CN1133498C - Molecular sieve desulfurizer and its preparation - Google Patents
Molecular sieve desulfurizer and its preparation Download PDFInfo
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Abstract
The present invention relates to a molecular sieve type desulfurizer used for removing organic sulfides from liquefied petroleum gas or light oil products and a preparing method of the molecular sieve type desulfurizer. The main component of the desulfurizer is an X-shaped or Y-shaped molecular sieve prepared by modifying lanthanum with a high valence state, cerium with a high valence state or mixed light rare earth element cations with a high valence state, and the exchange degree of the metal cations with a high valence state is 70% to 95%. Specially, the desulfurizer can be used for directly removing neutral organic sulfides from liquefied petroleum gas or light oil products by adopting a physical adsorption method, the adsorption capacity is large, and the desulfurizing rate is high; in addition, the desulfurizer has the characteristics of long regeneration period, convenient regeneration, long service life and repeated regeneration and use.
Description
Technical field
The present invention relates to a kind of preparation method of molecular sieve type desulfurizing agent of the organic sulfur compound that is used for removing liquefied petroleum gas or light-end products.
Background technology
Along with the development of modern petrochemical technology, a lot of effective catalysts are more and more harsher to the content requirement of the sulphur in the raw material.On the other hand, environmental protection standard is more and more tighter, and the total sulfur content in the petrochemicals has been proposed stricter requirement.Sulphur in the petrochemicals can be divided into organic sulfur and inorganic sulfur.Inorganic sulfur mainly is a hydrogen sulfide, adopts different desulfurizing agents and corresponding sulfur removal technology to be easier to remove.Organic sulfur compound comprises nonpolar organic sulfur compounds (or claiming neutral organic sulfur compound) such as mercaptan polarity organic sulfur compound and thioether, thiophenol, sulphur oxygen carbon, carbon disulfide, thiophene, disulphide; The method of organic sulfide removal commonly used has hydro desulfurization and catalytic oxidation at present.Hydro desulfurization is to remove after the above-mentioned organic sulfur in the hydrocarbon ils (comprising liquefied petroleum gas, naphtha, catalytic gasoline, aviation kerosine, lam-oil, diesel oil) is hydroconverted into inorganic sulphide, and this method cost is higher.Catalytic oxidation is the thioether that mercaptan is changed into no stink, and disulfide etc. are used solvent extraction, but the precision of desulfurization can not satisfy the requirement that raw material contains low-sulfur.U.S. Pat 4204947 has been introduced a kind of method of smart removal of mercaptans, serviceability temperature height not only, and the regeneration condition harshness also can only remove mercaptan, and powerless to the organic sulfur of other form.Chinese patent CN 85103555A has introduced a kind of iron-manganese-zinc desulfurizing agent, though it has the advantage of organic sulfide removal kind wide ranges, desulfurization temperature is greater than 350 ℃, and so high desulfurization temperature then can't use for sweetening of hydrocarbons.
Molecular sieve has many purposes in physics, physical chemistry and chemical technology, be suitable as the separation that selective absorbent is finished each component in the mixture most, and as catalyst.Utilize X type molecular sieve to remove H in the natural gas
2S and mercaptan are existing to be used, but can not be used for removing neutral organic sulfur compound.U.S. Pat 5146039 has proposed the method that the cation-modified molecular sieve of a kind of usefulness removes the content sulfide in the hydrocarbon, the used molecular sieve of this method is by copper, silver, the zinc modified cation as A type, X type or Y zeolite, can only under the condition of heating, carry out desulfurization to containing the hydrocarbon that sulphur concentration is lower than 20ppm in the use, thereby its sulfur capacity is less.US5057473 has proposed a kind of desulfuration adsorbent of reproducible molecular sieve carrier, with copper and lanthanum successively as the modified cation of 13X type molecular sieve, ion-exchange used time of contact is 24 and 48 hours, the temperature of ion-exchange is room temperature and 75～80 ℃, the molecular sieve of exchange back gained is used for the total sulfur that comprises hydrogen sulfide of the hydrocarbon that flows is removed, in the experiment that removes fuel of internal combustion engine of being lifted under about 250 ℃ of temperature, can remove 60% total sulfur through 1 hour backflow; Adopt the chemisorbed method during this desulfuration adsorbent desulfurization, then adopt corresponding oxidized regenerating method during regeneration, thereby regeneration complexity and service life are shorter.
