DE1518091A1 - Process for the production of heavy phenols - Google Patents

Description

PATENT ADVOCATE
DR.-ING. GLAUS REINLÄNDER

8 MUNICH
ZEPPELINSTRASSE 73.

JROGIL Spoilt «anonymous ·

77, ru · d «llroeeenil 1518091

Pari ·, 6, France

• Process for the preparation of heavy phenols

The invention relates to a process for the production of heavy Phenols on entapreohwnd eyklo-aliphatic Jaueretoffverbindungen and in particular on the production of aaphtol by more or less severe «dehydration of alcohols and / or ketone derivatives des Naphtalena, precautionary for the production of = * -Baphtol · au · & -Tetralol and / or «-letralone.

None of the previously proposed processes for the production of heavy inenols by dehydration of entepTeohandtr eyklo-aliphatic compounds have been completely satisfactory «Nn s. B. a catalytic · metal in a very active form» such as unused ·· fianey-Nick «l _v Ilatinacawae * ue *., For dehydrogenation de · hydroxy- or de · oxy ~ 1- xetranydro-1, 2 _e 5, 4- Haphtalens is used, equilateral tetrahydro-5, 6 »7t 8- naphthol 1 is formed, the sp &ter" ore is difficult to separate from de "e * .- Saphtol shown below. Anderereeit · yield dl · known «au · the oxides or Met & iliechen strings (possibly with each other gealeoht) existing catalysts sum Dehydrierensu low speeds in the dehydrogenation _t which β nc" glicht that the secondary reactions of dehydrogenation "in · UberaüSi ^ e Hollenbach play «The same laughing part« r-

BADORlQiNAL

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gives "I" when you work with catalysts, that is, through precipitation of finely dispersed metals on early £ «, which In general, the catalytic metals are used, in particular activated soles, clay, oxides of the elements in columns III to VIII des yeriodl & chen Systata », in particular Al ^ O ,, TiO ^ t SiO ^, Cr ^ O, or this · oxide · containing compounds ·

On the other hand, the invention enables the dehydration of the dual aliphatic cycle to be carried out very sharply in order to obtain a heavy load with an excellent yield and with very small by-products and / or letralonen old elevated U "- setsungsgrad, which can rise to about 100 j>, convenient to get free of letraiiydronaphtol.

The invention was based on experiments with various catalysts used in the dehydrogenation of syclo-aliphatic compounds with a view to the production of corresponding heavy phenols, this led to the discovery of a new lateaohe order of magnitude · The dehydration of the alipiatic cycle should be sharply dehydrated «should not contain the catalytic hatred" acidic state ", but should be completely neutral or be completely neutral. According to these investigations, the" acidic states " - ie compounds or groups can have an "acidic property," ie it can be found in activated carbons, in active silicic acid-containing silicon oxides, in the known catalytic agents X10 ₂ "Al ₂ O, Cr ₂ O, etc." undesirable in the dehydrogenation in question according to the invention

The method according to the invention consists primarily in the fact that the BAD ORiGiNAL

909 * 851/1688 '.

-Alaliatic hydrogen compounds in a fluid state • When heated in an "e", a catalyst for dehydrogenation can now be subjected, or one or more finely divided catalytic metals may be divided on an iron or an oxide or ... inter alia Gay who are ecii ^ it with a basic or completely neutral £ .igen and without a üeütandtöil itit aaurer Li ^^ wiCiia £ t in free 2uut <iid down ^ eßc ^ la ^ cn

The Kuta,> tluohen metals uie ale catalyst _fc eniw.ß the hrflndung vur. '. Endbur oind ₉ can inübeeondere i.1-, Cu, Fe ₉ Co, Cr it ₉ and the other itt lalle α tr * lutin & rupj e "a ·

