MXPA99012108A - Two phase hydroprocessing - Google Patents

Abstract

A process where the need to circulate hydrogen through the catalyst is eliminated. This is accomplished by mixing and/or flashing the hydrogen and the oil to be treated in the presence of a solvent or diluent in which the hydrogen solubility is"high"relative to the oil feed. The type and amount of diluent added, as well as the reactor conditions, can be set so that all of the hydrogen required in the hydroprocessing reactions is available in solution. The oil/diluent/hydrogen solution can then be fed to a plug flow reactor packed with catalyst where the oil and hydrogen react. No additional hydrogen is required, therefore, hydrogen recirculation is avoided and trickle bed operation of the reactor is avoided. Therefore, the large trickle bed reactors can be replaced by much smaller tubular reactor.

Description

TWO-PHASE HYDROPROCESSING DESCRIPTION OF THE INVENTION This application is a continuation in part of the North American provisional application, Serial No. 60 / 050,599, filed on June 24, 1997. The present invention is directed to an apparatus and process of hydroprocessing of two phases, where the need to circulate hydrogen gas through the catalyst is eliminated. This is achieved by mixing and / or reducing the hydrogen and oil to be treated in the presence of a solvent or diluent in which the solubility of the hydrogen is high in relation to the oil feed. The present invention is also directed to hydrocracking, hydroisomerization and hydrodemetalization. In hydroprocessing which includes hydrotreating, hydrotherminating, hydrorefining and hydrocracking, a catalyst is used to react the hydrogen with a petroleum fraction, distillates or waste, for the purpose of saturating or removing sulfur, nitrogen, oxygen, metals or other contaminants, or for the reduction of molecular weight (cracking). Catalysts that have special surface properties are required in order to provide the activity necessary for the desired reaction (s).

In conventional hydroprocessing it is necessary to transfer hydrogen from a liquid phase vapor phase where it will be available to react with a petroleum molecule on the surface of the catalyst. This is achieved by circulating large volumes of hydrogen gas and oil through a catalyst bed. The oil and hydrogen flow through the bed and the hydrogen is absorbed into a thin film of the oil that is being distributed over the catalyst. Because the amount of hydrogen required can be very large, from 1000 to 5000 SCF / bbl of liquid, the reactors are very large and can operate in severe conditions, from a few hundred psi to 5000 psi, and temperatures around 204.44 ° C-482.22 ° C (400 ° F - 900 ° F). A conventional system for processing is shown in U.S. Patent No. 4,698,147, issued to McConaghy, Jr. on October 6, 1987, which describes a SHORT RESIDENCE TIME HYDROGEN DONOR DILUENT CRACKING PROCESS. McCanaghy '147 mixes the inflow with a donor diluent to supply the hydrogen for the cracking process. After the cracking process, the mixture is separated into used product and diluent, and the diluent used is regenerated by partial hydrogenation and returned to the inflow for the passage of cracking. Note that McConaghy '147 substantially changes the chemical nature of the donor diluent during the process to be able to donate the hydrogen necessary for the cracking. Also, the McConaghy '147 process is limited by the higher temperature restrictions due to the assembly of the coil and the increased production of light gas, which establishes an economically imposed limit on the closest cracking temperature of the process. U.S. Patent No. 4,857,168 issued to Kubo et al. On August 15, 1989 describes a METHOD BY HYDROCRACKING HEAVY FRACTION OIL. Kubo '1_6_8 uses both a donor diluent and a hydrogen gas to supply the. hydrogen for the improved cracking catalyst process. _Kubo '168 discloses that an adequate supply of a heavy fraction of oil, donor solvent, hydrogen gas, and a catalyst will limit the formation of coke in the catalyst and the formation of coke can be substantially or completely eliminated. Kubo '168 requires a cracking reactor with a catalyst and a separate hydrogenation reactor with catalyst. Kugo'168 is also based on the breakdown of the donor diluent to supply hydrogen in the reaction process. The prior art suffers from the need to add hydrogen gas and / or the additional complexity of rehydrogenating the donor solvent used in the cracking process. In this way, there is a need for a simplified and improved hydroprocessing apparatus and method. In accordance with the present invention, a process has been developed wherein the need to circulate hydrogen gas through the catalyst is eliminated. This is achieved by mixing and / or reducing the hydrogen and oil to be treated in the presence of a solvent or diluent in which the solubility of the hydrogen is "high" in relation to the oil feed for the hydrogen to be in solution. The type and amount of diluent added as well as the reactor conditions can be set so that all the hydrogen required in the hydroprocessing reactions is available in solution. The oil / diluent / hydrogen solution can then be fed to a reactor, such as a tubular reactor or plug flow, packed with catalyst where the oil and hydrogen react. No additional hydrogen is required, therefore, recirculation of hydrogen is avoided and operation of the percolating bed of the reactor is also avoided. Therefore, large percolating bed reactors can be replaced by much smaller reactors (see Figures 1, 2 and 3). The present invention is also directed to hydrocracking, hydroisomerization, hydrodemetalization and the like. As described above, the hydrogen gas is mixed and / or reduced together with that stored in feed and a diluent such as a recycled hydrophobic product, an isomerized product or a recycled demetalated product to place the hydrogen in solution and then the mixture is passed through on a catalyst. A principal object of the present invention is to provide an improved two-phase hydroprocessing system, process, method and / or apparatus. Another object of the present invention is to provide a process of hydrocracking, hydroisomerization, Fischer-Tropsch and / or improved hydrodemetalization. Other objects and the further scope of the application of the present invention will be obvious from the following detailed description, taken in conjunction with the accompanying drawings, wherein like parts are designated by like reference numerals. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flowchart of the schematic process of a diesel hydrotreater. Figure 2 is a flowchart of the schematic process of a waste hydrotreater. Figure 3 is a schematic process flow diagram of a hydroprocessing system.