Summary of the invention
What the purpose of this invention is to provide that adsorption capacity is big in a kind of use, removal efficiency is high, regeneration is convenient, the life-span is grown directly removes the preparation method of the molecular sieve desulfurizer of the organic sulfur compound in liquefied petroleum gas or the light-end products with physisorphtion.
For realizing the molecular sieve desulfurizer of the object of the invention, its Main Ingredients and Appearance is modified X-type or the Y zeolite after high valence state metal cation exchange, and be characterized in: high valence state metal cation is lanthanum, cerium or mixed light rare earth element, and exchange degree is 70%～95%.
The exchange degree of above-mentioned modified X-type molecular sieve is 82%～95%.The exchange degree of preferred modified X-type molecular sieve is 82%～86%.
The exchange degree of above-mentioned Modified Zeolite Y is 70%～75%.The exchange degree of preferred Modified Zeolite Y is 70%～73.5%.
Preparation method for the molecular sieve desulfurizer of realizing the object of the invention comprises the steps: 1. to select for use X type or the former powder of Y zeolite; 2. prepare concentration and be the aqueous solution liquid in return of the high valence state metal cation that contains lanthanum, cerium or mixed light rare earth element of 0.05～0.2mol/l; 3. adopting ion-exchange, with exchange liquid molecular screen primary powder is carried out ion-exchanged, is 70%～95% until exchange degree, obtains modified X-type or Y zeolite.
Used molecular screen primary powder is the former powder of X type in the said method; The ion-exchange that adopts is a reverse-flow type normal pressure ion-exchange, and return time is 2～6 hours; With the filtration of molecular sieve powder, oven dry, roasting after the exchange, roasting time is 2～4 hours, and sintering temperature is 450～500 ℃; To adopt above-mentioned reverse-flow type normal pressure ion-exchange to carry out exchanging modification the second time through putting into above-mentioned exchange liquid after the cooling of the molecular sieve powder after the roasting, and make the exchange degree of modified X-type molecular sieve reach 82%～86%.Hocketing exchanges modification and roasting, can make the exchange degree of modified X-type molecular sieve reach 86%～95%.
Used molecular screen primary powder is the former powder of Y type in the said method; The ion-exchange that adopts is a reverse-flow type normal pressure ion-exchange, and return time is 2～6 hours; With the filtration of molecular sieve powder, oven dry, roasting after the exchange, roasting time is 2～4 hours, and sintering temperature is 450～550 ℃; To adopt above-mentioned reverse-flow type normal pressure ion-exchange to carry out exchanging modification the second time through putting into above-mentioned exchange liquid after the cooling of the molecular sieve powder after the roasting, and make the exchange degree of Modified Zeolite Y reach 70%～73.5%.Hocketing exchanges modification and roasting, can make the exchange degree of this property Y zeolite reach 73.6%～75%.
The ion-exchange that adopts in the said method is the high-pressure ion exchange process, and keeping the exchange temperature in high-pressure bottle is 150～300 ℃, and swap time 〉=3～4 hour make exchange degree reach 70%～95%.
Used molecular screen primary powder is the former powder of X-shaped in the above-mentioned high-pressure ion exchange process, and be 3～4 hours swap time, makes exchange degree reach 82～86%.
Used molecular screen primary powder is the former powder of X type in the above-mentioned high-pressure ion exchange process, and made exchange degree reach 86%～95% greater than 3～4 hours swap time.
