CN104383874A - Purification adsorbent based on mesoporous molecular sieve material and preparation method and application of purification adsorbent based on mesoporous molecular sieve material - Google Patents
Purification adsorbent based on mesoporous molecular sieve material and preparation method and application of purification adsorbent based on mesoporous molecular sieve material Download PDFInfo
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Abstract
The invention relates to a purification adsorbent based on a mesoporous molecular sieve material and a preparation method and application of the purification adsorbent based on the mesoporous molecular sieve material. The purification adsorbent based on the mesoporous molecular sieve material is characterized by comprising the following components in percentage by weight: 20%-60% of a mesoporous molecular sieve, 35%-75% of activated aluminum oxide and 3%-20% of metal components. The preparation method of the purification adsorbent based on the mesoporous molecular sieve material is characterized by comprising the following steps: firstly, mixing the mesoporous molecular sieve material, the activated aluminum oxide and the metal components, then carrying out extruding or disc granulation, and finally aging and activating so as to obtain an adsorbent product which is applicable to a temperature variation adsorption or pressure variation adsorption technology, and can work under a gas phase or liquid phase condition. Compared with the prior art, the prepared adsorbent containing the mesoporous molecular sieve has the advantages of being large in adsorption material duct, more beneficial to the adsorption of macromolecular impurities (such as disulphide), uniform in adsorption duct distribution, low in heat adsorption effect, and the like and has the deep adsorption function.
Description
Technical field
The present invention relates to a kind of adsorbent and its preparation method and application, especially relate to a kind of purifying adsorbent based on meso-porous molecular sieve material and its preparation method and application.
Background technology
Ethene, propylene, benzene, toluene etc. are the important base stocks of modern chemical industry, these raw materials are mainly from petrochemical industry, but along with the fast development of Modern Coal-based Chemical, via coal also directly or indirectly (through synthesis gas or methyl alcohol) obtained these basic chemical raw materials.In addition, the alkane that some traditional handicrafts are discarded, also cleaved, as the raw material of industry.
The raw materials such as these alkane, alkene, benzene homologues, owing to originating difference, the impurity all containing variety classes and quantity, needs to be further purified, to meet rigors or the environmental requirement of subsequent technique process.After obtaining methyl alcohol via coal gasification, in the ethene obtained by Methanol, propylene or aromatic hydrocarbons, containing a small amount of methyl alcohol, dimethyl ether, propionic aldehyde etc., these oxygenatedchemicals impurity have had a strong impact on the activity of follow-up polymerization catalyst.In the hydrocarbon raw material of being originated by petrochemical industry or gas industry, also may containing micro-sulfur-bearing, nitrogen-containing compound etc., this also needs to purify as far as possible, to adapt to the process specifications improved constantly.
Adsorption method of separation is the common methods such as purification alkane, alkene, aromatic hydrocarbons stream, and the key of purification is selection and the manufacture thereof of adsorbent.
In US Patent No. 6111162, report adopts silica gel to be adsorbent, Adsorption oxygenatedchemicals from hydrocarbonaceous gas stream.European patent EP 0229994 utilizes the molecular sieve of the faujasite structure of micropore, as X, Y zeolite and LZ-210 zeolite, and the dimethyl ether in the liquid C3 ~ C5 alkane of adsorbing and removing, alkene.US Patent No. 4371718 discloses the method adopting aluminium oxide to remove methyl alcohol as adsorbent from butene feedstock.
Chinese patent CN1806029 discloses a kind of method removing dimethyl ether from alkane, olefin stream, and the method utilizes dipping technique, by micro porous molecular sieve Zn, Mg ionic impregnation modification, to reduce the fuel factor of adsorbent when at adsorption cleaning.Chinese patent CN102463101 then adopts similar technology, utilizes alkali metal ion to exchange, and reaches the object reducing adsorbent heat.
