CN101921615B - Reforming system and method for side-drawing and isolating benzene from evaporation dehydration system - Google Patents
Reforming system and method for side-drawing and isolating benzene from evaporation dehydration system Download PDFInfo
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- CN101921615B CN101921615B CN2009100870494A CN200910087049A CN101921615B CN 101921615 B CN101921615 B CN 101921615B CN 2009100870494 A CN2009100870494 A CN 2009100870494A CN 200910087049 A CN200910087049 A CN 200910087049A CN 101921615 B CN101921615 B CN 101921615B
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000018044 dehydration Effects 0.000 title claims abstract description 34
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 34
- 238000001704 evaporation Methods 0.000 title claims abstract description 34
- 230000008020 evaporation Effects 0.000 title claims abstract description 34
- 238000002407 reforming Methods 0.000 title claims abstract description 22
- 238000000605 extraction Methods 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 238000011084 recovery Methods 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 23
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims description 21
- 238000009835 boiling Methods 0.000 claims description 20
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 239000003502 gasoline Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- LCEDQNDDFOCWGG-UHFFFAOYSA-N morpholine-4-carbaldehyde Chemical compound O=CN1CCOCC1 LCEDQNDDFOCWGG-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical group O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 11
- 239000003921 oil Substances 0.000 description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 17
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 239000005864 Sulphur Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000007689 inspection Methods 0.000 description 9
- 238000012545 processing Methods 0.000 description 7
- 238000001833 catalytic reforming Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000010771 distillate fuel oil Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 239000003269 fluorescent indicator Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HYERJXDYFLQTGF-UHFFFAOYSA-N rhenium Chemical compound [Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re][Re] HYERJXDYFLQTGF-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The invention discloses a reforming system and method for fecundating aromatic hydrocarbons from naphtha. The system comprises a heating device and a reaction device and is characterized in that the reaction device is connected with a high-pressure isolator which is connected with a stabilizer system; the lower part of the stabilizer system is connected with an extraction system by a pipeline; the extraction system is connected with an evaporation dehydration system by a pipeline on the one hand and is connected with a first recovery tower by a pipeline on the other hand; the upper part of the first recovery tower is used for drawing benzene via a pipeline and the lower part thereof is connected with a second recovery tower by a pipeline; the upper part of the second recovery tower is used for drawing mixed aromatic hydrocarbons via a pipeline and the lower part thereof is connected with the extraction system by a pipeline; the top of the evaporation dehydration system is used for directly drawing water via a pipeline; the evaporation dehydration system is provided with a side-draw hole for drawing light raffinate oil; the bottom of the evaporation dehydration system is connected with the other reaction device by a pipeline and the heating device; and the other end of the other reaction device is connected with the high-pressure isolator by a pipeline. The system and the method have the advantage of greatly improving the handling capacity, liquid yield, aromatic hydrocarbon yield and hydrogen output.
Description
Technical field
The present invention relates to a kind of reforming system and method thereof, particularly a kind of reforming system of side-drawing and isolating benzene from evaporation dehydration system and method thereof.
Background technology
Along with the fast development of automotive industry and the petrochemical industry growth to the aromatic hydrocarbons demand; the particularly increasingly stringent requirement of country to environment protection, catalytic reforming gasoline becomes one of blend component desirable in New standard gasoline with its high-octane rating, low alkene and Trace Sulfur.A large amount of hydrogen of catalytic reforming by product are again for improving oil quality, and the industry of development hydrogenation provides a large amount of cheap hydrogen sources.Therefore, catalytic reforming, as the important oil refining process of producing stop bracket gasoline and aromatic hydrocarbons, is being brought into play more and more important effect in oil refining, chemical engineering industry.
Catalytic reforming unit is pressed the catalyst regeneration mode, mainly can be divided at present semi-regenerative reforming and CONTINUOUS REFORMER two classes.Two class catalytic reforming units are because having different separately characteristics, the Raw material processing requirement different by it by each refinery and selecting.
Semi-regenerative reforming is because plant investment is little, flexible operation, and process cost is low, is suitable for the different characteristics such as industrial scale, still takies critical role.
Since platinum/rhenium catalyst comes out, the research of semi-regenerative reforming catalyzer and application have obtained sufficient development, have arrived quite high level.Half-regeneration reformer faces the pressure that enlarges processing power mostly, the capacity expansion revamping approach that yes deals with problems, but increase little device for load, if can be by improving catalyst activity, increasing the charging air speed, thereby improve unit capacity, is best method.On the other hand, the reformer feed source presents diversified trend, and the secondary processing oil such as the petroleum naphtha of low arene underwater content and coker gasoline proportion in reformer feed strengthens, and the in poor quality trend of reformer feed is more and more obvious.The in poor quality of raw material is had higher requirement to catalyst activity.