Used molecular screen primary powder is the former powder of Y type in the above-mentioned high-pressure ion exchange process, and be 3～4 hours swap time, makes exchange degree reach 70%～73.5%.
Used molecular screen primary powder is the former powder of Y type in the above-mentioned high-pressure ion exchange process, and made exchange degree reach 73.6%～75% greater than 3～4 hours swap time.
The ion-exchange that adopts in the said method is a continous way normal pressure ion-exchange, makes exchange liquid flow through the fixed bed that molecular screen primary powder is housed from top to bottom, and the fixed bed temperature is 85～95 ℃, and the time is 3～10 days, makes exchange degree reach 70%～86%.
The used molecular screen primary powder of above-mentioned continous way normal pressure ion-exchange is the former powder of X type, and exchange degree is 82%～86%.
The used molecular screen primary powder of above-mentioned continous way normal pressure ion-exchange is the former powder of Y type, and exchange degree is 70%～73.5%.
The concentration that said method preferably exchanges liquid is 0.05～0.09mol/l.
The present invention has positive effect: (1) can carry out the characteristics of physical absorption based on molecular sieve, for overcoming it to the low shortcoming of neutral organic sulfur compound adsorption capacity, one aspect of the present invention is utilized the rare earth metal cation of high valence state, molecular sieve is carried out modification, make local location raising electrostatic field intensity in the molecular sieve pore passage, neutral sulfide molecules in the hydrocarbon material flow is polarized to be adsorbed easily thereby make, and has therefore improved adsorption capacity and adsorption efficiency to organic sulfur compound greatly; The present invention controls on the other hand and selects to make ion-exchange degree to reach 〉=70% degree, and molecular sieve is greatly improved the adsorption capacity and the adsorption efficiency of neutral organic sulfur compound.(2) because of molecular sieve of the present invention is applicable to organic sulfur, especially neutral organic sulfur compound are carried out jumbo physical absorption and desorption, so after being applied to produce, the desulfurization degree height, sulfur capacity is big, the regeneration period is long, regeneration technology is also more convenient, thereby greatly reduce production cost and operating cost, make industrial applications become possibility.Desulfurizing agent of the present invention can be widely used in organic sulfide removal in the hydrocarbon oil containing surphurs such as liquefied petroleum gas, gasoline, kerosene, diesel oil.Confirm that through industrial experiment it once penetrates Sulfur capacity greater than 1.5～2.5% (weight), iterative regenerable is more than 1000 times.(3) because of carrying out industrialization in the oil refining industry, the restriction sieve technology that the invention solves in the prior art or sulfur capacity is little or service life is short removes the bottleneck problem that neutral organic sulfur compound is used; So of the present invention applying will make the quality of hydrocarbon ils goods (also claiming oil product) be greatly improved, to adapt to the new social demand and the environmental requirement of continuous appearance.
Below in conjunction with specific embodiment and desulfurized effect test purpose of the present invention, principle and effect are described further.But content of the present invention is not limited to this fully.
In concrete implementation process, rare earth metal to be exchanged is prepared into nitrate or hydrochloride, nitrate or hydrochloride are made as the aqueous solution that exchanges liquid, the concentration of exchange liquid is 0.05～0.2mol/L, the concentration of preferred 0.05～0.09mol/L.Again molecular screen primary powder is contacted with the exchange liquid phase and make this property of molecular sieve, the method of modification adopts 1. reverse-flow type normal pressure ion-exchange: X type or Y zeolite reflux in exchange liquid repeatedly, through once filter, wash after the exchange, dry, high-temperature roasting, and then carry out exchanging the second time, so that repeated exchanged repeatedly is up to reaching required exchange degree.Exchange and high-temperature roasting hocket, and can improve exchange degree and exchange efficiency.2. continous way normal pressure ion-exchange: be contained in molecular sieve in the packed column or on the fixed bed, metal salt solution exchanged continuously by molecular sieve, reach necessary requirement until exchange degree.In order to improve exchange degree, can raise to the packed column heating by heat conducting method and exchange temperature.Preferred exchange temperature is 81 ℃～95 ℃.3. high-pressure ion exchange process is about to exchange liquid and molecular sieve places closed container, and ion-exchange is carried out in closed system, temperature can rise to about 150～300 ℃, and under corresponding temperature, pressure is also corresponding to be improved, exchange process is strengthened, improved exchange degree and exchange efficiency.