Figure 4 is a schematic process flow diagram of a multi-stage reactor system. Figure 5 is a flowchart of the schematic process of a 1200 BpSD hydroprocessing unit. A process has been developed where the need to circulate hydrogen gas or a separate hydrogen phase through the catalyst has been eliminated. This is achieved by mixing and / or reducing the hydrogen and oil to be treated in the presence of a diluent solvent having a relatively high solubility for the hydrogen so that the hydrogen is in solution. The type and amount of diluent added, as well as the reactor conditions, can be established so that all the hydrogen required in the hydroprocessing reactions is available in solution. The oil / diluent / hydrogen solution can then be fed to a plug flow reactor, a tubular reactor, or another reactor packed with catalyst where the oil and hydrogen react. No additional hydrogen is required, therefore, the recirculation of hydrogen is avoided and the operation of the trickling bed is also avoided. In this way, large percolating bed reactors can be replaced by much smaller or simple reactors (see Figures 1, 2 and 3).

In addition to using much smaller or simple rectors, the use of a hydrogen recycle compressor is avoided. Because all of the hydrogen required for the reaction is available in solution in advance of the reactor, there is no need to circulate hydrogen gas within the reactor and there is no need for the recycle compressor. The elimination of the recycle compressor and the use of, for example, plug flow reactors or tubular reactors greatly reduces the capital cost of the hydrotreating process. Most of the reactions that are carried out in the hydroprocessing are highly exothermic and as a result a great part of the heat is generated in the rector. The temperature of the reactor can be controlled using a recycle stream. A controlled volume of reactor effluence can be recycled back to the front of the reactor and can be mixed with fresh fuel and hydrogen. The recycle stream absorbs part of the heat and reduces the temperature rise through the reactor. The temperature of the reactor can be controlled, by controlling the temperature of the fresh fuel and the amount of recycling. In addition, because the recycle stream contains molecules that have already reacted, it also serves as an inert diluent.

One of the biggest problems with hydroprocessing is the coking of the catalyst. Because the reaction conditions can be quite severe, the cracking can be carried out on the surface of the catalyst. If the amount of available hydrogen is not sufficient, the cracking can lead to the formation of coke and deactivate the catalyst. Using the present invention for hydroprocessing, the coking can be almost eliminated because there is always sufficient hydrogen available in solution to prevent coking when cracking reactions are carried out. This can lead to a much longer catalyst life and reduce operating and maintenance costs. FIGURE 1 shows a schematic processing flow diagram for a diesel hydrotreater generally designated by the numeral 10. The fresh feed broth 12 is pumped by means of the feed loading pump 14 to the combination area 18. The fresh feed broth 12 is then combined with hydrogen 15 and the hydrotreated feed 16 to form a fresh feed mix 20. The mixture 20 is then separated in the separator 22 to form the first separator waste gases 24 and a separate mixture. The separated mixture is combined with the catalyst 32 in the reactor 34 to form the reacted mixture. The reaction mixture is divided into two product streams, the recycling flow 42 and the continuation flow 50. The recycling flow 42 is pumped by the recycling pump 44 to become the hydrotreated feed 16 which is combined with the fresh feed 12 and the hydrogen 15. The continuation flow 50 flows into the separator 52 where the second gas 54 Waste from the separator is removed to create the separated flow 60 reacted. The reacted separated flow 60 then flows into the reducer 62 to form reductant waste gases 64 and the separated reduced flow 70. The reacted separated reduced flow 70 is then pumped into the trap 72 where the waste gases 74 of the trap are removed to form the output product 80. FIGURE 2 shows a schematic process flow diagram for a waste hydrotreater generally designated by the number 100. The fresh feed broth 110 is combined with a solvent 112 in a combination area 114 to form feed 120 of combined solvent. The combined solvent feed 120 is then pumped by the loading pump 122 of the solvent feed to the combination area 124. The combined solvent feed 120 is then combined with the hydrogen 126 and the hydrotreated feed 128 to form the hydrogen-solvent-feed mixture 130. The hydrogen-solvent-feed mixture 130 is then separated in the first separator 132 to form the first waste gases 134 from the separator and the separated mixture 140. The separated mixture 140 is combined with the catalyst 142 in the reactor 144 to form a reacted mixture. The reacted mixture 150 is divided into two product streams, the recycle stream 152 and the continuation stream 160. The recycling flow 152 is pumped by the recycling pump 154 to become the hydrotreated feed 128 which is combined with the solvent feed 120 and the hydrogen 126. The continuation flow 160 flows into the second separator 162 where the gases 164 of the second separator are removed to create the separated flow 170 reacted. The reacted separated flow 170 then flows into the reducer 172 to form the waste gases 174 of the reducer and the separated reduced flow 180 reacted. The waste gases 174 of the reducer are cooled by the condenser 176 to form the solvent 112 which is combined with the incoming fresh feed 110. The reacted separated reduced flow 180 then flows into the trap 182 where the waste gases 184 of the trap are removed to form the output product 190.

