CN104549141B - Hetero-atom molecular-sieve adsorbent and preparation method thereof - Google Patents
Hetero-atom molecular-sieve adsorbent and preparation method thereof Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
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Abstract
The present invention relates to a kind of hetero-atom molecular-sieve adsorbent and preparation method thereof, the problems such as purification precision that mainly solves to exist in existing olefin adsorption purification techniques adsorbent is low, adsorption capacity is low, regenerating stability is poor.The present invention molecular sieve progress modification is made up of binding agent shaping by using ion exchange or infusion process at least two metal cations of introducing the technical scheme of solid absorbent and preparation method thereof, preferably solves the problem, in the adsorption cleaning industrial production available for various olefin-type materials removing sulfur-containing compound.
Description
Technical field
Hetero-atom molecular-sieve adsorbent being modified the present invention relates to a kind of bimetallic ion modification and preparation method thereof.
Background technology
Propylene is as important basic organic chemical raw material, and widely used, demand expands day by day.Olefin(e) disproportionation technology is to increase
Produce one of effective ways of propylene.C4One of the raw material of alkene as olefin(e) disproportionation, composition is complex, and source is different, composition
It is different.Because the course of conveying of various processes and raw material makes C4In the water, alcohol, the oxygen-containing chemical combination such as ether that are not often waited containing quantity
Thing and the non-hydrocarbon compound such as sulfur-bearing, nitrogenous.Sulfur-containing compound is stronger to the toxicity of catalyst in numerous impurity, micro sulfur-containing impurities
Will inactivate catalyst poisoning in Downstream processing production.And the presence of sulfide not only influences downstream product quality, pollution
Environment, it can also corrode production equipment sometimes, cause potential safety hazard.Therefore, want fully rationally to utilize alkene, matter of utmost importance is exactly
Purification removing sulfur-containing impurities are carried out to it.As catalysis technique updates, catalyst activity improves, while is also easier to be poisoned
Inactivation.The deep desulfuration of raw material is increasingly becoming C4The key for being processed further utilizing Deng low-carbon alkene.
Sulfide in low-carbon alkene mainly includes hydrogen sulfide, cos, methyl mercaptan, ethyl mercaptan, dimethyl sulphide, rosickyite
Alcohol, dimethyl disulfide, the first and second disulfides, carbon disulfide and the sulphur of diethyl two etc..Not only total class is various, and much kind vulcanizations
Thing chemical property is active, and various sulfide mutually convert under certain conditions.Meanwhile as the low-carbon alkene of industrial chemicals, nothing
By be for produce the ethene of polymer, propylene be also used as raw material conversion n-butene, isobutene, their corresponding production technologies
Requirement to sulfide content is more harsh, general to require to be removed to below 1ppm, even requires content more in some cases
It is low, i.e., need have higher requirement according to different productions.Therefore, the removing for sulfur-containing compound in low-carbon alkene is depth
Sweetening process.Or the technology technique of previous literature report excessively complexity is, it is necessary to carry out multistep removing.Generally for mercaptan, sulphur
Hydrolysis is hydrogen sulfide to the organosulfur impurities such as ether, cos needs at relatively high temperatures, then under normal temperature or low temperature
Hydrogen sulfide is removed, the technique is referred to as " Layer cake " technique by image, not only complex process but also energy consumption is very high.Existing work
Skill, generally purify precision and do not reach production requirement, while there is also the problem such as working sulfur capacity is low.With numerous purification techniques phases
Than process for adsorption desulfuration, there is the advantages that purification precision is high, and technique is simple and convenient to operate.The key problem of this technology is still
It is the exploitation of high-efficiency adsorbent.
The porous masses such as activated carbon, silica gel, aluminum oxide and molecular sieve are commonly used for adsorbent.Although active carbon desulfurization technology pin
There is certain efficiency to the removing of the sulfur-containing compounds such as mercaptan and thioether, but generally require aerobic participation reaction, for low-carbon alkene
The sweetening process of such inflammable, explosive component, it is not recommended that use, the simple charcoal absorption removing sulfuldioxide by absorption, still
In the presence of selectivity is low, working sulfur capacity is low, desulfurization degree is low etc. a series of problems.
