Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
• • 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
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
  • C10G67/0454—Solvent desasphalting
  • C10G67/0463—The hydrotreatment being a hydrorefining

Definitions

• This invention relates to a process for producing heavy heating oils having low sulfur contents. More particularly, the invention relates to a practical and economical process for the removal of sulfur from crude oils serving as starting materials in the production of heavy heating oils.
• Heavy heating oils are obtained by processing of crude oils as atmospheric residues such as top oil residues, as vacuum residues, as thermal cracking residues, in viscosity breaking, etc. It is possible to employ mixtures of the various types of residues, assuming that they are otherwise compatible, as heating oils. In addition, there are conventionally used as heavy heating oils brown coal tars, coal tars, oil shale tars and generator tars.
• S heavy oil or viscous oil
• M middle oil
• L light oil
• EL extra light oil
• Heating oils are liquid fuels derived from petroleum, oil shale, coal tars or brown coal tars and are especially suitable as fuel for furnaces and for combustion purposes.
• the heating oils are subdivided into the types EL (extra light oil), L (light oil), M (middle oil) and S (heavy oil).
• EL extra light oil
• L light oil
• M medium oil
• S light oil
• the properties and characteristic values of the residual products of petroleum processes which are more viscous than heating oil S may, on account of the variety of the crude oils and the manner of their processing, not be standardized and they must in each case be expressly determined.
• heating oils having low sulfur contents by utilizing as starting materials crude oils low in sulfur. Such possibilities are fairly limited, as can be appreciated, because of the raw material situation. As a result, numerous processes have been proposed, in order to lower the sulfur content of heating oils, as for example utilizing chemical reactions.
• a preliminary step is carried out prior to the actual desulfurization, in which the starting oil product is treated with large surface area materials in the presence of small amounts of hydrogen, in an attempt to at least remove a part of the ash of the charged product from the catalyst.
• the primary object of the invention is to provide a process for producing desulfurized heavy heating oils whereby economy of operation is obtained.
• Another object of the invention is to provide a process for the production of heavy heating oil of low sulfur content, meeting the commercial requirements of storage and heat stability.
• Still another object of the invention is to provide a process for the production of heavy heating oil of low sulfur content which is readily miscible with other oils having a lower C/H ratio.
• the present invention consists in a process for preparing heavy heating oil having a low sulfur content which comprises the steps of:
• phase (C) in the third step it is possible to substitute for phase (C) in the third step other residual oils.
• the process of the invention has the advantage that only slight, technically non-disturbing quantities of ash are deposited on the catalyst, and as a result the life period of the catalyst is prolonged considerably, and furthermore a lower hydrogen consumption is required for the hydrogenating desulfurization.
• the first step of the process in accordance with the invention advantageously is carried out, as for example, as de-asphaltizing, or as a vacuum-distillation.
• the starting heavy oils as for example top-oil residue
• propane or other hydrocarbon having a lower C/I-I ratio.
• Such treatment results in a rafiinate (B which contains but little asphalt and little ash, and also an extract (C which contains substantially all of the asphalt and the ash. It is possible by suitable regulation of the treatment conditions to obtain an entirely ash-free raffinate (B
• the extract (C which is obtained is depending on the starting product (A), a more or less viscous mass.
• the starting top-oil residue can for example be subjected to a de-asphaltizing treatment wherein through suitable selection of the pressure and temperature conditions and the proportions of, for example, propane to oil, the quantity of extract (C is decreased to about 330% of the initial charge, and most preferably to l20% of the top-oil-residue charged.
• the extract (C as obtained is in a brittle and dry form and may be comparatively easily broken up or pulverized.
• it is also possible to vary the resulting ratio of raffinate (B to extract (C by selecting the charge product (A) according to its asphalt content and also its boiling point.
• the preferred form of carrying out the second step of the process is a hydrogenating desulfurization.
• the choice of the desulfurization conditions depends not only on these requirements, but also on the boiling point of the product (B) to be desulfurized.
