US3876534A - Method for the removal of non-saturated and/or aromatic hydrocarbons from saturated paraffin hydrocarbons and a device to embody said method - Google Patents

Method for the removal of non-saturated and/or aromatic hydrocarbons from saturated paraffin hydrocarbons and a device to embody said method Download PDF

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US3876534A
US3876534A US315840A US31584072A US3876534A US 3876534 A US3876534 A US 3876534A US 315840 A US315840 A US 315840A US 31584072 A US31584072 A US 31584072A US 3876534 A US3876534 A US 3876534A
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aromatic
gaseous
compounds
process according
hydrocarbons
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US315840A
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Alfred Davidsohn
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Ballestra SpA
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Ballestra SpA
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Priority claimed from IT1310971A external-priority patent/IT942070B/it
Priority claimed from IT1297072A external-priority patent/IT1005506B/it
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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
    • C10G17/00—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge
    • C10G17/09—Refining of hydrocarbon oils in the absence of hydrogen, with acids, acid-forming compounds or acid-containing liquids, e.g. acid sludge with acid salts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates generally to a method and device for the complete removal of non-saturated or/and aromatic hydrocarbons or other sulphonatable compounds from saturated paraffin hydrocarbons and particularly to a method and device for producing white oils from portions of crude oil with a high distillation point, containing relatively large quantities of sulphonatable aromatic compounds.
  • White oils are a particular type of highly refined mineral oils containing only paraffin hydrocarbons and isoparaffins (napbtenics). They are used for various purposes, when the absence of colour. taste and smell is absolutely required. Various types of white oils are produced and, correspondingly to the use they are intended for, they differ from one another according to the degree of refining and their viscosity.
  • the raw material for obtaining said whiteoils consists of various types of hydrocarbons (paraffinic, naphtenic, aromatic) and small quantities of organic compounds containing sulphur, oxygen and nitrogen.
  • aromatic hydrocarbons (mono-, di-, policondensate) with shorter or longer parafi'inic side-chains, branched or straight, and organic compounds containing sulphur, oxygen and nitrogen. are responsible for color, taste, smell and irritation of the human skin, and are to be removed during the refining process.
  • a sul phonation process is used for removing said undesirable compounds.
  • sulphonation with Oleum is a reaction wherein the sulphonating agent is used in large excess, whereby a considerable part of the mono-sulphonic acids soluble in oil, and thus usable as by-products, are degraded to insoluble polysulphonic acids which cannot be used at all as by-products.
  • gaseous 50 derived directly from the combustion of proportioned amounts of molten sulphur and from the subsequent catalytic transformation of the produced into S0 whose high reactivity is reduced by the fact that it is diluted in the carrier gas consisting of nitrogen, oxygen and small quantities of 50
  • gaseous SO obtained as above is used as sulphonating agent, difficulties may arise in separating the non-sulphonated portion of oil and the sulphonic acids soluble in oil from the insoluble sludges consisting mainly of polysulphonic acids.
  • the percentage of sulphonatable compounds is relatively high, e.g., higher than it is often very difficult, if not impossible to separate said acid sludges from the treated material. Not only the separation through sedimentation difficult, but even centrifugation is very difficult or technically impossible (that is not practical on an industrial scale in an economically convenient manner).
  • said sludges are viscous and sticky, they tend to stick onto the walls of the reaction vessels, separation vessels or centrifuges.
  • Said secondary reactions are largely responsible for the viscous nature of the formed acid sludges. the loss of valuable oilsoluble petro-sulphonates, and the formation of excessive amounts of sulphur trioxide which must be removed from the exhaust gases of the apparatus, so as to meet the more and more stringent laws against air pollution.
  • Such a type of solvent based on portions of Kerosene" type fractions with a distillation range between and 280C, is largely used in the production of aerosol products, for instanse cosmetics, and as solvents for pesticides.
  • this type of solvent too is obtained by sulfonating, e.g., through gaseous S0 the non-paraffinie components, e.g., the aromatic or olefines compounds and other sulphonatable compounds, present in feedstock.
  • this invention achieves the advantages shown in the above paragraphs 1 to 4 in producing white oils, starting with crude oils with a high content of sulphonatable compounds, by premixing the starting material consisting of high molecular weight oil compounds with a starting material consisting of lower molecular weight fractions, the latter having also a lower viscosity and a lower distillation range.
