DE1770412C3 - Modification of the process for reforming heavy fuel - Google Patents

Description

The invention relates to a modification ι method for reforming heavy fuel Pressures between atmospheric and atmospheric using a reforming analyzer the platinum group.

Reforming with platinum-aluminum oxide analyzers is one of the most important mineral oil converting mechanisms for improving the quality of petrol to produce gasoline products with a higher octane rating much and make significant cost savings. for example, an increase of Reformaiausbeute by only about 0.5 vol ¹ Vi) an annual Ertragsverbcsscrung the refineries ίο many million marks. Furthermore, any reduction in the amount of platinum required in a reforming catalyst results in considerable savings, which can also run into millions of marks, while at the same time substantially conserving the usually limited platinum reserves.

There are several publications dealing with the influence of moisture on reforming deal using platinum metal catalysts are known. For example, in the ao US-PS 27 72 217 stated that reforming catalysts, the oxides or sulfides of metals Groups IV, V, VI, VII and VIII comprise, after regeneration, contain about 0.2 to 1.0% by weight of water. The US patent recommends that the regenerated catalyst be adjusted to a moisture content in the range of about 0.1 to 0.8 Gcw.- °, o to dry in a stripping zone. But it is also known that the moisture content of the introduced into a Refoiniicrreaktor Catalyst is not the only source of moisture in the reactor.

The US-PS 28 42 482 describes a reforming process in which the Rückfiilirgas about 0.5 vol contains ⁰ / · water. This water concentration contributes, however, to a water vapor parallel pressure of approximately 10 mm of mercury at a total reactor pressure of approximately 3.8 atmospheres and approximately 44 mm Hg at a total reactor pressure of approximately 14 atmospheres. On the other hand, a reforming treatment is considered to be relatively dry if the moisture content of the effluent from the last reaction zone, expressed as the partial pressure of water at about 14 atmospheres total pressure, is less than 0.4 mm Hg and preferably about 0.05 to about 0.2 mm Hg amounts to.

In US Pat. No. 3,110,703, which relates to reforming in the presence of a platinum-alumina catalyst, it is stated that the chlorine content of the catalyst in at least the initial catalytic Rcaktionszone tends to rise to an undesirable concentration, resulting in hydrocracking favored. However, this unsatisfactory result can be counteracted by limiting the surface area of the catalyst to values from about 1 to about 300 m ² / g and preferably from about 9 to about 130 m 2 / g. It is claimed that with these surface sizes the halogen uptake or the increased hydrocracking activity of the platinum-alumina catalyst is substantially reduced by avoiding excessively high chlorine contents and thus excess hydrocracking of naphthenes in the first reforming zone.

In tier US-PS 29 52 611 is a regenerative reforming process described with plain catalyst, in which the expediency of a maintenance of moisture contents below about 100 parts per million is explained using a combination of emergency dryers, return gas dryers, Regeneration gas dryers and other

took to achieve and maintain the desired moisture content. However, it should be noted in particular that the US-PS expressly states that at moisture contents below 100 Tcile-per-million a very rapid and surprising increase in the reformate yield is achieved when naphthenic Gulf Coast heavy gasoline in the presence of a plaline catalyst with a platinum content in the range from about 0.3 to about 0.6 Gewichts.- ^0, u when combined with a halogen in a concentration in the range of about 0.5 to about l, 5Gew.- ° / o be processed. The US patent further indicates that the super-dry mode of operation essentially eliminates halogen stripping during the oil supply operating period and thereby ensures an essentially constant halogen content.

In the main patent 12 07 534 is a method for reforming heavy gasoline under pressure between atmospheric pressure and 7G, 3 atm using a platinum group reforming catalyst and setting of the water vapor partial pressure described at which one in the reaction zone Adjusts water vapor partial pressure so that the withdrawing reaction mixture has a water vapor partial pressure of 0.2 mm Hg or less, measured at 14.05 atmospheres. It can be heavy fuel with a water content of at most 0.0015 percent by weight can be used. According to In a particular embodiment of the known process, a catalyst can be used which has a surface area of at least 200 nv- / g and a moisture content that is no more than 1.1 weight percent greater than the moisture content of the catalyst after firing at 1250 ° C is during 48 hours.

