CN101597509B - Recombinant Alkylation Catalytic Distillation Desulfurization Method - Google Patents
Recombinant Alkylation Catalytic Distillation Desulfurization Method Download PDFInfo
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- CN101597509B CN101597509B CN 200810114386 CN200810114386A CN101597509B CN 101597509 B CN101597509 B CN 101597509B CN 200810114386 CN200810114386 CN 200810114386 CN 200810114386 A CN200810114386 A CN 200810114386A CN 101597509 B CN101597509 B CN 101597509B
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- 238000004821 distillation Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 26
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- 230000023556 desulfurization Effects 0.000 title claims abstract description 19
- 238000005804 alkylation reaction Methods 0.000 title abstract description 10
- 230000029936 alkylation Effects 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 92
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- 238000000605 extraction Methods 0.000 claims description 30
- 210000000689 upper leg Anatomy 0.000 claims description 20
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- 239000007791 liquid phase Substances 0.000 claims description 11
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- 238000011049 filling Methods 0.000 claims description 10
- 239000012808 vapor phase Substances 0.000 claims description 9
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- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
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- 229920005989 resin Polymers 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005215 recombination Methods 0.000 claims description 2
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 abstract description 14
- 239000011593 sulfur Substances 0.000 abstract description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 4
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- 239000002283 diesel fuel Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 150000003464 sulfur compounds Chemical class 0.000 description 8
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- 235000009508 confectionery Nutrition 0.000 description 7
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 230000002152 alkylating effect Effects 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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Abstract
The invention relates to a recombinant alkylation catalytic distillation desulfurization method, which is characterized in that a gasoline raw material to be desulfurized is separated into light fraction and heavy fraction, the light fraction and the heavy fraction are respectively introduced into different positions of a catalytic distillation tower, a feed inlet of the light fraction is lower than a feed inlet of the heavy fraction, a solid acid catalyst is filled in the catalytic distillation tower, the operating pressure of the catalytic distillation tower is 0.1-0.5 MPa, the temperature of a reaction zone is 80-200 ℃, and the liquid space velocity is 0.1h < -1 > -20 h < -1 >; olefin contained in the gasoline is fully utilized to react with sulfur-containing compounds in the gasoline, so that the boiling point of the sulfur-containing compounds is obviously improved, and the sulfur transfer degree is higher; the sulfur in the gasoline is effectively removed without losing octane value; achieving the dual purposes of desulfurization and olefin reduction; the construction investment is small, the operation condition is mild, and the process is easy to control.
Description
Technical field
The present invention relates to a kind of alkene that contains in the gasoline and be the sulfur method of alkylating agent.
Background technology
At present, catalytic cracking (FCC) gasoline accounts for more than 75% of China's gasoline composition, brings the sulphur impurity more than 90% in the gasoline product into.Therefore, the sulfide content in the production clean gasoline product needed decrease FCC gasoline.The contained pure and mild thioether class of sulfur of FCC gasoline is less, and thiophene expects that class accounts for more than 80% of sulfide total amount.Hydrogenating desulfurization (HDS) is the FCC gasoline desulfur technology of present widespread use, and the sulfide kind that it can remove is many, and reaction conversion ratio is high, but the alkene in the lighting end is easy to the while by saturated, and gasoline octane rating is reduced.Alkylating desulfurization refers to gasoline is contacted with an acidic catalyst, make thiophene-type sulfide that gasoline contains and the alkene generation alkylated reaction in the gasoline, generate the higher alkylated substituted thiazoline fen of boiling point, through distillment sulfide is transferred in the last running again and gone, thereby the sulphur content in the reduction gasoline fraction, alkylating desulfurization technological operation condition relaxes, sweetening effectiveness is good, the alkene loss is few, keep gasoline octane rating, need not consume hydrogen and hydrogenation catalyst, process cost is low, is a kind of very competitive desulfurization technology.
About patent and the bibliographical information of alkylation desulfurization of gasoline as follows:
The disclosed method of US5599441 is take solid acid as catalyzer, the thiophene-type sulfide in reactor in the catalytic gasoline and olefin alkylation reaction, the sulfide of generation higher.The reactor discharging enters separation column again, tells the petroleum naphtha of low-sulfur from cat head, and higher boiling sulfur compound is delivered to selective hydrogenation device with tower bottoms and carried out hydrogenating desulfurization.This method is during take full cut as raw material, and the thiophene transformation efficiency is lower.
