CN101970103A - Regeneration of solid adsorbent - Google Patents
Regeneration of solid adsorbent Download PDFInfo
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- CN101970103A CN101970103A CN2008801280286A CN200880128028A CN101970103A CN 101970103 A CN101970103 A CN 101970103A CN 2008801280286 A CN2008801280286 A CN 2008801280286A CN 200880128028 A CN200880128028 A CN 200880128028A CN 101970103 A CN101970103 A CN 101970103A
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
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- 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
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- 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
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3408—Regenerating or reactivating of aluminosilicate molecular sieves
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
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- 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
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
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- B01J20/30—Processes for preparing, regenerating, or reactivating
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- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
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- B01D2253/102—Carbon
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Abstract
The present invention refers to a method of solvent-free regeneration of a solid adsorbent capable of adsorbing sulfones and/or sulfoxides comprising regenerating said adsorbent having sulfones and/or sulfoxides adsorbed thereon by exposing said adsorbent to a heat treatment at a temperature equal or less than 500 C. A further invention refers to a method of separating sulfoxides and/or sulfones from a petroleum based hydrocarbon stream comprising contacting activated carbon comprising -C=O, -COOH, -C-O and -OH functional groups on its surface with said petroleum based hydrocarbon stream.
Description
Technical field
The present invention relates to a kind of method of solvent-free regeneration that is used for separating the solid absorbent of sulfoxide and/or sulfone from petroleum-based hydrocarbon stream.
Background technology
Sulphur is ubiquity in all raw materials, and described raw material comprises crude oil, coal and contains the ore of common metal (as aluminium, copper, zinc, lead and iron).When the fuel that contains sulphur (for example coal and oil) burns, and when from oil, extracting gasoline, perhaps when from ore, extracting metal, form SO
xGas.SO
xGas is (as SO
2) be dissolved in the water vapour forming acid, and interact to form people and harmful sulfate and the other products of environment with airborne other gas and particle.
For example, surpass 65% (perhaps more than 13,000,000 ton/year) and be discharged into airborne SO
2From power plant, those coal-burning power plants particularly.SO
2Other source come the raw-material industrial equipment of metallic ore, coal and crude oil freely for its product, perhaps combustion fuel, coal or the oily vehicles.
The SO of discharging
x, especially in children and the elderly, can cause respiratory disease, and add the heart and lung diseases that restitution is sent out.For example, SO
2With airborne other chemical reaction to form small sulphate particle.When being inhaled into, these materials are assembled in lung, and relevant with disease, expiratory dyspnea and death too early with the Respiratory symptoms that increases the weight of.(for example one day) discharges high-caliber SO in addition, in a short time
2For the people who suffers from asthma, feel bad especially.The ever-increasing volume of traffic has increased the weight of these problems on the street.
SO
xAlso can cause the formation of acid rain, acid rain destroys forest and crops, changes soil constitution, and makes lake and river acidifying and be not suitable for fish growth.The long-term exposure that continues has changed the natural diversity of plant and animal in the ecosystem.Acid rain also quickens the damage of construction material and paint, comprises monument, statue and the carving that can not restore.
Discharge SO when as already noted, hydrocarbon-based fuel (for example diesel oil, gasoline or kerosene) also contains burning
xThe sulfur-containing compound of gas.The main sulfur-containing compound that is present in the current liquid hydrocarbon fuel is thiophenes and alkyl-substituted derivatives thereof.
But for example the environmental problem that is caused by sulfur-containing compound that is discharged in the environment by the factory and the vehicles (as automobile and aircraft) is not unique adverse effect.Sulfur-containing compound in the fuel also suppresses to use the noble metal catalyst of catalytic converter of the automobile of these fuel.This inhibition to catalyst also causes non-complete combustion of fuel, therefore causes discharging unburnt hydrocarbon, carbon monoxide and nitrogen oxide in vehicle exhaust.But these materials also influence the people's that are exposed to these materials health really.
Therefore, because the adverse effect of sulfur-containing compound in environment reason and the hydrocarbon fuel, a target of the industry is further to reduce the content of sulfur-containing compound in the hydrocarbon fuel.For above-mentioned reasons, the legislator of industrialized country, the limit value of the tolerable content by reducing sulfur-containing compound in the hydrocarbon fuel has constantly increased bigger pressure to refinery plant.In the future can be contemplated that the limit of the tolerable content of sulfur-containing compound in the hydrocarbon fuel will be limited in about 15ppm.Though this limit is reduced continuously by the legislator on the one hand, but because the decline of crude oil reserve, sulfur content in the crude oil that industry is used increases, and forces the refining industry to use the crude oil with higher sulfur content (sulfur content is increased to from about 1.13% of nineteen ninety and was contemplated to about 1.27% in 2010) like this.Therefore, the sector urgently needs effective removal of sulfur-containing compound.
Usually the use diverse ways carries out the industrial sulphur removal from fuel.A kind of method that is called hydrodesulfurization (HDS) method for example is described in GB 438,354.HDS relates to hydrogen catalysis and handles fuel, sulfur-containing compound is converted into hydrogen sulfide H
2S, by Crouse's method with hydrogen sulfide and then be converted into elementary sulfur.
The another kind of method of fuel ultra-deep desulfurization is oxidation sweetening (ODS), wherein fuel contacts with oxidant (for example hydrogen peroxide, ozone, nitrogen dioxide and TBHP), so that be polar organic compound with the sulfur-containing compound selective oxidation that exists in the fuel.This method is used after HDS usually, so that the sulfur content in the hydrocarbon fuel is brought down below the obtainable content of independent use HDS.The oxidation product of sulfur-containing compound is sulfoxide and sulfone in the ODS method, yet the latter is a primary product.
In order to realize whole success, method for designing is separated from hydrocarbon stream and removed resulting sulfoxide and sulfone have been become and has pressed in the ODS method.Two kinds of different routes that can be by solvent extraction by name, absorption or the combination of the two are carried out sulfoxide and are separated with sulfone.For example described in WO 2005/097951, the common used material that is used to adsorb comprises for example charcoal, hydrotalcite, ion exchange resin, zeolite, silica-alumina and silica gel.
But solvent extraction is usually directed to expensive solvent and complicated solvent is handled operation, for example reclaims and recirculation schemes.Though absorption does not need to use solvent on solid absorbent, the adsorbent that exhausts regeneration subsequently depends on various desorb liquid fluxs or diluent specially.Therefore, the effective regeneration of the adsorbent of use is a kind of mode of the cost of reduction extraction and separation method.
