EP0156614B1 - Cokéfaction de résidu en présence d'un donneur d'hydrogène - Google Patents
Cokéfaction de résidu en présence d'un donneur d'hydrogène Download PDFInfo
- Publication number
- EP0156614B1 EP0156614B1 EP85301883A EP85301883A EP0156614B1 EP 0156614 B1 EP0156614 B1 EP 0156614B1 EP 85301883 A EP85301883 A EP 85301883A EP 85301883 A EP85301883 A EP 85301883A EP 0156614 B1 EP0156614 B1 EP 0156614B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrogen
- donating
- diluent
- feedstock
- zone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004939 coking Methods 0.000 title claims description 23
- 239000000852 hydrogen donor Substances 0.000 title claims description 18
- 239000000571 coke Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 32
- 238000009835 boiling Methods 0.000 claims description 25
- 239000003085 diluting agent Substances 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- 229930195733 hydrocarbon Natural products 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 239000000386 donor Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 3
- 239000003921 oil Substances 0.000 description 35
- 239000000047 product Substances 0.000 description 16
- 230000003111 delayed effect Effects 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- -1 that is Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
- C10B57/045—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing mineral oils, bitumen, tar or the like or mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/005—Coking (in order to produce liquid products mainly)
Definitions
- the present invention relates to a process for obtaining increased yields of liquid hydrocarbons from coking feedstocks by introducing hydrogen-donating hydrocarbon material together with the feedstock.
- a gas oil and/or residuum is heated rapidly to coking temperature, initiating thermal breakdown, and passed into a coking drum, where the hot material continues thermal breakdown and conversion to lighter hydrocarbons and coke.
- Coke yields in such processes can be as large as 30% or more, and the production of large amounts of this low-valued material is uneconomic.
- Processes known in the art include the manufacture of premium coke, that is, coke having a low coefficient of thermal expansion (CTE), which is higher-valued than conventional coke.
- CTE coefficient of thermal expansion
- Wilson et al in U.S. Patent 3 617 513, disclosed a process for converting coal into liquid hydrocarbon products.
- Coal was slurried with a hydrogen donor solvent boiling in the range from 177°C to 482°C, liquefied and the bottoms, containing liquid liquefaction products, non-liquefied solid coal particles and unconsumed hydrogen-donor solvent was passed to a fluid coking zone.
- Operating conditions in the fluid coking zone included temperatures of from 538°C to 816°C.
- the present invention provides a method for treating heavy hydrocarbonaceous oil feedstock, comprising:
- the invention also resides in a method for reducing the amount of coke production in the coking of heavy hydrocarbonaceous oil feedstock, comprising the steps as listed above.
- the process of the invention utilises a hydrogen-donating hydrocarbon diluent to provide sufficient hydrogen to add to at least a portion of the radicals that are created from the residuum feedstock when it is exposed to temperatures in the coking range, i.e. from 420°C to 500°C.
- the hydrogen-donating diluent has a boiling range from 180°C to 400°C, preferably from 200°C to 350°C, at atmospheric pressure.
- the donor diluent can be a highly aromatic light cycle oil generated in a catalytic cracking process; the oil is partially hydrogenated by known methods to produce a hydrogen donor diluent containing, for example, tetralin and substituted tetralins.
- hydrogen-donating compounds and hydrogen donor precursors together comprise at least 40 percent of the hydrogen donor diluent.
- Hydrocarbons boiling in the upper portion of the aforementioned broad boiling range that is, boiling from about 350°C to 400°C, generally participate to a minor degree, if at all, as hydrogen-donating materials during donor hydrocracking.
- Some of those hydrocarbons, called herein hydrogen donor precursors are converted during donor hydrocracking into compounds that can be partially hydrogenated to hydrogen-donating compounds boiling in the aforementioned broad boiling range.
- the hydrogen-donating diluent can advantageously include materials boiling up to 400°C.
- the proportion of hydrogen-donating hydrocarbon diluent in relation to the residuum feedstock can be from about 0.02:1 to 1.0:1, preferably from 0.15:1 to 0.5:1.
- a portion of the hydrogen donor requirement can be supplied by recycled hydrogen donor material obtained by fractionating the coker liquids product and partially hydrogenating at least a portion of a 180°C to 400°C donor precursor fraction, or preferably a 200°C to 350°C fraction, to produce a recycle hydrogen donor material.
- the ratio of recycle hydrogen donor material to fresh hydrogen donor material can be from 0.1:1 to 2:1.
- the temperature of the reaction mass entering the coker from a transfer tube can be in the range from 420°C to 500°C, preferably from 450°C to 500°C.
