CN109482143A - A kind of adsorbent and its preparation and application for purifying low-carbon alkene - Google Patents
A kind of adsorbent and its preparation and application for purifying low-carbon alkene Download PDFInfo
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- CN109482143A CN109482143A CN201710820762.XA CN201710820762A CN109482143A CN 109482143 A CN109482143 A CN 109482143A CN 201710820762 A CN201710820762 A CN 201710820762A CN 109482143 A CN109482143 A CN 109482143A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- 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
- B01J20/183—Physical conditioning without chemical treatment, e.g. drying, granulating, coating, irradiation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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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
- B01J20/28014—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 form
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- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- C07—ORGANIC CHEMISTRY
- 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
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Abstract
The present invention relates to a kind of adsorbent and its preparation method and application for purifying low-carbon alkene, which is grouped as by groups such as molecular sieve, aluminium oxide, active regulators.Preparation method of the invention includes: to combine the method to pulverize and sieve that mother bulb is made using quick balling-up first, then the additional proportion and frequency of granular material and active regulator are controlled during long ball, the method of sample ball solidified using aquation health later, and it is processed by shot blasting, is finally dried and calcination activation after hardening.Compared with prior art, preparation method of the invention has mother bulb preparation efficiency height, finished product yield height and simple and easy feature, is well suited for industrialized production；Adsorbent using this method preparation has component uniform, and particle size distribution range is narrow, wears away low, high mechanical strength and uniform feature.Deep removal of the adsorbent for various oxygenatedchemicals impurity in low-carbon alkene.
Description
Technical field
The invention belongs to technical field of absorbent, are a kind of adsorbent and preparation method thereof for low-carbon alkene purification,
The adsorbent is used to remove the impurity compositions such as oxygenatedchemicals from low-carbon alkene.
Background technique
Low-carbon alkene refers to that the light olefins such as ethylene, propylene and butylene, low-carbon alkene are important basic chemical, is changing
The industries such as chemical industry, the energy, electronics are learned to be widely used.Traditional alkene is mainly obtained using petroleum as raw material by cracking, and
In recent years, the light olefins output prepared using coal as raw material for meeting China's energy characteristics gradually rises.Wherein, coal is through methanol system
Alkene (CTO and MTO) and preparing propylene from methanol (MTP and FMTP) are representative process routes, and device capbility has reached 850 at present
Ten thousand tons, the accounting about 20% in the entire alkene production capacity in China, with the operation successively of new projects, the following accounting is expected to further mention
It rises.In addition, the direct preparing low-carbon olefins technology of synthesis gas also has made some progress, it is expected to comparatively fast realize commercialization.It expects
The year two thousand twenty, China's coal-to-olefin (methanol-to-olefins) production capacity are up to 15,000,000 tons or so, and accounting will in entire alkene production capacity
Close to 30%.
Different from the product of conventional petroleum route, contain in the low-carbon alkene that preparing light olefins from methanol or synthesis gas are directly produced
There are more methanol, methyl ether, aldehyde, ketone compounds, water and carbon dioxide is added, so that the oxygenatedchemicals in low-carbon alkene
Purification and removing necessitate and important link.In commercial plant, most impurity can be removed by rectifying, but
There is still a need for the guard beds for using operating cost relatively low or purification bed to be further removed in depth for remaining micro oxygen containing compound, no
Then these micro oxygenatedchemicals can generate toxic action to the olefin polymerization catalysis in downstream, influence properties of product, this
There is also condensed at low temperature to block pipeline outside, causes the risk of safety accident.Industrially, by guard bed or purification bed need by
The concentration of the oxygenatedchemicals such as methanol, methyl ether, aldehyde, ketone, water and carbon dioxide in low-carbon alkene is reduced to 1ppm hereinafter, this is right
The performance of the adsorbent wherein loaded proposes high requirement.In addition, coal is that last decade just starts to be commercialized through methanol-to-olefins
Various technology problems have occurred in the novel big chemical project of operation, more covering devices in driving and operation, undergo driving and parking
Often, individual device even needs several years that could run well completely, this leads to the catalyst of multiple workshop sections or absorption
Agent is impacted by unusual service condition, so that not up to projected life occur need to change in advance the case where agent.Therefore Persisting exploitation
The adsorbent of the purification low-carbon alkene of high-performance and high quality is that have very much industrial utility value.
In recent years, some Patent datas disclose the adsorbent of oxygenatedchemicals in several purification low-carbon alkenes.Uop Inc.
