CN106237652B - Method is selectively adsorbing and separating using molecular sieve as adsorbent - Google Patents
Method is selectively adsorbing and separating using molecular sieve as adsorbent Download PDFInfo
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- CN106237652B CN106237652B CN201510317289.4A CN201510317289A CN106237652B CN 106237652 B CN106237652 B CN 106237652B CN 201510317289 A CN201510317289 A CN 201510317289A CN 106237652 B CN106237652 B CN 106237652B
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Abstract
The present invention, which provides, a kind of new improved is selectively adsorbing and separating method, wherein using molecular sieve as adsorbent, for the raw mixture comprising target components to be separated, the specific purge step using purging agent is combined after adsorbent bed not fully saturated adsorption step, and is wherein also used with the adsorbent bed of specific structure design.
Description
Technical field
The present invention relates to it is a kind of new it is improved be selectively adsorbing and separating method, wherein using molecular sieve as adsorbent,
For the raw mixture comprising target components to be separated, combined after adsorbent bed not fully saturated adsorption step
Using the specific purge step of purging agent, and wherein also use with the adsorbent bed of specific structure design.
Background technique
The mankind are very long using the history of adsorbent, most common such as with charcoal come moisture absorption, elimination peculiar smell.With science and technology
Progress, Emathlite, diatomite and active carbon are in occasions such as decoloration, deodorization, moisture absorption, dryings using more and more extensive.It
The right discovery of zeolite and the synthesis of later molecular sieve, have further opened new chapter for absorption and catalytic field.
Since absorption property of the different adsorbents to different material is different, many research and development are carried out around adsorbing separation
Work so that adsorption separation technology rapidly develops, and is widely applied in fields such as petroleum, chemical industry, pharmacy, environmental protection.
It in adsorbing separation, is selectively adsorbing and separating and is chiefly used in admixture of isomeric compound similar in boiling point, such as from diformazan
Adsorption stripping dimethyl benzene in benzol mixture from dichloro benzol mixture when adsorbing separation m-dichlorobenzene is all selective suction
Attached isolation technics.
It is disclosed in CN95112773.X and a kind of separates meta-xylene and ortho-xylene from mixed xylenes and ethylbenzene
Method, wherein Mixed XYLENE and ethylbenzene under adsorption conditions with gas phase state by equipped with MFI type zeolite adsorbent of molecular sieve
Adsorbent bed with selective absorption ethylbenzene and paraxylene, inhaling excess is meta-xylene and ortho-xylene, inhales excess warp later
Rectifying obtains meta-xylene and ortho-xylene.
The method of a kind of pressure-variable adsorption separating paraxylene and ethylbenzene from C8 aromatic hydrocarbons is disclosed in CN01812659.6,
The middle nonacid mesoporous molecular sieve that selection is aligned using MFI type separates two in C8 aromatic hydrocarbons in isothermal gas phase at high temperature under high pressure
Toluene and ethylbenzene.
A kind of method of gas phase selection adsorbing separation mixed dichlorobenzene is disclosed in CN99113692.6, wherein mixing dichloro
Benzene is with gas phase state by zeolite adsorbent, and adsorbent selection absorption paracide, suction excess is m-dichlorobenzene, neighbour two
Chlorobenzene and micro paracide, the paracide being adsorbed are desorbed under desorption conditions, inhale excess through conventional rectification and obtain purity
M-dichlorobenzene greater than 99.7%.
A kind of method with hydrophobic silicalite liquid-phase selective adsorption, separation and mixing of dichlorobenzene is disclosed in CN1315217A,
It is middle to use MFI type hydrophobic silicalite at least two dichlorobenzene isomer mixture of adsorbing separation under liquid-phase condition, adsorbent choosing
Absorption paracide and/or o-dichlorohenzene are selected, unadsorbed m-dichlorobenzene can directly be recycled from inhaling in excess stream, paracide
And/or o-dichlorohenzene can directly pass through desorption separation.
A kind of side of benzene di-substituted isomer complex phase adsorbing separation on hydrophobic silicalite is disclosed in CN1749226A
Method, wherein using N before bed adsorption contraposition substituent reaches saturation or after saturation2It is blown in progress, it is therefore an objective to which stripping bed is dead
Raw mixture in space, is then desorbed, wherein in the obtained extract of the midbarrel blown and desorption together
It collects, compared with raw mixture, para-isomer is only slightly enriched in the midbarrel+extract, it is also necessary to be returned
Adsorption process carries out adsorption treatment again.
In addition, the micro-content organism contained in water can also be using extraordinary molecular sieve absorption in treatment of industrial water
Agent is selectively adsorbing and separating, it is possible thereby to remove and be enriched with the organic matter, the special type adsorbent of molecular sieve can also be with
It reuses after regeneration.
Processing and the recovery method of a kind of acetone wastewater are disclosed in CN101219818A, wherein inhaling using zeolite molecular sieve
Fufen from recycling waste water in acetone, it is characterised in that acetone wastewater will be contained by zeolite molecular sieve adsorption column to adsorb waste water
In acetone, the acetone being then adsorbed is desorbed under high-temperature gas desorption conditions, while adsorbent is regenerated, after desorption
Acetone is through condensing recovery.
Therefore, in the prior art, for the raw mixture comprising target components to be separated, it is selectively adsorbing and separating
It mainly include adsorption step and desorption, wherein raw mixture is obtained mainly by absorption containing non-targeted in adsorption step
The suction excess stream of component, and be substantially saturated in desorption adsorbent bed by the way that acquisition is desorbed mainly containing target components
Logistics is desorbed, in addition, it is mixed to remove residual raw materials in bed to blow operation in can also being introduced between adsorption step and desorption
Object is closed, and the raw mixture of stripping is then made to return to the absorption of adsorption step further progress.
Summary of the invention
It is selectively adsorbing and separating process based in the prior art, the invention proposes a kind of new improved selectivity to inhale
Attached separation method, wherein being inhaled using molecular sieve as adsorbent for the raw mixture comprising target components to be separated
The specific purge step using purging agent is combined after the not fully saturated adsorption step of attached dose of bed, and is wherein also used
With the adsorbent bed of specific structure design.
Specifically, selective absorption is carried out to raw mixture as adsorbent using molecular sieve the present invention provides a kind of
Isolated method, the raw mixture include target components to be separated, method includes the following steps:
Adsorption step, wherein making raw mixture along first direction by adsorbent bed, adsorbent bed along first
The exit in direction, which is collected, inhales excess stream, continues adsorption process, until the adsorbance of adsorbent bed upper target components is by dynamic
Penetrate absorption meter reach 65-99.5% until；
Purge step, wherein make purge agent pass through in a second direction it is adsorbent bed, it is adsorbent bed in a second direction
Exit collect purge stream, continue purge, to remove the non-target components in adsorbent bed, wherein second direction
It is identical as first direction；
Desorption, wherein making desorbing agent along third direction by adsorbent bed, adsorbent bed along third direction
Exit collect desorption logistics, continue desorption process, until the concentration of target components in desorption logistics is constant or vary less
Until, wherein third direction is identical as first direction, contrary or is mutually perpendicular to, and preferably contrary or is mutually perpendicular to, more preferably
It is mutually perpendicular to；With
Optional circulation step is recycled wherein being repeated in above-mentioned each operating procedure.
