CN108126664A - It is a kind of to remove the method for oxygenate impurity in alkene for the modified molecular screen of purification of light olefins and using it - Google Patents
It is a kind of to remove the method for oxygenate impurity in alkene for the modified molecular screen of purification of light olefins and using it Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
Abstract
The method of oxygenate impurity in alkene is removed the present invention provides a kind of modified molecular screen for purification of light olefins and using it.The modified molecular screen is to be modified using metallo-organic compound, the method includes：Olefin stream containing oxygenate impurities such as water, ether, aldehyde, ketone, alcohol, the mol sieve beds being modified by metallo-organic compound, obtains high-purity olefin stream.It can regenerate mol sieve beds with inert gas purge under the high temperature conditions after mol sieve beds saturation.By the purified alkene of the method for the present invention, particularly isobutene, reach high-purity standard, can be used for polymerizeing order reaction and organic synthesis.
Description
Technical field
The side of oxygenate impurity in alkene is removed the present invention relates to a kind of modified molecular screen for purification of light olefins and using it
Method.
Background technology
Double bond group in alkene has good reactivity, and hydrogenation, halogenation, hydration, halogen hydrogenation, hypohalogenous acids can occur
The addition reactions such as change, Sulfation, epoxidation, polymerization, the also oxidable fracture that double bond occurs, generation aldehyde, carboxylic acid etc..
Alkene is also main industrial chemicals in the industrial production, and the large alkene industrial chemicals being widely used at present has second
Alkene, propylene, 1- butylene, 2- butylene, isobutene etc. due to the difference of production technology, all contain in most of olefin products
Oxygen containing compound, oxygen containing compound are mainly the compounds such as some water, ether, alcohol, ketone, aldehyde, although physical property and the difference of alkene
It is not larger, but the difficulty detached from alkene is larger, and industry is general to be handled in a manner that rectifying or washing rectifying are combined, energy
Consumption is higher.Such as the oxygenate impurities such as methanol, dimethyl ether, water in MTBE cracking preparing isobutenes, PO by-products TBA cracking preparing isobutenes
In the impurity such as methanol, acetone, methyl tertiary butyl ether(MTBE), methyl ethyl ketone, isobutylaldehyde, the tert-butyl alcohol, water, methanol is raw materials for ethylene production,
The impurity such as the methanol, dimethyl ether, the propionic aldehyde that are generated in the technique of propylene can only generally be removed by the techniques such as solvent absorption, refined
Most oxygenate impurities, the presence of trace oxygenate impurity often influence the high-end applications in olefinic monomer downstream, need to pass through depth
The olefinic monomer of high-purity could be obtained by changing purification technique.
United States Patent (USP) US339536 extracts the PO by-products TBA reaction solutions cracked using alkane, obtains rich in IB
Oil phase isolates the water phase containing oxygenate impurity, and the isobutene that rectifying obtains high-purity, United States Patent (USP) are carried out to oil phase
US20040092778, which is disclosed, a kind of is separated by distillation the method for dimethyl ether and methanol in C4 alkene, Chinese patent
CN103382146A detaches the oxygenate impurity in isobutene using the method for washing, rectifying.Above-mentioned patent is by the way of rectifying
Purification of light olefins, energy consumption is higher, and the olefin product purity of acquisition is relatively low, generally 99.9% hereinafter, trace oxygenate impurity is to alkene
Downstream application exist influence, generally require to handle by advanced purification process.
Chinese patent CN103495378A discloses a kind of using kaolin, aluminium oxide, submicron molecular sieve as the micro- of component
Ball adsorbent, the method for removing the methanol of trace, dimethyl ether, propionic aldehyde in olefin stream, the oxygenate impurity each component content in alkene
1ppm is processed by 10-200ppm hereinafter, Chinese patent CN102942436A is disclosed and a kind of will be used metal oxide modified
Molecular sieve absorption isobutene in trace carbinol, dimethyl ether, MTBE, TBA, water method, after processing oxygenatedchemicals by
300ppm descends to 1-10ppm, and does not refer to the adsorption effect to trace acetone, methyl ethyl ketone etc..Above-mentioned two patents lack
Point is that the content of oxygenate impurity in requirement olefin feedstock is low, total amount in 300ppm hereinafter, and oxygenate impurity type it is less,
To adsorption effects unobvious such as the acetone, the methyl ethyl ketone that are referred in this patent.
