CN106345520B - A kind of low-temp recovery method of catalyst for ethanol delydration to ethylene - Google Patents
A kind of low-temp recovery method of catalyst for ethanol delydration to ethylene Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a kind of low-temp recovery method of catalyst for ethanol delydration to ethylene, for the low-temp recovery method the following steps are included: decaying catalyst and oxidant are carried out contact treatment, the oxidant is to contain perchloric acid, perchlorate and H2O2At least one of oxide aqueous solution or steam；It is passed through regeneration treatment gas and regeneration treatment is carried out to decaying catalyst, the regeneration treatment gas includes that the oxygen content in oxygen-containing gas, ozone and diluent gas and the regeneration treatment gas is 0.2~21%, wherein, reaction bed temperature when regeneration treatment is 80~300 DEG C；Cooled down with high pure nitrogen purging catalyst bed and control the oxygen content in reactor and is down to 0.5% hereinafter, terminating the catalyst for ethanol delydration to ethylene after being regenerated.Low-temp recovery method of the invention greatly reduces catalyst regeneration temperature, and then reduces plant investment and operating cost.
Description
Technical field
The invention belongs to the technical fields of catalyst, more particularly, are related to a kind of catalyst for ethanol delydration to ethylene
Low-temp recovery method.
Background technique
Ethylene is important basic petrochemical raw material, can be used to produce a variety of important Organic Chemicals.However due to
In short supply, the rise of crude oil price and the conventional petroleum route production ethylene bring environmental problem of oil supply, non-traditional stone
Oil circuit line production ethylene will have very big market prospects.
Currently, catalyst for ethanol delydration to ethylene mainly includes Al2O3With two kinds of System Catalysts of molecular sieve, wherein the former
Reaction temperature height (370 DEG C~470 DEG C), process units investment and energy consumption are higher.Chinese patent CN103157503A is disclosed
A kind of producing ethylene from dehydration of ethanol molecular sieve catalyst, framework silicon-aluminum molar ratio can regulate and control in a big way, while have strong
, there is higher activity and selectivity at acid and weak acid center to reaction product, and its reaction temperature is lower (220 DEG C~280 DEG C), should
As long as the commercial plant of technology can meet process conditions using typical thermal-conductive oil, which greatly reduces industrial production equipment
Energy consumption and operating cost.But molecular sieve catalyst acidity is stronger, is easy to produce carbon distribution and covering catalyst active sites cause to urge
Agent inactivation, at regular intervals must regenerate catalyst, the regeneration method provided in the patented technology must be passed through
Air or oxygen, which is warming up to 500 DEG C, could regenerate completely, and regeneration temperature is higher, and plant investment is higher, and long term high temperature regenerates meeting
Molecular sieve lattice is destroyed, to form skeleton defect, while high temperature makes charcoal and is easy to cause catalyst surface active component to be sintered
Cause catalyst that cannot regenerate recovery initial activity.
In conclusion the above reason will eventually lead to the activity and stability decline of molecular sieve catalyst, while can shorten
Its service life, it is therefore necessary to which a kind of more preferably catalyst recovery process is provided.
Summary of the invention
Leave out to solve the problems, such as that existing producing ethylene from dehydration of ethanol molecular sieve catalysts regeneration temperature is higher, it is of the invention
Purpose is to provide a kind of low-temp recovery method of catalyst for ethanol delydration to ethylene.
The present invention provides a kind of low-temp recovery method of catalyst for ethanol delydration to ethylene, the low-temp recovery method packet
Include following steps:
A, decaying catalyst and oxidant are subjected to contact treatment, the oxidant be containing perchloric acid, perchlorate and
H2O2At least one of oxide aqueous solution or steam；
B, it is passed through regeneration treatment gas and regeneration treatment is carried out to decaying catalyst, the regeneration treatment gas includes oxygenous
Oxygen content in body, ozone and diluent gas and the regeneration treatment gas is 0.2~21%, wherein when regeneration treatment
Reaction bed temperature be 80~300 DEG C；
C, with high pure nitrogen purging catalyst bed cool down and control the oxygen content in reactor be down to 0.5% hereinafter,
Terminate the catalyst for ethanol delydration to ethylene after being regenerated.