Zeolite molecular sieve has predictable high efficiency screening function, while also has ion exchangeable, adsorptivity and catalysis
The features such as property, thus it is widely used in numerous necks such as agricultural, building materials, chemical industry, environmental protection, the energy, medicine, national defence and new material
Domain.Around some existing reported in literature of molecular sieve adsorption desulfurization, but current molecular sieve desulfurizer still suffers from that purification precision is low, inhales
The problems such as attached capacity is low, regenerating stability is poor.
United States Patent (USP) U.S.5843300, it was recently reported that prepared by the X molecular sieve exchanged with alkali metal or alkaline-earth metal ions
Adsorbent, the sulfide particularly sulfide with phenyl ring is removed from FCC feedstock.KX molecular sieves are a kind of effective adsorbents,
The especially race's metallic element palladium of load regulation eight（Pd）And platinum（Pt）Adsorbent desulfurized effect more preferably, used adsorbent can be
It is regenerated under higher temperature in atmosphere of hydrogen.The Sulfur capacity of desulfurizing agent is 0.2~0.6%, and the work Sulfur capacity after regeneration has dropped
It is low.
United States Patent (USP) U.S.20060191821 is reported, and a kind of gaseous state, the hydrocarbon component of oily are in the case where facing hydrogen state
Deep absorption desulfurization technology.It is a kind of containing the promoter effect of zinc oxide and oxide form under to the hydrocarbon component containing sulfide
Carry out desulfurization.The adsorbent can be regenerated in the air of dilution by roasting.This method is for sulfide in lower carbon number hydrocarbons
Removing, it is higher operation temperature to be present, high energy consumption, and necessarily causes unsaturated hydrocarbons under hydro condition, and hydrogenation side reaction occurs, draws
Play a series of problems, such as purification efficiency reduces.
Chinese patent CN1482210A provides a kind of adsorption refining gasoline by catalyst cracking.The technology utilizes two kinds of suctions
Attached dose removes to the sulfide in catalytically cracked gasoline.A kind of mixture using aluminum oxide, titanium oxide and molecular sieve is
Carrier, saturation spray or dipping are using one or more of oxides of the metallic elements such as zinc, cobalt, nickel, copper, lead, iron as activated centre
The adsorbent of preparation, the mercaptan sulfur in selective absorption catalytically cracked gasoline.Another kind of adsorbent be with aluminum oxide, titanium oxide and
The mixture of molecular sieve is carrier, and one or more of oxides in saturation spray or impregnated transition metallic element are lived for absorption
Property center, the thiophene sulphur in selective absorption catalytically cracked gasoline.Above two adsorbent is seated in two absorbers respectively
In, adsorbent reactivation is desorbed and/or aoxidized its absorption with a kind of solvent or mixed light-hydrocarbon after adsorbent adsorption saturation respectively
Sulfur-containing compound.After selective deep desulfuration, mercaptan sulfur content is less than 10 μ g/g in catalytically cracked gasoline, and total sulfur content is low
In 300 μ g/g.As can be seen that although this technology has certain desulfurized effect, but the sulfur content after desulfurization in sample is still very
It is high.
In summary, although having reported adsorbent and the corresponding purification method that some are used for olefin stream in previous literature,
But the adsorption cleaning depth that adsorbent in concrete application be present is low, adsorption capacity is low, purification precision is low, adsorption capacity is low, regeneration
The problems such as stability difference.Although faujasite molecular sieve NaX and NaY have stronger polarity, the especially removing to polar impurity
There is higher removal efficiency, be usually used in the adsorption cleaning of various gases, liquid charging stock.Existing NaX and NaY molecules
Sieve adsorbant one side adsorption cleaning depth is low, and product purity can not meet downstream production requirement.Adsorption capacity is limited simultaneously, makes
The dosage and purifier of adsorbent are bulky, add device Meteorological, and frequent regeneration also makes operation become complicated.
