US2035467A - Treatment of hydrocarbons - Google Patents

Description

March 31, 1936. W. F|ARAGHER ET AL l 2,035,467

TREATMENT OF .KHY'DROCARBONS Filed .July 11, 1932 fz sheets-Sheet i '3mm/gms Warren Faragzcfr 22D mntl N, wk

Mrch 3l, 1936. w. F. FARAGHER ET AL 2,035,467

TREATMENT OF HYDROCARBONS Filed July 11, 1932 2 sheets-sheet 2 oLuM'N Inventors Waren E Farlghc REACTION CHAMBER Patented Mar. 31, 1936 PATENT: ori-"ics:n

2.03am TREATMENT or nrDnocAnBoNs warren F. Faraghof, Woodbury, N. J., and" Eugene J. Houdry, Paris, France, assignors to Houdry Process Corporation', Dover, Del., a corporation of Delaware Application July 11, 1932, sono! No. 621,83@

' 6 claims. v(o1. 19e- 52) This invention relates to processes and apparatus for the treatment of hydrocarbons, especially in the rening of the same through contact with an active mass capable of Vregeneration in situ. In certain aspects it may be considered as an 4improvement upon or further de- V velopment of the processes and apparatus disl scription which follows.

'Ihe treatment of both theV gaseous and low lboiling liquid products of conversion with a refining catalyst to produce a finished product results in a necessary 'limitation` of the 'period of operation of the refining catalyst due to the fact that all the gaseous products are refined whether or not it is desirable to utilize them in a refined state. It is desirable to increase the effective period of operation ofthe refining catalyst in order that a correspondingreduction in the cost of operation may be realized. We have found that a considerable portion of the load may be removed from the refining catalyst'by separating the low boiling liquid hydrocarbons from the gaseous hydrocarbons or fixed gases resulting from the conversion of higher boiling hydrocarbons and by refining these vlower boiling hydrocarbons apart from the gases. Since the sulphur compounds which rapidly poison the refining catalyst are for the most part in gaseous form as a result of the cracking or transforming operation, the diversion of the so-called fixed gases leaves for' removal bythe refining catalyst only the small quantity of sulphur remaining in theI low boiling, hydrocarbons and also relieves it of the polymerizing of certain higher unsaturated hydrocarbons normally present in the fixed gases. The latter may be directed to fuel lines or otherwise used as desired. Inasm'uch1 as the fixed gases contain lhydrogen, they may be used in small amount and for a short period as reducing gas to complete the regeneration of the catalyst, especially when it comprises or consoning of thecatalyst.

ing hydrocarbons.

tains a metallic oxide.` If the material undergoing transformation is a sweet crude or `a distillate of the same, the xed gases may be taken directly from 'the line, -.as the quantity used is too small to produce any appreciable poi- On the other hand, if the material is a. sulphur or sour crude or a distillate of the same, purification of the fixed gases is essential before use as reducing gas. In either case the separated gases may be passed w through an absorber to prevent loss of low boil- The invention frther contemplates a stabilizing step after the separation of gases butJ in advance of the refining operation, the gases from the stabilizer being directed into the main 'gas line. l

In order to illustrate the invention and the manner of its use, concrete embodiments thereof are shown in the accompanying drawings,l in

which l Fig. `1 is a somewhat diagrammatic side elevational view of one form of theinvention; and Fig. 2 is a lview similar to Fig. 1 of. another form, in which provision is made for purifying theflxed gases and for stabilizing the desired 25 product in advance of the rening operation.

Referring to the simpler form of the invention (for the treatment of sweet crudes ordistillates) disclosed in Fig. 1, the charge of material to be converted,`preferably in a partially heated state, is admitted through valved line 2 and passed with or without admixture of water or steam from valved line 4 through line 6 vinto a heating device such as pipe still 8. The vapors and unvaporized portion of the charge may pass 35 through valved vapor line Ill into a separator I2 where the unvaporized portion is separated from the vapor and passes as a liquid through valved line I4, heat exchanger I6, valved line I8 into a vented storage tank 20. 'I'he vapors .pass 0 through line 24into any suitable conversion apparatus as by one of two valved lines 26 or 28 leading to insulated catalyst- chambers 30 and 32, respectively, which contain suitable catalytic material for effecting the desired transforma- 45.