One embodiment of the low-temp recovery method of catalyst for ethanol delydration to ethylene according to the present invention, the inactivation catalysis
Agent is to use during producing ethylene from dehydration of ethanol and deactivated modified molecular sieve catalyst, wherein works as ethanol conversion
96% is dropped to hereinafter, being then determined as that catalyst loses activity.
One embodiment of the low-temp recovery method of catalyst for ethanol delydration to ethylene according to the present invention, the perchlorate
For KClO4、NaClO4And NH4ClO4At least one of.
One embodiment of the low-temp recovery method of catalyst for ethanol delydration to ethylene according to the present invention, the oxidant
Dosage is 1~150%, preferably the 10~50% of decaying catalyst weight；In the oxidant concentration of oxide be 1~
60wt%, preferably 10~20wt%.
One embodiment of the low-temp recovery method of catalyst for ethanol delydration to ethylene according to the present invention, the contact treatment
When reaction bed temperature be 80~300 DEG C, time of the contact treatment is 3~30 hours.
One embodiment of the low-temp recovery method of catalyst for ethanol delydration to ethylene according to the present invention, the regeneration treatment
Ozone concentration in gas is 10~500ppm.
One embodiment of the low-temp recovery method of catalyst for ethanol delydration to ethylene according to the present invention, the diluent gas
For nitrogen or water vapour.
One embodiment of the low-temp recovery method of catalyst for ethanol delydration to ethylene according to the present invention, the regeneration purge
Processing is the oxygen content since regeneration treatment gas is 0.2~1%, while stepping up reaction bed temperature
It steps up the regeneration purge that the oxygen content in regeneration treatment gas goes forward side by side row order segmentation to 5~21% to handle, wherein control
The time of regeneration treatment is 3~30 hours.
One embodiment of the low-temp recovery method of catalyst for ethanol delydration to ethylene according to the present invention, the regeneration purge
Processing specifically includes following sub-step:
Control reaction bed temperature is 100~150 DEG C and to control oxygen content be 0.2~1%, and purging 0.5~5 is small
When；
Control reaction bed temperature is 150~200 DEG C and to control oxygen content be 0.2~1%, and purging 0.5~5 is small
When；
Control reaction bed temperature is 150~200 DEG C and controls oxygen content 1~2%, is purged 0.5~5 hour；
Control reaction bed temperature is 200~300 DEG C and controls oxygen content 1~2%, is purged 0.5~5 hour；
Control reaction bed temperature is 200~300 DEG C and controls oxygen content to be 2~5%, purge 0.5~5 hour；
Control reaction bed temperature is 200~300 DEG C and to control oxygen content be 5~21%, is purged 0.5~5 hour,
So far the regeneration treatment of step B is completed.
The present invention is regenerated using the molecular sieve catalyst that low temperature method inactivates carbon distribution, with existing high temperature (> 500 DEG C)
Regeneration techniques are compared, the beneficial effects of the present invention are:
(1) catalyst regeneration is just realized at a lower temperature, the media such as typical thermal-conductive oil can meet industrial requirement, thus
Greatly reduce plant investment and operating cost；
(2) coke-burning regeneration is realized to catalyst at a lower temperature, avoids catalyst surface active member biscuit firing, guarantees to urge
Agent has longer service life.
Specific embodiment
All features disclosed in this specification or disclosed all methods or in the process the step of, in addition to mutually exclusive
Feature and/or step other than, can combine in any way.
Any feature disclosed in this specification unless specifically stated can be equivalent or with similar purpose by other
Alternative features are replaced.That is, unless specifically stated, each feature is an example in a series of equivalent or similar characteristics
?.
Generally, the low-temp recovery method of catalyst for ethanol delydration to ethylene of the invention is first by the catalysis after inactivation
Agent is contacted with the oxidant containing oxide, is then passed through the regeneration purge gas containing oxygen and ozone again and 80~300
Regeneration treatment is carried out in a low temperature of DEG C, thus to obtain regenerated catalyst.
Low-temp recovery method of the invention is suitable for the molecular sieve catalyst of producing ethylene from dehydration of ethanol.Specifically, of the invention
Involved in decaying catalyst be to be used during producing ethylene from dehydration of ethanol and deactivated modified molecular sieve catalyst,
In, when ethanol conversion drops to 96% hereinafter, being then determined as that catalyst loses activity.