Patent US6632766 invents a kind of compound adsorbent for purifying hydrocarbon stream, by zeolite, aluminium oxide and metal (alkali metal or
Alkaline-earth metal) composition, the 10% of mole metering of metal needed for the content of metal component is at least equilibrium zeolite lattice negative charge,
Solidify in room temperature to 200 DEG C after absorbent component mixed-forming, is then activated and obtains final products.Middle petrochemical industry patent
CN101884905 has invented a kind of adsorbent and preparation method thereof, molecular sieve and binder (silica gel or aluminium oxide) shaping and roasting
Afterwards, it is impregnated into the salting liquid of alkali metal, re-dry activation, obtained adsorbent has the oxygenatedchemicals in C2~C5 alkene
There is higher adsorption capacity, and regeneration temperature is low.Molecular sieve is then first passed around metal ion and changed by patent CN102744035
Property, molding is then carried out with binder activated alumina or silica again, ion-exchange molecular sieve adsorbent is made.BASF is public
Department patent US20110079145 discloses a kind of adsorbent of hypoergia for removing oxygenatedchemicals from olefin stream, the suction
Attached dose is made of zeolite, aluminium oxide and alkali metal, and metal component is first impregnated on zeolite and then is prepared by mixing into aluminium oxide
Type object, the adsorption capacity of loss oxygenatedchemicals that in this way can be less while reducing sorbent reactions.Patent
CN105289477 discloses the adsorbent of imurity-removal and its application in a kind of coal chemical industry olefin feed, and adsorbent is by zeolite molecules
Sieve, mesoporous material and metal component composition, wherein molecular sieve is modified through metal ion exchanged first, meso-porous alumina through metal from
Impurity in olefin stream can be reduced to 0.1ppm by sub- solution impregnation, strip or spherical sample after mixed-forming.Specially
Sharp CN106423114 discloses a kind of cleanser, preparation method and application of the coal through impurity in methanol olefin polymerization, and cleanser is by compound
Type molecular sieve, rare earth oxide and activated alumina composition, spherical adsorbent are after above-mentioned material mixes by rotational forming system
, for diameter between 1~5mm, the presence of rare earth oxide increases the stability of adsorbent, in high temperature not easy-sintering, resists
Coking Behavior is strong.
In addition, there are also Patent data use silica gel and active carbon for main component to the oxygenatedchemicals in hydro carbons into
Row purification and removal.United States Patent (USP) US6111162 is reported using silica gel as adsorbent, and adsorbing and removing contains from hydrocarbon raw material
Oxygen compound.Diameter is respectively millimetre-sized silica gel particle and active carbon particle by patent CN104248941 and CN104248944
Carrier impregnation may be respectively used in absorption into the salting liquid of metal active constituent, by the cleanser that oxidation and drying process obtain
Volatile oxidn in MTO and MTP tail gas, purified oxide content are less than 0.5ppm.This kind of product is because absorption is held
It measures limited, is mainly used in depollution of environment field, and in big Chemical Manufacture, to being seated in guard bed and/or purification bed
Adsorbent, do not require nothing more than it with high purification precision, while requiring have high adsorption capacity and excellent reaction regeneration
Performance.
Therefore in Chemical Manufacture, removing to oxygenatedchemicals in low-carbon alkene logistics, adsorbent it is main
Component includes molecular sieve, aluminium oxide and metal etc..Wherein there is better choice absorption property by the molecular sieve of metal-modified, it is right
The removing precision of oxygenatedchemicals is high, and can reduce side reaction activity；And aluminium oxide is relatively relatively mild adsorbent, simultaneous
The removal to acidic components can be supplemented while caring for adsorbance, furthermore aluminium oxide plays contribution function to intensity as carrier.It closes
The removing of oxygenatedchemicals in low-carbon alkene, existing patented technology are mainly various fine from carrying out with square degree to adsorbent
The regulation of change promotes its absorption and reaction regeneration performance constantly and perfect, but as industrial products, adsorbent
Molding and preparation method largely determine the comprehensive performance of product, preparation method of the available data to this kind of adsorbent
Exploitation also compare shortage and it is not deep enough, mostly only preparation method is briefly described.
The molding preparation of globular molecule sieve and adsorbent, which generally selects, first to be prepared mother bulb and grows up again molding method.Patent
CN103071539 provides a kind of method of molecular sieve roller forming, after mixing by molecular sieve and Aluminum sol (or silica solution)
Roller forming makes mother bulb, and then adding powder makes mother bulb grow up, and obtained sample ball carries out shaping, polishing in trimmer
And solidification.Patent CN102049246 invents a kind of preparation method of adsorbent of molecular sieve, first mixes molecular sieve, clay and water
Conjunction prepares bulb, then carries out long ball using same raw material, polishes later, last drying and roasting.The mother bulb system of such methods
Standby low efficiency, it is general then to need a few hours less, it is more, need prepare mother bulb within more than ten hour；And it prepares and completes in finished ball
Afterwards, it is often necessary to the qualified products of target size are screened out, other sample balls are then grown up as mother bulb again after being pulverized, this
A process will lead to the multiple crushing and repeated growth of some materials, be unfavorable for improving finished product production while increasing production cost
Rate；Further for the case where introducing containing active component glue is needed during long ball, the component distribution that will lead to sample is produced
Raw deviation, i.e., the material for repeatedly crushing and reusing can contact more glues, to contain more key components, cause
The component distribution of product ball and performance difference are bigger than normal.
To sum up, the adsorbent removed for oxygenatedchemicals in low-carbon alkene logistics, the exploitation work of preparation method
Work be also short of very much, how efficient component of preparing is uniform, and particle size distribution range is narrow, wear away it is low, high mechanical strength and uniformly
Adsorbent product be the technical field major issue.
Summary of the invention
The object of the present invention is to provide a kind of spherical adsorbents and preparation method thereof for purifying low-carbon alkene.
It is high that technical problem to be solved by the invention is to provide a kind of mother bulb preparation efficiencies, and finished ball yield is high, and very
It is suitble to the preparation method of the adsorbent of industrialized production.Adsorbent using this method preparation has component uniform, particle diameter distribution
Narrow range wears away low, high mechanical strength and uniform feature.The adsorbent is used for the various oxygenatedchemicals in low-carbon alkene
Impurity is removed in depth.