FIGURE 3 shows a schematic process flow for a hydroprocessing unit generally designated by the number 200. The fresh feed broth 202 is combined with a first diluent 204 in a first combination area 206 to form the first diluent feed 208. The first diluent feed 208 is then combined with a second diluent 210 in a second combination area 212 to form the second diluent feed 214. The second diluent feed 214 is then pumped by the diluent feed charge pump 216 to a third combination area 218. The hydrogen 220 is admitted to the hydrogen compressor 222 to produce a 224 compressed hydrogen. The compressed hydrogen 224 flows to the third combination area 218. The second diluent feed 214 and compressed hydrogen 224 are combined in a third combination area 218 to form a hydrogen-diluent-feed mixture 226. The hydrogen-diluent-feed mixture 226 then flows through the feed-product exchanger 228 which heats the mixture 226, during the use of the third separator expeller 230, to form the first exchanger flow 232. The first flow 232 of the exchanger and the first recycling flow 234 are combined in the fourth combining area 236 to form the first recycling feed 238. The first recycling feed 238 then flows through the first feed-product exchanger 240, which heats the mixture 238, by using the first eje 242 of exchanger rectifier exchanged to form the second flow 244 of the exchanger. The second flow 244 of the exchanger and the second recycling flow 246 are combined in a fifth combination area 248 to form the second recycle feed 250. The second recycling feed 250 is then mixed in the feed-recycle blender 252 to form the feed-recycling mixture 254. The feed-recycling mixture 254 then flows into the separator 256 of the rea entrance. The feed-recycle mixture 254 is separated in the rea inlet separator 256 to form the waste gases 258 from the rea inlet separator and the mixture 260 separated from the inlet. The waste gases 258 from the rea inlet separator are heated or otherwise removed from the present system 200. The inlet-separated mixture 260 is combined with the catalyst 262 in the rea 264 to form the reacted mixture 266. The reacted mixture 266 flows into the separator 268 of the rea. Reacted mixture 266 is separated in rea 268 at the outlet of the rea to form waste gases 270 from the rea outlet separator and mixture 272 separated from the outlet. The waste gases 270 from the rea outlet separator flow from the rea outlet separator 268 and are then heated or otherwise removed from the present system 200. The separated outlet mixture 272 flows out of the rea outlet separator 268 and it is divided into a large recycling flow 274 and the separate output mixing 276 in a first divided area 278. The large recycling flow 274 is pumped through the recycling pumps 280 to the second divided area 282. The large recycle stream 274 is divided into the combination area 282 in the first recycle stream 234 and the second recycle stream 246 which are used as discussed above. The separated mixture of continuation outlet 276 leaves the first area 278 divided and flows into the effluent heater 284 to become the flow 286 of heated effluent. The heated effluent stream 286 flows into the first rectifier 288 where it is divided into the first rectifier eje 290 and a first rectifier flow 292. The first eje 290 rectifier and the first rectifier flow 292 flows separately within the second exchanger 294 where its temperature difference is reduced. The exchanger transforms the first ejector 290 rectifier to a first interchangeable rectifier ejector 242 which flows into the first feed-product exchanger 240 as described above. The first feed-product exchanger 240 cools the first rectifier ejector 242 exchanged even further to form the first double cooled expeller 296. The first double cooled extruder 296 is then cooled by a condenser 298 to become the first condensed expeller 300. The first condensed expeller 300 then flows into a reflux accumulator 302 where it is divided into the expeller 304 and a first diluent 204. The expeller 304 is expelled from the system 200. The first diluent 204 flows into the first area 206 in combination to combine with the fresh feed broth 202 as previously discussed. The exchanger transforms the first rectifier flow 292 to a first exchanged rectifier flow 306 which flows into the third separator 308. The third. separator 308 divides the first exchanged rectifier flow 306 into a third separator expeller 230 and a second rectified flow 310. The third ejector 230 separator flows to exchanger 228 as previously described. The exchanger 228 cools the third separator expeller 230 to form the second cooled expeller 312. The second cooled expeller 312 is then cooled by the condenser 314 to become the condensed third expeller 316. The third condensed expeller 316 then flows into the reflux accumulator 318 where it is divided into the reflux accumulator 320 and the second diluent 210. The reflux accumulator 320 is expelled from the system 200. The second diluent 210 flows into the second area. 212 of combination to bring the system 200 together as previously discussed. The second rectified flow 310 flows into a second