CN105289477B - The adsorbent of imurity-removal and its application in coal chemical industry olefin stream - Google Patents
The adsorbent of imurity-removal and its application in coal chemical industry olefin stream Download PDFInfo
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- CN105289477B CN105289477B CN201510801038.3A CN201510801038A CN105289477B CN 105289477 B CN105289477 B CN 105289477B CN 201510801038 A CN201510801038 A CN 201510801038A CN 105289477 B CN105289477 B CN 105289477B
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Abstract
Adsorbent and its application the present invention relates to imurity-removal in coal chemical industry olefin stream, adsorbent are prepared using the raw material of following components and parts by weight content：Zeolite molecular sieve 1~99, mesoporous material 1~99, metal component 0.01~10, at least one of at least one of 1 race of load regulation, the metal of the 2nd race or the 11st race or metal oxide on zeolite molecular sieve, 3 race of load regulation on mesoporous material, the 4th race, the metal of the 11st race or the 12nd race or metal oxide.Compared with prior art, oxygenatedchemicals in olefin stream can be down to ppb grades (weight ratios) by the present invention, and the adsorbent for removing oxygenatedchemicals is relatively low to the ethylene in olefin stream and the adsorption activity of propylene.
Description
Technical field
The present invention relates to a kind of adsorbent, adsorbent more particularly, to imurity-removal in a kind of coal chemical industry olefin stream and
It is applied.
Background technology
Coal chemical industry refers to using coal as raw material, coal is made to be converted into gas, liquid and solid fuel and chemistry through chemical process
The process of product.Traditional alkene is mainly made by petroleum cracking, and coal-to-olefin is methanol to be made by coal, then by methanol through dimethyl ether
Continue low-carbon alkene of the dehydration generation including ethylene and propylene.Wherein have formaldehyde, carbon monoxide, carbon dioxide, water etc.
Substance generates, also the complete dimethyl ether of unreacted and methanol.It can be seen that compared with traditional petroleum cracking alkene, coal
The major impurity of base methanol-to-olefins is oxygenatedchemicals.The presence of carbon dioxide not only in cryogenic separation under cryogenic conditions because
Form dry ice so as to occluding device and pipeline, can also destroy the activity of polymerization catalyst, influence point of polymerization speed and polyethylene
Son amount.Existing polyolefin catalyst is lower and lower for the acid impurities content requirement in alkene, and prior art generally requires alkene
Before polymerization, the acid impurities such as CO2 content need to be removed to 0.l ppm (w) left and right to hydrocarbon, be gathered with the height for meeting olefin polymerization catalyst
Close catalytic activity.
The presence of trace oxygenates can destroy olefin polymerization catalysis activated centre or participate in polymerisation in alkene,
It reduces the capacity of orientation of catalyst or forms randomness living chain, can not only reduce the activity, selectivity and receipts of effective catalyst
Rate, but also the performances such as the density of polymer, viscosity, molecular weight, the degree of cross linking, isotacticity can be had an impact, in some instances it may even be possible to it leads
It causes to stop work, stop production, decline the product quality, production efficiency and economic benefit of factory.
The purification techniques of existing olefin removal oxygenatedchemicals mainly has two broad aspects of rectifying and absorption.
The oxygenatedchemicals in alkene can be reduced to certain level, such as specially using means such as fractionation, distillation, rectifying
Sharp US200400927N, CN10973831A, CN10993321A.But fail the oxygenatedchemicals in alkene being reduced to ppm
Grade is horizontal, such as further to be removed, and need to use the means such as multistage rectifying, batch rectification, could meet polymer grade olefin
In requirement to oxygenates level, operating cost is big.And absorbing process has the characteristics that low temperature, easy to operate, can drop significantly
Lower operational cost.
Report uses silica gel as adsorbent in patent US6111162, the Adsorption oxygenatedchemicals from hydrocarbonaceous gas stream, but
Adsorption effect is not obvious.EP 0229994 utilizes the molecular sieve of the faujasite structure of micropore, such as X, Y type molecular sieve and LZ-
210 zeolites, the dimethyl ether in adsorbing and removing liquid C3~C5 alkane, alkene produce a large amount of heat of adsorption, easily during use
Cause olefin oligomerization, influence the quality of later stage alkene, alkane.US4371718 is disclosed using aluminium oxide as adsorbent from fourth
In alkene raw material remove methanol method, but in patent aluminium oxide duct it is small, remove alkene in impurity type it is limited.
CN102463101 carries out alkali metal ion exchange using molecular sieve, achievees the purpose that reduce adsorbent heat of adsorption.It will
It is molecular sieve modified to be effectively reduced heat of adsorption, but in practical applications, need molecular sieve being effectively molded, Cai Nengying
In being purified for alkene.CN1806029 discloses a kind of method that dimethyl ether is removed from alkane, olefin stream, and this method is
Using dipping technique, micro porous molecular sieve Zn, Mg ionic impregnation is modified, to reduce thermal effect of the adsorbent in adsorption cleaning
It should.When the molecular sieve after modification and basis material being molded in patent, but finding that molecular sieve content is high, the wear resistence of adsorbent
It is poor；And basis material content it is high when, it is impossible to reach the requirement of alkene deep purifying.