Therefore providing a kind of can improve processing power, and naphtha fecundation aromatic hydrocarbons reforming system and the method thereof of raising liquid yield, aromatic production, octane value and hydrogen output just become this technical field urgent need to solve the problem.
Summary of the invention
One of purpose of the present invention is to provide and a kind ofly can improves processing power, and improves the naphtha fecundation aromatic hydrocarbons reforming system that liquid yield, aromatic production and hydrogen yield provide the high-octane rating product simultaneously.
For achieving the above object, the present invention takes following technical scheme:
A kind of naphtha fecundation aromatic hydrocarbons reforming system, comprise heating unit, the reaction unit be attached thereto; It is characterized in that: described reaction unit is divided into two portions, the first and/or second reaction unit (and/or more reaction units) is connected with evaporation and dehydration system by high-pressure separator, stabilizer tower system and extraction system, described extraction system is connected with the first and second recovery towers again, described evaporation and dehydration system is connected with the 3rd and/or the 4th reaction unit (and/or more reaction units) again, and described evaporation and dehydration system is provided with side line extraction mouth.
A kind of naphtha fecundation aromatic hydrocarbons reforming system, comprise heating unit, the reaction unit be attached thereto; It is characterized in that: described reaction unit bottom is connected with high-pressure separator by pipeline; Described high-pressure separator is connected with the stabilizer tower system by pipeline, and is connected with Material supply system by pipeline and compression set; Described stabilizer tower system bottom is connected with extraction system by pipeline; Described extraction system is connected with evaporation and dehydration system by pipeline on the one hand; Described extraction system is connected with first recovery column by pipeline on the other hand; Described first recovery column top is by pipeline extraction benzene, and bottom is connected with second recovery column by pipeline; Described second recovery column top is by pipeline extraction BTX aromatics, and bottom is connected with extraction system by pipeline; Described evaporation and dehydration system top is by the pipeline recovered water, described evaporation and dehydration system sidepiece is raffinated oil by pipeline extraction lightweight, described evaporation and dehydration system bottom is connected with another reaction unit (the 3rd reaction unit) by pipeline and heating unit, and the other end of described another reaction unit is connected with described high-pressure separator with refrigerating unit by pipeline.
A kind of optimal technical scheme, it is characterized in that: described reaction unit first is connected with the second reaction unit (after the second reaction unit, can with more reaction unit, be connected by heating unit) by second heating unit again, and then is connected with described high-pressure separator.
A kind of optimal technical scheme, it is characterized in that: described another reaction unit first is connected with the 4th reaction unit (can be connected with more reaction unit again by heating unit after the 4th reaction unit) by the 4th heating unit, and then is connected with described high-pressure separator.
A kind of optimal technical scheme is characterized in that: two reactors of described reaction unit for connecting up and down are connected by heating unit therebetween.
A kind of optimal technical scheme is characterized in that: two reactors of described another reaction unit for connecting up and down are connected by heating unit therebetween.
Another object of the present invention is to provide the raising processing power, and improves the naphtha productive aromatic hydrocarbon reforming method that liquid yield, aromatic production and hydrogen yield provide the high-octane rating product simultaneously.
Foregoing invention purpose of the present invention reaches by the following technical programs:
A kind of naphtha productive aromatic hydrocarbon reforming method, its step is as follows: the feed naphtha that boiling range is 80-185 ℃, after the heating unit heating, enters reaction unit and is reacted; The temperature in of described reaction unit is 470-530 ℃, and inlet pressure is 1.0-1.6MPa, and the feed volume air speed is 3.0-5.0h
-1; The gained reaction product enters high-pressure separator and carries out the high pressure separation after heat exchange is cooling, and the service temperature of described high-pressure separator is 35-45 ℃, and working pressure is 1.2-1.4MPa; After high pressure separates, a gained hydrogen part is sent outside, and a part is back to feed line and another reaction unit through compression set, the described hydrogen returned or advance into pipeline at process furnace, or enter pipeline after process furnace; The gained reformate enters the stabilizer tower system and is processed, and the tower top temperature of described stabilizer tower system is 100-120 ℃, and pressure is 0.8-1.05MPa, and column bottom temperature is 220-240 ℃, and pressure is 0.85-1.10MPa, and reflux ratio is 0.90-1.15; Overhead extraction dry gas, liquefied gas and a small amount of water; The reformed oil that at the bottom of tower, the gained boiling range is 35-196 ℃ enters extraction system and is processed, the service temperature of described extraction system is 100-150 ℃, working pressure is 0.6-1.0MPa, solvent ratio is 3.0-8.0, return and wash than being 0.5-1.0, solvent for use is tetramethylene sulfone, N-formyl morpholine, one or more mixing in Tetraglycol 99; After extracting, extraction system is extracted oil out and is entered first recovery column, and the tower top temperature of described first recovery column is 85-90 ℃, and pressure is 0.1-0.2MPa (absolute pressure), and column bottom temperature is 175 ℃, and pressure is 0.15-0.25MPa (absolute pressure); Top extraction benzene, the bottom production enters second recovery column, and the service temperature of described second recovery column is 110-155 ℃, and working pressure is 0.02-0.05MPa (absolute pressure); Extraction BTX aromatics in top is as gasoline mediation product or, directly as aromatic hydrocarbon product, the bottom production returns and enters extraction system; All the other components of described extraction system enter the evaporation and dehydration system cutting of dewatering through top, and the head temperature of described evaporation and dehydration system is 110-130 ℃, and pressure is 0.4-0.6MPa, and bottom temp is 210-240 ℃, and pressure is 0.45-0.65MPa, total reflux; The a small amount of water of top extraction; Side line extraction mouth temperature is 128-153 ℃, and pressure is 0.41-0.61MPa, and the extraction lightweight is raffinated oil, and described lightweight is raffinated oil and not only be can be used as gasoline mediation product but also can be used as ethylene cracking material; Described evaporation and dehydration system bottom extraction treated oil, the gained treated oil enters another reaction unit and is reacted after heating, and the temperature in of described another reaction unit is 470-530 ℃, and inlet pressure is 1.0-1.6MPa, and the feed volume air speed is 1.0-2.0h
-1; The gained reaction product enters high-pressure separator after heat exchange is cooling.