The disclosed method of US6024865 is first petroleum naphtha to be divided into four cuts in rectifying tower:＜60 ℃, 60 ℃-177 ℃, 177 ℃-221 ℃ and＞221 ℃, again two cuts of centre are introduced respectively the alkylation reactor of two different conditions, carry out the alkyl sulfur shift reaction, wherein lighter cut utilizes the alkene that self contains to carry out alkylated reaction under relatively gentle condition, heavier cut then needs additional low-carbon alkene or low-carbon alcohol as alkylating agent, is relatively carrying out alkylated reaction under the exacting terms.Fractionate out at last the petroleum naphtha of low-sulfur and the heavy petrol of sulfur-bearing, the cut of sulfur-bearing is mixed with＞221 ℃ of cuts go again hydrogenating desulfurization.
US2003029776 discloses the method for a kind of two-stage alkyl sulfur shift reaction desulfurization.At first process gasoline with acid solution, to deviate from basic nitrogen compound, then pretreated gasoline is introduced first step reactor, under 172 ℃ of conditions, carry out alkylated reaction, again further reaction in second stage reactor (temperature is 122 ℃), at last separation is light, restructuring divides, and restructuring divides goes hydrogenator to carry out hydrogenating desulfurization.
US6059962 discloses a kind of multistage alkylating desulfurization technique, at first with the raw material fractionation, the cut of drawing one 60 ℃-221 ℃ from side line enters first step alkylation reactor, allowing wherein, the part sulfocompound is converted into the higher alkylate of boiling point, then the product fractionation with the first alkylation reactor is the lighting end of low-sulfur and the last running of high-sulfur, second stage alkylation reactor is introduced in last running, sulfocompound is transferred in the heavier cut.
US20030042175 discloses a kind of sulfur method, and the first step is deviate from first the diolefine in the gasoline; Second step carries out thioetherification reaction, makes mercaptan and olefine reaction in the gasoline generate thioether; The 3rd step was fractionation, drew side line removal of alkylation reaction device at the rectifying section of tower, returned rectifying tower after the reaction again, and tower bottoms directly goes hydrogenating desulfurization.The disclosed method of USP20020166798 is different with it to be to draw side line removal of alkylation reaction device at the stripping section of tower, does not return rectifying tower after the reaction, but goes hydrogenating desulfurization.
CN1267536 discloses a kind of method of distillate alkylating desulfurization, is in the presence of acid catalyst, and distillate is contacted with dry gas or liquefied gas, alkylated reaction occurs, and distill cutting.
CN101007965 discloses a kind of alkylated reaction device that is composed in parallel by a plurality of reactors, when the catalyzer in the reactor need to be regenerated, stock oil is switched to regenerated solvent or gas, the recyclable recycling of solvent after the regeneration switches to stock oil and proceeds alkylated reaction behind the catalyst regeneration.
The deficiency that prior art exists is the alkene that does not reasonably distribute in the raw material.The characteristics of alkene and thiophene-type sulfide alkylated reaction are, low-carbon alkene reacts than higher olefins is easier, and lower boiling thiophenic sulfur compound is than the easier reaction of high boiling point thiophenic sulfur compound.Existing technology is not all separated low-carbon alkene with lower boiling thiophenic sulfur compound, low-carbon alkene is easy to react with lower boiling thiophenic sulfur compound in this case, occupied the position of substitution, and the boiling point of the alkylthrophene derivative that generates is not high enough, so the sulphur transfer effect is bad.
Summary of the invention
The purpose of this invention is to provide a kind of method that adopts the hydrocarbon restructuring to combine with catalytic distillation, good low-carbon alkene at first contacts with the thiophenic sulfur compound of higher to allow reactive behavior, be conducive to generate more high boiling sulfide, on the other hand, allow more lower boiling thiophenic sulfur compound contact with long-chain olefin, make remarkable raise simple to operate of boiling point of alkylate, mild condition, the method for the gasoline desulfur that sweetening effectiveness is good.
