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公开(公告)号：DE934069C
公开(公告)日：1955-10-13
申请号：DEST002071
申请日：1950-09-01
Applicant: STANDARD OIL DEV CO
IPC: C07F9/04 , C10L1/26 , C10M135/04
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公开(公告)号：FR1101073A
公开(公告)日：1955-09-27
申请号：FR1101073D
申请日：1954-05-21
Applicant: STANDARD OIL DEV CO
IPC: C10M141/10
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公开(公告)号：FR1099233A
公开(公告)日：1955-08-31
申请号：FR1099233D
申请日：1954-03-23
Applicant: STANDARD OIL DEV CO
IPC: B01J23/96
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Patent Agency Ranking
公开(公告)号：GB733799A
公开(公告)日：1955-07-20
申请号：GB2598452
申请日：1952-10-16
Applicant: STANDARD OIL DEV CO
IPC: C10G35/14
Abstract: In a continuous process for hydroforming hydrocarbons boiling in the motor fuel boiling range in a reaction zone, in the presence of a dense turbulent bed of hydroforming catalyst, of the type wherein finely-divided particles of catalyst are withdrawn continuously from the reaction zone, are transferred to a regeneration zone wherein the carbon content of the catalyst particles is reduced and are then returned to the reaction zone, the regenerated catalyst to oil charging weight ratio is from 0.5 to 1.5 and the regenerated catalyst particles are returned directly to the reaction zone without previously contacting with hydrogen-containing gases. It is preferred to effect substantially complete generation of the catalyst, e.g. as is shown by the presence of free oxygen in the flue gases from the regenerator and by the presence of less than 0.3 and preferably of less than 0.1 weight per cent of carbon in the regenerated catalyst and by substantially complete oxidation of the catalytic metal to the highest valency form. The feed stock to the reactor may be a petroleum fraction, e.g. a virgin naphtha or a cracked naphtha or it may be a Fischer-Tropsch naphtha. The feed-stock is preheated alone or in admixture with recycle gas. The preheating is ordinarily carried out to temperatures of about 800-1000 DEG F. and the preheated feedstock may be supplied to the reactor separately or in admixture with hydrogen-rich recycle gas. The recycle gas when introduced separately may be preheated to 1150-1300 DEG F. prior to its introduction into the reactor. The hydroforming reactor vessel should be operated at 550-950 DEG F., preferably at about 900 DEG F., and at pressures between about 50 and 500 pounds per square inch. The regenerator is preferably operated at substantially the same pressure as the reactor vessel and at 1050-1300 DEG F. Suitable catalysts include Group VI metal oxides such as molybdenum oxide, chromium oxide or tungsten oxide, or mixtures thereof, upon a carrier such as activated alumina or zinc aluminate spinel. Minor amounts of stabilizers and promoters such as silica, calcium oxide, ceria or potassia can be included in the catalyst. Two types of reactor-regenerator systems are described and illustrated, one being a side-by-side reactor-regenerator system whilst the other has the regenerator arranged above the reactor with the regenerated catalyst stand-pipe extending downwardly through the dense reactor bed, the regenerated catalyst in each case being returned directly into the dense catalyst bed in the reactor. The regenerated catalyst is stripped with air or nitrogen and may also be further stripped with small amounts of nitrogen before returning it into the reaction zone. Examples are given in which catalytically cracked naphtha is used as the feed gas in a hydroforming plant operating at 200 pounds per square inch gauge pressure using a molybdenum oxide on alumina catalyst, a regenerated catalyst to oil ratio of 1 and reactor temperatures of about 900 DEG F. The results obtained without pretreatment of the regenerated catalyst with hydrogen are compared with those obtained with a 15-minute pretreat with hydrogen at 900 DEG F. and 200 p.s.i.g., the heat formed during the pretreatment being quickly dissipated to a fluid sand bath surrounding the catalyst bed. The results are also compared with those obtained by a process in which the regenerated catalyst is pretreated with hydrogen at 1004 DEG and 996 DEG F. respectively for 10-15 seconds.