Among the Xr-j ^ er, which for the catalyoatur according to the invention atlEuüen author fc-eei ^ n, "are Luöiöche oxides, inebe-« others those of the b ₄ tltt 1 and II dee yerlodltschen oysterne and . voreugeweiat CaO ₉ M ^ O ₉ CuO and ZnO SrO ₉ toil can but also the oxides of Kieeelcro4 "vei'.crivlen in completely neutral form, eg, B. \ 1b Kieatl-J α No" a <- acids.. State ¹¹ eritLilt. Dieo · (JXJ de can u in / ertinduxi ^ u ^ een old, he .'- these aiud mentioned above are used ₉ ·

The ai.Vül _d & λ gates according to the invention contain in the ali ^ ea a 20 to 100 »in particular l> 0 to 100 GoAiciitateile du3 fine tables Mete He to 100 Gewioftteteiie dee ir

The ileratuliuttg -dtjr Katalyeatoren can be done η .el * beit-inuten Yerfi »üren, 2. - · by /.iücüen the .tetails in Hede with the rulver dee ^ ewahltun Tr ^^ ere, durGb ^ emtsinsanes filling etc. , whereupon the id806 is cut into a separate torch for patillation or granulation, and is added by means of coding with oxygen

■■ · "'■■■" ■. BAD OL

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a feapersitr »dl · vorsugswsi ·· gielon or littleetene la der Böh the temperature at which the catalyst should work.

Another invention consists in the hydration at an extremely high temperature, with a high value in the mowing of the sled door Reaction · »liquid a« tell «n · se is inebeeondtre advantageous» at the »boiling point eelbet under atmoephariecbe« Sruok or under another pressure, £. B. 1 to 5 at, su arltlten.

If the myclo-aliphatic chemical compound being treated is oxir-1- ' tetrahydro-1, 2, 3t 4 * oaphthalene, ie ^ <· tetraion, the best application temperature is n _v ao oc "Va |> ntol iu obtained , at 200 to 550 ° C. The reaction rate and the degree of unset sun * are not as high as the temperature su and dl The results are particularly good because of the boiling point of the reaction, which is below 25 ° and 290 ° G atmospheric ·· Sruok according to the definition of the ttesstsungsfradee. Si ··· te »perut doors increase to 305 to 340 ° C, if im works under an» absolute pressure of f to 3 kg / en, which can be of interest *.

In this particular case, the s / klo-aliphatisoht terblendung sua Dehydrate Hjrdroxj-1-Xetrahydro-1, 2, 3, 4-Laphthalene or Tetralol let «deepen temlsoh · dehydration above 240 ° 0 is essential, • There follows a special method of the invention Execution forsi, which means that the reaction takes place in two different ways is carried out

1 · jSrfcitcung bis · sun boiling point below a · reduced · »Sruok« it • Terweilselt lner courses in catalytic R&D »u» gsrwl · the goose transferring fetralol into the state of the setralon.

BAD ORS-S!> JAL

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2 “Treatment for an etark raised leaper door” wit welter above is specified, which is suitable for da * tstralon

Of course, this particular version uses eo much of 'the letralol itself' like the initial situation, more or less Contained by all connection «The first section may be advantageous like «to be performed under a pressure of 400 to 760 mm Hg» which corresponds to boiling temperatures of approximately 225 to 250 ° C «

After, veaentlichen, supplementary feature DÜA erfindungegeaäßett method · the .Yirkaamkeit is tig by ao kr Λ as li

der KontaktflüeoitiKelt due Kütalysator * verbSert. This Bewird in the case of the catalyst in a solid structure get »that the au treating flüaaig & sit aebr BOi.nell ^ uer Through the layer, other means are passed on according to one special feature of the invention in the introduction of an inert (phase £ · B * üticketuff, in the KontuktflüeaifcKfcit dea K ^ taljt .tors. Uie introduction should be used with a chilled amount in certain Jronzen, in particular 150 to 200 «al the Yoluaen of the catalytic Rauaea pro Hour »take place ·

The method of the invention k ^ nn two types veracjaleaene au · - are guided 'and'was' it a solid layer of the catalyst · ait or grains ä ^ m Katalys & tora in suspension in the Heaktionsmilieu.

