CN105505458A - Production method of low-sulfur gasoline with high octane value - Google Patents
Production method of low-sulfur gasoline with high octane value Download PDFInfo
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Abstract
The invention discloses a production method of a low-sulfur gasoline with a high octane value. The method comprises the following steps: introducing raw materials (gasoline and hydrogen gas) into a reactor, contacting the raw materials with a desulfurization adsorbent to carry out adsorption desulfurization so as to obtain low-sulfur gasoline gas and a desulfurization adsorbent to be generated; subjecting the low-sulfur gasoline to a treatment to remove n-alkane so as to obtain a gasoline product rich in non-normal alkane, and burning, oxidizing, regenerating, reducing, and recycling the adsorbent to be generated. Through the technical scheme mentioned above, the sulfur content of the gasoline product is reduced after the adsorption desulfurization and n-alkane removal treatment; the octane value of gasoline is increased on the basis that the alkene content of gasoline is not changed, (or the octane value can be maintained in a certain range under the situation that the alkene content of gasoline is reduced); and the separated n-alkane can be used a chemical raw material with a high additional value.
Description
Technical field
The present invention relates to a kind of production method of high-octane rating low-sulphur oil.
Background technology
Gasoline octane rating is a kind of numerical index weighing gasoline Ulva Pertusa burning capacity in cylinder, and its value height represents that anti-knocking property are good.
Along with the increasingly stringent of world's environmental regulation, each state is all improving constantly the quality standard of gasoline products.Content of sulfur in gasoline and olefin(e) centent are the important indicators weighing gasoline cleaning degree, consider to require that the sulphur content gasoline and olefin(e) centent are more low better from the angle of environmental protection.
At present in gasoline desulfur technology, what economically feasible, application were ripe has catalytic gasoline selective hydrogen addition technology, catalytic distillation technology and adsorption desulfurize technology.Gasoline hydrodesulfurizationmethod (back end hydrogenation) technology is at the bottom of a kind of cost of investment, hydrogen consumption less and effectively can reduce the method for content of sulfur in gasoline.The olefin(e) centent reduced in gasoline is also by adopting the method for selective hydrogenation to realize usually.But, no matter be hydrogenating desulfurization, or selective hydrogenation and olefin hydrocarbon removal, all can, because of the alkene in gasoline by significantly hydrotreated lube base oil, cause gasoline octane rating to lose serious.
In the method for traditional raising gasoline octane rating, one improves the octane value of gasoline by adding high-octane number component such as methyl tertiary butyl ether (MTBE), aromatic hydrocarbons etc. in the oil, but the aromatic hydrocarbons etc. added may have disadvantageous effect to the quality of gasoline or to environmental protection; Another kind is the production technique by optimizing gasoline, in catalytic cracking reaction process, such as introduce octane enhancing additive to obtain stop bracket gasoline, but in the method, the raising of gasoline octane rating is normally because the increase of olefin(e) centent in gasoline causes, and does not meet the requirement of modern environmental protection to gasoline low olefin-content.
Therefore, in the urgent need to a kind of production method of new high-octane rating low-sulphur oil.
Summary of the invention
The object of this invention is to provide a kind of production method of new high-octane rating low-sulphur oil.
The method comprises: (1) feed gasoline and hydrogen enter reactor, contacts with the desulfuration adsorbent entering reactor, carries out adsorption desulfurize reaction, obtains low-sulphur oil oil gas and desulfuration adsorbent to be generated; (2) described low-sulphur oil gas-oil separation is obtained low-sulphur oil, this low-sulphur oil is carried out the process of de-normal paraffin, obtain the gasoline products that non-n-alkane content is 80-100 % by weight; (3) desulfuration adsorbent to be generated after carrying sulphur enters fluid bed regenerator, regenerates with rejuvenating gas contacts; (4) desulfuration adsorbent after regeneration enters in reducer, reduces with reducing gas; (5) desulfuration adsorbent after reduction returns this reactor bottom fluidized-bed reactor.
Preferably, wherein in step (2) described gasoline products, the content of non-n-alkane is 90-100 % by weight, non-n-alkane of the present invention refers to other component in gasoline except normal paraffin, comprises isoparaffin, naphthenic hydrocarbon, alkene, aromatic hydrocarbons etc.
