CN1323130C - Hydro-delayed coking method - Google Patents
Hydro-delayed coking method Download PDFInfo
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- CN1323130C CN1323130C CNB2004100298727A CN200410029872A CN1323130C CN 1323130 C CN1323130 C CN 1323130C CN B2004100298727 A CNB2004100298727 A CN B2004100298727A CN 200410029872 A CN200410029872 A CN 200410029872A CN 1323130 C CN1323130 C CN 1323130C
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- 238000004939 coking Methods 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000000571 coke Substances 0.000 claims abstract description 101
- 239000007789 gas Substances 0.000 claims abstract description 58
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 27
- 239000003502 gasoline Substances 0.000 claims abstract description 25
- 230000003111 delayed effect Effects 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 44
- 238000010411 cooking Methods 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000011301 petroleum pitch Substances 0.000 claims description 2
- 238000004230 steam cracking Methods 0.000 claims description 2
- 238000004227 thermal cracking Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 239000011593 sulfur Substances 0.000 abstract description 10
- 239000012263 liquid product Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 239000002283 diesel fuel Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 66
- 230000008569 process Effects 0.000 description 32
- 239000005864 Sulphur Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000005587 bubbling Effects 0.000 description 17
- 239000000725 suspension Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 230000001698 pyrogenic effect Effects 0.000 description 11
- 238000004508 fractional distillation Methods 0.000 description 10
- 230000005855 radiation Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 241000282326 Felis catus Species 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000009866 aluminium metallurgy Methods 0.000 description 4
- 238000005235 decoking Methods 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 230000003321 amplification Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000000852 hydrogen donor Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000009671 shengli Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Coke Industry (AREA)
Abstract
The present invention relates to a hydrogenation delayed coking method. Coking stock and optional coking circulation oil contact hydrogen and catalysts before entering a coke tower, hydrogenated oil is added into the coking materials and the optional coking circulation oil, the mixed materials are depressurized and enter a coking heating furnace to be heated to a coking temperature, the mixed materials enter a coke tower then, generated coke stays in the coke tower, and coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil. The method increases the yield of liquid products, reduces the sulfur content of coke, reduces the coking tendency of furnace tubes and extends operation cycles of heating furnaces.
Description
Technical field
The present invention relates to a kind of with the refining hydrocarbon ils of hydrogen and refining after the thermal non-catalytic cracking multistage processes of hydrocarbon ils, more particularly, be a kind of hydrogenation delayed coking method.
Background technology
Because investment and process cost are low, can become heavy oil conversion products such as costly liquid and refinery coke, delayed coking still is to be subjected to the Heavy Oil Processing Technology that people generally pay attention to.In the actual procedure, people run into such technical barrier, promptly for the coking raw material of poor quality, wish to improve liquid as far as possible and receive, and reduce dry gas and coking yield.Simultaneously, the inferior coking raw material high to foreign matter contents such as sulphur reaches 1.2～1.5% as the CHARACTERISTICS OF SHENGLI VACUUM RESIDUE WITH sulphur content, and the Middle East dregs of fat oil sulphur content of China's import is especially up to 2～6%.Adopt existing delayed coking unit to process the residual oil raw material of impurity such as high sulfur-bearing, the sulphur content of one of its product coke reaches more than 2%, be difficult to as the aluminium metallurgy coke, even because of the restriction of environmental protection aspect, acting as a fuel also is underproof coke.At present, aluminium metallurgy is in great demand with coke in the world, and China only aluminium metallurgy reaches 4,200,000 tons with the annual demand of coke.Coke is mainly with the lattice of how much determining the price of its sulphur content, and sulphur content is a sulphur content less than 40% of 1.5% coke price greater than 2% coke price.Wax tailings in the coking distillate is as another product of delayed coking, and foreign matter contents such as its sulphur also raise because of coking processing high-sulfur inferior raw material, also can cause the high problem of catalytic gasoline product sulphur content, or increase catalytic unit investment and process cost.The coker gasoline in the coking distillate and the foreign matter contents such as sulphur of coker gas oil also raise because of coking processing high-sulfur inferior raw material, cause its hydro-refining unit investment and process cost to increase.