For example, WO 2005/116169 has described use alkali lye and has made the solid alkaline adsorbent reactivation.In WO2005/097951, pentane, hexane, benzene,toluene,xylene or its mixture are as the strippant of adsorbent reactivation.
Therefore, need be used for separating and extracting the improved method of adsorbent reactivation of the method for sulfoxide and sulfone from hydrocarbon stream.
Summary of the invention
The present invention relates to a kind of method of solvent-free regeneration of the solid absorbent that can adsorb sulfone and/or sulfoxide, described method comprises by being equal to or less than 500 ℃ or be equal to or less than 350 ℃ or under the temperature between about 200 to 350 ℃ described adsorbent is exposed, heat-treat, make the described adsorbent reactivation that is adsorbed with sulfone and/or sulfoxide on it.
The adsorbent that can be used for method of the present invention can be zeolite, active carbon or layered double-hydroxide (LDH).
When using active carbon as adsorbent, can carry out surface preparation, make on activated carbon surface, contain functional group (for example-C=O ,-COOH ,-C-O or-OH), to improve the adsorption capacity of adsorbent.
Method of the present invention also comprises to be made adsorbent and contains the sulfoxide that remains to be adsorbed and/or the petroleum-based hydrocarbon stream of sulfone contact on adsorbent surface.
The invention still further relates to and use method of the present invention from petroleum-based hydrocarbon stream, to separate sulfoxide and/or sulfone.
Description of drawings
When in conjunction with non-limiting example and accompanying drawing consideration, can understand the present invention better with reference to the specific embodiment, wherein:
Fig. 1 is illustrated in the structure of findable different thiophene in the hydrocarbon fuel (for example diesel oil).Fig. 1 a explanation molecular weight is the structure of 200 dibenzothiophenes sulfoxide.Fig. 1 b to Fig. 1 e illustrates after oxidation (for example, in the ODS method), thiophene in left side (Fig. 1 b and Fig. 1 d) and the corresponding sulfone in right side (Fig. 1 c and Fig. 1 e).In Fig. 1 d and Fig. 1 e, R is methyl or ethyl.Four kinds of modal sulfone thing classes in the diesel oil distillate are dibenzothiophenes (DBT) sulfone, 4-MDBT (4-MDBT) sulfone, 4, and the 6-dimethyl Dibenzothiophene (4,6-DMDBT) with 4,6-diethyl dibenzothiophenes (4,6-DEDBT).
The adsorption capacity that Fig. 2 is illustrated in 25 ℃ of following active carbons (AC-SP) increases along with the increase of time.In Fig. 2, drawn adsorption capacity (mg-S/g-A) and time (minute) relation.Use the first order reaction pattern, estimate that the kinetic constant of this adsorption method is at least 1.2h
-1
Fig. 3 represents to be used to measure the result of the GC-FID (flame ionisation detector) of all kinds sulfone class concentration.Use in WO 2005/116169 disclosed catalyst of transition metal oxide after 180 ℃ of following oxidations 5 hours, inoxidized model diesel oil (model diesel) (promptly, as a kind of model diesel oil in the table 5, wherein thiophene is also not oxidized is sulfone) the peak (last figure) of four thiophene disappear.On the contrary, the peak (middle figure) that four corresponding sulfones occur.With after adsorbent (the being active carbon) absorption herein, the peak of sulfone also disappear (figure below).
In Fig. 4 a, adsorption capacity (mg-S/g-A) is mapped with respect to the residue S in the model diesel oil (ppm).The adsorption isotherm of Fig. 4 a explanation AC-SP.Dotted line meets uncommon (Freundlich) thermoisopleth in the Freund.In Fig. 4 b, with the amount (wt%) of the aromatic compounds in the model diesel oil relation with respect to adsorbent/diesel oil (mg/g).By this figure as seen, the amount of aromatic compounds is constant in the model diesel oil.The amount of aromatic compounds does not change after absorption in Fig. 4 b explanation model diesel oil, and this shows in the presence of aromatic compounds, uses the adsorption method of active carbon to have selectivity for sulfone.
Fig. 5 represents to have the Utopian structure of the layered double-hydroxide of interlayer carbonate anion.Each parameter of definition in Fig. 5 is as the width of c-parameter, d-spacing, interlayer spacing and shepardite layer.
Fig. 6 represents to use the GC-FID that is used to reclaim the washing step of the diesel oil of adsorbent entrained and the non-polar solven of aromatic compounds (as n-hexane) and obtains to analyze.Fig. 6 explanation exists hexane (C6) and model diesel component (n-tetradecane (C14) and tert-butyl benzene (TBB)).The amount of C14 and TBB descends along with each extra hexane wash, and the amount of hexane (C6) does not descend, and this explanation hexane can be used for reclaiming the diesel oil of carrying secretly in the adsorbent.In any hexane wash solution, do not find sulfone.This result confirms that washing step does not influence adsorbent reactivation, and sulfone is not by desorb in hexane wash; But this step is effective reclaim valuable diesel product from adsorbent.
The specific embodiment
In first aspect, the present invention relates to a kind of method of solvent-free regeneration of the solid absorbent that can from hydrocarbon stream, adsorb sulfone and/or sulfoxide, described method comprises by described adsorbent being exposed being equal to or less than under 500 ℃ the temperature, heat-treat, make the described adsorbent reactivation that is adsorbed with sulfone and/or sulfoxide on it.
Method of the present invention makes adsorbent reactivation without any need for solvent,, removes sulfone and/or sulfoxide from the surface of adsorbent that is, saves the device that cost and simplification are used to make adsorbent reactivation equipment like this.
Consistent with the implication of common acceptance, be used for absorption of the present invention be meant on the interface between the immiscible phase (solid, liquid or steam) will be wherein one mutually or the component of two-phase attracts and the character of the interfacial film (" absorbate ") that simmer down to is adsorbed.Be adsorbed as by intermolecular or interatomic force discontinuity and the elementary heat mechanical property at the interface that causes.Absorption is different with absorption, is absorbed as material and diffuses in the liquid or solid to form dispersion.The term sorption comprises this two processes, and desorb is a reverse process.Being adsorbed as of several types is known, and comprises in the present invention.Physical absorption is the reversible adsorption by weak interaction only.Under the situation of physical absorption, covalent bonding does not take place between adsorbent and absorbate.Chemisorbed is to relate to interactional absorption stronger between absorbate and the adsorbent, follows the atomic rearrangement in absorbate or between the absorbate usually.Under the situation of chemisorbed, between the surface of adsorbent and absorbate, react.