  • fractions with a distillation temperature between l20 and 280C may be used.
  • Starting starting materials of high molecule weight consisting of high molecular weight oil fractions, i.e. oil compounds with a distillation temperature above 320C are used. It is to be noted that the temperature gap between the end point of the distillation range of the lower molecular weight fraction and the starting point of the distillation range of the higher molecular weight fraction is advantageous as it facilitates subsequently the separation of the refined products bby distillation.
  • the low boiling point fractions. after the refining by the sulphonation method. are commercially valuable products commonly known as Deodorized” solvents. or “Deodorized white spirits” and/or Deodorized kerosene.
  • the effect of such pre-mixing is not only to change the character of the starting material, e.g.. by decreasing the viscosity. lowering the reaction temperature. but also to change the character of the acid sludge.
  • the lower molecular weight sulphonatable com pounds of the lower fraction have also a much lower viscosity. whereby the acid sludges of the mixture treated by sulphonation. become less viscous. more fluid. and retain less treated material.
  • the still slightly acid mixture is subject to the usual steps of neutralization. alkaline washing. and so on. the sulphonated compounds. soluble in oil. are thus removed by known methods. e.g.. by a washing with hydroalcoholic solutions.
  • the acid free mixture is then subjected to distillation. thereby separating the higher molecular weight material from the lower molecular weight material.
  • the temperature gap between the upper end point of the distillation range of the lower molecular weight fraction and the starting point of the distillation range of the higher molecular weight fraction is particularly advantageous so as to effect such a separation without difficulty.
  • its application range may be widely arranged as larger both for variation of the starting material. (feedstock) and for obtaining lowest amounts of aromatic compounds rcmaining in the refined products when said lowest limit is to be reduced to some dozens of parts per million.
  • the sulphonation reaction of said compounds is effected by using a substantially limited quantity of S diluted in an inert carrier gas.
  • Object of said variation of the invention is to avoid such an inconvenience, by ensuring a high degree of removals of the aromatic hydrocarbons from the refined end product.
  • said portions containing large quantities of sulphonable aromatic compounds is characterized in that said fractions of high distillation range crude oil are previously mixed with fractions of lower distillation crude oils also containing sulphonatable aromatic compounds. Said mixture is then subjected to sulphonation. separation of the sludges consisting of the oil insoluble sulphonic acids. neutrualization and separation of the oil soluble sulphonic acids; finally the refined lower fraction is distilled off between 120 and 280C leaving the higher fraction boiling above above 320C. so as to obtain first compounds known as deo-kerosene and then white oils.
  • the fraction of high distillation range crude oil may contain 35% by weight of sulphonable compounds.
  • the fraction of low distillation range crude oil may contain sulphonable compounds up to 30% by weight.
  • the sulphonation of the mixture of crude oil fraction. the separation of the insoluble sludges. the neutralization. and the separation of the oils soluble sulphonic acids, are effected in several stages.
  • kynematic viscosity between 12 and 35 cts (At contents of sulphonable compounds up to 35% by weight;
  • the starting of fraction of hydrocarbons with a low distillation point has the following characteristics
  • said aromatic hydrocarbons are sulphonated in at least two stages in a series of reactors where the mixture is treated with the sulphonating agent fed into the reactors in parallel.
  • Such a method according to the invention is characterized in that the sulphonating agent is fed in parallel in decreasing portions at the stage subsequent to the first one. and the excess of sulphonating agent is removed from the last stage. is fed to the first one, so that said sulphonating agent is present in excess in the last reaction vessel, while the aggregate amount of sulphonating agent is used is about equal to the stoichiometric amount.
  • said sulphonating agent consists of gaseous 80;, which is obtained by burning molten sulphur and then transforming the obtained 80; into 50;. in presence of a catalyst.
  • the gaseous reagent so obtained has the following volume composition:
  • Said gaseous sulphonating agent is fed into the liquid feedstock to be treated and dispersed therein by stirring so as to limit as much as possible polysulphonation of the aromatic components.
  • the feeding of said two reagents to each reaction step is accompanied by the removal of the insoluble compounds produced by the sulphonation of the aromatic portion, so that such a portion, already sulphonated. cannot participate in the successive treatment of said liquid mix.