The present invention is realized by the following technical programs:
A kind of gasoline desulfating method comprises following process: 1. isolate light constituent from sour gasoline; 2. the rest part of described light constituent and gasoline stocks is introduced respectively in the catalytic distillation tower that solid acid catalyst is housed, the feed entrance point of light constituent is lower than the feed entrance point of rest part; 3. the alkene in the light constituent (such as C5=) contacts at lower reaction zone with the thiophene-type sulfide of higher, under the solid acid catalyst effect alkylated reaction occurs, and generates more high boiling sulfide; 4. the alkene of more lower boiling thiophene-type sulfide and middle runnings (such as C6=) descends the low carbon olefin gas of reaction zone surplus also will rise to reaction zone participation reaction at upper reaction zone generation alkylated reaction in addition; 5. low-sulphur oil is from the extraction of catalytic distillation cat head; 6. higher boiling sulfur compound is accompanyed or follow the tower bottoms extraction, a kind of gasoline desulfating method is characterized in that: gasoline stocks to be desulfurization is separated into lighting end and last running, introduce respectively the different positions of catalytic distillation tower, the opening for feed of lighting end is lower than the opening for feed of last running, filling solid acid catalyst in the reaction zone of catalytic distillation tower, the working pressure of catalytic distillation tower is 0.1MPa～0.5MPa, and reaction zone temperature is 80 ℃～200 ℃, and the liquid air speed is 0.1h-1～20h-1.
A kind of preferred version, it is characterized in that: at first gasoline is separated into gas phase and liquid phase by flash tank, then vapor phase stream thigh and liquid phase stream stock are not introduced from the different heights position of catalytic rectifying tower, the opening for feed of vapor phase stream thigh is positioned at the reaction zone bottom, the opening for feed of liquid phase stream thigh is positioned at the reaction zone middle part, the overhead extraction low-sulphur oil, tower bottoms with enter separation column after the high boiling point hydrocarbon ils mixes, the fractionation overhead distillate mixes with catalytic distillation cat head distillate, the fractionation tower bottoms is partly recirculated to the separation column opening for feed, the part extraction.
A kind of preferred version, it is characterized in that: at first gasoline is separated into gas phase and liquid phase by flash tank, then vapor phase stream thigh and liquid phase stream stock are not introduced from the different heights position of catalytic rectifying tower, the opening for feed of vapor phase stream thigh is positioned at the reaction zone bottom, the opening for feed of liquid phase stream thigh is positioned at the reaction zone middle part, introduces high boiling point hydrocarbon ils, overhead extraction low-sulphur oil at the middle part of stripping section, tower bottoms is partly recirculated to the opening for feed of high boiling point hydrocarbon ils, the part extraction.
A kind of preferred version, it is characterized in that: at first gasoline is introduced preliminary fractionator (separation column 1), isolate lighting end from cat head, the boiling point of lighting end≤65 ℃, then lighting end and all the other cuts are introduced from the different heights position of catalytic rectifying tower respectively, the opening for feed of lighting end is in the reaction zone bottom, the opening for feed of all the other cuts is positioned at the reaction zone middle part, catalytic distillation cat head extraction low-sulphur oil, tower bottoms with enter separation column 2 after the high boiling point hydrocarbon ils mixes, the overhead distillate of separation column 2 mixes mutually with catalytic distillation cat head distillate, and the tower bottoms of separation column 2 is partly recirculated to opening for feed, the part extraction.
A kind of preferred version, it is characterized in that: at first gasoline is introduced preliminary fractionator (separation column 1), isolate lighting end from cat head, the boiling point of lighting end≤65 ℃, then lighting end and all the other cuts are introduced from the different heights position of catalytic rectifying tower respectively, the opening for feed of lighting end is positioned at the reaction zone bottom, the opening for feed of all the other cuts is positioned at the reaction zone middle part, the high boiling point hydrocarbon ils is introduced at middle part at stripping section, the overhead extraction low-sulphur oil, tower bottoms is partly recirculated to the opening for feed of high boiling point hydrocarbon ils, the part extraction.
Described solid acid catalyst is selected from one or more in sulfonate resin, molecular sieve, the solid phosphoric acid.
The effect of invention
Compared with prior art, effect of the present invention is:
Take full advantage of alkene and the reaction of the sulfide in the gasoline that gasoline itself contains, significantly improve the boiling point of sulfide, the degree that sulphur is shifted is higher; Sulfide in the effective elimination gasoline and do not lose octane value; Reach desulfurization and the dual purpose of falling alkene; Construction investment is little, and operational condition is gentle, and process is easy to control.
Description of drawings
Fig. 1 is the schematic flow sheet of the embodiment of the invention 1.
Fig. 2 is the schematic flow sheet of the embodiment of the invention 2.
Fig. 3 is the schematic flow sheet of the embodiment of the invention 3.
Fig. 4 is the schematic flow sheet of the embodiment of the invention 4.