How can existing delayed coking unit be improved, improve liquid receives as far as possible, reduce dry gas and coking yield? or for the high-sulfur inferior raw material, when improving the liquid receipts, change Impurity Distribution such as sulphur, reduce, make coke quality reach the aluminium metallurgy above level of coke as the sulphur content in the coke, do foreign matter contents such as coking distillate sulphur reduce as far as possible? if accomplish this point, then obviously the economic benefit that improves coker is had very great help.
US4394250 discloses a kind of catalytic coking method, and this method improves the coking distillate yield and reduces coking yield at process furnace inlet injection hydrogen and catalyzer.Because be subjected to only 20-200psig (about 0.14-1.4MPaG) of the restriction of furnace tubing and coke drum reaction conditions such as pressure, the amplification of coking distillate yield is not too large, when particularly processing the high-sulfur inferior raw material, the sulphur content of coke is higher.
US5711870 discloses the preceding delayed coking method that injects hydrogen donor of a kind of process furnace, and this method can improve the coking distillate yield, reduces coke and gas recovery ratio.This method does not add catalyzer, and the amplification of coking distillate yield is not too large, and when particularly processing the high-sulfur inferior raw material, the sulphur content of coke is higher.
US4919793 discloses a kind of improved coking method, this method is to increase thermally splitting pipe (soaking pipe) before process furnace, hydrogen-rich gas or hydrogen are injected the thermally splitting pipe, at 200-650psig (about 1.4-4.5MPaG), 400-650 (about 204-343 ℃), hydrogen-oil ratio 30-300SCF (about 5.3-53Nm
3/ m
3) stop 10-90min under the condition, the residual oil raw material before the coking heater is carried out hydro-upgrading in the thermally splitting pipe, improve coke chemicals liquid and receive and character by improving coking raw material, reduce coke, gas recovery ratio.This method is emphasized the catalyst-free condition, and the amplification of coking distillate yield is not too large, and when particularly processing the high-sulfur inferior raw material, the sulphur content of coke is higher.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of hydrogenation delayed coking method, significantly to improve the sulphur content of liquid product yield and reduction coke.
Method provided by the invention comprises: coking raw material, optional coking recycle oil are before advancing coke drum, contact with hydrogen, catalyzer, hydrogenated oil enters coke drum through entering after the step-down after coking heater is heated to coking temperature, the coke that generates is stayed in the coke drum, and coking oil gas obtains cooking gas, coker gasoline, coker gas oil, wax tailings through separation.
Method of the present invention improves the quality of coke, also improved the quality and the yield of coker gasoline, coker gas oil, wax tailings, reduced the tube coking tendency, prolonged the furnace operation cycle.
Description of drawings
Fig. 1 is conventional delayed coking method schematic flow sheet.
Fig. 2 is the schematic flow sheet of one of hydrogenation delayed coking method embodiment provided by the invention.
Fig. 3 is two a schematic flow sheet of hydrogenation delayed coking method embodiment provided by the invention.
Embodiment
Conventional delayed coking process is as follows:
Coking raw material advances coking heater through the laggard coking fractional distillation column of heat exchange with coking recycle oil and is heated to coking temperature and advances coke drum, because the pyrogenic reaction aggregate performance is heat absorption, coking raw material and coking recycle oil rely in coke drum and absorb self heat generation pyrogenic reaction, carrying out along with reaction, temperature of charge descends, it is low 30 ℃～80 ℃ than its temperature in to reach overhead oil temperature degree in this coke drum, the coke that generates is stayed in the coke drum, and the cooking gas of generation and coking distillate advance coking fractional distillation column with part turning oil and isolate cooking gas, coker gasoline, coker gas oil, wax tailings.The coke drum outer wall is established thermal insulation layer, the operation coke drum fills burnt behind suitable height, change the tower operation, change coking raw material and advance second coke drum, the origin operation coke drum carries out cold Jiao and decoking operation, to change tower be a coking operation cycle to each coke drum to being full of coke from feed switched, and a coking cycle is 16～48 hours.