Specifically, an exemplary embodiment of the present invention, the low-temp recovery side of the catalyst for ethanol delydration to ethylene
Method includes following multiple steps.
Step A:
Decaying catalyst and oxidant are subjected to contact treatment, wherein oxidant be containing perchloric acid, perchlorate and
H2O2At least one of oxide aqueous solution or steam.First decaying catalyst is contacted with oxidiferous oxidant is wrapped
Processing, in 80~150 DEG C of at a temperature of calcination, can achieve removing Coke Precursor on Catalyst Used, while making subsequent 100~
When 300 DEG C of oxygen-containing gas processing, the available better protection of modified molecules sieve structure.Wherein, perchlorate can be
KClO4、NaClO4And NH4ClO4At least one of.
When carrying out oxidant contact treatment, the dosage for controlling oxidant is the 1~150% of decaying catalyst weight, excellent
It is selected as 10~50%；The concentration of oxide is 1~60wt%, preferably 10~20wt% in used oxidant.Concentration mistake
Height will lead to the catalyst choice after regeneration and reduce.Concentration is too low, then repeatedly catalyst activity can also reduce after regeneration, leads
Catalyst life is caused to reduce.
Also, reaction bed temperature when controlling contact treatment is 80~300 DEG C, while controlling the time of contact treatment
It is 3~10 hours.When practical operation, when oxidant is gaseous state, directly the catalyst bed of inactivation can be cooled to
80~300 DEG C, then pass to the contact treatment that above-mentioned oxidant carries out 3~10 hours；When oxidant is liquid, can will lose
Catalyst bed living, which takes out, simultaneously carries out contact treatment with oxidant, followed by recharging.
Step B:
It is passed through regeneration treatment gas and regeneration treatment is carried out to decaying catalyst, wherein regeneration treatment gas includes oxygenous
Oxygen content in body, ozone and diluent gas and regeneration treatment gas is 0.2~21%, wherein urging when regeneration treatment
Agent bed temperature is 100~300 DEG C.
It is some with the extension of the duration of runs along with certain side reactions in the production process of producing ethylene from dehydration of ethanol
Molecular by-products are deposited on catalyst surface, and the acid activity center for plugging catalyst micropore, covering catalyst causes to urge
The main reason for agent activity gradually decreases, and wherein carbon distribution is catalyst inactivation.It is passed through regeneration treatment gas and carries out regeneration treatment
Realize that catalyst regeneration, principle are the regeneration gas containing oxygen, ozone, Ke Yiyu indeed through the mode for burning carbon
Carbon distribution reaction, generates the gaseous materials such as carbon monoxide, carbon dioxide, so that catalyst micropore and activated centre can be extensive
It is multiple.And the oxidisability of ozone is stronger, can also reduce and burn carbon temperature, allows temperature of the regenerative process at 100~300 DEG C
Lower progress.
Specifically, oxygen-containing gas can be air or purity oxygen.Ozone concentration in above-mentioned regeneration treatment gas is preferred
For 10~500ppm.It excessively acutely causes catalyst bed temperature runaway to generate security risk in order to avoid burning carbon reaction when regeneration, needs
Diluent gas to be added in regeneration treatment gas, diluent gas can be nitrogen or water vapour.
, according to the invention it is preferred to which the flow velocity for controlling regeneration treatment gas is 0.5~5m3/min。
When carrying out regeneration purge processing, first since the oxygen content in regeneration treatment gas be 0.2~1%, by
Step steps up oxygen content in regeneration treatment gas and goes forward side by side row order section to 5~21% while improving reaction bed temperature
The regeneration purge of formula is handled, wherein the time for controlling regeneration treatment is 3~30 hours.It is preferred that 10~20 hours, the time is too short,
It is incomplete to burn carbon；Time is too long, especially under the conditions of elevated oxygen level when, molecular sieve structure can be damaged.
