CN104667861B - A kind of sulfur method of the desulfuration adsorbent for gasoline and gasoline - Google Patents
A kind of sulfur method of the desulfuration adsorbent for gasoline and gasoline Download PDFInfo
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Abstract
The present invention provides the sulfur method of a kind of desulfuration adsorbent for gasoline and gasoline。The desulfuration adsorbent of the present invention, molecular sieve and activated carbon by processing through alkali respectively obtain as composite carrier load active metal components, wherein, described active metal one or more elements in periodic chart IA, IIA, VIII, IB, IIB and group vib。This desulfuration adsorbent Sulfur capacity is big, long service life, and this external regeneration process is simple。
Description
Technical field
The present invention relates to a kind of desulfuration adsorbent, particularly relate to the sulfur method of a kind of desulfuration adsorbent for gasoline and gasoline。
Background technology
Chinese commodity gasoline have about 70% to originate from heavy oil catalytic cracking process, owing to heavy oil feedstock contains substantial amounts of sulfur, nitrogen, oxygen heteroatom compound and gum asphalt, catalytically cracked gasoline not only sulfur content is high, possibly together with substantial amounts of olefin component, in merchantable gasoline, the sulfur of more than 90% comes from catalytically cracked gasoline, and this makes the sulfur content of China's gasoline will far beyond the sulfur content of external gasoline。Therefore, how reducing Sulfur Content in Catalytic Cracking Gasoline is the key reducing merchantable gasoline sulfur content。Particularly the whole nation on January 1st, 2018 is about in state five gasoline quality standard carried out regulation gasoline sulfure content not higher than 10ppm, explore and promote deep desulfurization of gasoline technology become petroleum refining industry in the urgent need to。
The desulfurization technology that oil refining industry adopts is divided into hydrodesulfurization and non-hydrodesulfurization, and wherein hydrodesulfurization is present main desulfurization approach, but when only sulfur content being down under 10ppm by this technique, a large amount of saturation of olefins cause octane number to be greatly lowered。Non-hydrodesulfurization is divided into again the technology such as absorption desulfurization, oxidation sweetening, abstraction desulfurization, biological desulphurization, research absorption desulfurization technology widely at present, because it carries out when normal temperature and pressure, energy consumption is low, octane number loses hardly, is one of potential deep desulfuration approach。
For absorption desulfurization technology, the absorption Sulfur capacity of adsorbent and selectivity are cores。By the selection of carrier and active metal and compatibility being optimized the performance of these two aspects, being the focus of research, also having the report that comparison is many。
The IRVAD technology developed jointly by Black&VeatchPritchardInc. and AlcoaIndustrialChemicals adopts multistage fluidized bed suction type, alumina host selectivity solid absorbent is used to process liquid hydrocarbon, in adsorption process, adsorbent adverse current contacts with liquid hydrocarbon, and reverse the reaction with regenerated heat air-flow (such as hydrogen) of used adsorbent is regenerated。The desulfurization degree of this technology is up to more than 90%, but this adsorbent selectivity is not high, and absorption Sulfur capacity is limited, and regenerative process relative complex。
The S-Zorb technique of Phillips oil company research and development is to adopt a kind of specific adsorbent to carry out desulfurization when facing hydrogen, this adsorbent is using zinc oxide, silicon dioxide, aluminium oxide as carrier and the metal component such as load C o, Ni, Cu, it can adsorb the sulphur atom in sulfide, so as to retain on the sorbent, the hydrocarbon moieties of sulfide is then discharged back in process-stream, thus realizing sweetening process。This technique does not produce H in course of reaction2S, thus avoiding H2S and alkene react generation mercaptan again。But, this desulfurization technical matters operating condition is relatively harsh, and the temperature of desulphurization reaction is 343～413 DEG C, and pressure is 2.5～2.9MPa。