Method provided by the invention is so concrete enforcement:
One of embodiment:
The present invention improves by the delay coking process to routine, a kind of hydrogenation coking process is proposed, promptly between radiation fresh feed pump and coking heater, increase suspension bubbling bed hydroprocessing reactor, improve radiation fresh feed pump top hole pressure, make it become suspension bubbling bed hydroprocessing reactor feed pump simultaneously, after injecting a certain amount of catalyzer in the coking raw material of radiation fresh feed pump outlet and the turning oil, inject on suspension bubbling bed hydroprocessing reactor top, inject hydrogen at suspension bubbling bed hydroprocessing reactor lower part, coking raw material and turning oil are at high temperature, high pressure, under the condition that hydrogen and catalyzer exist, in suspension bubbling bed hydroprocessing reactor, carry out hydrogenation reaction.It generates oil and enters process furnace be heated to coking temperature and advance coke drum and carry out pyrogenic reaction again after decompression, the coke that generates is stayed in the coke drum, and the cooking gas of generation and coking distillate advance coking fractional distillation column with part turning oil through coke cat head gas pipeline and isolate cooking gas, coker gasoline, coker gas oil, wax tailings.Like this before pyrogenic reaction by introducing the floating bed hydrogenation reaction of coking raw material and turning oil, make the product of device distribute and the bigger change of Impurity Distribution generation such as sulphur.
Two of embodiment:
The present invention is by improving the coking raw material pump discharge pressure, make the coking raw material pump become the fresh feed pump of suspension bubbling bed hydroprocessing reactor simultaneously, stock oil through feedstock pump boost, heat exchange and process furnace convection zone and partial radiation section enter suspension bubbling bed hydroprocessing reactor top after being heated to certain temperature, enter in the preceding raw material of reactor and inject a certain proportion of catalyzer, inject hydrogen at reactor lower part, hydrogenation reaction takes place in coking raw material in suspension bubbling bed hydroprocessing reactor under the condition that high temperature, high pressure, hydrogen, catalyzer exist.It generates oil and enters through decompression again and enter coke drum after the process furnace radiation section is heated to coking temperature and carry out pyrogenic reaction, the coke that generates is stayed in the coke drum, and the cooking gas of generation, coker gasoline, coker gas oil, wax tailings enter coking fractional distillation column with the part coking recycle oil through coke cat head gas pipeline and isolate cooking gas, coker gasoline, coker gas oil, wax tailings and coking recycle oil.The coking recycle oil of telling at the bottom of the tower can partly or entirely return the feed circuit freshening, also can be used as oil fuel and goes out device.Like this before pyrogenic reaction by introducing the floating bed hydrogenation reaction of coking raw material and turning oil, make the product of device distribute and bigger change takes place Impurity Distribution such as sulphur.
Described coking raw material is selected from residual oil, thermal cracking residue or its mixture of long residuum, vacuum residuum, petroleum pitch, heavy distillate, catalytically cracked oil or clarified oil, preparing ethylene by steam cracking, its sulphur content is more preferably greater than 1 heavy %, or Kang Shi carbon residue is greater than 13 heavy %, or viscosity (80 ℃) is greater than 1000mm
2/ s, or asphalt content is greater than 2 heavy %, or acid number is greater than the residual oil of 0.5%mgKOH/g.The coking raw material character that the present invention relates to is poor more, shows technical superiority of the present invention more.
The suspension bubbling bed hydroprocessing reactor that the present invention increases can be a vertical reactor, hydrogen advances from reactor lower part, gas phase goes out from reactor top, coking raw material and turning oil and catalyzer portion from it advance, hydrogenated oil goes out from its underpart, and reactor lower part has vapor distributor, and the foam removal net is arranged at top, the reactor middle part is provided with the facility that vapour-liquid fully contacts, as is provided with sieve tray or filler.
The gas phase that goes out from reactor top goes recycle compressor to boost to 4.5～30.0MPaG after cooling and isolating lime set, turn back to reactor lower part again, the hydrogen of system consumption adds to the recycle compressor outlet by the outer new hydrogen of device after make-up hydrogen compressor boosts to corresponding pressure.The generation oil that goes out from reactor lower part enters coking heater and is heated to 475 ℃～550 ℃ coking temperatures behind the 1.5～5.0MPaG that reduces pressure, advance coke drum through the furnace outlet transfer line again and carry out pyrogenic reaction.
