EP0175511B1 - Visbreaking process - Google Patents
Visbreaking process Download PDFInfo
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- EP0175511B1 EP0175511B1 EP85306152A EP85306152A EP0175511B1 EP 0175511 B1 EP0175511 B1 EP 0175511B1 EP 85306152 A EP85306152 A EP 85306152A EP 85306152 A EP85306152 A EP 85306152A EP 0175511 B1 EP0175511 B1 EP 0175511B1
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- EP
- European Patent Office
- Prior art keywords
- hydrogen
- oil
- content
- visbreaking
- process according
- 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
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- 238000000034 method Methods 0.000 title claims description 35
- 230000008569 process Effects 0.000 title claims description 30
- 239000000852 hydrogen donor Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 150000002898 organic sulfur compounds Chemical class 0.000 claims abstract description 10
- 239000003921 oil Substances 0.000 claims description 41
- 239000003208 petroleum Substances 0.000 claims description 14
- 239000000295 fuel oil Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 7
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000386 donor Substances 0.000 description 4
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000010763 heavy fuel oil Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011269 tar Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- -1 thiol compounds Chemical class 0.000 description 3
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000010690 paraffinic oil Substances 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 description 1
- KEIFWROAQVVDBN-UHFFFAOYSA-N 1,2-dihydronaphthalene Chemical compound C1=CC=C2C=CCCC2=C1 KEIFWROAQVVDBN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 101150110302 RND3 gene Proteins 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- C10G9/007—Visbreaking
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/32—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions in the presence of hydrogen-generating compounds
- C10G47/34—Organic compounds, e.g. hydrogenated hydrocarbons
Definitions
- This invention relates to the processing of residual petroleum charge stocks by visbreaking in the presence of certain highly aromatic hydrogen-donor materials.
- Visbreaking or viscosity breaking, is a well-known petroleum refining process in which reduced crudes are pyrolyzed, or cracked, under comparatively mild conditions to provide products having lower viscosities and pour points, thus reducing the amounts of less-viscous and more valuable blending oils required to make the residual stocks useful as fuel oils.
- the visbreaker feedstock usually consists of a mixture of two or more refinery streams derived from sources such as atmospheric residuum, vacuum residuum, furfural-extract, propane-deasphalted tar and catalytic cracker bottoms. Most of these feedstock components, except the heavy aromatic oils, behave independently in the visbreaking operation.
- the severity of operation for a mixed feed is limited greatly by the least desirable (highest coke forming) components.
- the crude or resid feed is passed through a heater and heated to about 425 to about 525°C and at about 450 to about 7000 kPa.
- Light gas-oil may be recycled to lower the temperature of the effluent to about 260 to about 370°C.
- Cracked products from the reaction are flash distilled with the vapor overhead being fractionated into a light distillate overhead product, for example gasoline and light gas-oil bottoms, and the liquid bottoms being vacuum fractionated into heavy gas-oil distillate and residual tar.
- U.S. Patent 3,691,058 describes the production of single ring aromatic hydrocarbons (70-220°C) by hydrocracking a heavy hydrocarbon feed (565°C-) and recycling 3270 ⁇ C and 220°C+ product fractions to extinction. This is integrated with visbreaking of residua in the presence of 1-28 weight % free radical acceptor at 370 to 480°C in the presence or absence of hydrogen (to enhance residua depolymerization).
- U.S. Patent 3,691,058 describes the production of single ring aromatic hydrocarbons (70-220°C) by hydrocracking a heavy hydrocarbon feed (565°C-) and recycling 3270 ⁇ C and 220°C+ product fractions to extinction. This is integrated with visbreaking of residua in the presence of 1-28 weight % free radical acceptor at 370 to 480°C in the presence or absence of hydrogen (to enhance residua depolymerization).
- Patent 4,067,757 describes a process comprising passing a resid up through a bed of inertia solids (packed bed reactor) in the presence or absence of 9-1800 Nm 3 hydrogen per m 3 resid at 400 to 540°C to enhance the production of middle distillate (175-345°C).
- U.S. Patent 2,953,513 proposes the production of hydrogen-donors by partial hydrogenation of certain distillate thermal and catalytic tars, boiling above 370°C, containing a minimum of 40 weight % aromatics, to contain H/C ratios of 0.7-1.6.
- the resid feed is then mixed with 9-83 volume % of hydrogen-donor and thermally cracked at 427-482°C to produce low boiling products.
- U.S. Patent 4,090,947 describes a thermal cracking process (425-540°C) for converting resids into lighter products in the presence of 10-500 volume % hydrogen-donor.
