SA00210076B1 - Hydrogenation of unalkylated or unalkylated aromatic compounds using a catalyst containing visible macropores. - Google Patents

Abstract

Abstract: The present invention relates to a process for the hydrogenation of at least one monocyclic or polycyclic aromatic compound that may be unaltered or substituted by at least one alkyl group by connecting the aromatic compound or compounds to a gas containing hydrogen in the presence of a catalyst comprising at least One metal of transition group 8 of the periodic boundary. As an active metal used as a support, the support contains visible macropores.

Description

Y alkyl unsubstituted or alkylated aromatic aromatic compounds hydrogenation 0132010165 containing visible pores catalyst using a catalyst Full description Background of the invention Unsubstituted or aromatic hydrogenation compounds The present invention relates to an aliphatic hydrogenation process to give monocyclic or polycyclic alkyl aromatic compounds substituted with an aromatic gas by delivering the compound “cyclohexane” to benzene for example from ALIEN. Macropores contain visible pores catalyst contains hydrogen in the presence of a catalyst this hydrogenation is carried out mostly in cyclohexane to benzene there are many processes for hydrogenation and 1880N 000C (research; for example » patent nickel role gaseous or liquid over the catalyst and patent 1 ASA FAY US Patent © 03V 489 US invention in cyclohexane to benzene typical the main part of the vad vat apy is hydrogenated thereafter in One or more secondary reactions. cyclohexane a primary reaction and conversion to 0 The reaction of hydrogenation with extreme heat release requires careful selection of temperature and period. It is necessary to quench any significant formation (pals control) to achieve complete transformation at high selectivity. With a face that appears at a relatively high temperature. The cyclopentane methyl specification requires 1 ppm and typical benzene content > 001. The residue content of cyclohexane (n-hexane) n-paraffines is ppm. The content of 001 > cyclopentane methyl ed etc.) is also important. These undesirable compounds form in some way often at grades of n-pentane that can only be separated from the cyclopentane methyl Jie product by relatively high hydrogenation temperature and by combined separation processes (by extraction, refining, or as described in the cyclohexane patent used) catalyst (use a particle filter). catalyst; It is desirable to carry out the hydrogenation at the lowest possible temperatures. However; This is limited by the fact that it ends; Depending on the type of hydrogenation catalyst used; The efficiency of hydrogenation of the catalyst, which is economical, is sufficient to achieve temporal-spatial yields only at a relatively high temperature. v

The platinium 5 nickel catalysts used for the hydrogenation of benzene have a series of defects. the

of gall catalyst nickel is very sensitive to sulfur containing impurities in cbenzene so that it

It is important whether using very pure benzene for hydrogenation or as described in the German patent 1 5 014 the use of a platinium catalyst that bears a high sulphur content

© a prophet in the main reaction so as to protect the secondary reaction loaded with the nickel catalyst Another possibility is to process the catalyst prentum (German patent 4 1 Yoo) or to produce a catalyst sala using ion exchangers 0 ( German Patent 4445 44 1.) However;

The production of these catalysts is complex and expensive. The Lad hydrogenation can be performed over nickel nickel (US Patent VYY 707 9); But the drawback is the rapid combustion of this material

0 catalyst. Homogeneous hydrogenation nickel catalysts (0668257 (EP-A) can also be used however; these catalysts are water sensitive, such that the benzene used must be dried in a drying column to a residual water content > 1 ppm prior to hydrogenation An additional disadvantage of the homogenized catalyst is that it cannot be regenerated.

Platinium catalysts have fewer defects than nickel catalysts but are higher for yield.

0 catalysts nickel 5 platinum both require the use of very high hydrogenation temperatures which

It can lead to significant formation of unwanted by-products.

ruthenium catalysts Lelia is not used to hydrogenate benzene to cyclohexane but there are references in the patent publication to the use of ruthenium-containing catalysts for this application:

Rhyl Pt Pd Processed With 'Ru Per US Patent No. 95871©; Suspension catalysts Y. Lower makes the Pt (Pd) material however; the use of benzene from cyclohexane used to prepare the catalyst is very expensive. Moreover, the creation and detection of the catalyst is complicated and expensive in the case of catalysts outstanding.