According to the present invention, wherein adsorption step carry out to a certain extent i.e. it is adsorbent bed not yet be saturated when, such as
Generally in adsorbent bed upper target components adsorbance by Kinetic penetration absorption meter at most 99.5%, preferably up to 98% and more
Stop adsorption step when preferably up to 96% and start purge step, agent and raw mixture charging side are purged in purge step
To identical, so that purging path is identical as absorption path, thus drives and sweep adsorbent bed interior residual raw materials mixture and pass through again
Cross absorption path, allow target components therein by it is unsaturated it is adsorbent bed on remaining adsorption site further inhale
Attached, i.e., the described residual raw materials mixture carries out supplement absorption during being migrated by purging, adsorbs after purging in this way
Agent bed is practically free of or contains only a small amount of non-target components, and obtained purge stream itself or separates with purging agent as logical
The composition for the purge stream crossed after mutually separating such as water separation of oil or liquid phase separation is also very close to inhale excess stream, they are very
Extremely can with inhale excess stream merge collection and then be further processed, and to it is purged it is adsorbent bed be desorbed after,
Desorption logistics obtained is also practically free of or contains only a small amount of non-target components.
Therefore, it is proposed, according to the invention, by being blown in the unsaturated adsorption process and purge step in combined application adsorption step
Path purge (purge and supplement and adsorb) in the same direction identical with absorption path is swept, can as much as possible guarantee adsorbent
The target components being adsorbed are primarily present in bed, so that the target components purity of the desorption logistics obtained in subsequent desorption
It is higher, the efficiency of absorption and desorption is which thereby enhanced, so as to realize efficiently separating for target components and non-target components, is made
Where the advantages of entire adsorption separation process is more efficient, this is also technical solution of the present invention.
According to the present invention, in adsorption step, the adsorbance of adsorbent bed upper target components is adsorbed according to Kinetic penetration
Amount is to measure.In the art, Kinetic penetration adsorbance is the distinctive performance parameter of adsorbent itself, usually in certain temperature
Institute's adsorbable target components amount when reaching Kinetic penetration point with adsorbent under pressure, with Unit Weight or unit volume adsorbent
Average value meter.
In the art, when measuring the Kinetic penetration adsorbance of adsorbent, generally a certain amount of adsorbent is filled in
In adsorbent bed, make liquid or gas with determining target components concentration under the temperature and pressure to determine that flow is logical
It crosses adsorbent bed, measures target components concentration in oral fluid body or gas, when target components concentration in outlet liquid or gas
Think adsorbent bed when reaching corresponding critical value to be penetrated by target components, the suction of Unit Weight or volume of adsorbent at this time
Attached capacity just corresponds to the Kinetic penetration adsorbance that the adsorbent is directed to target components.
According to the present invention, wherein the molecular sieve as adsorbent can be various suitable types usually used in this field
Molecular sieve, usually can selected from MFI type zeolite such as ZSM-5, FER type zeolite such as ferrierite, BEA type zeolite such as β zeolite and
High silicon FAU type zeolite such as Y zeolite and overstable gamma zeolite, the preferably na-pretreated zeolite of these zeolites or binder free na-pretreated zeolite, nothing
Binder hydrophobic type zeolite or hydrophilic zeolite, more preferably MFI type binder free hydrophobic silicalite or binder free
Silicalite-1 zeolite, the typically any suitable size and shape of the adsorbent of molecular sieve, for example, its average particle size
Generally 1-5mm, preferably 2-3mm and shape are generally spherical or cylindrical body etc..
It is selectively adsorbing and separating in method in of the invention, purges agent and the selection of desorbing agent can be by logical in this field
Normal standard carries out, and in general, the target components contained in raw mixture may be adsorbed agent and adsorb by force, and purge agent and
Desorbing agent may also be adsorbed by adsorbent, but degree of absorption is weaker for target components, i.e., will not be with target group
Point competition occupies bed adsorption site, and they are usually inert in system, i.e., cannot with purged or be desorbed
The interaction such as substance, in addition, also requiring them to be separated from each other as easily as possible with the substance for being purged or being desorbed, such as
It can be easily separated from each other by mutually separating such as liquid phase separation or water separation of oil or rectifying to realize, these are right
For those skilled in the art be all it is well known, i.e., those skilled in the art can these usual standards based on this field come
It correspondingly selects and using purging agent and desorbing agent.
According to the present invention, wherein purging agent and desorbing agent are preferably further selected according to separation ratio, wherein making to take off
Attached dose of separation ratio βTarget components/desorbing agent> 1, preferably 1-10, and make the separation ratio β for purging agentTarget components/purging agent≥
βTarget components/desorbing agent, preferably 2-100, more preferably 3-50.
Specifically, it is proposed, according to the invention, wherein the separation of desorbing agent is than the separation and desorbing agent for target components
The ratio between separation, purge separation the ratio between of the separation than separation and purging agent for target components of agent,
Separation is then each substance in the amount and its ratio between amount in non-molecular sieve absorption phase in molecular sieve absorption phase, wherein de-
Attached dose is defined respectively as with the separation ratio for purging agent:
With
According to the present invention, by purging the further selection of agent and desorbing agent above it is found that the purging agent and desorbing agent can
With identical or different, and purge separation ratio of the separation of agent than being greater than or equal to desorbing agent, that is to say, that purging agent
Separation be less than or equal to desorbing agent separation, i.e., purging agent be adsorbed intensity generally not stronger than be desorbed
Agent, and the separation of desorbing agent ratio βTarget components/desorbing agent> 1 and preferably 1-10, that is, require the separation of desorbing agent in certain journey
It is lower than target components on degree, so as to be adsorbed agent bed adsorption to a certain extent.