It is as follows that the present invention solves technical solution used by above-mentioned technical problem:
A kind of adsorbent and its preparation and application for purifying low-carbon alkene, adsorbent material is by molecular sieve, aluminium oxide
It is formed with active regulator, wherein molecular sieve chooses one of 13X, Y, SAPO-34, ZSM-5,5A or a variety of, aluminium oxide choosing
Take fast shedding, active regulator chooses the hydroxide of alkali metal and/or alkaline-earth metal, one in heat decomposable soluble-salt
Kind or a variety of, each raw material weight ratio are as follows: molecular sieve 20~59.5%, aluminium oxide 40~79.5%, active regulator be 0.5~
13%；Preparation method of the invention includes: to combine the method to pulverize and sieve that mother bulb is made using quick balling-up first, then in length
The additional proportion and frequency of granular material and active regulator are controlled during ball, the solidification of sample ball later uses aquation health
Method, and be processed by shot blasting after hardening, be finally dried and obtain final products after roasting.
The preparation method of adsorbent described in technical solution of the present invention, comprising the following steps:
(1) molecular sieve, alumina powder are weighed by material rate, is sufficiently mixed by mechanical stirring；
(2) mixed granular material is added in balling-up pot, in pot body rotation process, is uniformly added into containing Active Regulation
The aqueous solution of agent, pot is interior to generate spherical material；
(3) spherical material obtained in step (2) is transferred in vibrating screen and carries out crushing and screening process, vibrating screen packet
Include upper layer and lower layer sieve, the crushing of material be on upper screen by the way of mechanical equipment rubbing and pressure and/or manual rubbing and pressure into
Capable, the granule materials that two layers of sieve intermediate screening takes are mother bulb, and the too small material of size can pass through two layers of sieve；
(4) mother bulb particle obtained in step (3) is transferred in balling-up pot, in pot body rotation process, in batches plus
Enter granular material, the powder doses being added every time be initial mother bulb weight 1/8 to 1/2 between, and every time be added powder
And then the directly proportional active regulator aqueous solution of weight is added after shape material and realizes growing up for spherical sample, wherein powder
The proportion of material and active regulator aqueous solution it is identical as in step (2) with when concentration；In sample ball growth process, lead to
The feeding interval for crossing control each batch raw material, and/or adds additional water, guarantee spherical sample in real time containing water quality 20~
Between 50%, preferably 30~40%；Stop adding materials when sample ball is grown up to target size range, the target of spherical sample
Size range is 1~5mm of diameter, preferably 2~3mm；Obtained sample ball can directly carry out next step curing process, can also select
It selects and sample is directly sealed to preservation, carry out curing process again later；
(5) solidification of sample ball is carried out by the way of aquation health, and is directly processed by shot blasting after hardening, finally
Carry out drying and the calcination activation of sample ball.
The preparation method of adsorbent described in technical solution of the present invention, it is characterised in that: wherein the revolving speed of balling-up pot is every
It is selected between 10~50 turns of minute, it is 20~40 turns preferably per minute, and the velocity of rotation of balling-up pot is greater than step in step (2)
Suddenly the velocity of rotation used when spherical sample is grown up in (4) usually wants 5~15 turns big per minute；Wherein active regulator is water-soluble
The mass concentration of liquid is 1~20%, and the additional amount of additional amount and powder raw material is in direct ratio, and the two quality is 0.5 than range
~0.75:1 is adopted when wherein the proportion and concentration of active regulator aqueous solution are grown up with spherical sample in step (4) in step (2)
Active regulator aqueous solution is identical, and active regulator aqueous solution is disposably continuously added in step (2), step (4)
Middle active regulator aqueous solution is and then added after granular material is added every time, and its additional amount and the batch powdery
Inventory is in direct ratio.
The preparation method of adsorbent described in technical solution of the present invention, it is characterised in that: wherein vibrating screen in step (3)
The aperture of upper layer and lower layer sieve is different, and the aperture of upper screen selects between 0.4~1mm, the aperture of lower screen 0.2~
Selected between 0.8mm, and upper screen aperture be greater than lower screen aperture, two mesh size differences 0.2~0.5mm it
Between；The material that two layers of sieve is wherein passed through in step (3) returns in balling-up pot, newly adds the powder equally matched being sufficiently mixed
Shape material, and then be added with newly plus the directly proportional active regulator aqueous solution of powder doses, repeat the above steps (2) and
Step (3) is crushed and screened by quick rotation molding combination and prepares mother bulb particle；Wherein pass through two layers sieve material return at
In ball pot, in balling-up pot rotation process, dry material is first added, then property is continuously added to the water containing active regulator again
Solution.
The preparation method of adsorbent described in technical solution of the present invention, it is characterised in that: addition contains active regulator
It selects pipeline the methods of introduce, spray, splash when aqueous solution, preferably sprays, more preferably uniformly spray.
The preparation method of adsorbent described in technical solution of the present invention, it is characterised in that: the wherein sample ball in step (4)
In growth process, by controlling the feeding interval of each batch raw material and/or adding additional water, guarantee that spherical sample has properly
Real-time water content；Wherein the feeding interval of each batch raw material is 2~20min, and preferably 5~15min, wherein sample ball is excellent
Choosing contains water quality between 20~50%, and preferably 30~40%.