On the other hand, adsorptive selectivity is poor, and a large amount of alkene are also adsorbed while adsorbing oxygenatedchemicals, and released during olefin adsorption compared with
More heats bring adverse effect to adsorption efficiency.In addition, the alkene remained in regenerative process in adsorbent duct is at high temperature
Charing, which easily occurs, declines performance of the adsorbent.
The content of the invention
One of technical problems to be solved by the invention be exist in the prior art adsorbent purification precision it is low, absorption hold
Measure the problems such as low, regenerating stability is poor.Present invention offer one kind at least carries out modification to molecular sieve by two kinds of metal cations and changed
Property the technical scheme of solid absorbent and preparation method thereof is made by binding agent shaping, the adsorbent is used for C2~C6Alkene is former
The adsorption cleaning of sulfur-containing compound in material, there is the advantages of purification depth is high, and adsorption capacity is high and heat of adsorption is relatively low.Institute of the present invention
The two of technical problems to be solved are to provide a kind of preparation of the adsorbent corresponding with solving the adsorbent of one of technical problem
Method.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of hetero-atom molecular-sieve is provided
Adsorbent, by weight percentage, including following components：
A) 10.0 ~ 80.0% molecular sieve carrier, molecular sieve carrier are selected from X-type, Y types, L-type, MCM types, modenite, ZSM
At least one of type zeolite and beta molecular sieve；
B) 0.01~9.99% lanthanide metal oxide；
C) 0.01~10.0% at least one metal oxygen selected from periodic table of elements VIII, IB races and Group IIB element
Compound；
D) 10.0~85.0% binding agent, binding agent are selected from least one of aluminum oxide and silica.
In above-mentioned technical proposal, mole silica alumina ratio SiO of molecular sieve carrier2/Al2O3Preferred scope be 1~50；Molecule
Sieve mole silica alumina ratio SiO of carrier2/Al2O3Most preferred range be 1~10；Lanthanide series metal is in hetero-atom molecular-sieve adsorbent
Selected from least one of La, Ce, Pr, Nd and Pm；With adsorbent weight percentages, lanthanide metal oxide content it is preferred
Scope is 0.01 ~ 6.0%；Hetero-atom molecular-sieve adsorbent is selected from the preferred of periodic table of elements VIII, IB races and Group IIB element
Scheme is selected from least one of Ni, Pd, Pt, Cu, Ag, Au, Zn, Co and Cd；Selected from periodic table of elements VIII, IB races and
The most preferably scheme of at least one metal oxide of Group IIB element be NiO, CuO and ZnO combination metal oxide or ZnO,
CuO and CdO combination metal oxide；With adsorbent weight percentages, selected from periodic table of elements VIII, IB races and IIB
The preferred scope of the content of at least one oxide of race's element is 0.01 ~ 8.0%；Component c) preferred scheme be NiO, CuO and
ZnO composition.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：The preparation method of solid absorbent,
Comprise the following steps：
A) salting liquid pair selected from least one of lanthanide series metal cation for being 0.1~1.0mol/L with molar concentration
Carried out selected from least one of X-type, Y types, L-type, MCM types, modenite, ZSM types zeolite and beta molecular sieve molecular screen primary powder
Ion-exchanged, solid-to-liquid ratio 1：3~1：20, ion-exchange temperature is 20~150oC, swap time are 2~80 hours,
Exchange times are 1~5 time, modified that lanthanide series metal modified molecular screen is made；
B) salt selected from least one of periodic table of elements VIII, IB races and Group IIB element metal cation is matched somebody with somebody
Be made molar concentration be 0.1~0.6mol/L solution, lanthanide series metal modified molecular screen made from step a) is impregnated or
Ion-exchange treatment, modified molecular screen precursor is made；
C) add and make binding agent by weight percentage for 10.0~85.0% silica or aluminum oxide, mixed-forming,
Dry, hetero-atom molecular-sieve adsorbent is made after roasting.