  • a portion of liquid compounds treated in each stage, after the separation of the insoluble portion. is partly recycled so as to dilute both the sulphonable portion of the liquid compound to be treated and the gaseous reagent which is dispersed within the liquid mass of the compound to be treated.
  • the device for embodying the process according to the invention comprises a set of reaction vessels in series for the passage between each other of the liquid mix to be treated. feeding in parallel the gaseous reagent, as well as removing, by separating devices, the insoluble compounds obtained by the reaction in each individual reaction vessel, removing devices for the unreacted gaseous portions from the corresponding reaction vessel, said devices for removing the gaseous reaction from the last reaction vessel are connected to the feeding device of said gaseous reagent to the first reac tion vessel.
  • the device according to the invention further comprises agitators for dispersing said gaseous reagent within the mix of liquid feedstock to be treated and thermoregulators suitable to ensure the desired temperature in the various zones of each reaction vessel.
  • each reaction vessel is divided into two overlapped elements both formed by an upper cylindric zone joined at its bottom to a conical or frusto-conical zone; wherein said upper element penetrates the lower one by a cylindric projection so as to originate in the upper zone of the lower element an annular section for collecting the liquid reaction mixture; a suitable baffle being arranged at the opening of said cylindric projection of the upper element. so as to prevent the fluid current coming from the upper element from removing the layer of insoluble compounds of the reaction deposited on the bottom of said lower element.
  • FIG. I shows a general flow diagram of the process according to the invention
  • FIG. 2 shows in greater details the part of the apparatus wherein the sulphonation of the unsaturated hydrocarbons, according to a first variation of embodiment. is effected;
  • FIGS. 3, 4 and 5 are similar to FIG. 2, but refer to three further variations of the apparatus for embodying the invention.
  • FIG. 6 shows in enlarged scale one of the reaction vessels shown in FIG. 4 above.
  • the sulphonation device 1 receives jointly from 2 the heavy portion of crude oil from which the pure paraffinic compounds are to be derived, from 3 the portion of crude oil from which the socalled deo-kerosene is to be derived, and finally from 4 the gaseous S0 diluted in a carrier gas consisting mainly of nitrogen. oxygen and smaller portions of S0 It is to be noted that numeral 4 does not denote a stock of S0 but a device for the proportioned product ion thereof.
  • the apparatus for producing proportionally S0 comprises. as above said, a proportioning means of molten sulphur, a combustion means for same for producing S0 and finally a catalyst chamber (converter) for transforming into 80
  • the percent of SO; in the gas coming from 4 is between 5 and 12%. preferably about 771, which value corresponds to the contents of S0 normally obtained when molten sulphur is burned and converted to S0
  • the molten sulphur, and thus indirectly 50,-, coming from 4 is proportioned, so as to provide said S0 in a quantity relating to the molecular weight and the average contents of sulphonable compounds in feed stocks.
  • the reaction vessel 1 is provided with stirring and thermoregulating devices, generally consisting of suitably selected refrigerating systems. such as cooling coils and the like.
  • the liquid mix coming from I contains insoluble polysulphonic acids. which are separated in 5, oil soluble monosulphonic acids, which are neutralized and then separated in 6, as well as paraffinic compounds which were not sulphonated and are conveyed to the distillation tower.
  • the so-called deo-kerosene distills, while the white oil which distills at a considerably higher temperature. above 320C, and remains as bottom.
  • the sulphonation may by divided into more reaction steps in series, each of them formed in sequence by a reaction vessel receiving 50, in parallel, by a separator for the insoluble sludges, by a neutralizer-separator for the oil soluble sulphonic acids.
  • Said mix is treated at a temperature between 35 and 40C with 27 kgs of gaseous 80;, mixed with a carrier gas in a percentof 7%; such a gaseous mixture contains 50;, coming directly from a combustion for producing 80 from molten sulphur.
  • the materials participating therein are left depositing: 6] kgs of green acids are thus obtained, which are to be disposed by burning.
  • 6] kgs of green acids are thus obtained, which are to be disposed by burning.
  • 164 kgs of Acid oil which is subjected to washing with a hydroaclcoholic solution of sodium hydroxide.
  • I4 kgs of sulphonated products soluble in oil, are obtained.
