CN108435131A - A kind of high heap density solid adsorbent, preparation method and the usage - Google Patents

A kind of high heap density solid adsorbent, preparation method and the usage Download PDF

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CN108435131A
CN108435131A CN201810227417.XA CN201810227417A CN108435131A CN 108435131 A CN108435131 A CN 108435131A CN 201810227417 A CN201810227417 A CN 201810227417A CN 108435131 A CN108435131 A CN 108435131A
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heap density
solid adsorbent
density solid
high heap
molecular sieve
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肖永厚
周梦雪
贺高红
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Panjin Institute of Industrial Technology Dalian University of Technology DUT
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Panjin Institute of Industrial Technology Dalian University of Technology DUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers

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Abstract

A kind of high heap density solid adsorbent of present invention offer, preparation method and the usage, the high heap density solid adsorbent includes the following each component of weight proportion：1~70 part of molecular sieve carrier；MgO、CaO、SrO、BaO、Li2O、Na2O and K21~80 part of one or more modified alkaline earths in O or alkali metal oxide；Al2O3And/or SiO20~50 part；The high heap density solid adsorbent is sheet, and heap density is 0.65~1.3g/cm3；The diameter and thickness ratio of high heap density solid adsorbent is 0.2~15.The high heap density solid adsorbent of the present invention has purification depth high, adsorption capacity height and the good advantage of regenerating stability, the problems such as solving purification depth in the prior art, adsorption capacity and regenerating stability can be widely used in the adsorption cleaning industrial production of various hydrocarbon raw materials removing oxygenatedchemicals.

Description

A kind of high heap density solid adsorbent, preparation method and the usage
Technical field
The present invention relates to adsorbent and its application technology more particularly to a kind of high heap density solid adsorbent, its preparation sides Method and purposes.
Background technology
Propylene is as important basic organic chemical raw material, and widely used, demand is growing.Olefin(e) disproportionation technology is to increase Produce one of the effective ways of propylene.C4Raw material one of of the alkene as olefin(e) disproportionation, composition is complex, and source is different, ingredient It is different.Since the transmission process of various processes and raw material makes C4In often contain the oxygen-containing chemical combination such as water in varying numbers, alcohol, ether Object and the non-hydrocarbon compounds such as sulfur-bearing, nitrogenous.Sulfur-containing compound is stronger to the toxicity of catalyst in numerous impurity, micro sulfur-containing impurities Catalyst poisoning inactivates during Downstream processing will be made to produce.And the presence of sulfide not only influences downstream product quality, pollution Environment can also corrode production equipment, cause security risk sometimes.Therefore, want to fully and rationally use 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 being also easier to be poisoned Inactivation.The deep purifying of raw material is increasingly becoming C4The key utilized is further processed in equal low-carbon alkenes.
Compared with rectifying, absorption techniques, absorption has the characteristics that energy saving (low temperature or room temperature), efficiently separates, is easily operated, It is widely used in the industrial process such as gas, liquid charging stock purification, dehumidifying.Especially when impurity content is very low, the purification of absorption is deep Degree is far above other purification process, therefore absorption is more suitable for the fine subtractive process of raw material impurity.Silica gel, aluminium oxide and molecule The porous masses such as sieve are commonly used for adsorbent.United States Patent (USP) US 6111162 is reported using silica gel as adsorbent, from hydro carbons original Adsorbing and removing oxygenatedchemicals in material.United States Patent (USP) US 4371718 reports aluminium oxide and is removed from butene feedstock as adsorbent Remove methanol.European patent EP 0229994 is disclosed from liquid C3- C5The method that dimethyl ether is removed in alkene.The molecular sieve Adsorbent has faujasite structure, including X-type, Y type molecular sieve and LZ-210 zeolites.Preferred olefin stream flows automatically Change the C of bed catalytic cracking (FCC)4- C5Hydrocarbon stream.The patent US 4465870 of U.S. Publication, it has been reported that use 13X, 5A molecular sieve It is adsorbed and removed C4Middle methanol, water and methyl tertiary butyl ether(MTBE).The patent CN 1806029A of Exxon.Mobil chemical patents Corp's application Disclose a kind of method removing dimethyl ether from olefin stream.The solid absorbent main component that the invention uses is molecular sieve Or the metal oxide impregnated with Zn, Mg plasma.The molecular sieve includes small, neutralizes large pore molecular sieve with 4 membered rings to 12 The framework types of membered ring or bigger.But the adsorption capacity of the adsorbent is only 0.1~1.0wt%.