The process for purification of notification number a kind of inferior patrol that has been the patent disclosure of CN1162515C, its adsorbent adopts alkali metal or exchanged X, Y, L or β zeolite of alkaline-earth metal ions, and desorbing agent adopts C1～C5Little molecular fat alcohols, ethers, one or more mixture in ketone compounds；After inferior patrol adsorbs with adsorbent contact at 20～250 DEG C, saturated adsorbent purges first with blowing medium, carries out desorption and regeneration followed by desorbing agent。The method desulfurization concentration is limited, and inferior patrol sulfur content after refining can be down to 100 μ g/g。
Publication number is the preparation method of a kind of modified activated carbon adsorption desulfurizing agent of patent disclosure of CN101804325A, it is with cocoanut active charcoal for carrier, add the oxidants such as concentrated nitric acid, concentrated sulphuric acid or Ammonium persulfate. and be modified back loading copper, silver, nickel, cerium isoreactivity component, activity component metal oxide content accounts for the 1-20% of activated carbon weight, namely obtains desulfurizing agent after drying。This desulfurizing agent is low to the selectivity of sulfur, and Sulfur capacity is limited, and sorbent life is shorter in addition。
In sum, not enough below adsorption desulfurizing agent ubiquity of the prior art: 1, desulfurization depth is inadequate, it is difficult to take off sulfur to below 5ppmw；2, adsorbent specific surface area is relatively low, and absorption Sulfur capacity is relatively limited；3, the operating condition of sweetening process is harsh and energy consumption big, and operating cost is higher；4, sweetening process is unfriendly to environment；5, the selectivity of desulfurizing agent is low, and the life-span is shorter；6, complex process during desulfurizer regeneration。Up to now, there is no the adsorption desulfurizing agent overcoming above-mentioned multiple deficiency preferably。
Summary of the invention
The present invention provides the sulfur method of a kind of desulfuration adsorbent for gasoline and gasoline, and this desulfuration adsorbent at least has the advantages such as Sulfur capacity is big, long service life, renovation process are simple。
The present invention provides a kind of desulfuration adsorbent for gasoline, molecular sieve and activated carbon by processing through alkali respectively obtain as composite carrier load active metal components, wherein, described active metal one or more elements in periodic chart IA, VIII, IB, IIB and group vib。
In complex carrier of the present invention, the mass ratio of molecular sieve and activated carbon is (20-80): (80-20), it is preferred to (20-60): (80-40)。
Further, the type of described molecular sieve is X-type, Y type or ZSM-5 type。The present invention to adopted X-type and type ZSM 5 molecular sieve without strict restriction；The framework silicon-aluminum atomic ratio of described Y type molecular sieve is not less than 3.0 (xrd method mensuration)。Additionally, the activated carbon that the present invention is to adopting is without strict restriction, its specific surface generally can be 1000m2About/g。
In the present invention, the active metal selected from periodic chart IA race is such as potassium (K), sodium (Na) etc.；Active metal selected from periodic chart VIII is such as ferrum (Fe), cobalt (Co), nickel (Ni) etc.；Active metal selected from periodic chart IB race is such as copper (Cu), silver (Ag) etc.；Active metal selected from periodic chart Group IIB is such as zinc (Zn) etc.；Active metal selected from periodic chart group vib is such as molybdenum (Mo) etc.。
Further, described active metal is selected from least 2 kinds in Ni, Fe, Ag, Co, Mo, Zn and K。Wherein, Ni load capacity on complex carrier can be 10-30%；Fe load capacity on complex carrier can be 5-15%；Ag load capacity on complex carrier can be 5-10%；Co load capacity on complex carrier can be 5-10%；Mo load capacity on complex carrier can be 5-10%；Zn load capacity on complex carrier can be 5-15%；K load capacity on complex carrier can be 5-15%。This load capacity is the load capacity on every kind of each comfortable complex carrier of active metal。
Further, described active metal load capacity on complex carrier is 2-30%, it is preferred to 5-25%, more preferably 5-20%。On complex carrier during the two or more active metal of load, described load capacity is the total load amount of active metal。