Wherein, the condition of regeneration treatment is affected to regenerative process.When general bed temperature is lower, no matter oxygen content
It is big or small, it burns carbon and is not easy completely.When oxygen content is low, when not only needing higher bed temperature but also needing longer burning carbon
Between, it otherwise burns carbon and is not easy completely.And oxygen content is up to a certain degree, bed temperature can be burnt completely in a certain range
Carbon.But only under certain oxygen content, temperature, which just significantly affects, burns carbon and spends completely and required time.And oxygen content is big, it is empty
Speed is big, and temperature is high, it is fast and complete to burn carbon, but have larger temperature rise, be easy to cause temperature runaway, especially commercial plant, once temperature runaway is not
Controllably, as a result, it is catastrophic.Thus selecting comparatively ideal burning carbon program is that multi-segment program burns carbon.From compared with low temperature, low oxygen
Content starts to burn carbon, and first the carbon of catalyst surface is burnt up；It heats up again later, burns up the carbon distribution in molecular sieve pore passage；With containing
The reduction of carbon amounts, steps up oxygen content, so that the carbon distribution of state of aggregation is also burned off, completes the regeneration of catalyst.
More specifically, the regeneration purge processing of step B specifically includes following sub-step:
1) control reaction bed temperature is 100~150 DEG C and controls oxygen content to be 0.2~1%, and purging 0.5~5 is small
When；2) control reaction bed temperature is 150~200 DEG C and controls oxygen content to be 0.2~1%, is purged 0.5~5 hour；3)
Control reaction bed temperature is 150~200 DEG C and controls oxygen content 1~2%, is purged 0.5~5 hour；4) control is urged
Agent bed temperature is 200~300 DEG C and controls oxygen content 1~2%, is purged 0.5~5 hour；5) catalyst bed is controlled
Layer temperature is 200~300 DEG C and controls oxygen content to be 2~5%, purge 0.5~5 hour；6) reaction bed temperature is controlled
For 200~300 DEG C and to control oxygen content be 5~21%, purges 0.5~5 hour, so far completes the regeneration treatment of step B.
When practical operation, carry out step A contact treatment after, directly in the reactor according to above-mentioned regeneration purge at
The program of reason carries out regeneration treatment to decaying catalyst.
Step C:
Cooled down with high pure nitrogen purging catalyst bed and control the oxygen content in reactor and is down to 0.5% hereinafter, knot
Shu Zaisheng regenerated after catalyst for ethanol delydration to ethylene.
Specifically, the technique that can be directly cooled to 220~300 DEG C of reaction temperature and carry out producing ethylene from dehydration of ethanol.
Wherein, the purity of the nitrogen used is 99.9% or more.
It should be understood that above embodiment and following embodiment that the present invention is described in detail are merely to illustrate the present invention rather than limit
The scope of the present invention processed, some nonessential improvement and tune that those skilled in the art's above content according to the present invention is made
It is whole to all belong to the scope of protection of the present invention.Specific parameter etc. is also only an example in OK range in following embodiments,
I.e. those skilled in the art can be done in suitable range by the explanation of this paper and be selected, and not really want to be defined in Examples below
In specific value and specific steps.
The catalyst that following embodiment uses is catalyst (embodiment disclosed in Chinese patent CN102806101A
1), catalyst specific be the preparation method comprises the following steps: the hour ZSM-5 molecular sieve powder that 90 parts of silica alumina ratios are 25 is added to the water,
Add 2 parts of phosphoric acid solutions (85 problems, %), 1.5 parts of lanthanum nitrates, 0.5 part of strontium nitrate, be stirring evenly and then adding into 10 parts intend it is thin
Diaspore, 3 parts of citric acids, then extrusion, then dries and is placed on 450 DEG C roasting 4 hours in Muffle furnace, take 20 after crushing and screening
The particle of~40 mesh, catalyst needed for being made.