For CN102639228A by the way that metal component is added in micro-pore zeolite molecular sieve first, progress is molecular sieve modified,
Heat of adsorption is reduced, then adsorbent is made with components mechanical mixtures such as aluminium oxide, to enhance the absorption to oxygenatedchemicals impurity.It should
The modification that patent clearly proposes aluminium oxide can increase the adsorption strength of adsorbent to a certain extent in adsorbent, but into
The pore passage structure of type adsorbent does not design, constrains the utilization rate of molecular sieve.
CN103495378A proposed using kaolin as inert base, aluminium oxide or inorganic silicon-aluminum mixture as binding agent,
Using submicron molecular sieve as active component, the microsphere adsorbing agent of certain particle size distribution is prepared, is reached while heat of adsorption is reduced
Purify the effect of alkane, alkene.With kaolin, aluminium oxide or inorganic silicon-aluminum mixture, submicron molecular sieve or active constituent, system
The microsphere adsorbing agent of standby certain particle size removes methanol, dimethyl ether, the propionic aldehyde of trace in olefin stream under high pressure low temperature, and
Using the adsorbent reactivation technique of low-voltage high-temperature.But the pore passage structure of formed absorbent is not designed, is unfavorable for adsorbent again
Raw, regeneration energy consumption is higher.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind being capable of deep removal
The method of impurity in coal chemical industry olefin stream, and the solid absorbent used, have adsorption capacity is big, absorption fuel factor is low,
The features such as rate of adsorption is fast, regeneration energy consumption is small.
The purpose of the present invention can be achieved through the following technical solutions：
The adsorbent of imurity-removal in coal chemical industry olefin stream, is prepared into using the raw material of following components and parts by weight content
It arrives：Zeolite molecular sieve 1~99, mesoporous material 1~99, metal component 0.01~10.
Wherein, on zeolite molecular sieve in the metal or metal oxide of 1 race of load regulation, the 2nd race or the 11st race at least one
Kind, at least one of 3 race of load regulation on mesoporous material, the 4th race, the metal of the 11st race or the 12nd race or metal oxide.
Preferably, the raw material of adsorbent is following components and parts by weight content：Zeolite molecular sieve 1~50, mesoporous material 40
~99, metal component 0.01~10.
It is further preferred that the raw material of adsorbent is following components and parts by weight content：Zeolite molecular sieve 15~40, mesoporous material
Material 50~99, metal component 0.01~10.
The zeolite molecular sieve for LTA types, MFI type, 3A, 4A in FAU type molecular sieves, 5A, 10X, 13X, NaY,
At least two or two or more mixtures in NaKY, ZSM Series Molecules sieve, through the 1st race, the 2nd race, the 11st race's metal or metal
Potassium chloride, potassium nitrate, potassium sulfate, potassium oxide, magnesium nitrate, magnesium sulfate, magnesium chloride, magnesia, calcium nitrate, sulfuric acid in oxide
One or more of calcium, calcium oxide, calcium chloride, copper nitrate, copper sulphate, copper oxide, copper chloride carry out ion exchange.It is specific real
The process of applying is：Molecular sieve is placed in a concentration of 0.01~5mol/L at least one solution of above-mentioned metal or metal oxide,
In 1500hr-12~4 hours are stirred under rotating speed, wash drying, obtain carrying out the molecular sieve after ion exchange, carried metal group
Point.
The mesoporous material is mesopore silicon oxide, mesoporous TiO 2, meso-porous alumina, mesoporous zircite, mesoporous oxygen
Change one or more of gallium, and through the 3rd race, the 4th race, the 11st race, the lanthanum nitrate of the 12nd race, lanthana, cerous nitrate, oxidation
Cerium, zirconium nitrate, zirconium sulfate, zirconium oxide, copper nitrate, copper sulphate, copper oxide, copper chloride, zinc nitrate, zinc sulfate, zinc chloride, oxidation
The mesoporous material of one or more of loads in zinc.The mesoporous material is preferably the meso-porous alumina after infusion process is modified.
Specific implementation process is：Meso-porous alumina is immersed in a concentration of 0.01~5mol/L's of above-mentioned metal or metal oxide
In solution, through spontaneously drying, roasting, can obtain load has the meso-porous alumina of metal or metal oxide.
Zeolite molecular sieve, with spin or extruded moulding, obtains the particle of certain particle size distribution, granularity point with mesoporous material
Cloth is preferably 0.5~4mm, and the solid particle intensity after being molded is not less than 25N, and is characterized through BET, the ratio of solid absorbent
Surface area is more than 380m2/g。
The molding of extrusion method is selected, dry 0.1~15h, solid absorbent is obtained after fired at 90~120 DEG C.Molding
Solid particle intensity later is not less than 15N, and is characterized through BET, and the specific surface area of solid absorbent is more than 380m2/g。
The adsorbent and coal chemical industry olefin stream contact under gas phase or liquid phase in fixed bed, solid absorbent and coalification
Work olefin stream contacts on a fixed bed, adsorbent use pressure swing adsorption technique, condition for temperature between 10~60 DEG C, operation
Pressure range can be implemented between 0.1~3MPa.It is gas phase or liquid phase that the time of contact, which depends on olefin stream, gas feed
When, air speed (GHSV) is more than 1500h-1；During liquid feed, air speed (LHSV) is in 0.1~50h-1Between.Make coal chemical industry alkene object
Impurity concentration in stream is down to 100ppb from 2500ppm.