According to Hauptpaient 12 07 534, an undried recirculation gas builds up the water pressure slightly to 0.5 to 2.0 mm Hg partial pressure, which, however, results in a lower volume _{bulge of C 5} + reformate from a charge with a boiling range from C ₅ to one End point of 121 ° C than when maintaining a partial pressure of the final outflow of the reforming zone in the range of about 0.05 to about 0.2 mm Hg. It should be noted that the information in these DT-AS relates to the use of a catalyst which comprises 0.6% by weight of platinum on an aluminum oxide carrier with a content of up to about 0.7% by weight of chlorine.

The object of the invention is to create a method for reforming heavy gasoline in which a particularly high utilization of the platinum metal takes place and the use of a catalyst is made possible which has a lower platinum metal content than the platinum catalysts previously used as well as the catalyst which is used according to the main patent 12 07 534 has.

The modification of the process for reforming heavy gasoline at pressures between atmospheric pressure and 70.3 atü using a reforming catalyst of the platinum group and setting the water vapor partial pressure, whereby the water vapor partial pressure is set in the reaction zone so that the withdrawing reaction mixture has a water vapor partial pressure of at most 0.2 mm Hn, measured at 14.05 atmospheres, is characterized in that a platinum catalyst is used which contains less than 0.45% by weight of ¹ Vu of platinum, and that the amount of moisture in the incoming material is regulated that the process moisture level is balanced and a high hydrogen purity of the recycle stream is maintained, at least comparable to that obtained with a reforming catalyst containing at least 0.6% by weight platinum. If necessary, the moisture balance in the circuit can be maintained by adding water to the recycle stream. The feedstock is normally dried prior to introduction into the first reactor.

The method according to the invention thus provides

represents an improvement of the process according to the main patent by adding to the process of the invention the moisture content is regulated in a special way; this enables the use of a Catalyst with a lower platinum content. The Ver-

driving according to the invention can be carried out with advantage as a low-pressure reforming process.

The method according to the invention enables an optimal design of a low-pressure re-

Formierverfahrcns, such that the method, for example still belongs to the group of non-regenerative reforming processes, namely without undesirable reduction in platinum utilization, the hydrogen purity of the return gases and

the "Reformation product selectivity with regard to the desired Oclan quality.

A relationship was established between the water content of the feed in ml / m ³ and the water partial pressure of the final reactor effluent in

mm Hg for reforming using practically perfect gas dryers developed. This relationship is:

π -6.29Ch ₁ Q- 3.5 * IQ " ⁵ -MG _n (R +

Ph, c =

On the other hand, if the recycle gas separator located downstream of the last reforming reactor is operated under sufficiently elevated temperature conditions, so that entrained Water is carried overhead in the recycle gas stream withdrawn therefrom, the relationship takes the following between the water content of the feed and the overhead product of the separator Shape to:

π ■ 6.29 C _Hi0 · 3.5 -IQ -'- MG _n

fL ^ L) + R ₊ G

For the above equations, the following applies: Pu ₁ O ~ Wasscrpartialdruck, in mm Hg;

π - overall thickness, in mm Hg; C _H Q - water content of heavy gasoline, in

inl / nV (= Tcilc-per-million); MG _n - molecular weight of heavy gasoline;

Q _n - Specific weight of the heavy gasoline Heavy gasoline through the regulated addition of water in g / cm ³ ; precisely adjusted and a relatively equal = molar increase in heavy gasoline, which is necessary distribution in the feed to the Rc when passing through the reactors, formation can be guaranteed. Hs (eighth GC ^5, that water in the Schwcrbcnzinbcschickung residential 2 to 2 5) to bc MoI product / mole of heavy gasoline ^{"D 's' lcr;} zn ^LLJ f about 100 Tcilc-per-Millioii is soluble G = Mol. Excess recycle gas per mole of P '" ⁰ , so the amount of soluble water is considerable - heavy mineral (usually 1 to 1.5); ^llch _n ^{] ml} } " ^ak . ^ύκ ™ ^» «» Ρ ^dcr crfindungsgc- "..,, .., ..... ,,," .., measured benefits required amount, which the krili R = total ruckiuhrvcrhaltms Mol Ruck- _{lo sd) cn Grcn / cn jjß [jcr r} . _{Rfin (iu | 1} underlines.