In above-mentioned technical proposal, the preferred scope of solid-to-liquid ratio is 1 in step a) in preparation method：5~1：10, selected from group of the lanthanides
The preferred scope of at least one of metal cation mole concentration is 0.1~0.3mol/L, the preferred model of ion-exchange temperature
Enclose for 20~90oC, the preferred scope of swap time is 2~20 hours, and the preferred scope of exchange times is 1~3 time；Step b)
In the preferred scope of molar concentration be 0.2~0.4mol/L；Periodic table of elements VIII, IB races and IIB are selected from step b)
The salt of at least one of race's element metal cation is nitrate, oxalates, citrate or acetate；The ion of molecular sieve
Exchange degree is 1~99%.
The absorption that described hetero-atom molecular-sieve adsorbent is used for the 1- butylene containing low concentration dimethyl disulfide is net
Change in reaction, on fixed bed device, reaction condition is：The MPa of reaction pressure 3.0, reaction temperature 30oTwo in C, 1- butylene
The liquid volume air speed of content 5~1000 ppmv, the 1- butylene of methyl disulfide is 0.5~10 h-1。
In above-mentioned technical proposal, the preferred scope of DMDS ether content is 10~500 ppmv in 1- butylene, wherein
1ppmv refers to volume fraction, contains hundred a ten thousandths.
The present invention is exchanged part or all of cation in framework of molecular sieve with lanthanide series metal by ion exchange, using leaching
I B, Group IIB metal are incorporated into molecular sieve surface and skeleton by stain method or ion-exchange, then using activated alumina or oxygen
SiClx is that Ion exchange-Size exclusion solid absorbent is made in binding agent shaping.By lanthanide metal ion exchange and VIII, IB,
The introducing of Group IIB metal is modified the duct of molecular sieve, is not destroyed framework of molecular sieve, but enhances molecule
The stability of sieve skeleton frame, lanthanide metal ion and VIII, IB, Group IIB metal ion are positioned at the S of the β cages of zeolite molecular sieveI
Position, stabilize the skeleton of molecular sieve.It is positioned at S in zeolite molecular sieve supercageIIAnd SIIIVIII, IB on position, Group IIB metal
Ion is the adsorption site of desulfurization, and various metals ion has preferable by synergy in the sulfide removing of alkene
Suction-operated.Lanthanide metal ion is added on skeleton silicone hydroxyl and aluminium hydroxyl in molecular sieve cage by polarization and inducing action
Migration probability of the electronics into cage, increases the cloud density in molecular sieve cage, hydroxyl is shown stronger acidity, B acid
Intensity increase, has been correspondingly improved the adsorption capacity of adsorbent.In addition, the molecular sieve of ion exchange has stronger energy of adsorption
Power, activated alumina and silica also have certain adsorbing and removing ability to oxygenatedchemicals in itself as binding agent, pass through
The solid absorbent of binding agent shaping is due to two formed between molecular sieve microcellular structure and binding agent and molecular sieve in itself
Secondary pore passage structure has higher adsorption capacity to oxygenatedchemicals impurity, so as to improve the adsorption capacity of porous adsorbent.
Thus, purification precision that the adsorbent of preparation solves existing adsorbent simultaneously is low, adsorption capacity is low, regenerating stability is poor etc. one
Series of problems.The present inventor is found through experiments that for metal oxide auxiliary agent, in binding agent, molecular sieve and lanthanide series metal
In the case of oxide content identical, while the auxiliary agent that Multimetal oxide auxiliary agent compares one-component is added, it has more
Good adsorption activity, regeneration 5 times is later to be penetrated adsorbance and can improve more than 10%, is achieved unexpected technique effect, is led to
Cross desulfurizing agent prepared by the present invention and achieve preferable technique effect.