Preferably, wherein comprise from the process of described de-normal paraffin: the fractionation by adsorption of described low-sulphur oil being carried out absorptive separation column normal paraffin.
Preferably, wherein said fractionation by adsorption is carried out in the absorptive separation column that many groups are in parallel, and each group absorptive separation column comprises the absorptive separation column of 1-3 series connection.
Preferably, the sorbent material that wherein said fractionation by adsorption is used is be selected from least one in 5A molecular sieve, silica gel and aluminum oxide; The condition of adsorption operations is: temperature 220-350 DEG C, pressure 0.2-1.0MPa, volume space velocity 0.5-2.0 hour during feeding liquid
-1, the residence time is 10-500 second.
Preferably, wherein said fractionation by adsorption also comprises: desorbing agent is passed into absorptive separation column and carry out desorption manipulation.
Preferably, the desorbing agent that wherein said fractionation by adsorption is used is be selected from least one in nitrogen, hydrogen, ammonia steam, water vapor, carbonic acid gas, methane, Sweet natural gas and refinery gas; The temperature of desorption manipulation is 150-400 DEG C, and desorbing agent feed volume air speed is 30-70 hour
-1, desorption time is 2-8 minute.
Preferably, wherein the process of the described de-normal paraffin of step (2) comprises: in described low-sulphur oil, add urea carry out urea clathration reaction, obtain inclusion reaction mixture; From described inclusion reaction mixture, filter to isolate urea inclusion, obtain described gasoline products.
Preferably, the operational condition of wherein said urea clathration reaction is: feed intake mass ratio 1-3, the temperature of reaction 20-60 DEG C of urea and feed gasoline, inclusion reaction time 15-40 minute.
Preferably, step (2) also comprises: be urea inclusion described in the hot-water cure of 60-98 DEG C by temperature, reclaims and obtains normal paraffin.
Preferably, the process of the described de-normal paraffin of step (2) comprises: described low-sulphur oil is gone out normal paraffin by solvent extraction and separation.
Preferably, wherein said solvent-extracted operational condition is: extraction solvent for use is 1-5 with being extracted quality of gasoline ratio, extraction time 1-10 minute, temperature-30 is to-1 DEG C, and extraction solvent for use is be selected from one or more in hydrochloric ether, ether, ester and ketone.
Preferably, wherein said desulfuration adsorbent comprises zinc oxide, silicon oxide and aluminum oxide, and this desulfuration adsorbent is also containing nickel and/or cobalt.
Preferably, the condition of wherein said adsorption desulfurize reaction is: temperature 250-450 DEG C, pressure 0.2-4MPa, weight hourly space velocity 0.5-80 hour
-1, hydrogen to oil volume ratio is 0.01-1000Nm
3/ m
3.
Preferably, the condition of wherein said adsorption desulfurize reaction is: temperature 300-400 DEG C, pressure 0.8-3MPa, weight hourly space velocity 4-50 hour
-1, hydrogen to oil volume ratio is 1-600Nm
3/ m
3.
Preferably, the condition of wherein said coke burning regeneration is: temperature is 500-800 DEG C, and pressure is 0.1-4MPa; Catalyst residence times 5-40 minute; Described oxygenous atmosphere is using the air of air, nitrogen dilution or oxygen rich gas as fluidizing medium.
Preferably, the condition of wherein said coke burning regeneration is: temperature is 580-700 DEG C, and pressure is 0.1-1MPa, catalyst residence times 15-30 minute.
Preferably, the condition of wherein said reduction treatment is: temperature 200-600 DEG C, pressure 0.1-4.0MPa, catalyst residence times 30-200 minute; Described reducing atmosphere is for fluidizing medium with the reduzate of hydrogen.
Preferably, the condition of wherein said reduction treatment is, temperature is 300-500 DEG C, and pressure is 0.1-3.0MPa, catalyst residence times 60-150 minute.
Preferably, wherein said feed gasoline is be selected from least one in catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and pressure gasoline.
Preferably, the boiling range of wherein said feed gasoline is 30-220 DEG C.