The amounts of hydrogen that the reaction tower inlet injects is 50～2000Nm
3/ m
3(20 ℃ of volumes of raw material), replenishing new hydrogen amount is 10～300Nm
3/ m
3(20 ℃ of volumes of raw material).The catalyzer inlet or on the radiation pump intake pipeline, also can on raw material surge tank or feedstock pump gangway pipeline, also can inject separately on reactor top in the coking raw material system on the reactor inlet pipeline.The catalyzer injection rate is 0.01～10 heavy % of material quantity, and the catalyst activity component is metal, metal oxide, the metallic sulfide of carbon dust and VIII family element, as Fe, Fe
2O
3, Fe
3O
4, FeS, FeSO
4, FeSO
3Deng.The catalyzer that injects can be water miscible, also can be oil-soluble.
Coking raw material and the turning oil temperature of reaction in reaction tower is 300～425 ℃, and the residence time is that benchmark is calculated as 3～600 minutes with 20 ℃ of coking fresh material, or under the identical benchmark, its air speed is 0.1～20h
-1, the reaction stagnation pressure is 4.5～30.0MPaG, the hydrogen dividing potential drop is 3.0～25.0MPaG.
Outlet Temperature in Delayed Coking Furnace is 475 ℃～550 ℃, and the coke tower top pressure is 0.1～0.3MPaG, and the recycle ratio of device is 0～1.0.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Fig. 1 is conventional delayed coking method schematic flow sheet.
A conventional stove two tower delayed coking method flow processs are as follows: raw material enters surge tank 2 by pipeline 1, enter coking fractional distillation column 12 bottoms by surge tank 2 bottoms through pipeline 3, with the heat exchange of coking oil gas part, the bottoms material advances coking heater 6 by pipeline 5 and is heated to coking temperature after radiation fresh feed pump 4 boosts, before the process furnace inlet, inject water to slow down tube coking by the coking material of pipeline 16 in boiler tube, the coking material that goes out process furnace advances coke drum 8 (or coke drum 10) by pipeline 7 (or pipeline 9), pyrogenic reaction takes place in coking raw material in coke drum, the coke that generates is stayed in the coke drum, coking oil gas goes out the coke cat head and advances coking fractional distillation column 12 by pipeline 11, isolate cooking gas, coker gasoline, coker gas oil, wax tailings, cooking gas, coker gasoline is derived by pipeline 13, coker gas oil is derived by pipeline 14, wax tailings is derived by pipeline 15, and coking recycle oil returns coking system.Coke drum 8,10 24 hours was a timed interval blocked operation with a coking cycle, a coking cycle finishes, coke drum 8 is full of coke, and the furnace outlet material switches to the burnt process of filling that coke drum 10 repeats coke drum 8, and coke drum 8 carries out operations such as cold Jiao, decoking.
Fig. 2 is the schematic flow sheet of one of hydrogenation delayed coking method embodiment provided by the invention.
One of hydrogenation delayed coking method embodiment provided by the invention flow process is as follows: raw material enters surge tank 2 by pipeline 1, enter coking fractional distillation column 12 bottoms by surge tank 2 bottoms through pipeline 3, with the heat exchange of coking oil gas part, the bottoms material enters suspension bubbling bed hydroprocessing reactor 18 tops by after pipeline 5 and the catalyst mix from pipeline 28 after radiation fresh feed pump 4 boosts, hydrogen enters suspension bubbling bed hydroprocessing reactor 18 bottoms by pipeline 27, and material and catalyzer and hydrogen carry out reversely contacting and hydrogenation reaction taking place fully.Generating oil goes out at the bottom of the reactor after reducing valve 29 decompressions, enter process furnace 6 by pipeline 19 and be heated to coking temperature, inject water at its process furnace inlet through the coking material of pipeline 16 in boiler tube, the coking material that goes out process furnace advances coke drum 8 (or coke drum 10) by pipeline 7 (or pipeline 9), pyrogenic reaction takes place in coke drum through the coking raw material behind the hydrogenation, the coke that generates is stayed in the coke drum, coking oil gas goes out the coke cat head and advances coking fractional distillation column 12 by pipeline 11 and isolate cooking gas, coker gasoline, coker gas oil, wax tailings, cooking gas, coker gasoline is derived by pipeline 13, coker gas oil is derived by pipeline 14, wax tailings is derived by pipeline 15, and coking recycle oil returns coking system.Coke drum 8,10 24 hours was a timed interval blocked operation with a coking cycle, a coking cycle finishes, coke drum 8 is full of coke, and the furnace outlet material switches to the burnt process of filling that coke drum 10 repeats coke drum 8, and coke drum 8 carries out operations such as cold Jiao, decoking.The gas at suspension bubbling bed hydroprocessing reactor 18 tops advances cold anticyclone vapour liquid separator 22 via heat exchange water cooler 20, pipeline 21 successively, the light oil of separator 22 bottoms drains into separation column 12 by pipeline 23, the recycle hydrogen at separator 22 tops advances recycle compressor 26 by pipeline 25 and boosts, by pipeline 27 bubbling bed hydroprocessing reactor 18 bottoms of advancing to suspend, establish part recycle hydrogen outfall pipeline 24 density of hydrogen with Control Circulation hydrogen at separator 22 tops, the required new hydrogen of system is mended by pipeline 17.