- the relationship of time in the heating zone and temperature of that zone is governed by the nature of the heavy hydrocarbonaceous oil being treated. Oils that tend to crack easily are kept for a shorter residence time or at a lower temperature, or both, than oils that are more refractory.
- the heavy hydrocarbonaceous oil feedstock can comprise a residuum from atmospheric or vacuum distillation of conventional crude oil, or an atmospheric or vacuum residuum of heavy oil or bitumen.
- bitumen can be used as the feedstock oil.
- Mixtures of the above-mentioned oils can also be fed to the process.
- a high temperature requires a short residence time in the heating zone, as is known to those skilled in the art.
- the temperature maintained in a coke drum is generally 16wer than the material in the transfer tube, and can be from 400°C to 480°C.
- Operating pressure can be from atmospheric, i.e. 101 kPa, to about 600 kPa, preferably from 200 kPa to 400 kPa.
- the liquid product material obtained from an overhead stream off the coke drum can be fractionated. At least a portion of a material boiling in the heavy gas oil range, i.e. above 400°C, can be recycled to be mixed with fresh residuum feedstock.
- the bottoms recycle-to-fresh residuum feed ratio can be up to about 0.4:1. In refinery operation, a bottoms recycle-to-fresh feed ratio of 0.1:1 to 0.3:1 is generally sufficient to remove the entire heavy gas oil product.
- both hydrogen donor material and heavy gas oil can be recycled.
- the hold time of reaction mass in the coke drum can be from 5 minutes to 60 minutes.
- delayed coking according to the invention is performed using two coke drums alternately. When one of the drums is filled with coke, it is disconnected from the preheating furnace and the coke product is discharged while the other drum is being filled with reaction mass from a preheating furnace via a transfer tube. The initial reaction mass entering either coke drum after startup of that drum is subjected to a longer period of exposure to coking conditions than the last reaction mass prior to shutdown of that drum. The method of the invention can be performed in such refinery conditions.
- Figure 1 the single drawing, represents a preferred form of apparatus for carrying out the process of the invention.
- vacuum residuum feedstock is fed by lines 11 and 13 to surge drum 2.
- Partially hydrogenated light cycle oil is fed by line 12, and blended with residuum to be fed into drum 2 by line 13, and optionally recycled gas oil is added by line 17.
- the resulting blend is taken through line 14 to coker preheating furnace 6 where it is heated to coking temperature, typically 420°C to 500°C, thence by line 15 to coke drum 7 or coke drum 7a.
- the drum not being filled at the time is cut off from the system by valves 3 and 4 or 3a and 4a.
- the drum After a suitable holding period in the coke drum, at a temperature from 400°C to 480°C, and a pressure substantially lower than the pressure in the preheating furnace 6, during which period coker overheads are removed by line 16 to fractionator 8 from which products from gases to heavy gas oil are withdrawn by lines 21 to 24, the drum is taken out of service and its coke content removed via line 18 or 18a.
- at least a portion of heavy gas oil boiling above 400°C can be recycled via line 17 for further treatment in the coker, and if desired, all of the heavy gas oil can be thus converted to lighter petroleum products or to coke. Where such stream is not recycled, it can advantageously be fed to a fluid catalytic cracking zone.
- a portion of the hydrogen donor requirement can be satisfied by passing through line 19 at least a portion of the gas oil fraction in line 23 boiling between 180°C and 400°C, preferably between 200°C and 350°C, partially hydrogenating the gas oil in hydrogenation zone 9 and recycling the resulting recycle hydrogen donor material through line 20 to blend with fresh donor fed by line 12.
- the blend was heated to 493°C in a commercial-scale coker furnace at 1.48 MPa (absolute) and passed through a pressure reducing valve into a coke drum where the reaction mass was held at 471°C and 240 kPa as the coke drum filled with coke.
- Coker overheads were taken off the fractionator with yields (net of the added cycle oil) shown as Run 1 in Table 1.
- the coke product contained 12 percent Volatile Combustible Matter (VCM).