Although in conclusion reported in previous literature some for olefin stream adsorbents and corresponding purification method, But the problems such as adsorption cleaning depth in concrete application there are adsorbent is low, adsorption capacity is low, regenerating stability is poor.Although octahedral Zeolite molecular sieve, NaX and NaY have stronger polarity, especially have the spies such as higher removal efficiency to the removing of polar impurity Point is usually used in the adsorption cleaning of various gases, liquid charging stock.There are adsorption cleaning depths for existing NaX and NaY molecular sieve adsorbent Spend low, product purity cannot meet downstream production requirement.Adsorption capacity is limited simultaneously, regeneration effect is poor, makes the dosage of adsorbent And purifier is bulky, increases device Meteorological, frequent regeneration also makes operation become complicated.The present invention is quasi- to be passed through At least one of group ia or group iia metal cation are introduced into framework of molecular sieve and duct by ion exchange, are reached It is net to the absorption of the oxygenatedchemicals such as dimethyl ether in low-carbon alkene to improve adsorbent to the effect modified molecular sieve pore passage Change precision and adsorption capacity.
Invention content
It is an object of the present invention to which the purification precision for being directed to current adsorbent is low, adsorption capacity is low, regenerating stability is poor Problem proposes that a kind of high heap density solid adsorbent, the adsorbent have purification depth high, adsorption capacity height and regenerating stability Good advantage can be widely used in the adsorption cleaning industrial production of various hydrocarbon raw material removing oxygenatedchemicals.
To achieve the above object, the technical solution adopted by the present invention is：A kind of high heap density solid adsorbent, including weight The following each component of proportioning：
1~70 part of molecular sieve carrier；
MgO、CaO、SrO、BaO、Li2O、Na2O and K2One or more modified alkaline earths or alkali metal oxide 1 in O~ 80 parts；
Al2O3And/or SiO20~50 part；
The high heap density solid adsorbent is sheet, and the heap density of high heap density solid adsorbent is 0.65~1.3g/ cm3；The diameter and thickness ratio of high heap density solid adsorbent is 0.2~15.
Further, the heap density solid adsorbent includes the following each component of weight proportion：
20~60 parts of molecular sieve carrier；
10~50 parts of one or more alkali metal oxides in MgO, CaO and BaO；
Al2O3And/or SiO20~40 part.
Further, the molecular sieve carrier is one or more mixed in A types, X-type, Y types and ZSM type zeolite molecular sieves Close object, preferably X-type and/or Y type molecular sieve, more preferably X-type molecular sieve.
Further, the alkali metal oxide is MgO and/or CaO.
Further, the heap density of the high heap density solid adsorbent is 0.82~1.0g/cm3；High heap density solid The diameter and thickness ratio of adsorbent is 0.5~6.
Another object of the present invention also discloses a kind of preparation method of high heap density solid adsorbent, including walks as follows Suddenly：
Step 1, molecular sieve modified, it is 1%~20% alkaline-earth metal salt solution to molecule to use mass percent concentration Sieve carries out ion-exchanged, and modification temperature is 20~80 DEG C, mixing time 4~12 hours；
Step 2, drying obtain modified molecular screen, and drying temperature control is 70~140 DEG C, is dried 1~12 hour；
Step 3 is granulated, and modified molecular screen is uniformly mixed in proportion with alkaline earth oxide, through tabletting or comminutor Granulating and forming, granular size are controlled in 10~80 mesh；
Step 4 beats piece, using one or more as remover, the remover in graphite, magnesium stearate and stearic acid Addition is the 2~6% of sorbent precursor body gross mass, and product and releasing agent that step 3 is prepared are stirred evenly, are put into In mold, particle diameter is controlled in 2.5~5mm, beats sheetmolding with tablet machine, sorbent precursor body is made；
Step 5, drying, drying temperature are controlled at 70~140 DEG C, are dried 1~12 hour；
Step 6, roasting；Calcination temperature is controlled at 300~700 DEG C, roasts 1~12 hour, high heap density is obtained after roast Solid absorbent.
