CN103143321A - Gasoline desulfurization adsorbent and preparation method thereof - Google Patents
Gasoline desulfurization adsorbent and preparation method thereof Download PDFInfo
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- CN103143321A CN103143321A CN2013100929776A CN201310092977A CN103143321A CN 103143321 A CN103143321 A CN 103143321A CN 2013100929776 A CN2013100929776 A CN 2013100929776A CN 201310092977 A CN201310092977 A CN 201310092977A CN 103143321 A CN103143321 A CN 103143321A
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Abstract
The invention provides a gasoline desulfurization adsorbent and a preparation method thereof, and relates to an absorbent and a preparation method thereof, wherein type 122 faintly acid phenolic aldehyde series cation exchange resin is used as the raw material of the absorbent, a transition metal is loaded on a precursor through ion exchange, the metal loading capacity is regulated, carbonization and activation are performed, and the specific surface area and the pore volume of the absorbent are regulated, and the absorbent is used for selectively absorbing and removing chemical sulfides; besides, the absorbent is loaded with spherical active carbon material of copper element. The preparation method comprises the following steps of: performing ion exchange between granular raw material and soluble copper salt solution; drying the granular raw material loaded with copper; baking the dry particles; and activating the baked particles by an activator, thereby obtaining the absorbent good in sphericity and high in mechanical strength. The absorbent has high absorption capacity and absorption selectivity for thiophene sulfides; and the raw material of preparation is easy to gain and the preparation method is simple.
Description
Technical field
The present invention relates to a kind of adsorbent and preparation method thereof, particularly relate to a kind of gasoline desulphurization sorbent and preparation method thereof.
Background technology
The sulfur content that reduces in gasoline, diesel oil is one of subject matter that faces in the Clean Fuel Production technology.Sulfur-containing compound in fuel oil generates oxysulfide (SO through burning
x), be discharged in atmosphere and can cause acid rain, thereby environment is caused severe contamination.In addition, the acidic materials that produce after these oxides and water are met can corrode engine and crankcase components.The more important thing is SO
xBe the mortifier of vehicle exhaust reforming catalyst, can significantly reduce the vehicle exhaust converter to nitrogen oxide (NO
x), the transformation efficiency of imperfect combustion hydro carbons and particle etc.Therefore, sulfur content is important indicator relevant with corrosion and environmental protection in fuel oil, and the sulfur content that must reduce in fuel oil just can reach the production requirement of clean fuel.
At present, industrial more ripe desulfurization of fuel oil technology is hydrodesulfurization (HDS), this technology can effectively remove the sulfide in gasoline, make sulfur content be reduced to certain level, but to the thiophene-type sulfide in gasoline and derivative thereof (as benzothiophene, 4, removing 6-dimethyl Dibenzothiophene etc.) is very difficult, if will the production super-low sulfur even without the gasoline of sulphur, the production cost that hydrogen consumption, equipment investment and operating cost are brought will sharply rise, and this has also just limited further developing of technique.Therefore, " green " technology that the thiophene-type sulfide that is difficult to remove for the HDS method and derivative thereof carry out deep desulfuration-adsorption desulfurize method becomes the focus of numerous scholar's research.Adsorption desulfurize can carry out under normal temperature and normal pressure, have do not face hydrogen, simple to operate, equipment investment is few, pollution-free, do not lose octane number and diesel cetane-number, but production super-low sulfur fuel wet goods advantage is especially more effective to removing of thiophene-type sulfide in gasoline.The key of adsorption desulfurize is selection and the preparation of adsorbent, a lot of adsorbents such as molecular sieve, aluminium oxide all have the ability that removes sulfur-containing compound from oil product, particularly active carbon class adsorbent can selective absorption a series of sulfur-containing compounds, as mercaptan, thioether, thiophenes etc.Spherical activated charcoal is a kind of of Carbon Materials, by obtaining after the macromolecule resin material charing, containing by what the crystallite charcoal formed the new material that enriches pore structure and transitional pore structure.Spherical activated charcoal is as the carrier of adsorbent, has certain molecular sieving effect, high strength, heat resistance, resistance to acids and bases, chemical stability is good, specific area is large, hole size and a series of advantage such as distribution is adjustable thereof.Make spent ion exchange resin carry out the load of metal component on Carbon Materials as carbon precursor, with respect to methods such as dipping, depositions, have the advantages such as exchange is even, load capacity is controlled, the metal-carbon compound that makes has unique performance, has shown good adsorption desulfurize performance.
Summary of the invention
The object of the present invention is to provide a kind of gasoline desulphurization sorbent and preparation method thereof, the present invention uses 122 type faintly acid phenolic type cation exchange resins to be raw material, by ion-exchange, transition metal is loaded on presoma, allocate its content of metal, through charing and activation, allocate its specific area and pore volume, directional preparation selective absorption desulfurizing agent.