The specific embodiment
Embodiment 1,
Take by weighing the commercially available silica alumina ratio of 40g at 2.2 to 3.0 X type molecular screen primary powder, place the ground conical flask of 500ml, add in return that the 250ml concentration of liquid is the lanthanum nitrate hexahydrate of 0.09mol/L, the reverse-flow type normal pressure ion-exchange of employing is carried out swap operation: the conical flask that will be connected with return duct places and added hot reflux on the electric furnace 4 hours.Cooled and filtered, washing, oven dry, roasting is 2～4 hours in 490 ℃ of high temperature.After the cooling, carry out the swap operation second time, reflux after 3 hours, by analysis, record exchange degree and reach 86%.
At this moment, cooling, the molecular sieve powder that takes out after exchanging filter, wash, dry, and roasting is 2～4 hours in 490 ℃ of high temperature, makes finished product A.
Embodiment 2,
All the other are with embodiment 1, and difference is: exchange liquid is the cerous nitrate solution of 0.1mol/L, exchanges the back, exchange degree reaches 85%, makes finished product B.
Embodiment 3,
All the other are with embodiment 1, and difference is: exchange liquid is the mixed light rare earth nitrate solution of 0.15mol/L, makes exchange degree and reaches 82.5% finished product C.Mixed light rare earth is produced by rare earth factory of Baotou Iron and Steel Company, and in the mixed light rare earth nitrate solution, lanthanum nitrate accounts for 50%, cerous nitrate accounts for 21%, europium nitrate accounts for 0.175%.
If will obtain this property molecular sieve of higher exchange degree (for example from 86% to 95%), can exchange and roasting by same process once more or repeatedly by two finished product A, B or the C that hand over two roasting methods to obtain the foregoing description 1 to embodiment 3, meet the requirements of finished product until obtaining exchange degree.
Embodiment 4,
Take by weighing the commercially available silica alumina ratio of 50g at the former powder of 3.0 to 5.0 Y zeolite, place the ground conical flask of 500ml, add in return that the 300ml concentration of liquid is the lanthanum nitrate hexahydrate of 0.09mol/L, the reverse-flow type normal pressure ion-exchange of employing is carried out swap operation: the conical flask that will be connected with return duct places and added hot reflux on the electric furnace 5 hours.Cooled and filtered, washing, oven dry, roasting is 2～4 hours in 530 ℃ of high temperature.After the cooling, carry out the swap operation second time, reflux after 4 hours, by analysis, record ion-exchange degree and reach 73.5%.At this moment, cooling, the molecular sieve powder that takes out after exchanging filter, wash, dry, and roasting is 2～4 hours in 530 ℃ of high temperature, makes finished product D.
Embodiment 5,
All the other are with embodiment 4, and difference is: exchange liquid is the cerous nitrate solution of 0.1mol/L, exchanges the back, exchange degree reaches 72%, makes finished product E.
Embodiment 6,
All the other are with embodiment 4, and difference is: exchange liquid is the mixed light rare earth nitrate solution of 0.15mol/L, makes ion-exchange degree and reaches 70.5% finished product F.Mixed light rare earth is produced by rare earth factory of Baotou Iron and Steel Company, and in the mixed light rare earth nitrate solution, lanthanum nitrate accounts for 50%, cerous nitrate accounts for 21%, europium nitrate accounts for 0.175%.