The preparation method of adsorbent described in technical solution of the present invention, it is characterised in that: aquation health, which refers to, makes sample straight
It connects and hydration reaction occurs in turn with water vapor acting；Wherein the water vapour humidity in space locating for sample is more than or equal to 50%, humidity
Preferably greater than or equal to 80%, wherein the temperature of aquation health is 40~200 DEG C, and the time is 3~48h；The aquation health side
There are two types of formulas: (1) aquation health is carried out in steam generator and/or in the space full of water vapour, and steam box may be selected, steam
Vapour room, steam bag etc.；(2) sample ball is put into togerther in heating device together with sealed package, using sample itself steam into
Row aquation health；When health temperature is less than or equal to 100 DEG C, both the above mode may be selected and carry out aquation health, when selection
When health temperature is greater than 100 DEG C, mode need to be planted using (2), and be sealed to sample ball using pressure-resistant kettle, can choose
It is filled with water in bottom, carries out aquation health in the water vapour that high temperature generates using it.
The preparation method of adsorbent described in technical solution of the present invention, it is characterised in that: wherein the polishing of sample ball be
It is carried out in balling-up pot, the sample after solidification is transferred in balling-up pot, rotation polishing, 0.5~3h of polishing time；The drying of sample
Temperature be 50~150 DEG C, drying time be 3~for 24 hours；The temperature of sample calcination activation be 400~600 DEG C, calcining time be 1~
6h。
The application of adsorbent prepared by the method for the present invention, it is characterised in that: the adsorbent and low-carbon alkene logistics are in gas
It mutually or under liquid phase is contacted in fixed bed, oxygenatedchemicals impurity concentration therein can be made to be down to 1ppm or less；Described in wherein
Low-carbon alkene refers to ethylene, propylene and butylene, and wherein oxygenatedchemicals impurity refers to methanol, ethyl alcohol, methyl ether, ether, water, an oxygen
Change one of carbon, carbon dioxide, COS, formaldehyde, acetaldehyde, acetone, butanone, formic acid, acetic acid or a variety of.
Compared with existing well-known technique, the invention has the following advantages that
1, mother bulb preparation efficiency is high
The preparation of adsorbent mother bulb of the invention combines the method to pulverize and sieve to carry out using quick rotation balling-up, exists first
Glue is continuously rapidly joined in balling-up pot, and the spherical material to differ in size is generated in the short time, the material strength obtained in this way is low,
It is easy to be pulverized and sieved by the method for rubbing and pressure, the granule materials among two layers of sieve are mother bulb.Relative to conventional method,
Time needed for this preparation method can greatly shorten mother bulb preparation.
2, finished ball yield is high, and low energy consumption for material consumption, and process is simple to operation
Effect by meeting the two-stage sieve of size requirement can obtain the mother bulb that size distribution is concentrated, then powder is added portionwise
Shape material and active regulator component, while spherical sample is controlled with suitable water content, carry out long ball.The present invention passes through tight
Lattice control the size of mother bulb, control the water content of sample in growth process, advantageously ensure that sample ball is uniformly grown up, can finally subtract
The workload crushed after the youthful and the elderly's ball because size distribution ranges are big, improves production efficiency, reduces cost, is suitble to industry
Metaplasia produces.
3, spherical adsorbent product quality is high
The method of the present invention, which passes through, controls suitable mother bulb size, charging sequence, feeding quantity and ratio and feeding interval etc.,
In conjunction with aquation health, polishing and calcination activation, the prepared active component of spherical adsorbent is uniform, particle size distribution range
It is narrow, wear away low, sample ball high mechanical strength and uniform feature.The adsorbent is used for oxygenatedchemicals in low-carbon alkene logistics
Removing, the content of the oxygenatedchemicals such as methanol therein, methyl ether, water, carbon dioxide and aldehyde, ketone can be reduced to 1ppm with
Under, which also has bed temperature stable and uniform in use, the low feature of regeneration temperature.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
A kind of adsorbent and preparation method thereof for purifying low-carbon alkene, adsorbent material is by 13X molecular sieve, fast shedding
It is formed with active regulator, wherein granular material 13X molecular sieve and the mixing mass ratio of fast shedding are 45:55, active regulator
The mass ratio formula of aqueous solution are as follows: 100 parts of water, 3 parts of sodium carbonate, 4 parts of sodium hydroxides, 5 parts of sodium acetates；
Preparation method the following steps are included:
(1) material molecular sieve and fast shedding are thoroughly mixed 30min in mixing machine.
(2) it weighs the mixed granular material of 30kg to be transferred in balling-up pot, be turned in pot body with 30 turns of speed per minute
During dynamic, quick continuous uniform sprays into 18kg active regulator aqueous solution, generates diameter from grade to number in pot within 1h
Centimetre spherical material to differ in size.
(3) above-mentioned material being transferred in vibrating screen and carries out crushing and screening process, crushing is carried out by the way of rubbing and pressure,
Vibrating screen upper screen aperture is 20 mesh, and lower screen aperture is 30 mesh, and the granule materials that upper layer and lower layer sieve intermediate screening takes are
Mother bulb；Material across two layers of sieve is back in balling-up pot, adds dry material and Active Regulation that weight ratio is 1:0.6
Agent aqueous solution, repeat step (2) and
(3) mother bulb preparation is carried out.
