1 DEG C/min be warming up to 130 DEG C reduction 3h, by H2It is switched to N2, close heating mantle
Power supply is cooled to room temperature, closes N2It is passed through air speed 3000h-1Air 10h.With air speed 3000h-1N21h is purged, volume is passed through
Air speed is 6000h-1Unstripped gas, and it is that 1.5MPa carries out hydrogenation reaction to adjust pressure, and product carries out online with gas-chromatography
It analyzes, the catalyst reaction result under such state is denoted as cat7.Evaluation result is shown in Table 2 and Fig. 1-3.
From Fig. 1-3 and table 2 as can be seen that the catalyst initial activity directly driven of oxidation state is low, at very high temperatures
High activity can be just shown, this is easy for causing to react temperature runaway.Compared with the catalyst of in-situ reducing, carried out through the method for the present invention
The catalyst of prereduction and Passivation Treatment, especially cat1, cat2 and cat 3, what can be stablized is present in air atmosphere, and
And activity and ethylene selectivity are substantially suitable.
2 reaction temperature window of table
Wherein T1Reach temperature when 20ppm for outlet acetylene molar concentration；T2For outlet ethylene molar content relative to
Ethylene molar content in unstripped gas lacks temperature when 3%；Reaction temperature window is T2-T1, the bigger expression of reaction temperature window
More insensitive to temperature change, stability is better, is more not easy temperature runaway.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of outer prereduction of device of ethylene front-end hydrogenation catalyst and deactivating process for the treatment of, which is characterized in that including：
(1) pre-reduction treatment is carried out by the hydrogenation catalyst of active constituent of Pd and Ag to oxidation state；
(2) processing is passivated to the hydrogenation catalyst after pre-reduction treatment, passivating process is as follows：Under normal pressure, nitrogen protection
30-50 DEG C of passivation temperature is cooled to, the oxygen-containing gas for being passed through a concentration of 0.61%-5.0% of oxygen mole is passivated, Zhi Houtong
Enter air to continue to be passivated 9-11h.
2. according to the method described in claim 1, it is characterized in that：Pre-reduction described in step (1) is as follows：In normal pressure
Under, using pure hydrogen as reducing gas, with the heating rate temperature programming of 0.5-2.0 DEG C/min to 125-135 DEG C, keep 2-4h.
3. according to the method described in claim 1, it is characterized in that：The volume of the reducing gas used when step (1) prereduction
Air speed is 2500-3500h-1, heating total time is 1-3h.
4. method according to claim 1 or 2, it is characterised in that：Protection gas nitrogen volume space velocity in step (2) is
2500-3500h-1。
5. method according to claim 1 or 2, it is characterised in that：Step (2) is passivated by the way of constant temperature passivation,
Or by the way of alternating temperature passivation.
6. method according to claim 1 or 2, it is characterised in that：Oxygen is mole dense in oxygen-containing gas in step (2)
Degree is stepped up by following eight gradients to be passivated, and each concentration keeps 20-40min, wherein the molar concentration ladder of oxygen
Degree is：0.61%-0.64%, 0.95%-0.98%, 1.25%-1.29%, 1.73%-1.77%, 2.11%-2.15%,
2.40%-2.44%, 3.24%-3.28%, 4.97%-5.0%, the volume space velocity of the corresponding oxygen-containing gas of each concentration gradient
For：3410-3440h-1、3710-3730h-1、4010-4040h-1、4610-4630h-1、5210-5230h-1、5810-5830h-1、
4310-4330h-1、2810-2830h-1。
7. method according to claim 1 or 2, it is characterised in that：Oxygen is mole dense in oxygen-containing gas in step (2)
Degree is stepped up by following eight gradients to be passivated, and each concentration keeps 30min, wherein the molar concentration gradient of oxygen
For：0.61%, 0.97%, 1.27%, 1.75%, 2.13%, 2.42%, 3.26%, 5.0%, each concentration gradient is corresponding
The air speed of oxygen-containing gas is：3420h-1、3720h-1、4020h-1、4620h-1、5220h-1、5820h-1、4320h-1、2820h-1。
8. method according to claim 1 or 2, which is characterized in that in step (2), oxygen is mole dense in oxygen-containing gas
Degree is by adjusting N2Flow and O2Flow control.
9. method according to claim 1 or 2, it is characterised in that：The volume space velocity of air described in step (2) is
2500-3500h-1。
10. method according to claim 1 or 2, it is characterised in that：In step (1), oxidation state is activity with Pd and Ag
The hydrogenation catalyst of ingredient, carrier component is the complex carrier of aluminium oxide, titanium oxide or aluminium oxide and titanium oxide, to add hydrogen
On the basis of the weight of catalyst, the weight content of Pd is 0.01%-3.0%, and the weight content of Ag is 0.01%-5.0%.
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| CN115254124A (en) * | 2021-04-30 | 2022-11-01 | 中国石油化工股份有限公司 | Preparation method of pre-reduction type hydrogenation catalyst |
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| WO2015057313A1 (en) * | 2013-10-18 | 2015-04-23 | Exxonmobil Chemical Patents Inc. | A hydrogenation catalyst, its method of preparation and use |
| CN103706228A (en) * | 2013-12-26 | 2014-04-09 | 西北化工研究院 | Pre-reducing type manganese series desulfurizing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115254124A (en) * | 2021-04-30 | 2022-11-01 | 中国石油化工股份有限公司 | Preparation method of pre-reduction type hydrogenation catalyst |
| CN115254124B (en) * | 2021-04-30 | 2024-03-12 | 中国石油化工股份有限公司 | Preparation method of pre-reduction hydrogenation catalyst |
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