• this phase is composed of constituents boiling above 490 (3., sharper hydrogenation conditions must be selected. This applies equally to the conditions of pressure as well as of temperature. Desulfurization may be readily ellected at about 40 atmospheres with entirely satisfactory results. Under certain circumstances, however, it may be necessary to utilize pressures of 500 atmospheres.
• the temperature in general between 300 and 450 C.
• the temperature is essentially responsible for the degree of desulfurization.
• cracking or splitting of some of the hydrocarbons cannot be avoided, especially if the desulfurization is to be carried to a very high degree, as for example to 0.1%.
• the desulfurization is carried out without any difficulties, as this charge product (B) is substantially free from ash to begin with as well as from any difiicultly hydrogenizable highly aromatic compounds, such as asphalts, oil-resins, etc.
• the catalyst may be steadily subjected to throughputs of charge (B) with satisfactory operable running times for the catalyst of up to several months.
• a further advantage of the process of the invention over direct hydrogenation of top-oil residue by passage of the charge over a fixedly positioned catalyst consists in the decrease of the hydrogen required to efiiciently effect the hydrogenating desulfurization.
• Heating oil represents, by its physical properties, a colloid system of asphalts in oil.
• An asphaltic nucleus adsorbs high-molecular aromatic hydrocarbons, which have a somewhat lower C/H ratio than the asphalts themselves.
• highly aromatic hydrocarbons are adsorbed, whose C/H ratio is somewhat lower than that preceding the deposition of highly aromatic hydrocarbons taking place, until the C/H ratio of the most external layer substantially corresponds to that of the dispersion phase, thus the oil.
• a system of such layerings around an asphalt nucleus is defined as a micelle. It is obvious that a particular micelle is destroyed if the C/H ratio of the surrounding medium is disturbed by hydrocarbons having a lower C/H ratio. Said in another Way, a heating oil is more stable, the more insensitive it is against changes of the C/H ratio on diluents therefor.
• the asphalts after they have been precipitated by adsorption thereon of a hydrocarbon having a low C/H ratio, as, for example, propane, subsequently may, in accordance with the invention, again be recolloidized by the third step of the process, namely by admixture with an oil, whose C/H ratio has been lessened through bydrogenation, that is, that without any difficulties the extract (C asphalt rich and ash rich) can absorb the desulfurized residue (E derived from the asphalt and ash poor ratfinate (B) It is furthermore most surprising that heating oils of other derivation may be admixed with the heating oil (F) without any impairment of its stability.
• a hydrocarbon having a low C/H ratio as, for example, propane
• step 1 is carried out by means of a vacuum-distillation and followed by steps 2 and 3 as above described.
• a heating oil is regarded as stable if, on storage as well as on being subjected to heat, no dry carbon-rich sludge, or only small amounts of such sludge are formed. In no event should the sludge formed amount to more than 1%, and most advantageously to not more than 0.2% (M. M. Marshall, Schweizer Archiv fuer angewandtetechnik undtechnik, 23, 273 ff./ 1957).
• certain tests have been developed, the aim of which it is, to bring about the separation, through artificially induced aging or through alteration of the C/ H ratio of the oil phase, a dry carbonrich sludge, the exact quantity of which serves as a measure of the stability of the heating oil. Included in these tests are the Hot-Filtration test and the Butlin test.
• the Hot-Filtration test is carried out according to the mehod described by W. I. van Kerkvoort, M. B. E. and A. I. I. Nieuwstad in Journal of the Institute of Petroleum 37, pages 596 if. (1951), and comprises the following: 10 g. oil are filtered at C. in vacuum through an A2 Gooch crucible the frit of which is covered with a paper filter (Schleicher & Schiill, No. 575). The amount of filtered-off sludge is gravimetrically determined. In order to evaluate the influence of aging, a sample of the same oil is kept for 24 hours at a temperature of 100 C. and then the quantity of sludge formed,
• the Butlin test determines the flocculation of sludge produced by a change of the C/H ratio of the oil phase, which may be brought about in that the heating oil is mixed with a thinner oil, i.e., with an oil which possesses a lower C/H ratio than the heating oil itself.