Embodiment 1:
After catalyst inactivation (after ethanol conversion drops to 96% or less), which is regenerated, by bed temperature
Degree is down to 150 DEG C, is passed through containing H2O2Steam (concentration 1%, usage amount be catalyst weight 150%) contact treatment 0.1
Hour, reaction bed temperature is then down to 100 DEG C, with 0.5m3The gas flow rate of/min by containing 1% oxygen,
The regeneration purge gas of the ozone of 500ppm and remaining nitrogen purges catalyst bed 0.5 hour；150 DEG C are warming up to, with
0.5m3The gas flow rate of/min is by the regeneration purge gas containing 1% oxygen, the ozone of 500ppm and remaining nitrogen to catalysis
Agent bed purges 0.5 hour；Controlling bed temperature is 150 DEG C, with 0.5m3The flow velocity of/min will contain 2% oxygen, 500ppm
Ozone and the regeneration purge gas of remaining nitrogen catalyst bed is purged 0.5 hour；200 DEG C are warming up to, with 0.5m3/min
Gas flow rate the regeneration purge gas containing 2% oxygen, the ozone of 500ppm and remaining nitrogen purges catalyst bed
0.5 hour；Controlling bed temperature is 200 DEG C, with 0.5m3The flow velocity of/min will contain 5% oxygen, the ozone and residue of 500ppm
The regeneration purge gas of nitrogen purges catalyst bed 0.5 hour；Controlling bed temperature is 300 DEG C, with 0.5m3The stream of/min
Speed purges the regeneration purge gas containing 21% oxygen, the ozone of 500ppm and remaining nitrogen 0.5 hour to catalyst bed.
Finally lead to 99.9% or more nitrogen and reaction bed temperature is down to 280 DEG C of reaction temperature, and ensures oxygen content in reactor
0.5% is down to hereinafter, so far catalyst regeneration is completed.
Embodiment 2:
After catalyst inactivation (after ethanol conversion drops to 96% or less), which is regenerated, by bed temperature
Degree is down to room temperature and is taken out, the KClO for being then 1% with 150% and the concentration for accounting for catalyst weight by catalyst4Aqueous solution exists
It is contacted at a temperature of 80 DEG C 10 hours, Catalyst packing is then returned into reactor and is warming up to 150 DEG C, with 5m3The gas stream of/min
Speed purges the regeneration purge gas containing 0.2% oxygen, the ozone of 10ppm and remaining nitrogen 5 hours to catalyst bed；
200 DEG C are warming up to, with 5m3The gas flow rate of/min is by the regeneration containing 0.2% oxygen, the ozone of 10ppm and remaining nitrogen
Purge gas purges catalyst bed 5 hours；Controlling bed temperature is 200 DEG C, with 5m3The flow velocity of/min will contain 1%
The regeneration purge gas of oxygen, the ozone of 10ppm and remaining nitrogen purges catalyst bed 5 hours；300 DEG C are warming up to, with
5m3The gas flow rate of/min is by the regeneration purge gas containing 1% oxygen, the ozone of 10ppm and remaining nitrogen to catalyst bed
Layer purging 5 hours；Controlling bed temperature is 300 DEG C, with 5m3The flow velocity of/min will be containing 2% oxygen, the ozone of 10ppm and surplus
The regeneration purge gas of remaining nitrogen purges catalyst bed 5 hours；Controlling bed temperature is 300 DEG C, with 5m3The flow velocity of/min
Regeneration purge gas containing 5% oxygen, the ozone of 10ppm and remaining nitrogen purges catalyst bed 5 hours.Finally lead to
Reaction bed temperature is down to 280 DEG C of reaction temperature by 99.9% or more nitrogen, and ensures that oxygen content is down in reactor
0.5% hereinafter, so far catalyst regeneration is completed.
Embodiment 3:
After catalyst inactivation (after ethanol conversion drops to 96% or less), which is regenerated, by bed temperature
Degree is down to room temperature and is taken out, the NaClO for being then 60% with 50% and the concentration for accounting for catalyst weight by catalyst4Aqueous solution exists
It is contacted at a temperature of 80 DEG C 1 hour, Catalyst packing is then returned into reactor and is warming up to 125 DEG C, with 1m3The gas flow rate of/min
Regeneration purge gas containing 0.5% oxygen, the ozone of 100ppm and residual steam purges catalyst bed 1 hour；
175 DEG C are warming up to, with 1m3The gas flow rate of/min is by the regeneration containing 0.5% oxygen, the ozone of 100ppm and residual steam
Purge gas purges catalyst bed 1 hour；Controlling bed temperature is 175 DEG C, with 1m3The flow velocity of/min will contain 1.5%
Oxygen, 100ppm ozone and residual steam regeneration purge gas to catalyst bed purge 1 hour；250 DEG C are warming up to,
With 1m3The gas flow rate of/min is by the regeneration purge gas containing 1.5% oxygen, the ozone of 100ppm and residual steam to catalysis
Agent bed purges 1 hour；Controlling bed temperature is 250 DEG C, with 1m3The flow velocity of/min by containing 3.5% oxygen, 100ppm it is smelly
The regeneration purge gas of oxygen and residual steam purges catalyst bed 1 hour；Controlling bed temperature is 250 DEG C, with 1m3/min
Flow velocity the regeneration purge gas containing 10% oxygen, the ozone of 100ppm and residual steam is 1 small to catalyst bed purging
When.Finally lead to 99.9% or more nitrogen and reaction bed temperature is risen to 280 DEG C of reaction temperature, and ensures that oxygen contains in reactor
Amount is down to 0.5% hereinafter, so far catalyst regeneration is completed.