In US Patent 077657 Ru treated with Cr is used to prepare cyclohexane vo however; Hydrogenation takes place at Asia Ar and a large amount of unwanted by-products is generated. US Patent 5546 AVY ? Specifies catalysts supported by ALO; for the preparation of cyclohexane these catalysts (Jai as an active metal; a noble metal of transition group A from

£ the periodic table in association with the alkali metal 5 teknitium or runium however; The hydrogenation of 6027©6 can be carried out with a selectivity of only 799.0 over these catalysts. Finally US patent No. YEE VEE? Hydrogenation catalysts and 0 td-” describe a ruthenium booster that is said to be suitable among others; hydrogenation of benzene however; 0 catalysts contain at least 75 active metals and a complex and expensive 0-17 preparation. GENERAL DESCRIPTION OF THE INVENTION The object of the present invention is to provide a process for hydrogenation of monocyclic or polycyclic aromatic compounds which may be unsubstituted or substituted by at least one alkyl group to form (Jia) cycloaliphatic compound in particular benzene. cyclohexane This process makes it possible to obtain cycloaliphatic compounds with a selectivity of Ale and a high space-time yield Jas We found that this goal is achieved through a process of hydrogenation at least one aromatic monocyclic compound or A polycyclic that may be unaltered or altered by at least one alkyl group by connecting the aromatic compound or compounds to a hydrogen-containing gas in the presence of 00 catalysts containing at least a metal of transition group A of the periodic table ; In particular ruthenium as an active metal used for reinforcement has visible pores. We found with astonishment that these aromatic compounds could be hydrogenated selectively and with stacy-high yields of the corresponding cycloaliphatic compounds over catalysts containing visible pores even at temperatures much lower than those used in prior art. At lower temperatures SY can be used according to the present invention; Formation of unwanted by-products such as cyclopentane methyl or other n-paraffines is virtually completely suppressed so that complex mining of the cycloaliphatic compound becomes unnecessary. An additional advantage of using ruthenium as an active metal is its very low price compared to other hydrogenation metals such as rhodium i platinium “palladium [Yo] in the application of [hina] The present invention provides this process in which the catalyst includes as an active metal at least one metal Of transition group A of the periodic table either alone or in combination with at least one metal of transition group 1 first of the periodic table used for its support yr.

average area diameter of at least 0 nm and surface area of BET not more than [Ta 710 g in which the amount of active metal is between 0.09 to 7700 by weight; Depending on the total weight of the catalyst (1 catalyst).Sh preferably the average area diameter of the support in this catalyst is at least 1 + μm and the BET surface area is not greater than 10 [To g (catalyst 0 1a). DETAIL DESCRIPTION OF THE INVENTION Further, the present invention provides this process in which the catalyst includes as an active metal at least one metal of transition group A of the periodic table either alone or combined with at least one metal one from transition group 1 or from the periodic table in a quantity from 1.00 to 0 770 by weight; by the total weight of the catalyst; used for reinforcement in it from 01 to 750 pore size created by visible pores having a pore diameter in the range of − nm to 00001 nm and from 90 to 7980 pore size BIG by means of medium pores having a pore diameter of range from? to 0 nm where the sum of the proportions of the pore sizes increases up to 70010 (1 catalyst). Supports that can be used are as a rule all supports that contain visible pores; i.e. 01 supports are those that contain exclusively visible pores and supports that contain not only visible pores but also mesopores and/or micropores 1086:000:65. as an active mineral; Tames can be used for all transition group A metals of the periodic table. preferred active metals are rothenium sl nickel ccobalte «palladium rhodium «platinium or a mixture of two or more thereof; ruthenium is particularly preferred. Among the group 0 transition metals 1 or 17 or other transition groups 1 nor of the periodic table that can be used by the cla method as a principle any or all of them by the water method, preference is given to the use of copper and/or .runium The terms 'pa 40 pore' and 'medium pore' used for the purposes of the present invention are somehow defined in Pure Appl.

Chem.,"45", p.79(1976) are intended as pores having a diameter δ of −50 » nm (visible pores) or having a diameter in the range from * nm to − nm (medium pores). “Micropores” are defined somehow as in the reference above and refer to pores having a diameter < Y nm.