Using the adsorbent of the present invention, in N2In atmosphere, 280oAnticipated under C 8 hours, be cooled to room temperature.In pressure
For 3.0 MPa, temperature 30oC, liquid volume air speed are 1 h-1Under, to containing 500 ppmv dimethyl disulfide impurity
1- butene feedstocks carry out adsorption cleaning, DMDS ether content after purification in 1- butene feedstocks up to 0.5 below ppmv,
The adsorption capacity that penetrates of dimethyl disulfide penetrates adsorption capacity than similar skill up to 35 more than mg/g, dimethyl disulfide
Art improves more than 40%, and the adsorbent of preparation has preferable reproducibility, and desulfurization performance does not almost decline after 5 regeneration
Subtract.Achieve preferable technique effect.
Below by embodiment, the invention will be further elaborated, but the scope of the present invention is not limited by these examples
System.
Embodiment
【Embodiment 1】
Contain Ce3+And Ni2+The NaY molecular sieve of two kinds of ion exchanges and shaping using activated alumina as binding agent are adsorbed
Agent preparation process is as follows.First, the NaY molecular sieve original powder that 10 g silica alumina ratios are 10 is accurately weighed.Then, molar concentration is prepared
For 0.4 mol/L Ce (NO3)3The ml of solution 100, above-mentioned 10 g NaY molecular sieve originals powder is added into 100 ml Ce (NO3)3It is molten
In liquid, i.e., it is 1 according to solid-to-liquid ratio：10 condition, 90oUnder C, it is sufficiently stirred, exchanges 6 hours.Filter, rushed with deionized water
Wash.Repeat aforesaid operations three times.Same method prepares the Ni (NO that molar concentration is 0.3 mol/L3)2Solution, it is according to solid-to-liquid ratio
1：3 condition, 50oUnder C, it is sufficiently stirred, exchanges 12 hours, carries out ion exchange three times by this condition, obtained after drying
The molecular sieve precursor of exchange.Then, 10g alumina powders are weighed, are molded by binding agent of aluminum oxide, naturally dry, in atmosphere
550 oUnder C, it is calcined 2 hours.Grind, sieving takes 10~20 mesh, 300oC drying is no longer reduced up to quality, obtains ion friendship
Change molecular sieve molded adsorbent.
The adsorption cleaning performance evaluation of low concentration dimethyl disulfide in 1- butylene is carried out on fixed bed device.Test bar
Part is：3.0 MPa, 30oThe content of dimethyl disulfide is about 500 ppmv in C, 1- butylene, and liquid volume air speed is 1 h-1, a diameter of 830~1700 μm of absorbent particles, bed ratio of height to diameter is 6：1.The preactivated or regeneration temperature of adsorbent, passes through
The temperature of thermal analysis experiment measure desorption peaks is defined as 300 oC.Appraisal result and regeneration temperature are given in Table 2.
【Embodiment 2】
Contain Ce3+、Ni2+And Cu2+The NaY molecular sieve of three kinds of ion exchanges and the shaping using activated alumina as binding agent
Adsorbent preparation process is as follows.First, the NaY molecular sieve original powder that 10 g silica alumina ratios are 10 is accurately weighed.Then, preparation mole
Concentration is 0.1 mol/L Ce (NO3)3The ml of solution 200, above-mentioned NaY molecular sieve original powder is added into 200 ml Ce (NO3)3Solution
In, i.e., it is 1 according to solid-to-liquid ratio：20 condition, 20oUnder C, it is sufficiently stirred, exchanges 80 hours.Filter, rushed with deionized water
Wash.Repeat aforesaid operations twice.Same method prepares the Ni (NO that molar concentration is 0.6 mol/L3)2Solution, it is according to solid-to-liquid ratio
1：3 condition, 150oUnder C, it is sufficiently stirred, exchanges 2 hours, four secondary ion exchanges is carried out by above-mentioned condition.Hereafter, equally
Method prepares the Cu (NO that molar concentration is 0.1 mol/L respectively3)2Solution, it is 1 according to solid-to-liquid ratio：5 condition, 150oC
Under, it is sufficiently stirred, exchanges 2 hours, hereafter, carry out the molecular sieve precursor exchanged after primary ions exchange is dried.Then, claim
10g alumina powders are taken, are molded by binding agent of aluminum oxide, naturally dry, in atmosphere 550oUnder C, it is calcined 2 hours.Grind,
Sieving takes 10~20 mesh, 300oC drying is no longer reduced up to quality, obtains Ion exchange-Size exclusion formed absorbent.