Further, step 1 is molecular sieve modified, uses mass percent concentration molten for 1%~10% alkali salt Liquid carries out ion-exchanged to molecular sieve, and modification temperature is 50~70 DEG C, mixing time 6~8 hours, the alkali salt Solution is Ca (NO3)2And/or Mg (NO3)2Solution (aqueous solution).
Further, remover described in step 4 is magnesium stearate.
Further, remover addition described in step 4 is the 3~5% of sorbent precursor body gross mass.
Another object of the present invention also discloses a kind of high heap density solid adsorbent in C2~C6Contain in olefin feedstock The purposes in the adsorption cleaning field of oxygen compound.
Further, purposes of the high heap density solid adsorbent in removing 1- butene feedstocks in dimethyl ether, in temperature Degree is 10~60 DEG C, and pressure is 0~4.0MPa, and liquid volume air speed is 1~5h-1Under conditions of, contain 200~1000ppm bis- The 1- butene feedstocks of methyl ether are inhaled by being filled with the reactor of the high heap density solid adsorbent sheet solid absorbent Attached purification, the 1- butene feedstocks after being purified.
The present invention provide it is a kind of by using ion exchange or infusion process by the Ith A or one or more elements of the IIth A races It introduces molecular sieve and piece is beaten using a kind of technical solution of post forming method to molecular sieve pore passage and surface progress modification The technical solution that molding is made and preparation method thereof, the present invention is high, and heap density solid adsorbent can be used for C2~C6In olefin feedstock The adsorption cleaning of oxygenatedchemicals has many advantages, such as that purification depth is high, and adsorption capacity height and regenerating stability are good.Specifically, originally Invention has the following advantages compared with prior art：
The heap density of molecular sieve is to influence one of the key factor of adsorbent absorption sulfur capacity.The technical side that the present invention uses In case, in forming process, using secondary shaping tech, the removers such as a small amount of stearic acid, magnesium stearate, forming method is only added Simply, conventional shaping method is overcome, such as extrusion or roller forming must add Ludox binder in the process, cause to adsorb The active component content of agent reduces, and adsorbent activity and stability is caused to reduce.By the adsorbent for playing piece post forming preparation Heap density and intensity have more apparent improvement.First by being granulated, mobility of sample during beating piece is increased The adhesion beaten during piece is avoided, while increasing the heap density and mechanical strength of sample.Make the absorption through playing piece preparation Agent contains the adsorbent of more multimass in same admission space, and during adsorption assessment, identical liquid volume is empty In the case of speed, there is more excessive adsorbent participation effect, to which the adsorbent prepared by the above method can be in high liquid Under volume space velocity, higher activity is kept for a long time.
The heap density measure of high heap density solid adsorbent (chip solid adsorbent) is placed on immediately after sample roasting It is spare that room temperature is down in drier.Adsorbent mass is accurately weighed using balance, then with large volume of graduated cylinder (100~ Its volume 200ml) is measured, is beaten every time compact as possible between making particle, it is ensured that measurement result accurate response actual result.Pass through The quality and admission space of actual measurement calculate adsorbent heap density.
The intensity of high heap density solid adsorbent is strong using the DLII type intelligence particles of Dalian Chemical Research ＆. Design Inst.'s production Analyzer is spent to measure.To ensure that the accuracy measured, every batch of sample duplicate measurements 5 times are averaged as final measurement.
Using the high heap density solid adsorbent of the present invention, in N2In atmosphere, is anticipated at 300 DEG C 6 hours, be cooled to room Temperature.It is 0~4.0MPa in pressure, temperature is 0~60 DEG C, and liquid volume air speed is 1~5h-1Under, to containing 200~1000ppmv The 1- butene feedstocks of dimethyl ether impurity carry out adsorption cleaning, and the diformazan ether content after purification in 1- butene feedstocks is up to 0.5ppmv Hereinafter, dimethyl ether penetrates adsorption capacity up to mg/g or more, the adsorption capacity that penetrates of dimethyl ether is improved than similar technique 30% or more, the adsorbent of preparation has preferable reproducibility, and desulfurization performance is not almost decayed after 5 regeneration.It achieves Preferable technique effect.