+ the content of the active metal is generally from about 1.09 to about 770 ro by weight; preferably from about 1500 to about 1 ro by weight and in particular from about 11 to about 78 ro by weight; in each case according to the total weight of the catalyst used; With contents used preferably in preferred catalysts 1 and 7 described below referenced one at a time in the discussion of these catalysts oo. Lad follows.” We will now describe the preferred catalysts in more detail. Description based on the use of ruthenium as an active metal by example. however; The details below are also usable for other active minerals that may be used; as knowledge here. Catalyst 1 v. The catalysts 1 used according to the present invention can be industrially produced using at least one metal of transition group A of the periodic table and; at will; At least one metal from transition group 1 first of the periodic table of a suitable support. The use of a metal or metals can be achieved by soaking the fortifier in salt water solutions; eg aqueous metal salt solutions; Sle aqueous ruthenium salt solutions; Sprinkle the corresponding metal salt solutions 0 on the support material or by other suitable methods. Suitable mineral salts from transition group 10 7 or A of the periodic table are nitrate nitrate, absorbent and “carboxylate” carbonate “cacetonate acetyl” compounds “chloro” nitro compounds or amine compounds of metals the interview; of nitrozyl nitrate nitrate is my favourite. In the case of catalysts that not only have a metal of transition group A of periodic table 0 but Lad additional metals are used as active metal for the support csupport mineral salts or mineral salt solutions can be used simultaneously or sequentially. Stents coated or soaked with a mineral salt solution are subsequently dried; preferred at ps to 0 Aggie) and; at will; Calcined at 000’C to 100’C; preferably from Ror to +5?*C. In Ala soaking season; catalyst dried; if desired; Calcined Yo as described above after each step Soaking The order of the active substances used can be chosen as desired. ‎yr.

b Support material coated and dried op if desired; The calcifier is subsequently activated by treatment in a gas stream including free hydrogen at from about BRT to about 100”C; preferably from about Rarer to about 460”C. The gaseous stream preferably consists of 0 to 7000 By volume Hy and from 0 to 750 by volume Ny 0 solution or solutions of the mineral salt used for the support or supports in this quantity the total active metal content; in each case dependent on the total weight of the catalyst; it is of about 1 to 770 by weight preferably from about 1.01 to about 72 by weight more preferably from about 1 to about 720 by weight and in particular from about 1.06 to about 71 by weight. Catalyst 1 preferably from about 0.01 to 0 about [Ya g] preferably more than about 06 to [Tao g of catalyst in particular from 1.06 to about 7 Ya g of catalyst The surface area of the metal is determined by the chemisorption method described in: “Characterization of Heterogeneous Catalysts” published in: New York OAL pages FEF) in the catalyst 1 used according to the present invention ; The surface area ratio of the active metal(s) ve to that of the catalyst support material is preferably less than about 065 with a minimum of about 0.065. The support material that can be used to produce the catalyst used according to the present invention is such units that visible pores and has a mean hi average pore of at least about OR nm; preferably at least about 100 nm; particularly at least ovr nanometers and having a BET © surface area of not more than about [To 71 g; preferably not greater than about 1210[ com] more preferably not greater than about 10 [Tp g; in particular not greater than about [Ta g] and particularly preferably not greater than 7 m”/g. The micropore fungus of the support is preferably from about 0 fas to about 100 µm preferably from about fasion to about ov µm. The BET flat area is preferably from about 1.7 to about com [Ta Vo ve preferably from about 1.6 to about 10 m"/g; in particular from about 0 to about [foo g] and particularly preferably from about 1.9 to [TeV Jaa g.