Fahrmatcnal / MoI Schwcrbcnzin; During an implementation of the Rcfor-

K = vapor-liquid-equilibrium-equilibrium concentration, in which a heavy-duty imposition in

stanlc for water in the separator. Association with one formed in the company

wasscrstoflrcidien recirculation gas is supplied, is

Surprisingly, the water separated from the reformate outflow was determined according to the invention that a reforming catalyst with a material recycle gas preferably initially had a relatively low platinum content, generally a water content below about 5 percent a million not more than about half the platinum chalk and preferably dried to a water content of not commonly used reforming catalysts, more than about 2 percent million, before the process according to the invention results in a feed of the hydrogen recycle gas stream with the mode of operation which is at least equivalent to the heavy fuel concentration combined will. Although it is not important for those who normally use the fuel, both the recycle gas and the formicrcatalysts with a higher platinum rating can achieve the heavy gasoline with a water content as low as bar. In particular, it has been found that, in order to dry the above, it may be convenient to use a hydrogen purity of the recycle gas separated from the reformate product 25 in this way and so the catalyst required according to the invention is 0.35% by weight. %> Platinum in the wcscnt- precise regulation of the moisture content upright which can be kept the same as it otherwise can be kept. On the other hand, the drying of the recirculation gas with only a platinum catalyst of 0.6% by weight fulfills the double function of achieving platinum at the same time. This essential technical improvement is possible by removing other undesirable constituents such as chlorine and by removing the hydrogen sulfide or hydrogen sulfide from the gas. The partial pressure of water included in the reforming can also be carried out in the manner explained above, in the above-described manner, in the more conveniently maintained, precise control of the desired, relatively narrow limits of moisture content, simply by bringing about. In order to achieve the surprising and continuous controlled addition of water to the unforeseeable advantages described here, the samlbchangung is to be fed to the first of a plurality of specific reforming zones which are decisive in the reforming process. Sources of Water Pay Attention When Reforming Hydrocarbons

to dedicate. The water content can be increased by using platinum group metal reforming catalysts, material dryers, recycle gas dryers, and - in some cases it is not uncommon to use three or more reactors - regeneration gas dryers in the sequential arrangement; Relatively seldom regeneration of the catalyst, the heavy gasoline in combination with the hydrogen-rich gas will be regulated under such control devices. In order to achieve the results that the heavy gasoline has advantages that can be achieved, however, a formator product with the desired octane number, in particular, a drying of the hydrogen-rich one is formed. In this series of reactors, recycle gases are maintained down to a very low temperature and pressure conditions chosen below about 5 parts-per-million and preferably that dehydrogenation of naphtha is below about 2 parts-per-million, prior to Methanes to aromatics and a dehydrocyclization of the dried recycle gas with which the paraffins enters the heavy gasoline feedstock to be reformed in the most favorable manner in the successive reaction zones. Consideration. Thereafter, water is then preferably used in, for example, sufficient quantities for the controlled adjustment of the other, the dehydration of the moisture content of the reforming within the naphthenic is mainly carried out in the first reactor , relatively narrow limits and to a lesser extent in the second and third reactors added to the zen. third reactor, while the dehydrocyclization

In general, heavy gasoline feeds reactions accompanied by some hydrocracking for reforming in the boiling range of about C ₅ and isomerization are predominantly in the hydrocarbons proceeding up to a sicde-end second and third reaction zone, point of about 138 ° or 143 If, on the other hand, a reforming plant, for example, can also have such a high end, four reaction zones, the temperature will be about 204 ° C. After a special conversion of naphthenes predominantly in the first characteristic of the invention, the setting of the and the second reaction zone will take place, while the moisture content is facilitated to a value suitable for the process for the other reactions of dehydrocyclization by also facilitating the 65 Hydrocracking and isomerization are carried out primarily in heavy gasoline to a very low moisture content in the third and fourth reaction zones, and then the moisture content.

burrows that the operating pressure is usually below about 2K, 1 iitii and generally in the range of about 14.05 to about 24.0 am.