A kind of optimal technical scheme, it is characterized in that: the reaction product of described reaction unit is first after second heating unit heating, enter the second reaction unit reaction (or connecting again more heating unit and corresponding reaction unit after the second reaction unit), the gained reaction product enters high-pressure separator after heat exchange is cooling again.
A kind of optimal technical scheme, it is characterized in that: the reaction product of described another reaction unit is first after the 4th heating unit heating, enter the 4th reaction unit reaction (or connecting again more heating unit and corresponding reaction unit after the 4th reaction unit), the gained reaction product enters high-pressure separator after heat exchange is cooling again.
Extraction system described in the present invention is that the patent No. is disclosed extraction system in 200310103541.9 and 200310103540.4, comprises solvent recuperation, water wash system, returns the system of washing etc.
The system of stabilizer tower described in the present invention and evaporation and dehydration system are conventional system, comprise tower, air-cooler, watercooler, return tank, reflux pump and column bottoms pump etc.
Process furnace described in the present invention and condensing works are conventional device.
Used catalyst described in the present invention in reactor is conventional reforming catalyst.
Beneficial effect:
The advantage of naphtha fecundation aromatic hydrocarbons reforming system of the present invention and method thereof is: with existing catalytic reforming process, compare, in naphtha fecundation aromatic hydrocarbons reforming system of the present invention and method, reacted product is after extracting and dehydration by evaporation under than low reaction pressure, the treated oil generated with enter another reactor after recycle hydrogen mixes and further react, make the processing power of system of the present invention improve, liquid yield, aromatic production and hydrogen yield improve greatly, the high-octane rating product is provided simultaneously, in addition owing to having isolated benzene, make the benzene content of premium blend component BTX aromatics greatly reduce.
Below by the drawings and specific embodiments, the present invention will be further described, but and do not mean that limiting the scope of the invention.
The accompanying drawing explanation
The schematic flow sheet that Fig. 1 is the embodiment of the present invention 1.
The schematic flow sheet that Fig. 2 is the embodiment of the present invention 2.
The schematic flow sheet that Fig. 3 is the embodiment of the present invention 3.
Embodiment
Embodiment 1
As shown in Figure 1, be the schematic flow sheet of the embodiment of the present invention 1.By boiling range, be 80-185 ℃, sulphur content is 0.5ppm, nitrogen content 0.5ppm, metal content is 5ppb, water content 5ppm, and Determination of Alkane Content is 70% (m), naphthene content is 28% (m), aromaticity content is 2% (m), and octane value (RON) is that 42,20 ℃ of density are 732 kg/ms
3, the paraffinic base that flow is 12.5 tons/hour is made with extra care feed naphtha (a) and is first passed through heat exchange, then, after process furnace 1-1 heating, enters reactor 2-1 and reacted, and the feed volume air speed is 3.0h
-1; The temperature in of described reactor 2-1 is 530 ℃, and inlet pressure is 1.0MPa (absolute pressure); The gained reaction product, after process furnace 1-2 heating, enters reactor 2-2 and is reacted, and the temperature in of described reactor 2-2 is 530 ℃, and inlet pressure is 1.0MPa (absolute pressure); Reaction product enters high-pressure separator 4 through heat exchange and condenser 3 after cooling and carries out the high pressure separation, and the service temperature of described high-pressure separator 4 is 35 ℃, and working pressure is 1.2MPa (absolute pressure); After high pressure separates, a gained hydrogen part is sent (b) outside, and its flow is 0.591 ton/hour, and pure hydrogen flow is 0.438 ton/hour, and hydrogen yield is 3.50% (weight); Other hydrogen is back to process furnace 1-1 and process furnace 1-3 through compressor 5, and wherein being back to the front hydrogen to oil volume ratio of process furnace 1-1 is 800: 1, and entering the front hydrogen to oil volume ratio of process furnace 1-3 is 1200: 1 (first carrying out heat exchange before entering process furnace); Entering stabilizer tower system 6 through high-pressure separator 4 gained reformates is processed, the tower top temperature of