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公开(公告)号：GB733636A
公开(公告)日：1955-07-13
申请号：GB2488852
申请日：1952-10-03
Applicant: STANDARD OIL DEV CO
IPC: C10G11/18
Abstract: Crude petroleum oil is contacted with hot cracking catalyst whereby the oil is completely vaporized and a substantial proportion of the heavy constituents are cracked to gas oil with only moderate production of coke and light gases, the effluent from the craking zone is passed to a fractionation zone wherein gasoline, gas oil and a heavy bottoms fraction are separated, the gas oil is subjected to catalytic cracking in a second cracking zone, the effluent from the second cracking zone is passed back to the fractionation zone, and a major portion of the heat required for the process is derived by burning carbon formed during the cracking. Crude oil, supplied through line 1, divides into two portions, 55-90 per cent being passed to preheater 5 and the remainder being introduced through line 9 into the lower part of fractionator 11. The oil is preheated to 500-550 DEG F. in preheater 5, and is then mixed in line 13 with regenerated catalyst particles (50-100 microns) at 1050-1150 DEG F. A low activity catalyst such as activated clay is employed, the proportion being such (5 to 30 lb. per lb. of oil) that a dry catalyst/oil vapour suspension at 850-1100 DEG F. enters reactor 15. This reactor comprises a vertical transfer line with a ratio of length/diameter of 8 : 1 to 12 : 1, and the suspension passes up the line at a linear velocity of 10 to 100 feet/sec., whereby the oil vapours are retained therein for a relatively short time (1-25 seconds). Under these conditions the heavy fractions are cracked to form gas oil, only small quantities of gasoline, coke and gas being formed. The suspension is passed from line 15 into gas/solids separator 19, and the separated catalyst is withdrawn through standpipe 21 wherein it is stripped and aerated by inert gas introduced through taps t. The carbonized catalyst travels round U-bend 22 and is then suspended in air, supplied via lines 23, and passed up riser line 25 into regenerator 30, wherein a dense fluidized bed of the particles is maintained. While the carbon is burned off the catalyst, the latter is raised to 1050-1150 DEG F. The hot regenerated catalyst is stripped and returned to line 13 via standpipe 33 and U-bend 34. U-bends 22 and 34 contain catalyst particles at maximum fluid density and act as gas seals in the catalyst circulation system. Part of the catalyst in circuit must be replaced by fresh catalyst (0.2 to 1 lb. per barrel of crude) in order to compensate for permanent de-activation by the deposition of inorganic ash constituents. The spent catalyst is withdrawn via line 37, and the fresh catalyst is supplied via line 35. The vapours leaving separator 19 are passed via line 39 to fractionator 11, the temperature of the bottom section of which is maintained at about 700-800 DEG F. by feeding in cold crude oil via line 9. Gas and gasoline are withdrawn from the head of the fractionator, heavy naphtha is withdrawn via line 49, heating oil (B.R. 400-550 DEG F.) is withdrawn via line 47, and gas oil (B.R. 550-1200 DEG F.) is withdrawn via line 57. The heavy fraction withdrawn from the base of the fractionator is recycled via line 43 to reactor 15, or all or a part of it may be withdrawn via line 45 for use as a heavy fuel oil. The gas oil withdrawn through line 57 is mixed in line 61 with catalyst particles at 1050-1150 DEG F., the amount of catalyst (5-25 lb. per lb. of oil) being such that the mixture enters reactor 60 at 900-1000 DEG F. The catalyst is preferably a high-activity material, such as a synthetic silica-alumina gel containing 10 to 20 per cent of alumina and having a particle size of 50 to 100 microns. The catalyst is maintained as a dense fluidized bed in rector 60, and the cracking therein is more severe than in the first stage. Contaminated catalyst is regenerated in regenerator 70, wherein a dense fluidized bed of catalyst is also maintained; and the regenerated catalyst is returned via standpipe 72 to line 61. The cracked oil vapours withdrawn from reactor 60 are passed via line 76 to the base of fractionator 11. In a modification, catalyst withdrawn from the second cracking stage may be used as the catalyst for the first stage. In this case, catalyst is passed from regenerator 70 to line 13 via line 77; and fresh catalyst is supplied to the second stage via line 79. If the volatility of the product gasoline is too low, a small fraction of heavy naphtha may be branched off line 49 via line 80, and introduced into reactor 60 for cracking into lower boiling products; in this case, both cracking stages may be operated at lower temperatures, e.g. 825-925 DEG F.