rectifier 322 where it is divided into a third rectifier expeller 324 and a first end flow 326. The first final stream 326 then leaves the system 200 for further use or processing. The third ejector 324 rectifier flows into the condenser 328 where it cools to become the third condenser 330. The third condensed expeller 330 flows from the condenser 328 into the fourth separator 332. The fourth separator 332 divides the third condensed expeller 330 to form the fourth separator expeller 334 and the second final flow 336. The fourth ejector 334 separator is ejected from the system 200. The second final flow 336 then leaves the system 200 for further use or processing. FIGURE 4 shows a schematic process flow diagram for a 1200 BPSD hydroprocessing unit generally designated by the number 400. The fresh feed broth 401 is verified at a first verification point 402 for its acceptable input parameters of approximately 126.66 ° C (260 ° F) at 20 psi, and 1200 BBL / D. The fresh feed broth 401 is then combined with a diluent 404 in a first area 406 combined to form the combined diluent-feed 408. The combined diluent-feed 408 is then pumped by the diluent-feed loading pump 410 through the first verification orifice 412 and the first valve 414 to the second combining area 416. Hydrogen 420 enters a 37.77 ° C (100 ° F), 500 psi, and 40,000 SCF / HR parameters within hydrogen compressor 422 to produce 424 compressed hydrogen. The hydrogen compressor 422 compresses the hydrogen 420 to 1500 psi. The compressed hydrogen 424 flows through the second checkpoint 426 where its acceptable input parameters are verified. The compressed hydrogen 424 flows through the second verification orifice 428 and the second valve 430 to the second combination area 416. The first verification port 412, the first valve 414 and the FFIC 434 are connected to the FIC 432 which controls the input flow of the combined diluent-feed 408 into the second combination area 416. Likewise, the second verification hole 428, the second valve 430, and the FIC 432 are connected to the FFIC 434 which controls the inflow of the compressed hydrogen 424 into the second combination area 416. The combined diluent-feed 408 and compressed hydrogen 424 are combined in a second combination area 416 to form the 440 hydrogen-diluent-feed mixture. The parameters of the mixture are approximately 1500 psi and 2516 BBL / D which are verified in a fourth verification point 442. The hydrogen-diluent-feed mixture 440 then flows through the feed-product exchanger 444 which heats the hydrogen-diluent-feed mixture 440, through the use of the rectified product 610, to form the stream 446 of the product. exchanger. The power-product exchanger 444 works at approximately 2,584 MMBTU / HR. The flow 446 of the exchanger is checked at the fifth verification point 448 to gather the information about the parameters of the flow 446 of the exchanger.

The flow 446 of the exchanger then travels inside the pre-heater reactor 450 which is capable of heating the exchange flow 446 to 5.0 MMBTU / HR to create the preheated flow 452. The preheated flow 452 is verified at a sixth check point 454 and by the TIC 456. The fuel gas 458 flows through the third valve 460 and is verified by the PIC 462 to supply the fuel for the reactor. heater 450. PICT 462 is connected to a third valve 460 and an TIC 456. Pre-heated flow 452 is combined with recycle flow 464 and a third combination area 466 to form pre-heated recycle flow 468. The pre-heated recycle flow 468 is monitored at the seventh verification point 470. The pre-heated recycle flow 468 is then mixed to a feed-recycle mixer 472 to form the feed-recycle mix 474. The feed-recycling mixture 474 then flows into the separator 476 of the reactor. The reactor inlet separator 476 has the parameters of 152.4 cm I. D. x 3,048 m -0 cm S / S (60"I.D. x 10 '0" S / S). The feed-recycle mixture 474 is separated in the separator 476 from the reactor inlet to form the gases 478 from the inlet of the reactor separator and the mixture 480 separated from the inlet. The waste gases 478 from the reactor inlet separator flow from the inlet separator 476 through the third verification orifice 482 which is connected to the Fl 484. The waste gases 478 from the reactor inlet separator then lie through Xa. valve 486, passing through the eighth check point 488 and then heated or otherwise removed from the present system 400. LIC 490 is connected to both the fourth valve 486 and the reactor inlet 476. Separate inlet mixture 480 flows out of reactor inlet 476 with parameters of approximately 310 ° C (590 ° F) and 1500 psi which are verified at a ninth verification point 500. Separate 480 inlet mixture is it combines with the catalyst 502 in the reactor 504 to form the reacted mixture 506. The mixture 506 is verified by the TIC 508 and at a tenth verification point 510 for the verification control The 506 mixture reacted has parameters of 318.33 ° C ( 605 ° F) and 1450 psi as it flows into the reactor outlet separator 512. The reacted mixture 506 is separated in the reactor outlet separator 512 to form waste gases 514 from the reactor outlet separator and the