Adsorbent is respectively less than 0.01mg/kg to the adsorption capacity of ethylene and propylene in coal chemical industry olefin stream, and impurity includes
It is one or more in methanol, water, dimethyl ether, formaldehyde or carbon dioxide.
The adsorbent is in 100~5000h-1Under using high pure nitrogen as regenerating medium, 60~150 under 0.1~0.2MPa
2~10h is activated at DEG C, being regenerated using temperature programming for 0.1~2h, the absorption after regeneration are then re-activated at 150~500 DEG C
The carbon left of agent is less than 0.001wt%, and the adsorbent after regeneration is applied to gas phase or liquid phase coal chemical industry olefin stream
In to the adsorption experiment of impurity, one way run time still reaches 80h (gas phase) or more than 350h (liquid phase), with the solid before inactivation
Adsorbent adsorbing contaminant capacity is suitable.And solid absorbent is reused 100 times or more, the absorption of impurity is remained to reach
The requirement of deep purifying.
Furthermore, it is understood that by the solid absorbent of inactivation, in air speed (GHSV) 100~500h-1Under high pure nitrogen, use is low
Temperature-elevated process desorption by heating regeneration.It is characterized in that, under 0.1~3.0MPa using 2 DEG C/min temperature programmings to 60~
150 DEG C of sections activate 2~10h at preferably 120 DEG C；Later 150~500 are warming up to using 10 DEG C/min under 0.1~3.0MPa
Between DEG C, 0.1~2h, preferably 0.5h are activated at preferably 300 DEG C.
Solid absorbent prepared by the present invention, by mesoporous material with metal or metal oxide modified, zeolite molecular sieve
After carrying out ion exchange, due to duct prosperity, the utilization rate of molecular sieve is improved, significantly reduces being inhaled in molding for molecular sieve
Usage amount in attached dose, improves regenerability, reduces fuel factor.Solid absorbent used and gas phase or liquid phase coal chemical industry alkene
When logistics contacts, 0.01mg/kg is less than to ethylene in coal chemical industry olefin stream and propylene adsorption capacity, i.e., solid absorbent is to coal
The adsorption activity of ethylene and propylene in chemical industry olefin stream is weaker.
Compared with prior art, the present invention has the following advantages：
1st, solid absorbent is big to the adaptability range of impurity
Solid absorbent described in the purification technique of coal chemical industry olefin stream of the present invention, using the molecular sieve of different crystal forms
It is combined and carries out modified optimization.It avoids dopant species and increases interference to absorption property, water in usual olefin stream
In the presence of that can reduce adsorption capacity of the adsorbent to other oxygenatedchemicals impurity, the presence of carbon dioxide can be also influenced for diformazan
The absorption of the ethers impurity such as ether, the present invention due to improving the utilization rate of molecular sieve, A types and X molecular sieve or FAU types,
In multiple combinations mode between ZSM series equimolecular sieve, moieties is allowed to sieve the effect for playing adsorptive hindrance impurity, and led
Body portion still has deep purifying ability for oxygenatedchemicals such as methanol, dimethyl ether, the formaldehyde in coal chemical industry, by purification
Alkene reaches polymer grade requirement.
2nd, solid absorbent has higher isolation of purified ability
Solid absorbent according to the present invention still is able to reach wanting for olefin stream deep purifying under larger air speed
It asks.Using mesoporous material as shaping assistant, molding solid absorbent forms " mesoporous-micropore " multistage effect of holes.Containing miscellaneous
When the olefin stream of matter is contacted with solid absorbent, by mesoporous material preenrichment impurity molecule therein, impurity molecule is being situated between
Molecular sieve is traveled further into during Porous materials Dynamic Adsorption, and is retained by molecular sieve, and due to the difference of diffusional resistance, greatly
Amount olefin hydrocarbon molecules are cleaned after mesoporous material, and minute quantity enters molecular sieve, so as to achieve the purpose that deep purifying alkene.
3rd, the absorption fuel factor of solid absorbent is low
Molecular sieve after metal or metal oxide modified reduces adsorption capacity to a certain extent, so as to drop
Low heat of adsorption；And the meso-porous alumina after metal or metal oxide modified largely improves adsorption energy
Power, but the adsorption capacity of aluminium oxide in itself is far smaller than adsorption capacity of the molecular sieve to olefin hydrocarbon molecules and impurity molecule.Therefore, originally
Invention increases meso-porous alumina solid respectively by molecular sieve and meso-porous alumina using different metal or metal oxide modified
Ratio in body adsorbent.Due to reducing ratio of the molecular sieve in solid absorbent, and then effectively reduce solid absorption
The fuel factor of agent.