The method of molecular sieve absorption at present can only handle the alkene of the impurity containing micro oxygen containing, and high-content can not also be made to contain oxa-
The olefinic monomer that the alkene of matter is directly processed into polymer grade (is usually the total amount of oxygenate impurity<30ppm), it needs to seek a kind of high
The minimizing technology of high-content oxygenate impurity in the alkene of effect reduces the cost of alkene purification.
Invention content
One of the objects of the present invention is to provide a kind of points for purification of light olefins, using metallo-organic compound modification
Son sieve.
Another object of the present invention is to provide the preparation method of above-mentioned modified molecular screen.
It is still another object of the present invention to provide a kind of methods using above-mentioned modified molecular screen purification of light olefins.Use the party
The alkene deep purifying of high-content oxygenate impurity can be reached the standard of polymerizing olefin monomers, this method is to raw material olefin by method
In oxygenate impurity type and content requirement it is relatively low, adsorbent renewable repeated use, production efficiency is high, effectively solves existing
Have and the three high problems such as high, the purification cost height of high energy consumption, absorption ingredient requirement are refined in technique.
To reach more than goal of the invention, the technical solution adopted by the present invention is as follows：
A kind of modified molecular screen for purification of light olefins, for the molecular sieve that metallo-organic compound is modified, modified gold
Belong to the metallic element in organic compound to be one or more in I B, II B, VI B and VII B B metals, preferably Cr, Cu, Zn
With it is one or more in Mn；Metal-organic organic compound is prepared as the compound containing double carboxyls, preferably oneself
One kind in diacid, glutaric acid and terephthalic acid (TPA).In modified molecular screen, metal-organic content is 10-50wt%,
It is preferred that 20-30wt%；Surplus is molecular sieve.
It is 3A, 4A, in 5A, 13X, type ZSM 5 molecular sieve to prepare molecular sieve used in the modified molecular screen of the present invention
It is one or more.
Heretofore described modified molecular screen preparation method is：According to reaction ratio, the metal of B metal is aoxidized
After the mixed in hydrochloric acid dissolving of object, the compound containing double carboxyls and 2-8mol/L, seal and stand 5-10h at 200-300 DEG C and obtain
Slurry is obtained, molecular sieve powder is mixed into slurry, stirs evenly postcooling to room temperature, suction filtration, and cleaned with acetone,
Gained granulating powders are obtained modified molecular screen by 250-350 DEG C of drying.
Utilize the method for the oxygenate impurity in the modified molecular screen removal alkene of the present invention：Modified point is loaded in absorption tower
Son sieve particle is as adsorbent, and the olefin stream containing oxygenate impurity enters from modified molecular screen bed lower end, and tower top outflow is oxygen-containing
The extremely low purified olefin stream of impurity.The modified molecular screen particle is preferably spherical for spherical shape, bar shaped, cylinder etc., spherical shape
The grain size of modified molecular screen particle is preferably 0.2-0.5cm.In absorption tower, 10-80 DEG C of temperature, preferably 20-50 DEG C；Pressure (table
Pressure) 0-2.0MPa, preferably 0.3-1.0MPa；The air speed of olefin stream is 0.4-10h-1, preferably 0.5-2h-1。
In the present invention, the oxygenate impurity in alkene before purification contains oxygen element including water and ether, aldehyde, ketone, alcohol etc.
One or more in organic compound, the organic compound containing oxygen element specifically includes common in commercial olefin
The tertiary fourth of methanol, ethyl alcohol, propyl alcohol, butanol, the tert-butyl alcohol, dimethyl ether, ethyl methyl ether, methyl tertiary butyl ether(MTBE), ethyl tert-butyl ether (ETBE), isopropyl
Base ether, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, acetone, methyl ethyl ketone, formic acid etc..Alkene containing oxygenate impurity flows through Organometallic
It is mutual by intermolecular force between the oxygenatedchemicals and modified molecular screen in alkene during polymer modified mol sieve beds
So as to firmly adsorb the water in olefin stream and oxygen-containing organic impurities in modified molecular sieve surface, it is net to reach depth for absorption
Change the purpose of alkene.
The total amount of oxygenate impurity is 0.01-5wt%, preferably 0.1-2wt% in not purified alkene in the present invention, through this
The amount of oxygenate impurity in the purified alkene of invention modified molecular screen<15ppm.