Fig. 3 is two a schematic flow sheet of hydrogenation delayed coking method embodiment provided by the invention.
Two flow processs of hydrogenation delayed coking method embodiment provided by the invention are as follows: raw material enters surge tank 2 by pipeline 1, be heated to certain temperature through convection zone and the partial radiation section that pipeline 3, feedstock pump 4, interchanger 30, pipeline 31 enter process furnace 6 successively by surge tank 2 bottoms, after pipeline 5 and catalyst mix from pipeline 28, enter suspension bubbling bed hydroprocessing reactor 18 tops, hydrogen enters suspension bubbling bed hydroprocessing reactor 18 bottoms by pipeline 27, and material and catalyzer and hydrogen carry out reversely contacting and hydrogenation reaction taking place fully.Generating oil goes out at the bottom of the reactor after reducing valve 29 decompressions, the radiation section that is entered process furnace 6 by pipeline 19 is heated to coking temperature, inject water at its process furnace inlet through the coking material of pipeline 16 in boiler tube, the coking material that goes out process furnace advances coke drum 8 (or coke drum 10) by pipeline 7 (or pipeline 9), pyrogenic reaction takes place in coke drum through the coking raw material behind the hydrogenation, the coke that generates is stayed in the coke drum, coking oil gas goes out the coke cat head and advances coking fractional distillation column 12 by pipeline 11 and isolate cooking gas, coker gasoline, coker gas oil, wax tailings, cooking gas, coker gasoline is derived by pipeline 13, coker gas oil is derived by pipeline 14, wax tailings is derived by pipeline 15, and heavy wax tailings is drawn coker through column bottoms pump 32 by pipeline 33 by coking fractional distillation column 12. Coke drum 8,10 24 hours was a timed interval blocked operation with a coking cycle, a coking cycle finishes, coke drum 8 is full of coke, and the furnace outlet material switches to the burnt process of filling that coke drum 10 repeats coke drum 8, and coke drum 8 carries out operations such as cold Jiao, decoking.The gas at suspension bubbling bed hydroprocessing reactor 18 tops advances cold anticyclone vapour liquid separator 22 via pipeline 21, heat exchange water cooler 20 successively, the light oil of separator 22 bottoms drains into separation column 12 by pipeline 23, the recycle hydrogen at separator 22 tops advances recycle compressor 26 by pipeline 25 and boosts, by pipeline 27 bubbling bed hydroprocessing reactor 18 bottoms of advancing to suspend, establish part recycle hydrogen outfall pipeline 24 density of hydrogen with Control Circulation hydrogen at separator 22 tops, the required new hydrogen of system is mended by pipeline 17.