Specific implementation mode
The present invention is further described with reference to embodiments：
Embodiment 1
Present embodiment discloses a kind of high heap density solid adsorbent containing MgO and ion-exchanged NaX molecular sieves The preparation process of (chip solid adsorbent), the high heap density solid adsorbent is as follows：First, 2.89g Mg are accurately weighed (NO3)2·6H2O is dissolved in 46.11ml deionized waters, is configured to Mg (NO3)2Solution.Then, the 9.8g sial that will accurately weigh up Contain Mg (NO than being added to above-mentioned 30ml for 2 NaX molecular screen primary powders3)2Solution in, i.e., according to solid-to-liquid ratio be 1:5 item Part is sufficiently stirred at 60 DEG C, exchanges 12h.Filtering is rinsed with deionized water.Aforesaid operations are repeated, are exchanged altogether three times.It is dry The molecular sieve precursor exchanged afterwards.9.8g MgO are weighed, modified NaX and MgO are sufficiently mixed, made by comminutor Grain.0.4g magnesium stearates are added as remover, stirs evenly, is put into suitable mold, particle diameter controls 2.5~ 5mm, then sheetmolding is beaten with tablet machine, sorbent precursor body is made.Naturally dry in air at 500 DEG C, roasts 2 hours.Mill It is broken, sieving take a diameter of 830~1700 μm of absorbent particles, at 300 DEG C drying until quality no longer reduce, obtain chip solid Adsorbent.Heap density, the resistance to compression mechanical strength of adsorbent are measured using previously described method.
Adsorption cleaning of the high heap density solid adsorbent to low concentration dimethyl ether in 1- butylene is carried out on fixed bed device Performance evaluation.Experiment condition is：3.0MPa, 30 DEG C, the content of dimethyl ether is about 200ppmv, liquid volume air speed in 1- butylene For 1h-1, a diameter of 830~1700 μm of high heap density solid absorbent particles, bed ratio of height to diameter is 6:1.High heap density solid is inhaled Attached dose before carrying out adsorption experiment, preactivated 6 hours at 300 DEG C, appraisal result is given in Table 2.
Embodiment 2
Present embodiment discloses a kind of high heap density solid adsorbent containing MgO and ion-exchanged NaX molecular sieves (chip solid adsorbent), preparation process is as follows：First, 4.05g Mg (NO are accurately weighed3)2·6H2O be dissolved in 66ml go from In sub- water, it is configured to Mg (NO3)2Solution.Then, the NaX molecular screen primary powders that the 14g silica alumina ratios accurately weighed up are 2 are added to It states containing Mg (NO3)2Solution in, i.e., according to solid-to-liquid ratio be 1:5 condition is sufficiently stirred at 60 DEG C, exchanges 12h.Filtering, It is rinsed with deionized water.Aforesaid operations are repeated, are exchanged altogether three times.The molecular sieve precursor exchanged after drying.Weigh 5.6g Modified NaX and MgO are sufficiently mixed, are granulated by comminutor by MgO.0.4g magnesium stearates are added as remover, stir It mixes uniformly, is put into suitable mold, particle diameter control beats sheetmolding in 2.5~5mm, then with tablet machine, and adsorbent is made Presoma.Naturally dry in air at 500 DEG C, roasts 2 hours.Grind, be sieved take absorbent particles a diameter of 830~ 1700 μm, at 300 DEG C drying until quality no longer reduce, obtain chip solid adsorbent.It is measured using previously described method Heap density, the resistance to compression mechanical strength of adsorbent.
Adsorption cleaning of the high heap density solid adsorbent to low concentration dimethyl ether in 1- butylene is carried out on fixed bed device Performance evaluation.Experiment condition is：3.0MPa, 30 DEG C, the content of dimethyl ether is about 200ppmv, liquid volume air speed in 1- butylene For 1h-1, a diameter of 830~1700 μm of high heap density solid absorbent particles, bed ratio of height to diameter is 6:1.High heap density solid is inhaled Attached dose before carrying out adsorption experiment, preactivated 6 hours at 300 DEG C, appraisal result is given in Table 2.