Chinese patent CN1230247 is by the component such as zeolite, aluminium oxide mechanical mixture to prepare adsorbent, and adsorbent Middle molecule sieve is the zeolite molecular sieve of micropore, and the alumina composition of interpolation plays peptizaiton, to reduce the heat of adsorption of adsorbent.Chinese patent CN102639228 is by being first added into by metal component in micro-pore zeolite molecular sieve, carrying out modified molecular screen, reduces heat of adsorption, then obtains adsorbent, to strengthen the absorption to oxygenatedchemicals impurity with the component mechanical mixture such as aluminium oxide.
Chinese patent 102921373A proposes the preparation method synthesizing a kind of adsorbent of molecular sieve with fabricated in situ and ion-exchange, and adsorbent duct prepared by the method is evenly distributed, and heat of adsorption effect is low, has degree of depth adsorption function.
It is inert base that Chinese patent 103495378A proposes with kaolin, aluminium oxide or inorganic silicon-aluminum mixture are as binding agent, be active component with submicron molecular sieve, prepare the microsphere adsorbing agent of certain particle size distribution, while reducing heat of adsorption, reach the effect of purification alkane, alkene.
The adsorbent that above-mentioned patent adopts mainly contains silica gel, aluminium oxide, molecular sieve and the combination between them.The molecular sieve wherein used is the zeolite molecular sieve of micropore, and as X-type, A type, Y type, ZSM type molecular sieve etc., these molecular sieve bore diameters are generally 0.3 ~ 1.5nm.When adopting micro porous molecular sieve adsorption cleaning, heat of adsorption is comparatively large, easily causes hydrocarbon-based polymeric; During absorption regeneration, regeneration temperature is also higher, is unfavorable for energy-conservation.
Summary of the invention
Object of the present invention is exactly provide one can remove micro oxygen containing compound in alkane, alkene, benzene homologues to overcome defect that above-mentioned prior art exists or containing compound (please supplement be compound) containing xx, and heat of adsorption is lower, purifying adsorbent based on meso-porous molecular sieve material that regeneration temperature is also lower and preparation method thereof.
Object of the present invention can be achieved through the following technical solutions: a kind of purifying adsorbent based on meso-porous molecular sieve material, it is characterized in that, this adsorbent comprises following weight percent composition: mesopore molecular sieve 20% ~ 60%, activated alumina 35 ~ 75%, metal component 3 ~ 20%.
Described adsorbent comprises following weight percent composition: mesopore molecular sieve 35% ~ 45%, activated alumina 50 ~ 60%, metal component 3 ~ 10%.
Described mesopore molecular sieve is mesoporous MCM type, mesoporous SBA type, the mixture of one or more in mesoporous X-type molecular sieve, and described mesopore molecular sieve duct is 2 ~ 50nm, and particle size is between 0.1 ~ 10um.
Described mesopore molecular sieve duct preferably 2 ~ 10nm.
Described metal component is from alkali metal, alkaline-earth metal, Zn or Cu.
Based on a preparation method for the adsorbent of meso-porous molecular sieve material, it is characterized in that, the method is mixed with activated alumina by mesopore molecular sieve, extruding pelletization or disc granulation, aging, activation after obtain adsorbent product; The opportunity that adds of described metal component is: before granulation or after granulation or aging after.
The feed postition of described metal component is for directly input, spray input or dipping add.
Described extruding pelletization or disc granulation make bar shaped or spheric granules, and particle diameter is 0.5 ~ 5mm.
Described aging be by granulation gained particle aging 0.5 ~ 12h of hydration at 70 DEG C ~ 150 DEG C; Described activation is that the material after aging is taken out post-drying, then at 200 DEG C ~ 450 DEG C conditions activation 0.5 ~ 4h.
Based on an application for the purifying adsorbent of meso-porous molecular sieve material, it is characterized in that, purifying adsorbent is used for Temp .-changing adsorption or pressure swing adsorption technique absorption alkane, alkene or benzene homologues; The condition of work of obtained purifying adsorbent is gas phase or liquid phase.
The logistics that final finished product adsorbent can be used for processing includes but not limited to the logistics containing saturated and/or unsaturated hydrocarbons, especially processes low-carbon alkanes, olefines logistics, as ethene, and propylene and butylene.These logistics are by containing one or more of following pollutant: H
2o, O
2, CO, CO
2, the oxygenatedchemicals such as alcohol, ether, H
2s, COS, CS
2, mercaptan, the sulfur-containing compound such as thioether, NH
3, the nitrogen-containing compound such as amine.