A

Particularly consistent with (Ny) using BET adsorption. The surface area of the support is determined by the (Hy) method. Determination of the average distance diameter and area volume distribution is carried out by DIN pore gauge. 66131

In particular in accordance with DIN 66133 with Hy face, the determination of the mean pore diameter and area volume distribution is carried out by means of a pore gauge

Specific to DIN 66133 in accordance with © the pore size distribution of the support can advantageously be mostly dimorphic with a distribution of nm in a dimorphic distribution representing yo nm and about ©0000 surface area having a maximum diameter of about approx. A particular application of the invention. G and have a double distribution [Ta 1, the # additional preference given to the abutment is that which has a surface area

Lor the shape of the pore diameter. The pore size of this preferred support is preferably around 0 mm/vol. “carbon” Jl Jin Support materials with visible pores that can be used are; on titanium dioxide “silicone dioxide < aluminum oxide “carbide” silicone visible pore activators or mixtures of zine oxide “magnesium oxide zirconium dioxide aluminum oxide two or more”; With particular preference given to the use of vo.zirconium dioxide which 137 74 48436 DE-A and its production may be found in 1 other details relating to the catalyst whose content is fully incorporated as a reference in the present application. SUPPORT MATERIALS THAT CAN BE USED For the production of catalysts 1a used according to the present invention; the average diameter of the Ugly are visible pores 0 representing a preferred application of the catalyst - 0

Vo nanometers; a surface area of not more than 1.5 nm; preferably at least 11 pores at least g face [Tao g; In particular preferably not more than [Ta 01] preferably not more than cpa [Ta gm. The average pore diameter of the existing used support [Ta©] is preferably no greater than pals µm. surface area 00 to 1.9 µm; particularly from Yoo to 1.1 in the range of reinforcement; particularly preferred from #,; Bale g of [Ta Ve to 1.7 stent preferably from vo $0 g of stent; Special from [Ta© to 19 g of stent; Particularly from [Ta 01 to gm of the pillar. This catalyst; It also has the doped-shaped pore diameter distribution [Ta 7 to q described above with similar distributions and the corresponding preferred pore size. Additional details relating to the material whose content is fully incorporated as a reference in 956 04 7419 DE-A Catalyst 1A may be found in the present application.

Y catalyst ° include catalysts? used according to the present invention one or more metals of transition group A of the periodic table as active compound(s) on call material as Hana specifies a preference is given to use palladium “ruthenium” and/any rhodium as active compound(s). The ¥ catalysts used according to the present invention Lelia can be produced using at least one active metal of transition group A of the periodic table; og cauthenium is preferred if 0 is desired; At least one metal from Transition Group 1 or 1 of the periodic table of the appropriate support. The application of a metal or metals can be achieved by soaking the support in aqueous mineral salt solutions; for example. ruthenium salt solutions by spraying solutions of a corresponding metal salt on the support or by other suitable methods. Mineral salts suitable for the preparation of mineral salt solutions are aitrate “nitrozyl nitrate” acetyl “carboxylate” carbonate +: 5 tablespoons; “chloro compounds 1150 or Vo amine compounds of metals ALE with preference to nitrate and -nitrozyl nitrate in the case of catalysts including many active metals used for the support; It can use mineral salts or solutions of mineral salts simultaneously or in succession. Stents coated or impregnated with a mineral salt solution are dried after Lad; With temperatures from 0°C to 051°C is preferred. If desired, these supports can be calcined at BART >” to 100°C; preferably from +5©”*°C to 460°C. "restaurant. The encapsulated stents are subsequently activated by curing in a gaseous stream; Including free hydrogen at from 1*C to 100”C; preferably from 100*C to 450°C and particularly from 10*C to 000”C. Gaseous Lil preferably consists of 0 to 70010 by volume of Hy and 0 to 75 0 by volume Ny if we use two or more active metals for the supports and the application is executed successfully; it can dry the vo-support at from 100°C to 100°C if desired; Calcifies at 000"C to 0 C after each application. The order of application of the mineral salt solution can be chosen as desired.

ys A solution of mineral salt is used for the support or supports in such quantity that the metal content is 0.100 by weight; preferred over 701 to 1.09 to 7270 by weight; preferably over 100 active by weight; According to the total weight of the catalyst.‎ 71 to 1, “by weight, especially from Te to m"/g of 10 preferably the total metal surface area on the catalyst from 09 to g of material Catalyst preferably more than [Ya© to 1.06 of the catalyst; particularly preferable from 0 g catalyst.Metal surface area measured by chemisorption method [Ta * to 0 published in: New York "Characterization of Heterogeneous Catalysts" described in: 301-374 p. (VAL) used according to the present invention; the metal surface area ratio or Y in the catalyst is preferably less than about oo, FY The active metal to that of the catalytic support material is less than about 0 coven or less; although the lower limit is about 1.06 and in particular about 1 used according to invention Y the support materials that can be used to produce the materials The present catalyst contains visible pores and intermediate pores. * Of about leh the supports which can be used according to the present invention have a lin pore distribution and with a face JY to 01 is preferred over about JE to 01 Preferably from about Soe to about ve to about 775 pore size created by visible pores having a special pore diameter of 19 from about