  • I51 kgs ofa mix free of acids are obtained, which then undergo distillation.
  • the products obtained were: 67 kgs of green acids and I kgs of acid oils which were washed with a hydroalcoholic solution of sodium hy drate, so as to give 15 kgs of oil-soluble sulphonated compounds and I45 kgs of a refined mix free of acids and consisting of deodorized kerosene and white oils.
  • FIGS. 2 to 6 show preferred variations of apparatus utilization in one of the steps of the claimed process.
  • said process could be used for sulphonating sulphonatable compounds where the main reaction product consists of sulphonic acids, or for removing the sulphonable compounds through sulphonation from raw materials different in proportion from the ones above mentioned and to which the process of this invention is particularly directed,
  • the device according to the invention comprises a set of four reaction vessels 5], 52. 53 and 54, and first of which has also and primarily the task of pre-mixing the mixture of reagents.
  • a stirring device, e.g. of a helical nature, 57 is provided in the core of each reactor, that is at a given distance from the bottom thereof, for the reasons mentioned herebelow.
  • the liquid mix to be treated is introduced to close said stirring means 57 in the reactor-mixer 51, through 55.
  • the exhaust gases caused by the reaction and collecting in the upper part of reaction vessels 51, 52 and 53 are removed through the discharge conduits 58, 59 and 60 ending within the common collecting manifold 6].
  • the gaseous collecting within the upper part of the last reaction vessel 54 and still containing gaseous reagent are fed to the core of reaction vessel 51 through a conduit 56 which is positioned like conduit 55, close said stirring means 57.
  • the liquid mix which reacted with the gaseous reagent coming from conduit 56, is removed from the bottom of reaction vessel SI. Said liquid is made to pass through a heat exchanger 62 and then is fed to the core of reaction vessel 52 close to said stirring means 57, like conduit 55, by means of conduit 66.
  • reaction vessels 52, 53 and 54 are fed in parallel the gaseous reagent through conduit 63, 64 and 65, all of them being fed by a common manifold 66.
  • Conduits 63, 64 and 65 discharge close to said stirring means 57, so as to ensure the largest dispersion of said gaseous reagent simultaneously to its entering the individual reaction vessels.
  • the amount of gaseous reagent entering the reaction vessels 52, 53 and 54 is substantially larger than the one entering the reactormixer 51; consequently, in reaction vessels 52, 53 and 54 occurs in a considerable way the deposition of the insoluble compounds due to the sulphonation of aromatic hydrocarbons, said insoluble compounds collecting on the bottom of the reaction vessels are removed therefrom, either periodically or continuously, through discharge conduits 67, 68 and 69 all opening into a common manifold 70.
  • FIG. 3 differs from the preceding one only because it is provided with means to deposit greater quantities of insoluble sulphonic compounds already in the reactor-mixer 151-, that requires a conduit 167 for recovering said insolible materials from the bottom of the first reaction vessel. At the same time, the liquid mix already treated in the first reactor is fed in series to the core of the second reaction vessel through a conduit 166.
  • the other parts of the device shown in FIG. 3 0perate in the same way as those shown in FIG. 2.
  • FIGS. 4 and 5 refer to the use of reaction vessels of the type shown in FIG. 6, whose constructive features will be described in details herebelow. Anyhow, it clearly appears that according to FIGS. 4 and 5 each reaction vessel is subdivided into an upper reaction zone 25] and a lower zone of decantation and separation 251".
  • conduit 166 feeds the second reaction vessel and so on.
  • conduit 73', 73" may be restricted to the starting steps of the device.
  • the reaction vessel shown therein is the second of the ones shown in FIG. 4.
  • the upper part 252 comprises jackets 80,81 for controlling the temperature of the reaction vessel walls. and jackets 82, 83 are similarly provided for the lower zone of part 252'.
  • the very reaction vessel 252 comprises a funnel part 84 ending with a cylindric conduit 85 which extends inside the deposit chamber 252", so as to create an annular chamber 86 which receives the liquid mix separating from the insoluble sludges which deposited onto the bottom of part 252'.
  • the cylindric body 85 In order to prevent the liquid jet mixed with insoluble acid sludge coming from 252'. from causing a turbulence on the bottom of part 252". and disturbing the deposit of the insoluble sludgesthe cylindric body 85 widens in its lower part and opens in front of a transversal baffle 87 which prevents the fluid current coming down vertically, from mingling the deposited sludges with the liquid portion which just parted therefrom.