(4) 20 kilograms of mother bulb obtained in step (3) are transferred in balling-up pot, in pot body with 20 turns of speed per minute
In rotation process, granular material and active regulator aqueous solution are added in batches, is firstly added 5 kilograms of granular material every time, connects
Uniform 3 kilograms of aqueous solution containing active regulator of sprinkling；Control and be divided into 5 between the feed time of each batch raw material~
10min, spherical sample adhesion, water content about 35% stop addition when sample ball is grown up to diameter within the scope of 2~3mm
Material.
(5) the spherical sample that step (4) obtains is transferred directly in vaporium and carries out aquation health, vaporium humidity is big
In 90%, temperature is 80 DEG C, and the time is for 24 hours；Sample after health is transferred to rotation polishing in balling-up pot, and revolving speed is per minute
20 turns, time 1h；Sample drying processing is carried out after polishing, temperature is 60 DEG C, time 12h；Calcination activation is finally carried out, temperature
Degree is 500 DEG C, time 3h, this experiment and sample mark S1.
Comparative example 1
With embodiment 1, but do not use quick rotation balling-up that the method to pulverize and sieve is combined to prepare mother bulb, and do not use mother
The mode grown up again after ball screening prepares product ball, i.e., step (2), (3) and (4) change in embodiment 1 is as follows:
It weighs the mixed material of 30kg to be transferred in balling-up pot, in pot body with 20 turns per minute of speed rotation process
In, 18kg active regulator aqueous solution is uniformly sprayed into using normal speed, and add part water, generate diameter after about 3h in pot
From some tens of pm to the spherical material of grade size, and there is the bulky grain of small part Centimeter Level；Then divide directly in the pot
Raw material is added in batch, is firstly added 5 kilograms of granular material every time, and then uniformly aqueous solution 3 of the sprinkling containing active regulator is public
Jin；Guarantee spherical sample adhesion, water content about 35%, when the diameter of most of sample ball increases to by control feeding interval
Stop adding materials when within the scope of 2~3mm, obtained sample ball is denoted as balling-up；Above-mentioned sample is transferred to vibrating screen to sieve
Divide processing, wherein sample ball of the diameter within the scope of 2~3mm is qualified finished product, and the place of step (5) is then carried out with embodiment 1
Reason, other too big and too small spherical samples are transferred to pulverizer, are back in balling-up pot after crushed, add dry material and
Active regulator aqueous solution carries out mother bulb preparation.
Other preparation processes are the same as embodiment 1, this experiment and sample mark C1.
The quality index of the experimental result and spherical sample of embodiment 1 and comparative example 1 is compared, such as the following table 1.It can
See, when not using quick rotation balling-up that the method that pulverizes and sieves is combined to prepare mother bulb, and grow up again after not using mother bulb to sieve
When mode prepares product ball, the balling-up size distribution ranges that spin obtains are wide, and it is lower that sieving obtains qualified output, and needs
The balling-up material for returning to pulverization process is more, i.e., comparative example 1 increases energy consumption, and reduces yield, furthermore to the strong of finished ball
It is unfavorable to spend.
The experiment of 1 adsorbent of table and properties of samples comparison
| Number | Balling-up particle diameter distribution | Crush rework material amount | Production | Particle Crush Strength |
| S1 | 2.2~2.8mm | Seldom | It is high | 49.9N |
| C1 | 1~4mm | It is more | It is low | 42.5N |
Comparative example 2
With embodiment 1, but do not use quick rotation balling-up that the method to pulverize and sieve is combined to prepare mother bulb, i.e., using general
Speed prepares mother bulb, and prepares product ball in such a way that mother bulb screening is grown up again, and the step (2) in embodiment 1 is changed
It is as follows:
It weighs the mixed granular material of 30kg to be transferred in balling-up pot, be rotated in pot body with 20 turns of speed per minute
Cheng Zhong is uniformly sprayed into 18kg active regulator aqueous solution using normal speed, and adds part water, is generated directly in pot after about 3h
Spherical material of the diameter from some tens of pm to grade size, and have the bulky grain of small part Centimeter Level.
Other preparation processes are the same as embodiment 1, this experiment and sample mark C2.
The quality index of the experimental result and spherical sample of embodiment 1 and comparative example 2 is compared, such as the following table 2.It can
See, when the method for not using quick rotation balling-up combination to pulverize and sieve prepares mother bulb, when preparing mother bulb only with general speed,
The preparation efficiency of mother bulb declines to a great extent, therefore reduces production, while affecting the intensity and abrasion property of finished ball.
The experiment of 2 adsorbent of table and properties of samples comparison
| Number | Mother bulb preparation efficiency | Production | Particle Crush Strength | Rate of wear |
| S1 | It is average 1h/ batches, high | It is high | 49.9N | 0.46% |
| C2 | It is average 3h/ batches, low | It is low | 42.4N | 0.54% |
Comparative example 3
With embodiment 1, but in step (4) during long ball, non-strict control every batch of granular material and Active Regulation
The additional proportion of agent aqueous solution, real-time sample water content have greater than 50%, and sample ball is caused to stick together, and size has size point
Change phenomenon.
Other preparation processes are the same as embodiment 1, this experiment and sample mark C3.
