CN104549141A - Heteroatom zeolite adsorbent and preparation method thereof - Google Patents
Heteroatom zeolite adsorbent and preparation method thereof Download PDFInfo
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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
- B01J20/10—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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- 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
- B01J20/30—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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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/60—Synthesis on support
- B01J2229/62—Synthesis on support in or on other molecular sieves
Abstract
The invention relates to a heteroatom zeolite adsorbent and a preparation method thereof and mainly aims at solving the problems that purifying accuracy of an adsorbent is low, adsorption capacity is low and regeneration stability is poor in existing olefin adsorption purification. The preparation method comprises the following steps: introducing at least two metal cations by adopting an ion exchange or impregnation method for modifying zeolite, and moulding by virtue of a binding agent, so as to obtain a solid adsorbent. By adopting the technical scheme, the problems are relatively well solved, and the heteroatom zeolite adsorbent provided by the invention can be applied to adsorption purification industrial production and can be used for removing sulphur compounds in various olefin raw materials.
Description
Technical field
The present invention relates to hetero-atom molecular-sieve adsorbent of a kind of bimetallic ion modification modification and preparation method thereof.
Background technology
Propylene is as important basic organic chemical raw material, of many uses, demand expanding day.Olefin(e) disproportionation technology is one of effective ways of propylene enhancing.C
4alkene is as one of the raw material of olefin(e) disproportionation, and composition is comparatively complicated, and source is different, and composition is different.Because the course of conveying of various processes and raw material makes C
4in the normal oxygenatedchemicals such as water, alcohol, ether that do not wait containing quantity and sulfur-bearing, the non-hydrocarbon compound such as nitrogenous.In numerous impurity, sulfur-containing compound is comparatively strong to the toxicity of catalyst, catalyst poisoning inactivation during micro-sulfur-containing impurities will make Downstream processing produce.And the existence of sulfide not only affects downstream product quality, contaminated environment, sometimes also can corrode production equipment, cause potential safety hazard.Therefore, want the abundant Appropriate application of alkene, matter of utmost importance is carried out purification to it exactly and is removed sulfur-containing impurities.Along with catalysis technique upgrades, catalyst activity improves, and also more easily poisoning and deactivation occurs simultaneously.The deep desulfuration of raw material also becomes C gradually
4deng the key of the further processing and utilization of low-carbon alkene.
Sulfide in low-carbon alkene mainly comprises hydrogen sulfide, cos, methyl mercaptan, ethyl mercaptan, dimethyl sulphide, propanethiol, dimethyl disulfide, the first and second disulfides, carbon disulfide and diethyl two sulphur etc.Not only total class is various, and good multiple sulfide chemical property is active, and various sulfide transforms under certain conditions mutually.Simultaneously, as the low-carbon alkene of industrial chemicals, no matter be used to the ethene of production polymer, propylene or n-butene, isobutene as feedstock conversion, their corresponding production technologies are all comparatively harsh to the requirement of sulfide content, General Requirements is removed to below 1ppm, even require that content is lower, namely has higher requirement according to different need of production in some cases.Therefore, be deep desulfurization process for removing of sulfur-containing compound in low-carbon alkene.Previous literature report technology otherwise technique is too complicated, need to carry out multistep and remove.Usually hydrolysis is at relatively high temperatures needed to be hydrogen sulfide for organosulfur impurities such as mercaptan, thioether, cos, then under normal temperature or low temperature, hydrogen sulfide is removed, this technique is called " Layer cake " technique by image, and not only complex process but also energy consumption are very high.Existing technique, purification precision does not reach production requirement usually, there is the problems such as working sulfur capacity is low simultaneously yet.Compared with numerous purification techniques, process for adsorption desulfuration, has purification precision high, the advantages such as technique is simple, easy to operate.The key problem of this technology remains the exploitation of high-efficiency adsorbent.
The porous masses such as active carbon, silica gel, aluminium oxide and molecular sieve are commonly used for adsorbent.Although active carbon desulfurization technology removes for the sulfur-containing compound such as mercaptan and thioether have certain efficiency, but generally need aerobic to participate in reaction, for the sweetening process of such inflammable, the explosive component of low-carbon alkene, do not advise adopting,, still there is selective low, the series of problems such as working sulfur capacity is low, desulfurization degree is low in the simple charcoal absorption removing sulfuldioxide relying on absorption.