【Embodiment 3】
Contain Ce3+、Ni2+ 、Cu2+And Zn2+The NaY molecular sieve of four kinds of ion exchanges and using activated alumina as binding agent
The preparation of formed absorbent.The preparation of adsorbent is carried out according to the same method of embodiment 2.Simply in exchange process, prepare
Molar concentration is 0.5 mol/L Ce (NO3)3The ml of solution 30, that is, it is 1 to change solid-to-liquid ratio：3,120oUnder C, fully stir
Mix, exchange 4 hours, exchanged three times.Ni is carried out successively according to same condition2+ 、Cu2+Exchange.Passing through Ni (NO3)2、
Cu(NO3)2After exchange, under similarity condition, with 0.6 mol/L Zn (NO3)2Solution is 1 by solid-to-liquid ratio：5 to swap 5 small
When, the molecular sieve precursor that is exchanged after drying.Then, 10g alumina powders are weighed, are molded by binding agent of aluminum oxide, it is natural
Dry, in atmosphere 550oUnder C, it is calcined 2 hours.Grind, sieving takes 10~20 mesh, 300oC drying is until quality no longer subtracts
It is few, obtain Ion exchange-Size exclusion formed absorbent.
【Embodiment 4】
Contain Ce3+、Ni2+And Zn2+The NaY molecular sieve of three kinds of ion exchanges and the shaping using activated alumina as binding agent
The preparation of adsorbent.The preparation of adsorbent is carried out according to the same method of embodiment 2.Simply in exchange process, preparation mole
Concentration is 1.0 mol/L Ce (NO3)3The ml of solution 60, it is 1 to change solid-to-liquid ratio：6,80oUnder C, it is sufficiently stirred, exchanges 4
Hour, exchanged three times.Prepare 0.5 mol/L Zn (NO3)2Solution 50ml, it is 1 to change solid-to-liquid ratio：5,60oUnder C,
It is sufficiently stirred, exchanges 24 hours, the molecular sieve precursor exchanged after drying.Then, 2g alumina powders are weighed, using aluminum oxide as
Binding agent is molded, naturally dry, and in atmosphere 550oUnder C, it is calcined 2 hours.Grind, sieving takes 10~20 mesh, 300oC dries
It is dry until quality is no longer reduced, obtain Ion exchange-Size exclusion formed absorbent.
【Embodiment 5~20】
Each step according to embodiment 1 prepares solid absorbent with condition and checked and rated.Simply change composition or prepare bar
Part, the condition of change are listed in table 1, and its appraisal result is listed in table 2.
