CN103170305A - Modified gasoline desulfurization adsorbent and preparation method thereof - Google Patents
Modified gasoline desulfurization adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses modified gasoline desulfurization adsorbent and a preparation method thereof and relates to a gasoline desulfurization adsorbent and a preparation method thereof. The adsorbent is used for deeply removing thiophene as well as a derivative thereof and benthiophene in the gasoline; the adsorbent is 13X molecular sieve adsorbent loaded with Ag ion; the sliver element content is 3%-5% of the total weight of the adsorbent; and the silver element is in an ionic form. The preparation method of the modified gasoline desulfurization adsorbent comprises the following steps of: roasting and pre-treating adsorbent carrier particle materials; carrying out ion exchange between the carrier particles with the soluble silver salt; washing the loaded carrier particles; drying the particle materials; and roasting and activating the dried particles. According to the modified gasoline desulfurization adsorbent and the preparation method thereof disclosed by the invention, the adsorbent carrier is easily available and cheap; the preparation method is simple and easy to implement; the service life of the adsorbent is longer and can be circulated and regenerated; and the regenerated adsorbent has better desulfurization performances.
Description
Technical field
The present invention relates to a kind of gasoline desulphurization sorbent and preparation method thereof, particularly relate to gasoline desulphurization sorbent of a kind of modification and preparation method thereof.
Background technology
The ultra-deep desulfurization of gasoline has become a major issue that needs to be resolved hurrily in world wide.Combustion of sulfur in gasoline generates oxysulfide (SO
x) be one of pollutant main in atmosphere, it is discharged in air can form acid rain, destroys ecological environment.In addition, sulfur oxide also can the corrosion and damage engine components, make motor-driven vehicle gas disposal catalyst poisoning, reduce its catalytic activity, increase the discharging of particulate pollutant, increase the weight of the pollution of urban environment.Therefore, the restriction sulfur content is an important indicator in automobile-used car gage, is also the key factor of estimating the gasoline cleaning degree.
At present, industrial main employing hydrodesulfurization technology (HDS) reduces sulfide in petrol content.Hydrodesulfurization is comparative maturity and a desulfur technology of large-scale application, sulfide content (approximately being down to 200-300 μ g/g) in can decrease gasoline is if but will carry out deep desulfuration with the more difficult realization of requirement (being not more than 50 μ g/g) to sulfur content of the gasoline standard that satisfies up-to-date formulation.This is that the hydrogenation reaction activity of the armaticity heterocycle sulfide such as thiophene and derivatives, benzothiophene and derivative thereof is very low because in the hydrogenation process of routine, Stability Analysis of Structures, and carbon-sulfur bond is difficult to fracture.If thiophene-type sulfide is reacted, need to more carry out the corresponding increase of equipment investment and operating cost under the exacting terms such as high reaction temperature, pressure and a large amount of noble metal catalysts.And deep hydrodesulfurizationof, under the condition that consumes a large amount of hydrogen, easily make the olefin saturated in gasoline, reduce the product octane number.Be difficult to problem to gasoline deep processing in order to solve hydrodesulfurization, a kind of desulfur technology that is rich in application prospect-adsorption desulfurize technology receives the concern of researcher.
The adsorption desulfurize technology have implement easily, the sulfur content of gasoline can be down to very low, the advantages such as loss of octane number is little, product yield is high, do not consume hydrogen, adsorbent recyclable regenerative, being particularly useful for removing the thiophene-type sulfide in gasoline, is the advanced technology of producing at present super low-sulfur oil.The research emphasis of adsorption desulfurize is selection and the preparation of sorbent material.The desulfuration adsorbent that exploitation has high selectivity and a high sulfur capacity is the key factor that can the adsorption desulfurize technology large-scale promotion application.The material category that is suitable as adsorbing agent carrier is a lot, such as molecular sieve, activated alumina, active carbon etc., and they all have stronger adsorption capacity.Therefore, select carrier and modification method for preparing particularly important according to adsorbate character and adsorption mechanism.The 13X molecular sieve is a kind of of zeolite molecular sieve, has the three-dimensional aluminosilicates metallic crystalline structure that the sial tetrahedron forms, and is a kind of strong polar adsorbent of pore size homogeneous.It has the advantages such as pore size homogeneous, specific area are large, good stability, is widely used in drying and the purification of gas, selexol process and as catalyst carrier.By suitable modification is carried out on 13X molecular sieve surface, introduce transition metal ions, the adsorbent of molecular sieve of metal is carried in preparation, and thiophene-type sulfide is had adsorption capacity preferably.
Summary of the invention
The object of the present invention is to provide gasoline desulphurization sorbent of a kind of modification and preparation method thereof, desulfurizing agent is for the adsorbing and removing of thiophene and derivatives and benzothiophene, use the 13X molecular sieve as adsorbing agent carrier, by the ion exchange in solution load silver ion on adsorbing agent carrier, through calcination activation, preparation selective desulfurization adsorbent is used for the thiophene-type sulfide that selective absorption removes gasoline.