In this way, it is proposed, according to the invention, purging agent primarily serves the work of residual raw materials mixture in purging and removal bed sheaf space
With without occupying the adsorption site on adsorbent bed with target components competition, also, due to adsorbing in the present invention
Start purge step when agent bed unsaturation and purging path is identical as absorption path, can make to be moved in bed by purging agent purging
Target components in the residual raw materials mixture of shifting are further adsorbed by adsorption site remaining in bed, so that leaving bed
The content of target components is at a fairly low in purge stream, i.e., the mainly non-target components for finally purging and removing, so that gained is blown
Sweep logistics may not be needed return adsorption step carry out adsorbing separation again, it might even be possible to optionally with purging agent separating as passed through
It mutually separates as merged collection with suction excess stream after water separation of oil or liquid phase separation and being then further processed, and takes off later
Attached dose then mainly supplants target components from adsorbent bed, but will not during quickly through adsorbent bed quilt
It is excessively firmly attached on adsorbent bed, and then realizes the desorption of target components well, make adsorbent bed obtain " again
It is raw ", it is possible thereby into next absorption, purging and de-adsorption cycle.
According to the present invention, wherein it is adsorbent bed to pass through raw mixture along first direction, make to purge agent along second party
To by adsorbent bed, and make desorbing agent along third direction by adsorbent bed, wherein second direction and first direction phase
Together, third direction is identical as first direction, contrary or is mutually perpendicular to, and preferably contrary or is mutually perpendicular to, more preferably mutually hangs down
Directly, and wherein the adsorbent bed draw ratio along first direction be greater than or equal to it is adsorbent bed in a second direction and third direction
Draw ratio.
Therefore, it is proposed, according to the invention, raw mixture usually along the higher route of draw ratio by adsorbent bed, so as to
Relatively sufficiently to carry out adsorption process in longer stroke, purging agent is usually and raw mixture is in adsorbent bed interior stream
To identical, i.e. purging path is usually identical as absorption path, sweeps the remnants of migration to make to be purged agent in purge to drive
Raw mixture by absorption path, is adsorbed target components therein further, thus makes target in purge stream again
Constituent content is very low, finally, desorbing agent and raw mixture it is adsorbent bed it is interior flow to identical, contrary or be mutually perpendicular to,
It preferably contrary or is mutually perpendicular to, is more preferably mutually perpendicular to, so as to effectively realize the desorption of target components.
According to the present invention, it is adsorbent bed can be to be cylindric adsorbent bed, wherein filled with absorption inside cylindrical body
Agent, cylindrical body top and lower part are respectively equipped with distribution and collection space and distribution and collect porous plate, and third direction is excellent at this time
Choosing and the first and second direction contraries, therefore desorption can be more effectively carried out.
According to the present invention, adsorbent bed or case shape is adsorbent bed, and wherein box house is filled with absorption
Agent, cabinet are respectively equipped with distribution and collection space and distribution in horizontal cross and vertical longitudinal both ends and collect porous
Plate, third direction is preferably mutually perpendicular to the first and second directions at this time, therefore distance is desorbed may be shorter, desorption time also phase
Should be shorter, to further increase desorption efficiency.
According to the present invention, wherein adsorption step and purge step can be respectively under normal pressure or pressurization in gas phase or liquid phase shapes
It is carried out under state, and desorption can carry out under gas phase or liquid phase state under normal pressure, pressurization or vacuum, that is, adsorb and purge
It is carried out usually under normal pressure or pressurization with gas phase or liquid phase, and being desorbed then can be under normal pressure, pressurization or vacuum with gas phase or liquid
Mutually carry out, this point with it is almost the same in the prior art.
According to the present invention, wherein raw mixture can isomer di-substituted for benzene series or three substituent of benzene series
Mixture, it may include dimethylbenzene, diethylbenzene, ethyl methyl benzene, dichloro-benzenes, chlorotoluene, chloroethene benzene that wherein benzene series is di-substituted
Deng aligning substituent at this time is usually target components, and wherein three substituent of benzene series may include dichlorotoleune, dichloro ethylbenzene
Deng, 1,2,5- tri- substituents or 1 at this time, 2,4- tri- substituents are usually target components, and purge agent then can selected from water vapour,
CO2、C1-C4Hydrocarbon, air, nitrogen and argon gas.
According to the present invention, when benzene series is di-substituted or the admixture of isomeric compound of three substituent of benzene series is as raw material mixing
When object, wherein the content of target components may be relatively high in raw mixture, but is generally not more than 80wt%, preferably no greater than
70wt%, more preferably no higher than 60wt%, and it is not less than 1wt%, preferably not less than 3wt%, wherein in the absorption of target components
Amount stops adsorption step when reaching 68-96%, preferably 70-95% by Kinetic penetration absorption meter, wherein holding with adsorption step
Continuous time τ is compared, and the duration of purge step is generally 0.01-5 τ, preferably 0.05-1 τ, and when target in desorption logistics
Stop desorption when the content of component is lower than 0.5wt%, preferably shorter than 0.3wt%.
Further, it is proposed, according to the invention, when benzene series is di-substituted or the admixture of isomeric compound conduct of three substituent of benzene series
When raw mixture, wherein raw mixture, purging agent and desorbing agent can be fed according to the weight (hourly) space velocity (WHSV) of this field routine, example
Such as, the weight (hourly) space velocity (WHSV) of raw mixture and desorbing agent is generally respectively 0.1-5h-1, preferably 0.3-2.5h-1, more preferable 0.5-
1.5h-1, and purging agent weight (hourly) space velocity (WHSV) be generally 0.1-10h-1, preferably 0.2-5h-1, more preferable 0.3-3h-1。
According to the present invention, when benzene series it is di-substituted as xylene mixture be raw mixture when, it is preferred to purge agent at this time
For water vapour or C1-C4Hydrocarbon, desorbing agent are preferably toluene, wherein as raw mixture xylene mixture, as purging agent
Water vapour or C1-C4Hydrocarbon and toluene as desorbing agent are usually preheated to 140-170 DEG C of rear feeding to adsorbent bed under normal pressure
Layer is to be adsorbed, purged and be desorbed under gas phase state.
According to the present invention, when benzene series it is di-substituted as dichloro benzol mixture be raw mixture when, it is preferred to purge agent at this time
For air, nitrogen or C1-C4Hydrocarbon, desorbing agent are preferably chlorobenzene, wherein as the dichloro benzol mixture of raw mixture, as blowing
Sweep the air, nitrogen or C of agent1-C4Hydrocarbon and chlorobenzene as desorbing agent are usually preheated to 180-200 DEG C of rear feeding extremely under normal pressure
It is adsorbent bed to be adsorbed, purged and be desorbed under gas phase state.