Zeolite molecular sieve has predictable high efficiency screening function, also has the features such as ion exchangeable, adsorptivity and catalytic simultaneously, is thus widely used in the various fields such as agricultural, building materials, chemical industry, environmental protection, the energy, medicine, national defence and new material.Have some reported in literature around molecular sieve adsorption desulfurization, but still there is the problems such as purification precision is low, adsorption capacity is low, regenerating stability is poor in current molecular sieve desulfurizer.
United States Patent (USP) U.S.5843300, reports the adsorbent prepared with the X molecular sieve that alkali metal or alkaline-earth metal ions exchange, removes the sulfide of sulfide particularly with phenyl ring from FCC raw material.KX molecular sieve is a kind of effective adsorbent, and especially the adsorbent desulfurized effect of load regulation eight race metallic element palladium (Pd) and platinum (Pt) is better, can be regenerated in atmosphere of hydrogen at relatively high temperatures with the adsorbent of mistake.The Sulfur capacity of desulfurizing agent is 0.2 ~ 0.6%, and the work Sulfur capacity after regeneration decreases.
United States Patent (USP) U.S.20060191821 reports, and the hydrocarbon component of a kind of gaseous state, oily is facing the deep absorption desulfurization technology under hydrogen state.A kind of containing the promoter effect of zinc oxide and oxide form under desulfurization is carried out to the hydrocarbon component containing sulfide.This adsorbent can be regenerated by roasting in the air of dilution.The method removes for lower carbon number hydrocarbons medium sulphide content, there is operating temperature higher, and energy consumption is high, and must cause unsaturated hydrocarbons under hydro condition, hydrogenation side reaction occurs, causes the series of problems such as purification efficiency reduction.
Chinese patent CN1482210A provides a kind of adsorption refining gasoline by catalyst cracking.This technology utilizes two kinds of adsorbents to remove the sulfide in catalytically cracked gasoline.A kind of mixture of aluminium oxide, titanium oxide and molecular sieve that utilizes is for carrier, the adsorbent that saturated spray or dipping are prepared for activated centre with one or more oxides of the metallic elements such as zinc, cobalt, nickel, copper, lead, iron, the mercaptan sulfur in selective absorption catalytically cracked gasoline.Another kind of adsorbent is with the mixture of aluminium oxide, titanium oxide and molecular sieve for carrier, and the oxide of one or more in saturated spray or impregnated transition metallic element is adsorption activity center, the thiophene sulphur in selective absorption catalytically cracked gasoline.Above-mentioned two kinds of adsorbents are seated in two absorbers respectively, respectively adsorbent saturated rear with a kind of solvent or mixed light-hydrocarbon by adsorbent reactivation desorption with or be oxidized the sulfur-containing compound of its absorption.After selective deep desulfuration, in catalytically cracked gasoline, mercaptan sulfur content is less than 10 μ g/g, and total sulfur content is lower than 300 μ g/g.Can find out, although this technology has certain desulfurized effect, the sulfur content after desulfurization in sample is still very high.
In sum, although reported some adsorbents for olefin stream and corresponding purification method in previous literature, the problems such as the adsorption cleaning degree of depth that there is adsorbent in embody rule is low, adsorption capacity is low, purification precision is low, adsorption capacity is low, regenerating stability is poor.Although faujasite molecular sieve NaX and NaY has stronger polarity, especially to the features such as there is higher removal efficiency that remove of polar impurity, be usually used in the adsorption cleaning of various gas, liquid charging stock.Existing NaX and NaY molecular sieve adsorbent on the one hand the adsorption cleaning degree of depth are low, and product purity can not meet downstream production requirement.Simultaneously adsorption capacity is limited, make the consumption of adsorbent and purifier bulky, add device Meteorological, frequent regeneration also makes operation become complicated.On the other hand, adsorptive selectivity is poor, also adsorb a large amount of alkene, and during olefin adsorption, releasing more heat transfer brings adverse effect to adsorption efficiency while absorption oxygenatedchemicals.In addition, charing at high temperature easily occurs the alkene remained in regenerative process in adsorbent duct makes performance of the adsorbent decline.