Embodiment 3
Present embodiment discloses one kind containing MgO, ion-exchanged NaX molecular sieves and Al2O3Chip solid adsorbent (chip solid adsorbent), preparation process is as follows：First, 0.06g Mg (NO are accurately weighed3)2·6H2O is dissolved in 1ml deionizations In water, it is configured to Mg (NO3)2Solution.Then, the NaX molecular screen primary powders that the 0.2g silica alumina ratios accurately weighed up are 2 are added to It states 1ml and contains Mg (NO3)2Solution in, i.e., according to solid-to-liquid ratio be 1:5 condition is sufficiently stirred at 60 DEG C, exchanges 12h.It crosses Filter is rinsed with deionized water.Aforesaid operations are repeated, are exchanged altogether three times.The molecular sieve precursor exchanged after drying.Weigh 16g MgO, 3.4g Al2O3, by modified NaX, MgO and Al2O3It is sufficiently mixed, is granulated by comminutor.It is stearic that 0.4g is added Sour magnesium is stirred evenly as remover, is put into suitable mold, and particle diameter control is beaten in 2.5~5mm, then with tablet machine Sorbent precursor body is made in sheetmolding.Naturally dry in air at 500 DEG C, roasts 2 hours.It grinds, being sieved takes adsorbent Particle diameter be 830~1700 μm, at 300 DEG C drying until quality no longer reduce, obtain chip solid adsorbent.Using front The method of introduction measures heap density, the resistance to compression mechanical strength of adsorbent.
Adsorption cleaning of the high heap density solid adsorbent to low concentration dimethyl ether in 1- butylene is carried out on fixed bed device Performance evaluation.Experiment condition is：3.0MPa, 30 DEG C, the content of dimethyl ether is about 200ppmv, liquid volume air speed in 1- butylene For 1h-1, a diameter of 830~1700 μm of high heap density solid absorbent particles, bed ratio of height to diameter is 6:1.High heap density solid is inhaled Attached dose before carrying out adsorption experiment, preactivated 6 hours at 300 DEG C, appraisal result is given in Table 2.
Embodiment 4~18
It prepares and checks and rates with condition according to each step of embodiment 1.Only change alkali or alkaline earth metal oxide Type, content, the silica alumina ratio of molecular sieve, molecular sieve type, Al2O3Or SiO2Compositions or the preparation condition such as type and content, change The condition of change is listed in table 1, and adsorbent is before carrying out adsorption experiment, and preactivated 6 hours at 300 DEG C, appraisal result is listed in Table 2.
Table 1
Table 2
Comparative example 1
The unmodified NaY molecular sieve adsorbent preparation process of extruded moulding is as follows：First, it is 5 accurately to weigh 10g silica alumina ratios NaY molecular sieve original powder.Then, the dilute nitric acid solution 100ml that mass percent concentration is 15% is prepared, it is spare.Accurately weigh 2.5g Al2O3, the Al that will weigh up2O3It is sufficiently mixed uniformly with above-mentioned NaY molecular sieve original powder.Measuring mass percent concentration is 15% dilute nitric acid solution 8ml slowly, is equably added drop-wise in said mixture, then uses banded extruder extruded moulding.After molding Sample dry or dry, then in air at 500 DEG C, roast 4 hours.It grinds, being sieved takes absorbent particles a diameter of 830 ~1700 μm, preactivated 6 hours at 300 DEG C, obtain molecular sieve molded adsorbent.Component and content after preparation is in table 1 In provide.
The adsorption cleaning performance evaluation of low concentration dimethyl ether in 1- butylene is carried out on fixed bed device.Experiment condition is： 3.0MPa, 30 DEG C, the content of dimethyl ether is about 200ppmv in 1- butylene, and liquid volume air speed is 1h-1, absorbent particles diameter It it is 830~1700 μm, bed ratio of height to diameter is 6:1.Adsorbent is before carrying out adsorption experiment, preactivated 6 hours at 300 DEG C, Appraisal result is given in Table 2.It is checked and rated by the evaluation condition of embodiment 1.Contain dimethyl ether after purification in 1- butene feedstocks The adsorption capacity that penetrates of 0.99ppmv, adsorbent are 28.5mg/g adsorbents, and after adsorbent reactivation 5 times, purification precision is reduced to The adsorption capacity that penetrates of 1.3ppmv, adsorbent are reduced to 25.6mg/g adsorbents.