In one embodiment, described active metal is K and Ni；Further, K load capacity on complex carrier is 5-15%, the Ni load capacity on complex carrier is 10-25%；Further, on complex carrier, the mass ratio of K and the Ni of load is (0.2-0.5): 1。
In another embodiment, described active metal is Zn and Fe；Further, Zn load capacity on complex carrier is 5-15%, the Fe load capacity on complex carrier is 8-15%；Further, on complex carrier, the mass ratio of Zn and the Fe of load is (0.5-1): 1。
The preparation method that the present invention also provides for a kind of above-mentioned desulfuration adsorbent, comprises the following steps:
The molecular sieve processed through alkali respectively and activated carbon are made complex carrier in proportion；
The described complex carrier soluble salt solutions of described active metal is impregnated, by roasting after the dry materials after dipping, obtains described desulfuration adsorbent。
In one embodiment, described alkali process include respectively to molecular sieve and activated carbon according to molecular sieve or activated carbon: alkali: water be (0.1-2): (0.05-2): the mass ratio of (4-15) mixes, and remain dry after stir process 0.1-24h under the temperature conditions of 0-120 DEG C, and described alkali-treated journey includes at least one times。
Alkali is processed the alkali adopted without strict restriction by the present invention, for instance can adopt the NaOH solution of 0.10-1.0mol/L。Further, the temperature of stir process can be 30-100 DEG C, and the time can be 1-10h；Further, the temperature of stir process can be 70-80 DEG C, and the time can be 2-4h。Dry temperature after described stir process such as can be 100-120 DEG C, and the time can be such as 5-8h。Described alkali-treated journey can be once or twice。
In the present invention, the soluble salt solutions of described active metal can be such as sulfate liquor, nitrate solution etc., it is preferred to sulfate liquor。Described dipping can be incipient impregnation, it is the impregnation method that this area is conventional, concrete operations can be such as: when normal gentle agitation, the soluble salt solutions of described active metal is dripped in described complex carrier, until complex carrier aggregates into spherical, then stand a period of time (such as 1-3h)。Particularly, on complex carrier during two kinds of active metal components of load, on described complex carrier, first impregnate the soluble salt solutions of the first active metal, after scrubbed, dry and roasting, impregnate the soluble salt solutions of the second active metal again, scrubbed, dry and roasting, can be prepared by the complex carrier of two kinds of active metal components of load。
During dipping, can require according to the load capacity on each comfortable complex carrier of above-mentioned various active metals and active metal total load amount on complex carrier requires that (the two or more active metal components of load) converts each active metal soluble-salt consumption when dipping。
Further, drying as 12-24h dry at 90-120 DEG C the material after dipping, it is preferred to dry 18-24h at 110-120 DEG C。To carrying out roasting after the dry materials after dipping at 450-640 DEG C of roasting 4-6h。
Further, described to when carrying out roasting after the dry materials after dipping, including dried material being cooled to room temperature, being first warming up to 400 DEG C with 6 DEG C/min speed, then being warming up to 450-640 DEG C with 3 DEG C/min speed。
The present invention also provides for the sulfur method of a kind of gasoline, including: utilizing the desulfuration adsorbent described in any of the above-described item that gasoline carries out absorption desulfurization, described absorption desulfurization is to utilize fixed bed atmospheric pressure to carry out, and the temperature controlling absorption desulfurization is 20-100 DEG C, for instance 30-80 DEG C。Particularly, when carrying out absorption desulfurization, the flow velocity controlling gasoline is 0.3-1mL/min, for instance for 0.5mL/min。
Further, described gasoline can be catalytically cracked gasoline。
The present invention also provides for the renovation process of a kind of any of the above-described described desulfuration adsorbent, and including described desulfuration adsorbent order to be regenerated carries out steam washing, the nitrogen of 200-400 DEG C dries, and nitrogen cooling。