higher boiling liquid is then withdrawn through valved line 46, heat exchanger 48, and valved line 50 into vented storage tank 52. The vapors of the lower boiling hydrocarbons pass through vapor line 54 into condenser 56 with the resulting mixture of liquid and gaseous hydrocarbons passing through valved line 58 into gas separator 60,l

whence the separated liquid condensate passes through valved line-62 into receiver 64. The vapors from gas separator 60 are removed through valved line 6|. A portion of the liquid condensate may be used to control column 44 by means of valved line 66` leading to pump 68 which discharges through valved line 10 and distributor 12.

'Ihe major portion of the liquid condensate is transferred for rening through valved line 14, valved line 16, valved line 18, heat exchanger 0, valved line 80, heat exchanger 82, valved line 84 into a second heating device or pipe still 86. A valved line 19 may be used to control the flow of unreiined low boiling hydrocarbons through or around heat exchanger I0. The extent to which the feed to pipe still 86 is heated may also be controlled by a direct valved line 81. The vaporized mixturefrom pipe still 86 passes through vapor line 88 into one of two valved lines 90 or 92 leading to insulated catalyst chambers 94 and, respectively, which contain suitable catalytic material for effecting the desired rening.

The resulting products, substantially in vapor` phase, issue either through valved line 98 or |00 into vapor line |02 whence they pass through heat exchanger 82 and vapor line |04 into the bottom of a second fractionating column |06, where separationis e'ectedbetween the lower boiling vapors and higher boiling liquid. The higher boiling liquid is withdrawn by valved line |08, through heat'exchanger 0, and valved line ||2, into vented storage tank ||4. The vapors of the lower boiling hydrocarbons pass through valved vaporline ||6 into condenser 8 with the resulting mixture of liquid and gaseous hydrocarbons passing through valved line |20 into gas separator |22, whence the separated liquid condensate passes through valved line |24 into receiver |26. A portion of this liquid condensate may be used for the control of column |06 byv means of valved line |28, pump |30, valved line |32 and distributor |34. Vapors from gas separator |22 are removed through valved line |23. 'I'he major portion of the liquid condensate, which is the nished product, is passed by valved line |36 into vented storage tank |38'. If final separation of higher boiling liquid hydrocarbons is not required; the refined vapors from line |04 may pass by valved line |40 directly into line I I6.

The charging stock, such as a gas oil, may be forced from avstorage tank |46 through valved line |48 by means of pump |50 into valved line .|52 and. thence through heat exchanger 48, valved line |54, heat exchanger 40, line |56, heatfexchanger I6 and iinally into line 2 as partially heated charging stock. 'Valved line |55 may be 'used to control the ow of charging stock through generation. Thus each chamber alternates in function. The chambers are supplied with catalysts suitable for their respective operations and in such shape and form as to permit regeneration in place. Certain suitable catalytic materials for conversion and refining are disclosed in the copending application of Eugene J. Houdry, Serial No. 600,581, led March 23, 1932 comprising adsorbent or catalytically active substances such as active or activated hydrosilicate of alumina,

`without or with additional non-active or active materials including finely divided metals or metallic oxides. The preferred operating temperatures for the conversion or transforming catalyst are from 800 to l000 F., and for the rening catalyst from 400 to 650 F.

The regeneration of the catalysts in chambers and 32 is effected by passing suitable fluids through valved inlets |62 and |64 and venting the resulting products or fumes through valved outlets |66 and |68. Similarly, the regeneration of the catalysts in chambers 84 and 96 is effected by admitting regenerating iiuids through valved inlets |10 and |12, and discharging the resulting gases through valved outlets |14 and |16. If the catalysts comprise or contain metals or reducible metallic oxides, the nal stage of regeneration may be accomplished by the use of a small quantity of reducing gas which may be obtained by tapping gas line 8| as by valved lines |18 or |80 to the refining chambers and by valved line |82 or |84 to the conversion chambers. The purpose of this step is the reduction of a part of the metallic oxide in the catalyst to metal to insure the subsequent removal of elementary sulphur. regeneration of catalysts may be accomplished by the processes disclosed in the copending application of Eugene J. Houdry, Serial No. 604,997, filed April 13, 1932, and the operating temperatures during regeneration will depend to a considerable extent upon the catalysts used. For

regeneration byA oxidation, the temperature -should not fall below 800 F., and if the catalysts 'above 1050 F.