4th, regeneration cost is low
The present invention uses meso-porous alumina, and as shaping assistant, meso-porous alumina is weaker to the adsorption strength of impurity, passes through
Temperature programming, under cryogenic, the alkene being attached in meso-porous alumina duct are parsed；Since molecular sieve is in solid suction
Accounting in attached dose declines, therefore can moderately reduce the recovery time under hot conditions, significantly reduces solid absorption
The regeneration energy consumption of agent.
Description of the drawings
Fig. 1 is meso-porous alumina small-angle diffraction XRD spectra used in Example 1.
If stronger diffraction maximum that Fig. 2 θ=0.87 ° occurs corresponds to (100) crystal face characteristic peak of meso-porous alumina, 1.48 °,
1.8 ° there is weaker diffraction maximum, correspond to (110) crystal face of meso-porous alumina and (200) crystal face respectively.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Comparative example 1
The common aluminium oxide of 100kg is taken, the roller forming in granulating disc takes out after being shaped to 2~3mm particles, 60
Under the conditions of DEG C, water spray vapour complete hydration, ageing process, hydro-combination process is 6 hours, rear to take out in 120 DEG C of drying, and at 450 DEG C
Under the conditions of prompt activation, obtain molding.It is D1 by sample number into spectrum.
Embodiment 1
Take 100kg meso-porous aluminas, small-angle diffraction XRD spectrums as shown in Figure 1, in granulating disc roller forming, into
Type is takes out after 2~3mm particles, under the conditions of 60 DEG C, spray water vapour completion hydration, ageing process, hydro-combination process is 6 hours, after
It takes out in 120 DEG C of drying, and the prompt activation under the conditions of 450 DEG C, obtains molding.It is S1 by sample number into spectrum.
Embodiment 2
Taking 100kg, the roller forming in granulating disc is shaped to 2~3mm through Lanthanum nitrate modified meso-porous alumina
It is taken out after grain, under the conditions of 60 DEG C, spray water vapour completion hydration, ageing process, hydro-combination process is 6 hours, and rear taking-up is dried in 120 DEG C
It is dry, and the prompt activation under the conditions of 450 DEG C, obtain molding.It is S2 by sample number into spectrum.
Comparative example 2
45kg 13X molecular sieves is taken to be mixed with 55kg active aluminium oxide, the roller forming in granulating disc, molding
To be taken out after 2~3mm particles, under the conditions of 60 DEG C, water spray vapour complete hydration, ageing process, hydro-combination process be 6 hours, after take
It is dried for 120 DEG C, and the prompt activation under the conditions of 450 DEG C, obtains molding.It is D2 by sample number into spectrum.
Embodiment 3
45kg 13X molecular sieves is taken to be mixed with 55kg meso-porous aluminas, the roller forming in granulating disc, it is shaped to 2~
Taken out after 3mm particles, under the conditions of 60 DEG C, water spray vapour complete hydration, ageing process, hydro-combination process is 6 hours, it is rear take out in
120 DEG C of drying, and the prompt activation under the conditions of 450 DEG C, obtain molding.It is S3 by sample number into spectrum.
Embodiment 4
45kg 13X molecular sieves is taken to be mixed with 55kg through Lanthanum nitrate modified meso-porous alumina, the spin in granulating disc
Molding, takes out after being shaped to 2~3mm particles, under the conditions of 60 DEG C, spray water vapour completion hydration, ageing process, hydro-combination process 6
Hour, it is rear to take out in 120 DEG C of drying, and the prompt activation under the conditions of 450 DEG C, obtain molding.It is S4 by sample number into spectrum.
Embodiment 5
30kg 13X molecular sieves is taken to be mixed with 70kg through Lanthanum nitrate modified meso-porous alumina, the spin in granulating disc
Molding, takes out after being shaped to 2~3mm particles, under the conditions of 60 DEG C, spray water vapour completion hydration, ageing process, hydro-combination process 6
Hour, it is rear to take out in 120 DEG C of drying, and the prompt activation under the conditions of 450 DEG C, obtain molding.It is S5 by sample number into spectrum.
Embodiment 6
20kg 3A molecular sieves, 20kg13X molecular sieves is taken to be mixed with 60kg's through Lanthanum nitrate modified meso-porous alumina,
Roller forming in granulating disc takes out after being shaped to 2~3mm particles, under the conditions of 60 DEG C, water spray vapour completion hydration, is aged
Process, hydro-combination process are 6 hours, rear to take out in 120 DEG C of drying, and the prompt activation under the conditions of 450 DEG C, obtain molding.It will
Sample number into spectrum is S6.
Embodiment 7
Being mixed through Lanthanum nitrate modified meso-porous alumina for 20kg13X molecular sieves and 80kg is taken, is rolled in granulating disc
Ball forming takes out after being shaped to 2~3mm particles, and under the conditions of 60 DEG C, spray water vapour completion hydration, ageing process, hydro-combination process is
It is 6 hours, rear to take out in 120 DEG C of drying, and the prompt activation under the conditions of 450 DEG C, obtain molding.It is S7 by sample number into spectrum.