The objective of the invention is to be achieved through the following technical solutions:
A kind of gasoline desulphurization sorbent of modification is used for deep removal gasoline thiophene and derivatives and benzothiophene, and described adsorbent is the 13X adsorbent of molecular sieve of loaded Ag ion, and the constituent content of silver is 3%～5% of adsorbent gross weight; Silver element is ionic state.
A kind of gasoline desulphurization sorbent preparation method of modification, described method comprises following preparation steps:
(a) the raw material roasting pretreatment of adsorbing agent carrier particle;
(b) make the carrier granular of step (a) and silver soluble salting liquid carry out ion-exchange;
(c) make carrier granular washing after the load of step (b);
(d) make the feed particulate material of step (c) dry;
(e) make the dried particle calcination activation of step (d).
The gasoline desulphurization sorbent preparation method of described a kind of modification, described adsorbing agent carrier particle is the 13X molecular sieve, and its bulk density is 0.66g/ml, and granularity is 2.0-2.8mm, rate of wear≤0.15%, Static Water is adsorbed as 24 %, and ethylene absorption is 18 %.
The gasoline desulphurization sorbent preparation method of described a kind of modification, the raw material sintering temperature of described adsorbing agent carrier particle is 300-370 ℃, and roasting time is 2.5-4h, and roasting is carried out under nitrogen protection.
The gasoline desulphurization sorbent preparation method of described a kind of modification, described silver soluble salting liquid is liquor argenti nitratis ophthalmicus, and concentration is 0.2mol/L, and ion-exchange time is 12h.
The gasoline desulphurization sorbent preparation method of described a kind of modification, described carrier granular washing is washed until eluate detects without silver ion for deionized water.
The gasoline desulphurization sorbent preparation method of described a kind of modification, described feed particulate material baking temperature is 100-120 ℃, be 8-12h drying time.
The gasoline desulphurization sorbent preparation method of described a kind of modification, the sintering temperature of described dried particle roasting is 400-500 ℃, roasting time is 5-6h.
Advantage of the present invention and effect are:
Adsorbing agent carrier of the present invention is easy to get and is cheap, and the preparation method is simple and easy to do, and the service life of adsorbent is longer, can circular regeneration, and the adsorbent after regeneration still has desulfurization performance preferably.Through the adsorption experiment detection, the thiophene-type sulfide in gasoline is had higher adsorbing and removing ability, cost is lower, and the adsorption process contamination-free produces, and good economic and practical is arranged, and meets environmental requirement.
The specific embodiment
The present invention is described in detail below in conjunction with embodiment.
The present invention rinses after the 13X molecular sieve is soaked 3-5h with deionized water repeatedly, then uses the alcohol solution dipping 2-3h of 70%-75%, and then uses deionized water rinsing, is placed on oven dry in vacuum drying chamber.
The 13X molecular sieve that cleaned is positioned in vacuum tube furnace, at N
2Heating rate with 3 ℃/min under atmosphere rises to 300 ℃, then rises to 370 ℃ with the speed of 5 ℃/min, keeps 2.5-4h at this temperature, is down to room temperature with identical speed after roasting finishes.
According to the certain density liquor argenti nitratis ophthalmicus of ion-exchange equivalent preparation, pretreated 13X molecular sieve is immersed in liquor argenti nitratis ophthalmicus, carry out ion-exchange 12h.After end to be exchanged, wash molecular sieve with deionized water, until eluate detects without silver ion.
Be positioned in vacuum drying chamber the molecular sieve after exchange dry.
Dried molecular sieve is positioned in vacuum tube furnace, at N
2Heating rate with 3 ℃/min under atmosphere rises to 300 ℃, then rises to 500 ℃ with the speed of 5 ℃/min, keeps 5-6h at this temperature, is down to room temperature with identical speed after roasting finishes, and obtains the 13X molecular sieve sweetneing adsorbent of load silver ion.
The adsorbing agent carrier that adopts in the present invention is the 13X molecular sieve that Tianjin southization catalyst Co., Ltd produces, its technical parameter is: bulk density is 0.66g/ml, and granularity is 2.0-2.8mm, rate of wear≤0.15%, Static Water is adsorbed as 24 %, and ethylene absorption is 18 %.