The modified molecular screen particle packing of the present invention is in absorption tower, after modified molecular screen bed adsorption saturation, Ke Yitong
Cross regeneration treatment：It is regenerated by way of high temperature inert gas purging.Regenerated operation temperature is 80-300 DEG C, preferably 150-
200℃；The preferred nitrogen of inert gas, the air speed of inert gas purge is 1-30h-1, preferably 5-15h-1.Absorption tower may be used
The mode of multitower serial or parallel connection, generally using three towers, wherein the modified molecular screen bed of a tower is regenerated after absorbing saturation
Processing.
Alkene of the present invention is usually the liquefaction alkene of C3-C8.
Compared with prior art, the present invention advantage is：
The molecular sieve that is modified in the present invention using metallo-organic compound, the specific surface area of molecular sieve can be by before modified<
2000m2It is promoted to 3000-4000m2, adsorption capacity is obviously improved；Due to metal-organic introducing, make in oxygenate impurity
Interaction force enhancing between oxygen and adsorbent, it is easier to be adsorbed and removed, while to the absorbed species of oxygenate impurity more
Extensively, good purification；The network structure that metallo-organic compound is formed has certain Deformation Features in high-temperature process, utilizes
After its molecular sieve being modified reaches adsorption saturation, the impurity of absorption can be sloughed by way of high-temperature gas purging, reaches regeneration
Purpose, and then reuse, production efficiency is high, and purification is at low cost.
Specific embodiment
Present invention combination example below is described in further detail, but the scope of the invention is not limited to these realities
Apply example.Contain in the isobutene that olefin stream is cracked with the more conjugated oxidation production propylene oxide by-product tert-butyl alcohol of oxygenate impurity type
The removal of oxygen impurities illustrates.
The content of oxygenate impurity is determined using gas chromatographic analysis in alkene, gas phase analysis condition：Shimadzu gas chromatograph,
RTX-WAX pillars, 60 DEG C of holding 5min；10 DEG C/min rises to 80 DEG C, keeps 5min；10 DEG C/min rises to 100 DEG C, keeps
5min；10 DEG C/min rises to 160 DEG C, keeps 15min.
Metal-organic content detection uses Shimadzu Atomic Absorption Spectrometer, model AA-6880.
Embodiment 1
It is prepared by modified molecular screen
2.5g chromium oxide is weighed with 5.4g terephthalic acid (TPA)s in the hydrochloric acid solution of 100mL concentration 5mol/L, stirring and dissolving
After completely, heated sealed maintains 5h to obtain paste liquid to 220 DEG C, and 29.2g3A points are added with stirring in the paste liquid
Son sieve powder, after continuously stirring 30min, is cooled to room temperature, and sedimentation filters, and pale green powder, 300 DEG C of bakings are obtained after acetone cleaning
Dry, the metallo-organic compound compounds content of atomic absorption spectrum detection Cr is 21.3wt%, and molecular sieve content is
78.7wt% is granulated into the spherical shape of grain size 3mm.
Alkene purifies
Insert the molecular sieve of 100ml spherical shapes modification in absorption tower, pressure 0.5Mpa, 30 DEG C, air speed 1.5h-1Under conditions of,
Contain water 0.25wt%, methanol 0.05wt%, acetone 0.1wt%, tert-butyl alcohol 0.04wt%, methyl tertiary butyl ether 0.03wt%, first
Ethyl ketone 0.02wt%, isobutylaldehyde 0.01wt% isobutene raw material from bottom of towe enter absorption tower processing after, tower top outflow alkene
The content of middle water is 5ppm, and the total amount of oxygen-containing organic compound impurity is 3ppm.
Embodiment 2
It is prepared by modified molecular screen
3.6g chromium oxide is weighed with 8.1g terephthalic acid (TPA)s in the hydrochloric acid solution of 100mL concentration 5mol/L, stirring and dissolving
After completely, heated sealed maintains 5h to obtain paste liquid to 275 DEG C, and 28.1g3A points are added with stirring in the paste liquid
Son sieve powder, after continuously stirring 30min, is cooled to room temperature, and sedimentation filters, and pale green powder, 330 DEG C of bakings are obtained after acetone cleaning
Dry, the metallo-organic compound content of atomic absorption spectrum detection Cr is 29.4wt%, molecular sieve content 70.6wt%, is granulated
Into the spherical shape of grain size 3mm.