Fig. 2 is a diagrammatic lay-out of a complete treating plant for handling any type of petroleum Iproduct, either a crude or a distillate, and either sweet or "sour. While somewhat more expensive in first cost, due to the inclusion of apparatus additional to that disclosed in Fig. 1, it has such flexibility of control that it may be operated substantially like the plant shown in Fig'. 1, but has many advantages thereover. For example, it provides for the removal of low boiling vapors which may-be entrained with the fixed gases issuing from the separator which follows the i'lrst fractionating column. 'Ihese vapors are condensed and the condensate, after a second gas separation, is directed into the line of raw low boiling hydrocarbons which pass to the rening section. 'I'he `vapor pressure of this raw product may be reduced by stabilizing the same prior to refining. All of the fixed gases resulting from absorption, from the second separating step, and from the stabilizing step, may then be subjected to a purifying treatment, whichincludes the removal of all sulphur compounds. A portion of this purifled gas may be used as a reducing gas to complete the regeneration of the refining catalyst, as described in connection with the plant shown in Fig. 1, with the advantage thatcomplete removal. of sulphur vcompounds from the gas ,avoids any vpoisoning whatever of the catalyst through the The' Much of the apparatus and many of the cono nections disclosed in Fig. 2 conform to those shown in Fig. 1, and, as such, bear the same reference characters. The major difference between the two figures resides inthe apparatus for treatment of the converted products after primary condensation following the first fractionation and prior to the refining operation, and the new features appearing in Fig. 2 are made readily disf tinguishable by bearing reference characters above 200. Since, for the most part, the invention concerns itself with the refining of hydrocarbns, it is, in certain respects, immaterial what apparatus isused to begin the treatment lof the starting material. In order to emphasize the fact that `theprlmary, conversion may be by any known, or suitable, or desired apparatus, a conventional reaction, soaking, or vaporizng cham-,- beris indicated at I3 l(Fig. 2) to receive the starting material, at conversion or cracking temperature, from pipe still 3 by line II, the cracked or converted vapors leaving reaction chamber I3 through valved line 201.

through valved line 30 yto be fractionated, and

l the liquid residue leaving through valved line I5 for storage tank 20. i

Beginning now at gas separator 00, the gases leaving by valved line. 3| enter an absorber 202 of any desired type, and leave by valved line 203. The absorber shown uses a low boiling liquid condensate which enters through valved lin'e 204 to scrub the gases, the enriched-'condensate or absorbent leaving by valved line 205 which discharges into a heater or still 200, where the absorbed vapors are stripped from the low boiling condensate which leaves as lean absorbent l 'Ihe stripped vapors pass by valved line 200 into condenser 209, thence by valved line 2I0 into a second gas separator 2| I; from which'the liquid condensate passes by valved line 2|2 into receiver 2|3, while the gases from separator 2|| pass by valved line 2|! into main gas line 203.

The raw liquid product 'of the desired boiling range in. receiver 2|3 is drained by valved line 2 Il into the valved line 2I0 from receiver 34. Before passing the raw liquid product from these two sources to vliquid line 14 which leads to the reilning section of the apparatus, it is preferable, in most instances, to eife'ct stabilization of the same by .removing the gases and very light vapors which are dissolved in the liquid and which increase its vapor pressure to lan undesirable ex. tent. 'Ihis is effected by conducting the, raw liquid by valvedllne 2| 1 into a stabilizer 2i0- of any known or desired type from which the vapors escape through valved line 2|! into main gas line '233, while the stabilized. raw liquid is discharged drawn for fuel and other l.purposes Kthrough vvalved connection 222. Ii'or purification, it is withdrawn through valved line 223, passed through heat exchangernl and into an addi- 'tional heaterr22loi' any suitable or desired type,-

where its temperature is raised suiliclently to progases give up a portion of their heat to the unpurified gases in line 223) -and line 232, into purified gasline 233, from which valved connections and |00 lead to refining cases 04 and 90. The valved connection 234 beyond line |30 permits the withdrawal of purified gas for use as fuel or for other special purpms requiring a sulphur-free gas.