The present invention looks for another way, and is different from prior art and improves octane value by adding high-octane number component in gasoline, but is reached the object improving gasoline octane rating by the low octane rating component reduced in gasoline.By technique scheme of the present invention, the gasoline products sulphur content obtained through adsorption desulfurize process, de-normal paraffin process reduces, and make the octane value of gasoline be improved when not improving content of olefin in gasoline, or appropriateness can also keep the octane level of gasoline when content of olefin in gasoline reduces, and the isolated normal paraffin of institute is all right as very useful industrial chemicals.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the schematic flow sheet of the production method of high-octane rating low-sulphur oil according to a kind of embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of production method of new high-octane rating low-sulphur oil, the method comprises: feed gasoline and hydrogen are entered this reactor by (1) bottom fluidized-bed reactor, with the desulfuration adsorbent counter current contact entered from reactor head, carry out adsorption desulfurize reaction, obtain low-sulphur oil oil gas and desulfuration adsorbent to be generated; (2) described low-sulphur oil oil gas drawn from reactor head and obtain low-sulphur oil after condensation, this low-sulphur oil being carried out the process of de-normal paraffin, obtain the gasoline products that non-n-alkane content is 80-100 % by weight; (3) sweetening agent to be generated after carrying sulphur enters fluid bed regenerator, regenerates with rejuvenating gas contacts; (4) desulfuration adsorbent after regeneration enters in reducer, reduces with reducing gas; (5) desulfuration adsorbent after reduction returns this reactor bottom fluidized-bed reactor.
According to the present invention, in step (2) described gasoline products, the content of non-n-alkane is 90-100 % by weight.
A kind of preferred implementation of the present invention is: the process of the described de-normal paraffin of step (2) comprises: the fractionation by adsorption of gained low-sulphur oil being carried out in absorptive separation column normal paraffin.
The preferred embodiment of one of the present invention is: described fractionation by adsorption can be carried out in the absorptive separation column that many groups are in parallel, preferably carries out in 2-5 group absorptive separation column; Each group absorptive separation column can comprise the absorptive separation column of 1-3 series connection.Absorptive separation column parallel connection use is the treatment capacity in order to improve raw material, and the adsorption and desorption process of fractionation by adsorption can be enable to hocket; Absorptive separation column series connection use is the separating effect in order to improve normal paraffin and non-n-alkane, the suction excess oil obtained after primary sorption is separated, again through fractionation by adsorption, obtain having the suction excess oil of more high-content non-n-alkane, thus improve the octane value inhaling excess oil; The quantity of the absorptive separation column that series and parallel connections uses can be determined according to actual needs.
According to the present invention, described fractionation by adsorption sorbent material used can use known by those skilled in the art can the sorbent material of routine of selective adsorption normal paraffin, the present invention has no particular limits it.Under preferable case, described sorbent material be selected from 5A molecular sieve, silica gel, aluminum oxide one or several.The critical diameter of normal paraffin molecule is about 0.49nm, and isoparaffin, naphthenic hydrocarbon and aromatic hydrocarbon are all at more than 0.55nm, so, effective pore radius 0.50-0.54nm porous material especially molecular sieve can use as sorbent material of the present invention.Effective pore radius due to 5A molecular sieve is 0.51nm, between normal paraffin molecule and the critical diameter of non-n-alkane molecule, therefore normal paraffin is only had can to enter its duct, thus normal paraffin can be separated from mixture, therefore more preferably, described sorbent material is 5A molecular sieve.
According to the present invention, the condition of described adsorption operations can be: temperature 220-350 DEG C, pressure 0.2-1.0MPa, volume space velocity 0.5-2.0 hour during feeding liquid
-1, the residence time is 10-500 second.
According to the present invention, wherein said fractionation by adsorption also comprises: desorbing agent is passed into absorptive separation column and carry out desorption manipulation.
According to the present invention, described desorbing agent can for being selected from least one in nitrogen, hydrogen, ammonia steam, water vapor, carbonic acid gas, methane, Sweet natural gas and refinery gas; The temperature of desorption manipulation is 150-400 DEG C, and desorbing agent feed volume air speed is 30-70 hour
-1, desorption time is 2-8 minute.
As another preferred embodiment of the present invention, the process of the described de-normal paraffin of step (2) comprises: in described low-sulphur oil, add urea carry out urea clathration reaction, obtain inclusion reaction mixture; From described inclusion reaction mixture, filter to isolate urea inclusion, obtain described gasoline products.Normal paraffin can form channel-style inclusion compound with urea, and isoparaffin, naphthenic hydrocarbon and aromatic hydrocarbons can not form inclusion compound with urea clathration, and this principle therefore can be utilized to be separated from feed gasoline by normal paraffin.