tenn the Flüseigkeiten, the i "essential tetralone and / or Tetrülol" contained in laphtol dehydrated * * _# ind described in de ^ a fixed .Schicht of the catalyst of the invention q.uer sown by 'tre' s, as the further ollen · it is recommended that the JLat & lyaator has the shape of lozenges or corns »their exhalations

BAD ORiQiNAL

909851/1688

»Wipe 0.5 and 10 κ» and vorstigsit ·! * · »Wipe 2 and Su lie · Too large · Dimensions lead su a sealeehteis recess doe. Catalyst, while u small Loss of charge and the dangers of the aeolmatlon by crushing the grains. Dl · linear ödBuhwlndlgkälten the flow through the Heaktlonsflüeeigkelt cross below the katalytiechen layer are preferably swi $ chen 4 and 10 © m / h _:: i!, @ Sbesondere swlscütä 10 and 40 a / h, bereofesiet Fuei * (Sin tomm f ^ r ^ isfetun ^ e

At & g & AaeSilfeiJiiEi ^ a & iSite t: 4u iä © £ - £. ^: u. ^ 3J? 'fi®tic3s ^r in JM * p # m ^ ion in the

* MMab ^^ umHM & uliikui ^ slnÄ di * b © v © ff «iagtea Iteesäungen der kur, ^ r ^ © rifiger al * bei d © ff * · ten üctiiuht. üi «can« between 0,1 and 5 lie, jedosh iat e * be »cs?« if ele »wiacüen 0,1 and 1 11βά · α. The separation of catalj emtore from the treated flüeaigi-with after the activity below 0.1 ata is difficult, while the surner Ubtr is not easily kept in suepeneion, as it leads to a slight degree of dehydration · £ nt »preohend the üigeneohsft der Flüebigkeit and de * Katalyautore the ÖuspAOtion 10 to 40 iewlohteteile de» Kutal ^ emtor · to 100 parts by weight of the fluid contain · Prevention level · · i »t da« ratio never 20 to 30 to 100 Weight * parts.

Invention processes can be interrupted or continuous _& · lead values »· I« «wide case let ββ tr desired, several Heaktlon ·« · kaiaeern la Seih · sw use «», u «the quick achievement of the« Owt- • etsuagagrad ·· la J> biiingigfc «it from ί- * ι · Ssltf m, lz> ~ * durah dl« la Eede

Heaktioa geittaiieelete «* i ^ s": - neciC3§l, ®ielieB «..

erflnduiigagea & e · Learn "kai" sit 3i3.f0 ^ t £ - £ @ hi "£ er well-known" M8g "fuärt werdisn ^ ill" mi.% "in ·" KaV-al ^ eater In one

- ORIGINAL BATHROOM-

09851/1688.

feeten Schient or a Suapensids wirkaa «work * Di · Torrichtung a with a firm schioht, dl «in the following beeohriebon and shown in the payment iat »seigt ein · nloht restrictive · Treatment method based on an exemplary, very sweekaallgen execution forum.

Exactly the drawing "which shows" * of the device serves the piston or the tube 1 as a buffer for the liquid obtained by the hydrogenation in the reaction alkali 4, while the starting material is outside the container 15 koaat. The 8peiaepuape 16 promotes the Plüsaigkeit of dea container 15 via the rail of the catalytic converter, which is arranged in the Heaktioaskaaesr 4. On the other hand fieaktlonskanaer the treated liquid obtained from dea piston 1 "which is again of aufgenoaaen ^ w üalaufpuape a. The liquid passes through the torrent 3 and reaches the catalyst in the reaction chamber 4 at a normal temperature. B. 250 ° 0.

The Keaktionskaaaer iat old (not shown) Krhitsereinrlohtuneen provided that a preheating of the layer of the catal ^ eater in the Reaction caaoier 4 times. In its upper part has the Heaktionskaaer an extension 5 »from welehea part an overflow 6 au dea Piston 1 has the extension $ above old one Process column 7, in which the outgoing from the reaction liquid Däapf · reach »whether reach the Koadeneator β se. At the Underside of the condenser «· a decanter vessel 10 is provided, in dea daa gessaaelte lasser is separated and bsi ti is evacuated » while the hydrogen through a suction 9 at the top of the Decanter escapes. The liquid clarified at the bottom of the decanting facility 10 passes through the line 12 and the piston 1.