The objective of the invention is to be achieved through the following technical solutions:
A kind of gasoline desulphurization sorbent, described adsorbent is raw material with 122 type faintly acid phenolic type cation exchange resins, by ion-exchange, transition metal is loaded on presoma, allocate its content of metal, through charing and activation, allocate its specific area and pore volume, be used for the sulfide that selective absorption removes chemical property; The spherical activated charcoal material of its sorbent-loaded copper.
Described a kind of gasoline desulphurization sorbent, described copper are the simple substance attitude, and the content of copper is 0.5%～5% of adsorbent gross weight.
A kind of preparation method of gasoline desulphurization sorbent, the method comprises the following step:
(a) with feed particulate material and the exchange of soluble copper salt solion;
(b) make the feed particulate material drying of the supported copper of step (a);
(c) make the dried particles roasting of step (b);
(d) make particle activation after step (c) roasting with activator.
The preparation method of described a kind of gasoline desulphurization sorbent, described feed particulate material is the faintly acid phenolic type cation exchange resin, and its performance indications are: CEC 4.35～4.80mmol/g, water content are 60～80%, wet apparent density is 1.05～1.15 g/ml, granularity 0.315～1.25mm; Described soluble copper salting liquid is copper nitrate solution, and concentration is 0.2mol/l; Ion-exchange time is 24h.
The preparation method of described a kind of gasoline desulphurization sorbent, described baking temperature is 50～100 ℃, be 8～16h drying time.
The preparation method of described a kind of gasoline desulphurization sorbent, described roasting is to carry out under nitrogen protection, and sintering temperature is 500～700 ℃, and roasting time is 0.5～2.5h.
The preparation method of described a kind of gasoline desulphurization sorbent, described activator is CO
2Activation temperature is 700～900 ℃, and soak time is 0.5～2.5h.
The specific embodiment
The present invention is described in detail below in conjunction with embodiment.
The invention provides a kind of novel Carbon Materials adsorption desulfurizing agent, the preparation method is provided simultaneously, use 122 type faintly acid phenolic type cation exchange resins to be raw material, by ion-exchange, transition metal is loaded on presoma, allocate its content of metal, through charing and activation, allocate its specific area and pore volume, directional preparation selective absorption desulfurizing agent is used for the sulfide that selective absorption removes different chemical character.The charcoal material precursor that adopts in the present invention is the 122 type faintly acid phenolic type cation exchange resins that Anhui Samsung resin Co., Ltd produces, and its parameter is: CEC 4.35～4.80mmol/g, water content are 60～80%, wet apparent density is 1.05～1.15 g/ml, granularity 0.315～1.25mm.
The preparation method of this adsorbent comprises the following steps:
1, fill post after 122 type resins are soaked 12h with deionized water, cross post with the NaOH of 4～5wt% and the hydrochloric acid solution of 4～5wt% respectively, discharge rate is controlled at (1.8～2.0) mlL
-1, then be washed till neutrality with deionized water, according to the certain density nitrate solution of exchanging equivalent preparation of resin, controlling discharge rate is (1.8～2.0) mlL
-1Cross post, until till in efflux, concentration of metal ions was initial concentration, the drying box that is placed in 120 ℃ was dried.
2, sample being placed in the drying box of 70 ℃ dries.
3, sample being placed in vacuum tube furnace, is 100mlmin at flow
-1N
2Under protection with 5 ℃ of min
-1Heating rate be warmed up to 600 ℃, roasting 1h is then with 5 ℃ of min
-1Heating rate be warming up to 800 ℃, under 800 ℃, passing into flow is 60mlmin
-1CO
2Activation 2h, activation is cooled to room temperature after finishing under the protection of nitrogen, obtain the resin-based ball-type active carbon of supported copper.
4, copper-loaded spherical activated charcoal is boiled about half an hour in boiling water, dissolve DDGS, dry in the drying box of 120 ℃, get copper-loaded spherical activated charcoal, be denoted as Cu-SAC.
Thiophene-type sulfide used herein refers to thiophene, the 3 methyl thiophene, 2 in gasoline, 5-thioxene and benzothiophene.
Embodiment 1:
Configuration contains thiophene, 3 methyl thiophene, 2, and the mixed solution of 5-thioxene, benzothiophene and normal heptane, mass fraction are respectively 0.026%, 0.030%, 0.034%, 0.041% and 99.869%, are designated as MG.