According to the present invention, utilize the character that urea is soluble in water, the normal paraffin of inclusion in urea can be separated, can use temperature be such as that the hot water of 60-98 DEG C processes isolated described urea inclusion, recovery obtains normal paraffin, and gained normal paraffin can also as very useful industrial chemicals.In addition for the isolated aqueous solution of urea of the present invention; can adopt and well known to a person skilled in the art that technique means reclaims the urea in aqueous solution of urea; such as utilize the reduction of the solubility with temperature of urea in water and this character reduced; urea is cooled separate out; thus reach the object reclaiming urea; reduce production cost, and be conducive to environment protection.
According to the present invention, urea clathration is an exothermic process, is conducive to inclusion reaction at lesser temps, and excess urea can make inclusion reaction balance move right.Therefore under preferable case, the operational condition of urea clathration can be: feed intake mass ratio 1-3, the temperature of reaction 20-60 DEG C of urea and feed gasoline, inclusion reaction time 15-40 minute.
As another preferred embodiment of the present invention, the process of the described de-normal paraffin of step (2) comprises: described low-sulphur oil is gone out normal paraffin by solvent extraction and separation, is separated and obtains being rich in the solvent phase of normal paraffin and being rich in the gasoline products of non-n-alkane; To the isolated solvent phase being rich in normal paraffin, can pass through heating and gasifying solvent, solvent is separated with normal paraffin, the solvent that obtains is reclaimed in condensation can recycle, isolated normal paraffin can use as industrial chemicals, and wherein said Heating temperature is 30-80 DEG C.
According to the present invention, utilize solvent under low temperature to the different solubility of the non-n-alkane in feed gasoline and normal paraffin, employing solvent selectivity extracts, by the normal paraffin extracting and separating in feed gasoline, obtain the gasoline products being rich in non-n-alkane, under preferable case, the operational condition of described extracting and separating is: the mass ratio of extraction solvent for use and feed gasoline is 1-5, extraction time 1-10 minute, temperature-30 is to-1 DEG C.
According to the present invention, according to rule of similarity, preferably, extraction solvent for use is at least one in hydrochloric ether, ether, ester and ketone.
According to the present invention, the sorbent material for desulfurization that described desulfuration adsorbent can be known to the skilled person, such as load metal oxide sorbent material or be loaded with the load metal oxide sorbent material of metallic promoter agent, wherein, load metal oxide sorbent material can comprise zinc oxide, silicon oxide and aluminum oxide, described load metal oxide sorbent material also comprises nickel and/or cobalt, with the gross weight of sorbent material for benchmark, the content of zinc oxide is the heavy % of 10-85, the content of silicon oxide is the heavy % of 5-80, the content of aluminum oxide is the heavy % of 5-30, surplus is nickel and/or cobalt.
In the present invention, the operational condition of described adsorption desulfurize is: temperature 250-450 DEG C, pressure 0.2-4MPa, weight hourly space velocity 0.5-80 hour
-1, hydrogen to oil volume ratio is 0.01-1000Nm
3/ m
3.Under preferable case, the operational condition of adsorption desulfurize is: temperature 300-400 DEG C, pressure 0.8-3MPa, weight hourly space velocity 4-50 hour
-1, hydrogen to oil volume ratio is 1-600Nm
3/ m
3.
It should be noted that, the operational condition of described adsorption desulfurize and used catalyst etc. all according to the requirement of product to sulphur content, can be determined by those of ordinary skill in the art, and the present invention has no particular limits.
According to the present invention, the condition of described coke burning regeneration is well-known to those skilled in the art, and the present invention has no particular limits it.Such as, the condition of described coke burning regeneration can be: temperature is 500-800 DEG C, and pressure is 0.1-4MPa, catalyst residence times 5-40 minute; Described oxygenous atmosphere is using the air of air, nitrogen dilution or oxygen rich gas as fluidizing medium.Under preferable case, the condition of described coke burning regeneration is: temperature is 580-700 DEG C, and pressure is 0.1-1MPa, catalyst residence times 15-30 minute.