Wherein: 10, pretreater 101, pipeline 102, pipeline 103, pipeline 104, pipeline 105, pipeline 106, pipeline 20, flash tank 201, pipeline 202, pipeline 203, pipeline 204, pipeline 205, pipeline 206, pipeline 30, catalytic distillation tower 31, upper conversion zone 32, lower conversion zone 33, rectifying section 34, stripping section 35, upper conversion zone 2 36, intermediate fractionation section 40, separation column 50, preliminary fractionator
Embodiment
Embodiment 1
By reference to the accompanying drawings 1, technique of the present invention is further specified.
Catalytic distillation tower is divided into four parts: upper conversion zone 31, lower conversion zone 32, rectifying section 33 and stripping section 34.The FCC gasoline stocks is connected with pretreater 10 through pipeline 101, is connected with flash tank 20 by pipeline 102 again.Flash drum overhead is connected with the conversion zone bottom of catalytic distillation tower 30 by pipeline 103, and C3～C5 olefin feedstock is connected by pipeline 106 conversion zones bottom.The bottom of flash tank by pipeline 104 and catalytic distillation tower 30 upper conversion zone 31 and lower conversion zone 32 between be connected.Cat head connects complete condenser by pipeline 201, and pipeline 202 is connected with complete condenser with catalytic distillation tower overhead extraction mouth and is connected.Be connected with the middle part of separation column 40 after converging with pipeline 105 by pipeline 203,204 at the bottom of the tower, pipeline 105 is connected with diesel oil or high boiling hydrocarbon ils feedstock.The fractionation cat head is connected with catalytic distillation overhead line 202 by pipeline 205.Separation column bottom connection line 206.
The FCC gasoline stocks enters pretreater through pipeline 101 and removes basic nitrogen, enters flash tank 20 by pipeline 102 again.Conversion zone bottom by flash tank vapor phase stream thigh is out introduced catalytic distillation tower by pipeline 103 optionally suitably replenishes C3～C5 alkene by pipeline 106 according to the difference that the FCC gasoline stocks forms.Between upper conversion zone 31 and lower conversion zone 32, introduce catalytic distillation tower by pipeline 104 by flash tank liquid phase stream thigh out.Overhead vapours enters complete condenser by pipeline 201, and the part lime set refluxes, its as distillate from pipeline 202 extraction.Liquid portion vaporization at the bottom of the tower, remaining is by pipeline 204, with mixes from the diesel oil of pipeline 105 or high boiling hydrocarbon ils cut after introducing separation column 40.The fractionation overhead distillate mixes with catalytic distillation cat head distillate by pipeline 205, as low-sulphur oil.The fractionation tower bottoms is the diesel oil distillate with sulphur.
The FCC gasoline stocks is added the pretreater that Zeo-karb is housed, and operational condition is 0.3MPa and 85 ℃; The gasoline of processing is passed into flash tank, and pressure-controlling is at 0.12MPa; Introduce respectively catalytic distillation tower by flash tank gas and liquid out, the liquid phase stream thigh enters tower from the centre of two conversion zones, the vapor phase stream thigh enters tower from the lower curtate of conversion zone, tower top temperature is 70 ℃, column bottom temperature is 161 ℃, working pressure is 0.1MPa, conversion zone filling macropore sulfuric acid resin and solid phosphoric acid catalyst, rectifying section and stripping section filling Stainless Steel Cloth filler; Sweet gasoline is from overhead extraction; Introduce separation column after tower bottoms and diesel oil mix, fractionation tower temperature is 170 ℃, and column bottom temperature is 230 ℃, and overhead distillate mixes as sweet gasoline with catalytic distillation cat head distillate, and tower bottoms partly is circulated to the separation column opening for feed, all the other extraction.
Embodiment 2
Knot and accompanying drawing 2 further specify technique of the present invention.
The FCC gasoline stocks enters pretreater through pipeline 101 and removes basic nitrogen, enters flash tank 20 by line 102 again.Conversion zone bottom by flash tank vapor phase stream thigh is out introduced catalytic distillation tower by line 103 optionally suitably replenishes C3～C5 alkene by 106 according to the difference that the FCC gasoline stocks forms.Between upper conversion zone 31 and lower conversion zone 32, introduce catalytic distillation tower by line 104 by flash tank liquid phase stream thigh out.Diesel oil or high boiling hydrocarbon ils cut are introduced the stripping section of catalytic distillation tower by line 105.Overhead vapours enters complete condenser by 201, and the part lime set refluxes, all the other as distillate from line 202 extraction.Liquid portion vaporization at the bottom of the tower, all the other are by 203,204 extraction.