Jae to about 90 nm and from about 00001 nm to about 90 in the range from about more preferably from about 70 to about 7960 and in particular JA preferably from about © to about particular from about 75 to About 788 of the pore volumes are generated by intermediate pores having a diameter of .710010 nm; Whereas the sum of the ratios of pore sizes is JY 000 pores out of about YS the total pores of the supports used; According to the present invention it is from about 0.08 to pas g. [Tam 1 to 1 “cm”/g and in particular from about VY to 11 g; Preferably [Tan 0

Yo The average pore diameter of the supports used according to the present invention is from about * to ,

VY nm and in particular from about 9 to about 15 nm (JA nm; preferably from about nm. - 0 L

1 g of support; Taos approx. Joe Preferably support surface area of approx

You g of support and in particular from about [Ta Tor to about Yer preferably more than about g of the reinforcement material. [Ta 701 to about in particular in agreement with Np the surface area is determined Support method 1 using Hy face adsorption. Determination of the mean pore diameter and size distribution is carried out with a DIN 66131 pore gauge ©

Special DIN 66133 in accordance with Although as a principle all support materials known in the production of catalysts having a “carbide” silicone “carbon pore size distribution” defined above can be used; The detail is given for the use of “zirconium dioxide” titanium dioxide, silicone dioxide “aluminium oxide” as two stimulants or mixtures thereof; Preferably more oxide “magnesium dioxide 0. zirconium dioxide 5 aluminium oxide whose contents are 147 YE 4854 DE-A More details regarding the catalyst may exist?” on the occasion Fully incorporated for reference in the present application. Process execution Monoaromatic using all the compounds (San fans) in the process of the present invention; it vo has one or more alkyl rings or polycyclic which may be either unsubstituted or bearing here an alkyl group either singly or as mixtures of two or more of these; preferably singly. The length of groups to -C1 preferred to 'C30' is generally a 0©1- to alkyl not subject to any special restrictions; but groups to -01 in particular To 04- Groups 1 bjlah Specific examples of starting materials for the present process C18 are the following: aromatic compounds are, in particular, diphenyl methane < kumene and toluene benzene alkyl-naphthalene triphenyl methane <hexabenzene 5 heptabenzene «<tetrabenzene Substituted alkyl-tetralines cenatheracine Substituted alkyl-enatheracines «naphthalene «dae .tetraline .cyclohexane to tacrine benzene in the present process; Detail is given for the hydrogenation of Yo*"C to 1"C in the process of the present invention; hydrogenation is generally carried out at from about 8"C to 00C; preferably from about *7C to 100C; preferably more than about 00 yy,

Aste 00 and in particular from about RRA to 100”C. Hana It is possible to use lower temperatures when using ruthenium as the active metal. The pressure used is usually el from 1 bar preferably from about 1 to about 7000 J more preferably from about 01 to 90 bar. The process of the present invention can be performed either continuously or in batches. With preference given to 0 for the continuous procedure. in the continuous process procedure; The amount of hydrogenated aromatic compound is from about Gee to about ? kg per liter of catalyst per hour; Preferably more than about 57 to about "kg per liter of catalyst per hour. As hydrogenation gases, it is possible to use any Jedi gases that are free hydrogen and do not contain

0 Harmful amounts of a .CO Jie catalyst toxin for example; Reuse can be used

Formation of waste gases. Give preference to the use of pure hydrogen as hydrogenation gas.

The hydrogenation of the present invention may be performed in the presence or absence of a solvent or diluent; That is, it is not necessary to carry out hydrogenation in solution.

as a solvent or diluent; Any suitable solvent or suitable diluent may be used. not

The choice is important as long as the solvent or diluent used is able to form a homogeneous solution

With aromatic compound to gradate.