In general, can use any adsorbent that is applicable to the object of the invention.Solid absorbent, it is presented for purposes of illustration to relate to solid absorbent herein, and usually heat endurance height and bore dia are little, cause the surface area that exposes bigger like this, therefore make the adsorption capacity height.With regard to purpose of the present invention, can use bore dia above 0.4nm or 0.7nm.But the present invention also can use bore dia to be lower than 0.4nm or surpass the adsorbent of 0.7nm.
Dissimilar adsorbents all can be used for the present invention, can distinguish by they being divided into different kinds usually.For example, the adsorbent that contains the oxygenatedchemicals that is generally hydrophily and has polarity comprises various materials, for example zeolite, diatomite or aluminium oxide.Form another kind of adsorbent based on carbon compound, this class adsorbent is generally hydrophobicity and has nonpolarly, and comprises various materials, for example active carbon.
The solid absorbent that can be used for the above kind of method of the present invention is the solid absorbent that can adsorb sulfoxide and/or sulfone in its surface.Usually, sulfoxide and/or sulfone are separated from hydrocarbon stream (for example hydrocarbon stream that has reacted the ODS method).Especially, the adsorbent that can be used for method of the present invention can be zeolite, active carbon, aluminium oxide, diatomite and layered double-hydroxide (LDH).Other technical specification that can be used for the adsorbent of method of the present invention finds in paragraph and the table 4 below.
Zeolite is mineral or synthetic compound, but it is characterized by the macrocation of alumino-silicate tetrahedron framework ion-exchange and the hydrone of loose combination.The general formula of zeolite can be used X
y 1+, 2+Al
x 3+Si
1-x 4+O
2NH
2O represents.Because the oxygen atom in the framework is shared by two tetrahedrons separately, therefore (Si, Al) ratio with O accurately is 1: 2.Pass through Al: the amount that the formal charge of Si ratio and these macrocations is regulated the macrocation (X) of existence.Typical macrocation is alkali metal and alkaline-earth metal, for example Na
+, K
+, Ca
2+, Sr
2+And Ba
2+Macrocation by framework oxygen and hydrone coordination rests in the big cavity of crystal structure; These cavitys and passage even allow organic molecular selectivity to pass through.Therefore, zeolite is widely used as molecular sieve.
The zeolite (CAS 1318-02-1) that can be used for method of the present invention for example is zeolite A (CaO/Al
2O
3Ratio is 0.5-1.0; Bore dia is 0.41nm), HY zeolite (SiO
2/ Al
2O
3Ratio is 12; Bore dia is 0.74nm), H-modenite (MOR) (SiO
2/ Al
2O
3Ratio is 20; Bore dia is 0.70-0.65nm), HZSM5 (SiO
2/ Al
2O
3Ratio is 50; Bore dia is 0.53nm-0.56nm), H β zeolite (SiO
2/ Al
2O
3Ratio is 25; Bore dia is 0.66nm-0.67nm), Na-modenite (MOR) (SiO
2/ Al
2O
3Ratio is 13; Bore dia is 0.70nm-0.65nm).
The another kind of adsorbent that can be used for method of the present invention is a diatomite.Diatomite is also referred to as Celite
, and form by the unconsolidated porous low-density deposit of forming by diatomaceous opalescence silica residues fully basically.Term diatomite (diatomaceous earth), diatomite (kieselguhr), diatomite (diatomite) and diatom ooze (diatomaceous ooze) be synonym basically, and difference is the pattern that deposit exists.Diatomite (diatomaceous earth) is the unconsolidated deposit that appears in fossil fresh water and the marine accumulation thing, and diatomite (diatomite) is its lithification equivalent.Diatom ooze (diatomaceous ooze) typically refers to the deposit of finding that is rich in diatom in present ocean or fresh water environment.Diatomite (kieselguhr) is also translated into infusorial earth (infusorial earth), is meant the old term of the precursor inclusion of the diatom in the Infusoria (that is all micro-animals).
Diatomaceous typical chemical composition is 86% silica, 5% sodium, 3% magnesium and 2% iron.Can be used for the optional free CE-545 of diatomite, the CE-535 of method of the present invention and the group that CE-501 forms.Following table has been enumerated various diatomaceous compositions.
Table 1
In the method for the invention, aluminium oxide also can be used as adsorbent.Aluminium oxide is for having chemical formula Al
2O
3The amphoteric oxide of aluminium.The example that can be used for the aluminium oxide of method of the present invention is Al
2O
3-A, Al
2O
3-B.These aluminium oxide are also referred to as the activated alumina that produces from aluminum salt solution by precipitation reaction, and way is, for example, and by hot post processing alumina hydrogel, or by calcining α-aluminium hydroxide or shock heating processing at low temperatures.Aluminium oxide be characterized as its high-ratio surface (about 300m
2/ g).
Aluminium hydroxide also can be used for method of the present invention.Aluminium hydroxide, Al (OH)
3, be the most stable form of aluminium under standard conditions.Aluminium hydroxide exists with fossil water aluminium ore (gibbsite) (being also referred to as gibbsite (hydrargillite)) form at occurring in nature.Closely-related have hydroxide aluminium oxide Al O (OH) and an aluminium oxide Al
2O
3, difference only is losing of water.Aluminium hydroxide has the typical metal hydroxides structure that contains hydrogen bond.Aluminium hydroxide is made up of hydroxyl and the aluminum ions bilayer that occupies the octahedral body opening 2/3rds between two-layer.
The another kind of adsorbent that can be used for method of the present invention is an active carbon.Active carbon is an amorphous carbon, it is characterized in that the surface area of per unit volume is very big, makes active carbon be specially adapted to realize purpose of the present invention.In general, active carbon can be collected gas, liquid or dissolved substances on the surface in its hole.For many gases or liquid, the weight of the material that is adsorbed is near the weight of active carbon.Absorption on active carbon has selectivity, compared with polar substances, is partial to adsorb apolar substance.
Almost any carbon raw material can be used for preparing active carbon.Shuck (particularly coconut), coal, petroleum coke and other residue of graininess, bulk or ball shape form are the exemplary materials example that can be used for the adsorbent product.