described stabilizer tower system 6 is 100 ℃, and pressure is 0.8MPa (absolute pressure), and column bottom temperature is 220 ℃, pressure is 0.85MPa (absolute pressure), and reflux ratio (m/m) is 0.90; Overhead extraction dry gas, liquefied gas and a small amount of water (c), its flow is 2.273 tons/hour; Gained reformed oil at the bottom of tower (boiling range is 35-196 ℃) enters extraction system 8 and is processed, the service temperature of described extraction system 8 is 100 ℃, and working pressure is 0.6MPa (absolute pressure), and solvent ratio is 3.0, return and wash than being 0.5, solvent for use is tetramethylene sulfone; After extraction system 8 extractings, gained is extracted oil out and is entered first recovery column 9-1, and the tower top temperature of described first recovery column is 85 ℃, and pressure is 0.1MPa (absolute pressure), and column bottom temperature is 175 ℃, and pressure is 0.15MPa (absolute pressure); Top extraction benzene (g), the purity of gained benzene is 99.99%, and freezing point is 5.45 ℃, and 20 ℃ of density are 879 kg/ms
3, flow is 0.258 ton/hour; The bottom production enters second recovery column 9-2, and the service temperature of described second recovery column is 110 ℃, and working pressure is 0.02MPa (absolute pressure); Top extraction BTX aromatics (e), the gained BTX aromatics can be used as gasoline and is in harmonious proportion product or directly as aromatic hydrocarbon product, its boiling range is 80-196 ℃, sulphur content trace (inspection does not measure), non-aromatics content is 2.0% (m), and aromaticity content is 98.0% (m), and benzene content is 0.32% (m), octane value (RON) is that 129,20 ℃ of density are 861 kg/ms
3, flow is 8.906 tons/hour, aromatics yield is 71.88% (weight); The bottom production returns and enters extraction system; After extraction system 8 extractings, the top that gained is raffinated oil through extraction system 8 enters evaporation and dehydration system 7 and is dewatered, the head temperature of described evaporation and dehydration system 7 is 110 ℃, pressure is 0.4MPa (absolute pressure), bottom temp is 210 ℃, pressure is 0.45MPa (absolute pressure), total reflux; The a small amount of water of top extraction (d), its flow is 0.001 ton/hour; Described evaporation and dehydration system 7 side line extraction mouth temperature are 128 ℃, pressure is 0.41MPa (absolute pressure), extraction lightweight raffinate oil (f), the boiling range that described lightweight is raffinated oil is 35-75 ℃, sulphur content trace (inspection does not measure), non-aromatics content is 99.9% (m), aromaticity content is 0.1% (m), octane value (RON) is that 69,20 ℃ of density are 564 kg/ms
3, flow is 0.473 ton/hour, it not only can be used as gasoline mediation product but also can be used as ethylene cracking material; Total liquid yield is 77.09%; Described evaporation and dehydration system 7 bottom extraction treated oils are as the charging of reactor 2-3, the boiling range of gained treated oil is 35-186 ℃, sulphur content trace (inspection does not measure), non-aromatics content is 98.8% (m), aromaticity content is 1.2% (m), octane value (RON) is that 63,20 ℃ of density are 738 kg/ms
3, flow is 4.401 tons/hour; The gained treated oil enters reactor 2-3 and is reacted after process furnace 1-3 heating, and the temperature in of described reactor 2-3 is 530 ℃, and inlet pressure is 1.0MPa (absolute pressure); The gained reaction product enters reactor 2-4 reaction after process furnace 1-4 heating, and the temperature in of described reactor 2-4 is 530 ℃, and inlet pressure is 1.0MPa (absolute pressure), and the feed volume air speed is 1.0h
-1; The gained reaction product with enter high-pressure separator 4 through heat exchange and condenser 3 after cooling after the reaction product of described reactor 2-2 is mixed.
Wherein pack into the ratio of catalytic amount of each reactor is:
Reactor 2-1: reactor 2-2=1: 1.5;
Reactor 2-3: reactor 2-4=1: 2.
The present invention's reforming catalyst used is a kind of Pt, Re reforming catalyst, its carrier mixes by a certain percentage for the mono-diaspore of GM and the mono-diaspore of Ziegler synthesising by-product SB that adopts aluminium colloidal sol deep fat ageing process to make, the compound γ-aluminium sesquioxide that two concentrated Kong Feng are arranged made through moulding, roasting.On catalyzer, Pt content is 0.10～1.00 heavy %, and Re content is 0.10～3.00 heavy %, and Cl content is 0.50～3.00 heavy %, and this catalyzer has the characteristics of high reactivity, highly selective and low carbon deposit.