The FCC gasoline stocks is added the pretreater that Zeo-karb is housed, and operational condition is 0.1MPa and 22 ℃; Pass into flash tank after the gasoline of processing is heated to 120 ℃, pressure-controlling is at 0.12MPa; Introduce respectively catalytic distillation tower by flash tank gas and liquid out, the liquid phase stream thigh enters tower from the centre of two conversion zones, the vapor phase stream thigh enters tower from the lower curtate of conversion zone, diesel oil is added from the stripping section middle part, tower top temperature is 86 ℃, and column bottom temperature is 232 ℃, and working pressure is 0.1MPa, conversion zone filling macropore sulfuric acid resin and solid phosphoric acid catalyst, rectifying section and stripping section filling Stainless Steel Cloth filler; Sweet gasoline is from overhead extraction; The diesel oil that tower bottoms can partly be circulated to catalytic distillation tower adds entrance, all the other extraction.
Embodiment 3
By reference to the accompanying drawings 3, technique of the present invention is further specified.
Catalytic distillation tower is divided into six parts: rectifying section 33, stripping section 34, upper conversion zone 31, upper conversion zone 2 35, lower conversion zone 32, intermediate fractionation section 36.The FCC gasoline stocks is connected with pretreater 10 through pipeline 101, is connected with preliminary fractionator 50 by pipeline 102 again.The preliminary fractionator top is connected with the conversion zone bottom of catalytic distillation tower 30 by pipeline 103, and C3～C5 olefin feedstock is connected by pipeline 106 conversion zones bottom.Preliminary fractionator bottom by pipeline 104 and catalytic distillation tower 30 upper conversion zone 2 35 and lower conversion zone 32 between be connected.Cat head connects complete condenser by pipeline 201, and pipeline 202 is connected with complete condenser with catalytic distillation tower overhead extraction mouth and is connected.Be connected with the middle part of separation column 40 after converging with pipeline 105 by pipeline 203,204 at the bottom of the tower, pipeline 105 is connected with diesel oil or high boiling hydrocarbon ils feedstock.The fractionation cat head is connected with catalytic distillation overhead line 202 by pipeline 205.Separation column bottom connection line 206.
The FCC gasoline stocks enters pretreater through pipeline 101 and removes basic nitrogen, enters preliminary fractionator 50 by pipeline 102 again.Eject the stream thigh that comes by preliminary fractionator and introduce by pipeline 103 bottom the conversion zone of catalytic distillation tower, optionally suitably replenish C3～C5 alkene by pipeline 106 according to the difference that the FCC gasoline stocks forms.Between conversion zone 35 and conversion zone 32, introduce catalytic distillation tower by pipeline 104 by prefractionation tower reactor stream thigh out.Overhead vapours enters complete condenser by pipeline 201, and the part lime set refluxes, its as distillate from pipeline 202 extraction.Liquid portion vaporization at the bottom of the tower, remaining is by pipeline 204, with mixes from the diesel oil of pipeline 105 or high boiling hydrocarbon ils cut after introducing separation column 40.The fractionation overhead distillate mixes with catalytic distillation cat head distillate by pipeline 205, as low-sulphur oil.The fractionation tower bottoms is the diesel oil distillate with sulphur.
The FCC gasoline stocks is added the pretreater that Zeo-karb is housed, and operational condition is 0.3MPa and 30 ℃; The gasoline of processing is passed into preliminary fractionator, and pressure-controlling is at 0.1MPa; Prefractionation cat head distillate and tower bottoms are introduced respectively catalytic distillation tower, prefractionation tower reactor liquid enters tower from the centre of conversion zone 35 and conversion zone 32, prefractionation cat head liquid enters tower from the lower curtate of conversion zone 32, catalytic distillation cat head temperature is 99 ℃, column bottom temperature is 197 ℃, working pressure is 0.3MPa, conversion zone filling solid phosphoric acid catalyst, rectifying section and stripping section filling Stainless Steel Cloth filler; Sweet gasoline is from overhead extraction; Introduce separation column after tower bottoms and diesel oil mix, fractionation tower temperature is 170 ℃, and column bottom temperature is 230 ℃, and overhead distillate mixes as sweet gasoline with catalytic distillation cat head distillate, and tower bottoms partly is circulated to the separation column opening for feed, all the other extraction.
Embodiment 4
Knot and accompanying drawing 4 further specify technique of the present invention.