Because raw material has carried out reactions such as hydrogenating desulfurization, denitrogenation, hydro-upgrading earlier, carry out pyrogenic reaction again, the liquid yield of Zui Da raising device has reduced coking yield like this, the sulphur of product such as coker gasoline, coker gas oil, wax tailings, nitrogen content reduce simultaneously, and the sulphur content of coke reduces.The advantage of this technology is to have improved coke quality, also improved the quality of coker gasoline, coker gas oil, wax tailings, reduced coker gasoline, the investment of coker gas oil back end hydrogenation refining plant and process cost, and the tooling cost of wax tailings catalytic cracking and raising catalytic gasoline quality.In addition,, and contain gas such as a certain amount of hydrogen in the hydrogenated oil, reduced the tube coking tendency, prolonged the furnace operation cycle because the material that advances coking heater has carried out hydro-upgrading.
The following examples will give further instruction to present method, but therefore not limit present method.
The used coking raw material of embodiment and Comparative Examples is a high-sulfur vacuum residuum inferior, and its character is as shown in table 1.The used hydrogenation catalyst of embodiment is FeSO
4(average diameter of particles is 40～100 μ m), catalytic amount account for the heavy 500ppm of raw material.
Comparative Examples
Comparative Examples is to test on medium-sized tester according to conventional delayed coking method flow process, and operational condition and product distribute as shown in table 2, and the main character of coke and coking distillate is as shown in table 3.As can be seen from Table 2, the total liquid yield of coker gasoline, coker gas oil, wax tailings is 68.4m%; As can be seen from Table 3, the sulphur content of coke is up to 3.3m%.
Embodiment
Embodiment tests on medium-sized tester according to two flow process of hydrogenation delayed coking method embodiment provided by the invention, and operational condition and product distribute as shown in table 2, and the main character of coke and coking distillate is as shown in table 3.As can be seen from Table 2, the total liquid yield of coker gasoline, coker gas oil, wax tailings is 70.7m%; As can be seen from Table 3, the sulphur content of coke only is 1.45m%, and the sulphur of coker gasoline, coker gas oil, wax tailings, nitrogen content are all than the corresponding reduction of Comparative Examples.
Table 1
| Material name | The high-sulfur poor residuum |
| Density (20 ℃), g/cm 3 | 0.9862 |
| Sulphur content, m% | 2.25 |
| Nitrogen content, m% | 0.86 |
| Bituminous matter, m% | 2.3 |
| Aromatic hydrocarbons and colloid, m% | 70.8 |
| Carbon residue, m% | 13.7 |
| Ash content, m% | 0.06 |
| 80 ℃ of kinematic viscosity, mm 2/s | 1275.2 |
Table 2
| Comparative Examples | Embodiment | |
| Operational condition | ||
| Operational cycle, h | 24 | 24 |
| The furnace outlet temperature, ℃ | 500 | 500 |
| Recycle ratio | 0.4 | 0.4 |
| The coke tower top pressure, MPaG | 0.15 | 0.15 |
| The stokehold water injection rate, m% | 2 | 2 |
| The catalyzer injection rate, ppm | - | 500 |
| The hydrogen injection rate, Nm 3/m 3 | - | 800 |
| The hydrogenation reaction temperature, ℃ | - | 365 |
| Hydrogenation reaction pressure, MPaG | - | 10.0 |
| The hydrogenation reaction air speed, h -1 | - | 1.0 |
| Product distributes, m% | ||
| Cooking gas | 8.5 | 8.3 |
| Coker gasoline | 13.1 | 14.8 |
| Coker gas oil | 32.4 | 36.8 |
| Wax tailings | 22.9 | 7.8 |
| Heavy wax tailings | - | 11.3 |
| Get rid of oil and loss | 2.5 | 2.5 |
| Coke | 21.6 | 18.5 |
| Add up to | 100.0 | 100.0 |
Table 3
| Comparative Examples | Embodiment | |
| Coke part character | ||
| True density (green coke), g/cm 3 | 1.379 | 1.352 |
| Sulphur content, m% | 3.3 | 1.45 |
| Ash content, m% | 0.22 | 0.43 |
| Volatile matter, m% | 11.9 | 12.5 |
| Wax tailings * part character | ||
| Density (20 ℃), g/cm 3 | 0.9302 | 0.9193 |
| Sulphur content, m% | 1.82 | 0.82 |
| Nitrogen content, m% | 0.78 | 0.45 |
| Carbon residue, m% | 0.25 | 0.08 |
| 100 ℃ of kinematic viscosity, mm 2/s | 3.525 | 3.453 |
| Coker gas oil part character | ||
| Density (20 ℃), g/cm 3 | 0.8356 | 0.8283 |
| Sulphur content, m% | 0.66 | 0.32 |
| Nitrogen content, m% | 0.28 | 0.15 |
| Coker gasoline oil part character | ||
| Density (20 ℃), g/cm 3 | 0.7376 | 0.7358 |
| Sulphur content, m% | 0.58 | 0.22 |
| Nitrogen content, mg/kg | 210 | 90 |
Annotate:
*The wax tailings of the embodiment wax tailings of attaching most importance to.