Embodiment 8
The measure of solid absorbent isosteric heat of adsorption
The isosteric heat of adsorption of gas-solid absorption system is measured using SGC technologies
The core of adsorption system by be placed under constant temperature distribution pond, adsorption tank and connection both needle-like
Valve forms, and adsorbent is placed in adsorption tank.Valve A is kept to close, and pressurize to distribution pond before each experiment starts, treat distribution
In him after temperature and pressure stability, valve is opened, the gas in distribution pond is made to flow through valve and enters adsorption tank, is sent out in adsorption tank
Raw absorption.Distribution pond body product has been subjected to calibration, therefore just may know that how many gas passes through distribution pond by pressure change in advance
Flow into adsorption tank.The heat that adsorption tank externally discharges is measured by SGC devices.SGC devices by adsorption tank outside sensor
The little differential pressure sensor composition of both gas chuck, a reference unit and connection.Gas chuck, reference unit and distribution pond are put
Under identical constant temperature.In adsorption process, the heat that adsorbent is released is inhaled by the Sensor Gas in sensor chuck
It receives, pressure rises after gas absorbs heat, pressure difference is formed between reference unit, and pass through little differential pressure sensor and show.
The heat that adsorption tank discharges is mapped with pressure difference variation by calibration, it will be able to measure the heat of adsorption process release.
Sample in Examples 1 to 7 and comparative example 1~2 is respectively applied to SGC technologies and measures its isosteric heat of adsorption, specifically
It the results are shown in Table 1.
Embodiment 9
The purification of solid absorbent application gas phase coal chemical industry olefin stream
Solid absorbent in Examples 1 to 7 and comparative example 1~2 is respectively applied in gas phase coal chemical industry olefin stream
The absorption of impurity.Specific implementation process is：
A certain amount of solid absorbent (Examples 1 to 4, comparative example 1~2) is fitted into reactor.In 500h-1Volume is empty
The high pure nitrogen of fast (GHSV) is flowed down activates 2h with 200 DEG C, is cooled to 25 DEG C.Make unstripped gas for ethylene, wherein containing 100ppm
Methanol, 100ppm dimethyl ether, 10ppm water, 5ppm formaldehyde, 50ppm carbon dioxide gas, 25 DEG C, 1atm, volume space velocity
(GHSV) it is 2000h-1Lower continuous feed.Tail gas after adsorbent is contacted with olefin stream is connected with helium ion chromatography, online to examine
The content of impurity in alkene is surveyed, when detecting dimethyl ether in tail gas (0.5ppm), terminates operation, records the one way fortune of adsorbent
The row time.
The different adsorbents of table 1 are to the one way run time of impurity absorption in gaseous ethene
Embodiment 10
Solid absorbent is applied to the purification of liquid phase olefin logistics
Solid absorbent in Examples 1 to 7 and comparative example 1~2 is respectively applied in liquid hydrocarbon coal chemical industry olefin stream
The removing of impurity.Specific implementation process is：
Liquid propylene raw material is 20 × 10- 6Dimethyl ether (DME), about 450 × 10- 6Methanol (MeOH), 20 × 10- 6Propionic aldehyde
(Propa) propylene (molar ratio).A certain amount of adsorbent (Examples 1 to 4, comparative example 1~3) is packed into reactor respectively
In.It sets background value pressure value and is pressurized to 1.5MPa as 1.5MPa, then with high pure nitrogen, be then shut off high pure nitrogen, open liquid
Constant current pump intake and its port of export using pressure difference with liquid propene are full of, reset counterbalance valve pressure by state propylene steel cylinder switch
It is worth for 2.3MPa, opens high pure nitrogen, be pressurized to 2.3MPa, close high pure nitrogen, constant flow pump is opened, according to 37.00h-1's
The continuous feed under conditions of outlet pressure 2.3MPa of WHSV air speeds, the liquid by adsorbing separation is through vaporization and gas-liquid separation
Afterwards, by the content of gas-chromatography on-line checking methanol, dimethyl ether and propionic aldehyde, one way run time is recorded.Experimental result is such as
Shown in table 2.
The different adsorbents of table 2 are to the one way run time of impurity absorption in liquid propylene
Embodiment 11
The regeneration of solid absorbent
Examples 1 to 7 and 1~2 solid absorbent of comparative example are applied in embodiment 12 and 13, when absorption tail gas detects
To (0.1ppm) during dimethyl ether, raw material gas cylinder is closed, stops charging.Counterbalance valve pressure value is adjusted, is gradually reduced to 0.1MPa,
High pure nitrogen switch is opened, in about 300h-1Under volume space velocity (GHSV), regenerated using temperature programming.It is adopted under 0.1MPa
With 2 DEG C/min temperature programmings to 120 DEG C, 4h is activated；250 DEG C are warming up to using 10 DEG C/min under 0.1MPa later, activation
0.5h.After being cooled to room temperature, reproducing adsorbent product is obtained.