- the hydrogen-donor is produced by hydrotreating premium coker gas oil (345 ⁇ 480°C) alone or blended with gas oil produced in the thermal cracker.
- U.S. Patent 4,292,168 proposes upgrading heavy hydrocarbon oils without substantial formation of chat by heating the oil with hydrogen and a hydrogen transfer solvent without a catalyst at temperatures of about 320-500°C and a pressure of 2200-18000 kPa for a time of about 3-30 minutes.
- Examples of hydrogen-donor transfer solvents include pyrene, fluoranthene, anthracene and benzanthracene.
- U.S. Patent 4,292,686 describes a process for contacting a resid with a hydrogen-donor at 350-500°C and a pressure of 2-7 MPa with liquid hourly space velocities ranging from 0.5-10.
- European Patent Application 133,774 describes a process for the production of fuel oil products in which the formation of coke of filtration sediment is suppressed by visbreaking heavy petroleum residua under liquid phase, non-catalytic conditions in the presence of certain hydrogen-donor materials and in the absence of added free hydrogen.
- heavy petroleum oil feed stocks containing deleterious contaminants such as sulfur and nitrogen compounds, asphaltenes and metals, can be visbroken at high severities to provide lower molecular weight fuel oil products of improved viscosity and pour point characteristics.
- the process of that invention offers the potential of substantially eliminating and/or reducing the need for cutter stock to meet fuel oil product viscosity specifications.
- the present invention represents an improvement in the visbreaking process described in that application and involves introducing an organic sulfur compound into the heavy petroleum residual oil before it is subjected to visbreaking in the presence of a hydrogen donor material.
- the hydrogen-donor material used in the process of the invention is a thermally stable, polycyclic aromatic of hydroaromatic distillate mixture which results from one or more petroleum refining operations.
- the hydrogen-donor preferably has an average boiling point in the range of 230 to 510°C and an A.P.I. gravity below 20°C.
- suitable hydrogen-donors are highly aromatic petroleum refinery streams, such as fluidized catalytic cracker (FCC) "main column” bottoms, FCC “light cycle oil,” and theremofor catalytic cracker (TCC) "syntower” bottoms, all of which contain a substantial proportion of polycyclic aromatic hydrocarbon constituents such as naphthalene, dimethyl naphthalene, anthracene, phenanthrene, fluorene, chrysene, pyrene, perylene, diphenyl, benzothiophene, tetralin and dihydronapthalene, for example.
- FCC fluidized catalytic cracker
- TCC light cycle oil
- TCC theremofor catalytic cracker
- Such refractory petroleum materials are resistant to conversion into higher (lower molecular weight) products by conventional non-hydrogenative procedures.
- these petroleum refinery residual and recycle fractions are hydrocarbonaceous mixtures having an average carbon to hydrogen ratio above about 1:1, and an average boiling point above 230°C.
- FCC main column bottoms refinery fraction is a highly preferred donor for use in the process of the invention.
- a typical FCC main column bottoms (or FCC clarified slurry oil (CSO)) contains a mixture of constituents as represented in the following mass spectrometric analysis:
- a typical FCC main column bottoms or clarified slurry oil has the following analysis and properties:
- Another preferred hydrogen-donor material is a light cycle oil (LCO) taken from the main tower fractionator in a FCC operation of the riser type in which the LCO results from a distillation cut point not substantially above about 370°C.
- LCO light cycle oil
- a typical FCC light cycle oil has the following analysis and properties:
- FCC main tower bottoms and light cycle oils are obtained by the catalytic cracking of gas oil in the presence of a solid porous catalyst. More complete descriptions of the production of these petroleum fractions can be found in U.S. Patents 3,725,240 and 4,302,323, for example.
- Catalytically cracked stocks such as clarified slurry oils and light cycle oils are preferred hydrogen-donor materials because of their unique physical properties and chemical constituents.
- a critical aspect of the hydrogen-donor material is the particular proportions of aromatic naphthenic and paraffinic moities and the type and content of aromatic and naphthenic structures together with a high content of alpha hydrogen provides a superior hydrogen-donor material.
- the hydrogen transfer ability of a donor material can be expressed in terms of specific types of hydrogen content as determined by proton nuclear magnetic resonance spectral analysis. Nuclear magnetic resonance characterization of heavy hydrocarbon oils is well developed. The spectra 60 (c/sec) are divided into four hands (H alpha , H beta , Hg amma and H Ar ) according to the following frequencies in Hertz (Hz) and chemical shift (delta):
- H Ar protons are attached to aromatic rings and are a measure of aromaticity of a material.
- H alpha protons are attached to non-aromatic carbon atoms themselves attached directly to an aromatic ring structure, e.g., alkyl groups and naphthenic ring structures.