Further, described renovation process, first adopt 130-180 DEG C of steam purging 1-3h to wash including to described desulfuration adsorbent to be regenerated, then adopt 200-400 DEG C of nitrogen to purge 10-60min and be dried, finally adopt the nitrogen of room temperature to purge 10-60min and cool down。
The enforcement of the present invention, at least has the advantage that
1, the desulfuration adsorbent of the present invention adopts the molecular sieve processed through alkali respectively and activated carbon as complex carrier, and the specific active metal components of load on this complex carrier, not only Sulfur capacity big, to the selectivity of sulfur is good and also desulfurization depth is high, sulfur can be taken off to 1ppmw (by mass 1/1000000th)；In addition long service life, environment is comparatively friendly。
2, the desulfuration adsorbent of present invention process condition when gasoline carries out desulfurization is gentle, can carrying out, thus having saved energy consumption, reducing running cost under normal pressure and lower temperature。
3, the desulfuration adsorbent renovation process of the present invention is simple, easily operated, and the desulfuration adsorbent of regeneration is before use without hydrogen reducing, environmental protection and economy；In addition desulfuration adsorbent can repeatedly regenerate, and remains able to maintain good desulfurized effect after regeneration。
Accompanying drawing explanation
Fig. 1 is the type ZSM 5 molecular sieve of embodiment 1 adsorption/desorption isotherms before and after alkali processes；
Fig. 2 is the type ZSM 5 molecular sieve of embodiment 1 pore size distribution curve before and after alkali processes。
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearly, below in conjunction with embodiments of the invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that, described embodiment is a part of embodiment of the present invention, rather than whole embodiments。Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention。
Embodiment 1
1, the molecular sieve through alkali process and activated carbon are prepared
By NaOH solution warming-in-water that two parts of 500mL concentration is 0.3mol/L to after about 70 DEG C, it is added thereto to the type ZSM 5 molecular sieve of 25g and the activated carbon of 25g respectively, after stirring about 200 minutes, immediately mixture ice bath is down to room temperature, filter and use deionized water filtration washing filter cake repeatedly, until the pH value of filter liquor is after about 7, gained filter cake is placed in the baking oven of 110 DEG C dry 4h, prepares the type ZSM 5 molecular sieve processed through alkali and the activated carbon processed through alkali respectively；Wherein, type ZSM 5 molecular sieve alkali process before and after adsorption/desorption isotherms and pore size distribution curve see Fig. 1 and Fig. 2 respectively。
Additionally, adopt the automatic physical adsorption appearance of ASAP2000 type to measure specific surface area and the pore-size distribution of type ZSM 5 molecular sieve and activated carbon, result is as shown in table 1。
The specific surface area of table 1ZSM-5 type molecular sieve and activated carbon and aperture
As shown in Figure 1: alkali ZSM-5 molecular sieve before treatment shows the distinctive I type isothermal line of micropore character, and its desorption isotherm almost overlaps with adsorption isotherm；And the ZSM-5 molecular sieve after alkali process shows the obvious IV type isothermal line of feature, it presents lasting adsorbed state in whole measurement pressure limit until saturation pressure, and first along with the slow desorption of the reduction of pressure during desorption, when pressure reaches a certain value, desorption rate increases suddenly, form comparatively precipitous change curve, continuation then as pressure reduces and overlaps with adsorption isotherm, thus creates mesoporous (mesopore) in a large number in the ZSM-5 molecular sieve after the process of explanation alkali。
As shown in Figure 2, alkali ZSM-5 molecular sieve before treatment, mainly based on micropore, had wider distribution before 2nm, had a small peak at 3.5nm place, there is no that hole occurs after 4nm, and using the calculated average pore size of t-plot method is about 2.3nm；ZSM-5 molecular sieve after alkali process still had partial pore to be distributed before 2nm, and had a strong peak, place, peak height to be almost alkali at about 3.8nm and process about 11 times of front ZSM-5 molecular sieve, also have comparatively wide in range pore size distribution after 4nm。