mixture 516 The exhaust gases 514 from the reactor outlet flow from the reactor separator 512 through the verifier 515 for the ICP 518. The waste gases 514 from the reactor exit separator then travels past or by the eleventh checkpoint 520 and through the fifth valve 522 and then heated or otherwise removed from the present system 400. The reactor outlet separator 512 is connected to the controller in the LIC 524. The separator 512 of reactor output has parameters of 152.4cm x 3.048m - Ocm S / S (60"ID x 10 '-0"S / S) The separated outlet mixture 516 flows out of the reactor outlet separator 512 and is divided into both the recycle flow 464 and the separate 526 mixture of the continuation outlet in the first division area 528. The recycling flow 464 is pumped through the recycling pumps 530 and passes through the twelfth verification point 532 into the fourth verification hole 534. The fourth verification hole 534 is connected to the FIC 536 which it is connected to _TIC 508. The FIC 536 controls the sixth valve 538. After the recycling flow 464 leaves the fourth verification orifice 534, the flow 464 flows through the sixth valve 538 and over the third combination area 466 where it is combined with preheated flow 452 as previously discussed. The output separated mixture 526 leaves the first division area 528 and flows through the seventh valve 540 which is controlled by the LIC 524. The output separated mixture 526 then flows through the thirteenth verification point 542 toward the heater 544 effluent. The separated outlet mixture 526 then travels within the heater 544 effluent which is able to heat the separated outlet mixture 526 to 3.0 MMBTU / HR to create the flow 546 of heated effluent. The flow 546 heated effluent is verified by the TIC 548 and at a fourteenth verification point 550. The fuel flow gas 552 flows through the eighth valve 554 and is verified by the PIC 556 to supply the fuel for the effluent heater 544. The PIC 556 is connected to the eighth valve 554 and the TIC 548. The heated effluent stream 546 flows through the fourteenth verification point 550 into the rectifier 552. The rectifier 552 is connected to the LIC 554. The vapor 556 flows into the rectifier 552 through the twenty-fifth point 558 verification. The flow 560 of the return diluent also flows into the rectifier 552. The rectifier 552 has parameters of 106.68cm I.D. xl6.4592m-Ocm S / S (42"I.D. x 54'-0" S / S). The diluent 562 of the rectifier flows out of rectifier 552 through the testers for TIC 564 and through the fifteenth verification point 566. The diluent 562 of the rectifier then flows through condenser 568 ovhd. rectifier. The condenser 568 ovhd. The rectifier uses flow C S / R 570 to change the diluent 562 of the rectifier to form the condensed diluent 572. The condenser 568 ovhd. Rectifier has parameters of 5.56 MMBTU / HR. The condensed diluent 572 then flows into the reflux accumulator 574 of the rectifier. The accumulator 574 rectifier reflux has parameters of 106.68cm I.D. x 3,048m - Ocm S / S (42"I.D. x lO'-O" S / S). The rectifier reflux accumulator 574 is verified by the LIC 592. The reflux accumulator 574 of the rectifier divides the condensed diluent 572 into three streams: the drain stream 576, the gas stream 580 and the diluent stream 590. The drainage stream 576 flows from the accumulator 574 of the reflux of the rectifier and passes through the verifier 578 outside the system 400. The gas stream 580 flows out of the accumulator 574 rectifier reflow, by a monitor for PIC 582 through the ninth valve 584 through the 15th checkpoint 586 and exit the 400 system. The ninth valve 584 is controlled by the PIC 582. The stream 590 of the diluent flows outside the accumulator 574 of the reflux of the rectifier, by the eighteenth check point 594 and through the pump 596 to form the stream 598 of the pumped diluent. The stream 598 of pumped diluent is then divided into diluent 404 and flow 560 of back diluent in a second area 600 divided. The diluent 404 flows from the second division area 600, through the tenth valve 602 and the third verification point 604. The diluent 404 then flows from the third verification point 604 to the first combination area 406 where it is combined with fresh feed broth 401 as previously discussed. The flow 56Q of the return diluent flows from the second division area 600, passing through the nineteenth verification point 606, through the eleventh valve 608 and into the rectifier 552. The eleventh valve 608 is connected to the TIC 564. The rectified product 610, f.light outside the rectifier 552, passing through the twenty-first verification point 612 and inside the exchanger 444 to form the exchanged rectified product 614. The exchanged rectified product 614 then flows through the twenty-second verification point 615 and through the pump 616 of the product. The exchanged rectified product 614 flows from the pump 616 through the fifth check hole 618. The sixth verification orifice 618 is connected to the Fl 620. The exchanged rectified product then flows from the sixth verification orifice 618 to the twelfth valve 622. The twelfth valve 622 is connected to the LIC 