- VCM Volatile Combustible Matter
- the process of the invention is thus shown to be effective in lowering the production of coke on both laboratory-scale and commercial-scale apparatus. Additional advantages are that the process produces a more saturated gasoline product than conventional processes, and reduces fouling of furnace tubes in the heating zone.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Coke Industry (AREA)
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA450003 | 1984-03-20 | ||
| CA000450003A CA1246481A (fr) | 1984-03-20 | 1984-03-20 | Cokefaction de residus en presence d'hydrogene donneur |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0156614A2 EP0156614A2 (fr) | 1985-10-02 |
| EP0156614A3 EP0156614A3 (en) | 1987-08-05 |
| EP0156614B1 true EP0156614B1 (fr) | 1990-12-12 |
Family
ID=4127451
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP85301883A Expired - Lifetime EP0156614B1 (fr) | 1984-03-20 | 1985-03-19 | Cokéfaction de résidu en présence d'un donneur d'hydrogène |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0156614B1 (fr) |
| JP (1) | JPS60238388A (fr) |
| AU (1) | AU580035B2 (fr) |
| BR (1) | BR8501214A (fr) |
| CA (1) | CA1246481A (fr) |
| DE (1) | DE3580859D1 (fr) |
| ES (1) | ES8608564A1 (fr) |
| NO (1) | NO851067L (fr) |
| ZA (1) | ZA851903B (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105505449A (zh) * | 2015-11-27 | 2016-04-20 | 中国海洋石油总公司 | 一种供氢焦化方法 |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0718265A (ja) * | 1993-07-01 | 1995-01-20 | Kurita Water Ind Ltd | 石油化学プロセス用汚れ防止剤 |
| US6919017B2 (en) * | 2002-04-11 | 2005-07-19 | Conocophillips Company | Separation process and apparatus for removal of particulate material from flash zone gas oil |
| US9039889B2 (en) * | 2010-09-14 | 2015-05-26 | Saudi Arabian Oil Company | Upgrading of hydrocarbons by hydrothermal process |
| CN105331390A (zh) * | 2015-11-27 | 2016-02-17 | 中国海洋石油总公司 | 一种供氢延迟焦化的方法 |
| US20230168157A1 (en) * | 2021-11-29 | 2023-06-01 | Petróleo Brasileiro S.A. - Petrobras | System and method for evaluation of the deposition in tubes of the furnaces of a delayed coking unit |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3617513A (en) * | 1969-01-03 | 1971-11-02 | Exxon Research Engineering Co | Coking of heavy feedstocks |
| JPS5455005A (en) * | 1977-10-12 | 1979-05-01 | Chiyoda Chem Eng & Constr Co Ltd | Cracking of heavy hydrocarbons to lighter grade |
| US4213846A (en) * | 1978-07-17 | 1980-07-22 | Conoco, Inc. | Delayed coking process with hydrotreated recycle |
| US4176046A (en) * | 1978-10-26 | 1979-11-27 | Conoco, Inc. | Process for utilizing petroleum residuum |
| DE2949935C2 (de) * | 1979-12-12 | 1985-06-05 | Metallgesellschaft Ag, 6000 Frankfurt | Verfahren zur Umwandlung von hochsiedenden Rohölen in erdölähnliche Produkte |
| CA1122914A (fr) * | 1980-03-04 | 1982-05-04 | Ian P. Fisher | Methode de valorisation des hydrocarbures lourds |
| US4385980A (en) * | 1981-02-26 | 1983-05-31 | Conoco Inc. | Coal treating process |
-
1984
- 1984-03-20 CA CA000450003A patent/CA1246481A/fr not_active Expired
-
1985
- 1985-03-13 ZA ZA851903A patent/ZA851903B/xx unknown
- 1985-03-15 AU AU40022/85A patent/AU580035B2/en not_active Ceased
- 1985-03-18 NO NO851067A patent/NO851067L/no unknown
- 1985-03-18 ES ES541382A patent/ES8608564A1/es not_active Expired
- 1985-03-19 DE DE8585301883T patent/DE3580859D1/de not_active Expired - Lifetime
- 1985-03-19 BR BR8501214A patent/BR8501214A/pt unknown
- 1985-03-19 EP EP85301883A patent/EP0156614B1/fr not_active Expired - Lifetime
- 1985-03-20 JP JP60054765A patent/JPS60238388A/ja active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105505449A (zh) * | 2015-11-27 | 2016-04-20 | 中国海洋石油总公司 | 一种供氢焦化方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| NO851067L (no) | 1985-09-23 |
| ES541382A0 (es) | 1986-07-16 |
| BR8501214A (pt) | 1985-11-12 |
| EP0156614A3 (en) | 1987-08-05 |
| AU4002285A (en) | 1985-09-26 |
| ZA851903B (en) | 1985-10-30 |
| DE3580859D1 (de) | 1991-01-24 |
| EP0156614A2 (fr) | 1985-10-02 |
| ES8608564A1 (es) | 1986-07-16 |
| JPS60238388A (ja) | 1985-11-27 |
| AU580035B2 (en) | 1988-12-22 |
| CA1246481A (fr) | 1988-12-13 |
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