Meanwhile, table 1 result shows: the type ZSM 5 molecular sieve mesopore volume and the average pore size that process through alkali enlarge markedly, and illustrate that a large amount of micropore is changed into mesopore, thus forming mesoporous and micropore composite pore structural；The total specific surface area of activated carbon, total pore volume, mesopore volume and the average pore size that process through alkali all increase to some extent。
2, complex carrier is prepared
By the above-mentioned type ZSM 5 molecular sieve through alkali process with after the activated carbon of alkali process mixes according to mass ratio 40:60, it is placed in mortar and grinds to form powdery, be subsequently placed in the baking oven of 120 DEG C and dry 6h, prepare complex carrier。
3, desulfuration adsorbent is prepared
First adopt K2SO4The complex carrier of above-mentioned preparation is carried out incipient impregnation by solution, scrubbed, dry and after roasting, then adopts NiSO4To impregnating K2SO4The complex carrier of solution carries out incipient impregnation, scrubbed, dry and after roasting, prepares desulfuration adsorbent；
Above-mentioned washing, dry and roasting are particularly as follows: by after the material deionized water wash after dipping, 120 DEG C dry 20 hours, after dried material is cooled to room temperature, are first warming up to 400 DEG C with the speed of 6 DEG C/min, it is warming up to 550 DEG C again, roasting 4 hours at 550 DEG C with the speed of 3 DEG C/min。
In the desulfuration adsorbent of above-mentioned preparation, K load capacity on complex carrier is about 5%, and Ni load capacity on complex carrier is about 10%, and on complex carrier, the mass ratio of K and the Ni of load is 0.5:1。
Embodiment 2
1, the molecular sieve through alkali process and activated carbon are prepared
By NaOH solution warming-in-water that two parts of 500mL concentration is 0.2mol/L to after about 80 DEG C, it is added thereto to the Y type molecular sieve of 25g and the activated carbon of 25g respectively, after stirring about 120 minutes, immediately mixture ice bath is down to room temperature, filter and use deionized water filtration washing filter cake repeatedly, until the pH value of filter liquor is after about 7, gained filter cake is placed in the baking oven of 120 DEG C dry 3h, prepares the Y type molecular sieve processed through alkali and the activated carbon processed through alkali respectively；Specific surface area and the pore-size distribution of Y type molecular sieve and activated carbon are as shown in table 2。
The specific surface area of table 2Y type molecular sieve and activated carbon and aperture
2, complex carrier is prepared
By the above-mentioned Y type molecular sieve through alkali process with after the activated carbon of alkali process mixes according to mass ratio 20:80, it is placed in mortar and grinds to form powdery, be subsequently placed in the baking oven of 110 DEG C and dry 6h, prepare complex carrier。
3, desulfuration adsorbent is prepared
First adopt ZnSO4The complex carrier of above-mentioned preparation is carried out incipient impregnation by solution, scrubbed, dry and after roasting, then adopts Fe2(SO4)3To impregnating ZnSO4The complex carrier of solution carries out incipient impregnation, scrubbed, dry and after roasting, prepares desulfuration adsorbent；
Above-mentioned washing, dry and roasting are particularly as follows: by after the material deionized water wash after dipping, 110 DEG C dry 24 hours, after dried material is cooled to room temperature, are first warming up to 400 DEG C with the speed of 6 DEG C/min, it is warming up to 450 DEG C again, roasting 6 hours at 450 DEG C with the speed of 3 DEG C/min。
In the desulfuration adsorbent of above-mentioned preparation, Zn load capacity on complex carrier is about 10%, and Fe load capacity on complex carrier is about 10%, and on complex carrier, the mass ratio of Zn and the Fe of load is 1:1。
Embodiment 3
1, the molecular sieve through alkali process and activated carbon are prepared