- H beta protons are attached to carbon atoms which are in a second position away from an aromatic ring, and Hg amma protons are attached to carbon atoms which are in a third position or more away from an aromatic ring structure. This can be illustrated by the compounds shown in the accompanying drawing (Fig. 1).
- H AI protons are important because of their strong solvency power.
- a high content of H al p ha protons is particularly significant because H alpha protons are labile and are potential hydrogen-donors.
- the hydrogen-donor material used in the process of the invention has a hydrogen content distribution in which the H Ar proton content is from 20 to 50 percent and the H alpha proton content is at least 20 percent, preferably from 20 to 50 percent.
- the alpha-hydrogen content should be at least 1.9 wt. % (20% of total hydrogen content).
- the balance of the hydrogen is non-alpha hydrogen.
- Hydrogen-donors possessing the desired hydrogen content distribution can be obtained as a bottoms fraction from the catalytic or hydrocracking of gas oil stocks in the moving bed or fluidized bed reactor processes.
- a high severity cracking process results in a petroleum residuum solvent having an increased content of HA r and H alpha protons and a decreased content of the less desirable non-alpha hydrogen.
- hydrocarbons having the same general process deviation may or may not have the desired proton distribution.
- FCC/MCB #1 and #2 and FCC/ CSO #1 and #2 have the desired proton distribution while FCC/MCB #3 and #4 and FCC/CSO #3 do not.
- the highly aromatic hydrogen donor component is derived from petroleum, it will be noted that the SRC recycle solvent closely resembles FCC/MCB 01 and #2.
- the organic sulfur compound which is introduced into the residuum to be subjected to visbreaking is preferably one in which there is present an active thiol (-SH) group.
- Suitable compounds in this respect include thiophenol, dodecanethiol and benzothiophene.
- Dibenzothiophene on the basis of present knowledge, is not a suitable sulfur compound.
- refinery streams obtained from the extraction of paraffinic oils to remove aromatics can contain sufficient sulfur compounds having sufficient thiol functionality and can be added to the residuum, directly or indirectly.
- Another method of introducing the organic sulfur compound into the heavy residuum is to sulfonate the aromatic extract derived from extracting a paraffinic oil with phenol or furfural, for example to remove aromatic compounds; the sulfonated aromatics are then mildly hydrogenated to form the organic sulfur compound suitable for addition to heavy residua for visbreaking.
- Techniques for aromatic extraction, sulfonation, and hydrogenation are well known in the art.
- Still another source of thiol compounds is the extract obtained by contacting a hydrocarbon stream containing thiophenols with an alkaline solution, such as sodium hydroxide in water or alcohol, decanting the alkaline phase, and then acidifying the solution to release the thiol compounds.
- the thiol compounds can be separated and mixed with the heavy residua.
- This technique provides a means for removing sulfur from one portion of a refinery stream and utilizing the sulfur in another part of the refinery process.
- Hydrocarbon streams that can be used in the manner include aromatic (furfural) extracts from lube oil stock and cycle oil stock.
- a viscous hydrocarbon oil feed is supplied by line 4 to visbreaking heater 8.
- the feed is blended with hydrogen donor materials supplied through line 6 in an amount from 0.1 to 50 weight percent, preferably from 0.1 to 20 weight percent based on the resid charge (a weight ratio of hydrogen-donor to resid of 0.001 to 0.5, preferably 0.001 to 0.2).
- Organic sulfur compounds are added through line 2 to provide an amount equivalent to 0.05 to 10 percent by weight of sulfur in the stream flowing to line 2.
- the amount added is equivalent to from 0.5 to 5 percent sulfur.
- Mild thermal cracking of the resid under visbreaking conditions occurs in visbreaker 8 and produces a visbreaker effluent stream carried by line 10. This stream is cooled by admixture with a quench stream from line 14, and the visbreaker effluent continues through line 12 to distillation column 22 where it is fractionated to obtain C s -gases (C 3 , C 4 and lower) and a C s -135°C naphtha fraction from the top through line 24.
- a 220°C+ fraction if taken off as a bottoms stream through line 16 where portions may be recycled as a quench stream through line 14, recovered as heavy fuel oil through line 18 or, via line 20, blended with cutter stock to meet fuel oil product specifications.
- the overhead fraction removed from the distillation column in line 24 is passed through a cooler separator 26 which is operated under conditions effective to separate the incoming liquid into a C s -off-gas stream 28, mainly C 3 or C 4 and lower, and a C 5 -135°C naphtha fraction which is taken off via line 30. Because of the quality of the hydrogen-donor, it can be removed in admixture with the heavy oil fraction and used directly as heavy fuel oil, thus avoiding the need for separatioon.