Comparative example 2
The unmodified NaX adsorbent of molecular sieve preparation process of extruded moulding is as follows：First, it is 2 accurately to weigh 10g silica alumina ratios NaX molecular screen primary powders.Then, the dilute nitric acid solution 100ml that mass percent concentration is 15% is prepared, it is spare.Accurately weigh 2.5g Al2O3, the Al that will weigh up2O3It is sufficiently mixed uniformly with above-mentioned NaX molecular screen primary powders.Measuring mass percent concentration is 15% dilute nitric acid solution 8ml slowly, is equably added drop-wise in said mixture, then uses banded extruder extruded moulding.After molding Sample dry or dry, then in air at 500 DEG C, roast 4 hours.It grinds, being sieved takes absorbent particles a diameter of 830 ~1700 μm, preactivated 6 hours at 300 DEG C, obtain molecular sieve molded adsorbent.Component and content after preparation is in table 1 In provide.
The adsorption cleaning performance evaluation of low concentration dimethyl ether in 1- butylene is carried out on fixed bed device.Experiment condition is： 3.0MPa, 30 DEG C, the content of dimethyl ether is about 200ppmv in 1- butylene, and liquid volume air speed is 1h-1, absorbent particles diameter It it is 830~1700 μm, bed ratio of height to diameter is 6:1.Adsorbent is before carrying out adsorption experiment, preactivated 6 hours at 300 DEG C, Appraisal result is given in Table 2.It is checked and rated by the evaluation condition of embodiment 1.Contain dimethyl ether after purification in 1- butene feedstocks The adsorption capacity that penetrates of 0.97ppmv, adsorbent are 29.3mg/g adsorbents, and after adsorbent reactivation 5 times, purification precision is reduced to The adsorption capacity that penetrates of 1.2ppmv, adsorbent are reduced to 26.7mg/g adsorbents.
Comparative example 3
The MgO adsorbent preparation process of extruded moulding is as follows：First, MgO powders 10g is accurately weighed.Then, quality is prepared The dilute nitric acid solution 100ml that percent concentration is 15%, it is spare.Accurately weigh 2.5g Al2O3, the Al that will weigh up2O3With it is above-mentioned MgO powder is sufficiently mixed uniformly.The dilute nitric acid solution 8ml that mass percent concentration is 15% is measured, slowly, is equably added drop-wise to It states in mixture, then uses banded extruder extruded moulding.Sample after molding is dried or is dried, then in air at 500 DEG C, roasting It burns 4 hours.Grind, being sieved takes a diameter of 830~1700 μm of absorbent particles, preactivated 6 hours at 300 DEG C, obtain into Type MgO adsorbents.Component and content after preparation are given in Table 1.
The adsorption cleaning performance evaluation of low concentration dimethyl ether in 1- butylene is carried out on fixed bed device.Experiment condition is： 3.0MPa, 30 DEG C, the content of dimethyl ether is about 200ppmv in 1- butylene, and liquid volume air speed is 1h-1, absorbent particles diameter It it is 830~1700 μm, bed ratio of height to diameter is 6:1.Adsorbent is before carrying out adsorption experiment, preactivated 6 hours at 300 DEG C, Appraisal result is given in Table 2.It is checked and rated by the evaluation condition of embodiment 1.Contain dimethyl ether after purification in 1- butene feedstocks The adsorption capacity that penetrates of 0.88ppmv, adsorbent are 30.6mg/g adsorbents, and after adsorbent reactivation 5 times, purification precision is reduced to The adsorption capacity that penetrates of 1.0ppmv, adsorbent are reduced to 28.2mg/g adsorbents.
It can be seen that from the results of comparison of 2 embodiment of table and comparative example and solved well by technical solution provided by the invention Determined adsorbent purification precision is low, the problems such as adsorption capacity is low, regenerating stability is poor, achieve preferable technique effect.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution The range of scheme.