Embodiment 4:
After catalyst inactivation (after ethanol conversion drops to 96% or less), which is regenerated, by bed temperature
Degree is down to room temperature and is taken out, the HClO for being then 20% with 10% and the concentration for accounting for catalyst weight by catalyst4Aqueous solution exists
It is contacted at a temperature of 80 DEG C 5 hours, Catalyst packing is then returned into reactor and is warming up to 125 DEG C, with 1m3The gas flow rate of/min
Regeneration purge gas containing 1% oxygen, the ozone of 50ppm and residual steam purges catalyst bed 1 hour；Heating
To 175 DEG C, with 1m3The gas flow rate of/min is by the regeneration purge gas containing 1% oxygen, the ozone of 50ppm and residual steam
Body purges catalyst bed 1 hour；Controlling bed temperature is 175 DEG C, with 1m3The flow velocity of/min by containing 2% oxygen,
The ozone of 50ppm and the regeneration purge gas of residual steam purge catalyst bed 1 hour；250 DEG C are warming up to, with 1m3/
The gas flow rate of min blows catalyst bed oxygen, the ozone of 50ppm and the regeneration purge gas of residual steam containing 2%
It sweeps 1 hour；Controlling bed temperature is 250 DEG C, with 1m3The flow velocity of/min will be containing 5% oxygen, the ozone of 50ppm and remaining steaming
The regeneration purge gas of vapour purges catalyst bed 1 hour；Controlling bed temperature is 250 DEG C, with 1m3The flow velocity of/min will contain
The regeneration purge gas of 21% oxygen, the ozone of 50ppm and residual steam purges catalyst bed 1 hour.Finally lead to
Reaction bed temperature is risen to 280 DEG C of reaction temperature by 99.9% or more nitrogen, and ensures that oxygen content is down in reactor
0.5% hereinafter, so far catalyst regeneration is completed.
Embodiment 5:
After catalyst inactivation (after ethanol conversion drops to 96% or less), which is regenerated, by bed temperature
Degree is down to 100 DEG C, is passed through containing NH4ClO4Steam (concentration 10%, usage amount be catalyst weight 50%), be warming up to
120 DEG C and contact treatment 5 hours, then at such a temperature with 1m3The gas flow rate of/min will contain 1% oxygen, 50ppm
The regeneration purge gas of ozone and remaining nitrogen purges catalyst bed 1 hour；175 DEG C are warming up to, with 1m3The gas of/min
Flow velocity purges the regeneration purge gas containing 1% oxygen, the ozone of 50ppm and remaining nitrogen 1 hour to catalyst bed；
Controlling bed temperature is 175 DEG C, with 1m3The flow velocity of/min by containing 2% oxygen, the ozone of 50ppm and remaining nitrogen again
Raw purge gas purges catalyst bed 1 hour；250 DEG C are warming up to, with 1m3The gas flow rate of/min by containing 2% oxygen,
The regeneration purge gas of the ozone of 50ppm and remaining nitrogen purges catalyst bed 1 hour；Controlling bed temperature is 250 DEG C,
With 1m3The flow velocity of/min is by the regeneration purge gas containing 5% oxygen, the ozone of 50ppm and remaining nitrogen to catalyst bed
Purging 1 hour；Controlling bed temperature is 250 DEG C, with 1m3The flow velocity of/min will contain 21% oxygen, the ozone and residue of 50ppm
The regeneration purge gas of nitrogen purges catalyst bed 1 hour.Finally lead to 99.9% or more nitrogen for reaction bed temperature
280 DEG C of reaction temperature are risen to, and ensures that oxygen content is down to 0.5% hereinafter, so far catalyst regeneration is completed in reactor.