Embodiment 12
Solid absorbent carbon left detects
Take in the solid absorbent of the purification of liquid phase olefin logistics, by the solid absorbent sample S1 after inactivation~
S7, D1, D2 and temperature programming regeneration after sample S1~S7, D1, D2, for infrared carbon sulfur analyzer detect solid absorbent
In carbon left.Concrete outcome is shown in Table 3.
Specific embodiment is：In small crucible after being roasted at 1000 DEG C, the solid for accurately weighing 0.1g or so is inhaled
Attached dose of sample, typing computer.Comburant tungsten particle, abrasive grit are added in crucible, is shaken up.Crucible is put into carbon sulphur instrument bracket, is pressed
Lower lifting handle, crucible automatic lifting to gas circuit seal.Start analysis program on computer again, instrument heats automatically, is oxygenated combustion
It burns.Analysis system records CO2, phosphorus content is calculated automatically.After analysis, lifting handle is pressed, crucible drops to raw bits, uses
Crucible tongs take out crucible, throw away to special useless crucible case.
Carbon left/% after the regeneration of 3 solid absorbent of table
| Solid absorbent | D1 | S1 | S2 | D2 | S3 | S4 | S5 | S6 | S7 |
| Before regeneration/% | 0.173 | 0.198 | 0.195 | 4.295 | 3.586 | 3.634 | 2.956 | 2.834 | 2.306 |
| After regeneration/＜ % | 0.001 | 0.001 | 0.001 | 0.013 | 0.006 | 0.001 | 0.001 | 0.001 | 0.001 |
Embodiment 13
The adsorbent of imurity-removal in coal chemical industry olefin stream, is prepared using the raw material of following components and content：Boiling
Stone molecular sieve 1kg, mesoporous material 99kg, metal component 0.01kg.Wherein, mixing of the zeolite molecular sieve for A types and X-type molecular sieve
Object has loaded potassium chloride and potassium nitrate, molecular sieve is placed in the potassium chloride and potassium nitrate solution of a concentration of 0.01mol/L,
1500hr-12 hours are stirred under rotating speed, wash drying, obtain carrying out the molecular sieve after ion exchange, carried metal component.It is situated between
Porous materials are mesopore silicon oxide, have loaded lanthanum nitrate, and mesopore silicon oxide is immersed in the lanthanum nitrate hexahydrate of a concentration of 0.01mol/L
In, through spontaneously drying, roasting, can obtain load has the mesopore silicon oxide of metal.
Zeolite molecular sieve, with roller forming, obtains particle of the size distribution in 0.5~4mm, is molded it with mesoporous material
Solid particle intensity afterwards is not less than 25N, and is characterized through BET, and the specific surface area of solid absorbent is more than 380m2/g。
The adsorbent and coal chemical industry olefin stream contact under gas phase or liquid phase in fixed bed, solid absorbent and coalification
Work olefin stream contacts on a fixed bed, adsorbent use pressure swing adsorption technique, condition for temperature between 10~60 DEG C, operation
Pressure range can be implemented between 0.1~3MPa.It is gas phase or liquid phase that the time of contact, which depends on olefin stream, gas feed
When, air speed (GHSV) is more than 1500h-1；During liquid feed, air speed (LHSV) is in 0.1~50h-1Between.Make coal chemical industry alkene object
Impurity concentration in stream is down to 100ppb from 2500ppm.
Adsorbent is respectively less than 0.01mg/kg to the adsorption capacity of ethylene and propylene in coal chemical industry olefin stream, and impurity includes
It is one or more in methanol, water, dimethyl ether, formaldehyde or carbon dioxide.
The adsorbent is in 100h-1Under using high pure nitrogen as regenerating medium, activate 10h at 60 DEG C under 0.1MPa, then
Being regenerated using temperature programming for 2h is re-activated at 150 DEG C, the carbon left of the adsorbent after regeneration is less than 0.001wt%, and
Adsorbent after regeneration is applied in gas phase or liquid phase coal chemical industry olefin stream to the adsorption experiment of impurity, when one way is run
Between still reach 80h (gas phase) or more than 350h (liquid phase), it is suitable with the solid absorbent adsorbing contaminant capacity before inactivation.It and will
Solid absorbent is reused 100 times or more, and the requirement for reaching deep purifying is remained to the absorption of impurity.
Embodiment 14
The adsorbent of imurity-removal in coal chemical industry olefin stream, is prepared using the raw material of following components and content：Boiling
Stone molecular sieve 50kg, mesoporous material 40kg, metal component 8kg.Wherein, mixing of the zeolite molecular sieve for X-type and ZSM-5 molecular sieve
Object has loaded copper nitrate, molecular sieve is placed in the copper solution of a concentration of 2mol/L, in 1500hr-1It is stirred under rotating speed 3 small
When, drying is washed, obtains carrying out the molecular sieve after ion exchange, carried metal component.Mesoporous material is meso-porous alumina, load
Meso-porous alumina is immersed in the zirconium nitrate of a concentration of 2mol/L, sulfuric acid zirconium solution, through naturally dry by zirconium nitrate, zirconium sulfate
Dry, roasting, can obtain load has the meso-porous alumina of metal.