Catalytic distillation tower is divided into six parts: rectifying section 33, stripping section 34, upper conversion zone 31, upper conversion zone 2 35, lower conversion zone 32, intermediate fractionation section 36.The FCC gasoline stocks connects pretreater 10 through pipeline 101, connects preliminary fractionator 50 by pipeline 102 again.The prefractionation cat head is by the conversion zone bottom of pipeline 103 connection catalytic distillation towers, and C3～C5 olefin feedstock is connected by pipeline 106 conversion zones bottom.Preliminary fractionator bottom by pipeline 104 and catalytic distillation tower 30 upper conversion zone 2 35 and lower conversion zone 32 between be connected.The catalytic distillation cat head connects complete condenser by pipeline 201, and pipeline 202 is connected with complete condenser with the overhead extraction mouth and is connected.Diesel oil or high boiling hydrocarbon ils cut are connected with the stripping section of catalytic distillation tower by pipeline 105.Be connected with pipeline, 203,204 at the bottom of the tower.
The FCC gasoline stocks enters pretreater through pipeline 101 and removes basic nitrogen, enters preliminary fractionator 50 by pipeline 102 again.Ejected the conversion zone bottom that the stream thigh that comes is introduced catalytic distillation towers by line 103 by preliminary fractionator, can be according to the composition different choice of FCC gasoline stocks suitably replenish C3～C5 alkene by 106.Between conversion zone 35 and lower conversion zone 32, introduce catalytic distillation tower by line 104 by out stream thigh at the bottom of the preliminary fractionator.Diesel oil or high boiling hydrocarbon ils cut are introduced the stripping section of catalytic distillation tower by line 105.Overhead vapours enters complete condenser by 201, and the part lime set refluxes, all the other as distillate from line 202 extraction.Liquid portion vaporization at the bottom of the tower, all the other are by 203,204 extraction.
The FCC gasoline stocks is added the pretreater that Zeo-karb is housed, and operational condition is 0.1MPa and 30 ℃; The gasoline of processing is passed into preliminary fractionator, and pressure-controlling is at 0.1MPa; Prefractionation cat head distillate and tower bottoms are introduced respectively catalytic distillation tower, prefractionation tower reactor liquid enters tower from the centre of two conversion zones 35 and 32, prefractionation cat head liquid enters tower from the lower curtate of conversion zone 32, kerosene is added from the stripping section top, tower top temperature is 93 ℃, and column bottom temperature is 236 ℃, and working pressure is 0.2MPa, reaction zone filling Y molecular sieve catalyzer, rectifying section and stripping section filling Stainless Steel Cloth filler; Sweet gasoline is from overhead extraction; The kerosene that tower bottoms partly is circulated to catalytic distillation tower adds entrance, all the other extraction.
Be compared as follows table by the yield of embodiment gained sweet gasoline and with the performance of raw material:
Claims (2)
1. method for desulfuration by recombination alkylate catalytic distillation, it is characterized in that: gasoline stocks to be desulfurization is separated into lighting end and last running by flash tank, introduce respectively the different positions of catalytic distillation tower, the opening for feed of lighting end is lower than the opening for feed of last running, the opening for feed of vapor phase stream thigh is positioned at the reaction zone bottom, the opening for feed of liquid phase stream thigh is positioned at the reaction zone middle part, high boiling hydrocarbon is introduced at middle part at stripping section, the overhead extraction low-sulphur oil, tower bottoms is partly recirculated to the high boiling hydrocarbon opening for feed, the part extraction, filling solid acid catalyst in the conversion zone of catalytic distillation tower, the working pressure of catalytic distillation tower is 0.1MPa～0.5MPa, and reaction zone temperature is 80 ℃～200 ℃, and the liquid air speed is 0.1h
-1～20h
-1
2. solid acid catalyst according to claim 1 is selected from one or more in sulfonate resin, molecular sieve, the solid phosphoric acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6024865A (en) * | 1998-09-09 | 2000-02-15 | Bp Amoco Corporation | Sulfur removal process |
| CN1583970A (en) * | 2003-08-20 | 2005-02-23 | 中国石油化工股份有限公司 | Desulfurizing method for distillate |
| CN1600834A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Method for modifying poor gasoline |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6024865A (en) * | 1998-09-09 | 2000-02-15 | Bp Amoco Corporation | Sulfur removal process |
| CN1583970A (en) * | 2003-08-20 | 2005-02-23 | 中国石油化工股份有限公司 | Desulfurizing method for distillate |
| CN1600834A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Method for modifying poor gasoline |
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