According to the present invention, the locking hopper that is regenerated catalyst through of drawing from revivifier is first delivered to fluidized bed reducer, and reduction treatment is carried out under reducing atmosphere in reducer, obtain reducing catalyst, to make the active desulfurization component that the high-valence state metal oxide back be oxidized in catalyzer is lower valency, then this reducing catalyst is turned back in described reactor continuously.The condition of described reduction treatment can be determined according to the situation of used catalyzer, and this is the known and understandings of those skilled in the art, the present invention to this without the need to being described in detail.Such as, the condition of described reduction treatment can be: temperature 200-600 DEG C, pressure 0.1-4.0MPa, catalyst residence times 30-200 minute; Described reducing atmosphere is for fluidizing medium with the reduzate of hydrogen.Under preferable case, the condition of described reduction treatment is: temperature is 300-500 DEG C, and pressure is 0.1-3.0MPa, catalyst residence times 60-150 minute.
In the present invention, described feed gasoline is be selected from least one in catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and pressure gasoline.
In the present invention, the boiling range of described feed gasoline is 30-220 DEG C.
Below by way of accompanying drawing, the present invention will be described.
Provided by the inventionly preferred embodiment press flow process shown in Fig. 1 and realize.
According to the flow process shown in Fig. 1, sulfur-bearing feed gasoline after preheating and hydrogen enter bottom reactor 2 through pipeline 1, contact with the desulfuration adsorbent in reactor, the strainer of reactor head is entered after desulfurization, carry out finish separation, feed gasoline after desulfurization and hydrogen are sent to the separation system 23 of follow-up de-normal paraffin through pipeline 3, isolate octane value low be rich in normal paraffin component, obtain the low-sulphur oil that octane value improves, the low-sulphur oil of the component and octane value raising that are rich in normal paraffin is exported by pipeline 24 and 25 respectively as product.Reacted desulfuration adsorbent to be generated draws off from reactor bottom and is sent to spent agent receptor 5 through pipeline 4, after air lift, once locking hopper 8 is sent to through pipeline 6 and 7 in spent agent receptor 5, after nitrogen replacement, change low pressure inert environment into from hydrogen gas environment, displacement gas is sent to roasting kiln through pipeline 9 and burns.Desulfuration adsorbent to be generated is then once delivered to spent agent charging stock tank 12 through pipeline 10 and 11, pipeline 13 by being equipped with guiding valve between spent agent charging stock tank 12 with revivifier 15 is connected, and desulfuration adsorbent to be generated enters fluid bed regenerator 15 through riser tube and controls to enter into the speed of revivifier by guiding valve.Oxygen-containing gas enters into revivifier by pipeline 14 from regenerator bottoms, desulfuration adsorbent to be generated also flows with oxygen-containing gas and contacts through burning sulphur in revivifier 15, the desulfuration adsorbent after regenerating is obtained after burning carbon, sulfur-containing smoke gas is delivered to sulphur system processed through pipeline 16 after regenerator overhead is separated with regenerative sulfur binding sorbent material or alkali cleaning removes SOx, regenerative sulfur binding sorbent material is transported to regenerator receptor 18 from revivifier top emulsion zone through pipeline 17, promote with nitrogen and be delivered to locking hopper 8 through pipeline 19 and 7 successively, replace by hydrogen air lift in locking hopper 8 and change hydrogen gas environment into after boosting, be delivered in reducer 21 through pipeline 10 and 20 successively and carry out reduction treatment, regenerative sulfur binding sorbent material after reduction treatment is delivered to the top of reactor 2 by pipeline 22, realize carrying out continuously of desulfuration adsorbent reaction.
Following embodiment and reference example are further elaborated to the present invention.But the present invention is not therefore subject to any restriction.
In each embodiment and comparative example, the feed gasoline used is a kind of catalytically cracked gasoline, and its character is as shown in table 1.
Table 1
| Density (20 DEG C), g/cm3 | 0.7620 |
| Boiling range (ASTM D86), DEG C | 45-220 |
| Initial boiling point | 45 |
| Final boiling point | 220 |
| Sulphur content, μ g/g | 1400 |
| Alkene, volume % | 25.7 |
| RON | 90 |
In various embodiments, the olefin(e) centent in gasoline measures according to the method for gas chromatography analysis method (ASTMD6733-01 (2011)); The research octane number (RON) (RON) of gasoline measures according to the standard method of GB/T5487-1995; The sulphur content of gasoline measures according to elemental analysis method (SH/T0842-2010); In gasoline, the content of non-n-alkane measures according to the method for gas chromatography analysis method (ASTMD6733-01 (2011)).