Alkene purifies
Insert the molecular sieve of 100ml spherical shapes modification in absorption tower, pressure 0.8Mpa, 20 DEG C, air speed 2h-1Under conditions of, contain
There are water 0.4wt%, methanol 0.15wt%, acetone 0.08wt%, tert-butyl alcohol 0.07wt%, methyl tertiary butyl ether 0.05wt%, first and second
Ketone 0.03wt%, isobutylaldehyde 0.01wt% isobutene raw material from bottom of towe enter absorption tower processing after, tower top outflow alkene in
The content of water is 8ppm, and the total amount of oxygen-containing organic compound impurity is 5ppm.
Embodiment 3
It is prepared by modified molecular screen
3.1g chromium oxide is weighed with 6.7g terephthalic acid (TPA)s in the hydrochloric acid solution of 100mL concentration 4mol/L, stirring and dissolving
After completely, heated sealed maintains 8h to obtain paste liquid to 250 DEG C, and 29.9g3A points are added with stirring in the paste liquid
Son sieve powder, after continuously stirring 30min, is cooled to room temperature, and sedimentation filters, and pale green powder, 260 DEG C of bakings are obtained after acetone cleaning
Dry, the metallo-organic compound content of atomic absorption spectrum detection Cr is 24.7wt%, molecular sieve content 75.3wt%, is granulated
Into the spherical shape of grain size 3mm.
Alkene purifies
Insert the molecular sieve of 100ml spherical shapes modification in absorption tower, pressure 1.5Mpa, 45 DEG C, air speed 3h-1Under conditions of, contain
There are water 0.29wt%, methanol 0.08wt%, acetone 0.12wt%, tert-butyl alcohol 0.05wt%, methyl tertiary butyl ether 0.06wt%, first and second
Ketone 0.02wt%, isobutylaldehyde 0.02wt% isobutene raw material from bottom of towe enter absorption tower processing after, tower top outflow alkene in
The content of water is 7ppm, and the total amount of oxygen-containing organic compound impurity is 3ppm.
Embodiment 4
It is prepared by modified molecular screen
2.5g chromium oxide is weighed with 5.4g terephthalic acid (TPA)s in the hydrochloric acid solution of 100mL concentration 3mol/L, stirring and dissolving
After completely, heated sealed maintains 10h to obtain paste liquid to 200 DEG C, and 29.2g13X is added with stirring in the paste liquid
Molecular sieve powder after continuously stirring 30min, is cooled to room temperature, and sedimentation filters, and pale green powder is obtained after acetone cleaning, 300 DEG C
Drying, the metallo-organic compound content of atomic absorption spectrum detection Cr is 21.3wt%, and molecular sieve content 78.7wt% makes
Grain is spherical into 3mm.
Alkene purifies
Insert the molecular sieve of 100ml spherical shapes modification in absorption tower, pressure 0.4Mpa, 50 DEG C, air speed 1h-1Under conditions of, contain
There are water 0.35wt%, methanol 0.10wt%, acetone 0.12wt%, tert-butyl alcohol 0.03wt%, methyl tertiary butyl ether 0.02wt%, first and second
Ketone 0.02wt%, isobutylaldehyde 0.01wt% isobutene raw material from bottom of towe enter absorption tower processing after, tower top outflow alkene in
The content of water is 6ppm, and the total amount of oxygen-containing organic compound impurity is 2ppm.
Embodiment 5
It is prepared by modified molecular screen
3.3g chromium oxide is weighed with 5.7g glutaric acids in the hydrochloric acid solution of 100mL concentration 8mol/L, stirring and dissolving is complete
Afterwards, heated sealed is to 220 DEG C, and 5h is maintained to obtain paste liquid, and 39.8g3A molecular sieves are added with stirring in the paste liquid
Powder after continuously stirring 30min, is cooled to room temperature, and sedimentation filters, and pale green powder is obtained after acetone cleaning, and 280 DEG C dry,
The metallo-organic compound content of atomic absorption spectrum detection Cr is 18.4wt%, and molecular sieve content 81.6wt% is granulated into
The spherical shape of grain size 3mm.