554. The rectified product 614 exchanged then flows out of the twelfth valve 622 through the twenty-third verification point 624 and inside the product cooler 626 where it cools to form the final product 632. The 626 cooled product uses CWS / R 628. The tierie product cooler measures 0.640 MMBTU / HR. The final product 632 flows out of the cooler 626, passing through the twenty-fourth verification point 630 and out of the system 400. FIGURE 5 shows a schematic process flow diagram for a multistage hydrotreater generally designated with the number 700. The feed 710 is combined with hydrogen 712 and first recycle stream 714 in area 716 to form a combined feed-hydrogen-recycling stream 720. The combined feed-hydrogen-recycling stream 720 flows into the first reactor 724 where it is reacted to form the first output stream 730 of the reactor. The first reactor outlet flow 730 is divided to form the first recycling stream 714 and the first continuation reactor flow 740 in the area 732. The first flow 740 of the continuation reactor flows into the trap 742 where the 744 Purge waste such as H2S, NH3, and H20 are removed to form the purged 750 stream. The purged stream 750 is then combined with additional hydrogen 752 and the second stream 754 of recycling area 756 to form the combined purged-hydrogenated-recycle stream 760. The combined purged-hydrogenated-recycle stream 760 flows into the saturation reactor 764 where it is reacted to form a second flow 770 out of the reactor. The second output stream 770 of the reactor is divided into area 772 to form the second recycle stream 754 and the product outlet 780. In accordance with the present invention, solvent removers include propane, butanes and / or pentanes. Other feed diluents include light hydrocarbons, light distillates, naphtha, diesel, VG0, previously hydroprocessed broths, recycled hydrofixed product, isomerized product, recycled demetalated product, or the like. Example 1 Diesel fuel is hydrotreated at 620 K to remove sulfur and nitrogen. Approximately 200 SCF of hydrogen must be reacted per barrel of diesel fuel to make the specification product. Hydrotreated diesel is chosen as a diluent. A tubular reactor operating at 620 K of outlet temperature with a recycle of 1/1 or 2/1 of feed ratio at 65 or 95 bar is sufficient to achieve the desired reaction. Example 2 The deasphalted oil is hydrotreated at 620 K to remove the sulfur and nitrogen and saturate the aromatics. Approximately 1000 SCF of hydrogen can be reacted per barrel of deasphalted oil to make the specification product. The heavy naphtha is chosen as the diluent and mixed with the feed on a base of equal volume. A tubular reactor operating at 620 K of outlet temperature and 80 bars with a recycle ratio of 2.5 / 1 is sufficient to provide all of the required hydrogen and allow a temperature rise of less than 20 K through the reactor. Example 3 Same as in Example 1 above except that the diluent is selected from the group of propane, butane, pentane, light hydrocarbons, light distillates, naphtha, diesel, VG0, previously hydroprocessed broths or combinations thereof. Example 4 Same as in Example 2 above except that the diluent is selected from the group of propane, butane, pentane, light hydrocarbons, light distillates, naphtha, diesel, VGO, previously hydroprocessed broths, or combinations thereof. Example 5 Same as in Example 3 above except that the feed is selected from the group of petroleum fractions, distillates, residues, waxes, lubricants, DAO, or fuels other than diesel fuel. Example 6 Same as in Example 4 above except that the feeder is selected from the group of petroleum fractions, distillates, residues, oils, waxes, lubricants, DAO, or similar to deasphalted oil. Example 7 A two-phase hydroprocessing apparatus and method is shown and described. Example 8 In a hydroprocessing method, the improvement comprises the step of mixing and / or reducing the hydrogen and oil to be treated in the presence of a solvent and diluent in which the solubility of hydrogen is relatively high compared to the feed of oil. Example 9 Example 8 above in which the solvent or diluent is selected from the group of heavy naphtha, propane, butane, pentane, light hydrocarbons, light distillates, naphthas, diesel, VGO, previously hydroprocessed broths, or combinations thereof. Example 10 Example 9 above wherein the feed is selected from the group of oil, petroleum fraction, distillate, waste, diesel fuel, deasphalted oil, waxes, lubricants, and the like. Example 11 A two-phase hydroprocessing method comprising the steps of mixing a feed with a diluent, saturating the diluent / feed mixture with hydrogen in front of a reactor, by reacting the feed / diluent / hydrogen mixture with a catalyst in the reactor to saturate or remove sulfur, nitrogen, oxygen, metals or other contaminants, or for molecular weight reduction or cracking. Example 12 Example 11 above wherein the reactor is maintained at a pressure of 500-5000 psi, preferably 1000-3000 psi. Example 13 Example 12 above also comprising the step of working the reactor under supercritical solution conditions so that there is no solubility limit.