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公开(公告)号：FR1097090A
公开(公告)日：1955-06-29
申请号：FR1097090D
申请日：1954-03-11
Applicant: STANDARD OIL DEV CO
IPC: A01N25/10
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49.发明专利
公开(公告)号：GB731815A
公开(公告)日：1955-06-15
申请号：GB229952
申请日：1952-01-28
Applicant: STANDARD OIL DEV CO
IPC: B01F5/02
Abstract: Systems for the alkylation of isoparaffins with an olefin in the presence of a liquid catalyst such as concentrated sulphuric acid, and for isopropanol extraction, employ a method of contacting the materials by injecting opposed streams of the materials into a confined liquid pool through terminally restricted jets (see Group II). Alkylation of isobutane and butylenes in the presence of sulphuric acid having a strength of from 90 to 95 per cent, is carried out at a temperature of from about 30 DEG to 60 DEG F. in a system wherein an emulsion of the reaction materials passes upwardly through each of a series of vessels such as the vessel 1, Fig. 4. Within the vessels 1 are arranged partitions 25 having perforations which receive pairs of conduits 28, 29 terminating in opposed jets 30. Upstream of each partition 25 is a manifold 31 for the supply of fresh olefin feed material. The emulsion, and the fresh feed materials entering through the manifolds 31, pass upwardly through the perforated plates 25 into the conduits 28, 29 and pass out of the jets 30 as opposed streams into the liquid pool constituted by the emulsion in the zones above the partitions 25 whereby the reaction materials are contacted. The system includes means for recycling some of the emulsion discharged from the last vessel 1 of the series and for recycling some of the acid obtained from a separator at the end of the series of vessels 1, from which separator hydrocarbon materials containing the desired alkylation products are passed on to fractionation means, not described. Excess isobutane derived from the fractionation step is recycled to the alkylation system. The Specification describes another example of a typical alkylation operation carried out in an apparatus in accordance with Fig. 4, and steam stripping means are referred to for the recovery of absorbed isobutylene from the acid from the separator, and for recovery of condensed butyl alcohol from the overhead from such regenerator operation. A gas is also recovered which may give a product containing isobutylene. The proportions of the constituents of the feed stock used in the two examples are specified. Several alternative arrangements of the jets are described (see Group II). A process of isopropanol extraction is carried out in a vessel 101, Fig. 2, which is initially filled with water into which kerosene-isopropyl alcohol mixture and water are injected through jets 103a, 104a respectively. Isopropanol extraction is also carried out in the apparatus of Fig. 10 (see Group II).ALSO: A method of contacting liquid materials consists in injecting opposed streams of the materials into a confined liquid pool through jets consisting of terminally restricted orifices of substantially equal diameter spaced apart by a distance not less than 0.3 and not more than 5 times the diameter of the jets, the injection being carried out so that there is a pressure drop across the jets of from 2 to 20, preferably 6 to 8, pounds per square inch. The method may be used for purposes such as to bring about absorption of one material in another, to bring about chemical reactions between two or more materials alone or in the presence of catalyst materials, or to form emulsions. In an apparatus for the treatment of gas oil for the removal of aromatic mercaptans, a confined liquid pool of oil and caustic soda solution is formed within a vessel 101 and opposed jets 103a, 104a are formed at the termination of inlets 103, 104 for oil and caustic soda solution respectively. The caustic soda solution flowing into the inlet 104 is a mixture of caustic soda solution circulated from the bottom of the vessel 101 by way of a line 106 and fresh caustic soda solution supplied by way of a line 107. Spent caustic soda solution is removed from the vessel 101 by way of a line 108. Treated gas oil from the vessel 101 passes along a line 109 into a line 110 in which it mixes with water supplied by a line 111, which is a mixture of water circulated from the bottom of a vessel 102 and fresh water supplied through a line 114. The line 110 terminates in a pair of opposed jets 110c in the vessel 102 and the water-oil mixture in the line 110 is divided into two separate opposed streams passing through the jets 110c into a confined liquid pool defined by the vessel 102. Water containing extracted residual caustic soda solution is continuously removed from the vessel 102 by way of a line 115. Treated washed gas oil is removed from the vessel 102 by way of a line 116. Several constructions and arrangements of opposed jets are described (see Group II), more particularly for use in apparatus for the alkylation of isoparaffins with an olefin in the presence of sulphuric acid, in which the confined liquid pool contains an emulsion of these materials, and for isopropanol extraction (see Group IV (b)).