By NaOH solution warming-in-water that two parts of 500mL concentration is 0.3mol/L to after about 80 DEG C, it is added thereto to the X-type molecular sieve of 25g and the activated carbon of 25g respectively, after stirring about 180 minutes, immediately mixture ice bath is down to room temperature, filter and use deionized water filtration washing filter cake repeatedly, until the pH value of filter liquor is after about 7, gained filter cake is placed in the baking oven of 100 DEG C dry 6h, prepares the X-type molecular sieve processed through alkali and the activated carbon processed through alkali respectively。
2, complex carrier is prepared
By the above-mentioned X-type molecular sieve through alkali process with after the activated carbon of alkali process mixes according to mass ratio 30:70, it is placed in mortar and grinds to form powdery, be subsequently placed in the baking oven of 120 DEG C and dry 6h, prepare complex carrier。
3, desulfuration adsorbent is prepared
First adopt K2SO4The complex carrier of above-mentioned preparation is carried out incipient impregnation by solution, scrubbed, dry and after roasting, then adopts NiSO4To impregnating K2SO4The complex carrier of solution carries out incipient impregnation, scrubbed, dry and after roasting, prepares desulfuration adsorbent；
Above-mentioned washing, dry and roasting are particularly as follows: by after the material deionized water wash after dipping, 120 DEG C dry 18 hours, after dried material is cooled to room temperature, are first warming up to 400 DEG C with the speed of 6 DEG C/min, it is warming up to 640 DEG C again, roasting 5 hours at 640 DEG C with the speed of 3 DEG C/min。
In the desulfuration adsorbent of above-mentioned preparation, K load capacity on complex carrier is about 5%, and Ni load capacity on complex carrier is about 15%, and on complex carrier, the mass ratio of K and the Ni of load is 0.3:1。
Embodiment 4
1, the molecular sieve through alkali process and activated carbon are prepared
By NaOH solution warming-in-water that two parts of 500mL concentration is 0.2mol/L to after about 70 DEG C, it is added thereto to the type ZSM 5 molecular sieve of 25g and the activated carbon of 25g respectively, after stirring about 90 minutes, immediately mixture ice bath is down to room temperature, filter and use deionized water filtration washing filter cake repeatedly, until the pH value of filter liquor is after about 7, gained filter cake is placed in the baking oven of 120 DEG C dry 3h；
The activated carbon of the type ZSM 5 molecular sieve sum repeat the above steps respectively once (namely alkali processes twice) that will obtain, prepares the type ZSM 5 molecular sieve processed through alkali and the activated carbon through alkali process；Specific surface area and the pore-size distribution of type ZSM 5 molecular sieve and activated carbon are as shown in table 3。
The specific surface area of table 3ZSM-5 type molecular sieve and activated carbon and aperture
2, complex carrier is prepared
By the above-mentioned type ZSM 5 molecular sieve through alkali process with after the activated carbon of alkali process mixes according to mass ratio 20:80, it is placed in mortar and grinds to form powdery, be subsequently placed in the baking oven of 100 DEG C and dry 8h, prepare complex carrier。
3, desulfuration adsorbent is prepared
First adopt ZnSO4The complex carrier of above-mentioned preparation is carried out incipient impregnation by solution, scrubbed, dry and after roasting, then adopts Fe2(SO4)3To dipping ZnSO4The complex carrier of solution carries out incipient impregnation, scrubbed, dry and after roasting, prepares desulfuration adsorbent；
Above-mentioned washing, dry and roasting are particularly as follows: by after the material deionized water wash after dipping, 120 DEG C dry 20 hours, after dried material is cooled to room temperature, are first warming up to 400 DEG C with the speed of 6 DEG C/min, it is warming up to 600 DEG C again, roasting 6 hours at 600 DEG C with the speed of 3 DEG C/min。
In the desulfuration adsorbent of above-mentioned preparation, Zn load capacity on complex carrier is about 5%, and Fe load capacity on complex carrier is about 10%, and on complex carrier, the mass ratio of Zn and the Fe of load is 0.5:1。
Comparative example 1
According to the preparation of embodiment 1 method after the type ZSM 5 molecular sieve that alkali processes, successively adopt K according to embodiment 1 method2SO4Solution and NiSO4This type ZSM 5 molecular sieve processed through alkali is carried out incipient impregnation by solution, and wash, dry, roasting, prepared desulfuration adsorbent。