Gas purifying chambers 220l and 221 contain any suitable or desired material for removing sul-v phur and/or other objectionable compounds or ternate operation and regeneration, andto altery nate in function, os that there vmay be contin-l uous operation of the entire plant. To restore the Ipurifying material to active condition, a regenerating medium of the same or different type as that used for catalyst refining chambers 34r and. 96 may be admitted by valved lines 230 and 231 to chambers 226 and 221, respectively, while the heat and fumes may be discharged through The operating temperatures for gaspurifyin'g chambers 220 and 700 F.

'Ihe regenerating connections to the gas fying chambers and to the refining chambers are such that each chamber Amay be regenerated independently of the others. 'Ihe length of time that any of the chambers maybe continued onstream will depend upon a number of factors, the principal ones being the amount of poison in the material acted upon, the quantity of material fed, and the quantity of .purifyingor catalytic material within the chamber.

We claim as our invention: 1. In the production of low boiling` hydrocarbons in the gasoline boiling rangestable against f oxidation from complex hydrocarbon vapors which include fixed gases, the process steps which comprise separating the iixed gases andthe desired low boiling material from the complex va' pors, stabilizingv the' .desired low boiling material by-removing entrained gases therefrom, subjecting the .thus stabilized material alone withouti any xed gas tothe action of a catalyst capable of inducing a reilningreaction to stabilize the gasoline against oxidation and of regenerationv in situ, and utilizing the gases including those resulting from the stabilizing step in the regener ation of the catalyst after-.a refining run.

2. In the production of low boiling vhydrocarbons, that process comprising the steps recited in Y claim 1 and in which the action of the catalyst on the stabilized material is effected in a single Y treatment inthe .650.l F.

221 may range from 350? to 3. In the production of low boiling hydrocarbons in the gasoline boiling range stable against oxidation from complex hydrocarbon vapors, the process steps which comprise separating the xed gases and the desired low boiling material from the complex vapors, stabilizing the desired low boiling material by removal of entrained gases, subjecting the thus stabilized material alone without any fixed gas to the action of a catalyst capable ot inducing Va refining reaction to stabilize the gasoline against oxidation and of regeneration in situ, purifying the separated fixed and uncondensed gases including those resulting from the stabilizing step of impurities including sulphur compounds, and utilizing the purified gases in the regeneration of the catalyst'.

4. The process of producing low boiling hydrocarbons according to the steps recited in claim 3 and in which the refining and stabilizing reaction against oxidation is effected in vapor phasein 'the temperature range of 400 to 650 F.

5. In the catalytic conversion of high boiling hydrocarbons into low boiling hydrocarbons stable against oxidation by subjecting the high boiling hydrocarbons to successive-treatment by two catalysts capable of regeneration in situ, thel process steps which comprise subjecting the high boiling hydrocarbons to conversion into low boiling hy-4 drocarbons with the aid of the rst catalyst, separating the high boiling products and the fixed gaseous products from the low boiling condensible products, subjecting the low boiling condensible products alone and Without xed gases ,to treatment by the second catalyst for rening and stabilization against oxidation, and utilizing said fixed gaseous products in the regeneration of the catalysts following the conversion and refining runs.

i 6. In the treatment oi' high boiling hydrocarbons to produce low boiling hydrocarbons in the gasoline boiling range stable against oxidation by subjecting the former to conversion, to fractionation, and the resulting condensible vapor products to the action of a reiining catalyst, the latter being capable of regeneration in situ and disposed in at least two chambers for alternate operation on stream and in regeneration, the process steps which comprise subjecting the low boiling products after conversion and fractionation to condensation, -removing the uncondensed gases from the low boiling condensate, revaporizing the said condensate and subjecting it alone without fixed gases to treatment by the renning catalyst in one chamber, and utilizing the uncondensed gases in `the regeneration of the rening catalyst in another chamber then oi! stream as to said condensate.

WARREN F. FARAGHER. EUGENE J. HOUDRY.

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