Comparative Examples 1:
122 type resins are carried out pretreatment: first use alcohol flushing, then rinse with 4～5wt%NaOH and hydrochloric acid, to remove organic in resin and inorganic residue.Get a certain amount of pretreated resin, be placed in 70 ℃ of dry 24h of vacuum drying chamber, then in vacuum tube furnace, at N
2Under protection with 5 ℃ of min
-1Heating rate be warmed up to 600 ℃, charing 1h, then be warming up to 850 ℃ is with 100mlmin
-1Flow pass into CO
2Activation 2h, activation is cooled to room temperature after finishing under the protection of nitrogen, obtain spherical activated charcoal, is denoted as SAC.
Embodiment 2:
Respectively the absorption property of adsorbent of the present invention and contrast adsorbent is estimated on preventing fixed bed adsorber.Under normal temperature and pressure conditions, it is that 8mm, length are in the 200mm adsorption column that 1g left and right adsorbent is loaded into an internal diameter, makes it flow through adsorption bed from bottom to top the pressurization of MG solution with the double plunger micro pump, and air speed is 4.8h
-1, regularly collect efflux in the exit.With the concentration of different sulfide in SP-3420 gas-chromatography (FPD detector) analytic sample, draw the breakthrough curve of sulfide, utilize integration method to calculate the saturated Sulfur capacity (in sulphur atom, unit is mg-sulphur/g-adsorbent) of adsorbent.The results are shown in the table I.
By the table I can find out adsorbent of the present invention to the absorption property of thiophene-type sulfide apparently higher than Comparative Examples, maximum to the adsorptive selectivity of benzothiophene, the adsorptive selectivity of thiophene is minimum.
Claims (7)
1. gasoline desulphurization sorbent, it is characterized in that, described adsorbent is raw material with 122 type faintly acid phenolic type cation exchange resins, by ion-exchange, transition metal is loaded on presoma, allocate its content of metal, through charing and activation, allocate its specific area and pore volume, be used for the sulfide that selective absorption removes chemical property; The spherical activated charcoal material of its sorbent-loaded copper.
2. a kind of gasoline desulphurization sorbent according to claim 1, is characterized in that, described copper is the simple substance attitude, and the content of copper is 0.5%～5% of adsorbent gross weight.
3. the preparation method of a gasoline desulphurization sorbent, is characterized in that, the method comprises the following step:
(a) with feed particulate material and the exchange of soluble copper salt solion;
(b) make the feed particulate material drying of the supported copper of step (a);
(c) make the dried particles roasting of step (b);
(d) make particle activation after step (c) roasting with activator.
4. the preparation method of a kind of gasoline desulphurization sorbent according to claim 3, it is characterized in that, described feed particulate material is the faintly acid phenolic type cation exchange resin, and its performance indications are: CEC 4.35～4.80mmol/g, water content are 60～80%, wet apparent density is 1.05～1.15 g/ml, granularity 0.315～1.25mm; Described soluble copper salting liquid is copper nitrate solution, and concentration is 0.2mol/l; Ion-exchange time is 24h.
5. the preparation method of a kind of gasoline desulphurization sorbent according to claim 3, is characterized in that, described baking temperature is 50～100 ℃, and be 8～16h drying time.
6. the preparation method of a kind of gasoline desulphurization sorbent according to claim 3, is characterized in that, described roasting is to carry out under nitrogen protection, and sintering temperature is 500～700 ℃, and roasting time is 0.5～2.5h.
7. the preparation method of a kind of gasoline desulphurization sorbent according to claim 3, is characterized in that, described activator is CO
2Activation temperature is 700～900 ℃, and soak time is 0.5～2.5h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107837808A (en) * | 2017-11-30 | 2018-03-27 | 上海拓径新材料科技股份有限公司 | The method that the copper-loaded method of macromolecule resin prepares copper-loaded solid carbon |
| CN110813242A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | Flue gas CO2Trapping material and method for producing same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041788A (en) * | 2012-12-17 | 2013-04-17 | 沈阳化工大学 | Adsorbent for removing thiophene-type sulfides in gasoline and preparation method thereof |
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- 2013-03-22 CN CN2013100929776A patent/CN103143321A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041788A (en) * | 2012-12-17 | 2013-04-17 | 沈阳化工大学 | Adsorbent for removing thiophene-type sulfides in gasoline and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 于维钊等: "负载金属球形活性炭的制备及其噻吩吸附性能", 《化工学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107837808A (en) * | 2017-11-30 | 2018-03-27 | 上海拓径新材料科技股份有限公司 | The method that the copper-loaded method of macromolecule resin prepares copper-loaded solid carbon |
| CN110813242A (en) * | 2018-08-13 | 2020-02-21 | 中国石油化工股份有限公司 | Flue gas CO2Trapping material and method for producing same |
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Application publication date: 20130612 |