Comparative example 1:
After catalyst inactivation (after ethanol conversion drops to 96% or less), which is regenerated, by bed temperature
Degree is down to 150 DEG C, the gaseous mixture of air and nitrogen is passed through, with 1m3The gas flow rate of/min will contain the mixed gas of 1% oxygen
(remaining group is divided into nitrogen, similarly hereinafter) purges catalyst bed 0.5 hour；350 DEG C are warming up to, with 1m3The gas flow rate of/min
Mixed gas containing 1% oxygen purges catalyst bed 0.5 hour；350 DEG C of bed temperature of control, with 1m3The stream of/min
Speed purges the mixed gas containing 2% oxygen 0.5 hour to catalyst bed；500 DEG C are warming up to, with 1m3The gas stream of/min
Speed purges the mixed gas containing 2% oxygen 0.5 hour to catalyst bed；500 DEG C of bed temperature of control, with 1m3/ min's
Flow velocity purges the mixed gas containing 5% oxygen 0.5 hour to catalyst bed；500 DEG C of bed temperature of control, with 1m3/min
Flow velocity will containing 21% oxygen mixed gas to catalyst bed purge 0.5 hour.Finally leading to 99.9% or more nitrogen will urge
Agent bed temperature is down to 280 DEG C of reaction temperature, and guarantees in reactor that oxygen content is down to 0.5% hereinafter, so far catalyst
Regeneration is completed.
Analysis and summary:
The activity rating of catalyst uses fixed bed reactors in the present invention, and loaded catalyst 10g is original with ethyl alcohol
Material, water (content 40%) are diluent, normal pressure, gas space velocity 2.0h-1, 280 DEG C of bed temperature, table 1 is listed to above-mentioned
Activity data made from embodiment 1 to 5 and comparative example 1 after evaluating catalyst 350 hours.
The activity rating table of the catalyst of 1 producing ethylene from dehydration of ethanol of table
| Title | Ethanol conversion % | Ethylene selectivity % |
| Embodiment 1 | 97.4 | 98.5 |
| Embodiment 2 | 99.0 | 99.6 |
| Embodiment 3 | 98.9 | 99.1 |
| Embodiment 4 | 99.5 | 99.9 |
| Embodiment 5 | 99.6 | 99.4 |
| Comparative example 1 | 98.0 | 98.2 |
Seen from table 1, after being regenerated using catalyst of the regeneration methods of the invention to producing ethylene from dehydration of ethanol, regeneration
Catalyst afterwards preferably, maintains preferable catalytic activity in the performance parameters such as ethanol conversion, ethylene selectivity.
In conclusion catalyst for ethanol delydration to ethylene low-temp recovery method of the invention under cryogenic conditions, it can be achieved that urge
The multiple regeneration of agent, reduces producing ethylene from dehydration of ethanol plant investment total value and regenerative operation expense, while low-temp recovery can
Catalyst physical structure is kept not to be damaged, to facilitate the service life of extension catalyst.
The invention is not limited to specific embodiments above-mentioned.The present invention, which expands to, any in the present specification to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (9)
1. a kind of low-temp recovery method of catalyst for ethanol delydration to ethylene, which is characterized in that the low-temp recovery method includes
Following steps:
A, decaying catalyst and oxidant are subjected to contact treatment, the oxidant is to contain perchloric acid, perchlorate and H2O2In
The aqueous solution or steam of at least one oxide；
B, be passed through regeneration treatment gas to decaying catalyst carry out regeneration treatment, the regeneration treatment gas include oxygen-containing gas,
Ozone and diluent gas and the oxygen-containing gas are air or purity oxygen, wherein the oxygen in the regeneration treatment gas
Content is 0.2~21%, and reaction bed temperature when regeneration treatment is 80~300 DEG C, and the regeneration treatment is from regeneration place
Oxygen content in process gases is 0.2~1% beginning, is stepped up at regeneration while stepping up reaction bed temperature
The regeneration purge that oxygen content in process gases goes forward side by side row order segmentation to 5~21% is handled, wherein controls the time of regeneration treatment
It is 3~30 hours；
C, cooled down with high pure nitrogen purging catalyst bed and control the oxygen content in reactor and be down to 0.5% hereinafter, terminating
Catalyst for ethanol delydration to ethylene after being regenerated.