It, at this time can be first when for example dichlorotoleune mixture is as raw mixture for three substituent of benzene series according to the present invention
First the raw material that can be used as being selectively adsorbing and separating is obtained by the dichlorotoleune mixture rectifying of five kinds of dichlorotoluene isomers to mix
The dichlorotoleune mixture for mainly containing three kinds of dichlorotoluene isomers of object, such as the raw mixture can contain 1 to be main,
2,4-DCT, 1,2,5- dichlorotoleune, 1, three isomer mixture of dichlorotoleune of 2,6-DCT, wherein 1,2,5-
Dichlorotoleune is target components, and purging agent at this time is preferably nitrogen, and desorbing agent is preferably chlorobenzene, wherein as raw mixture
Dichlorotoleune mixture and as purging agent nitrogen 200-260 DEG C of rear feeding is usually preheated under the gauge pressure of 0.1-0.5MPa
It is extremely adsorbent bed to be adsorbed and be purged under gas phase state and wherein usually pre- under normal pressure as the chlorobenzene of desorbing agent
Heat under gas phase state to 200-260 DEG C of rear feeding to adsorbent bed to be desorbed, and applied saying is " main herein
Containing " refer to that the total content of each component for mainly including is at least 50wt%, preferably at least 70wt%, more preferably extremely
Few 90wt%, and the total content of other non-principal each components for including is then seldom, such as no more than 50wt%, preferably more than
30wt%, and more preferably no more than 10wt%.
According to the present invention, wherein raw mixture may be waste water containing a small amount of organic matter or containing the organic of a small amount of water
Thing liquid body, wherein the useless Organic substance in water containing a small amount of organic matter is target components, water is mesh in the organic matter liquid containing a small amount of water
Component is marked, the organic matter can be selected from hexane, heptane, benzene, toluene, ethylbenzene, styrene, paraxylene, acetone, acetic acid, second
Alcohol, ethyl acetate, 1- propyl alcohol, 1,3- propylene glycol, n-butanol, methylamine, ethamine, propylamine, n-butylamine, formamide, acetamide, N,
Dinethylformamide, DMAC N,N' dimethyl acetamide, chloroform, cyclohexanone oxime and small-molecule drug intermediate such as medicine intermediate
With pesticide intermediate etc., wherein purging agent and desorbing agent can be each independently selected from water vapour, CO2、C1-C4Hydrocarbon, air, nitrogen
Gas and argon gas.
According to the present invention, when the waste water containing a small amount of organic matter or the organic matter liquid containing a small amount of water are as raw mixture
When, wherein the content of target components may be relatively low in raw mixture, for example, it is generally not more than 20wt%, it is preferably not high
In 15wt%, more preferably no higher than 10wt%, and it is not less than 0.01wt%, preferably not less than 0.03wt%, wherein in target group
The adsorbance divided stops adsorption step when reaching 90-99.5%, preferably 95-98% by Kinetic penetration absorption meter, wherein with suction
The duration τ of attached step is compared, and the duration of purge step is generally 0.001-0.5 τ, preferably 0.002-0.2 τ, and
The duration of desorption is generally 0.01-0.5 τ, preferably 0.02-0.2 τ.
According to the present invention, when the waste water containing a small amount of organic matter or the organic matter liquid containing a small amount of water are as raw mixture
When, wherein raw mixture, purging agent and desorbing agent can be fed according to the weight (hourly) space velocity (WHSV) of this field routine, for example, raw material is mixed
The weight (hourly) space velocity (WHSV) for closing object and desorbing agent is generally respectively 0.1-10h-1, preferably 0.2-5h-1, more preferable 0.25-2.5h-1, and purging
The weight (hourly) space velocity (WHSV) of agent is generally 0.1-50h-1, preferably 0.2-30h-1, more preferable 0.25-10h-1。
Agent is purged at this time when it is raw mixture that the waste water containing a small amount of organic matter, which such as contains acetone wastewater, according to the present invention
Water vapour, CO can be each independently selected from desorbing agent2、C1-C4Hydrocarbon, air, nitrogen and argon gas, wherein adsorption step is usual
It carries out under normal pressure, purge step and desorption usually carry out under 0.1-1.0MPa gauge pressure.
According to the present invention, when it is raw mixture that the waste water containing a small amount of organic matter, which such as contains dimethyl acetamide waste water, this
When purging agent and desorbing agent can be each independently selected from water vapour, CO2、C1-C4Hydrocarbon, air, nitrogen and argon gas, wherein adsorbing
Step and desorption usually carry out under normal pressure, and purge step usually carries out under 0.02-0.15MPa gauge pressure.
Detailed description of the invention
Carry out the method that the present invention will be described in more detail with reference to the accompanying drawing, in which:
Fig. 1 is the schematic diagram of one embodiment of the present invention；With
Fig. 2 is the schematic diagram of another embodiment of the invention.
Fig. 1 gives a kind of embodiment of the method for the present invention, wherein it is adsorbent bed to be cylindric adsorbent bed,
In inside cylindrical body be filled with adsorbent, the top of cylindrical body and lower part be respectively equipped with distribution space and collection space with
And it is distributed and collects porous plate；Raw mixture is passed through from adsorbent bed lower part, is inhaled excess stream and is adopted on adsorbent bed top
Out；Purging agent is passed through from adsorbent bed lower part, and purge stream produces on adsorbent bed top；Desorbing agent is from adsorbent bed
Top is passed through, and desorption logistics is produced in adsorbent bed lower part；Agent and raw mixture are wherein purged adsorbent bed interior
It flows to identical and desorbing agent and raw mixture and interior flows to contrary adsorbent bed.
Fig. 2 gives another embodiment of the method for the present invention, wherein adsorbent bed is that case shape is adsorbent bed,
It wherein is filled with adsorbent in box house, cabinet is respectively equipped with distribution and collection in horizontal cross and vertical longitudinal both ends
Space and distribution and collect porous plate left and right porous plate and upper and lower porous plate as illustrated in the drawing；Raw mixture is adsorbing
It is fed at agent bed left hand inlet port and along X-axis forward direction by adsorbent bed, suction excess stream is at adsorbent bed right-side outlet
Extraction；Purging agent is fed by adsorbent bed left hand inlet port and along X-axis forward direction by adsorbent bed, and purge stream is being adsorbed
It is produced at agent bed right-side outlet；Desorbing agent is fed by adsorbent bed top and along Y-axis negative sense by adsorbent bed, desorption
Logistics is produced from adsorbent bed lower part, wherein purging agent and raw mixture it is adsorbent bed it is interior flow to it is identical and de-
Attached dose and raw mixture are mutually perpendicular in adsorbent bed interior flow direction.
Specific embodiment
The invention is further illustrated by the following examples, but the model that the embodiment is not limit the invention in any way
It encloses.
In the examples below that, used adsorbent is that (patent is incorporated herein in its entirety according to patent CN1105906A
As reference) described in method production MFI type binder free hydrophobic silicalite, i.e. ZSM-5 type binder free hydrophobic silicalite
Or binder free Silicalite-1 zeolite, this kind of binder free hydrophobic silicalite are commercially available industrial products, have strong
Hydrothermal stability and strong acidproof and resistance to alkalescent, and due to being substantially free of aluminium in framework of molecular sieve, hydrophobicity is very strong, water suction
Very little is measured, and it is small can also specifically to roast 1-5 at 300-800 DEG C by simply roasting activity recovery after poisoning and deactivation
When can activity recovery and realize regeneration.