The activation of carbon is such process, handles carbon to open 1.2 a large amount of nanometer to 20 nanometer diameter scopes or up to the hole of 100 nanometer diameter scopes.After the activation, carbon has the high surface (500-1500m that causes adsorption phenomena
2/ g).In other words, 1 pound of (453.6g) carbon can provide the surface area that is equal to 6 football fields.Activation method comprises atmosphere and the heat thermal decomposition in stove that use is controlled.
With regard to purpose of the present invention, spendable active carbon for example is AC-SP, AC-LP, AC-MP, AC-G70R, AC-N or AC-A.Some experiments of using AC-SP and AC-A to carry out relating in this application as the example of active carbon.Advantageously, the adsorbent that is used for method of the present invention has selectivity for sulfone and sulfoxide.But active carbon also can be used for adsorbing other sulfur-containing compound, as hydrogen sulfide, sulphur or oxysulfide (Bagreev, A.; Rahman, H.; Deng the people; 2001; Carbon, the 39th volume, 1319-1326 page or leaf).The experiment of carrying out shows, and in the presence of the aromatic compounds in hydrocarbon stream (for example diesel oil), adsorbent has selectivity to sulfone and sulfoxide.In the experiment that the inventor carries out, use active carbon that this selectivity has been described.Be shown in the presentation of results of Fig. 4 b, the amount of aromatic compounds that is used for the model diesel oil of the present invention experiment changes after absorption, and this illustrate that in the presence of aromatic compounds the adsorption method of use active carbon has selectivity to sulfone.
Another group adsorbent that can be used for method of the present invention is layered double-hydroxide (LDH).LDH is for containing a class ion layered solid that has the positive charge layer of two types of metal cations and tradable hydration gallery anion (gallery anions).This is also referred to as the anionic property clay, is also referred to as hydrotalcite sample compound, and representative is accordingly based on the polytype of the mineral of [Mg-Al].Can be by coprecipitation method, induce hydrolysis and salt-oxide process to prepare.LDH uses formula [M usually
Z+ 1-xM
3+ x(OH)
2]
Q+(X
N-)
Q/nYH
2O represents.People can expect that one deck double-hydroxide (LDH) is stratified material (referring to Fig. 5, V.Rives, M.Angeles Ulibarri, 1999, Coordination Chemistry Reviews, the 181st volume, 61-120 page or leaf).The interlayer spacing can be determined by the XRD data.Unit cell parameter c=3 * d spacing, the width of d spacing=interlayer spacing+shepardite layer (according to S.Miyata, 1975, Clays and Clay Minerals, the 23rd volume, the 369th page,
).Some examples of LDH in table 2, enumerate (from A.Vaccari, 1998, Catalysis Today, the 41st the volume, the 53-71 page or leaf).
The composition of some natural anionic property clays of table 2, crystallography parameter and symmetry
Can influence the d spacing strongly by column.From A.Corma, 1997, Chem.Rev., the 97th volume, some examples of the cylindricality LDH compound of 2373-2419 page or leaf are shown in following table 3.
Table 3 has the acidity of different cationic cylindricality montmorillonites (PM)
| Sample | d 001(nm) | Surface area (m 2g -1) | It is acid that (μ v) |
| Al-PM | 1.73-1.89 | 190 | 425-442 |
| Zr-PM | 1.82 | 191 | 570 |
| Ti-PM | 1.50 | - | 620 |
| Fe-PM | 1.55 | 109 | 340 |
| Ni-PM | 1.48 | 58 | 228 |
| Al-Zr-PM | 1.56 | - | 390 |
| Al-Fe-PM | 1.58 | - | 340 |
| NaM | 1.28 | 51 | 86 |
The above-mentioned adsorbent of listing in table 2 and table 3 can be used for method of the present invention.
Treat to be meant sulfoxide and sulfone hereinbefore by adsorbent compound.These compounds for example are the oxidation product of thiophene in the hydrocarbon fuel (for example diesel oil) and other sulfur-containing compound.The example of thiophene and other sulfur-containing compound is the disulfide and the mercaptan of diphenyl sulfide, butyl sulfide, aminomethyl phenyl thioether, aliphatic series or aromatics, and heterocycle sulfur-containing compound, for example benzothiophene, dibenzothiophenes, 4-methyl-dibenzothiophenes, 4,6-dimethyl-dibenzothiophenes and three benzothiophenes and their other derivative.
Sulfoxide be contain the sulfinyl functional group that is connected with two carbon atoms compound (referring to formula (I); An example of Fig. 1 a explanation sulfoxide: the dibenzothiophenes sulfoxide).Sulfoxide can be regarded oxidized sulfide as.Sulfoxide use usually formula R-S (=O)-R ' expression, wherein R and R ' they are organic group.Key between sulphur and the oxygen atom is different from the conventional two keys (that is ketone) between carbon and the oxygen.S=O interacts and has static characteristic, causes significant dipole nature, has center of negative charge on oxygen.This bonding and tert-phosphine oxide R
3P=O is similar.Thioether is for being converted into the parent material of sulfoxide by organic oxidation.For example, oxidation state is 0 dimethyl sulfoxide (DMSO) for-2 dimethyl sulfide is oxidized to oxidation state.Further this compound of oxidation, dimethyl sulfoxide (DMSO) is converted into dimethyl sulfone, and wherein the oxidation state of sulphur is+2.Therefore, sulfone be contain the sulfonyl functional group that is connected with two carbon atoms compound (referring to formula (II); The example of sulfone is referring to Fig. 1 c and Fig. 1 e).The center sulphur atom is for two of the oxygen bonding two keys and have two other hydrocarbon substituents.The universal architecture formula be R-S (=O) (=O)-R ', wherein R and R ' they are organic group.
When for example in the ODS method when oxidized, the sulfur-containing compound key reaction in the hydrocarbon fuel is a sulfoxide, and further reaction is sulfone (referring to Fig. 1) subsequently.In the method for the invention, adsorbent that at first will be to be regenerated with contain the sulfoxide that remains on adsorbent surface, to be adsorbed and/or the petroleum-based hydrocarbon stream of sulfone and contact.Described petroleum-based hydrocarbon stream can be diesel oil, gasoline, gas oil and kerosene.As previously mentioned, the main sulfur-containing compound that is present in the current petroleum-based hydrocarbon stream is a thiophenes.For example, four kinds of modal thiophene compounds in the diesel oil are dibenzothiophenes (DBT) sulfone, 4-MDBT (4-MDBT) sulfone, 4, and the 6-dimethyl Dibenzothiophene (4,6-DMDBT) and 4,6-diethyl dibenzothiophenes (4,6-DEDBT) (also referring to table 5).