Example 14 Example 13 above which further comprises the step of removing heat from the reactor effluent, separating the diluent from the reacted feed, and recycling the diluent to a point upstream of the reactor. Example 15 A hydroprocessed, hydrotreated, hydroterminated, hydrorefined, hydrofixed product, or similar petroleum products produced by any of the Examples described above. Example 16 A reactor vessel that is used in the improved hydrotreating of the present invention includes a catalyst in relatively small tubes of 5.08 cm (2 inches) in diameter, with an approximate reactor volume of 1.1326 cm3 (40 ft3) and with the reactor built to withstand pressures of up to approximately only 3000 psi. Example 17 In a solvent stripping process, eight volumes of butane n are contacted with a volume of vacuum tower waste. After removing the tar, but before recovering the solvent of the deasphalted oil (DAO) the solvent / DAO mixture is pumped to approximately 1000-1500 and mixed with hydrogen, approximately 900 SCF H2 per barrel of DAO. The solvent / DAO / H2 mixture is heated to approximately 590K-620K and contacted with the catalyst to remove the sulfur, nitrogen and saturation of aromatics. After hydrotreating the butane is recovered from the hydrotreated DAO by reducing the pressure to approximately 600 psi. Example 18 At least one of the above examples includes multi-stage reactors, wherein two or more reactors are placed in series with the reactors configured in accordance with the present invention and the reactors being the same or different with respect to temperature, pressure , catalyst, or similar. Example 19 Additionally, Example 18 above, utilizes multi-stage reactors to produce specialty products, waxes, lubricants and the like. Briefly, hydrocracking is the breaking of carbon-carbon bonds and hydroisomerization is the rearrangement of the carbon-carbon bonds. Hydrodemetalization is the removal of metals, usually from vacuum tower or deasphalted oil residues, to prevent catalyst poisoning in catalytic disintegrators and hydrocrackers. EXAMPLE 20 Hydro-cracking: A volume of vacuum gas oil is mixed with 1000 SCF H2 per barrel of gas oil feed and mixed with two volumes of recycled hydro-cracked product (diluent) and passed over a hydro-cracking catalyst of 398.88 ° C (750 ° F) and 2000 psi. The hydrofixed product contained "20 percent naphtha, 40 percent diesel, and 40 percent residue." Example 21 Hydroisomerization: A feed volume containing 80 percent paraffin wax is mixed with 200 SCF H2 per barrel. feed and mix with a volume of product isomerized as a diluent and passed over an isomerization catalyst at 287.77 ° C (550 ° F) and 2000 psi The isomerized product has a deficient point of -1.11 ° C (30 ° F) ) and a VI of 140. Example 22 Hydrodemetalization: A feed volume containing 800 ppm total metals is mixed with 150 SCF H2 per barrel and mixed with a volume of recycled demetallized product and passed over a catalyst at 232.22 ° C (450 ° F) and 1000 psi The product contained 3 ppm of total metals, Generally, Fischer-Tropsch refers to the production of paraffins from carbon monoxide and hydrogen (CO &; H2 or synthesis gas). The synthesis gas contains C02, CO and H2 and is produced from several sources, mainly carbon or natural gas. The gas in synthesis is reacted on a specific catalyst to produce specific products. The Fischer-Tropsch synthesis is the production of hydrocarbons, almost exclusively paraffins, of CO and H2 on a supported metal catalyst. The classic Fischer-Tropsch catalyst is iron, however, other metal catalysts can also be used. The synthesis gas can and is used to produce other chemicals equally, mainly alcohols, although these are not Fischer-Tropsch reactions. The technology of the present invention can be used for any catalytic process where one or more components must be transferred from the gas phase to the liquid phase to react on the surface of the catalyst. Example 23 A two-phase hydroprocessing method, wherein the first phase is operated at conditions sufficient to remove sulfur, nitrogen, oxygen and the like (620 K, 100 psi), after which the H2S, NH3 and water pollutants they are removed and a second stage reactor is then operated under conditions sufficient for aromatic saturation.

Example 24 The process as described in at least one of the previous examples, wherein in addition to hydrogen, carbon monoxide (CO) is mixed with the hydrogen and the mixture is contacted with a Fischer-Tropsch catalyst for the synthesis of hydrocarbon chemicals. According to the present invention, a process of hydroprocessing, hydrotreating, hydrofinishing, hydrorefining, and / or improved hydrofisuring provides the removal of impurities from lubricating oils and waxes at a relatively low pressure and with a minimum amount of catalyst reducing or eliminating the need of forcing the hydrogen into a solution by pressure in the reactor vessel. and increasing the solubility of the hydrogen by adding a diluent or a solvent. For example, a diluent for a heavy cut is diesel fuel and a diluent for a light cut is pentane. On the other hand, while pentane is used as a diluent, one can achieve high solubility. In addition, using the process of the present invention, one can achieve more than one stoichiometric requirement of hydrogen in solution. Also, by using the process of the present invention one can reduce the cost by the pressure vessel and can use catalyst in small tubes in the reactor and thereby reduce the cost. In addition, by using the process of the present invention, one can eliminate the need for a hydrogen recycling compressor. Although the process of the present invention can be used in conventional equipment for hydroprocessing, hydrotreating, hydrofinishing, hydrorefining and / or hydrocracking, one can achieve the same or a better result using lower cost equipment, reactors, compressors of hydrogen. similar being able to run the process at a lower pressure and / or recycle the solvent, diluent, hydrogen, or at least a portion of the previously hydroprocessed broth or feed.