Alkene purifies
Insert the molecular sieve of 100ml spherical shapes modification in absorption tower, pressure 1.0Mpa, 60 DEG C, air speed 5h-1Under conditions of, contain
There are water 0.35wt%, methanol 0.10wt%, acetone 0.12wt%, tert-butyl alcohol 0.03wt%, methyl tertiary butyl ether 0.02wt%, first and second
Ketone 0.02wt%, isobutylaldehyde 0.01wt% isobutene raw material from bottom of towe enter absorption tower processing after, tower top outflow alkene in
The content of water is 8ppm, and the total amount of oxygen-containing organic compound impurity is 3ppm.
Embodiment 6
It is prepared by modified molecular screen
2.7g zinc oxide is weighed with 11.1g terephthalic acid (TPA)s in the hydrochloric acid solution of 100mL concentration 5mol/L, stirring and dissolving
After completely, heated sealed maintains 6h to obtain paste liquid to 210 DEG C, and 25.8g3A points are added with stirring in the paste liquid
Son sieve powder, after continuously stirring 30min, is cooled to room temperature, and sedimentation filters, and white powder, 300 DEG C of bakings are obtained after acetone cleaning
Dry, the metallo-organic compound content of atomic absorption spectrum detection Zn is 34.8wt%, molecular sieve content 65.2wt%, is granulated
Into the spherical shape of grain size 3mm.
Alkene purifies
Insert the molecular sieve of 100ml spherical shapes modification in absorption tower, pressure 1.6Mpa, 30 DEG C, air speed 0.5h-1Under conditions of,
Contain water 0.45wt%, methanol 0.15wt%, acetone 0.16wt%, tert-butyl alcohol 0.05wt%, methyl tertiary butyl ether 0.05wt%, first
Ethyl ketone 0.04wt%, isobutylaldehyde 0.03wt% isobutene raw material from bottom of towe enter absorption tower processing after, tower top outflow alkene
The content of middle water is 7ppm, and the total amount of oxygen-containing organic compound impurity is 4ppm.
Comparing embodiment 1
Insert the unmodified 3A molecular sieves of 100ml in absorption tower, pressure 0.5Mpa, 30 DEG C, air speed 1h-1Under conditions of, contain
There are water 0.25wt%, methanol 0.05wt%, acetone 0.1wt%, tert-butyl alcohol 0.04wt%, methyl tertiary butyl ether 0.03wt%, first and second
Ketone 0.02wt%, isobutylaldehyde 0.01wt% isobutene feedstock processing after, the content of water is 0.21wt%, methanol 0.04wt%,
Acetone 0.1wt%, tert-butyl alcohol 0.04wt%, methyl tertiary butyl ether 0.03wt%, methyl ethyl ketone 0.02wt%, isobutylaldehyde 0.01wt%.
Comparing embodiment 2
Insert the unmodified 13X molecular sieves of 100ml in absorption tower, pressure 0.5Mpa, 30 DEG C, air speed 1h-1Under conditions of, contain
There are water 0.25wt%, methanol 0.05wt%, acetone 0.1wt%, tert-butyl alcohol 0.04wt%, methyl tertiary butyl ether 0.03wt%, first and second
Ketone 0.02wt%, isobutylaldehyde 0.01wt% isobutene feedstock processing after, the content of water is 0.17wt%, methanol 0.04wt%,
Acetone 0.095wt%, tert-butyl alcohol 0.04wt%, methyl tertiary butyl ether 0.03wt%, methyl ethyl ketone 0.02wt%, isobutylaldehyde
0.009wt%.
Modified molecular screen absorbs the regeneration treatment after saturation in embodiment 1-6
Absorption tower bed temperature rises to 190 DEG C, air speed 10h-1Under conditions of, after nitrogen purging 20h, bed temperature is down to 25
DEG C, thermogravimetric analysis, no significant change are carried out to the modified molecular screen after regeneration.
1 regeneration effect of embodiment
Insert the molecular sieve in the embodiment 1 after 100ml regeneration treatments in absorption tower, pressure 0.4Mpa, 30 DEG C, air speed
1h-1Under conditions of, contain water 0.35wt%, methanol 0.10wt%, acetone 0.12wt%, tert-butyl alcohol 0.03wt%, methyl- tert fourth
Ether 0.02wt%, methyl ethyl ketone 0.02wt%, isobutylaldehyde 0.01wt% isobutene feedstock processing after, the content of water is 7ppm, is contained
The total amount of oxygen organic impurities is 2ppm.