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公开(公告)号：GB731806A
公开(公告)日：1955-06-15
申请号：GB2293651
申请日：1951-10-02
Applicant: STANDARD OIL DEV CO
Abstract: Isoparaffinic hydrocarbons are reacted with olefins in the presence of a liquid acid catalyst to form branched chain hydrocarbons boiling in the gasoline range, free from polymerization products, by feeding to a confined reaction zone an emulsion of the liquid catalyst and the major portion of the isoparaffin feed, and a mixture of the remaining isoparaffin feed and recycled reactants and reaction products free from catalyst, discharging the emulsion and mixture through opposed coaxial nozzles to impinge on each other, introducing fresh olefin feed into the reaction zone either in admixture with the said mixture, or as a separate stream directed towards the region of impingement of the streams of emulsion and mixture, withdrawing liquid from the reaction zone and separating it into a heavy, catalyst component which is recycled with the isoparaffin feed and a lighter fractionable component part of which is withdrawn for product recovery, the major portion being recycled with the remaining isoparaffin, to the reaction zone. As shown in Fig. 1, isobutane is fed at 29 and passed by pump 25 to a pipe 8 and header 9 in the lower portion of a reactor 1 which is divided into two chambers 1a, 1b by a plate 2 which carries a series of opposed nozzles 5. Acid catalyst joins the isobutane feed either from line 30 or line 24b and is optionally emulsified in a device 26 or heated at 27. The emulsion is discharged from chamber 16 through pipe 3 and nozzle 5 as a jet in chamber 1a. Olefin feed, e.g. butylene, enters at 28 together with a minor amount of isobutane and, mixed with catalyst free liquid from line 20, enters the reaction chamber through pipes 7, 6, 6a and 4 to be discharged by the other nozzle 5. Reaction products withdrawn at 10 are separated at 12 into a heavy catalyst containing component which passes down pipe 24 to join the main isobutane feed, and a lighter component, catalyst free and containing reaction products and excess isobutane reactant which leaves at 13. The major portion of this is recycled by line 20 to take up the olefin feed from 28 and a minor proportion is passed through separators 14 and 15 to a fractionating column 18 for product recovery. Catalysts employed may be sulphuric acid or mixtures thereof with phosphoric acid, hydrofluoric acid, or aluminium chloride boron fluoride complexes. 90 to 98 per cent sulphuric acid is preferred and reaction temperatures of 30 DEG to 60 DEG F. are specified. The total feed may comprise 15 per cent butylene, 70 per cent isobutane, the olefin feed preferably containing at least 40 per cent butylene and the paraffin feed containing at least 85 per cent of isobutane. The isobutane feed is preferably cooled to 25 DEG to 40 DEG F. in a cooler 32 and, to prevent freezing, a small amount of acid may be added at 30. The olefin feed may also be at the same temperature. The isobutane feed is preferably heated to 40 DEG to 80 DEG F. by heater 27 before entering the reactor through pipe 8. Alternatively, temperature control may be effected by allowing a portion of the materials fed to the reaction vessel to vaporize, and after recompression, recirculating them to produce an auto-refrigeration effect at the point of contact of the reactants in the reactor. The retention time in the zone X between the nozzles may be from 0.10 to 10 seconds and the residence time in the reactor 0.5 to 5 minutes. In a modification, Fig. 2, the emulsion of catalyst and isoparaffin from chamber 16 passes through pipe 3 to be discharged at nozzle 5 whilst recycled reactants enter pipes 7, 6a, 4 and are discharged through the other nozzle 5. The olefin is then