In the examples below that, used adsorbent of molecular sieve is the bead that average diameter is 2-3mm, used original
Suction excess stream, purge stream and the desorption logistics that material mixture and collection obtain finally exist with liquid form, these liquid phases
The composition of logistics is analyzed by gas-chromatography.
Embodiment
1 xylene mixture of embodiment is selectively adsorbing and separating
Using as shown in Figure 1 cylindric adsorbent bed, it is highly 0.2m, the bed is matched that bed internal diameter, which is 0.1m,
There is collet, 800g adsorbent bead is filled in bed, wherein raw mixture is composition dimethylbenzene mixing as shown in table 1 below
Object, using water vapour as purging agent, separation ratio βParaxylene/water vapourAbout 20, and using toluene as desorbing agent, point
From coefficient ratio βParaxylene/tolueneAbout 7.5, wherein adsorption step, purge step and desorption carry out under normal pressure.
Operating procedure is as follows:
Adsorption step, wherein xylene mixture is made to be preheated to 155 DEG C and with weight (hourly) space velocity (WHSV) 1h-1From adsorbent bed lower part
Charging is inhaled excess stream and produce from adsorbent bed top, obtains liquid phase suction excess stream through cooling, keeps the adsorbent bed temperature to be
It is 155 DEG C, lasting to feed, stop charging when paraxylene adsorbance reaches the 95% of its Kinetic penetration adsorbance, inhales at this time
The duration of attached step is 30min；
Purge step, wherein making the steam heating as purging agent to 160 DEG C and with weight (hourly) space velocity (WHSV) 1h-1From adsorbent bed
The charging of layer lower part, purge stream are produced from adsorbent bed top, and purge continues 2min, are obtained through cooling and water separation of oil
Purge stream oil phase is obtained, the purge stream oil mutually merges collection with suction excess stream；
Desorption, wherein the toluene as desorbing agent is made to be preheated to 155 DEG C and with weight (hourly) space velocity (WHSV) 1h-1From adsorbent bed
Top charging, desorption logistics are produced from adsorbent bed lower part, logistics are desorbed through the cooling liquid phase that obtains, to be desorbed in logistics to two
It is desorption terminal that toluene level, which is less than 0.2wt%, and the duration of desorption is 60min at this time；With
Above-mentioned each operating procedure is repeated in into next circulation.
Each logistics composition obtained after the completion of operation is as shown in table 1 below.
The composition of each logistics of the raw mixture and acquisition of 1 embodiment 1 of table
By the result of embodiment 1 it is found that using method of the invention, suction excess stream+purge stream oil phase obtained
Paraxylene content is very low in mixture flow, which can be obtained meta-xylene and the neighbour two of high-purity through later separation
Toluene and desorption logistics obtained can be obtained the paraxylene and ethylbenzene of high-purity after later separation, so as to reality
Existing four kinds of C8 components efficiently separate.
2 dichloro benzol mixture of embodiment is selectively adsorbing and separating
Using shown in FIG. 1 cylindric adsorbent bed, it is highly 0.2m, the bed is furnished with that bed internal diameter, which is 0.1m,
Collet is filled with 800g adsorbent bead in bed, and wherein raw mixture is composition dichloro-benzenes mixing as shown in table 2 below
Object employs nitrogen as to purge agent, separation ratio βParacide/nitrogenAbout 25, and using chlorobenzene as desorbing agent, separation
Coefficient ratio βParacide/chlorobenzeneAbout 1.5, wherein adsorption step, purge step and desorption carry out under normal pressure.
Operating procedure is as follows:
Adsorption step, wherein dichloro benzol mixture is made to be preheated to 193 DEG C and with weight (hourly) space velocity (WHSV) 1h-1From adsorbent bed lower part
Charging is inhaled excess stream and produce from adsorbent bed top, obtains liquid phase suction excess stream through cooling, keeps the adsorbent bed temperature to be
It is 193 DEG C, lasting to feed, stop charging when paracide adsorbance reaches the 70% of its Kinetic penetration adsorbance, inhales at this time
The duration of attached step is 6min；
Purge step, wherein the nitrogen as purging agent is made to be heated to 200 DEG C and with weight (hourly) space velocity (WHSV) 1h-1From adsorbent bed
Lower part charging, purge stream are produced from adsorbent bed top, and purge continues 1min, are obtained through the gentle liquid phase separation of cooling
Purge stream liquid phase, the purge stream liquid phase merge collection with excess stream is inhaled；
Desorption, wherein the chlorobenzene as desorbing agent is made to be preheated to 190 DEG C and with weight (hourly) space velocity (WHSV) 1h-1From adsorbent bed
Top charging, desorption logistics are produced from adsorbent bed lower part, logistics are desorbed through the cooling liquid phase that obtains, to be desorbed in logistics to two
It is desorption terminal that chlorobenzene content, which is less than 0.2wt%, and the duration of desorption is 15min at this time；With
Above-mentioned each operating procedure is repeated in into next circulation.
Each logistics composition obtained after the completion of operation is as shown in table 2 below.
The composition of each logistics of the raw mixture and acquisition of 2 embodiment 2 of table
By the result of embodiment 2 it is found that using method of the invention, suction excess stream+purge stream liquid phase obtained
Paracide content is very low in mixture flow, which can be obtained m-dichlorobenzene and the neighbour two of high-purity through later separation
Chlorobenzene, desorption logistics obtained can be obtained the paracide of high-purity through simple rectifying, so as to realize three kinds of dichloros
Benzene isomer mixture efficiently separates.
3 dichlorotoleune of embodiment, three isomer mixture is selectively adsorbing and separating
Using as shown in Figure 1 cylindric adsorbent bed, it is highly 0.2m, the bed is matched that bed internal diameter, which is 0.1m,
Have collet, 800g adsorbent bead be filled in bed, wherein raw mixture be composition it is as shown in table 3 below mainly contain 1,
2,4-DCT, 1,2,5- dichlorotoleune, 1, three isomer mixture of dichlorotoleune of 2,6-DCT, wherein 1,2,5-
Dichlorotoleune is target components, is employed nitrogen as to purge agent, separation ratio β1,2,5- dichlorotoleune/argon gasAbout 28, and use chlorine
Benzene is as desorbing agent, separation ratio β1,2,5- dichlorotoleune/chlorobenzeneAbout 2.1, wherein adsorption step and purge step under elevated pressure into
Capable and desorption carries out under normal pressure.