If will obtain this property molecular sieve of higher exchange degree (for example from 73.6% to 75%), can exchange and roasting by same process once more or repeatedly by two finished product D, E or the F that hand over two roasting methods to obtain the foregoing description 4 to embodiment 6, meet the requirements of finished product until obtaining exchange degree.
Embodiment 7,
Take by weighing the X type molecular screen primary powder of 40g, add in the 500ml autoclave, add 0.11mol/L lanthanum nitrate hexahydrate 250ml, temperature rises to about 250 ℃, and ion-exchange is carried out in closed system, under corresponding temperature, pressure is also corresponding to be improved, and 4 hours swap times are naturally after the cooling, filter, washing, oven dry, 480 ℃ of roastings 2 hours, make finished product G.After measured, ion-exchange degree reaches 88%.
Embodiment 8,
Take by weighing the former powder of Y zeolite of 40g, add 500ml autoclave loyalty, add 0.06mol/L lanthanum nitrate hexahydrate 350ml, temperature rises to about 250 ℃, and ion-exchange is carried out in closed system, under corresponding temperature, pressure is also corresponding to be improved, and 3.5 hours swap times are naturally after the cooling, filter, washing, oven dry, 550 ℃ of roastings 2 hours, make finished product H.After measured, ion-exchange degree reaches 72%.
Embodiment 9,
Take by weighing the X type molecular screen primary powder of 50g, molecular screen primary powder is contained in the packed column, with method rising exchange column (or fixed bed) temperature of heating wire energising heating.The exchange temperature of control molecular sieve is about 90 ℃.Preparation 0.06mol/L lanthanum nitrate hexahydrate makes lanthanum nitrate hexahydrate splash into molecular sieve continuously from top to bottom and exchanges, and continues exchange 5 days, and after measured, ion-exchange degree reaches 83%.
Embodiment 10,
Take by weighing the former powder of Y zeolite of 50g, molecular screen primary powder is contained in the packed column, with the temperature of the method rising exchange column of heating wire energising heating.The exchange temperature of control molecular sieve is about 90 ℃.Preparation 0.08mol/L lanthanum nitrate hexahydrate makes lanthanum nitrate hexahydrate splash into molecular sieve continuously from top to bottom and exchanges, and continues exchange 6 days, and after measured, ion-exchange degree reaches 70%.
Embodiment 11 to 16,
Relevant temperature, time, concentration conditions are identical with embodiment 1 to embodiment 6, and difference is, relevant equipment and material consumption are amplified 10～100 times.When carrying out the swap operation second time, after recording ion-exchange degree and reaching requirement numerical value, cooling, the molecular sieve powder that takes out after exchanging filter, wash, dry by the fire to moisture about 20%, the shape of the sphere of required mechanical strength, cylindrical, sheet or cloverleaf pattern is made in machine-shaping, carries out the finished product desulfurizing agent (especially removing neutral organic sulfur compound) that roasting promptly makes the removal of organic sulfur that is used for petroleum refining process again.
Embodiment 17 to 18,
Relevant temperature, time, concentration conditions are identical with embodiment 7 to embodiment 8, and difference is, relevant equipment and material consumption are amplified 10～100 times.When carrying out swap operation, after recording ion-exchange degree and reaching requirement numerical value, cooling, the molecular sieve powder that takes out after exchanging filter, wash, dry by the fire to moisture about 20%, the shape of the sphere of required mechanical strength, cylindrical, sheet or cloverleaf pattern is made in machine-shaping, carries out the finished product desulfurizing agent (especially removing neutral organic sulfur compound) that roasting promptly makes the removal of organic sulfur that is used for petroleum refining process again.
For obtaining bigger adsorption capacity and better adsorption effect, should note when preparing desulfurizing agent of the present invention following some:
1. the preferred X type molecular sieve of molecular sieve, the X type is compared with Y zeolite, and X type molecular sieve silica alumina ratio is low, and tradable cation is more than Y zeolite.The high-valence cationic that X type molecular sieve exchanges up is more than the Y type, so the adsorption capacity of modification X molecular sieve is greater than Modified Zeolite Y.