Embodiment 1:
The 13X adsorbent of molecular sieve of preparation load silver ion, and the thiophene in n-heptane solution is adsorbed.At first repeatedly rinse after the 13X molecular sieve being soaked 3-5h with deionized water, then use the alcohol solution dipping 2-3h of 70%-75%, and then use deionized water rinsing, be placed on oven dry in vacuum drying chamber.The 13X molecular sieve that cleaned is positioned in vacuum tube furnace, at N
2Heating rate with 3 ℃/min under atmosphere rises to 300 ℃, then rises to 370 ℃ with the speed of 5 ℃/min, keeps 2.5-4h at this temperature, is down to room temperature with identical speed after roasting finishes.According to the certain density liquor argenti nitratis ophthalmicus of ion-exchange equivalent preparation, pretreated 13X molecular sieve is immersed in liquor argenti nitratis ophthalmicus, carry out ion-exchange 12h.After end to be exchanged, wash molecular sieve with deionized water, until eluate detects without silver ion.Be positioned in vacuum drying chamber the molecular sieve after exchange dry.Dried molecular sieve is positioned in vacuum tube furnace, at N
2Heating rate with 3 ℃/min under atmosphere rises to 300 ℃, then rises to 500 ℃ with the speed of 5 ℃/min, keeps 5-6h at this temperature, is down to room temperature with identical speed after roasting finishes, and obtains the 13X molecular sieve sweetneing adsorbent of load silver ion.The preparation sulfur content be the thiophene, normal heptane mixed solution of 300 μ g/g as analog gasoline (MG-1), put into analog gasoline by certain finish than with adsorbent, adsorb the gasoline sample after filtration is adsorbed after reaching balance in closed container.With the sulfur content in the gas chromatographic analysis test sample that is equipped with the FPD detector.
Embodiment 2:
The 13X adsorbent of molecular sieve of preparation load silver ion, and the thiophene in n-heptane solution is adsorbed.At first repeatedly rinse after the 13X molecular sieve being soaked 3-5h with deionized water, then use the alcohol solution dipping 2-3h of 70%-75%, and then use deionized water rinsing, be placed on oven dry in vacuum drying chamber.The 13X molecular sieve that cleaned is positioned in vacuum tube furnace, at N
2Heating rate with 3 ℃/min under atmosphere rises to 300 ℃, then rises to 370 ℃ with the speed of 5 ℃/min, keeps 2.5-4h at this temperature, is down to room temperature with identical speed after roasting finishes.According to the certain density liquor argenti nitratis ophthalmicus of ion-exchange equivalent preparation, pretreated 13X molecular sieve is immersed in liquor argenti nitratis ophthalmicus, carry out ion-exchange 12h.After end to be exchanged, wash molecular sieve with deionized water, until eluate detects without silver ion.Be positioned in vacuum drying chamber the molecular sieve after exchange dry.Dried molecular sieve is positioned in vacuum tube furnace, at N
2Heating rate with 3 ℃/min under atmosphere rises to 300 ℃, then rises to 500 ℃ with the speed of 5 ℃/min, keeps 5-6h at this temperature, is down to room temperature with identical speed after roasting finishes, and obtains the 13X molecular sieve sweetneing adsorbent of load silver ion.The preparation sulfur content is that the benzothiophene, normal heptane mixed solution of 300 μ g/g is as analog gasoline (MG-2), put into analog gasoline by certain finish than with adsorbent, adsorb in closed container, filter the gasoline sample after being adsorbed after reaching balance.With the sulfur content in the gas chromatographic analysis test sample that is equipped with the FPD detector.
Embodiment 3:
The 13X adsorbent of molecular sieve of preparation load silver ion, and the thiophene in n-heptane solution is adsorbed.At first repeatedly rinse after the 13X molecular sieve being soaked 3-5h with deionized water, then use the alcohol solution dipping 2-3h of 70%-75%, and then use deionized water rinsing, be placed on oven dry in vacuum drying chamber.The 13X molecular sieve that cleaned is positioned in vacuum tube furnace, at N
2Heating rate with 3 ℃/min under atmosphere rises to 300 ℃, then rises to 370 ℃ with the speed of 5 ℃/min, keeps 2.5-4h at this temperature, is down to room temperature with identical speed after roasting finishes.According to the certain density liquor argenti nitratis ophthalmicus of ion-exchange equivalent preparation, pretreated 13X molecular sieve is immersed in liquor argenti nitratis ophthalmicus, carry out ion-exchange 12h.After end to be exchanged, wash molecular sieve with deionized water, until eluate detects without silver ion.Be positioned in vacuum drying chamber the molecular sieve after exchange dry.Dried molecular sieve is positioned in vacuum tube furnace, at N
2Heating rate with 3 ℃/min under atmosphere rises to 300 ℃, then rises to 500 ℃ with the speed of 5 ℃/min, keeps 5-6h at this temperature, is down to room temperature with identical speed after roasting finishes, and obtains the 13X molecular sieve sweetneing adsorbent of load silver ion.The preparation total sulfur content be the mixed solution of thiophene, 3 methyl thiophene, benzothiophene and normal heptane of 300 μ g/g as analog gasoline (MG-3), adsorb in preventing fixed bed adsorber.It is 8 mm that adsorbent is loaded into internal diameter, and length is in the adsorption column of 200 mm, and bed height is 80-120mm.With plunger displacement pump with analog gasoline be transported to adsorbent bed in, regularly collect the efflux sample in outlet.With the sulfur content in the gas chromatographic analysis test sample that is equipped with the FPD detector, calculate adsorbent to the adsorption capacity of each sulfur component.