Adsorbent can be applied and Temp .-changing adsorption, pressure swing adsorption technique, and feed stream and adsorbent contact are cleaned, and adsorption conditions comprises temperature between 20 ~ 100 DEG C, and pressure range is 0.1 ~ 8mpa, depends on that feed stream is gaseous state or liquid state time of contact; For liquid stream, be about 0.1 ~ 12h-1 with the time of contact that liquid hourly (LHSV) represents; When described hydrocarbon material flow is gaseous state, be about 300-10000h with the time of contact that gas space degree (GHSV) represents
-1.0.1ppm (weight ratio) is all less than containing oxygen, sulfur-bearing and nitrogen-containing compound in organic hydrocarbon stream after purification.
Need activation process before solid absorbent contacts with hydrocarbon material first, the condition of process be the dry nitrogen of heat or air by adsorbent bed, activation temperature, also can electrical heating activation between 200-350 DEG C.
The present invention adopts aperture to be the mesopore molecular sieve of 2 ~ 50nm, with activated alumina mixed-forming, ensure that article shaped has some strength by hydro-combination process, article shaped completes regeneration in lower temperature (200 ~ 450 DEG C) simultaneously, save energy consumption, it also avoid mesopore molecular sieve non-refractory shortcoming.The method achieve the commercial Application of mesopore molecular sieve in adsorption cleaning, improve alkane, effective adsorptive selectivity of alkene purifying adsorbent product and adsorption capacity.
Compared with prior art, the present invention has following features:
1, adsorbent has lower heat of adsorption
Mesopore molecular sieve has the characteristic of molecular sieve selective absorption.Because duct is larger, more be conducive to adsorb macromolecules (as disulphide etc.) impurity, absorption duct is evenly distributed, heat of adsorption effect is low, and has degree of depth adsorption function, can remove the carbon dioxide (CO in the alkane such as ethene or propylene, olefin stream simultaneously
2), hydrogen sulfide (H
2s), cos (COS), methyl alcohol, dimethyl ether, propionic aldehyde, mercaptan, ammonia etc. are containing the plurality of impurities compound of O-or S-or N-.In adsorption separation process, heat release is less, decreases the impact on being cleaned medium (alkane, alkene, aromatic hydrocarbons), as alkene purify time, heat of adsorption is little, and temperature is lower, decreases the polymerization of alkene at adsorbent surface, relatively improves adsorption capacity.
2, the regeneration temperature of adsorbent is low, is beneficial to energy-conservation.
The active force of mesopore molecular sieve and adsorbate is relatively weak, utilizes adsorbent activating and regenerating.
Adsorbent of the present invention goes for Temp .-changing adsorption or pressure swing adsorption technique, can meet the purified industrial requirement to oxygenatedchemicals, sulfur-containing compound and nitrogen-containing compound impurity in alkane, alkene, benzene homologues.
Accompanying drawing explanation
Fig. 1 is the BET adsorption/desorption spectrogram containing mesoporous MCM-41 adsorbent of molecular sieve product of preparation in embodiment 1;
Fig. 2 is the XRD spectra containing mesoporous MCM-41 adsorbent of molecular sieve product of preparation in embodiment 1.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
Spherical adsorbent preparation process containing MCM-41 mesopore molecular sieve is as follows:
With activated alumina or aluminium glue for binding agent; by 50kg (butt; as follows) MCM-41 mesopore molecular sieve mixes with 45kg activated alumina; roller forming in granulating disc; the mode of spray is adopted to add sodium hydroxide solution (Na2O butt 5kg); take out after being shaped to 1 ~ 3mm particle; under 100 DEG C of conditions, water spray vapour complete hydration, ageing process; hydration time is 4 hours; after take out in 150 DEG C of oven dry; and under 400 DEG C of conditions prompt activation, obtain shaping solid absorbent.