909851/1688

The suction 14 on the flask 1 is a cooling device, Prevent the laphthol cells from entering the atmosphere. . The · removal of the manufactured products »takes place via the · drain valve 13th

Di "reaction can" edium · "ine · intimate passage dtr Äeaktionsmleehung ron adequate long ·" but old "lner division are carried out in several routes in a rohrföraigen Torrichtun *, including here," faseοretoffprodukt in each of these su eliminate. Among other things, it is easy to achieve high throughput speeds of the liquid according to the invention, consequently the general sweep, which leads in a closed circle over the catalyst until the usual degree of conversion can be obtained. In the drawing, the gate direction is good for this operating mode. A specified volume of the starting material is placed in the container 15, including pumping this into the operation unit 4. The valve 17 1st now £, euci; loeeen and a & n can let the Itolauf ^ uape work continuously. The liquid runs in a closed circuit of parts 1 to 6, 10, 12 and 1, among others, while the iasaeretoff formed in fieaktlonskaaer 4 is drained through the outlet 9, the content of the flask 1 has the unsealed content of vaphthol (or another heavy one Phenol), this can be stopped via the valve 13, and a new charge of the output material of the container 15 is introduced into the device.

2> 1 charge is shown in a number of non-limiting examples Explained in the following description

example 1 Catalyst A. ... ~ " In the examples: sit A denotes a catalyst that is used in the

90W5T / 168 8 BÄDOH1S! MÄL "

the following is quietly inherited. One “laughs a part by weight of copper oxide. CuO ait swel parts by weight of zinc oxide ZnO and produces from it in Usual lais * pastilles. Two types of grains are soait manufactured!

I. i-astillen in sylinderlechtr Fora alt a high τοη 3 «β and a«

Basic diameter τοη 3 ball. Grains ait the selected sizes 0.2 to 0.5 aa »0.5 to 1 aa, 1 to 2 mm and 2 to 5 aa obtained by crushing the lozenges and be obtained by sieving.

In both cases the catalyst in hydrogen is swischen 100 ° and 275 ° C until a roll rsduslsrt _t · tandige Uasetsung of CuO in finely divided metallic copper is carried out.

£ atalyeator B

The catalyst referred to in the following examples consists from dea on Kieeelguhr in well-known leiee knocked down metal. £ r consists of 50 Qew.-ίί liokel un < does not contain any "acidic states".

The catalyst is described in a separate manner in Example 1 I. Cylindrical fastilles old 5x5 ″ from the abutments

XI · Four fingers τοη horns old the selected Grüfleni 0.2 to 0.5; 0.5 to 1j 1 to 2 \ 2 to 5 aa.

After the reduction of the rock oxide, the metallic oxide is oxidized the catalyst again oberflaohlioh In a sshr sparsaaea feise »ua stabilize this su.

Example 3

on a solid layer of the catalyst . .. ■

a device d «r in the Flg. the type shown is the

909851/1688 3AD on: ai

KesJctionskaaaer old a · «Inside ^ ueraohnitt of 18 ca old 1000 g d ·· Catalyst A in a Yllndrlacher Fon old the Apaeauunrfen 3x 3 η charged and pre-heated up to 250 ° C.

1700 g tetralone be vorerhltct at 250 ° C in dta piston 1, after which this now About dl · Τ · 11 · 2 to 6 in a ttunge of 7.5 l / h old a linear vieuchwindlgieili of 10 A / h -lutr iu dtr k * »WIy t laugh layer circulate laset · Dl · To» bamen «eteung the era Ltenen in Abbant.icK.bit from the 2nd time let in lutelle I

Beleplele 4 and 5 One works "1" in example 1. but at 230 and 200 ° C. I> 1 · Results are also given in Table I.