When reforming the type described here, a pressure reduction in the direction of the flow of the reaction participants is often displeased by the sequence of reformulations, which does not amount to more than the normal pressure drop when the reaction participants pass through the Kalaljsalorbelleu and the associated facilities At the inlet of each reactor, Rcfimpeibreathe in the range of about 427 to about 5 38 C and mostly not above about 527 ° C can be maintained. The temperature of the reaction material is usually adjusted between the individual reactors, and suitable ovens are usually provided for this purpose. In general, the pressure drop discussed above is such that the foremost or first reactor of the plant operates at a pressure which is about 1.4 to about 7.02 ath higher than the pressure of the last reactor in the process. Typically, an hourly space air velocity, based on weight and for each reaction stage, in the range of about 0.5 to about 20 is maintained, and sufficient hydrogen is supplied with the water-jet recycle gas that a hydrogen partial pressure in the reforming process is in the range of about 7.02 to about 21.1 ata is present. When reforming black carbon dioxide at a boiling point up to about 160 ° C for the production of reformate products with a relatively high octane number, naphthenic carbon dioxide is often preferred because it can easily be converted into aromatic components with a high cetane number. Hines of the other surprising features of the method according to the invention, however, lies in the fact that even Schwerben / incinsatz.matcrialicn, which are rich in paraffins, / u high octane reformate products can be converted into high bulges, namely with hydrogen: units, which with those are comparable, as they can otherwise only be achieved with catalysts from higher noble metals. The values given below show that when a heavy feedstock is catalytically reformed in the presence of a platinum group-tinctallic reforming catalyst under a combined reactor pressure of less than about 28.1 atmospheres and preferably less than about 21.1 atmospheres, there is a considerable increase in the hydrogen content of the stirring gas the yield of C + mil -Rcformatprodukl a catalyst can be achieved that is no longer than about 0.4 Gcw.- ⁿ .O comprises platinum the Η, -.. Rcinhcit of the recycle stream is preferably at a value of about ⁰ 6OMoI- O held.

In the reforming process according to the invention, the hot zinc feed can be dried by any of a number of different methods, e.g. By passing it through a solid desiccant such as alumina, molecular sieves, or contact with some other solid absorbent, or the heavy gasoline can be effectively dried by distillation to bring about a water content which is usually less than about 10 to 15 parts by weight. Million. The Rückführgos recovered from the effluent of the last reactor can be cooled and then, are dried by contact with a solid absorbent,? .. as a molecular sieve or other suitable solid absorbent material. Preferably, the recycle gas is contacted with the solid absorbent under conditions such that its water content is reduced to no more than about 2 volume percentages-per-million at 14.05 atmospheres; this corresponds to a partial pressure of water no more than about 0.02 mm Hg for a total pressure of 14.05 aiii.

The invention is illustrated in more detail below with the aid of examples in conjunction with the drawing.

Fig. 1 is a graph showing the influence of the hydraulic pressure, expressed as mm Hg in the effluent of the third reactor of a reforming, on the water flow of the recycle gas in a substantially steady state for operation using a catalyst with a pialin content of 0.35 Gcw .- '/ o shows. The operating conditions for each operating run shown in the diagram are detailed in Table 1 below. All in the fig. I plotted values are from Reformicrbchandlungcn 17.6 atm under processing a ₀ in the range of C - 143 ⁰ C boiling paraffinic heavy gasoline to a _C5 + product having a cetane number (R · 3!) Of 102.0.

The F i g. II shows values obtained with a catalyst containing 0.6% by weight of platinum; it shows according to FIG. 1 the influence of the water partial pressure on the hydrogen content of the return gas. It should be noted in particular that the slope of the lines delimiting the measured values in FIG. II is much smaller than in FIG. 1; This shows that the catalyst with 0.6 Gcw.- °, O platinum with respect to the partial pressure of water is much less sensitive than the catalyst with 0.35 wt ⁰ Zo platinum.

FIG. 111 reproduces the course of measured values as a function of time and shows how the points appearing in FIGS. I and II were obtained. In detail, Fig. 111 shows the hydrogen rate and the activity, measured by the required inlet temperature for a product with an octane number of 102, as a function of the operating time in an investigation of the aging in the platinum reforming. In Fig. III the water contents in the outflow of the third reactor during Bctricbsz.citcn. in which the hydrogen purity was essentially in a steady state. For example, it can be seen that from the 4th to the 11th day the H., - purity of the recycle ^{gas remained essentially constant at a value of about 72 0} Zo when the water partial pressure averaged about 0.7 mm Hg. On the other hand, from the 12th to about the 20th day, when the partial pressure of water in the middle was about 0.29 mmHg, the hydrogen content was about 70.5 °. However, from the 20th to the 30th day of the operating period, the hydrogen content and water content changed rapidly, indicating that the Rformicraniagc was not operating in a steady state. The values of FIG. III provided the points shown in FIG. II are marked by a circle. The remaining points of FIG. II and FIG. 1 were received from toilet orders in accordance with FIG. 111 for different operating positions in a test technical system.