The quality index of the experimental result and spherical sample of embodiment 1 and comparative example 3 is compared, such as the following table 3.It can
See, during long ball, the additional proportion of non-strict control every batch of granular material and active regulator aqueous solution leads to sample
When product water content is excessively high, the balling-up size distribution ranges that spin obtains are wider, and the output that sieving obtains qualification is lower, and sample
The intensity of product, specific surface and Kong Ronghui are obviously low.
The experiment of 3 adsorbent of table and properties of samples comparison
| Number | Balling-up particle diameter distribution | Production | Particle Crush Strength | Specific surface | Kong Rong |
| S1 | 2.2~2.8mm | It is high | 49.9N | 290m2/g | 0.47ml/g |
| C3 | 1.8~3.3mm | It is low | 34.8N | 202m2/g | 0.42ml/g |
Comparative example 4
With embodiment 1, but in step (4) during long ball, extend the feeding interval time of each batch raw material extremely
20min, and part water is added, keep the water content of sample between 30%~40%, in addition, sample is in water in step (5)
Change health not to be processed by shot blasting later, directly carries out the drying and roasting of next step.
Other preparation processes are the same as embodiment 1, this experiment and sample mark C4.
The quality index of the experimental result and spherical sample of embodiment 1 and comparative example 4 is compared, such as the following table 4.It can
See, during long ball, extends the feeding interval time of each batch raw material, but do not polished after aquation health
When processing, the intensity of finished ball can be improved, but worn away index and be deteriorated.
The comparison of 4 sample of sorbent property of table
| Number | Particle Crush Strength | Rate of wear | Specific surface | Kong Rong |
| S1 | 49.9N | 0.46% | 290m2/g | 0.47ml/g |
| C4 | 71.3N | 0.61% | 301m2/g | 0.46ml/g |
Comparative example 5
The temperature that calcination activation is finally carried out with embodiment 1, but in step (5) is 380 DEG C.
Other preparation processes are the same as embodiment 1, this experiment and sample mark C5.
The quality index of the experimental result and spherical sample of embodiment 1 and comparative example 5 is compared, such as the following table 5.It can
See, when the calcination activation temperature of sample ball is too low, to its intensity significant adverse, and influences wear hardness.
The comparison of 5 sample of sorbent property of table
| Number | Particle Crush Strength | Rate of wear |
| S1 | 49.9N | 0.46% |
| C5 | 40.2N | 0.54% |
Embodiment 2
With embodiment 1, but molecular sieve is SAPO-34 powder, the mass ratio formula of active regulator aqueous solution are as follows: 100 parts
Water, 5 parts of sodium bicarbonates, 2 parts of potassium hydroxide, 3 parts of sodium oxalates.
Other preparation methods and process are the same as embodiment 1, this experiment and sample mark S2.
The experimental result of embodiment 2 and the quality index of spherical sample such as the following table 6.As it can be seen that the mother bulb system of the method for the present invention
Standby high-efficient, finished ball yield is high, is suitble to industrial production application, and prepared adsorbent has particle size distribution range narrow, abrasion
It is low, the characteristics of high mechanical strength.
6 adsorbent experimental result of table and S2 sample ball property
| Experimental result | Mother bulb preparation efficiency | Balling-up particle diameter distribution | Crush rework material amount | Production |
| It is average 1h/ batches, high | 2~3mm is narrow | It is less | It is high | |
| Sample ball property | Particle Crush Strength | Rate of wear | Specific surface | Kong Rong |
| 46.1N | 0.38% | 320m2/g | 0.51ml/g |
Embodiment 3
With embodiment 1, only the additional proportion of granular material and active regulator aqueous solution is changed to 1:0.5.
Other preparation processes are the same as embodiment 1, this experiment and sample mark S3.As it can be seen that the adsorbent of the method for the present invention preparation
Uniform with component, this can contribute the uniformity of its mechanical strength, and be conducive to keep adsorbent in practical applications
Bed temperature stable and uniform, and the required temperature of regeneration can be reduced.
The EDX of the spherical sample of embodiment 3 forms result such as the following table 7.
The EDX of 7 S3 sample ball of table analyzes result (atomic percent of element)
| O | Na | Al | Si | |
| Centre of sphere region | 65.65% | 5.01% | 22.08% | 7.26% |
| Shell region | 63.64% | 5.27% | 23.45% | 7.64% |
Comparative example 6
With embodiment 3, but in step (4) during long ball, the proportion of granular material used is for 13X molecular sieve and fastly
The mixing mass ratio of shedding is 60:40, different from 45:55 used in step (2).
Other preparation processes are the same as embodiment 3, this experiment and sample mark C6.
The quality index of the experimental result and spherical sample of embodiment 3 and comparative example 6 is compared, such as the following table 8.It can
See, when step (4) is different with the proportion of granular material used by step (2), the centre of sphere and shell of prepared sample ball
Composition meeting bad student's difference in region, and will affect sample particle intensity and rate of wear, in addition find the finished product that comparative example 6 obtains
The shell of ball is easy to fall off, and shows that prepared sample ball is second-rate.
The comparison of 8 sample of sorbent property of table
| Number | Particle Crush Strength | Rate of wear | EDX analyzes result |
| S3 | 47.8N | 0.47% | The centre of sphere and shell composition are close |
| C6 | 36.4N | 0.58% | The centre of sphere and shell composition difference are larger |
Embodiment 4
With embodiment 2, only molecular sieve SAPO-34 and the mixing mass ratio of fast shedding are changed to 40:60.