In the present invention, total liquid yield equals that BTX aromatics, lightweight are raffinated oil, the flow sum of benzene is divided by the raw material inlet amount.
Aromatics yield equals the BTX aromatics flow and is multiplied by aromaticity content and adds that the flow of benzene is again divided by the raw material inlet amount.
Hydrogen yield equals to efflux the hydrogen amount and is multiplied by hydrogen purity again divided by the raw material inlet amount.
The physico-chemical property of reactor 2-1 and 2-2 used catalyst is as shown in the table:
| Specific surface area m 2/g | Intensity N/cm | Pore volume ml/g | Bulk density g/ml | Pt m％ | Re m％ |
| 192 | 183 | 0.52 | 0.75 | 0.25 | 0.25 |
The physico-chemical property of reactor 2-3 and 2-4 used catalyst is as shown in the table:
| Specific surface area m 2/g | Intensity N/cm | Pore volume ml/g | Bulk density g/ml | Pt m％ | Re m％ |
| 196 | 187 | 0.54 | 0.74 | 0.26 | 0.45 |
The present invention's measuring method used is (lower same):
1, boiling range: GB/T6536-1997 measured for petroleum product distillation method;
2, sulphur content: the total sulfur content assay method (ultraviolet fluorescence method) of SH/T0689-2000 light hydrocarbon and motor spirit and other oil products;
3, mercaptan sulfur: mercaptan sulfur assay method (potentiometric titration) in the GB/T1792-1988 distillate fuel oil;
4, alkane: SH/T0239-92 thin layer packed column chromatography;
5, aromatic hydrocarbons: GB/T11132-2002 liquid petroleum product hydro carbons assay method (fluorescent indicator adsorption method);
6, octane value: GB/T5487 testing octane number of gasoline method (organon);
7, density: GB/T1884-2000 crude oil and liquid petroleum product density experiment chamber assay method (densimeter method);
8, naphthenic hydrocarbon: SH/T0239-92 thin layer packed column chromatography;
9, metal in oil: the standard test methods of nickel, vanadium and iron in ASTM D 5708-2005 inductively coupled plasma (ICP) aes determination crude oil and trapped fuel;
10, nitrogen content: the SH/T0704-2001 chemoluminescence method is surveyed nitrogen (boat sample introduction).
Embodiment 2
As shown in Figure 2, be the schematic flow sheet of the embodiment of the present invention 2.By boiling range, be 80-185 ℃, sulphur content is 0.54ppm, nitrogen content 0.5ppm, metal content is 5ppb, water content 5ppm, and Determination of Alkane Content is 60% (m), naphthene content is 34% (m), aromaticity content is 6% (m), and octane value (RON) is that 50,20 ℃ of density are 738 kg/ms
3, the intermediate base that flow is 12.5 tons/hour is made with extra care feed naphtha (a) and is first passed through heat exchange, then, after process furnace 1-1 heating, enters reactor 2-1 and reacted; The feed volume air speed is 4.0h
-1; Wherein said reactor 2-1 by reactor 2-1 under upper and reactor 2-1 two reactors in series form, described reactor 2-1 go up and reactor 2-1 under temperature in be 500 ℃, inlet pressure is 1.3MPa (absolute pressure); Between two reactors, by process furnace 1-2, be connected; Enter high-pressure separator 4 through heat exchange and condenser 3 after cooling through products therefrom after reactor 2-1 reaction and carry out the high pressure separation, the service temperature of described high-pressure separator 4 is 40 ℃, and working pressure is 1.3MPa (absolute pressure); After high pressure separates, a gained hydrogen part is sent (b) outside, and its flow is 0.448 ton/hour, and pure hydrogen flow is 0.405 ton/hour, and hydrogen yield is 3.24% (weight); Other hydrogen is back to process furnace 1-1 and well heater 1-3 through compressor 5, wherein being back to the front hydrogen to oil volume ratio of process furnace 1-1 is 800: 1, and entering the front hydrogen to oil volume ratio of process furnace 1-3 is 1200: 1 (first carrying out heat exchange before entering reaction unit); Entering stabilizer tower system 6 through high-pressure separator 4 gained reformates