The F i g. IV shows the drastic effect of a

709 612/69

^y ίο

Regulated addition of water within the required amount of water. of 75 '.'. at a

measure provided i, rci "cn auhe activity, shown What ^ rpai üaklmck of 0.1 now results in Hc, is the

- η i ^UIX | \ ^{tlC l} "^ ^ril )" ^rimk ^ · "τ ΙΐΓ ^ -ι, μι, πμ WMsscrMolfudK,!. nid.l, Is im Cileich ^ ewich. angc-

\ ss r Iοΐ ι " ¹ ' ^CI " ^CI , ^{() Cl} i ^{in7ahI VOn 1 (12} · ^{uml dic s} <- · » ¹ '». '' «^ - '» ü »Ii, ·. I das 1l, - (ilefch, ewicht im

π 'ir η,''Γτ' T ₁ ⁰¹¹¹¹ T " ^{Sl! 1} , ^{mmen: IUS llcm 5 llm} ' ^{idl v} ""^ ^{! 1 s} " ^ <> * "'» <>■><< ■ I '· "Clwa 600 /.

e, ' ^C " ^Iabdlc ' ^^ nn.c.dme.en Wasse.Mofi, |, eeen solhe. From dJr Fig. VI each-

i ί "1 Τ '7 ^" ^ ¹ "^ ¹ ' ™ And doeh / u assume that the waterTolTabnal.me

c Ps _r i ί 1 Τ 7 ^ ^ ¹ "^ ¹ '™ An doeh / u assume that d, e WassersTolTabnal.me iCtlv T" Ι ν """" ¹ ' ^{dcr CIS} "-" ^{n of clw: i 7V} '' ■ ^{: illi} ^ ^; > fO »'o at a rate of about

iCtlv TΙ ν ^{n cl: i 7V} '■ ^{: illi} ^ ^; > f.Oo at a rate of about

• us il. ? η ^ ^lulc , ^A " ^l: ^ '" »chmend 0.14 to about O. ^« ,,, per rope. ie with a means

ⁱ ObISt-, "ofw" ^BcI ₁ ^nCbs i ^L ; ^lln : " ¹ ™" «■ ''« '»> ^u -ne„ a 0.4% per day. success, t. At this rate of

i c be vent _a cÄfi ¹ 'M'" ^{dCr ΑΠ} " ^W: '^ ™ «™haben l'me would be about 37.5 days

iη de S, n- - Τ "? ' Γ ^dc '" ^2? ' ^Ta S' ^{5 vc} » ^{b: i1} '"'<«I" i a. VI is equivalent to those with * T7 " L ι ³ " ⁵ " ^{in cincm} '^ fik.l 035 G»' Pltin

of 6 Γ Tu7- L , ι ^{in cincm} '^ furmiorka.alvsMtor of 0.35 Gcw .- »' o platinum

S ⁶ SS Ä ^lk XÄ S ""

gewiclitsi-content. Catalysts with ^I '"" ⁱ " ^sc " ^! " ^{1 crscllc} " ^c " ^Ki "'" ^crc

inh.-e from 0 1 <P mm H "Hi ^ -w ι"' ^{d: iL <} ' ^{wcnn dci} Wasserstol ^ chalt is smaller than

jiiijl, l of u, i 'i mm Hq. This water partial pressure ιΐ, -. N π ι ι. · ■,. . · _

cntsnnch eiwi 14S Trii, - i, -. \ iiii; _f / »/ ',,., ^lkm ^' lcichgcw icht / ustaiul corresponds (ie the

LiusprdLii ciwj i'i,; i 1 eue-je-Milhoii (volume base) |: _P , ". I"; ,,, -, ■,. . , · \. «Ι;

H "() in the return *, when the temperature Eh" cuchiiükc sgehall has been increased, the water

Separately, about 27C, the values' rW ^sc ^! "" ^ "" lt ^ s Gases "read Cllcicligcwidit very quickly

F i g. IV it can be seen that Sn c nsScwS ä "S? _Ui , '?' ^ ^Hlic ^ 7" ° ^hc » ^b - ^h ' ^Ct ' ^ ·. ^

dcn, ng the water flow rate of the return,, _s u R ^ fΞί "™. ^Bed "! f ^un 8 ^c . "J ^{n {IC} ^ '" ΐ /

after the above anccbcncn water cream spirit "οίν, 1,, ^ r- ⁰ ," ^ ^{1ΓΙ WirtI} ' ^d " ^{W: K} ? u