2. preferred La
3+Ion in return, because in the used high-valence cationic of modification, La
3+The polarity of the molecular sieve after the ion-exchange is the strongest, so adsorption capacity is bigger.
3. the exchange back requires exchange degree 〉=82% for this property X type molecular sieve, requires exchange degree 〉=70% for this property Y zeolite.The molecular sieve of modification is made the desulfuration adsorbent of the sphere of required mechanical strength, cylindrical, sheet or cloverleaf pattern through further machine-shaping.For increasing to the intensity of product desulfurizing agent, after modification, can add an amount of binding agent in the molecular sieve powder, as sweet soil of sheep etc., addition is not more than 30% (wt) of desulfurizing agent gross weight.
4. modification also can be adopted well-known with the product method of substitution.
Desulfurized effect is estimated:
The evaluation test of test desulfurizing agent is carried out in the pressurization evaluating apparatus, the reaction tube diameter 13MM of pressurization evaluating apparatus, and desulfurizing agent is respectively above-mentioned finished product A～H, and granularity is 40 orders, and charge weight is 10ml.Experimental condition: air speed is 2h
-1Temperature is 20～25 ℃; Pressure is 0.8MPa.Allow the liquefied petroleum gas that the contains organic sulfur compound reaction tube by the pressurization evaluating apparatus, (lowest detection amount 〉=0.2ppm) detects the content of sulphur with Microcoulomb instrument to the liquefied petroleum gas of import and export.
The liquefied petroleum gas that experimental raw is used is the C-4-fraction after gas divides, and total sulfur content is 40ppm, wherein H
2S content is 0.Organic sulfur comprises: C
3H
6S, C
4H
8S, C
4H
10S, C
5H
12S, C
6H
14S, C
7H
16S, C
2H
6S
2, C
3H
8S
2, C
4H
10S
2, C
5H
12S
2, C
2H
6S
3, C
4H
7NS.C in the organic sulfur
2H
6S
2≈ 72%, C
3H
8S
2≈ 8%, C
2H
6S
3≈ 14%, all the other ≈ 6%.
Result of the test sees Table 1.
Table 1: desulfurized effect contrast table
What different samples after modification and unmodified X type and Y zeolite desulfurized effect were mainly investigated in evaluation test relatively reaches the influence of regeneration to the desulfurizing agent desulfurized effect.In the process of the test, think when sulphur exists that when outlet has detected desulfurizing agent penetrates, the Sulfur capacity of this moment is for penetrating Sulfur capacity.
Data by table 1 can find out, it once penetrates the molecular sieve after the modification Sulfur capacity and improved 5～10 times than X type or the former powder of Y zeolite.
Regeneration tests: sample A, B, C, D, E, F, G, the H of sulfur-bearing are regenerated with 300 ℃ of high temperature nitrogen purgings, and the regeneration air speed is 500h
-1, regenerating, desulfuration efficiency still is more than 95% of original state after 50 times.
Claims (14)
1, a kind of preparation method of molecular sieve desulfurizer comprises the steps: 1. to select for use X type or the former powder of Y zeolite; 2. prepare concentration and be the aqueous solution liquid in return of the high valence state metal cation that contains lanthanum, cerium or mixed light rare earth element of 0.05～0.2mol/l; 3. adopting ion-exchange, with exchange liquid molecular screen primary powder is carried out ion-exchanged, is 70%～95% until exchange degree, obtains modified X-type or Y zeolite.
2, preparation method as claimed in claim 1 is characterized in that: used molecular screen primary powder is the former powder of X type; The ion-exchange that adopts is a reverse-flow type normal pressure ion-exchange, and return time is 2～6 hours; With the filtration of molecular sieve powder, oven dry, roasting after the exchange, roasting time is 2～4 hours, and sintering temperature is 450～500 ℃; To adopt above-mentioned reverse-flow type normal pressure ion-exchange to carry out exchanging modification the second time through putting into above-mentioned exchange liquid after the cooling of the molecular sieve powder after the roasting, and make the exchange degree of modified X-type molecular sieve reach 82%～86%.