The adsorption capacity that can be used for the adsorbent of method of the present invention is enumerated in table 4.As can be seen from Table 4, the high absorption capacity of active carbon, AC-SP is a 5.68mg-S/g-A (mg sulphur/g adsorbent; Perhaps about 38mg sulfone/g-A), AC-A is 5.58mg-S/g-A.In various zeolites, the HY zeolite shows the good adsorption ability, and adsorption capacity is 4.56mg-S/g-A, corresponding to about 30.1mg sulfone/g-A.
For example, can further improve the adsorption capacity of active carbon by chemical modification.With regard to this purpose, with citric acid or nitric acid pretreatment adsorbent.When contacting with active carbon with a kind of in these acid, between acid and carbon, react, new to form-C=O ,-COOH ,-C-O and-the OH key.
Each adsorbent has the limit that can have how many absorbates to be adsorbed in its surface.After adsorbent exhausts, sorbent treatment or regeneration are used for reusing.In general, regeneration is meant by some attributes with system and returns to or near its initial value system is returned in the whole bag of tricks of its original state any.Under situation of the present invention, regeneration is meant the adsorption capacity of recovering adsorbent, makes adsorbent can be used for further separating sulfoxide and/or sulfone from petroleum-based hydrocarbon stream.
In the method for the invention, by under 500 ℃ the temperature adsorbent being exposed to heat treatment and realizing regeneration being equal to or less than.Heat treatment has the effect (referring to table 6) that the adsorption capacity that makes adsorbent is partially or completely recovered.
In an example, heat-treat being equal to or less than under 350 ℃ the temperature.As in the embodiment of back as seen, under the temperature between about 200 ℃ to 350 ℃, heat-treat.Heat treated other favourable temperature is any temperature between 250 ℃ to 300 ℃ and these two values.Use this heat treatment, can avoid using solvent to regenerate, therefore, can keep regeneration cost low.If desired, can under nitrogen or air purge, regenerate.Purging is used for from removing the thing class of desorb near the adsorbent, to prevent to adsorb once more and promote further desorb.Purging also helps to set up stable thermal environment, that is, and and the stable temperature that is used to regenerate.When using method of the present invention, avoided the complicated pretreatment of any kind of.Compare therewith, for example, people (Sabio, E. such as Sabio E.; Gonz á lez, people such as J.F.; 2004, Carbon; The 42nd volume, the 2285-2293 page or leaf) use with the remaining organic step of oxidizing gas (for example being used to make the steam or the carbon dioxide of active carbon regeneration) gasification.
For the heat treatment in stove, can any speed improve temperature.In an example, with about 5 ℃/minute to about 10 ℃/minute speed, begin heating from room temperature, until reaching final temperature.For at adsorbent before the heat treatment under situation about storing under the higher temperature, can under this higher temperature, begin to improve temperature.
In general, heat-treat, until adsorbent by holomorphosis.In an example, heat treatment is carried out about 0.5 to about 2 hours.In another example, heat treatment is carried out about 1 hour.In some instances, adsorbent is exposed to heat treatment, need not any further preliminary treatment (" former state " is referring to Table III), and in another example, before the heat treatment that is used to regenerate, adsorbent is spent the night to about 100 ℃ of following vacuum drying in about 50 ℃.In an example, adsorbent is spent the night in about 60 ℃ of following vacuum drying.
In another example, before heat treatment, wash adsorbent with apolar substance.The apolar substance that is used to wash adsorbent can be n-hexane, heptane, octane, nonane, naphtha or its mixture.In the method for the invention, n-hexane only is used to reclaim the diesel oil and the aromatic compounds (referring to experiment D) of carrying secretly, and proposes to make adsorbent reactivation with hexane in WO 2005/097951.Select to use the non-polar solven washing or the adsorbent vacuum drying spent the night and further improved the economy of adsorption method.
Because sulfur-containing compound (as thiophene) is oxidized to sulfoxide and is oxidized to sulfone subsequently in the ODS method, method of the present invention can be used in particular for oxidation sweetening (ODS) method (also referring to Fig. 3).
The invention still further relates to and use method of the present invention from petroleum-based hydrocarbon stream (for example, diesel oil, gasoline, gas oil or kerosene), to separate sulfoxide and/or sulfone.In following examples, use the example of diesel oil conduct based on the hydrocarbon stream of sulfur-bearing oil.
One concrete aspect, a kind of method of separating sulfoxide and/or sulfone from petroleum-based hydrocarbon stream is provided, described method comprise make contain in its surface C=O ,-COOH ,-active carbon of C-O and-OH group contacts with petroleum-based hydrocarbon stream.Activated carbon modified in order to make to contain these functional groups in its surface, with citric acid or nitric acid pretreatment active carbon, with introduce C=O ,-COOH ,-C-O and-the OH group.
" contain " and mean including, but not limited to word and " contain " afterwards any material.Therefore, use term " to contain " and be meant that cited composition is needs or essential, and other composition is chosen wantonly, and can exist or can not exist.
" by ... form " mean including, but not limited to word " by ... form " afterwards any material.Therefore, wording " by ... form " be meant that cited composition is to need or essential, and do not have other composition.
The present invention of the exemplary description of this paper can suit, and specifically there are not enforcement down in disclosed any or multiple composition, one or more restrictions in this article.Therefore, for example, term " contain ", " comprising ", " containing " etc. should wide in range understandings and without limits.In addition; term of Cai Yonging and statement are with explaining but not restrictive term herein; and have no intention to use shown in these terms and the statement eliminating and the feature of describing or any equivalent of its each several part, but recognize, in claimed scope of the present invention, can carry out various modifications.Therefore, be understood that, though specifically disclose the present invention by preferred embodiment reaching optional feature, those skilled in the art can adopt and embody modification of the present invention disclosed herein and variant, and think that these modifications and variant are within the scope of the invention.
The present invention has been described herein widely and prevailingly.The narrower kind and the class composition that fall in the general open scope also belong to the present invention separately.Whether general description of the present invention comprises with limited clause and negativity restriction removes the situation of any theme material from generality is described, and specifically be cited irrelevant in this article with this material of removing.