  • Numeral 88 denotes a recycle pump and 89 a shutter through which is controlled the outflow of the insoluble sludges through conduit 67.
  • Said exchanger 90 cooperates with jackets 80 to 83 in keeping a temperature gradient betweenn the deposit chamber 252" and the very reaction chamber 252'.
  • the annular exchanger 91 arranged at the center of said cylindric pipe 85.
  • the starting material has the following composition by weight:
  • Such a starting product is to be purified of the unde- 6 sirable aromatic compounds by multiple step sulphonation according to the invention.
  • gaseous sulphur trioxide obtained from the combustion of molten sulphur and the subsequent transformation of S0 into S0 in presence of a catalyst.
  • the gaseous mix will have the following volume composition:
  • Boiling Point up to 30 wt 9i Sulfonahle Aromatic Compounds then b. sulfonating the resultant mixture by gaseous S c. separating and removing the resultant oil-insoluble sulfonic acid sludges. d. neutralizing the resultant liquid. e. extracting the oil-soluble sulfonic acids.
  • volume composition of said sulphonating agent is as follows:

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US315840A 1971-12-23 1972-12-18 Method for the removal of non-saturated and/or aromatic hydrocarbons from saturated paraffin hydrocarbons and a device to embody said method Expired - Lifetime US3876534A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT1310971A IT942070B (it) 1971-12-23 1971-12-23 Procedimento per produzione di olii bianchi da frazioni di petrolio greggio ad elevato punto di distil lazione contenenti quantita relati vamente elevate di composti aromati ci solfonabili
IT1297072A IT1005506B (it) 1972-10-19 1972-10-19 Procedimento per la depurazione spinta di idrocarburi paraffinici e o naftenici dalle frazioni di idrocarburi aromatici e dispositivo atto a realizzare tale procedimento

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US315840A Expired - Lifetime US3876534A (en) 1971-12-23 1972-12-18 Method for the removal of non-saturated and/or aromatic hydrocarbons from saturated paraffin hydrocarbons and a device to embody said method

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US (1) US3876534A (cs)
AR (1) AR229146A1 (cs)
BG (1) BG25653A3 (cs)
CS (1) CS198117B2 (cs)
DE (1) DE2263179A1 (cs)
FR (1) FR2164765B1 (cs)
PL (1) PL93752B1 (cs)
RO (1) RO70473A (cs)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021091758A1 (en) * 2019-11-05 2021-05-14 Saudi Arabian Oil Company Hydrocracking process and system including separation of heavy poly nuclear aromatics from recycle by sulfonation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0436549A (ja) * 1990-05-30 1992-02-06 Toshiba Corp 摺動部材およびこれを用いた周波数可変型冷媒圧縮機

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11203A (en) * 1854-06-27 Improvement in kerosene burning-fluids
US2079782A (en) * 1934-03-27 1937-05-11 Standard Oil Dev Co Process of deodorizing lubricating oils
US2581064A (en) * 1948-06-05 1952-01-01 Standard Oil Dev Co Treating oil with sulfur trioxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11203A (en) * 1854-06-27 Improvement in kerosene burning-fluids
US2079782A (en) * 1934-03-27 1937-05-11 Standard Oil Dev Co Process of deodorizing lubricating oils
US2581064A (en) * 1948-06-05 1952-01-01 Standard Oil Dev Co Treating oil with sulfur trioxide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021091758A1 (en) * 2019-11-05 2021-05-14 Saudi Arabian Oil Company Hydrocracking process and system including separation of heavy poly nuclear aromatics from recycle by sulfonation
US11279886B2 (en) 2019-11-05 2022-03-22 Saudi Arabian Oil Company Hydrocracking process and system including separation of heavy poly nuclear aromatics from recycle by sulfonation

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CS198117B2 (cs) 1980-05-30
DE2263179A1 (de) 1973-06-28
PL93752B1 (en) 1977-06-30
FR2164765A1 (cs) 1973-08-03
RO70473A (ro) 1982-09-09
BG25653A3 (bg) 1978-11-10
AR229146A1 (es) 1983-06-30
FR2164765B1 (cs) 1979-03-23

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