Operating procedure is as follows:
Adsorption step, wherein make three isomer mixture of dichlorotoleune be preheated at gauge pressure 0.3MPa 250 DEG C and with
Weight (hourly) space velocity (WHSV) 3h-1It is fed from adsorbent bed lower part, inhales excess stream and produced from adsorbent bed top, inhaled through the cooling liquid phase that obtains
Excess stream, keeping adsorbent bed temperature is 255 DEG C, lasting to feed, until 1,2,5- dichlorotoleune adsorbance reaches its dynamic
Stop charging when penetrating the 80% of adsorbance, the duration of adsorption step is 4min at this time；
Purge step, wherein the nitrogen as purging agent is made to be heated to 250 DEG C and at gauge pressure 0.3MPa with weight space-time
Fast 0.1h-1It is fed from adsorbent bed lower part, purge stream is produced from adsorbent bed top, and purge continues 3min, warp
Cooling gentle liquid phase separation obtains purge stream liquid phase, and the purge stream liquid phase merges collection with excess stream is inhaled；
Desorption, wherein the chlorobenzene as desorbing agent is made to be preheated to 210 DEG C and under normal pressure with weight (hourly) space velocity (WHSV) 1.5h-1From
Adsorbent bed top charging, desorption logistics are produced from adsorbent bed lower part, logistics are desorbed through the cooling liquid phase that obtains, with desorption
It is desorption terminal that 1,2,5- dichlorotoleune contents, which are less than 0.2wt%, in logistics, and the duration of desorption is 12min at this time；
With
Above-mentioned each operating procedure is repeated in recycle into next adsorbing separation.
Each logistics composition obtained after the completion of operation is as shown in table 3 below.
The composition of each logistics of the raw mixture and acquisition of 3 embodiment 3 of table
*Remarks: as three isomer mixture of the dichlorotoleune of raw mixture by five isomery of dichlorotoleune shown in table 3
Body mixture rectifying obtains, and wherein three isomer mixture of dichlorotoleune is obtained as overhead product
By the result of embodiment 3 it is found that using method of the invention, suction excess stream+purge stream liquid phase obtained
1,2,5- dichlorotoleune contents are very low in mixture flow, which can be used as tower bottom product acquisition purity through rectifying and reach
The 1 of 99.85wt%, 2,6-DCT, desorption logistics obtained can be used as tower bottom product through simple rectifying and obtain 1,2,4-
Dichlorotoleune and 1, the mixture of 2,5- dichlorotoleune, the mixture further crystallized or rectifying after can get high-purity 1,
2,4-DCT and 1,2,5- dichlorotoleune, so as to realize efficiently separating for three isomer mixture of dichlorotoleune.
It is selectively adsorbing and separating method it follows that of the invention and can be implemented in combination with rectifying and crystalline phase to dichloromethane
Five isomer mixture of benzene efficiently separates.
Therefore, it is proposed, according to the invention, reach one in adsorption bed unsaturation such as bed adsorption amount with Kinetic penetration absorption meter
Stop absorption when definite value and start to purge, and the purging path for wherein purging agent is identical as the absorption path of raw mixture, makes
Obtaining can be unsaturated when the target components in purge in bed in residual raw materials mixture again pass by absorption path
Remaining adsorption site continues to adsorb in bed, and the purge stream thus collected may not need undergoes adsorbing separation again,
But it can be collected together with suction excess stream after mutually separating (water separation of oil or liquid phase separate) with purging agent, and so obtain
Target components content is very low in mixture flow, target components content is also very high in desorption logistics obtained, so as to reality
Existing each component efficiently separates, and embodiment 1-3 confirms this point well.
Acetone is selectively adsorbing and separating in 4 waste water of embodiment
It is adsorbent bed using case shape as shown in Figure 2, bed along the inside dimension of X, Y, Z axis be respectively 0.28m,
0.2m and 0.05m, the bed are furnished with collet, are filled with 800g adsorbent bead in bed, and wherein raw mixture is composition
As shown in table 4 below contains acetone wastewater, uses air as purging agent, separation ratio βAcetone/airAbout 15, and use water
Steam is as desorbing agent, separation ratio βAcetone/water steamAbout 8, wherein adsorption step carries out under normal pressure, purge step and de-
Attached step carries out under elevated pressure
Operating procedure is as follows:
Adsorption step, wherein making containing acetone wastewater at normal temperatures and pressures with weight (hourly) space velocity (WHSV) 1h-1Entered by adsorbent bed left side
Mouthful place's charging and along X-axis forward direction by adsorbent bed, inhale excess stream and collected at adsorbent bed right-side outlet, it is lasting into
Material stops charging, at this time the duration of adsorption step when acetone adsorbance reaches the 98% of its Kinetic penetration adsorbance
For 5h；
Purge step, wherein with weight (hourly) space velocity (WHSV) 0.3h after making the air pressurized to 0.3MPa gauge pressure as purging agent-1By inhaling
It is fed at attached dose of bed left hand inlet port and along X-axis forward direction by adsorbent bed, purge continues 5min, goes out on the right side of bed
Obtained purge stream is collected at mouthful, and purge stream liquid phase is obtained after liquid phase separates, the purge stream liquid phase and suction excess stream
Merging can be used as discharge of wastewater up to standard after collecting；
Desorption makes adsorbent bed temperature up to 140 DEG C, then makes to be preheated to 120 DEG C using collet heating first
Water vapour is with weight (hourly) space velocity (WHSV) 0.5h-1By adsorbent bed top feed and along Y-axis negative sense by adsorbent bed, desorption logistics from
Logistics is desorbed through the cooling liquid phase that obtains in adsorbent bed lower part extraction, is less than 0.2wt% with content of acetone in liquid phase desorption logistics
For terminal, at this time the duration 2h of desorption is desorbed；With
Above-mentioned each operating procedure is repeated in into next circulation.
Each logistics composition obtained after the completion of operation is as shown in table 4 below.
The content of acetone of each logistics of the raw mixture and acquisition of 4 embodiment 4 of table
| Logistics | Containing acetone wastewater | Inhale excess stream+purge stream liquid phase | Logistics is desorbed |
| Content of acetone | 1.2wt% | 45ppmw | 13.9wt% |
By the result of embodiment 4 it is found that using method of the invention, can will be reduced containing the acetone concentration in acetone wastewater
The acetone soln that content is up to 13.9wt% in addition can also be obtained to 45ppmw to reach wastewater discharge standard, the acetone is molten
Liquid can be through further purifying to obtain acetone solvent.