Claims (9)
1. a kind of modified molecular screen for purification of light olefins, it is characterised in that：Molecular sieve is modified using metallo-organic compound,
Metallic element in the metallo-organic compound to be one or more in I B, II B, VI B and VII B B metals, preferably Cr,
It is one or more in Cu, Zn and Mn；The metal-organic organic compound is prepared as the chemical combination containing double carboxyls
One kind in object, preferably adipic acid, glutaric acid and terephthalic acid (TPA).
2. modified molecular screen according to claim 1, it is characterised in that：Based on modified molecular screen weight, Organometallic
It closes object and accounts for 10-50wt%, preferably 20-30wt%；Surplus is molecular sieve.
3. modified molecular screen according to claim 1 or 2, it is characterised in that：Molecular sieve in the modified molecular screen is
It is one or more in 3A, 4A, 5A, 13X and type ZSM 5 molecular sieve.
A kind of 4. method for preparing any one of the claim 1-3 modified molecular screens, which is characterized in that the method includes：
After the metal oxide of B metal, the compound containing double carboxyls and mixed in hydrochloric acid are dissolved, seal and quiet at 200-300 DEG C
Acquisition slurry is postponed, molecular sieve powder is mixed to slurry, cools down and dried after cleaning, granulation obtains modified molecular screen.
5. a kind of change using made from claim 1-3 any one of them modified molecular screen or method according to claim 4
The method of property molecular sieve purification alkene, which is characterized in that the method includes：Modified molecular screen particle is loaded in absorption tower, is contained
The olefin stream for having oxygenate impurity enters from the lower end of modified molecular screen bed, and tower top flows out purified olefin stream.
6. according to the method described in claim 5, it is characterized in that：The oxygenate impurity in alkene before purification include water, ether,
One or more in aldehyde, ketone and alcohol, based on olefin feed weight, the total amount of oxygenate impurity is 0.01- in the alkene before purification
5wt%, preferably 0.1-2wt%, the amount of oxygenate impurity in purified alkene<15ppm.
7. according to the method described in claim 5, it is characterized in that：The operating condition on absorption tower is：10-80 DEG C of temperature, preferably
20-50℃；Pressure 0-2.0MPa, preferably 0.3-1.0MPa；The air speed of olefin stream is 0.4-10h-1, preferably 0.5-2h-1。
8. according to claim 5-7 any one of them methods, it is characterised in that：After modified molecular screen bed adsorption saturation, lead to
It crosses and is regenerated using the mode that high temperature inert gas purges.
9. according to the method described in claim 8, it is characterized in that：Operation temperature during regeneration treatment is 80-300 DEG C, preferably
150-200℃；The preferred nitrogen of inert gas；The air speed of high temperature inert gas purging is 1-30h-1, preferably 5-15h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611087558.3A CN108126664B (en) | 2016-12-01 | 2016-12-01 | Modified molecular sieve for purifying olefin and method for removing oxygen-containing impurities in olefin by using modified molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611087558.3A CN108126664B (en) | 2016-12-01 | 2016-12-01 | Modified molecular sieve for purifying olefin and method for removing oxygen-containing impurities in olefin by using modified molecular sieve |
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| CN110314654A (en) * | 2019-07-24 | 2019-10-11 | 万华化学集团股份有限公司 | A kind of organic waste-gas adsorbant and preparation method thereof, organic waste gas treatment method |
| CN112126458A (en) * | 2019-06-25 | 2020-12-25 | 内蒙古伊泰煤基新材料研究院有限公司 | Method for removing oxygen-containing compounds in FT synthetic oil with different carbon numbers |
| CN113840651A (en) * | 2019-05-15 | 2021-12-24 | 利安德化学技术有限公司 | Method for drying propylene oxide |
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| CN101454260A (en) * | 2006-03-29 | 2009-06-10 | 巴斯夫欧洲公司 | Method for commercially obtaining propene |
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| CN113840651A (en) * | 2019-05-15 | 2021-12-24 | 利安德化学技术有限公司 | Method for drying propylene oxide |
| CN112126458A (en) * | 2019-06-25 | 2020-12-25 | 内蒙古伊泰煤基新材料研究院有限公司 | Method for removing oxygen-containing compounds in FT synthetic oil with different carbon numbers |
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| CN110314654B (en) * | 2019-07-24 | 2022-03-11 | 万华化学集团股份有限公司 | Organic waste gas adsorbent, preparation method thereof and organic waste gas treatment method |
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