Other preparation processes are the same as embodiment 2, this experiment and sample mark S4.
The centre of sphere of the spherical sample of embodiment 4 and the EDX analytical element composition in shell region are close, with embodiment 3, show
The inside and outside composition of sample ball prepared by the invention patent uniformly, can be conducive to keep bed temperature stable equal in industrial application
It is even, and the required temperature of regeneration can be reduced.
The property index test of spherical adsorbent is referring to national standard and professional standard in above embodiments and comparative example
Method carry out, usually sieve takes sample ball of the diameter between 2~2.8mm to be tested, wherein test specific surface and Kong Rong
When, sample ball is first subjected to pulverization process sampling and testing again, wherein EDX elemental analysis is first to be crushed sample ball, in sample
Portion is scanned characterization (wherein carbon is not included in), and in addition production is sample of the sieve diameter range between 2~3mm
Ball is measured and is compared.
Embodiment 5
Sample S1 in embodiment 1 is applied to the adsorbing and removing of oxygenatedchemicals impurity in liquid propylene logistics, process
It is as follows: adsorbent ball be crushed into 20~40 meshes, 4g is weighed and be packed into fixed bed reactors, bed fills up quartz sand up and down.?
500h-1Under the conditions of volume space velocity, it is passed through high pure nitrogen and carries out heating activation, be down to 40 DEG C of holdings after 250 DEG C of activation 2h.By bed
After high pure nitrogen punching press to 3MPa, liquid propylene material is pumped into certain air speed, the impurity composition in liquid propylene is difference
For the methanol, methyl ether and acetaldehyde of 150ppm.Propylene stream after bed acts on is depressurized and sufficiently after gasification, by online
Helium ionized gas phase chromatographic instrument tested and analyzed, wherein think that adsorbent penetrates when the concentration of dimethyl ether is more than 1ppm,
Experimental result is shown in the following table 9.S1 sample is S1-2, then the carded sliver by circulation absorption and the sample mark regenerated after totally 20 experiments
Part is in 500h-1The lower 100 DEG C of processing 2h of the stream of nitrogen gas of volume space velocity, 260 DEG C of processing 4h, experiment condition is the same, as a result sees below
Table 9.
Absorption property of 9 adsorbent of table to methanol, methyl ether and acetaldehyde in liquid propylene
It can be seen from the results above that finished ball yield is high present approach provides a kind of mother bulb preparation efficiency height, and
And it is well suited for the preparation method of the adsorbent of industrialized production.Have component equal using adsorbent prepared by the method for the present invention
Even, particle size distribution range is narrow, wears away low, high mechanical strength and uniform feature.The adsorbent is suitable for low-carbon alkene material
In various oxygenatedchemicals impurity be removed in depth.
Claims (13)
1. a kind of for purifying the preparation method of the adsorbent of low-carbon alkene, it is characterised in that:
The group of adsorbent is divided into molecular sieve, aluminium oxide, active regulator, each raw material weight ratio are as follows: molecular sieve 20~59.5%, oxygen
Change aluminium 40~79.5%, active regulator is 0.5~13%；
The preparation method of adsorbent, comprising the following steps:
(1) molecular sieve, alumina powder are weighed by material rate, is sufficiently mixed by mechanical stirring；
(2) mixed granular material is added in balling-up pot, and in pot body rotation process, continuous uniform addition contains Active Regulation
The aqueous solution of agent, pot is interior to generate spherical material；
(3) spherical material obtained in step (2) is transferred in vibrating screen carry out crush and screening process, vibrating screen include upper
Lower two layers of sieve, upper screen aperture are greater than lower screen aperture, and the crushing of material is on upper screen using mechanical equipment
What the mode of rubbing and pressure and/or manual rubbing and pressure carried out, the granule materials that two layers of sieve intermediate screening takes are mother bulb, the too small material of size
It can be across two layers of sieve；
(4) mother bulb particle obtained in step (3) is transferred in balling-up pot, in pot body rotation process, is added in batches former
Material, wherein be firstly added granular material, the powder doses being added every time is between 1/8 to the 1/2 of initial mother bulb weight, and
It is and then added after granular material is added every time and realizes spherical sample with the directly proportional active regulator aqueous solution of its weight
Grow up, the proportion of the granular material that wherein every batch of is added and active regulator aqueous solution with when concentration and step
(2) identical in；In sample ball growth process, by controlling the feeding interval of each batch raw material and/or adding additional water,
Guarantee spherical sample contains water quality between 20~50% in real time, and preferably 30~40%；When sample ball is grown up to target size
Stop adding raw materials when range, wherein the target size range of spherical sample is 1~5mm of diameter, preferably 2~3mm；Obtained sample
Product ball directly carries out next step curing process, also can choose and sample is directly sealed to preservation, carries out at solidification again later
Reason；
(5) solidification of sample ball is carried out by the way of aquation health, and is directly processed by shot blasting after hardening, is finally carried out
The drying of sample ball and calcination activation.