Other embodiment is in claim and non-limiting example.In addition, when feature of the present invention or aspect were described in the mode of Ma Kushi group, those skilled in the art can access, and therefore the present invention is described with any single member of Ma Kushi group or each member's subgroup form.
Experiment is described
The performance of solid absorbent and adsorption capacity
Tested the performance and the adsorption capacity of several solid absorbents, and in table 4, enumerated.All these adsorbents except that Ar-1 and Ar-2 are commercially available getting, and can be used for methods and applications of the present invention.
The performance of table 4 sorbent material and adsorption capacity
-AC-A production code member 161551; Activated charcoal (decolouring); CAS numbers 7440-44-0
-Al
2O
3CAS numbers 1344-28-1
-Al (OH)
3CAS numbers 21645-51-2
-Ar-1 contains 0.5%MgO, 96%SiO
2, 0.5%CoO and 3%Fe
2O
3, by weight.
-Ar-2 contains 0.5%MgO, 96%SiO
2, 0.5%CaO and 3%Fe
2O
3, by weight.
-Ar-1 and Ar-2 use SiO under room temperature
2Wet infusion process prepare.Behind the dipping, material in 120 ℃ of following dried overnight, is calcined down in 400 ℃ subsequently.Wet dipping or slurry dipping may be the most frequently used methods that is used for Preparation of Catalyst.This is the technology very commonly used that is used to prepare the catalyst of load, for example is described in " heterogeneous catalysis handbook (Handbook of Heterogeneous Catalysis) ", Ertl,
Helmut/Sch ü th, Ferdi/Weitkamp, Jens (editor), Wiley-VCH.Usually, the preparation method comprises precursor salt is joined in the carrier from the slurry in the excess solution.This method is commonly referred to ion-exchange, but more generally thinks wet dipping (WI).Also referring to J.T.Miller, M.Schreier, A.J.Kropf, and J.R.Regalbuto, 2004, catalysis magazine (Journal of Catalysis), the 225th volume, 203-212 page or leaf.
The SiO of these zeolite adsorbents of numeral the in-bracket []
2/ Al
2O
3Ratio.
-in manufacturer/supplier hurdle, illustrate that for dissimilar active carbons, any source material is used to make these active carbons.
For regeneration tests, owing to its good adsorption ability is used AC-SP and AC-A.
A. adsorption experiment and analysis thereof
The common N that before carrying out adsorption experiment, adsorbent is being flowed
2Descend in 120 ℃ following dry 2 hours; With zeolite sample in 120 ℃ dry 2 hours down, subsequently in 450 ℃ of calcinings 2 hours down.Drying steps only is a laboratory procedure, to guarantee being in identical condition (the identical initial conditions that are used for the performance of definite every kind of adsorbent) for all test adsorbents of adsorption test.In the practice of back, will no longer need this drying steps.Use BET (Bu Ete (Brunauer-Emmett-Teller)) technology to measure the surface area of adsorbent.Automatically adsorb in (Quantachrome Autosorb)-6B equipment at Kang Ta and to obtain the BET surface area, wherein with sample 200 ℃ of following vacuum outgas 5 hours.
A1. adsorption experiment
Use following program to carry out the absorption of sulfone.Use has the model diesel samples of the sulfone (from the oxidation of corresponding thiophene or the dissolving of pure sulphones) of known quantity.The composition of the model diesel oil that uses is shown in table 5.Therefore, table 5 has illustrated the thiophene through oxidation, that is, and and sulfone (following will illustrate also how thiophene is oxidized into sulfone).
The typical case of table 5 model diesel oil forms
| The component title | Concentration wt% | Concentration μ mol/g | Sulphur concentration ppmw |
| N-tetradecane | 88.54 | - | - |
| The DBT sulfone | 0.0680 | 3.144 | 100 |
| The 4-MDBT sulfone | 0.0724 | 3.144 | 100 |
| 4, the 6-DMDBT sulfone | 0.0768 | 3.144 | 100 |
| 4, the 6-DEDBT sulfone | 0.0856 | 3.144 | 100 |
| Naphthalene | 0.0403 | - | - |
| 2-methyl-naphthalene | 0.0447 | - | - |
| Tert-butyl benzene | 11.07 | - | - |
| Amount to | 100 | - | 400 |
The model diesel oil and the adsorbent (unless otherwise indicated, otherwise weight ratio is 20: 1) of fixed amount were stirred 24 hours in 350rpm, 25 ℃ of lower magnetic forces, be used for the equilibrium adsorption data.
A2. the analysis behind the adsorption experiment
In order to measure the dynamics data of the adsorption test that is shown in Fig. 2, use data from three different adsorption tests with various durations (that is, 30 minutes, 60 minutes with 120 minutes).The adsorption test method is with identical in three tests of all described in the preceding paragraph.In case reach the duration section of expectation, will test termination.For further analysis, use filter paper from model diesel oil, to leach with the adsorbent of crossing, and vacuum drying.
After each adsorption test, by remaining sulfone in x-ray fluorescence spectrometry (XRF or X-Ray Fluorescence) the rating model diesel oil that derives from Brooker (Bruker) AXS S4 Expore (referring to Jeyagowry T.Sampanthar, Huang Xiao waits the people; 2005, applied catalysis B: environment (Applied Catalysis B:Enviromental) 63, the 85-93 pages or leaves), the diesel oil that uses a model behind adsorption experiment carries out total sulfur XRF to measure the amount of sulphur, and is irrelevant with the structure or the character of sulfur-containing compound in the diesel oil.
Use GC-FPD (flame photometric detector) and GC-FID (flame ionisation detector) to measure the concentration of various types of sulfone thing classes.Use is equipped with HP-5 capillary column (L=30m; ID=0.25 μ m) and Agilent (Agilent) the 6890N device of flame photometric detector (FPD) or flame ionisation detector (FID) carry out gas chromatography (GC) and analyze.The column temperature program setting is that the speed with 40 ℃/minute raises from 50 ℃ to 250 ℃, is used for GC-FID and analyzes.The temperature profile that GC-FPD analyzes remains on 150 ℃, raises with 5 ℃/minute speed subsequently, to reach 240 ℃ final temperature.