Zeolite molecular sieve is with mesoporous material with extruded moulding, and dry 15h, solid absorption is obtained after fired at 90 DEG C
Agent.Solid particle intensity after molding is characterized not less than 15N through BET, and the specific surface area of solid absorbent is more than
380m2/g。
The adsorbent and coal chemical industry olefin stream contact under gas phase or liquid phase in fixed bed, solid absorbent and coalification
Work olefin stream contacts on a fixed bed, adsorbent use pressure swing adsorption technique, condition for temperature between 10~60 DEG C, operation
Pressure range can be implemented between 0.1~3MPa.It is gas phase or liquid phase that the time of contact, which depends on olefin stream, gas feed
When, air speed (GHSV) is more than 1500h-1；During liquid feed, air speed (LHSV) is in 0.1~50h-1Between.Make coal chemical industry alkene object
Impurity concentration in stream is down to 100ppb from 2500ppm.
Adsorbent is respectively less than 0.01mg/kg to the adsorption capacity of ethylene and propylene in coal chemical industry olefin stream, and impurity includes
It is one or more in methanol, water, dimethyl ether, formaldehyde or carbon dioxide.
By the solid absorbent of inactivation, in air speed (GHSV) 100h-1Under high pure nitrogen, using hypo-hyperthermia temperature programming
Desorption and regeneration.It is characterized in that, 10h is activated using 2 DEG C/min temperature programmings to 120 DEG C of sections under 0.1MPa；Exist later
It is warming up at 300 DEG C using 10 DEG C/min under 3.0MPa and activates 0.5h, the carbon left of the adsorbent after regeneration is less than
0.001wt%, and the adsorbent after regeneration is applied to the absorption in gas phase or liquid phase coal chemical industry olefin stream to impurity
Experiment, one way run time still reaches 80h (gas phase) or more than 350h (liquid phase), with the solid absorbent adsorbing contaminant before inactivation
Capacity is suitable.And solid absorbent is reused 100 times or more, the absorption of impurity is remained to reach wanting for deep purifying
It asks.
Embodiment 15
The adsorbent of imurity-removal in coal chemical industry olefin stream, is prepared using the raw material of following components and content：Boiling
Stone molecular sieve 15kg, mesoporous material 99kg, metal component 10kg.Wherein, zeolite molecular sieve is ZSM-5 molecular sieve and NaY molecules
The mixture of sieve has loaded magnesium chloride, magnesia, molecular sieve is placed in the magnesium solution of a concentration of 5mol/L, in 1500hr-1Turn
Speed lower 4 hours of stirring, drying is washed, obtains carrying out the molecular sieve after ion exchange, carried metal component.Mesoporous material is is situated between
Porous aluminum oxide has loaded zinc sulfate, zinc chloride, and zinc sulfate, the zinc chloride that meso-porous alumina is immersed in a concentration of 5mol/L are molten
In liquid, through spontaneously drying, roasting, can obtain load has the meso-porous alumina of metal.
For zeolite molecular sieve with mesoporous material using extruded moulding, the dry 0.1h at 120 DEG C obtains solid suction after fired
Attached dose.Solid particle intensity after molding is characterized not less than 15N through BET, and the specific surface area of solid absorbent is more than
380m2/g。
The adsorbent and coal chemical industry olefin stream contact under gas phase or liquid phase in fixed bed, solid absorbent and coalification
Work olefin stream contacts on a fixed bed, adsorbent use pressure swing adsorption technique, condition for temperature between 10~60 DEG C, operation
Pressure range can be implemented between 0.1~3MPa.It is gas phase or liquid phase that the time of contact, which depends on olefin stream, gas feed
When, air speed (GHSV) is more than 1500h-1；During liquid feed, air speed (LHSV) is in 0.1~50h-1Between.Make coal chemical industry alkene object
Impurity concentration in stream is down to 100ppb from 2500ppm.Adsorbent is to the adsorption energy of ethylene and propylene in coal chemical industry olefin stream
Power is respectively less than 0.01mg/kg, and impurity includes one or more in methanol, water, dimethyl ether, formaldehyde or carbon dioxide.
By the solid absorbent of inactivation, in air speed (GHSV) 500h-1Under high pure nitrogen, using hypo-hyperthermia temperature programming
Desorption and regeneration.It is characterized in that, using 2 DEG C/min temperature programmings to 150 DEG C under 3.0MPa, 2h is activated；Later in 3.0MPa
It is lower that 500 DEG C of activation 2h are warming up to using 10 DEG C/min.The carbon left of adsorbent after regeneration is less than 0.001wt%, and will again
Adsorbent after life is applied to the adsorption experiment of impurity in gas phase or liquid phase coal chemical industry olefin stream, and one way run time is still
Reach 80h (gas phase) or more than 350h (liquid phase), it is suitable with the solid absorbent adsorbing contaminant capacity before inactivation.And by solid
Adsorbent is reused 100 times or more, and the requirement for reaching deep purifying is remained to the absorption of impurity.