Claims (5)
1, a kind of hydrogenation delayed coking method, coking raw material enters coke drum with the coking recycle oil of choosing wantonly after coking heater is heated to coking temperature, the coke that generates is stayed in the coke drum, coking oil gas obtains cooking gas, coker gasoline, coker gas oil, wax tailings through separation, it is characterized in that coking raw material, optional coking recycle oil are before advancing coke drum, contact with hydrogen, catalyzer, hydrogenated oil enters coking heater after step-down, described catalyzer injection rate is 0.01～10 heavy % of material quantity.
2,, it is characterized in that described coking raw material is selected from the residual oil of long residuum, vacuum residuum, petroleum pitch, heavy distillate, catalytically cracked oil or clarified oil, preparing ethylene by steam cracking, thermal cracking residue or its mixture according to the method for claim 1.
3, according to the method for claim 1, it is characterized in that hydrogenation conditions is: stagnation pressure is 4.5～30.0MPaG, and the hydrogen dividing potential drop is 3.0～25.0MPaG, 300～425 ℃ of temperature, the volume ratio 50～2000Nm of hydrogen and raw material
3/ m
3
4,, it is characterized in that described catalyst activity component is the metal of VIII family element, metal oxide, metallic sulfide and carbon dust according to the method for claim 1.
5, according to the method for claim 1, it is characterized in that Outlet Temperature in Delayed Coking Furnace is 475 ℃～550 ℃, the coke tower top pressure is 0.1～0.3MPaG, the recycle ratio of device is 0～1.0.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100298727A CN1323130C (en) | 2004-03-31 | 2004-03-31 | Hydro-delayed coking method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100298727A CN1323130C (en) | 2004-03-31 | 2004-03-31 | Hydro-delayed coking method |
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| CN1676573A CN1676573A (en) | 2005-10-05 |
| CN1323130C true CN1323130C (en) | 2007-06-27 |
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| CNB2004100298727A Expired - Lifetime CN1323130C (en) | 2004-03-31 | 2004-03-31 | Hydro-delayed coking method |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305270B (en) * | 2013-06-25 | 2015-04-15 | 中石化南京工程有限公司 | Technique method of producing high-quality coke by residual oil or medium and low temperature coal tar |
| CN103305271B (en) * | 2013-06-25 | 2015-10-21 | 中石化南京工程有限公司 | The combined technical method of a kind of residual oil/middle coalite tar lighting |
| CN104927920B (en) * | 2014-03-21 | 2017-03-15 | 中国石油化工股份有限公司 | A kind of residuum coking method |
| CN109207186B (en) * | 2017-07-03 | 2021-06-11 | 中国石油化工股份有限公司 | Delayed coking process and coking liquids and/or cokes obtained therefrom |
| CN111425626B (en) * | 2019-01-10 | 2021-10-08 | 中石化广州工程有限公司 | Oil switching valve and use method thereof in delayed coking device |
| US11312912B2 (en) | 2019-05-29 | 2022-04-26 | Saudi Arabian Oil Company | Hydrogen-enhanced delayed coking process |
| CN113122303B (en) * | 2019-12-31 | 2022-06-07 | 中国石油化工股份有限公司 | Method and system for improving stability of needle coke production process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098336C (en) * | 2000-02-18 | 2003-01-08 | 中国石油化工集团公司 | Residue hydrogenating and delaying coking combined process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1098336C (en) * | 2000-02-18 | 2003-01-08 | 中国石油化工集团公司 | Residue hydrogenating and delaying coking combined process |
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