Embodiment 2
Spherical adsorbent preparation process containing mesoporous SBA-15 type molecular sieve is as follows:
With activated alumina or aluminium glue for binding agent; 35kg mesoporous SBA-15 type molecular sieve is mixed with 58kg activated alumina; roller forming in granulating disc; take out after being shaped to 1 ~ 2mm particle; under 90 DEG C of conditions, water spray vapour completes hydration, ageing process, and hydration time is 6 hours, takes out in 150 DEG C of oven dry afterwards; and under 400 DEG C of conditions prompt activation, obtain article shaped.This solids be impregnated in (butt 7kg) in the ZnCl2 solution of 0.5mol/l, flood 20 minutes under 70 DEG C of conditions, take out, double-steeping 20 minutes after drying, take out in 150 DEG C of oven dry, and under 300 DEG C of conditions prompt activation, obtain solid absorbent finished product.
Embodiment 3
Spherical adsorbent preparation process containing mesoporous X-type molecular sieve is as follows:
With activated alumina or aluminium glue for binding agent; mesoporous for 55kg X-type molecular sieve, 45kg activated alumina and 5kg magnesium carbonate (butt) are mixed; roller forming in granulating disc; take out after being shaped to 2 ~ 3mm particle; under 70 DEG C of conditions, water spray vapour completes hydration, ageing process, and hydro-combination process is 5 hours, takes out in 150 DEG C of oven dry afterwards; and under 450 DEG C of conditions prompt activation, obtain article shaped.
Embodiment 4
Bar shaped absorbent preparation process containing mesoporous X-type molecular sieve is as follows:
Take activated alumina as binding agent, mesoporous for 55kg X-type molecular sieve, 45kg activated alumina and 5kg magnesium carbonate (butt) are mixed, extrusion molding in banded extruder, bar shaped particle diameter is 1.6mm, under 70 DEG C of conditions, water spray vapour completes hydration, ageing process, and hydro-combination process is 5 hours, takes out in 150 DEG C of oven dry afterwards, and under 450 DEG C of conditions prompt activation, obtain article shaped.
Solid absorbent obtained in above-described embodiment 1 ~ 4 is carried out adsorption cleaning to the methyl alcohol in gas phase, liquid propylene, dimethyl ether, propionic aldehyde respectively, and concrete application and result are as shown in embodiment 5-6 below.
Embodiment 5
Methyl alcohol, dimethyl ether, propionic aldehyde adsorption cleaning in gas-phase propene
Respectively a certain amount of adsorbent (embodiment 1 ~ 4) is loaded in reactor.At about 500h
-1the high pure nitrogen of volume space velocity (GHSV) flows down in 200 DEG C of activation 4h, is then cooled to 25 DEG C.Make the propylene gas containing micro oxygen containing compound (10ppm methyl alcohol, 10ppm dimethyl ether, DME, 10ppm propionic aldehyde) with 2.4h
-1continuous feed under the flow velocity of mass space velocity (WHSV) and the pressure of 0.2MPa, tail gas through adsorbing passes through the content of gas-chromatography on-line checkingi methyl alcohol, dimethyl ether and propionic aldehyde, when in tail gas, the oxygenatedchemicals impurity content such as dimethyl ether equals 0.1ppm, the adsorption capacity of adsorbent to adsorbate is as shown in table 1.
The different adsorbent of table 1 is to the adsorption capacity of methyl alcohol, dimethyl ether and propionic aldehyde impurity in gas-phase propene
Embodiment 6
Methyl alcohol, dimethyl ether, propionic aldehyde adsorption cleaning in liquid propylene
Respectively a certain amount of adsorbent (embodiment 1 ~ 4) is loaded in reactor.At about 500h
-1the high pure nitrogen of volume space velocity (GHSV) flows down in 200 DEG C of activation 4h, is then cooled to 25 DEG C.Setting counterbalance valve force value is 1.5MPa, 1.5MPa is pressurized to again with high pure nitrogen, then close high pure nitrogen, open propylene liguid steel cylinder switch, utilize pressure reduction constant flow pump entrance and port of export liquid propene (content of methyl alcohol, dimethyl ether and propionic aldehyde is respectively 10ppm) thereof to be full of, resetting counterbalance valve force value is 3.0MPa, open high pure nitrogen, be pressurized to 3.0MPa, close high pure nitrogen, open constant flow pump, according to 1.8h
-1mass space velocity (WHSV) continuous feed under the condition of outlet pressure 3.0MPa, through adsorbing separation liquid through vaporization after, tail gas through adsorbing passes through the content of gas-chromatography on-line checkingi methyl alcohol, dimethyl ether and propionic aldehyde, run 320 hours, in tail gas, the oxygenatedchemicals impurity content such as dimethyl ether equals 0.1ppm, and the adsorption capacity of adsorbent to adsorbate is as shown in table 2.