AtBDiel Table Z 250 ° C 1 I. \ ι Tetrahydro byproducts heavy 2] \ na ^ htol easy 0 3 1 \ 0 5> 3 3 4 1 \ 0.1 6y 3.9 0.1 8Ji 5.2 0.1 9 * 7.3 a 27.0 0.1 13Ji 9.4 H 34.6 0 9Jt 12.7 4th I 40 0 15ff0ft t> * 4 a 41.2 0.1 '? # ** 13.6 6 h 41.9 ο, ι 15,5Jl 14.7 230 ° C 1 η 20.4 0.1 16 yrs 2 1 0 5 3 1 0 4 1 0 6 1 0 200 ° 0 1 I. 0 2 1 3 1 6 k 10 1 κ 28.4 l 50.2 ι 36.0 ι 38.5 ι 11,6Ji ι 13.6JI ι 15 * 1) 1 ι 19.5 * ι 22.1) 1 ah to: Ji Jt *

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Β / "

BslepJel 6

In dl «same device wl · b» l the previous examples 1000 g of catalyst B, which is described in Example 2, la is, ic sylindriecher For «with the dimensions $ χ J u One works ait 2000 g of Tetraion at 250 ° C old a Ualauf of 10 m / h. Ei · i-rgebnieö · «iod with the results of the game 7 to 9 in! Table II

oil works in Example 6, but at the boiling point, i. H·

at 2i> 6 to 280 ° C.

Example β

The procedure is as bein Example 7 but _t dl · lineuxe ueechwindifkeit

the liquid on the catalyst is kept at 24 m / h .

You work as in Example 8, but the sub-section becomes part of the bottom the He & JctionekaaxBer injected a nitrogen rate of 150 l / h. It is found that the addition of nitrogen to the Realetitmakiiseer has a beneficial effect on the reaction speed and the yield at lower nitrogen levels is determined by one Value, which with the device la used is of the order of γόη 150 to 200 1 / b. Lie iirkuag the addition is unfavorable for larger amounts of nitrogen.

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Xemterature 0 Table II To "anmen" et "un £ of the product · Tetrahydro By-product heavy B * i * cdel 1 except oi-JIapLtol ^ -Naputol borrows 1.5 1 6.2 5.0 250 ° C 0 21.9 * β.25 8.1 6th 1 , 5 h 27.1 * 9.7 5.0 1 H 31, fc> 4.25 4.0 7.0 258-280 ⁰ C. 0 $ b h 39.7 * 3.5 6.0 10.0 7th 0 .5 h 50.7 * 3.0 9.0 1.6 0 H 57.25 * 0.2 2.7 3.4 0 .5 h 36, ϋ * 0.2 2.8 4.7 8th 0 , 25 L 51.105 0.2 3.3 0.9 j , 50 h 2.4 7.7 2.4 , 75 ii > *.:, £ 7 2, t> 9.7 3.6 9 , «? 5 ii 51; - * 2.4 10.6 , 50 h 60, -A 10 , 75 Leiewiel

Continuous ArbcitawclBui Dtr -etrifcb lia ^ innt as bein üeie ^ iftl 6, and nudh üincr οtunae interrupted operation n ^ c nit'einer continuous, uieuden ZuiuUr uiid it ^ ube in a menu ^{of 1} 700 βΑ · Si · eumcccw. it £ un £ acr iib ^ tnoneenen Miaohung iet 26.2 ^ oc- | japbtol and 9 $ light and I)? - c «hwcrc itebttnprudukt'e.