Comparative example 2
According to the preparation of embodiment 1 method after the activated carbon that alkali processes, successively adopt K according to embodiment 1 method2SO4Solution and NiSO4This activated carbon processed through alkali is carried out incipient impregnation by solution, and wash, dry, roasting, prepared desulfuration adsorbent。
Comparative example 3
After directly the type ZSM 5 molecular sieve (processing without alkali) of embodiment 1 and activated carbon (processing without alkali) being mixed according to mass ratio 40:60, it is placed in mortar and is ground, be subsequently placed in the baking oven of 120 DEG C and dry 6h, prepare complex carrier。
Successively K is adopted according to embodiment 1 method2SO4Solution and NiSO4This complex carrier is carried out incipient impregnation by solution, and wash, dry, roasting, prepare desulfuration adsorbent。
Embodiment 5
Respectively desulfuration adsorbent prepared by above-described embodiment 1-4 and comparative example 1-3 is filled in fixed bed reactors, with Jinan catalytically cracked gasoline for raw material (its composition is in Table 4), it is under 30 DEG C and condition of normal pressure in temperature, the absorption desulfurization test of continuous 10 hours is implemented respectively with the flow velocity of 0.5mL/min, absorption Desulfurization Test Results is in Table 5, wherein Sulfur capacity is the total sulfur content (in gram) that 1g desulfuration adsorbent removes when the total sulfur content in gasoline stocks is down to below 10ppmw, such as, when Sulfur capacity is 0.514, representing the total sulfur content removed when the total sulfur content in gasoline stocks is down to below 10ppmw by 1g desulfuration adsorbent is 0.514g。
The composition of table 4 feed gasoline
The absorption Desulfurization Test Results of table 5 desulfuration adsorbent
As seen from the results in Table 5:
1, the adsorption desulfurizing agent desulfurization depth that prepared by the present invention is high, the sulfur in feed gasoline can be down to below 1ppmw in 4-5 hour in absorption desulfurization, and service life is up to about 8h；Additionally, its adsorption desulfurizing agent Sulfur capacity is big, particularly that the selectivity of thiophene and derivatives is good。
2, individually adopting when the molecular sieve of alkali process is as carrier, the service life of adsorption desulfurizing agent is greatly shortened；Individually adopting when the activated carbon of alkali process is as carrier, adsorption desulfurizing agent is low to the selectivity of sulfur；And during using the molecular sieve processed without alkali and activated carbon as complex carrier, Sulfur capacity is less, and service life is short。
Embodiment 6
Using the desulfuration adsorbent of embodiment 1-4 according to embodiment 5 method desulfurization to working sulfur capacity (i.e. adsorbent lost efficacy) as desulfuration adsorbent to be regenerated, steam purging is first adopted to wash desulfuration adsorbent to be regenerated, then adopt nitrogen to purge to be dried, the nitrogen finally adopting room temperature purges and cools down, and regeneration technology parameter is in Table 6。
Desulfuration adsorbent after regeneration repeats absorption desulfurization and regeneration according to embodiment 5 method, adopts and implements three absorption desulfurization and regenerate the desulfuration adsorbent after three times, carries out absorption desulfurization according to embodiment 5 method, and absorption Desulfurization Test Results is in Table 7。
The regeneration technology parameter of table 6 desulfuration adsorbent
Table 7 desulfuration adsorbent regenerates the absorption Desulfurization Test Results after three times
As seen from the results in Table 7:
After adopting above-mentioned renovation process that the desulfuration adsorbent of the present invention carries out repeatedly regeneration, desulfuration adsorbent remains able to maintain higher Sulfur capacity and good desulfurized effect。
Last it is noted that various embodiments above is only in order to illustrate technical scheme, it is not intended to limit；Although the present invention being described in detail with reference to foregoing embodiments, it will be understood by those within the art that: the technical scheme described in foregoing embodiments still can be modified by it, or wherein some or all of technical characteristic is carried out equivalent replacement；And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme。