is processed, the tower top temperature of described stabilizer tower system 6 is 102 ℃, and pressure is 0.95MPa (absolute pressure), and column bottom temperature is 227.5 ℃, pressure is 1.00MPa (absolute pressure), and reflux ratio (m/m) is 0.99; Overhead extraction dry gas, liquefied gas and a small amount of water (c), its flow is 1.226 tons/hour; Gained reformed oil at the bottom of tower (boiling range is 35-194 ℃) enters extraction system 8 and is processed, the service temperature of described extraction system 8 is 120 ℃, and working pressure is 0.8MPa (absolute pressure), and solvent ratio is 5, return and wash than being 0.7, solvent for use is the N-formyl morpholine; After extraction system 8 extractings, gained is extracted oil out and is entered first recovery column 9-1, and the tower top temperature of described first recovery column is 87 ℃, and pressure is 0.15MPa (absolute pressure), and column bottom temperature is 175 ℃, and pressure is 0.2MPa (absolute pressure); Top extraction benzene (g), the purity of gained benzene is 99.99%, and freezing point is 5.45 ℃, and 20 ℃ of density are 879 kg/ms
3, flow is 0.440 ton/hour; The bottom production enters second recovery column 9-2, and the service temperature of described second recovery column is 130 ℃, and working pressure is 0.035MPa (absolute pressure); Top extraction BTX aromatics (e), the gained BTX aromatics can be used as gasoline and is in harmonious proportion product or directly as aromatic hydrocarbon product, its boiling range is 80-194 ℃, sulphur content trace (inspection does not measure), non-aromatics content is 1.9% (m), and aromaticity content is 98.1% (m), and benzene content is 0.53% (m), octane value (RON) is that 131,20 ℃ of density are 862 kg/ms
3, flow is 9.200 tons/hour, aromatics yield is 75.72% (weight); The bottom production returns and enters extraction system; After extraction system 8 extractings, the top that gained is raffinated oil through extraction system 8 enters evaporation and dehydration system 7 and is dewatered, the head temperature of described evaporation and dehydration system 7 is 120 ℃, pressure is 0.5MPa (absolute pressure), bottom temp is 225 ℃, pressure is 0.55MPa (absolute pressure), total reflux; The a small amount of water of top extraction (d), its flow is 0.001 ton/hour; The side line extraction mouth temperature of described evaporation and dehydration system 7 is 141 ℃, pressure is 0.51MPa (absolute pressure), extraction lightweight raffinate oil (f), the boiling range that described lightweight is raffinated oil is 35-75 ℃, sulphur content trace (inspection does not measure), non-aromatics content is 99.8% (m), aromaticity content is 0.2% (m), octane value (RON) is that 70,20 ℃ of density are 571 kg/ms
3, flow is 1.185 tons/hour, it not only can be used as gasoline mediation product but also can be used as ethylene cracking material; Total liquid yield is 86.61%; The bottom extraction treated oil (as the charging of the second reactor 2-2) of described evaporation and dehydration system 7, the boiling range of gained treated oil is 35-184 ℃, sulphur content trace (inspection does not measure), non-aromatics content is 98.7% (m), aromaticity content is 1.3% (m), octane value (RON) is that 63,20 ℃ of density are 740 kg/ms
3, flow is 4.809 tons/hour; The gained treated oil is reacted through after process furnace 1-3 heating, entering reactor 2-2, described reactor 2-2 by reactor 2-2 under upper and reactor 2-2 two reactors in series form, between by process furnace 1-4 connection; Temperature under the upper and reactor 2-2 of described reactor 2-2 is 500 ℃, and inlet pressure is 1.3MPa (absolute pressure), and the feed volume air speed is 1.5h
-1; The gained reaction product enters high-pressure separator 4 through heat exchange and condenser 3 after cooling.
Wherein pack into the ratio of catalytic amount of each reactor is:
Reactor 2-1 is upper: under reactor 2-1=1: 2;
Reactor 2-2 is upper: under reactor 2-2=1: 2.5.