The procedure is as in Example 6 (1000 g of catalyst B. temperature point), but with a total of 2000 g of a solution of 76% of fetrolom and 24 / - oc-jetrulol. H eil half hour of Con t Uaeetgungsgreul leg Xetralol and 'j% bc-ia tetralone · di · Mi & c & ung contains 44 ^ ^ -

12th

Swei forricLtun ^ tii analogous to that divided in fi ^ · ύαΐ & ν & are Ia & · !!> ·

_N 909851/1688. _{n Λ}

arranged · Di · «rat · we * old 1000 g of the latalyeatore A is charged, among other things, a man bu.lt el« to an absolute pressure of 600 aa Hg · Si · «wide gate direction, a 1000 g of the catalyst B is charged and athether & t «oephurl * c £ iea pressure. The arrangement is continuously worked on with a mixture containing 62 pounds of tetralone and 3 % xetralol in an amount of 2000 g / h. The two Yorricut dips are kept at Jiedeteajperatur. One receives at the exit of the step device • ine Mi & oaung alt 11,5 * "-jiaphtol" b _f 2Jfr lelcüten, 3,7a heavy credit products and only Q ₉ Jt letralol. To as "output of" üeaktionakaamer wide contains the finished Misohung 57 ₉ 2 ^ o ^ Jlavhtol ₉ 11,5Ji light ""! • the usable dtoff · (tetralin, Iaphtal «n) _t ^ 6.7 empty and 1.4? t

13th

line Äeaktionek & aaer let ait aeoh «niaohen ▼ • r «j«; hett and a fluke condenser is aa output of the iueeeretoffee appropriate. 1000 g of Xetralon were kept at 250 ° C. and added 250 g of the catalyst * A in grains from 0.5 to 1 aa, see below, as in example 1 is described

laoh 5 hours Ee «per ti on the Uasetsun ^ sgrad is 7ü, 1 ^ ua4 the Krtrsg an «.-Saphtol 73 * ie ferh« J.tni · sa da «used up letralon · Above in addition, the greater part of the lebea products is reusable, because it consists of haphthalene and tetralin.

One works in a manner analogous to Example 13, but at the boiling point, ie at 256 to 280 ° C., and with constant agitation for 250 seconds of the catalyst A in törnera τοη 1 to 2 am. For 5 hours, the Uaaet «un £ Bgrad £ 83.6 and the proceeds from Λ-Nui-utol

BAD Ο 0 9 8:> 1/1 B 0 B

BsIsdIsI H

This work corresponds to example 14, except for the Kataly-Mutor A la grains of 0.2 and 0.5 aa · Bach 5 hours entered dsr Uaeetsun £ S * -rad 86.5 * and the Irtraf ana-Iapütol 78.5 *

Example 16 to 19 One works with Examples 14 and 15, but old 250 g of the Catalyst B. Dis fabslls XXZ is the result obtained.

Belsulel 20

One works «*» ie bein ν iepiei. '?. «» eruetst jsdoon the letralon duroh elB * Miscaunf tob 24Jt IetrsIo 1 and 76 * letrslon. Isoh 2 hours KsaktloB reaches the degree of oasis 10O ^ Te tr ^ Io 1 nod §9Jt Tetjraloa and dsr Irtra * an <* -Isphtol can be used Products 1st 91.5 *.

Tabs III catalyst B Dausr 0.5 M In 1 h 5 0 2 h

Example ABMsaunf USwetauafs
dar lörasr A

irtra «77.5 ^

1-2 m ttsssteuerag - OK * 74.8 * 79 .5 * 84.5 * 17th Krtra * 75.8 * 75.8 * 70 • 5 * 73.5 * 0.5-1 em QsWStSUBf -
Degree 74.2 * 82 , 2Jt 86.3 * 18th Krtrac 81 *
8th 71 , 7 * 76 _f 2 * 0.2-0.5 nm Income
degree ■ 60.2 * 80 , 9 * 85.5 * 19th ^Γ * if 0 9 8 51 83.2 *
/ 168 82 , 3 * 78%
C «AO CHIGiNAL

Si · table s «l ^ t den Itoetsaagfltfrad and dit Xrtra ^ e an ^ - in the ratio stm consumed fetrmloa · D * r ^ rOS «r · part d« r ! • bwiprodukt · is 1 — r aoob wlsdsr usable and the request to nutilichejn products in the ferhnltai · sua Tttraloa echwanJct «wiechen 97A and 92.5% correspond to the duration of the reaction.