The different adsorbent of table 2 is to the adsorption capacity of methyl alcohol, dimethyl ether and propionic aldehyde impurity in liquid propylene
Embodiment 7
Based on a preparation method for the purifying adsorbent of meso-porous molecular sieve material, comprise the following steps:
(1) mesopore molecular sieve 60%, activated alumina 37%, metal component 3% are mixed, extruding pelletization or disc granulation;
Described mesopore molecular sieve is mesoporous MCM type, and described mesopore molecular sieve duct is 2nm, and particle size is between 0.1 ~ 10um.Described metal component is from alkali metal.
(2) by step (1) gained particle aging 12h of hydration at 70 DEG C;
(3) material after aging is taken out post-drying, then activate 4 hours 200 DEG C of conditions, obtain shaping purifying adsorbent.
Be used for by final finished product adsorbent processing gaseous ethylene, adsorption conditions comprises temperature at 20 DEG C, and pressure range is 8mpa, is about 300h with the time of contact that gas space degree (GHSV) represents
-1.0.1ppm (weight ratio) is all less than containing oxygen, sulfur-bearing and nitrogen-containing compound in organic hydrocarbon stream after purification.
Embodiment 8
Based on a preparation method for the purifying adsorbent of meso-porous molecular sieve material, comprise the following steps:
(1) mesopore molecular sieve 20%, activated alumina 60%, metal component 20% are mixed, extruding pelletization or disc granulation;
Described mesopore molecular sieve is mesoporous SBA type, and described mesopore molecular sieve duct is 10nm, and particle size is between 0.1 ~ 10um.Described metal component is from alkaline-earth metal.
(2) by step (1) gained particle aging 1h of hydration at 150 DEG C;
(3) material after aging is taken out post-drying, then under 250 DEG C of conditions, activate 1 hour, obtain shaping purifying adsorbent.
Be used for by final finished product adsorbent processing gaseous ethylene, adsorption conditions comprises temperature between 30 DEG C, and pressure range is 1mpa, is about 1000h with the time of contact that gas space degree (GHSV) represents
-1.0.1ppm (weight ratio) is all less than containing oxygen, sulfur-bearing and nitrogen-containing compound in organic hydrocarbon stream after purification.
Embodiment 9
Based on a preparation method for the purifying adsorbent of meso-porous molecular sieve material, comprise the following steps:
(1) mesopore molecular sieve 20%, activated alumina 75%, metal component 5% are mixed, extruding pelletization or disc granulation;
Described mesopore molecular sieve is mesoporous SBA type, the mixture of mesoporous X-type molecular sieve, and described mesopore molecular sieve duct is 50nm, and particle size is between 0.1 ~ 10um.Described metal component is from alkaline-earth metal.
(2) by step (1) gained particle aging 0.5h of hydration at 150 DEG C;
(3) material after aging is taken out post-drying, then under 450 DEG C of conditions, activate 0.5 hour, obtain shaping purifying adsorbent.
Be used for by final finished product adsorbent processing liquid phenenyl class, adsorption conditions comprises temperature between 80 DEG C, and pressure range is 3mpa, is about 12h with the time of contact that liquid hourly (LHSV) represents
-1.0.1ppm (weight ratio) is all less than containing oxygen, sulfur-bearing and nitrogen-containing compound in the organic hydrocarbon stream of benzene class after purification.