Reference example 1
This reference example illustrates the preparation of adsorption desulfurize process gasoline
According to the flow process of Fig. 1 described above, feed gasoline listed by table 1 after preheating and hydrogen are entered this reactor bottom fluidized-bed reactor, catalyzer FCAS-R09 (being purchased from China PetroChemical Corporation's catalyzer Nanjing branch office) enters from the top of fluidized-bed reactor, feed gasoline and catalyzer FCAS-R09 counter current contact carry out adsorption desulfurize reaction, the operational condition of adsorption desulfurize reaction is: pressure 1.5MPa, temperature 350 DEG C, weight hourly space velocity 27 hours
-1, hydrogen to oil volume ratio is 300Nm
3/ m
3, obtain low-sulphur oil oil gas and desulfuration adsorbent to be generated, described low-sulphur oil oil gas drawn from reactor head and obtains low-sulphur oil after condensation.This low-sulphur oil is carried out to the mensuration of non-n-alkane, olefin(e) centent, sulphur content and research octane number (RON) (RON), the results are shown in Table 2.
Wherein, the regeneration condition in revivifier is: temperature is 600 DEG C, and pressure is 0.8MPa, and air is as fluidizing medium; Catalyst residence times 20 minutes.
The condition of reduction treatment in reducer is: temperature is 400 DEG C, and pressure is 2.0MPa, and hydrogen is as fluidizing medium; Catalyst residence times 120 minutes.
Embodiment 1
According to feed gasoline listed by the method processing list 1 identical with reference example 1, obtain low-sulphur oil.
Gained low-sulphur oil is passed into continuously internal diameter be 20cm, in-built 80cm height 5A adsorbent of molecular sieve absorptive separation column in, temperature be 260 DEG C, pressure be 0.3MPa, feeding liquid time volume space velocity be 1.5 hours
-1condition under carry out adsorption operations, the residence time is 300 seconds, and collects gained gasoline products (suction excess oil).
Absorptive separation column is switched to desorption manipulation after carrying out 15 minutes continuously by operation upon adsorption, in adsorption tower, pass into nitrogen, temperature be 200 DEG C, pressure is normal pressure, nitrogen volume space velocity is 50 hours
-1condition under desorption 8 minutes, collect desorption liquid normal paraffin.
Above-mentioned gasoline products (suction excess oil) is carried out to the mensuration of non-n-alkane content, olefin(e) centent, sulphur content and research octane number (RON) (RON), the results are shown in Table 2 for it.
Embodiment 2
According to feed gasoline listed by the method processing list 1 identical with reference example 1, obtain low-sulphur oil.
It is the absorptive separation column series connection of the 5A adsorbent of molecular sieve of 20cm, in-built 80cm height by two internal diameters.Gained low-sulphur oil is passed into continuously in first absorptive separation column and carries out fractionation by adsorption, and suction excess oil out from first absorptive separation column is passed in second absorptive separation column continuously carries out fractionation by adsorption, collect the gasoline products (suction excess oil) be separated from second absorptive separation column.The adsorption operations condition of first absorptive separation column is: when temperature is 320 DEG C, pressure is 0.5MPa, feeding liquid, volume space velocity is 1.0 hours
-1, the residence time is 200 seconds; The adsorption operations condition of second absorptive separation column is: when temperature is 280 DEG C, pressure is 0.8MPa, feeding liquid, volume space velocity is 1.6 hours
-1, the residence time is 100 seconds.
Absorptive separation column is switched to desorption manipulation after carrying out 15 minutes continuously by operation upon adsorption, in adsorption tower, pass into nitrogen, temperature be 200 DEG C, pressure is normal pressure, nitrogen volume space velocity is 50 hours
-1condition under desorption 6 minutes, collect desorption liquid normal paraffin.
Carry out the mensuration of non-n-alkane content, olefin(e) centent, sulphur content and research octane number (RON) (RON) to isolated gasoline products (suction excess oil) in above-mentioned second absorptive separation column, the results are shown in Table 2 for it.
Embodiment 3
According to feed gasoline listed by the method processing list 1 identical with reference example 1, obtain low-sulphur oil.