Table 1
Table 2
| Numbering | Dimethyl after purification Disulfide content (ppmv) | Dimethyl disulfide is worn Saturating adsorbance (mg/g Adsorbent) | Purification essence after regenerating 5 times Degree dimethyl disulfide contains Measure (ppmv) | Dimethyl after regenerating 5 times Disulfide penetrates absorption Measure (mg/g adsorbents) |
| 1 | 0.3 | 31.3 | 0.6 | 30.8 |
| 2 | 0.4 | 33.2 | 0.5 | 31.9 |
| 3 | 0.4 | 36.4 | 0.6 | 35.7 |
| 4 | 0.5 | 30.1 | 0.6 | 29.7 |
| 5 | 0.4 | 30.4 | 0.5 | 29.9 |
| 6 | 0.4 | 31.6 | 0.5 | 31.2 |
| 7 | 0.5 | 34.2 | 0.6 | 33.5 |
| 8 | 0.5 | 30.7 | 0.6 | 30.4 |
| 9 | 0.3 | 30.0 | 0.4 | 29.6 |
| 10 | 0.5 | 36.1 | 0.6 | 35.7 |
| 11 | 0.5 | 30.2 | 0.7 | 29.6 |
| 12 | 0.5 | 36.6 | 0.7 | 34.8 |
| 13 | 0.5 | 35.3 | 0.6 | 34.6 |
| 14 | 0.4 | 33.2 | 0.4 | 32.2 |
| 15 | 0.5 | 33.8 | 0.6 | 33.1 |
| 16 | 0.6 | 30.2 | 0.6 | 29.4 |
| 17 | 0.5 | 36.6 | 0.8 | 35.7 |
| 18 | 0.5 | 37.2 | 0.6 | 36.4 |
| 19 | 0.6 | 33.8 | 0.7 | 33.1 |
| 20 | 0.5 | 33.9 | 0.7 | 33.0 |
| Comparative example 1 | 0.9 | 19.6 | 1.2 | 17.6 |
| Comparative example 2 | 0.7 | 22.9 | 1.0 | 20.4 |
| Comparative example 3 | 0.8 | 23.9 | 1.1 | 21.4 |
【Comparative example 1】
It is accurate to weigh the NaY molecular sieve original powder that 10 g silica alumina ratios are 10, it is molded by binding agent of aluminum oxide, in atmosphere
550 oUnder C, it is calcined 2 hours.Grind, sieving takes 10~20 mesh, 300oUnder C, drying until quality no longer reduce, obtain from
Son exchanges molecular sieve molded adsorbent.Component and content after preparation are given in Table 1.
Checked and rated by the appreciation condition of embodiment 1.The ppmv containing dimethyl disulfide 0.9 in 1- butene feedstocks after purification,
The adsorption capacity that penetrates of adsorbent is 19.6 mg/g adsorbents, and after adsorbent reactivation 5 times, purification precision is reduced to 1.2
Ppmv, the adsorption capacity that penetrates of adsorbent are reduced to 17.6 mg/g adsorbents.
【Comparative example 2】
First, the NaY molecular sieve original powder that 10 g silica alumina ratios are 10 is accurately weighed.Then, it is 0.4 to prepare molar concentration
Mol/L Cu (NO3)2The ml of solution 100, above-mentioned NaY molecular sieve original powder is added into 100 ml Cu (NO3)2In solution, i.e., according to
Solid-to-liquid ratio is 1：10 condition, 90oUnder C, it is sufficiently stirred, exchanges 6h.Filter, use deionized water rinsing.Repeat above-mentioned behaviour
Make three times.With by Cu2+The NaY molecular sieve of ion exchange is adsorbent, and CuO contents are 5.0%, Al in the adsorbent2O3Content
It is 45% for 50%, NaY contents.Checked and rated by the appreciation condition of embodiment 1.Contain DMDS after purification in 1- butene feedstocks
The ppmv of ether 0.7, the adsorption capacity that penetrates of adsorbent is 22.9 mg/g adsorbents, and adsorbent is after 5 regeneration, purification essence
Degree is reduced to 1.1 ppmv, and the adsorption capacity that penetrates of adsorbent is reduced to 20.4 mg/g adsorbents.
【Comparative example 3】
First, the NaY molecular sieve original powder that 10 g silica alumina ratios are 10 is accurately weighed.Then, it is 0.4 to prepare molar concentration
Mol/L Ce (NO3)3The ml of solution 100, above-mentioned NaY molecular sieve original powder is added into 100 ml Ce (NO3)3In solution, i.e., according to
Solid-to-liquid ratio is 1：10 condition, 90oUnder C, it is sufficiently stirred, exchanges 6h.Filter, use deionized water rinsing.Repeat above-mentioned behaviour
Make three times.With by Ce3+The NaY molecular sieve of ion exchange is adsorbent, Ce in the adsorbent2O3Content is 5.0%, Al2O3Contain
It is 45% to measure as 50%, NaY contents.Checked and rated by the appreciation condition of embodiment 1.Contain dimethyl two after purification in 1- butene feedstocks
The ppmv of thioether 0.8, the adsorption capacity that penetrates of adsorbent is 23.9 mg/g adsorbents, and adsorbent is after 5 regeneration, purification
Precision is reduced to 1.0 ppmv, and the adsorption capacity that penetrates of adsorbent is reduced to 21.4 mg/g adsorbents.