The typical spectrum that GC-FID result is described is shown in Fig. 3.Disclosed catalyst of transition metal oxide is in 180 ℃ of following oxidations after 5 hours in WO 2005/116169 in use, and the peak of four thiophene of inoxidized model diesel oil (that is, as a kind of model diesel oil in the table 5, wherein thiophene is also not oxidized is sulfone) disappears.On the contrary, the peak that four corresponding sulfones occur.After charcoal absorption, the peak of sulfone also disappears.
The adsorption capacity of the adsorption dynamics adsorption kinetics data declaration active carbon (AC-SP) among Fig. 2 increases along with the increase of time.Use the first order reaction pattern, estimate that the kinetic constant of this adsorption method is at least 1.2h
-1
In order to understand, for example, measured the absorption property of active carbon in the existing system, comprise adsorption isotherm and adsorptive selectivity, the adsorption capacity when the sulfone of different equilibrium concentrations (after absorption in the diesel oil remaining sulfone).Shown in Fig. 4 a, adsorption capacity increases along with the increase of sulfur balance concentration.With these data and different thermoisopleth matches, and uncommon (Freundlich) thermoisopleth obtains best fit in the use Freund, that is,
q＝K·Ce
n (I)
Wherein q is an adsorption capacity, and the mg-S/g-A of unit, Ce are the equilibrium concentration of sulfone, represent with ppm sulphur.K is the constant of given absorption system.Comprise adsorbent, absorbate, matrix and temperature.Under exemplary cases, the concrete constant K and the n of system are respectively 0.0932 and 1.010.
Also measured the amount of aromatic compounds after adsorption test, with the selectivity of check acticarbon.Result among Fig. 4 b shows that the amount of the aromatic compounds after absorption in the model diesel oil remains unchanged, and this explanation uses the adsorption method of active carbon that sulfone is had selectivity in the presence of aromatic compounds.
The adsorpting data of mentioning herein is recorded as the milligram quantities (mg-S/g-A) of the sulphur that is adsorbed in every gram adsorbent.According to having used how many adsorbents, can control the sulfone that is adsorbed or the amount of sulfoxide.For example, use the adsorption capacity of 6mg sulphur/g active carbon, the described active carbon of 57g is exposed to the diesel oil that 1kg contains 350ppm sulphur, final sulfur content will be 10ppm.If use more adsorbent, then can further reduce sulfur content.
B. use citric acid or nitric acid to make the adsorbent modification
For introduce functional group (as-C=O ,-COOH ,-C-O and-OH), adsorbent (for example active carbon) must with citric acid and/or nitric acid reaction.
For example, for using citric acid to make the adsorbent modification, usage rate is the 1M citric acid solution of every 4g active carbon with 25ml.Mixture was vibrated under room temperature 30 minutes.Subsequently active carbon is leached, and in 50 ℃ of dried overnight.Use distilled water detergent active charcoal subsequently, do not change until in wash liquid, observing pH.Final drying before adsorption experiment is following dry 2 hours in 110 ℃.
In order to use Nitric Acid Modified, 70% red fuming nitric acid (RFNA) was refluxed 8 hours with active carbon, to handle active carbon.Ratio is 20g active carbon and 100ml nitric acid.After the backflow,, and, be about 7 until the pH of washings with the hot distilled water washing with activated carbon filtration.With active carbon in 60 ℃ of following vacuum drying 24 hours.
Use Fourier transform infrared spectroscopy figure (FTIR) to analyze to weigh whether have specific chemical bond and functional group.The Bruker Equinox 55FT-IR spectrometer that use contains mercury cadmium tellurides detector carries out FTIR.Sample of sorbent is ground, and with the KBr powder.The spectrometer sweep limits is 4000 to 400cm
-1FTIR spectrum confirms, formed new chemical bond (data not shown) after active carbon and nitric acid or citric acid reactions.
C. adsorbent reactivation
For the adaptability of reduction equipment and running cost and maintenance operation, the used heat treatment of renovation process of the present invention needs can operation in the temperature range (being lower than 500 ℃) of appropriateness in purifier.
In order to regenerate, will to leach from hydrocarbon stream with the adsorbent of crossing, and carry out in following three preparation processes one: spend the night in 60 ℃ of following vacuum drying, former state (that is, before heating without any processing) is perhaps used apolar substance (as n-hexane) washing.Use laboratory scale horizontal pipe furnace will be heated to different temperature with the adsorbent of crossing with 10 ℃/minute speed.Under nitrogen or air purge, will be placed in the quartz ampoule with the adsorbent of crossing, and under 200 ℃ to 350 ℃ temperature, heat 30 minutes to 2 hours.
Regeneration tests with the active carbon of crossing (AC-SP and AC-A) the results are shown in table 6.The adsorption capacity again of the adsorbent after the regeneration shows that the preparation condition of being studied (spend the night in 60 ℃ of following vacuum drying, former state is perhaps washed with n-hexane) does not influence the regeneration result.In fact, the adsorbent of using that will have the highest adsorption capacity was again regenerated 30 minutes down in 300 ℃ under without any pretreated former state condition.Equally, 250 ℃ to 300 ℃ regeneration temperature produces similarly good absorption result again.Be attributable to be used for again the diesel oil that only contains 193ppmw sulphur of adsorption experiment through the lower power of regeneration of vacuum drying AC-SP adsorbent (regenerating 30 to 60 minutes down) in 300 ℃.
The regeneration of the acticarbon that table 6 was used
Therefore, renovation process of the present invention provide a kind of effectively, mode is separated from the sulfur-bearing hydrocarbon stream and is removed sulfoxide and sulfone cheaply.
D. use apolar substance to reclaim the diesel oil and the aromatic compounds of carrying secretly
Use following program can obtain being shown in the figure of Fig. 6: the sample of sorbent (AC-SP) of 1g load is used 5ml hexane wash 15 minutes.Collect hexane wash solution, and use GC-FID to analyze (identical) with the method that is used to obtain Fig. 3.Adsorbent is preserved for washing next time.With identical step triplicate again, use the 5ml hexane, to wash equally loaded adsorbent at every turn.The GC-FID that is shown in Fig. 6 the analysis showed that, has hexane (C6) and model diesel component (n-tetradecane (C14) and tert-butyl benzene (TBB)).The amount of C14 and TBB descends along with each other hexane wash, and the amount of hexane (C6) does not descend, and this explanation hexane can be used for reclaiming the diesel oil of carrying secretly in the adsorbent.In any hexane wash solution, do not find sulfone.This result proves that washing step does not influence adsorbent reactivation, and sulfone is not by desorb in hexane wash; But this step is effective reclaim valuable diesel oil from adsorbent.