Claims (10)

1. a kind of high heap density solid adsorbent, which is characterized in that the following each component including weight proportion：
A) 1~70 part of molecular sieve carrier；
b)MgO、CaO、SrO、BaO、Li2O、Na2O and K2One or more modified alkaline earths in O or alkali metal oxide 1~80 Part；
c)Al2O3And/or SiO20~50 part；
The high heap density solid adsorbent is sheet, and the heap density of high heap density solid adsorbent is 0.65~1.3g/cm3；It is high The diameter and thickness ratio of heap density solid adsorbent is 0.2~15.
2. high heap density solid adsorbent according to claim 1, which is characterized in that the following each group including weight proportion Point：
A) 20~60 parts of molecular sieve carrier；
B) 10~50 parts of one or more alkali metal oxides in MgO, CaO and BaO；
c)Al2O3And/or SiO20~40 part.
3. high heap density solid adsorbent according to claim 1, which is characterized in that the molecular sieve carrier be A types, X-type, One or more mixtures in Y types and ZSM type zeolite molecular sieves.
4. high heap density solid adsorbent according to claim 1, which is characterized in that the alkali metal oxide be MgO and/ Or CaO.
5. high heap density solid adsorbent according to claim 1, which is characterized in that the high heap density solid adsorbent Heap density is 0.82~1.0g/cm3；The diameter and thickness ratio of high heap density solid adsorbent is 0.5~6.
6. the preparation method of high heap density solid adsorbent described in a kind of claim 1-5 any one, which is characterized in that including Following steps：
It is step 1, molecular sieve modified, use mass percent concentration for 1%~20% alkaline-earth metal salt solution to molecular sieve into Row ion-exchanged, modification temperature are 20~80 DEG C, mixing time 4~12 hours；
Step 2, drying obtain modified molecular screen, and drying temperature control is 70~140 DEG C, is dried 1~12 hour；
Step 3 is granulated, and modified molecular screen is uniformly mixed in proportion with alkaline earth oxide, is granulated through tabletting or comminutor Molding, granular size are controlled in 10~80 mesh；
Step 4 beats piece, and using one or more as remover in graphite, magnesium stearate and stearic acid, the remover is added Amount is the 2~6% of sorbent precursor body gross mass, and product and releasing agent that step 3 is prepared are stirred evenly, mold is put into In, particle diameter is controlled in 2.5~5mm, beats sheetmolding with tablet machine, sorbent precursor body is made；
Step 5, drying, drying temperature are controlled at 70~140 DEG C, are dried 1~12 hour；
Step 6, roasting；Calcination temperature is controlled at 300~700 DEG C, roasts 1~12 hour, high heap density solid is obtained after roast Adsorbent.
7. the preparation method of high heap density solid adsorbent according to claim 6, which is characterized in that step 1 molecular sieve changes Property, use mass percent concentration to carry out ion-exchanged to molecular sieve for 1%~10% alkaline-earth metal salt solution, it is modified Temperature is 50~70 DEG C, mixing time 6~8 hours, and the alkaline-earth metal salt solution is Ca (NO3)2And/or Mg (NO3)2Solution.
8. the preparation method of high heap density solid adsorbent according to claim 6, which is characterized in that demoulding described in step 4 Agent is magnesium stearate.
9. high heap density solid adsorbent is in C described in a kind of claim 1-5 any one2~C6Oxygen-containing chemical combination in olefin feedstock The purposes in the adsorption cleaning field of object.
10. a kind of dimethyl ether in removing 1- butene feedstocks of high heap density solid adsorbent described in claim 1-5 any one The purposes of impurity is 10~60 DEG C in temperature, and pressure is 0~4.0MPa, and liquid volume air speed is 1~5h-1Under conditions of, contain The 1- butene feedstocks of 200~1000ppm dimethyl ether are by being filled with the high heap density solid adsorbent sheet solid absorbent Reactor carry out adsorption cleaning, the 1- butene feedstocks after being purified.
CN201810227417.XA 2018-03-20 2018-03-20 A kind of high heap density solid adsorbent, preparation method and the usage Pending CN108435131A (en)

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