The physico-chemical property of reactor 2-1 used catalyst is as shown in the table:
| Specific surface area m 2/g | Intensity N/cm | Pore volume ml/g | Bulk density g/ml | Pt m％ | Re m％ |
| 192 | 183 | 0.52 | 0.75 | 0.25 | 0.25 |
The physico-chemical property of reactor 2-2 used catalyst is as shown in the table:
| Specific surface area m 2/g | Intensity N/cm | Pore volume ml/g | Bulk density g/ml | Pt m％ | Re m％ |
| 196 | 187 | 0.54 | 0.74 | 0.26 | 0.45 |
Embodiment 3
As shown in Figure 3, be the schematic flow sheet of the embodiment of the present invention 3.By boiling range, be 80-185 ℃, sulphur content is 0.45ppm, nitrogen content 0.5ppm, metal content is 5ppb, water content 5ppm, and Determination of Alkane Content is 47% (m), naphthene content is 42% (m), aromaticity content is 11% (m), and octane value (RON) is that 61,20 ℃ of density are 742 kg/ms
3, the cycloalkyl that flow is 12.5 tons/hour is made with extra care petroleum naphtha (a) and is first passed through heat exchange, then, after process furnace 1-1 heating, enters reactor 2-1 and reacted; The feed volume air speed is 5.0h
-1; The temperature in of described reactor 2-1 is 470 ℃, and inlet pressure is 1.6MPa (absolute pressure); The gained reaction product enters high-pressure separator 4 through heat exchange and condenser 3 after cooling and carries out the high pressure separation, and the service temperature of described high-pressure separator 4 is 45 ℃, and working pressure is 1.4MPa (absolute pressure); After high pressure separates, a gained hydrogen part is sent (b) outside, and its flow is 0.371 ton/hour, and pure hydrogen flow is 0.341 ton/hour, and hydrogen yield is 2.73% (weight); Other hydrogen is back to process furnace 1-1 and process furnace 1-2 through compressor 5, and wherein being back to the front hydrogen to oil volume ratio of process furnace 1-1 is 800: 1, and entering the front hydrogen to oil volume ratio of process furnace 1-2 is 1200: 1 (first carrying out heat exchange before entering process furnace); Entering stabilizer tower system 6 through high-pressure separator 4 gained reformates is processed, the tower top temperature of described stabilizer tower system 6 is 120 ℃, and pressure is 1.05MPa (absolute pressure), and column bottom temperature is 240 ℃, pressure is 1.10MPa (absolute pressure), and reflux ratio (m/m) is 1.15; Overhead extraction dry gas, liquefied gas and a small amount of water (c), its flow is 0.691 ton/hour; Gained reformed oil at the bottom of tower (boiling range is 35-192 ℃) enters extraction system 8 and is processed, the service temperature of described extraction system 8 is 150 ℃, and working pressure is 1.0MPa (absolute pressure), and solvent ratio is 8.0, return and wash than being 1.0, solvent for use is Tetraglycol 99; After extraction system 8 extractings, gained is extracted oil out and is entered first recovery column 9-1, and the tower top temperature of described first recovery column is 90 ℃, and pressure is 0.2MPa (absolute pressure), and column bottom temperature is 175 ℃, and pressure is 0.25MPa (absolute pressure); Top extraction benzene (g), the purity of gained benzene is 99.99%, and freezing point is 5.45 ℃, and 20 ℃ of density are 879 kg/ms
3, flow is 0.311 ton/hour; The bottom production enters second recovery column 9-2, and the service temperature of described second recovery column is 155 ℃, and working pressure is 0.05MPa (absolute pressure); Top extraction BTX aromatics (e), the gained BTX aromatics can be used as gasoline and is in harmonious proportion product or directly as aromatic hydrocarbon product, its boiling range is 80-192 ℃, sulphur content trace (inspection does not measure), non-aromatics content is 1.8% (m), and aromaticity content is 98.2% (m), and benzene content is 0.38% (m), octane value (RON) is that 134,20 ℃ of density are 865 kg/ms
3, flow is 9.113 tons/hour, aromatics yield is 74.08% (weight); The bottom production returns and enters extraction system; After extraction system 8 extractings, the top that gained is raffinated oil through extraction system 8 enters evaporation and dehydration system 7 and is dewatered, the head temperature of described evaporation and dehydration system 7 is 130 ℃, pressure is 0.6MPa (absolute pressure), bottom temp is 240 ℃, pressure is 0.65MPa (absolute pressure), total reflux; The a small amount of water of top extraction (d), its flow is 0.001 ton/hour; The side line extraction mouth temperature of described evaporation and dehydration system 7 is 153 ℃, pressure is 0.61MPa (absolute pressure), extraction lightweight raffinate oil (f), the boiling range that described lightweight is raffinated oil is 35-75 ℃, sulphur content trace (inspection does not measure), non-aromatics content is 99.7% (m), aromaticity content is 0.3% (m), octane value (RON) is that 71,20 ℃ of density are 575 kg/ms
3, flow is 2.014 tons/hour, it not only can be used as gasoline mediation product but also can be used as ethylene cracking material; Total liquid yield is 91.50%; The bottom extraction treated oil (as the charging of reactor 2-2) of described evaporation and dehydration system 7, the boiling range of gained treated oil is 35-182 ℃, sulphur content trace (inspection does not measure), non-aromatics content is 1.5% (m), aromaticity content is 98.5% (m), octane value (RON) is 64,20 ℃ of density, is 745 kg/ms
3, flow is 4.185 tons/hour; Described treated oil enters reactor 2-2 and is reacted after process furnace 1-2 heating, and the temperature in of described reactor 2-2 is 470 ℃, and inlet pressure is 1.6MPa (absolute pressure), and the feed volume air speed is 2.0h
-1; The gained reaction product enters high-pressure separator 4 through heat exchange and condenser 3 after cooling.
Wherein pack into the ratio of catalytic amount of each reactor is:
Reactor 2-1: reactor 2-2=1: 2.