909851/1688

Claims (14)

Patentanaprüch 1. Procedure for the preparation of pottery ihenols by dehydration of corresponding cyclo ~ aliphutic uuueretoffverbindungen, thereby (itskeuuzei .iint »t _t au ti the compounds in the liquid 2u * t * nd finer hrhitaun ^ in Am.eeenneit tiu ~ · Dehydrler-Katator · be cast them, the bewteht. · lion uua one or more catalytic redusiexten Met, the nut a Iruger UUD an oxide or au · 0Xjden with luöiochcr üdir neutral UEI ^^ nechuft and without a Bestundteil with v ... urtr i.iüjnacii. £ t im ireitn Zuatund niu (ler ^ esohlM4 (eii ) uind. 2 · Vuri \ her «n after Auapruoh 1, characterized« Uutt bis Cr catalytic metals Nl, Cu, Fe, Co / or metals of the xlutin ^ group be used· 3 · Process according to opening 1 or 2, by means of which oxides forming the catalyst, the oxides of the metals of Jaulte I and IX, inebwa ^ ndtire 'CaO, CuOt V ^and ZnO, are used. 4 · Procedure according to one of the tests 1 or 3, thereby known without, duS al · Trügeroxyd · a iiu ·· dee Silitiumdioxyda, invbeeonder « Kieselgtthr, which is free from "eauren zu et found * iet, is used. 5. Method η ^ ση one of the claims 1 to 4, characterized in that & eJtennzelohnet, that the dehydration is carried out at a temperature that equal to or close to the boiling temperature of the heat »flÜ» »i ^ - at a pressure equal to or different from that atmospheric pressure let 6. The method according to one of the speeches 1 to 5, characterized in that that the liquid ttoufctlonsmllieu vigorously during dehydration is moved". 9098B1 / 1688 DAD ORiGl 7. Method according to one of Claims 1 to 6, characterized in that that the catalyst is used in a solid layer, where ·! Its grains preferably have dimensions in the south-north-north of 2 practice up to 5 mm. 8. -Process according to one of Anbruche 1 to b, characterized in that that the catalyst is brought into ouapenaion in the reaction, its grains preferably being in the have the order of 0.1 to 1. 9 · Procedure for the production of τοη naphtol according to Jur t to ti, thereby ^ akenn-auionnöt, da. entaprucnendee ^ otrulon and / or Iiitruiol du-v ^ it-rt will. 10. Verfuhren to Uurotiven νυη (XN ^^ htol uub »-.Tetralin and / or ni.cn claim ^: j, thereby geKennaeichnet that one Tna f.οra door from 200 to 550 ° C at a pressure of 1 to 5 atm is applied, "although the heat should preferably boil. 11. Verifrua according to claim 10 with a siemlionen anxciuhorung of letralül, so as a ^ ekenn ^ uicLnet that au β ^ ot lit an I & ei-uratur • about 225 ° and 230 ° C with a pressure 400 to 760 mi Bg worked will »until the complete conversion of letralon · γ-fol ^ t 1st, after which a temperature iwiaohen 2i> 6 ° and 290 ° C under atmoa ^ härlschsa pressure is worked · Process according to claim 10 or 11, characterized in that the dehydrogenation is over a solid layer of the catalyst, which consists either of being deposited on SaO or of being deposited on oxygen a linear flow speed of 4 »i · 100 m / h * takes place. BATH 13 · Method according to Anaj.ruch IO odor 11, characterized ^ © denotes that a riepereion with 100 parts of the Auagon ^ smuterial · and 20
At 90! the catalyst hurries as " grains" which "Cu, because there is deposited on ZnO" or aua Ui only Lie ^ el ^ xxhr bejtn "at is formed and that heating while running for 1/2 to 2 hours 14. Verfuhren according to β in um claim · 1 Lie 13, Jc: lurch shows that an inartea Gaa, e.g. fi. btickatofl, into which reaction afluaoigkeit wi; rcnd the dehydration ulngobranch,
Ati8 · In a * ön _o e from 150 to 200 Vulu & tm ücö utioc »a i> ro
ütunde and per liter of ααβ katalytiiiunen ■ ■.;. M 909851/1688