Summary of the invention
One of technical problem to be solved by this invention there is the problems such as the purification precision of adsorbent is low, adsorption capacity is low, regenerating stability is poor in prior art.The invention provides and a kind ofly at least carry out modification by the shaping technical scheme making solid absorbent and preparation method thereof of binding agent by two kinds of metal cations to molecular sieve, this adsorbent is used for C
2~ C
6the adsorption cleaning of sulfur-containing compound in olefin feedstock, has the purification degree of depth high, the advantage that adsorption capacity is high and heat of adsorption is lower.Two of technical problem to be solved by this invention is to provide a kind of preparation method of the adsorbent corresponding with the adsorbent of one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: provide a kind of hetero-atom molecular-sieve adsorbent, by weight percentage, comprises following component:
A) 10.0 ~ 80.0% molecular sieve carriers, molecular sieve carrier is selected from least one in X-type, Y type, L-type, MCM type, modenite, ZSM type zeolite and beta molecular sieve;
B) lanthanide metal oxide of 0.01 ~ 9.99%;
C) at least one metal oxide being selected from periodic table of elements VIII, IB race and IIB race element of 0.01 ~ 10.0%;
D) binding agent of 10.0 ~ 85.0%, binding agent is selected from least one in aluminium oxide and silica.
In technique scheme, mole silica alumina ratio SiO of molecular sieve carrier
2/ Al
2o
3preferable range be 1 ~ 50; Mole silica alumina ratio SiO of molecular sieve carrier
2/ Al
2o
3most preferred range be 1 ~ 10; In hetero-atom molecular-sieve adsorbent, lanthanide series metal is at least one be selected from La, Ce, Pr, Nd and Pm; With adsorbent weight percentages, the preferable range of lanthanide metal oxide content is 0.01 ~ 6.0%; Hetero-atom molecular-sieve adsorbent is selected from periodic table of elements VIII, the preferred version of IB race and IIB race element is at least one be selected from Ni, Pd, Pt, Cu, Ag, Au, Zn, Co and Cd; Be selected from periodic table of elements VIII, the most preferably scheme of at least one metal oxide of IB race and IIB race element is the combination metal oxide of NiO, CuO and ZnO or the combination metal oxide of ZnO, CuO and CdO; With adsorbent weight percentages, be selected from periodic table of elements VIII, the preferable range of content of at least one oxide of IB race and IIB race element is 0.01 ~ 8.0%; Amount of component b) preferred version be the composition of NiO, CuO and ZnO.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of solid absorbent, comprises the following steps:
A) with at least one cationic salting liquid be selected from lanthanide series metal that molar concentration is 0.1 ~ 1.0 mol/L, ion-exchanged is carried out at least one molecular screen primary powder be selected from X-type, Y type, L-type, MCM type, modenite, ZSM type zeolite and beta molecular sieve, solid-to-liquid ratio is 1:3 ~ 1:20, and ion-exchange temperature is 20 ~ 150
oc, swap time is 2 ~ 80 hours, and exchange times is 1 ~ 5 time, modifiedly makes lanthanide series metal modified molecular screen;
B) salt of at least one metal cation be selected from periodic table of elements VIII, IB race and IIB race element is mixed with the solution that molar concentration is 0.1 ~ 0.6mol/L, lanthanide series metal modified molecular screen a) obtained to step floods or ion-exchange treatment, obtained modified molecular screen precursor;
C) add be by weight percentage 10.0 ~ 85.0% silica or aluminium oxide make binding agent, obtained hetero-atom molecular-sieve adsorbent after mixed-forming, drying, roasting.
In technique scheme, in preparation method step a) in the preferable range of solid-to-liquid ratio be 1:5 ~ 1:10, the preferable range being selected from least one cation mole concentration in lanthanide series metal is 0.1 ~ 0.3mol/L, and the preferable range of ion-exchange temperature is 20 ~ 90
oc, the preferable range of swap time is 2 ~ 20 hours, and the preferable range of exchange times is 1 ~ 3 time; Step b) in the preferable range of molar concentration be 0.2 ~ 0.4mol/L; Step b) in the salt of at least one metal cation that is selected from periodic table of elements VIII, IB race and IIB race element be nitrate, oxalates, citrate or acetate; The ion-exchange degree of molecular sieve is 1 ~ 99%.