• a mixture of xylene with isooctane Iso-octane acts to precipitate the sludge, xylene to dissolve it again.
• the quantity of oil mixture which is required serves as a measure of the quantity of sludge which was separated.
• the test is carried out according to the procedure set forth by B. G.
• the production of heating oils (F) is accomplished in that in the third step the phase (C), rich in asphalt and in ash, is admixed with the desulfurized heavy oil (E). It is, however, also possible to use only a portion of the phase (C), rich in asphalt and in ash, derived from the first step, and to use the remaining part in another wa as for example as starting material or mixing component for bitumina (Example 7) or as raw material for the production of synthetic gas, etc. (Example 8).
• heating oils (P) which do not contain more than 1% sulfur, if one absorbs the entire extract (C into the desulfurized hydrogenation residue (E If a sulfur content of more than 1% is possible, then there may be added a component having a greater sulfur content as top-oil residue (A). It is also possible to replace the phase (C), rich in asphalt and in ash, in the third stage with residual oils (A). In this connection the starting product (A) for the decomposition has proved particularly suitable (see Example 6).
• step 3 the desulfurized heavy oil (E) obtained in the second step, in which case the phase (C), rich in asphalt and in ash, obtained in the first step, is utilized for an entirely different use.
• the commercial heating oils are of different types and are classified not only according to the raw material source, but also with respect to the manner of their production.
• the classification is based on the analyses of various commercial products, which has been set out in Table 1 as Numbers 59.
• the sulfur and asphalt values as well as those for the boiling point curves and the solidifying point are different in each instance as are the values which are typical for new sludge formation.
• Example 3 illustrate appropriate compositions, flows and operating conditions which may be present and encountered in the practice of this invention:
• Example 1 In a de-asphaltizing-installation top-oil-residue (A) is extracted at 120 C. and atmospheres with a fivefold quantity of isobutane (vol./vol.) utilizing a countercurrent flow of materials. There is thereby obtained 84% of a ratfiniate (B and 16% of an extract (C 0 The C rafiinate contains 1.81% sulfur and the C extract 3.3% sulfur. The extract is brittle and may very easily be pulverized.
• the rafiinate (B is subjected to a hydrogenating desulfurization in the presence of a cobalt-molybdate catalyst at a through-put rate of 1 l g./l. catalyst/hr., a pressure of 500 atmospheres and with 2 Nm. l-l /kg. at 440 C. There is obtained 49.3 weight percent of a residue 340 C. and 50.7 weight percent lighter products.
• the extract (C is taken up in the hydrogenation residue (E of the raflinate under intensive stirring at 70-80 C.
• Example 2 The same C ratfinate (B as in Example 1 is subjected to a hydrogenating desulfurization using a cobalt-molybdate-catalyst (the catalyst is prepared in pellet form, the pellets having a 3 mm. diameter) at a through-put rate of 1 kg./l. catalyst/hr, but with a pressure of 300 atmospheres, 2 Nm. H /kg. and at a temperature of 445 C. There are obtained 49.9 weight percent of residue (E 340 C. and 50.1 weightperccnt of lighter products. After 239 days the experiment or run is discontinued; the catalyst throughout has retained its desulfurizing activity. About 7% coke has deposited on the catalyst; after the burningoff of the coke the run is continued.
• a cobalt-molybdate-catalyst the catalyst is prepared in pellet form, the pellets having a 3 mm. diameter
• the C extract is combined with the hydrogenation residue (C of the C ratrinate (E under intensive stirring. 58.7 weight percent of the top-oil-residue (A) charged are converted into heating oil (F) 340 C. with 0.92 weight percent sulfur (Table 3). In the aging no dry sludge is newly formed.
• Top-oil residue (A) is deasphaltized with propane at 63 C. and 40 atmospheres.
• the ratio of propane to top-oil-residue used in the deasphaltizing amounts to about 2:1 kg./kg.
• the C railinite (B) contains 1.88 Weight percent of sulfur and the C residue (C 3.73 weight percent of sulfur.