Claims (8)
1. the gasoline desulphurization sorbent of a modification, be used for deep removal gasoline thiophene and derivatives and benzothiophene, it is characterized in that, described adsorbent is the 13X adsorbent of molecular sieve of loaded Ag ion, and the constituent content of silver is 3%～5% of adsorbent gross weight; Silver element is ionic state.
2. the gasoline desulphurization sorbent preparation method of a modification, is characterized in that, described method comprises following preparation steps:
(a) the raw material roasting pretreatment of adsorbing agent carrier particle;
(b) make the carrier granular of step (a) and silver soluble salting liquid carry out ion-exchange;
(c) make carrier granular washing after the load of step (b);
(d) make the feed particulate material of step (c) dry;
(e) make the dried particle calcination activation of step (d).
3. the gasoline desulphurization sorbent preparation method of a kind of modification according to claim 2, is characterized in that, described adsorbing agent carrier particle is the 13X molecular sieve, its bulk density is 0.66g/ml, and granularity is 2.0-2.8mm, rate of wear≤0.15%, Static Water is adsorbed as 24 %, and ethylene absorption is 18 %.
4. the gasoline desulphurization sorbent preparation method of a kind of modification according to claim 2, is characterized in that, the raw material sintering temperature of described adsorbing agent carrier particle is 300-370 ℃, and roasting time is 2.5-4h, and roasting is carried out under nitrogen protection.
5. the gasoline desulphurization sorbent preparation method of a kind of modification according to claim 2, is characterized in that, described silver soluble salting liquid is liquor argenti nitratis ophthalmicus, and concentration is 0.2mol/L, and ion-exchange time is 12h.
6. the gasoline desulphurization sorbent preparation method of a kind of modification according to claim 2, is characterized in that, described carrier granular washing is washed until eluate detects without silver ion for deionized water.
7. the gasoline desulphurization sorbent preparation method of a kind of modification according to claim 2, is characterized in that, described feed particulate material baking temperature is 100-120 ℃, and be 8-12h drying time.
8. the gasoline desulphurization sorbent preparation method of a kind of modification according to claim 2, is characterized in that, the sintering temperature of described dried particle roasting is 400-500 ℃, and roasting time is 5-6h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709685A (en) * | 2015-12-31 | 2016-06-29 | 浙江工业大学 | Method using SiO2-CoO composite aerogel as absorbent to remove thiophene sulfur in gasoline |
| CN110152597A (en) * | 2018-02-05 | 2019-08-23 | 山东星火科学技术研究院 | A kind of selective desulfurization adsorbent |
| CN110354809A (en) * | 2019-07-18 | 2019-10-22 | 浙江工业大学 | One kind is with SiO2- APTES-Ag composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil |
| CN115301297A (en) * | 2022-08-02 | 2022-11-08 | 陕西海斯夫生物工程有限公司 | Cation exchange resin loaded with nano silver particles, preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041771A (en) * | 2012-12-17 | 2013-04-17 | 沈阳化工大学 | Petrol deep desulfurization adsorbent and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041771A (en) * | 2012-12-17 | 2013-04-17 | 沈阳化工大学 | Petrol deep desulfurization adsorbent and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105709685A (en) * | 2015-12-31 | 2016-06-29 | 浙江工业大学 | Method using SiO2-CoO composite aerogel as absorbent to remove thiophene sulfur in gasoline |
| CN105709685B (en) * | 2015-12-31 | 2018-02-27 | 浙江工业大学 | One kind is with SiO2CoO composite aerogels are the method that adsorbent removes thiophene sulphur in gasoline |
| CN110152597A (en) * | 2018-02-05 | 2019-08-23 | 山东星火科学技术研究院 | A kind of selective desulfurization adsorbent |
| CN110354809A (en) * | 2019-07-18 | 2019-10-22 | 浙江工业大学 | One kind is with SiO2- APTES-Ag composite aerogel is the method that adsorbent removes thiophene-type sulfide in fuel oil |
| CN110354809B (en) * | 2019-07-18 | 2022-03-01 | 浙江工业大学 | By SiO2Method for removing thiophene sulfides in fuel oil by using-APTES-Ag composite aerogel as adsorbent |
| CN115301297A (en) * | 2022-08-02 | 2022-11-08 | 陕西海斯夫生物工程有限公司 | Cation exchange resin loaded with nano silver particles, preparation method and application thereof |
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Application publication date: 20130626 |