Be used for by described hetero-atom molecular-sieve adsorbent in the adsorption cleaning reaction of the 1-butylene containing low concentration dimethyl disulfide, on fixed bed device, reaction condition is: reaction pressure 3.0 MPa, reaction temperature 30
ocontent 5 ~ 1000 ppmv of dimethyl disulfide in C, 1-butylene, the liquid volume air speed of 1-butylene is 0.5 ~ 10 h
-1.
In technique scheme, in 1-butylene, the preferable range of DMDS ether content is 10 ~ 500 ppmv, and wherein 1ppmv refers to volume fraction, containing 1,000,000/.
Cation lanthanide series metal part or all of in framework of molecular sieve is exchanged by ion-exchange by the present invention, adopt infusion process or ion-exchange that IB, IIB race metal is incorporated into molecular sieve surface and skeleton, then adopt activated alumina or silica to be that binding agent is shaping and make Ion exchange-Size exclusion solid absorbent.Modified by the duct of introducing to molecular sieve of lanthanide metal ion exchange and VIII, IB, IIB race metal, framework of molecular sieve is not made to be destroyed, but enhancing the stability of framework of molecular sieve, lanthanide metal ion and VIII, IB, IIB race metal ion are positioned at the S of the β cage of zeolite molecular sieve
iposition, stabilizes the skeleton of molecular sieve.Be positioned S in zeolite molecular sieve supercage
iIand S
iIIvIII, IB, IIB race metal ion on position is the adsorption site of desulfurization, and many kinds of metal ions, by synergy, has good suction-operated in the sulfide of alkene removes.Lanthanide metal ion to add on framework silicon hydroxyl and aluminium hydroxyl electronics to the migration probability in cage by polarization and inducing action in molecular sieve cage, increase the cloud density in molecular sieve cage, hydroxyl is made to show stronger acidity, B acid strength increases, and improves the adsorption capacity of adsorbent accordingly.In addition, the molecular sieve of ion-exchange has stronger adsorption capacity, activated alumina and silica also have certain adsorbing and removing ability as binding agent itself to oxygenatedchemicals, by the shaping solid absorbent of binding agent because the microcellular structure with molecular sieve itself and the Secondary Channel structure that formed between binding agent and molecular sieve have higher adsorption capacity to oxygenatedchemicals impurity, thus improve the adsorption capacity of porous adsorbent.Thus, the adsorbent of preparation solves the series of problems such as the purification precision of existing adsorbent is low, adsorption capacity is low, regenerating stability is poor simultaneously.The present inventor found through experiments for metal oxide auxiliary agent, at binding agent, when molecular sieve is identical with lanthanide metal oxide content, add the auxiliary agent that one-component compared by Multimetal oxide auxiliary agent simultaneously, it has better adsorption activity, regenerate 5 times later penetrate adsorbance and can improve more than 10%, achieve unexpected technique effect, the desulfurizing agent prepared by the present invention achieves good technique effect.
Use adsorbent of the present invention, at N
2in atmosphere, 280
oanticipate 8 hours under C, be cooled to room temperature.Be 3.0 MPa at pressure, temperature is 30
oc, liquid volume air speed is 1 h
-1under, adsorption cleaning is carried out to the 1-butene feedstock containing 500 ppmv dimethyl disulfide impurity, DMDS ether content after purification in 1-butene feedstock can reach 0.5 below ppmv, the penetrating adsorption capacity and can reach 35 more than mg/g of dimethyl disulfide, the adsorption capacity that penetrates of dimethyl disulfide improves more than 40% than similar technique, the adsorbent of preparation has good reproducibility, and after 5 regeneration, desulfurization performance is not almost decayed.Achieve good technique effect.
Below by embodiment, the invention will be further elaborated, but scope of the present invention is not by the restriction of these examples.