Claims (8)
1. the desulfuration adsorbent for gasoline, it is characterized in that, molecular sieve and activated carbon by processing through alkali respectively obtain as composite carrier load active metal components, wherein, described active metal one or more elements in K, Ni, Zn and Fe, in described complex carrier, the mass ratio of molecular sieve and activated carbon is (20-80): (80-20), described active metal load capacity on complex carrier is 2-30%。
2. desulfuration adsorbent according to claim 1, it is characterised in that the type of described molecular sieve is X-type, Y type or ZSM-5 type。
3. the preparation method of the desulfuration adsorbent described in claim 1 or 2, it is characterised in that comprise the following steps:
The molecular sieve processed through alkali respectively and activated carbon are made complex carrier in proportion；
The described complex carrier soluble salt solutions of described active metal is impregnated, by roasting after the dry materials after dipping, obtains described desulfuration adsorbent。
4. preparation method according to claim 3, it is characterized in that, described alkali process include respectively to molecular sieve and activated carbon according to molecular sieve or activated carbon: alkali: water be (0.1-2): (0.05-2): the mass ratio of (4-15) mixes, and remain dry after stir process 0.1-24h under the temperature conditions of 0-120 DEG C, and described alkali-treated journey includes at least one times。
5. preparation method according to claim 3, it is characterised in that to carrying out roasting after the dry materials after dipping at 450-640 DEG C of roasting 4-6h。
6. preparation method according to claim 5, it is characterized in that, described to when carrying out roasting after the dry materials after dipping, it is cooled to room temperature including by dried material, first it is warming up to 400 DEG C with 6 DEG C/min speed, then is warming up to 450-640 DEG C with 3 DEG C/min speed。
7. the sulfur method of a gasoline, it is characterised in that including: utilizing the desulfuration adsorbent described in claim 1 or 2 that gasoline carries out absorption desulfurization, described absorption desulfurization is to utilize fixed bed atmospheric pressure to carry out, and the temperature controlling absorption desulfurization is 20-100 DEG C。
8. the renovation process of the desulfuration adsorbent described in claim 1 or 2, it is characterised in that include described desulfuration adsorbent order to be regenerated is carried out steam washing, the nitrogen of 200-400 DEG C dries, and nitrogen cooling。
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510059630.0A CN104667861B (en) | 2015-02-04 | 2015-02-04 | A kind of sulfur method of the desulfuration adsorbent for gasoline and gasoline |
| PCT/CN2015/075887 WO2016123860A1 (en) | 2015-02-04 | 2015-04-03 | Gasoline deep desulfurization method |
| PCT/CN2015/075886 WO2016123859A1 (en) | 2015-02-04 | 2015-04-03 | Desulfurization adsorbent for petrol and petrol desulfurization method |
| PCT/CN2015/075888 WO2016123861A1 (en) | 2015-02-04 | 2015-04-03 | Method for upgrading catalytic cracking gasoline |
| US14/929,247 US9683183B2 (en) | 2015-02-04 | 2015-10-30 | Method for deep desulfurization of gasoline |
| US14/931,690 US10011779B2 (en) | 2015-02-04 | 2015-11-03 | Adsorbent for desulfurization of gasoline and method for desulfurization of gasoline |
| US14/940,027 US10266778B2 (en) | 2015-02-04 | 2015-11-12 | Method for upgrading fluid catalytic cracking gasoline |
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| CN108217650B (en) * | 2018-02-06 | 2021-04-09 | 西南石油大学 | Device for preparing activated carbon and performing adsorption desulfurization |
| CN110152612A (en) * | 2018-03-01 | 2019-08-23 | 济南开发区星火科学技术研究院 | A kind of crude oil absorption desulfurization desulfurizing agent |
| CN108795475A (en) * | 2018-07-10 | 2018-11-13 | 济南开发区星火科学技术研究院 | A kind of cracking gasoline process for adsorption desulfuration |
| CN113797869A (en) * | 2021-11-16 | 2021-12-17 | 天津天大天海化工新技术有限公司 | Carbon nine desulfurization method for ethylene cracking by using ultrasound |
| CN114146682A (en) * | 2021-12-10 | 2022-03-08 | 上海绿强新材料有限公司 | Renewable adsorbent for hydrogen sulfide removal and preparation method thereof |
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