Embodiment 10
Based on a preparation method for the purifying adsorbent of meso-porous molecular sieve material, comprise the following steps:
(1) mesopore molecular sieve 35%, activated alumina 55%, metal component 10% are mixed, extruding pelletization or disc granulation;
Described mesopore molecular sieve is mesoporous SBA type molecular sieve, and described mesopore molecular sieve duct is 100nm, and particle size is between 0.1 ~ 10um.Described metal component is from alkaline-earth metal.
(2) by step (1) gained particle aging 0.5h of hydration at 150 DEG C;
(3) material after aging is taken out post-drying, then under 450 DEG C of conditions, activate 0.5 hour, obtain shaping purifying adsorbent.
Be used for by final finished product adsorbent processing liquid phenenyl class, adsorption conditions comprises temperature between 50 DEG C, and pressure range is 5mpa, is about 0.1h with the time of contact that liquid hourly (LHSV) represents
-1.0.1ppm (weight ratio) is all less than containing oxygen, sulfur-bearing and nitrogen-containing compound in the organic hydrocarbon stream of benzene class after purification.
Claims (11)
1. based on a purifying adsorbent for meso-porous molecular sieve material, it is characterized in that, this adsorbent comprises following weight percent composition: mesopore molecular sieve 20% ~ 60%, activated alumina 35 ~ 75%, metal component 3 ~ 20%.
2. the purifying adsorbent based on meso-porous molecular sieve material according to claim 1, is characterized in that, described adsorbent comprises following weight percent composition: mesopore molecular sieve 35% ~ 45%, activated alumina 50 ~ 60%, metal component 3 ~ 10%.
3. the purifying adsorbent based on meso-porous molecular sieve material according to claim 1 and 2, it is characterized in that, described mesopore molecular sieve is mesoporous MCM type, mesoporous SBA type, the mixture of one or more in mesoporous X-type molecular sieve, described mesopore molecular sieve duct is 2 ~ 50nm, and particle size is between 0.1 ~ 10um.
4. the purifying adsorbent based on meso-porous molecular sieve material according to claim 3, is characterized in that, described mesopore molecular sieve duct preferably 2 ~ 10nm.
5. the purifying adsorbent based on meso-porous molecular sieve material according to claim 1 and 2, is characterized in that, described metal component is from alkali metal, alkaline-earth metal, Zn or Cu.
6., as claimed in claim 1 based on a preparation method for the adsorbent of meso-porous molecular sieve material, it is characterized in that, the method is mixed with activated alumina by mesopore molecular sieve, extruding pelletization or disc granulation, aging, activate after obtain adsorbent product; The opportunity that adds of described metal component is: before granulation or after granulation or aging after.
7. the preparation method of the adsorbent based on meso-porous molecular sieve material according to claim 6, is characterized in that, the feed postition of described metal component is for directly input, spray input or dipping add.
8. the preparation method of the adsorbent based on meso-porous molecular sieve material according to claim 6, is characterized in that, described extruding pelletization or disc granulation make bar shaped or spheric granules, and particle diameter is 0.5 ~ 5mm.
9. the preparation method of the adsorbent based on meso-porous molecular sieve material according to claim 8, is characterized in that, described aging be by granulation gained particle aging 0.5 ~ 12h of hydration at 70 DEG C ~ 150 DEG C; Described activation is that the material after aging is taken out post-drying, then at 200 DEG C ~ 450 DEG C conditions activation 0.5 ~ 4h.
10. as claimed in claim 1 based on an application for the purifying adsorbent of meso-porous molecular sieve material, it is characterized in that, purifying adsorbent is used for Temp .-changing adsorption or pressure swing adsorption technique absorption alkane, alkene or benzene homologues; The condition of work of obtained purifying adsorbent is gas phase or liquid phase.
The preparation method of 11. adsorbents based on meso-porous molecular sieve material according to claim 10, is characterized in that, the adsorption conditions of described purifying adsorbent be temperature between 20 ~ 100 DEG C, pressure range is 0.1 ~ 8mpa; When absorbate stream is liquid stream, be about 0.1 ~ 12h with the time of contact that liquid hourly (LHSV) represents
-1; When absorbate stream is gaseous state, be about 300-10000h with the time of contact that gas space degree (GHSV) represents
-1.
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