• the C ratfinate (B is subjected to hydrogenation desulfurization using therefor a cobalt-molybdate catalyst, a throughput of 1 kg/l. of catalyst/hr., a pressure of 200 atmospheres, 1.4 Nm. H /kg. and a temperature of 400 C.
• 18.5 weight percent of the C rafiinate (B charged are in this run converted into fission products 340 C.
• the hydrogenation residue (E of the C raftinate is mixed with the C extract (C 84.5 weight percent oi the top-oil-residue (A) charged are converted into heating oil (F) 340 C. having an 0.81 weight percent of sulfur (Table 4). In the aging 0.002 weight percent dry sludge are peptized.
• Example 4 In the manner set out in Example 3, a top-oil residue (A) is deasphaltized with propane.
• the top-oil-residue having a C/H ratio of 6.3:1 is decomposed into of a C rafiinate (B and 20% of a C extract (C
• the C raffinite (B contains 1.91 Weight percent of sulfur and the C extract (C 4.61 Weight percent of sulfur.
• the raftinate (B has a C/H ratio of 6.2:1, the extract (C 2. C/H ratio of 8:1.
• the C rafiinate (B is treated in a hydrogenation desulfurization using the same catalyst as employed in Example 3, a throughput of 1 kg./l. of catalyst/hr. but in this instance a pressure of 300 atmospheres, and 1.5 Nm. H /kg. at 410 C. 79 weight percent of the C rafiinate (B remains as hydrogenation residue (E characterized by its loW sulfur content.
• the residue has a C/H ratio of 5.9:1 and is admixed with the C extract (C 78.8 Weight percent of the top-oil-residue (A) which had been charged are obtained as heating oil (F) having a sulfur content of 1.01 weight percent (Table 5).
• 0.001 Weight percent dry sludge are peptized.
• Example 5 A top-oil-residue (A) is distilled in vacuo until 50 weight percent are removed by distillation.
• the vacuum distillate (B which is obtained is treated at 40 atmospheres, 380 C., a 1.5 Nm. H /kg. and a throughput of 1 kg./l. catalyst/hr. using a cobaltmolybdate cata- 9 lyst.
• 80 weight percent 340 C. are obtained.
• the hydrogenation residue (E is admixed with the vacuum residue (C in proportions whereby the mixture point of +23 C. and a dropping point of 29 C. is mixed together with an extract (C recovered from the butane deasphaltizing of top-oil-residue (A) having an ash content of 0.11 weight percent, a softening point Weight percent sum. test Weight percent asphalt Weight percent S Vise. units/50 O Vise. units/100 C solidification point. C Dropping point, C Soitening point, C Hot filtration test before/ contains 1 weight percent of sulfur. This is accom- 5 of +88 C. and a dropping point of +133 C. using the plished by admixing the hydrogenation residue (E with mixing ratio of 1:2.
• Example 6 The hydrogenation residue (E) which results fromthe C raffinate (B treated as set out in Example 4, is treat- A 3 fixt'l'act 1) is injected at about Under ed for the production of heating oil (F), using in the pp y of Water vapor and technically p yg into t t t i place f th c extract (c thg t i1- a cracking reactor.
• a process for preparing heavy heating oils having low sulfur contents comprising the steps of (1) subjecting an oil residue derived from a member selected from the group consisting of petroleum, oil shale, coal tar, brown coal tar, generator tar, and mixtures thereof (A) to a separation treatment in which said residue (A) is separated into an asphalt and ash rich phase (C) and an asphalt and ash poor heavy oil phase (B);
• step 3 the admixing is effected so that a heavy heating oil hav ing a low sulfur content not exceeding about 1% is formed.
• a process for preparing heavy heating oils having low sulfur contents comprising the steps of (1) subjecting an oil residue derived from a member selected from the group consisting of petroleum, oil shale, coal tar, brown coal tar, generator tar, and mixtures thereof (A) to :a separation treatment in which said residue (A) is separated into an asphalt and ash rich phase (C) and an asphalt and ash poor heavy oil phase (B) and (2) subjecting the asphalt and ash poor heavy oil phase (B) to a desulfurization treatment to obtain a desulfurized heavy oil phase (E).

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