Detailed description of the invention
[embodiment 1]
Containing Ce
3+and Ni
2+the NaY molecular sieve of two kinds of ion-exchanges and be that the formed absorbent preparation process of binding agent is as follows with activated alumina.First, the former powder of NaY molecular sieve that 10 g silica alumina ratios are 10 is accurately taken.Subsequently, the Ce (NO that molar concentration is 0.4 mol/L is prepared
3)
3solution 100 ml, adds 100 ml Ce (NO by the former powder of above-mentioned 10 g NaY molecular sieve
3)
3in solution, be namely the condition of 1:10 according to solid-to-liquid ratio, 90
ounder C, fully stir, exchange 6 hours.Filter, use deionized water rinsing.Repeat aforesaid operations three times.Same method preparation molar concentration is the Ni (NO of 0.3 mol/L
3)
2solution is the condition of 1:3 according to solid-to-liquid ratio, 50
ounder C, fully stir, exchange 12 hours, carry out three secondary ion exchanges by this condition, after drying, obtain the molecular sieve precursor exchanged.Then, take 10g alumina powder, be that binding agent is shaping with aluminium oxide, naturally dry, in atmosphere 550
ounder C, roasting 2 hours.Grind, sieve and get 10 ~ 20 orders, 300
oc is dried until quality no longer reduces, and obtains Ion exchange-Size exclusion formed absorbent.
Fixed bed device carries out the adsorption cleaning performance evaluation of low concentration dimethyl disulfide in 1-butylene.Experiment condition is: 3.0 MPa, 30
oin C, 1-butylene, the content of dimethyl disulfide is about 500 ppmv, and liquid volume air speed is 1 h
-1, absorbent particles diameter is 830 ~ 1700 μm, and bed ratio of height to diameter is 6:1.Preactivated or the regeneration temperature of adsorbent, the temperature being measured desorption peaks by thermal analysis experiment is defined as 300
oc.Appraisal result and regeneration temperature provide in table 2.
[embodiment 2]
Containing Ce
3+, Ni
2+and Cu
2+the NaY molecular sieve of three kinds of ion-exchanges and be that the formed absorbent preparation process of binding agent is as follows with activated alumina.First, the former powder of NaY molecular sieve that 10 g silica alumina ratios are 10 is accurately taken.Subsequently, the Ce (NO that molar concentration is 0.1 mol/L is prepared
3)
3solution 200 ml, adds 200 ml Ce (NO by former for above-mentioned NaY molecular sieve powder
3)
3in solution, be namely the condition of 1:20 according to solid-to-liquid ratio, 20
ounder C, fully stir, exchange 80 hours.Filter, use deionized water rinsing.Repeat aforesaid operations twice.Same method preparation molar concentration is the Ni (NO of 0.6 mol/L
3)
2solution is the condition of 1:3 according to solid-to-liquid ratio, 150
ounder C, fully stir, exchange 2 hours, carry out four secondary ion exchanges by above-mentioned condition.After this, same method prepares the Cu (NO that molar concentration is 0.1 mol/L respectively
3)
2solution is the condition of 1:5 according to solid-to-liquid ratio, 150
ounder C, fully stir, exchange 2 hours, after this, carry out the molecular sieve precursor obtaining after primary ions exchanges drying exchanging.Then, take 10g alumina powder, be that binding agent is shaping with aluminium oxide, naturally dry, in atmosphere 550
ounder C, roasting 2 hours.Grind, sieve and get 10 ~ 20 orders, 300
oc is dried until quality no longer reduces, and obtains Ion exchange-Size exclusion formed absorbent.
[embodiment 3]
Containing Ce
3+, Ni
2+, Cu
2+and Zn
2+the NaY molecular sieve of four kinds of ion-exchanges and take activated alumina as the preparation of formed absorbent of binding agent.The preparation of adsorbent is carried out according to the method that embodiment 2 is same.Just in exchange process, preparation molar concentration is the Ce (NO of 0.5 mol/L
3)
3solution 30 ml, namely changing solid-to-liquid ratio is 1:3,120
ounder C, fully stir, exchange 4 hours, carry out three times and exchange.Ni is carried out successively according to same condition
2+, Cu
2+exchange.Through Ni (NO
3)
2, Cu (NO
3)
2after exchange, under similarity condition, with the Zn (NO of 0.6 mol/L
3)
2solution is that 1:5 carries out exchange 5 hours by solid-to-liquid ratio, obtains the molecular sieve precursor exchanged after drying.Then, take 10g alumina powder, be that binding agent is shaping with aluminium oxide, naturally dry, in atmosphere 550
ounder C, roasting 2 hours.Grind, sieve and get 10 ~ 20 orders, 300
oc is dried until quality no longer reduces, and obtains Ion exchange-Size exclusion formed absorbent.