2. the preparation method of adsorbent according to claim 1, it is characterised in that:
Wherein the revolving speed of balling-up pot selects between 10~50 turns per minute, 20~40 turns preferably per minute；
Wherein the velocity of rotation of balling-up pot is greater than the velocity of rotation used when spherical sample is grown up in step (4) in step (2), leads to
Often want 5~15 turns big per minute.
3. the preparation method of adsorbent according to claim 1, it is characterised in that:
Wherein the mass concentration of active regulator aqueous solution is 1~20%, and additional amount is directly proportional to the additional amount of granular material
Example, the two quality are 0.5~0.75:1 than range；
It is used when wherein the proportion and concentration of active regulator aqueous solution are grown up with spherical sample in step (4) in step (2)
Active regulator aqueous solution is identical；
Wherein active regulator aqueous solution is that disposable continuous uniform is added in step (2)；
Wherein active regulator aqueous solution is and then to be added after granular material is added every time, and it adds in step (4)
It is in direct ratio to enter the powder doses that amount and the batch are added.
4. the preparation method of adsorbent according to claim 1, it is characterised in that:
Wherein the aperture of the upper layer and lower layer sieve of vibrating screen is different in step (3), and the aperture of upper screen is between 0.4~1mm
Selection, the aperture of lower screen select between 0.2~0.8mm, and upper screen aperture is greater than lower screen aperture, two sieves
Screen distance disparity range is 0.2~0.5mm.
5. the preparation method of adsorbent according to claim 1, it is characterised in that:
The material that two layers of sieve is wherein passed through in step (3) returns in balling-up pot, and it is identical newly to add the proportion being sufficiently mixed
And then granular material is added and newly adds the directly proportional active regulator aqueous solution of powder doses, repeat the above steps (2)
With step (3), is crushed and screened by quick rotation molding combination and prepare mother bulb particle；
The material for wherein passing through two layers of sieve returns in balling-up pot, in balling-up pot rotation process, has first added dry material, then
Property is continuously added to the aqueous solution containing active regulator again；
Selection pipeline introduces, sprays, splashes when the aqueous solution containing active regulator wherein is added in step (2) and step (4)
The methods of, it preferably sprays, more preferably uniformly sprinkling.
6. the preparation method of adsorbent according to claim 1, it is characterised in that:
Wherein in step (4) in the growth process of sample ball, by controlling the feeding interval of each batch raw material and/or adding volume
Outer water guarantees that spherical sample has suitable real-time water content；
Wherein the feeding interval of each batch raw material is 2~20min, preferably 5~15min；
Wherein sample ball preferably containing water quality between 20~50%, preferably 30~40%.
7. the preparation method of adsorbent according to claim 1, it is characterised in that:
Aquation health, which refers to, allows sample that hydration reaction directly occurs in turn with water vapor acting；
Wherein the water vapour humidity in space locating for sample is more than or equal to 50%, preferably greater than or equal to 80%；
Wherein the temperature of aquation health is 40~200 DEG C, and the time is 3~48h.
8. according to claim 1 or the preparation method of 7 adsorbents, it is characterised in that:
There are two types of the aquation Curing Methods:
(1) aquation health is carried out in steam generator and/or in the space full of water vapour, and steam box, vaporium may be selected
Or steam bag etc., wherein humidity is more than or equal to 50%, preferably greater than or equal to 80%；
(2) sample ball is put into togerther in heating device together with sealed package, carries out aquation health using the steam of sample itself,
Wherein humidity is more than or equal to 50%, preferably greater than or equal to 80%；
When health temperature is less than or equal to 100 DEG C, both the above mode may be selected and carry out aquation health；When the health temperature of selection
When greater than 100 DEG C, mode need to be planted using (2), and be sealed to sample ball using pressure-resistant kettle, can choose and contain in bottom
Water carries out aquation health in the water vapour that high temperature generates using it.
9. the preparation method of adsorbent according to claim 1, it is characterised in that:
The polishing of sample ball is carried out in balling-up pot, and the sample after solidification is transferred in balling-up pot and rotates polishing；
Wherein revolving speed is 10~50 turns per minute, 20~40 turns preferably per minute；
Wherein polishing time is 0.5~3h.
10. the preparation method of adsorbent according to claim 1, it is characterised in that:
The drying temperature of sample ball be 50~150 DEG C, drying time be 3~for 24 hours；
The temperature of sample ball calcination activation is 400~600 DEG C, and calcining time is 1~6h.
11. the preparation method of adsorbent according to claim 1, it is characterised in that:
Molecular sieve chooses one of 13X, Y, SAPO-34, ZSM-5,5A or a variety of；
Aluminium oxide chooses fast shedding；
Active regulator chooses hydroxide, nitrate, carbonate, bicarbonate, the formic acid of alkali metal and/or alkaline-earth metal
One of soluble-salts such as salt, acetate, oxalates, citrate are a variety of.
12. a kind of adsorbent that any preparation method of claim 1-11 prepares.
13. a kind of application of adsorbent described in claim 12, it is characterised in that:
The adsorbent is used for the oxygenatedchemicals impurity being removed in depth in low-carbon alkene logistics；
Wherein low-carbon alkene refers to one of ethylene, propylene and butylene or a variety of；
Wherein oxygenatedchemicals impurity refer to methanol, ethyl alcohol, methyl ether, ether, water, carbon monoxide, carbon dioxide, COS, formaldehyde,
One of acetaldehyde, acetone, butanone, formic acid, acetic acid are a variety of.
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