The amount of solvent or diluent used is not limited to any special method and can be chosen freely according to requirements but preference is given to quantities that lead to 7970-01 by weight the resistance of a solution of an aromatic compound to hydrogenation.

7 When the solvent is used, the product formed in the hydrogenation; A als esl with the cycloaliphatic compounds used as a solvent in the process of the present invention; If desired combined with other solvents or diluents. in each case; A portion of the product formed in the process may be mixed into an aromatic still to hydrogenate. The amount of product mixed in as a solvent or diluent preferably 1 to 51 times; in particular preferably from © to 10 times; Specifically from 0 to 01

Ye _ times; According to the weight of the aromatic compound to be hydrogenated. in particular; The present invention provides hydrogenation of the type entitled herein in which benzene is hydrogenated into cyclohexane in the presence of the catalyst? The definition here is at BA to 100"Celsius

yr.

YY

At from 100°C to 1000°C the metal benzene in a specific application of the process reacts alone. The active ruthenium is the invention illustrated by the following examples: Examples Example of catalyst production 0 Size lglg Circumference © mm CAV Medium/visible Pores in the form of aluminum oxide backing by Ly Mam total 44 cm?/g where <.04 cm?/g (770 total pore volume) of size AA) g [Tan 75 nm and 75 0001 nm to 90 pores having a diameter in the range of 0 000 nm average total pore diameter) created by pores having a diameter in the range − nm to Aqueous. Ruthenium nitrate (7) gm soaked with a solution of [Ta 768 nm and surface area 11 0 sq. The volume of the solution is absorbed by the support during imbibition, mostly corresponding to the pore size of the support, while the pitrate is dried. ¥) ruthenium used. The support that was previously soaked with a solution and activated (reduced) at 100 “”C in a stream of hydrogen. The ruthenium produced in this way has an area by weight of 75 g to ruthenium surface area and a surface area ratio [Ta of 7 not ruthenium D surface area A). Support catalyst is 00797 (catalyst Hydrogenation in the liquid phase eg 1 ml. Later 000 g of catalyst A is placed in a basket inside a pressure reactor of capacity 01 AACA Hydrogenation procedure using pure hydrogen at benzene A of 001 The reactor is filled with ov bar. The hydrogenation continues until the hydrogen absorption stops and later the reactor is opened. The capacity is 0 and the pressure of .cyclopentane methyl is 744.43; cyclohexane 7 may not be detected, for example, per milliliter. 001 a catalyst 01 is placed in a vessel inside a pressure reactor with a capacity of catalyst 01 The hydrogenation is carried out using pure hydrogen at benzene g of 001 later the reactor is loaded with vo bar The hydrogenation continues until it stops Hydrogen absorption and then emitted Ye and pressure 0.cyclopentane methyl 44.15 We could not detect cyclohexane reactor. Productivity ye in humiliations? in milliliters. Then 5010 A in a basket inside a pressure reactor with a capacity of catalyst g Of the catalyst, 01 percent Ye gm is placed. The hydrogenation is carried out using pure hydrogen at 10 benzene, the reactor is carried by a bar. Hydrogenation continues until the hydrogen is no longer absorbed and the reactor is subsequently blown. yield of 01 and pressure of .cyclopentane methyl was 744.49; No cyclohexane 0 lll 200 a was detected in a basket inside a pressure reactor of a catalyst capacity of 01 g of catalyst placed 5602606 g. Hydrogenation is carried out using pure hydrogen at 001 and the reactor is then loaded with a bar. Hydrogenation continues until hydrogen absorption stops and reactor 710 bleeds and hdl pressure on ppm of ov 44,548 cyclohexane is detected thereafter. Yield of 0.cyclohexane in cyclopentane methyl© eg Next; Without of catalyst an electrically heated flow reactor carried with ? kg of catalyst Pascal and 5/7 atm. Hydrogenation takes place continuously 10177 at benzene prior activation; Hydrogenation begins as an upward flow; With a portion of the hydrogenation product recycled by means of a circulating pump and mixed in 1 times the amount of hydrogenation product 01 cbenzene is added stream over the starting material in the reactor. According to the amount of continuously fed benzene an hour at the separator head. Amount of [Hy] 50010 liters of solvent. The reactor that corresponds to the space velocity above the catalyst is blowing 78.77 kg/l” per hour. The Pa product is pumped as an upper flow through the second hydrogenation reactor TY XY hydrogenation at 85 °C a. In this catalyst (secondary reactor) which has been preloaded in some way with ¥ kg of catalyst “0 ppm A+ benzene reactor; The hydrogenation product is not recycled. The hydrogenation product has a residue content of .cyclopentane methyl (determined by gas chromatography). ge + a was not discovered later; Without catalyst 1 kg of catalyst carrying electrically heated flow reactor with Pa and 100 °C. Hydrogenation takes place continuously 1017© upon benzene preactivation; The hydrogenation of vo begins as an upstream; With part of the hydrogenation product recycled by means of a circulating pump and mixed at once, the amount of hydrogenation product 51 benzene is added in an upper stream to a starting material from the reactor. According to the quantity of yr.