Claims (25)

1. CLAIMS 1. A two-phase hydroprocessing apparatus and method as described and shown here.
2. 2. The hydroprocessing method for treating an oil feed with hydrogen in a reactor, the improvement is characterized in that it comprises the step of at least mixing and reducing the hydrogen and the oil feed to be treated in the presence of a solvent or diluent so that the percentage of hydrogen in solution is greater than the percentage of hydrogen in the oil feed to form a double phase liquid feed / diluent / liquid mixture and then separate the gas from the liquid mixture upstream of the reactor.
3. 3. The method according to claim 2, characterized in that the solvent or diluent is selected from the group of heavy naphtha, propane, butane, pentane, light hydrocarbons, light distillates, naphtha, diesel, VGO, previously hydroprocessed broths, or combinations of the same.
4. 4. The method of compliance with the claim 3, characterized in that the feed is selected from the group of oil, petroleum fraction, distillates, waste, diesel fuel, deasphalted oil, waxes, lubricants and special products.
5. 5. A two phase liquid hydroprocessing method characterized in that it comprises the steps of mixing a feed with a diluent, saturating the diluent / feed mixture with hydrogen before a reactor to form a two phase liquid / diluent / liquid mixture, separating any gas of the two-phase liquid mixture before the reactor, by reacting the feed / diluent / hydrogen mixture with a catalyst in the reactor to saturate or remove the sulfur, nitrogen, oxygen, metals, contaminants, or for the reduction of molecular weight or the fissuring.
6. 6. The method of compliance with the claim 5, characterized in that the reactor is maintained at a pressure of 500 - 5000 psi.
7. 7. The method of compliance with the claim 6, characterized in that it additionally comprises the steps of working the reactor under conditions of supercritical solution so that there is no limit of solubility.
8. The method according to claim 5, characterized in that the process is the multi-step process using a series of two or more reactors.
9. 9. The method of compliance with the claim 7, characterized in that the step of removing the heat from the reactor effluent, separating the diluent from the reacted feed, and recycling the diluent up to a point upstream of the reactor.
10. The method according to claim 5, characterized in that the multiple reactors are used to saturate or remove the sulfur, nitrogen, oxygen, metals or contaminants or for the reduction of molecular weight or cracking.
11. The method according to claim 5, characterized in that a controlled portion of the reacted feed is mixed with the mixed feed before the reactor.
12. The method according to at least one of claims 8 and 10, characterized in that the first stage operates under conditions sufficient to remove sulfur, nitrogen, oxygen and contaminants from the feed, at least 620 K, 100 psi , after which, the contaminants H2S, H3 and water are removed and then a second phase reactor operates under conditions sufficient for the aromatic saturation of the processed feed.
13. The method according to at least one of claims 2 and 5, characterized in that in addition to hydrogen, CO (carbon monoxide) is mixed with the hydrogen and the resulting mixture of feed / diluent / hydrogen / CO is put into contact with a Fischer-Tropsch catalyst in the reactor for the synthesis of hydrocarbon chemicals.
14. 14. A hydroprocessed, hydrotreated, hydroterminated, hydrorefined, hydrofixed, wax, lubricant, hydrodemetallized, hydroismeate product or a Fischer-Tropsch product produced in at least one of the methods of at least one of claims 1-13 and 15- 2. 3.
15. 15. The method according to claim 5, characterized in that the reactor is maintained at a pressure of 1000-3000 psi,.
16. 16. The method according to claim 4, characterized in that the reactor is maintained at a pressure of 500-5000 psi.
17. 17. The method of compliance with the claim 4, characterized in that the reactor is maintained at a pressure of 1000-3000 psi.
18. 18. The method according to claim 4, characterized in that it comprises the step of putting the reactor to work under supercritical solution conditions so that there is no limit of solubility.
19. 19. The method according to claim 4, characterized in that the process is a multi-step process using a series of two or more reactors.
20. 20. The method according to claim 18, characterized in that it comprises the step of removing the heat from the reactor affluent, separating the diluent from the reacted feed, and recycling the diluent to a point upstream of the reactor.
21. 21. The method according to claim 4, characterized in that the multiple reactors are used to saturate or remove sulfur, nitrogen, oxygen, metals or contaminants, or for molecular weight reduction or cracking.
22. 22. The method according to claim 4, characterized in that a controlled portion of the feed to be reacted is mixed with the mixed feed before the reactor.
23. 23. The method of compliance with at least one of claims 19 and 21, characterized in that the first. phase operates under conditions sufficient for the removal of sulfur, nitrogen, oxygen and contaminants from the feed, at least 620 K, 100 psi, after which the H2S, NH3 and water pollutants are removed and a second phase reactor then it operates under sufficient conditions for the aromatic saturation of the processed feed.
24. 24. The apparatus or system for practicing at least one of the methods of at least one of claims 1-13 and 15-23.
25. 25. The apparatus or system according to claim 24 and shown in one of Figures 1-5.