- the process of the invention is suitable for upgrading a wide variety of heavy liquid hydrocarbon oils in which mixtures of at least 75 weight percent of the components boil over 370°C. Included in this class of materials are residual fractions obtained by catalytic cracking of gas oils, solvent extracts obtained during the processing of lube oil stocks, asphalt precipitates obtained from deasphalting operations, high boiling bottoms or resids obtained during vacuum distillation of petroleum oils and tar sand bitumen feedstocks.
- Visbreaking process conditions can vary widely based on the nature of the heavy oil material, the hydrogen-donor material and other factors. In general, the process is carried out at temperatures ranging from 350 to 485°C, preferably 425 to 455°C, at residence times ranging from 1 to 60 mintutes, preferably 7 to 20 minutes. The pressures employed will be sufficient to maintain liquid phase conditions usually 1480 to 7000 kPa.
- An importent aspect of the invention is the improvement of visbreaker performance by optimizing operation severity for heavy oil feedstocks.
- severity increased yields of distillate and gaseous hydrocarbons are obtained with a reduction in the amount of cutter oil required for blending to obtain specification-viscosity residual fuel oil.
- cutter oil required for blending to obtain specification-viscosity residual fuel oil.
- the use of certain hydrogen-donors in combination with certain organic sulfur compounds has been found to suppress the formation of sedimentation species and thus permit visbreaking at a higher severity consistent with the production of stable fuel oil.
- the visbreaking of a heavy petroleum feed stock conventionally carried out at, say, 427°C with a residence time of 500 seconds may be carried out at 427°C with a residence time of 800 seconds under the conditions of the invention to obtain a fuel oil product free of sedimenting species.
- the current stock requirement is substantially reduced and this represents a considerable financial savings.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Other Liquid Machine Or Engine Such As Wave Power Use (AREA)
- Investigation Of Foundation Soil And Reinforcement Of Foundation Soil By Compacting Or Drainage (AREA)
- Vehicle Body Suspensions (AREA)
- Vessels And Coating Films For Discharge Lamps (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT85306152T ATE34765T1 (de) | 1984-09-10 | 1985-08-30 | Verfahren zum viskositaetsabbau. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US64841384A | 1984-09-10 | 1984-09-10 | |
US648413 | 1984-09-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0175511A1 EP0175511A1 (en) | 1986-03-26 |
EP0175511B1 true EP0175511B1 (en) | 1988-06-01 |
Family
ID=24600680
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP85306152A Expired EP0175511B1 (en) | 1984-09-10 | 1985-08-30 | Visbreaking process |
Country Status (8)
Country | Link |
---|---|
EP (1) | EP0175511B1 (xx) |
JP (1) | JPS6166792A (xx) |
AT (1) | ATE34765T1 (xx) |
AU (1) | AU580617B2 (xx) |
CA (1) | CA1251155A (xx) |
DE (1) | DE3563063D1 (xx) |
ES (1) | ES8605020A1 (xx) |
ZA (1) | ZA856933B (xx) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7871510B2 (en) | 2007-08-28 | 2011-01-18 | Exxonmobil Research & Engineering Co. | Production of an enhanced resid coker feed using ultrafiltration |
US8100178B2 (en) | 2005-12-22 | 2012-01-24 | Exxonmobil Upstream Research Company | Method of oil recovery using a foamy oil-external emulsion |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU579005B2 (en) * | 1985-03-22 | 1988-11-10 | Mobil Oil Corporation | Hydrogenation process |
FR2607145B1 (fr) * | 1986-11-25 | 1990-06-08 | Inst Francais Du Petrole | Procede ameliore de conversion thermique de fractions lourdes de petrole et de residus de raffinage, en presence de composes oxygenes du soufre, de l'azote ou du phosphore |
US4814065A (en) * | 1987-09-25 | 1989-03-21 | Mobil Oil Company | Accelerated cracking of residual oils and hydrogen donation utilizing ammonium sulfide catalysts |