Claims (11)
1. the adsorbent of imurity-removal in coal chemical industry olefin stream, which is characterized in that the adsorbent uses following components and weight
The raw material of part content is prepared：Zeolite molecular sieve 1~99, mesoporous material 1~99, metal component 0.01~10；
Wherein, at least one of 1 race of load regulation, the metal of the 2nd race or the 11st race or metal oxide on zeolite molecular sieve are situated between
At least one of 3 race of load regulation on Porous materials, the 4th race, the metal of the 11st race or the 12nd race or metal oxide；
The zeolite molecular sieve for LTA types, MFI type, 3A, 4A in FAU type molecular sieves, 5A, 10X, 13X, NaY, NaKY,
At least two or two or more mixtures in ZSM Series Molecules sieve.
2. the adsorbent of imurity-removal in coal chemical industry olefin stream according to claim 1, which is characterized in that the suction
Attached dose of raw material uses following components and parts by weight content：Zeolite molecular sieve 1~50, mesoporous material 40~99, metal component
0.01~10.
3. the adsorbent of imurity-removal in coal chemical industry olefin stream according to claim 2, which is characterized in that the suction
Attached dose of raw material uses following components and parts by weight content：Zeolite molecular sieve 15~40, mesoporous material 50~99, metal component
0.01~10.
4. the adsorbent of imurity-removal in coal chemical industry olefin stream according to claim 1, which is characterized in that the boiling
One or more of stone molecular sieve metal or metal oxide through K, Mg, Ca or Cu carry out ion exchange, carried metal group
Point.
5. the adsorbent of imurity-removal, feature exist in coal chemical industry olefin stream according to any one of claim 1-3
In the mesoporous material is selected from mesopore silicon oxide, mesoporous TiO 2, meso-porous alumina, mesoporous zircite, mesoporous gallium oxide
In it is one or more.
6. the adsorbent of imurity-removal in coal chemical industry olefin stream according to claim 5, which is characterized in that Jie
Porous materials are selected from mesopore silicon oxide and meso-porous alumina.
7. the adsorbent of imurity-removal in coal chemical industry olefin stream according to claim 5, which is characterized in that Jie
Porous materials are selected from meso-porous alumina.
8. the adsorbent of imurity-removal in coal chemical industry olefin stream according to claim 5, which is characterized in that Jie
Hole material load Cu, Zn, La, Ce, Zr metal or metal oxide are at least one.
9. the adsorbent of imurity-removal, feature exist in coal chemical industry olefin stream according to any one of claim 1-3
In zeolite molecular sieve, with spin or extruded moulding, obtains the particle of certain particle size distribution, size distribution is with mesoporous material
0.5~4mm, specific surface area are more than 380m2/g。
10. the application of the adsorbent of imurity-removal in the coal chemical industry olefin stream according to any one of claim 1-9,
It is characterized in that, the adsorbent and coal chemical industry olefin stream contact under gas phase or liquid phase in fixed bed, make coal chemical industry alkene object
Impurity concentration in stream is down to 100ppb from 2500ppm, small to the adsorption capacity of ethylene and propylene in coal chemical industry olefin stream
In 0.01mg/kg, the impurity includes one or more in methanol, water, dimethyl ether, formaldehyde or carbon dioxide.
11. the application of the adsorbent of imurity-removal in coal chemical industry olefin stream according to claim 10, which is characterized in that
The adsorbent is in 100~5000h-1Under using high pure nitrogen as regenerating medium, activate 2 at 60~150 DEG C under 0.1~0.2MPa
Then~10h is re-activated being regenerated using temperature programming for 0.1~2h, the carbon residue of the adsorbent after regeneration at 150~500 DEG C
Amount is less than 0.001wt%.
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| CN106423114B (en) * | 2016-09-28 | 2019-09-20 | 大连海鑫化工有限公司 | One kind being used for hydrocarbon impurities purifying adsorbent, preparation method and application |
| CN106512926B (en) * | 2016-11-16 | 2018-12-11 | 上海绿强新材料有限公司 | Renewable micropore-mesopore composite material adsorbent and the preparation method and application thereof |
| CN108033460A (en) * | 2017-12-26 | 2018-05-15 | 大连海鑫化工有限公司 | A kind of new 3A molecular sieves and preparation method thereof |
| CN108499526B (en) * | 2018-01-16 | 2021-04-27 | 奥斯催化材料（大连)有限公司 | Preparation and application of adsorbent for removing impurities in propane material flow |
| CN108246249A (en) * | 2018-02-13 | 2018-07-06 | 大连海鑫化工有限公司 | It is a kind of to be used to remove adsorbent of the low thermal discharge of polar molecule in material and preparation method thereof |
| CN111097369A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Method for removing polar compounds |
| CN109759009A (en) * | 2019-03-07 | 2019-05-17 | 朱江凤 | Dimethyl ether adsorbent and the preparation method and application thereof |
| EP3978110A4 (en) * | 2019-05-31 | 2023-04-05 | China Petroleum & Chemical Corporation | Reversible enrichment material, preparation therefor, and application thereof |
| CN114425215B (en) * | 2020-10-13 | 2022-11-18 | 中国石油化工股份有限公司 | Low-temperature efficient recovery method for volatile organic compounds with coalescence adsorption grading |
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