The physico-chemical property of reactor 2-1 used catalyst is as shown in the table:
| Specific surface area m 2/g | Intensity N/cm | Pore volume ml/g | Bulk density g/ml | Pt m％ | Re m％ |
| 192 | 183 | 0.52 | 0.75 | 0.25 | 0.25 |
The physico-chemical property of reactor 2-2 used catalyst is as shown in the table:
| Specific surface area m 2/g | Intensity N/cm | Pore volume ml/g | Bulk density g/ml | Pt m％ | Re m％ |
| 196 | 187 | 0.54 | 0.74 | 0.26 | 0.45 |
Claims (3)
1. a naphtha productive aromatic hydrocarbon reforming method, its step is as follows: the feed naphtha that boiling range is 80-185 ℃, after the heating unit heating, enters reaction unit and is reacted; The temperature in of described reaction unit is 470-530 ℃, and the entrance absolute pressure is 1.0-1.6MPa, and the feed volume air speed is 3.0-5.0h
-1; The gained reaction product enters high-pressure separator and carries out the high pressure separation after heat exchange is cooling, and the service temperature of described high-pressure separator is 35-45 ℃, and the operation absolute pressure is 1.2-1.4MPa; After high pressure separates, a gained hydrogen part is sent outside, and a part is back to feed line and another reaction unit through compression set, the described hydrogen returned or advance into pipeline at process furnace, or enter pipeline after process furnace; The gained reformate enters the stabilizer tower system and is processed, the tower top temperature of described stabilizer tower system is 100-120 ℃, and absolute pressure is 0.8-1.05MPa, and column bottom temperature is 220-240 ℃, absolute pressure is 0.85-1.10MPa, and reflux ratio is 0.90-1.15; Overhead extraction dry gas, liquefied gas and a small amount of water; The reformed oil that at the bottom of tower, the gained boiling range is 35-196 ℃ enters extraction system and is processed, the service temperature of described extraction system is 100-150 ℃, the operation absolute pressure is 0.6-1.0MPa, solvent ratio is 3.0-8.0, return and wash than being 0.5-1.0, solvent for use is tetramethylene sulfone, N-formyl morpholine or Tetraglycol 99; After extracting, extraction system is extracted oil out and is entered first recovery column, and the tower top temperature of described first recovery column is 85-90 ℃, and absolute pressure is 0.1-0.2MPa, and column bottom temperature is 175 ℃, and absolute pressure is 0.15-0.25MPa; Top extraction benzene, the bottom production enters second recovery column, and the service temperature of described second recovery column is 110-155 ℃, and the operation absolute pressure is 0.02-0.05MPa; Extraction BTX aromatics in top is as gasoline mediation product or, directly as aromatic hydrocarbon product, the bottom production returns and enters extraction system; All the other components of described extraction system enter the evaporation and dehydration system cutting of dewatering through top, the head temperature of described evaporation and dehydration system is 110-130 ℃, and absolute pressure is 0.4-0.6MPa, and bottom temp is 210-240 ℃, absolute pressure is 0.45-0.65MPa, total reflux; The a small amount of water of top extraction; Be provided with side line extraction mouth, its temperature is 128-153 ℃, and absolute pressure is 0.41-0.61MPa, and the extraction lightweight is raffinated oil, and described lightweight is raffinated oil and not only be can be used as gasoline mediation product but also can be used as ethylene cracking material; Described evaporation and dehydration system bottom extraction treated oil, treated oil enters another reaction unit and is reacted after heating, and the temperature in of described another reaction unit is 470-530 ℃, and the entrance absolute pressure is 1.0-1.6MPa, and the feed volume air speed is 1.0-2.0h
-1; The gained reaction product enters high-pressure separator after heat exchange is cooling.
2. naphtha productive aromatic hydrocarbon reforming method according to claim 1, it is characterized in that: described reaction unit comprises the first reaction unit and the second reaction unit, the first reaction unit is connected by secondary heating mechanism with the second reaction unit.
3. naphtha productive aromatic hydrocarbon reforming method according to claim 2, it is characterized in that: described another reaction unit comprises the 3rd reaction unit and the 4th reaction unit, the 3rd reaction unit is connected by the 4th heating unit with the 4th reaction unit.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3640818A (en) * | 1969-10-31 | 1972-02-08 | Exxon Research Engineering Co | Hydroforming naphthas |
| US4975178A (en) * | 1988-05-23 | 1990-12-04 | Exxon Research & Engineering Company | Multistage reforming with interstage aromatics removal |
| CN201241102Y (en) * | 2008-06-04 | 2009-05-20 | 北京金伟晖工程技术有限公司 | Naphtha fecundation aromatic hydrocarbons reforming system |
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2009
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3640818A (en) * | 1969-10-31 | 1972-02-08 | Exxon Research Engineering Co | Hydroforming naphthas |
| US4975178A (en) * | 1988-05-23 | 1990-12-04 | Exxon Research & Engineering Company | Multistage reforming with interstage aromatics removal |
| CN201241102Y (en) * | 2008-06-04 | 2009-05-20 | 北京金伟晖工程技术有限公司 | Naphtha fecundation aromatic hydrocarbons reforming system |
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