Zung occurred and that the WasscrsfolIreinhcU '' here, I io w, ^{RutkillI 'r P; is} "very rapidly and before

the period of continuous water, the outlet of the third reactor

after the 30-tagC period in WeSCn ₁ IS _n I ₀ HsS> γ ^ Ϊ '"" ^ T ^{Wahrschci "Lich is dcr GrU" d}

stayed. "xonstdin lucrlur damwu see that the higher water partial

^{clk i} 'i

ieb. see that the higher water part

The F ic V zciot a Hhniidmn - · π η t , · ^{clriIck in c} 'cm first reactor the reforming reactions

Ka7aTv _S a, O ⁸ rak, S «" Tdif W si S Ικί _d t ₃₅ ^ f "" ⁸ '. ^ or all the catalyst in the second

Back to S ί Γ "™ ^Rcakt ° ^{r on Sei} "" ^{CUCS FcUCht} ' ^g "

Ka7aTv _S a, Orak, S «" Tdif W si S Ικί _d t ₃₅ ^ f "" ⁸ '. ^ or all catalyst in the second recycle gas at a technical BcS by ί Γ ", ™ ^Rcakt ° ^{r on Sei} "" ^{CUCS FcUCht} ' ^g "

guide ii Rffii di hi ™ ^kci ,? ⁿⁱ ™ ^U ^ " ¹ If ^{11 wordcn ist} "

g hnischen BcS by ί Γ,

tour of a refinery, here called Bc, ™ eWau N ^kci ,?. ⁿⁱ ™ ^U ^ " ¹ If ^{11 wordcn is} ". The operational continuations are η 5er, ^ If ", ^g ' ^{bt WCltCrC measure} S ^{cbIiche BcobaCh} ' table. Furthermore wunlc the w" 4 / "" ^ - l ^{cm; i} . ^{ß DCR} ™ "* ™ & and shows a content in the feed to the Rcformierbclnml" ^v ^ ^'eic \, ^aer effects of a relatively development during the first 48 Belricbsto ™ _a S "w,""£w"^"ΤΓ Ε ϋ " ^Wa ^ ^rkon2C » ^tration f 4.4 ml / m- (6 parts by weight-jc-Millior ~ 33 3 MoI ί "WasscrstoiTgclialt of the return gas on the one hand parts-jc-million) set. During this operation -,;! ^R ^, ^ormieru "S of a naphthenic blackbenzite space it was found that the effluent from Tm r", d, ^C1 " ^{Cm Reform} i" catalyst with 0.35 third reactor has a water content of 2 to 3 Mo ™ 45 ^ "! ^ ^ _C ^a ', ^{idcrerscits bci} processing tcilcn-per-million (0.02 to 0.03 mm Hg) showed at S ^p , ^araffi "! ^{sc 'LCN} heavy gasoline in the wescntetwa the 49th day of operation, water was in the Be t,,, ^S ^ ^Fcudlti 5keitsbedingungcn, hergeschickung at a rate of 25.8 ml / m "(36 overall η u ^ ^{dC" Flg] and VI} ^ the given parts-by-weight-per-million (200 mole-parts-per-million) a n, \ μ. investigation was the water spray, which soon afterwards led to a discharge a? s the 50 ?? Be ΤΪ ^CtWa °, ^{'24 Π} ™ ^{"8 Wühre"} led ^{d dCr} ^ i! third reactor containing a WasscrkonzenmT ^Bet nebstage, and then the water content

tion of 12 to 15 Molieilen-per-Million or J Π to ί T * ° 'f? !? ^{m Hg verrin} 8 ^ert · ^{Those with} Κ ^ Γ

0.16 mm Hg, at a pressure at the outlet of the dntt _en llt ^ ZI ^ T ⁸ ^ "^ ^water , ^st f ^ ?!

Reactor of 13.4 atmospheres. From the figure he is S? \ κ ^R _u ^eformie ™ ng a naphthen.sd.en

clearly that several days, here up to Sw ₃ 4Ta- ₅₅ It ^ ™ "^ ¹ ^ ^{with a content} X °" ^ '

gen, were required until the full effect of the S ' ^ZU , ^e ' ^nc _n ^m reformate product with an oc-