3, preparation method as claimed in claim 2 is characterized in that: hocket exchange modification and roasting make the exchange degree of modified X-type molecular sieve reach 86%～95%.
4, preparation method as claimed in claim 1 is characterized in that: used molecular screen primary powder is the former powder of Y type; The ion-exchange that adopts is a reverse-flow type normal pressure ion-exchange, and return time is 2～6 hours; With the filtration of molecular sieve powder, oven dry, roasting after the exchange, roasting time is 2～4 hours, and sintering temperature is 450～550 ℃; To adopt above-mentioned reverse-flow type normal pressure ion-exchange to carry out exchanging modification the second time through putting into above-mentioned exchange liquid after the cooling of the molecular sieve powder after the roasting, and make the exchange degree of Modified Zeolite Y reach 70%～73.5%.
5, preparation method as claimed in claim 4 is characterized in that: hocket exchange modification and roasting make the exchange degree of Modified Zeolite Y reach 73.6%～75%.
6, preparation method as claimed in claim 1 is characterized in that: the ion-exchange of employing is the high-pressure ion exchange process, and keeping the exchange temperature in high-pressure bottle is 150～300 ℃, and swap time 〉=3～4 hour make exchange degree reach 70%～95%.
7, preparation method as claimed in claim 6 is characterized in that: molecular screen primary powder is the former powder of X type, and be 3～4 hours swap time, makes exchange degree reach 82%～86%.
8, preparation method as claimed in claim 6 is characterized in that: molecular screen primary powder is the former powder of X type, and made exchange degree reach 86%～95% greater than 3～4 hours swap time.
9, preparation method as claimed in claim 6 is characterized in that: molecular screen primary powder is the former powder of Y type, and be 3～4 hours swap time, makes exchange degree reach 70%～73.5%.
10, preparation method as claimed in claim 6 is characterized in that: molecular screen primary powder is the former powder of Y type, and made exchange degree reach 73.6%～75% greater than 3～4 hours swap time.
11, preparation method as claimed in claim 1, it is characterized in that: the ion-exchange of employing is a continous way normal pressure ion-exchange, make exchange liquid flow through the fixed bed that molecular screen primary powder is housed from top to bottom, the fixed bed temperature is 85～95 ℃, time is 3～10 days, makes exchange degree reach 70%～86%.
12, preparation method as claimed in claim 11 is characterized in that: molecular screen primary powder is the former powder of X type, and exchange degree is 82%～86%.
13, preparation method as claimed in claim 11 is characterized in that: molecular screen primary powder is the former powder of Y type, and exchange degree is 70%～73.5%.
14, as the described preparation method of one of claim 1 to 13, it is characterized in that: the concentration of exchange liquid is 0.05～0.09mol/l.
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| CN101805640B (en) * | 2010-05-13 | 2012-12-26 | 天津大学 | High-temperature coal gas desulfurizing agent of composite oxides of mesoporous rare soil and preparation method thereof |
| CN103252211B (en) * | 2012-02-16 | 2016-08-10 | 中国石油天然气股份有限公司 | Molecular sieve desulfurizer and preparation method thereof |
| CN103816864B (en) * | 2013-10-29 | 2016-07-06 | 中国石油化工股份有限公司 | A kind of for removing adsorbent of disulphide and preparation method thereof in liquid hydrocarbon |
| CN105800642A (en) * | 2016-03-02 | 2016-07-27 | 江苏奥石科技有限公司 | Lanthanum-containing X type molecular sieve and preparation method thereof |
| CN108543515B (en) * | 2018-05-07 | 2021-03-02 | 辽宁石油化工大学 | Preparation method and application of REY molecular sieve adsorbent for ultra-deep removal of thiophene sulfides in gasoline |
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