FR2628437B1 (fr) * | 1988-03-14 | 1992-12-31 | Inst Francais Du Petrole | Procede de traitement thermique de charges hydrocarbonees en presence de polysulfures et de donneurs d'hydrogene |
US6800193B2 (en) | 2000-04-25 | 2004-10-05 | Exxonmobil Upstream Research Company | Mineral acid enhanced thermal treatment for viscosity reduction of oils (ECB-0002) |
US7338924B2 (en) | 2002-05-02 | 2008-03-04 | Exxonmobil Upstream Research Company | Oil-in-water-in-oil emulsion |
ES2543404T3 (es) | 2003-05-16 | 2015-08-19 | Exxonmobil Research And Engineering Company | Proceso de coquización retardada para producción de coque en granalla fluido |
US7645375B2 (en) | 2003-05-16 | 2010-01-12 | Exxonmobil Research And Engineering Company | Delayed coking process for producing free-flowing coke using low molecular weight aromatic additives |
US7658838B2 (en) | 2003-05-16 | 2010-02-09 | Exxonmobil Research And Engineering Company | Delayed coking process for producing free-flowing coke using polymeric additives |
US7727382B2 (en) | 2004-05-14 | 2010-06-01 | Exxonmobil Research And Engineering Company | Production and removal of free-flowing coke from delayed coker drum |
BRPI0511024A (pt) | 2004-05-14 | 2007-11-27 | Exxonmobil Res & Eng Co | processo de coqueificação retardada, e, coque |
EP1751257A2 (en) | 2004-05-14 | 2007-02-14 | Exxonmobil Research And Engineering Company | Inhibitor enhanced thermal upgrading of heavy oils |
BRPI0510984A (pt) | 2004-05-14 | 2007-12-04 | Exxonmobil Res & Eng Co | método para o melhoramento das propriedades de escoamento de uma carga de alimentação de óleo pesado por diminuição do seu módulo elástico, e, método de coqueificação retardado |
JP4982069B2 (ja) * | 2005-10-21 | 2012-07-25 | 日立造船株式会社 | 重質油の粘度低減方法 |
US7794587B2 (en) | 2008-01-22 | 2010-09-14 | Exxonmobil Research And Engineering Company | Method to alter coke morphology using metal salts of aromatic sulfonic acids and/or polysulfonic acids |
FR2969643B1 (fr) * | 2010-12-27 | 2014-11-21 | Total Raffinage Marketing | Procede de craquage catalytique pour le traitement d'une coupe a faible carbone conradson |
JP6199973B2 (ja) | 2012-08-24 | 2017-09-20 | サウジ アラビアン オイル カンパニー | 溶存水素を含有する原料のためのハイドロビスブレーキング方法 |
MX359374B (es) | 2013-10-22 | 2018-09-13 | Mexicano Inst Petrol | Aplicacion de una composicion quimica para la reduccion de la viscosidad de petroleos crudos pesados y extrapesados. |
CN110621737B (zh) * | 2017-09-27 | 2023-01-03 | 积水化学工业株式会社 | 成形用树脂组合物 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1476426A (en) * | 1973-07-03 | 1977-06-16 | Shell Int Research | Process for preparing white oils |
US4414102A (en) * | 1981-05-15 | 1983-11-08 | Mobil Oil Corporation | Process for reducing nitrogen and/or oxygen heteroatom content of a mineral oil |
US4401561A (en) * | 1981-12-21 | 1983-08-30 | Uop Inc. | Hydrotreating process with ammonia injection to reaction zone effluent |
-
1985
- 1985-08-21 AU AU46486/85A patent/AU580617B2/en not_active Ceased
- 1985-08-30 EP EP85306152A patent/EP0175511B1/en not_active Expired
- 1985-08-30 AT AT85306152T patent/ATE34765T1/de not_active IP Right Cessation
- 1985-08-30 DE DE8585306152T patent/DE3563063D1/de not_active Expired
- 1985-09-09 ES ES546809A patent/ES8605020A1/es not_active Expired
- 1985-09-09 CA CA000490217A patent/CA1251155A/en not_active Expired
- 1985-09-09 JP JP60197873A patent/JPS6166792A/ja active Pending
- 1985-09-10 ZA ZA856933A patent/ZA856933B/xx unknown
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8100178B2 (en) | 2005-12-22 | 2012-01-24 | Exxonmobil Upstream Research Company | Method of oil recovery using a foamy oil-external emulsion |
US7871510B2 (en) | 2007-08-28 | 2011-01-18 | Exxonmobil Research & Engineering Co. | Production of an enhanced resid coker feed using ultrafiltration |
Also Published As
Publication number | Publication date |
---|---|
CA1251155A (en) | 1989-03-14 |
EP0175511A1 (en) | 1986-03-26 |
ATE34765T1 (de) | 1988-06-15 |
ZA856933B (en) | 1987-04-29 |
ES8605020A1 (es) | 1986-03-01 |
JPS6166792A (ja) | 1986-04-05 |
AU4648685A (en) | 1986-03-20 |
ES546809A0 (es) | 1986-03-01 |
DE3563063D1 (en) | 1988-07-07 |
AU580617B2 (en) | 1989-01-19 |
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