[embodiment 4]
Containing Ce
3+, Ni
2+and Zn
2+the NaY molecular sieve of three kinds of ion-exchanges and take activated alumina as the preparation of formed absorbent of binding agent.The preparation of adsorbent is carried out according to the method that embodiment 2 is same.Just in exchange process, preparation molar concentration is the Ce (NO of 1.0 mol/L
3)
3solution 60 ml, change solid-to-liquid ratio is 1:6,80
ounder C, fully stir, exchange 4 hours, carry out three times and exchange.Prepare the Zn (NO of 0.5 mol/L
3)
2solution 50ml, change solid-to-liquid ratio is 1:5,60
ounder C, fully stir, exchange 24 hours, after drying, obtain the molecular sieve precursor exchanged.Then, take 2g alumina powder, be that binding agent is shaping with aluminium oxide, naturally dry, in atmosphere 550
ounder C, roasting 2 hours.Grind, sieve and get 10 ~ 20 orders, 300
oc is dried until quality no longer reduces, and obtains Ion exchange-Size exclusion formed absorbent.
[embodiment 5 ~ 20]
Prepare solid absorbent according to each step of embodiment 1 and condition and check and rate.Just change composition or preparation condition, the condition of change lists in table 1, and its appraisal result lists in table 2.
Table 1
Table 2
| Numbering | DMDS ether content (ppmv) after purification | Dimethyl disulfide penetrate adsorbance (mg/g adsorbent) | Regenerate purification precision DMDS ether content (ppmv) after 5 times | After regenerating 5 times, dimethyl disulfide penetrates adsorbance (mg/g adsorbent) |
| 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]
Accurately taking the former powder of NaY molecular sieve that 10 g silica alumina ratios are 10, is that binding agent is shaping with aluminium oxide, in atmosphere 550
ounder C, roasting 2 hours.Grind, sieve and get 10 ~ 20 orders, 300
ounder C, dry until quality no longer reduces, obtain Ion exchange-Size exclusion formed absorbent.Component after preparation and content provide in Table 1.
Check and rate by the appreciation condition of embodiment 1.Dimethyl disulfide 0.9 ppmv is contained in 1-butene feedstock after purification, the adsorption capacity that penetrates of adsorbent is 19.6 mg/g adsorbents, after adsorbent reactivation 5 times, purification precision is reduced to 1.2 ppmv, and the adsorption capacity that penetrates of adsorbent is reduced to 17.6 mg/g adsorbents.
[
comparative example 2]
First, the former powder of NaY molecular sieve that 10 g silica alumina ratios are 10 is accurately taken.Subsequently, the Cu (NO that molar concentration is 0.4 mol/L is prepared
3)
2solution 100 ml, adds 100 ml Cu (NO by former for above-mentioned NaY molecular sieve powder
3)
2in solution, be namely the condition of 1:10 according to solid-to-liquid ratio, 90
ounder C, fully stir, exchange 6h.Filter, use deionized water rinsing.Repeat aforesaid operations three times.With through Cu
2+the NaY molecular sieve of ion-exchange is adsorbent, and in this adsorbent, CuO content is 5.0%, Al
2o
3content is 50%, NaY content is 45%.Check and rate by the appreciation condition of embodiment 1.Dimethyl disulfide 0.7 ppmv is contained in 1-butene feedstock after purification, the adsorption capacity that penetrates of adsorbent is 22.9 mg/g adsorbents, adsorbent is after 5 regeneration, and purification precision 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 former powder of NaY molecular sieve that 10 g silica alumina ratios are 10 is accurately taken.Subsequently, the Ce (NO that molar concentration is 0.4 mol/L is prepared
3)
3solution 100 ml, adds 100 ml Ce (NO by former for above-mentioned NaY molecular sieve powder
3)
3in solution, be namely the condition of 1:10 according to solid-to-liquid ratio, 90
ounder C, fully stir, exchange 6h.Filter, use deionized water rinsing.Repeat aforesaid operations three times.With through Ce
3+the NaY molecular sieve of ion-exchange is adsorbent, Ce in this adsorbent
2o
3content is 5.0%, Al
2o
3content is 50%, NaY content is 45%.Check and rate by the appreciation condition of embodiment 1.Dimethyl disulfide 0.8 ppmv is contained in 1-butene feedstock after purification, the adsorption capacity that penetrates of adsorbent is 23.9 mg/g adsorbents, adsorbent is after 5 regeneration, and purification precision is reduced to 1.0 ppmv, and the adsorption capacity that penetrates of adsorbent is reduced to 21.4 mg/g adsorbents.