Gained low-sulphur oil 100kg is introduced in airtight stirring tank, then adds 200kg urea (chemically pure reagent), stirring reaction 35 minutes at 30 DEG C, produce throw out; Then filtering precipitate (urea inclusion), and collect the gasoline products being rich in non-n-alkane.
Above-mentioned gasoline products is carried out to the mensuration of non-n-alkane content, olefin(e) centent, sulphur content and research octane number (RON) (RON), the results are shown in Table 2 for it.
In gained throw out, add the hot water of 100kg60 DEG C, stir after 30 minutes, leave standstill and carry out profit layering, reclaim oil phase and obtain normal paraffin.
Embodiment 4
According to feed gasoline listed by the method processing list 1 identical with reference example 1, obtain low-sulphur oil.
Gained low-sulphur oil 100kg is introduced in extracting and separating tower, adds 200kg methylene dichloride, under-25 DEG C of conditions, extract 10 minutes, be then separated the gasoline products (raffinate oil) obtaining being rich in non-n-alkane.
Above-mentioned gasoline products is carried out to the mensuration of non-n-alkane content, olefin(e) centent, sulphur content and research octane number (RON) (RON), the results are shown in Table 2 for it.
Table 2
From the results shown in Table 2, according to method provided by the invention, the gasoline products sulphur content obtained through adsorption desulfurize process, de-normal paraffin process reduces, and make the octane value of gasoline be improved when not improving content of olefin in gasoline, or can the appropriate octane level recovering gasoline when content of olefin in gasoline reduces.
Below the preferred embodiment of the present invention is described in detail by reference to the accompanying drawings; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (21)
1. a production method for high-octane rating low-sulphur oil, the method comprises:
(1) feed gasoline and hydrogen enter reactor, contact with desulfuration adsorbent, carry out adsorption desulfurize reaction, obtain low-sulphur oil oil gas and desulfuration adsorbent to be generated;
(2) described low-sulphur oil gas-oil separation is obtained low-sulphur oil, this low-sulphur oil is carried out the process of de-normal paraffin, obtain the gasoline products that non-n-alkane content is 80-100 % by weight;
(3) desulfuration adsorbent to be generated after carrying sulphur enters fluid bed regenerator, regenerates with rejuvenating gas contacts;
(4) desulfuration adsorbent after regeneration enters in reducer, reduces with reducing gas;
(5) desulfuration adsorbent after reduction returns this reactor bottom fluidized-bed reactor.
2. production method according to claim 1, wherein in step (2) described gasoline products, the content of non-n-alkane is 90-100 % by weight.
3. production method according to claim 1, wherein the process of the described de-normal paraffin of step (2) comprises: the fractionation by adsorption of described low-sulphur oil being carried out in absorptive separation column normal paraffin.
4. production method according to claim 3, wherein said fractionation by adsorption is carried out in the absorptive separation column that many groups are in parallel, and each group absorptive separation column comprises the absorptive separation column of 1-3 series connection.
5. production method according to claim 3, wherein said fractionation by adsorption sorbent material used is be selected from least one in 5A molecular sieve, silica gel and aluminum oxide; The condition of adsorption operations is: temperature 220-350 DEG C, pressure 0.2-1.0MPa, volume space velocity 0.5-2.0 hour during feeding liquid
-1, the residence time is 10-500 second.
6. production method according to claim 3, wherein said fractionation by adsorption also comprises: desorbing agent is passed into absorptive separation column and carry out desorption manipulation.
7. production method according to claim 6, wherein said fractionation by adsorption desorbing agent used is be selected from least one in nitrogen, hydrogen, ammonia steam, water vapor, carbonic acid gas, methane, Sweet natural gas and refinery gas; The temperature of desorption manipulation is 150-400 DEG C, and desorbing agent feed volume air speed is 30-70 hour
-1, desorption time is 2-8 minute.
8. production method according to claim 1, wherein the process of the described de-normal paraffin of step (2) comprises:
In described low-sulphur oil, add urea carry out urea clathration reaction, obtain inclusion reaction mixture;
From described inclusion reaction mixture, filter to isolate urea inclusion, obtain described gasoline products.
9. production method according to claim 8, the operational condition of wherein said urea clathration reaction is: feed intake mass ratio 1-3, the temperature of reaction 20-60 DEG C of urea and feed gasoline, inclusion reaction time 15-40 minute.