Dimethyl acetamide is selectively adsorbing and separating in 5 waste water of embodiment
It is adsorbent bed using case shape as shown in Figure 2, bed along the inside dimension of X, Y, Z axis be respectively 0.28m,
0.2m and 0.05m, the bed are furnished with collet, are filled with 1500g adsorbent bead in bed, and wherein raw mixture is composition
Waste water containing dimethyl acetamide as shown in table 5 below employs nitrogen as purging agent and desorbing agent, separation ratio
βDimethyl acetamide/nitrogenAbout 4.5, wherein adsorption step and desorption carry out under normal pressure and purge step carries out under elevated pressure.
Operating procedure is as follows:
Adsorption step, wherein making waste water containing dimethyl acetamide at normal temperatures and pressures with weight (hourly) space velocity (WHSV) 0.5h-1By adsorbent
It is fed at bed left hand inlet port and along X-axis forward direction by adsorbent bed, suction excess stream is received at adsorbent bed right-side outlet
Collection, it is lasting to feed, stop charging when dimethyl acetamide adsorbance reaches the 98% of its Kinetic penetration adsorbance, inhales at this time
The duration of attached step is 12h；
Purge step, wherein being forced into the nitrogen as purging agent after 0.05MPa gauge pressure with weight (hourly) space velocity (WHSV) 0.2h-1By inhaling
It is fed at attached dose of bed left hand inlet port and along X-axis forward direction by adsorbent bed, purge continues 2min, goes out on the right side of bed
Obtained purge stream is collected at mouthful, and purge stream liquid phase is obtained after liquid phase separates, the purge stream liquid phase and suction excess
Stream can be used as discharge of wastewater up to standard after merging collection；
Desorption makes adsorbent bed temperature up to 250 DEG C, reaches 100 DEG C in temperature therebetween using collet heating first
When by the nitrogen for being preheated to 200 DEG C with weight (hourly) space velocity (WHSV) 4.0h-1Pass through adsorbent by adsorbent bed top feed and along Y-axis negative sense
Bed, desorption logistics are produced from adsorbent bed lower part, desorption logistics liquid phase are obtained through the gentle liquid phase separation of cooling, no longer to obtain
Logistics liquid phase must be desorbed or desorption thing liquid phase flow rate is rarely and terminal is desorbed, the duration of desorption is 0.5h at this time；With
Above-mentioned each operating procedure is repeated in into next circulation.
Each logistics composition obtained after the completion of operation is as shown in table 5 below.
The dimethylacetamide amine content of each logistics of the raw mixture and acquisition of 5 embodiment 5 of table
It, can be by the diformazan in waste water containing dimethyl acetamide by the result of embodiment 5 it is found that using method of the invention
Yl acetamide concentration is reduced to 30ppmw, to reach wastewater discharge standard, in addition can also obtain content is up to 30wt% two
Methyl vinyl amine aqueous solution, the dimethylacetamide solution can be through further purifying to obtain dimethylacetamide solvent.
That is, it is proposed, according to the invention, when carrying out wastewater treatment, the qualified discharge of waste water not only may be implemented, may be used also
To recycle the organic substance in waste water such as acetone and dimethyl acetamide, to improve the added value of wastewater treatment.Moreover, such as
What embodiment 4 and 5 was confirmed, when desorption direction is vertical with absorption direction, desorption time can be made to shorten, and then improve adsorbent bed
Service efficiency.
In addition, it is proposed, according to the invention, when carrying out wastewater treatment, since purge step is by the non-mesh of major part in bed
It marks component, that is, water and blows out bed, therefore, in desorption, this part water no longer expends energy and is desorbed, it is possible thereby to save
Substantial portion of process energy consumption, this is also advantages of the present invention place.
Claims (19)
1. a kind of method being selectively adsorbing and separating as adsorbent to raw mixture using molecular sieve, the raw material is mixed
Closing object includes target components to be separated, method includes the following steps:
Adsorption step, wherein making raw mixture along first direction by adsorbent bed, adsorbent bed along first direction
Exit collect inhale excess stream, continue adsorption process, until adsorbent bed upper target components adsorbance press Kinetic penetration
Until absorption meter reaches 65-98%；
Purge step, wherein make purge agent pass through in a second direction it is adsorbent bed, it is adsorbent bed in a second direction go out
Purge stream is collected at mouthful place, continues purge, to remove the non-target components in adsorbent bed, wherein second direction and the
One direction is identical；
Desorption, wherein making desorbing agent along third direction by adsorbent bed, in adsorbent bed going out along third direction
Desorption logistics is collected at mouthful, continues desorption process, until the concentration until target components in logistics are desorbed is constant or varies less,
Wherein third direction is identical as first direction, contrary or is mutually perpendicular to；With
Optional circulation step is recycled wherein being repeated in above-mentioned each operating procedure.
2. the method for claim 1 wherein the molecular sieves as adsorbent to be selected from MFI type zeolite, FER type zeolite, BEA type zeolite
With high silicon FAU type zeolite, the average particle size of the adsorbent of molecular sieve is 1-5mm and shape is spherical or cylindrical body.
3. method for claim 2, wherein being selected from the na-pretreated zeolite or soap-free emulsion polymeization of each zeolite as the molecular sieve of adsorbent
Agent na-pretreated zeolite, binder free hydrophobic type zeolite or hydrophilic zeolite.
4. method for claim 3, wherein the molecular sieve as adsorbent is selected from MFI type binder free hydrophobic silicalite or without viscous
Tie agent Silicalite-1 zeolite.
5. the method for any one of claim 1-4, wherein purging agent and desorbing agent are selected according to separation ratio, wherein making to take off
Attached dose of separation ratio βTarget components/desorbing agentFor 1-10, and make the separation ratio β for purging agentTarget components/purging agent≥βTarget components/desorbing agent,
Middle desorbing agent and the separation ratio of purging agent are defined respectively as:
With
6. the method for any one of claim 1-4, wherein the adsorbent bed draw ratio along first direction is greater than or equal to absorption
Agent bed in a second direction with the draw ratio of third direction.
7. the method for any one of claim 1-4, wherein it is adsorbent bed be it is cylindric adsorbent bed, wherein inside cylindrical body
Filled with adsorbent, at the top of cylindrical body and lower part is respectively equipped with distribution and collection space and distribution and collects porous plate, at this time
Third direction and the first and second direction contraries；Or it is adsorbent bed adsorbent bed for case shape, wherein box house is filled out
Filled with adsorbent, cabinet is respectively equipped with distribution and collection space and distribution and receipts in horizontal cross and vertical longitudinal both ends
Collect porous plate, third direction is mutually perpendicular to the first and second directions at this time.
8. the method for any one of claim 1-4, wherein adsorption step and purge step are respectively under normal pressure or pressurization in gas phase
Or it is carried out under liquid phase state and desorption carries out under gas phase or liquid phase state under normal pressure, pressurization or vacuum.