It can be seen that from the results of comparison of embodiment and comparative example and solved well by technical scheme provided by the invention
The problems such as purification precision of adsorbent is low, adsorption capacity is low, regenerating stability is poor, achieves preferable technique effect.
Claims (9)
1. a kind of hetero-atom molecular-sieve adsorbent, by weight percentage, including following components：
A) 10.0~80.0% molecular sieve carrier, molecular sieve carrier are selected from X-type, Y types, L-type, MCM types, modenite, the boiling of ZSM types
At least one of stone and beta molecular sieve；
B) 0.01~9.99% lanthanide metal oxide；
C) 0.01~10.0% NiO, CuO and ZnO mixture；
D) 10.0~85.0% binding agent, binding agent are selected from least one of aluminum oxide and silica,
The lanthanide series metal is selected from least one of Ce, Pr, Nd and Pm.
2. hetero-atom molecular-sieve adsorbent according to claim 1, it is characterised in that mole silica alumina ratio of molecular sieve carrier
SiO2/Al2O3For 1~50.
3. hetero-atom molecular-sieve adsorbent according to claim 2, it is characterised in that mole silica alumina ratio of molecular sieve carrier
SiO2/Al2O3For 1~10.
4. hetero-atom molecular-sieve adsorbent according to claim 1, it is characterised in that with adsorbent weight percentages, lanthanum
Series metal oxide content is 0.01~6.0%.
5. hetero-atom molecular-sieve adsorbent according to claim 1, it is characterised in that with adsorbent weight percentages,
The content of NiO, CuO and ZnO mixture is 0.01~8.0%.
6. the preparation method of the hetero-atom molecular-sieve adsorbent described in any one of claims 1 to 3, comprises the following steps successively：
A) with the salting liquid selected from least one of lanthanide series metal cation that molar concentration is 0.1~1.0mol/L to selected from
At least one of X-type, Y types, L-type, MCM types, modenite, ZSM types zeolite and beta molecular sieve molecular screen primary powder carries out ion
Exchange and be modified, solid-to-liquid ratio 1：3~1：20g/ml, ion-exchange temperature are 20~150 DEG C, and swap time is 2~80 hours, is handed over
Number is changed as 1~5 time, it is modified that lanthanide series metal modified molecular screen is made；
B) salt of Ni, Cu and Zn metal cation is configured to the solution that molar concentration is 0.1~0.6mol/L, step a) is made
The lanthanide series metal modified molecular screen obtained is impregnated or ion-exchange treatment, and modified molecular screen precursor is made；
C) add and make binding agent by weight percentage for 10.0~85.0% silica or aluminum oxide, mixed-forming, drying,
Hetero-atom molecular-sieve adsorbent is made after roasting.
7. the preparation method of hetero-atom molecular-sieve adsorbent according to claim 6, it is characterised in that solid-liquid in step a)
Than for 1：5~1：10g/ml, the molar concentration selected from least one of lanthanide series metal cation are 0.1~0.3mol/L, from
Sub- exchange temperature is 20~90 DEG C, and swap time is 2~20 hours, and exchange times are 1~3 time.
8. the preparation method of hetero-atom molecular-sieve adsorbent according to claim 6, it is characterised in that rubbing in step b)
Your concentration is 0.2~0.4mol/L.
9. the preparation method of hetero-atom molecular-sieve adsorbent according to claim 6, it is characterised in that Ni, Cu in step b)
Salt with Zn metal cations is nitrate, oxalates, citrate or acetate.
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| CN113845127A (en) * | 2021-09-26 | 2021-12-28 | 武汉工程大学 | Metal ion modified Y-type molecular sieve and preparation method and application thereof |
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