fed from pipe 32 to a pipe 31 terminating at a point between the nozzles 5. The invention is applicable to the use of fast reacting olefins such as propylene, amylene and isobutylene, whilst as paraffins, isopentane may also be used. Specification 731,815 is referred to.ALSO:Liquid reactants are contacted in a reaction zone in the presence of a liquid catalyst, immiscible therewith by emulsifying the liquid catalyst with a major portion of the least reactive of the fresh feed materials, mixing the remaining and minor proportion of said least reactive reactant with a major portion of the reactant materials withdrawn from the zone after contact therein and separation of catalyst, and injecting said emulsion and mixture into the reaction zone as coaxially opposed jetted streams impinging on each other within a body of said materials maintained in the zone, and introducing the most reactive material of the fresh reactant feed either in admixture with said stream of the mixture of the least reactive component and the recycled reactant materials or as a separate stream directed towards the region of impingement of the streams of emulsion and mixture. The method is particularly applicable to the reaction of isoparaffinic hydrocarbons with olefines to form branched chain saturated hydrocarbons boiling in the gasoline range, and to avoid undesired polymerization reactions. As shown in the Figure, a closed reactor 1 is divided into two chambers 1a, 1b by a transverse plate 2 through which a series of pairs of pipes 3 and 4 pass, terminating in opposed nozzles 5. The least reactive reactant, e.g. isobutane is fed at 29 and passed together with the liquid catalyst, such as sulphuric acid or mixtures thereof with phosphoric acid, hydrofluoric acid or complexes of aluminium chloride and boron fluoride from pipe 30, through a punch 25 and line 8 to the lower chamber 1b by a header 9. If desired this feed may be by-passed through a heat-exchanger 27 and emulsification enhanced by subdividing the feed and discharging it as opposed jets in a device 26 before entering pipe 8. This portion of the feed fills the chamber 1b and passes through plate 2 by pipe 3 to be discharged through nozzle 5. The most reactive component is fed at 28, mixed with recycled reactants (see below) from pipe 20 and passed through pipes 7, 6a and 4 to the other nozzle 5. Reaction products are withdrawn at 10 and passed through a separator 12 where the liquids are separated into a heavy component, consisting of catalyst which may be in part withdrawn at 24a and replenished at 24b, and a lighter component consisting of a fractionable mixture including reaction products and the excess of one of the reactants. The lighter component withdrawn at 13 is in part passed to additional separators 14 and 15 and to a fractionating tower 18, whilst part is recycled through pipes 20 and 7 to the reaction zone. The heavy component passes through line 24 to be mixed with the isobutane feed at 31 and is recycled to the reactor. In a modification, Fig. 2, the emulsion of catalyst and least reactive reactant from chamber 1b passes through pipe 3 to be discharged at nozzle 5 whilst recycled reactants enter pipes 7, 6a, 4 and are discharged through the other nozzle 5. The most reactive component, e.g. the olefine, is led from pipe 32 to a pipe 31 terminating at a point p between the nozzles 5. The reaction and feed temperatures are controlled as shown by heat exchangers 23, 32, 27, but if desired a portion of the materials supplied to the reaction vessel may be vaporized therein and after recompression, recirculated to produce an auto refrigeration effect at the point of contact of the reactants in the reactor. Specification 731,815 is referred to.
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