\o fed continuously benzene hour respiration at the apex of the spacer. Amount of [Hy liter of 0001 as solvent. kg/l” h. The 1.6 hydrogenation product of the space velocity offset reactor is pumped over the catalyst a second hydrogenation (secondary reactor) Jolie Pa in the form of an overflow through 1015º phe at in this reactor; The catalyst product does not recycle the 1 kg catalyst that has previously loaded with ppm (determined by benzene hydrogenation © analysis. The hydrogenation product has a residue content of 0.cyclopentane methyl gas chromatography). No hydrogenation was observed in the gas phase, for example

Lag g.Vo) milliliters of catalyst A 011 A flow (glass) reactor heated with oil is packed with benzene under ambient pressure. Hana; benzene evaporates after a previous activation; Hydrogenation begins - 0 sale through base (V, £1) = evaporator (60"C) and passes continuously in combination with hydrogen (molecular ratio kg/l*h. Condenses 1.7 spaces de jug Aggie') re in a single pass catalyst completely catalysts cyclohexane to benzene produced in a cold box device.In this way .cyclohexane may hydrogenate into cyclopentane methyl ppm 71 Discovery + as 0

Yo) a catalyst (glass) flow reactor heated in oil with 50 mL of daa catalyst at ambient atmospheric pressure. Hana benzene without prior activation; Cans Lad hydrogenation begins with an evaporator (60 "C) and passes continuously in combination with hydrogen (molecular ratio benzene evaporates 1 and space velocity Augie) Ye in a single pass at the catalyst through a base catalyst) 7,4:11 =

JAY was benzene kg/l*hr. shift 0

TY X05 A AO only at jes The condensed hydrogenation product is passed as an overflow in g of 500 Pa (liquid phase) through a downstream reactor tube which was previously loaded with ppm (determined by Analysis 1 benzene catalyst A. The hydrogenation product has a residue content of cyclopentane methyl .41 ppm (gas chromatography). has been discovered

Claims (1)

Elements_ of protection 1 1- A process of hydrogenation of benzene by means of contacting benzene with a gas containing hydrogen Y at a pressure of 1 bar to 01 bar and a temperature of 0*8 to Ast on 1 the presence of a catalyst comprising at least one Transition Group A metal of Periodic Table 1 either alone or in combination with at least one Transition Group 1 metal or ; of the periodic table in an amount from 0.01 to 7760 by weight based on the total weight of the catalyst “1 as an active metal applied to a support containing visible macropores of pore diameter above 010 nm; In which it is from 01 to 7860 pore size made of A visible macropores with pore diameter in the range from *0 nm to 00001 nm and from 0 4 5 * 4 to 74968 pore size made of Medium mesopores with pore diameter in the range 5 from ? to 00 nm; where the sum of the pore volume magnitudes is .7001 .cyclohexane to form benzene in which 1 of protection element Gy reacts “-1 process 1”- Gig process of protection 1 where the active metal used is rothenium alone. 1: +;- process Gay for any of the protective elements (All) where the support material includes titanium dioxide silicone dioxide “aluminum oxide” carbide silicone “carbon Y two actives or a mixture of the two or zine oxide “magnesium dioxide” zirconium dioxide v more than that. ‎Alec —0 01 In accordance with any of the foregoing claims; Cus hydrogenation is taking place continuously.