10. production method according to claim 8, wherein step (2) also comprises: be urea inclusion described in the hot-water cure of 60-98 DEG C by temperature, reclaims and obtains normal paraffin.
11. production methods according to claim 1, wherein the process of the described de-normal paraffin of step (2) comprises: described low-sulphur oil is gone out normal paraffin by solvent extraction and separation.
12. production methods according to claim 11, wherein said solvent-extracted operational condition is: extraction solvent for use is 1-5 with being extracted quality of gasoline ratio, extraction time 1-10 minute, temperature is-30 to-1 DEG C, and extraction solvent for use is be selected from one or more in hydrochloric ether, ether, ester and ketone.
13. production methods according to claim 1, wherein said desulfuration adsorbent comprises zinc oxide, silicon oxide and aluminum oxide, and this desulfuration adsorbent is also containing nickel and/or cobalt.
14. production methods according to claim 1, the condition of wherein said adsorption desulfurize reaction is: temperature 250-450 DEG C, pressure 0.2-4MPa, weight hourly space velocity 0.5-80 hour
-1, hydrogen to oil volume ratio is 0.01-1000Nm
3/ m
3.
15. production methods according to claim 14, the condition of wherein said adsorption desulfurize reaction is: temperature 300-400 DEG C, pressure 0.8-3MPa, weight hourly space velocity 4-50 hour
-1, hydrogen to oil volume ratio is 1-600Nm
3/ m
3.
16. production methods according to claim 1, the condition of wherein said coke burning regeneration is: temperature is 500-800 DEG C, and pressure is 0.1-4MPa; Catalyst residence times 5-40 minute; Described oxygenous atmosphere is using the air of air, nitrogen dilution or oxygen rich gas as fluidizing medium.
17. production methods according to claim 16, the condition of wherein said coke burning regeneration is: temperature is 580-700 DEG C, and pressure is 0.1-1MPa, catalyst residence times 15-30 minute.
18. production methods according to claim 1, the condition of wherein said reduction treatment is: temperature 200-600 DEG C, pressure 0.1-4.0MPa, catalyst residence times 30-200 minute; Described reducing atmosphere is for fluidizing medium with the reduzate of hydrogen.
19. production methods according to claim 18, the condition of wherein said reduction treatment is, temperature is 300-500 DEG C, and pressure is 0.1-3.0MPa, catalyst residence times 60-150 minute.
20. production methods according to claim 1, wherein said feed gasoline is be selected from least one in catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and pressure gasoline.
21. production methods according to claim 1, the boiling range of wherein said feed gasoline is 30-220 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106226408A (en) * | 2016-07-22 | 2016-12-14 | 北京赛普泰克技术有限公司 | A kind of cycle rate computational methods of the adsorbent of gasoline absorbing desulfurization device |
| CN110760337A (en) * | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | Method and equipment for desulfurizing aromatic hydrocarbon raw material |
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| CN102337153A (en) * | 2010-07-22 | 2012-02-01 | 中国石油天然气股份有限公司 | Hydrotreatment method of gasoline distillate oil |
| CN103789038A (en) * | 2014-02-28 | 2014-05-14 | 南京大学连云港高新技术研究院 | Method for producing high-cleanliness gasoline by full-range high-sulfur inferior gasoline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102337153A (en) * | 2010-07-22 | 2012-02-01 | 中国石油天然气股份有限公司 | Hydrotreatment method of gasoline distillate oil |
| CN103789038A (en) * | 2014-02-28 | 2014-05-14 | 南京大学连云港高新技术研究院 | Method for producing high-cleanliness gasoline by full-range high-sulfur inferior gasoline |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106226408A (en) * | 2016-07-22 | 2016-12-14 | 北京赛普泰克技术有限公司 | A kind of cycle rate computational methods of the adsorbent of gasoline absorbing desulfurization device |
| CN106226408B (en) * | 2016-07-22 | 2019-01-08 | 北京赛普泰克技术有限公司 | A kind of cycle rate calculation method of the adsorbent of gasoline absorbing desulfurization device |
| CN110760337A (en) * | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | Method and equipment for desulfurizing aromatic hydrocarbon raw material |
| CN110760337B (en) * | 2018-07-27 | 2022-12-13 | 中国石油化工股份有限公司 | Method and equipment for desulfurizing aromatic hydrocarbon raw material |
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