2. the low-temp recovery method of catalyst for ethanol delydration to ethylene according to claim 1, which is characterized in that the mistake
Catalyst living is to use during producing ethylene from dehydration of ethanol and deactivated modified molecular sieve catalyst, wherein works as ethyl alcohol
Conversion ratio drops to 96% hereinafter, being then determined as that catalyst loses activity.
3. the low-temp recovery method of catalyst for ethanol delydration to ethylene according to claim 1, which is characterized in that the height
Chlorate is KClO4、NaClO4And NH4ClO4At least one of.
4. the low-temp recovery method of catalyst for ethanol delydration to ethylene according to claim 1, which is characterized in that the oxygen
The dosage of agent is the 1~150% of decaying catalyst weight, and the concentration of oxide is 1~60wt% in the oxidant.
5. the low-temp recovery method of catalyst for ethanol delydration to ethylene according to claim 4, which is characterized in that the oxygen
The dosage of agent is the 10~50% of decaying catalyst weight, and the concentration of oxide is 10~20wt% in the oxidant.
6. the low-temp recovery method of catalyst for ethanol delydration to ethylene according to claim 1, which is characterized in that described to connect
Reaction bed temperature when synapsis is managed is 80~300 DEG C, and the time of the contact treatment is 3~30 hours.
7. the low-temp recovery method of catalyst for ethanol delydration to ethylene according to claim 1, which is characterized in that it is described again
Ozone concentration in raw processing gas is 10~500ppm.
8. the low-temp recovery method of catalyst for ethanol delydration to ethylene according to claim 1, which is characterized in that described dilute
Outgassing body is nitrogen or water vapour.
9. the low-temp recovery method of catalyst for ethanol delydration to ethylene according to claim 1, which is characterized in that it is described again
Raw purge specifically includes following sub-step:
Control reaction bed temperature is 100~150 DEG C and controls oxygen content to be 0.2~1%, purge 0.5~5 hour；
Control reaction bed temperature is 150~200 DEG C and controls oxygen content to be 0.2~1%, purge 0.5~5 hour；
Control reaction bed temperature is 150~200 DEG C and controls oxygen content 1~2%, is purged 0.5~5 hour；
Control reaction bed temperature is 200~300 DEG C and controls oxygen content 1~2%, is purged 0.5~5 hour；
Control reaction bed temperature is 200~300 DEG C and controls oxygen content to be 2~5%, purge 0.5~5 hour；
Control reaction bed temperature is 200~300 DEG C and to control oxygen content be 5~21%, purges 0.5~5 hour, so far
Complete the regeneration treatment of step B.
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| CN101455980A (en) * | 2007-12-13 | 2009-06-17 | 中国石油化工股份有限公司 | Regeneration method of oxidation-reaction inactive titanium silicon molecule sieve catalyst |
| CN101873892A (en) * | 2007-11-16 | 2010-10-27 | 埃克森美孚化学专利公司 | Catalyst recovery process |
| CN102059137A (en) * | 2010-11-18 | 2011-05-18 | 大唐国际化工技术研究院有限公司 | ZSM-5 zeolite catalyst for preparing propylene (MTP) from methanol, preparation method and regeneration method thereof |
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| CN101873892A (en) * | 2007-11-16 | 2010-10-27 | 埃克森美孚化学专利公司 | Catalyst recovery process |
| CN101455980A (en) * | 2007-12-13 | 2009-06-17 | 中国石油化工股份有限公司 | Regeneration method of oxidation-reaction inactive titanium silicon molecule sieve catalyst |
| CN102059137A (en) * | 2010-11-18 | 2011-05-18 | 大唐国际化工技术研究院有限公司 | ZSM-5 zeolite catalyst for preparing propylene (MTP) from methanol, preparation method and regeneration method thereof |
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