Water had been added, recognizable by the S "-Γ. '"^^ ^The - ^TO "? - ^

drastic increase in hydrogen purity dS S. ΐ. Drawn dashed line shows the off

Return gas flow of about 54 · /. on e wTein Mh Pf ^ * ^U " ^{d VI preserve} hydrogen guarantee

tel of 75 · /. _fi R ^efoi ™ 'erung cmes paraffinic heavy fuel with

On the other hand, FIG. VI shows the rate of the ^{ab "" f ™ S C} , ^halt ^ ° " ^{7 ° / o paraffins to a refor} " took the water purity, shown in percentage ν? ^? Λ '" ¹ J! ° ^{iner octane number of 100} ' ° - ^Οΐ 5ϊ ^Γ per day, in operations where 5S I? 'F ™ Ä-i ^mHch ' ^{that cine schr} ™ * ™ ^{ι1ι <} ¥ hydrogen content of the return gas is high ™! ^D. "" »^« Is the same effect on the hydrogen equilibrium (e.g. immediately after review 6, Z ϊ ^ ^{dCS return} flow when processing the moisture content), as FunkUoT £ i Jo _n H ^lde " ^VCrSch ' ^cdcncn Schwrbcnzinbeschickungea water partial pressurel For this purpose, refer to the following Lzu 2r ,? ^{Point at} " ^{the d} " = r water content "indicate:" If a reformer treatment is reduced in a given manner,

table

Pt-RcfoiniicruiiR, experimental-itechnischc plant

Pt reforming catalyst I't relationship Heavy fuel Type Mole percent conditions Octane number Commercial Weight limit 50/10/100 Sicdebcrcich, Paraffins Pressure, Cs +, R) 3 run per / cnt 28/72/100 ⁰ C Kuwait 72 atü 102.0 C. 0.35 28/72/100 Q-143 Kuwait Kirkuk 72/68 17.6 102.0 A. 0.35 50/100/100 cj-14 3 Kuwait 72 17.6 102.0 J 0.35 28/72/100 C ₆ -14 3 Kirkuk 68 17.6 102.0 E. 0.35 28/72/100 C ₆ -143 Kuwait 72 17.6 102.0 B. 0.35 28/72/100 C ₀ -143 Kuwait 72 17.6 102.0 K 0.60 28/72/100 C ₀ -143 Kuwait Kirkuk 72/68 17.6 102.0 L. 0.60 20/30/100 C.-143 Kirkuk 68 17.6 102.0 F. 0.35 28/72/100 CFi-143 Mixture (Bm !.) 49 17.6 100.0 M. 0.35 28/72/100 C _n -135 Kirkuk 68 14.04 102.0 η 0.35 28/72/100 C _n -143 Kuwait'Ki'kuk 68/72 17.6 102.0 Ci 0.375 C _n -143 Kuwait / Kirkuk 68/72 17.6 102.0 H 0.40 Outlet. C,! - 143 mixed 60-75 17.6 101.0 N 0.35 C ₆ -I 35 13.4 ') ') Third Reactor,

In addition 5 Hlatt drawings

Claims (5)

• u-- patent claims: 1. Modification of the process for reforming heavy gasoline at pressures between atmospheric pressure and 70.3 atü using a reforming catalyst of the platinum group and setting the water vapor partial pressure, whereby the water vapor partial pressure is set in the reaction zone so that the withdrawing reaction mixture has a water vapor partial pressure of at most 0.2 mm Hg, measured at 14.05 atmospheres, according to patent 1207 534, characterized in that a platinum catalyst is used which contains less than 45 wt. ^o / o platinum, and that the amount of moisture in regulates the incoming material so that the moisture level of the process is kept in equilibrium and a high hydrogen purity of the recycle stream is maintained, which is at least comparable to that obtained with a reforming catalyst containing at least 0.6% by weight of platinum can. 2. The method according to claim 1, characterized in that the amount of combined Moisture in the incoming material regulates so that the water vapor partial pressure of the Outflow from the procedure ranged from 0.1 to 0.2 mm Hg, measured at 14.05 atmospheres, located. 3. The method according to claim 1 or 2, characterized in that the amount of water, which is dispersed in the recycle stream fed to the process, at a value accordingly a water vapor partial pressure of 0.08 to 0.166 mm Hg, measured at 14.05 atmospheres, holds. 4. The method according to any one of claims 1 to 3, characterized in that the recycle stream obtained from the effluent is reduced to a moisture content below 5 parts per million and in particular not more than 2 parts per million before it is combined with the feed for the process Water dries. 5. The method according to any one of claims 1 to 4, characterized in that one for maintenance the desired amount of water in the process introduces water into the recycle stream.