9. the method for any one of claim 1-4, wherein raw mixture be that benzene series is di-substituted or three substituent of benzene series it is same
Isomeric mixtures, wherein benzene series is di-substituted is selected from dimethylbenzene, diethylbenzene, ethyl methyl benzene, dichloro-benzenes, chlorotoluene and chlorine
Ethylbenzene, contraposition substituent are target components, and wherein three substituent of benzene series is selected from dichlorotoleune and dichloro ethylbenzene, wherein 1,2,5- tri-
Substituent or 1,2,4- tri- substituents are target components, and purging agent is selected from water vapour, CO2、C1-C4Hydrocarbon, air, nitrogen and argon
Gas.
10. method for claim 9, wherein the content of target components not higher than 80wt% and is not less than in raw mixture
1wt%, wherein stop adsorption step when the adsorbance of target components reaches 68-96% by Kinetic penetration absorption meter, wherein
Compared with the duration τ of adsorption step, the duration of purge step is 0.01-5 τ, and when target components in desorption logistics
Content be lower than 0.5wt% when stop desorption.
11. method for claim 10, wherein the weight (hourly) space velocity (WHSV) of raw mixture and desorbing agent is respectively 0.1-5h-1, and purging
The weight (hourly) space velocity (WHSV) of agent is 0.1-10h-1。
12. the method for claim 11, wherein raw mixture is xylene mixture, and purging agent is water vapour or C1-C4Hydrocarbon,
Desorbing agent is toluene, wherein as raw mixture xylene mixture, as purging agent water vapour or C1-C4Hydrocarbon and work
It is preheated to 140-170 DEG C of rear feeding under normal pressure to adsorbent bed to be inhaled under gas phase state for the toluene of desorbing agent
Attached, purging and desorption.
13. the method for claim 11, wherein raw mixture is dichloro benzol mixture, and purging agent is air, nitrogen or C1-C4
Hydrocarbon, desorbing agent are chlorobenzene, wherein as raw mixture dichloro benzol mixture, as purging agent air, nitrogen or C1-C4
Hydrocarbon and chlorobenzene as desorbing agent are preheated to 180-200 DEG C of rear feeding to adsorbent bed under gas phase state under normal pressure
It adsorbed, purged and is desorbed.
14. the method for claim 11, wherein raw mixture be it is main contain 1,2,4-DCT, 1,2,5- dichlorotoleune,
1, three isomer mixture of benzotrichloride of 2,6-DCT, wherein 1,2,5- dichlorotoleune is target components, purging agent is
Nitrogen, desorbing agent are chlorobenzene, wherein the nitrogen as the dichlorotoleune mixture of raw mixture and as purging agent is in 0.1-
200-260 DEG C of rear feeding is preheated under the gauge pressure of 0.5MPa to adsorbent bed to be adsorbed and be purged under gas phase state,
Wherein it is preheated to 200-260 DEG C of rear feeding under normal pressure to adsorbent bed under gas phase state as the chlorobenzene of desorbing agent
It is desorbed.
15. the method for any one of claim 1-4, wherein raw mixture for the waste water containing a small amount of organic matter or contains a small amount of water
Organic matter liquid, wherein the useless Organic substance in water containing a small amount of organic matter is target components, in the organic matter liquid containing a small amount of water
Water is target components, the organic matter be selected from hexane, heptane, benzene, toluene, ethylbenzene, styrene, paraxylene, acetone, acetic acid,
Ethyl alcohol, ethyl acetate, 1- propyl alcohol, 1,3- propylene glycol, n-butanol, methylamine, ethamine, propylamine, n-butylamine, formamide, acetamide, N,
Dinethylformamide, n,N-dimethylacetamide, chloroform, cyclohexanone oxime and small-molecule drug intermediate, wherein purging agent
Water vapour, CO are each independently selected from desorbing agent2、C1-C4Hydrocarbon, air, nitrogen and argon gas.
16. the method for claim 15, wherein the content of target components not higher than 20wt% and is not less than in raw mixture
0.01wt%, wherein stop adsorption step when the adsorbance of target components reaches 90-98% by Kinetic penetration absorption meter,
In compared with the duration τ of adsorption step, duration of purge step be 0.001-0.5 τ and desorption it is lasting when
Between be 0.01-0.5 τ.
17. the method for claim 16, wherein the weight (hourly) space velocity (WHSV) of raw mixture and desorbing agent is respectively 0.1-10h-1, and purging
The weight (hourly) space velocity (WHSV) of agent is 0.1-50h-1。
18. the method for claim 17, wherein raw mixture is to purge agent containing acetone wastewater and desorbing agent selects each independently
From water vapour, CO2、C1-C4Hydrocarbon, air, nitrogen and argon gas, wherein adsorption step carries out under normal pressure, purge step and desorption step
Suddenly it is carried out under 0.1-1.0MPa gauge pressure.
19. the method for claim 17, wherein raw mixture is waste water containing dimethyl acetamide, agent and desorbing agent are purged respectively
Independently selected from water vapour, CO2、C1-C4Hydrocarbon, air, nitrogen and argon gas, wherein adsorption step and desorption under normal pressure into
Row, purge step carry out under 0.02-0.15MPa gauge pressure.
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| CN106925212A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | A kind of adsorbent and method for removing oxazole from acrylonitrile |
| CN108854434B (en) * | 2017-05-15 | 2021-06-04 | 中国石油化工股份有限公司 | Method and device for treating refinery VOCs waste gas |
| CN107954825A (en) * | 2017-11-21 | 2018-04-24 | 南京钟腾化工有限公司 | A kind of method that 2,6- dichlorotoleune is isolated in the dichlorotoleune from mixing |
| CN108264056B (en) * | 2018-03-02 | 2020-08-14 | 浙江吉瑞通新材料有限公司 | Method for synthesizing all-silicon Beta zeolite molecular sieve by sodium-free and solvent-free route |
| CN111943547B (en) * | 2020-03-28 | 2021-10-22 | 长江大学 | Method for preparing cement-based material carbonization internal curing agent through surface hydrophobic modification |
| CN112592255B (en) * | 2020-12-15 | 2023-01-24 | 江苏扬农化工集团有限公司 | Method for removing 3-chloropropene in epoxy chloropropane water layer |
| CN112843766B (en) * | 2020-12-29 | 2022-06-14 | 复榆(张家港)新材料科技有限公司 | Adsorption separation process for pressure swing adsorption separation solvent water binary azeotrope |
| CN113754543B (en) * | 2021-09-06 | 2022-09-20 | 南京工业大学 | Method for separating high-boiling-point isomer by utilizing gas phase adsorption of hierarchical pore silicon molecular sieve |
| CN114874068A (en) * | 2022-05-05 | 2022-08-09 | 南京工业大学 | Method for continuously producing high-purity o-chlorotoluene by adsorption separation method |
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