Claims (29)
1. the method for the solvent-free regeneration of the solid absorbent that can adsorb sulfone and/or sulfoxide, described method comprises:
By described adsorbent being exposed being equal to or less than under 500 ℃ the temperature, heat-treat, make the described adsorbent reactivation that is adsorbed with sulfone and/or sulfoxide on it.
2. method according to claim 1, wherein, described temperature is equal to or less than 350 ℃.
3. method according to claim 1, wherein, described temperature is between about 200 ℃ to about 350 ℃.
4. according to any described method in the aforementioned claim, wherein, described solid absorbent is selected from the group of being made up of zeolite, active carbon, aluminium oxide, diatomite and layered double-hydroxide.
5. method according to claim 4, wherein, described solid absorbent is an active carbon.
6. method according to claim 5, wherein, described active carbon is selected from the group of being made up of AC-SP, AC-LP, AC-MP, AC-G70R, AC-N and AC-A.
7. method according to claim 6, wherein, described active carbon is AC-SP or AC-A.
8. method according to claim 4, wherein, described solid absorbent is a zeolite.
9. according to any described method among the claim 1-8, wherein, described zeolite is selected from the group of being made up of zeolite A, HY, H-MOR, HZSM5, H β and NaMOR.
10. method according to claim 4, wherein, described solid absorbent is an aluminium oxide.
11. method according to claim 10, wherein, described aluminium oxide is selected from by Al (OH)
3, Al
2O
3-A and Al
2O
3The group that-B forms.
12. method according to claim 4, wherein, described solid absorbent is a diatomite.
13. method according to claim 12, wherein, described diatomite is selected from the group of being made up of CE-545, CE-535 and CE-501.
14. method according to claim 4, wherein, described solid absorbent is a layered double-hydroxide.
15. method according to claim 14, wherein, layered double-hydroxide is selected from the group of being made up of hydrotalcite, manasseite, igelstromite, sjogrenite, bouazzer, barbertonite, takovite, reevesite, saturating pyrope, sheet carbon magnesite, Al-PM, Zr-PM, Ti-PM, Fe-PM, Ni-PM, Al-Zr-PM, Al-Fe-PM and NaM.
16. according to any described method in the aforementioned claim, wherein, described regeneration is carried out under nitrogen or air purge.
17. according to any described method in the aforementioned claim, wherein, described regeneration was carried out about 0.5 hour to about 2 hours.
18. according to any described method in the aforementioned claim, wherein, described regeneration was carried out about 0.5 hour.
19. according to any described method in the aforementioned claim, wherein, described regeneration was carried out about 1 hour.
20. according to any described method among claim 4-7 and the 16-19, wherein, described adsorbent is for through pretreated active carbon, described preliminary treatment make activated carbon surface contain-C=O ,-COOH ,-C-O and-the OH group.
21. method according to claim 20, wherein, described adsorbent is through citric acid or nitric acid or the pretreated active carbon of its mixture.
22. according to claim 20 or 21 described methods, wherein, after preliminary treatment with described active carbon drying.
23. according to any described method in the aforementioned claim, wherein, with described adsorbent to be regenerated with contain the sulfoxide that remains on adsorbent surface, to be adsorbed and/or the petroleum-based hydrocarbon stream of sulfone and contact.
24. method according to claim 23, wherein, described petroleum-based hydrocarbon stream is selected from the group of being made up of diesel oil, gasoline, gas oil and kerosene.
25. method according to claim 24, wherein, described petroleum-based hydrocarbon stream is a diesel oil.
26. a method of separating sulfoxide and/or sulfone from petroleum-based hydrocarbon stream, described method comprise the surface contained-C=O ,-COOH ,-active carbon of C-O and-OH functional group contacts with described petroleum-based hydrocarbon stream.
27. method according to claim 26, wherein, described active carbon is through sour preliminary treatment, to introduce described functional group.
28., wherein, before carrying out described regeneration, wash described adsorbent with apolar substance according to any described method in the aforementioned claim.
29. method according to claim 28, wherein, described apolar substance is selected from the group of being made up of naphtha, n-hexane, heptane, octane, nonane and composition thereof.
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| US7186328B1 (en) * | 2004-09-29 | 2007-03-06 | Uop Llc | Process for the regeneration of an adsorbent bed containing sulfur oxidated compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1852966A (en) * | 2003-08-20 | 2006-10-25 | 环球油品公司 | Process for the desulfurization of hydrocarbonacecus oil |
| CN1965062A (en) * | 2004-03-30 | 2007-05-16 | 环球油品公司 | Process for the removal of sulfur-oxidated compounds from a hydrocarbonaceous stream |
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| CN105688870A (en) * | 2016-03-31 | 2016-06-22 | 烟台智本知识产权运营管理有限公司 | Preparation method of X-type molecular sieve/LDHs composite adsorbent for separating methane and nitrogen through pressure swing adsorption |
| CN107803192A (en) * | 2017-07-18 | 2018-03-16 | 华南理工大学 | A kind of oxidized desulfurization double-function catalyzing adsorbent clean regeneration process |
| CN109382388A (en) * | 2017-08-07 | 2019-02-26 | 中国石化扬子石油化工有限公司 | Method for preparing fresh dechlorinating agent from waste dechlorinating agent |
| CN109775794A (en) * | 2019-01-29 | 2019-05-21 | 南昌大学 | Recovery method of waste after a kind of LDH processing organic wastewater and products thereof and purposes |
| CN109775794B (en) * | 2019-01-29 | 2022-04-12 | 南昌大学 | Method for recycling waste generated after LDH treatment of organic wastewater, product and application thereof |
| CN114768754A (en) * | 2022-04-29 | 2022-07-22 | 福州城建设计研究院有限公司 | Preparation and regeneration method and application of Mg/Al layered double hydroxide formed adsorption particles with adsorption selectivity |
| CN114768754B (en) * | 2022-04-29 | 2024-05-14 | 福州城建设计研究院有限公司 | Preparation and regeneration methods and application of adsorption-selective Mg/Al layered double hydroxide formed adsorption particles |
| CN116726879A (en) * | 2023-07-18 | 2023-09-12 | 中国矿业大学(北京) | Zeolite activated carbon composite material and preparation method and application thereof |
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