As can be seen from the results of comparison of embodiment and comparative example, well solve the problems such as the purification precision of adsorbent is low, adsorption capacity is low, regenerating stability is poor by technical scheme provided by the invention, achieve good technique effect.
Claims (10)
1. a hetero-atom molecular-sieve adsorbent, by weight percentage, comprises following component:
A) 10.0 ~ 80.0% molecular sieve carriers, molecular sieve carrier is selected from least one in X-type, Y type, L-type, MCM type, modenite, ZSM type zeolite and beta molecular sieve;
B) lanthanide metal oxide of 0.01 ~ 9.99%;
C) at least one metal oxide being selected from periodic table of elements VIII, IB race and IIB race element of 0.01 ~ 10.0%;
D) binding agent of 10.0 ~ 85.0%, binding agent is selected from least one in aluminium oxide and silica.
2. hetero-atom molecular-sieve adsorbent according to claim 1, is characterized in that mole silica alumina ratio SiO of molecular sieve carrier
2/ Al
2o
3be 1 ~ 50.
3. hetero-atom molecular-sieve adsorbent according to claim 2, is characterized in that mole silica alumina ratio SiO of molecular sieve carrier
2/ Al
2o
3be 1 ~ 10.
4. hetero-atom molecular-sieve adsorbent according to claim 1, is characterized in that lanthanide series metal is at least one be selected from La, Ce, Pr, Nd and Pm; With adsorbent weight percentages, lanthanide metal oxide content is 0.01 ~ 6.0%.
5. hetero-atom molecular-sieve adsorbent according to claim 1, is characterized in that being selected from periodic table of elements VIII, IB race and IIB race element is at least one be selected from Ni, Pd, Pt, Cu, Ag, Au, Zn, Co and Cd; With adsorbent weight percentages, be selected from periodic table of elements VIII, the content of at least one oxide of IB race and IIB race element is 0.01 ~ 8.0%.
6. hetero-atom molecular-sieve adsorbent according to claim 1, is characterized in that amount of component b) be the mixture of NiO, CuO and ZnO.
7. 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 at least one cationic salting liquid be selected from lanthanide series metal that molar concentration is 0.1 ~ 1.0 mol/L, ion-exchanged is carried out at least one molecular screen primary powder be selected from X-type, Y type, L-type, MCM type, modenite, ZSM type zeolite and beta molecular sieve, solid-to-liquid ratio is 1:3 ~ 1:20, and ion-exchange temperature is 20 ~ 150
oc, swap time is 2 ~ 80 hours, and exchange times is 1 ~ 5 time, modifiedly makes lanthanide series metal modified molecular screen;
B) salt of at least one metal cation be selected from periodic table of elements VIII, IB race and IIB race element is mixed with the solution that molar concentration is 0.1 ~ 0.6mol/L, lanthanide series metal modified molecular screen a) obtained to step floods or ion-exchange treatment, obtained modified molecular screen precursor;
C) add be by weight percentage 10.0 ~ 85.0% silica or aluminium oxide make binding agent, obtained hetero-atom molecular-sieve adsorbent after mixed-forming, drying, roasting.
8. the preparation method of hetero-atom molecular-sieve adsorbent according to claim 7, it is characterized in that step a) in solid-to-liquid ratio be 1:5 ~ 1:10, the cationic molar concentration of at least one be selected from lanthanide series metal is 0.1 ~ 0.3mol/L, and ion-exchange temperature is 20 ~ 90
oc, swap time is 2 ~ 20 hours, and exchange times is 1 ~ 3 time.
9. the preparation method of hetero-atom molecular-sieve adsorbent according to claim 7, is characterized in that step b) in molar concentration be 0.2 ~ 0.4mol/L.
10. the preparation method of hetero-atom molecular-sieve adsorbent according to claim 7, is characterized in that step b) in the salt of at least one metal cation that is selected from periodic table of elements VIII, IB race and IIB race element be nitrate, oxalates, citrate or acetate.
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