CA1085812A

CA1085812A - Activated massive nickel catalyst

Info

Publication number: CA1085812A
Application number: CA249,954A
Authority: CA
Inventors: James L. Carter; Allan E. Barnett
Original assignee: Exxon Research and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 1975-05-14
Filing date: 1976-04-09
Publication date: 1980-09-16
Also published as: IT1059015B; DE2620554C3; JPS5624575B2; NL7604848A; DE2620554B2; AU511696B2; BR7603026A; FR2310802A1; JPS51137688A; NL176055B; FR2310802B1; GR59807B; GB1518878A; AU1281976A; NL176055C; BE841812A; DE2620554A1

Abstract

ABSTRACT OF THE DISCLOSURE

A process for forming a copper-nickel-silica catalyst and the catalyst is disclosed having a nickel surface area of about 55 to about 100 m2/g and a total surface area of 150 to 300 m2/g, the process comprising the steps of comingling a solution containing containing copper and nickel cations with a solution containing silicate anions, coprecipitating the copper nickel and silicate ions in an aqueous solution onto solid carrier particles. The use of this catalyst in a hydrogenation process is also disclosed.

Description

Thls invention relates to the activatlon of highly

2 active nickel-sillca catalysts having stabil~zed high ni~kel

3 surfaee areas which conta~n very little quantities of alka-

4 line metals~ In one aspect~ th~s invention relates to the

5 addition of copper in the preparation of a massi~e nickel

6 hydrogena~ion catalyst ~hereby facllita~ing the low tempera

7 ture reduction of the cataly~tD

8 The so called act~vat~on of supported n~ckel cata-

9 ly5ts9 i~e. 9 -~he red~ction of n~ckel oxide before the cata-lyst is utilized9 is usually conduc~ed at temperatures which 11 are very high in co~par~son ~o those at whieh the reduction 12 of bulk n~ckel oxide can be comple~edO It is a well~known 13 ~act that supported nickel oxide is more d~fficult to reduce 14 than wh~n unsuppor~ed and ~ha~ hi8h reduetion tempera~ures 15 promote sinteriLng ~f nickel. It is thought that, in many in-16 stances9 a better act~vity and/or a better poison capacity 7 could be ob~ained, if lower reduc~ion temperatures co~ld be 18 used.
9 ~he copper promotion of the subject invention re-~lates to the mass~ve nickel cataly3t descri~ed in U.SO
21 Patent NosO 3~697~445 and 3~859g370O These patents describe 22 catalys~s h~ing high niekel surface are~ and the relati4n-23 ship between the high nickel surface area and their act~vity.
24 The nickel surface area is measured in the manner descr~bed 2~ by Ya~es9 Taylor and Sinel~ ~n J0 Am~ Chem. Soc 86~ 2996 26 (1964)o 27 In U~S~ Patent 3,8599370 ~here is described a 28 proce~s for carefully controlling crit~cal conditions to 29 fo~m these~high nickel surface area catalysts wherein nickel catalysts prec~pitated in the presence of porous solid par-'Y~

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ticles can be made which have a nickel surface area yreater than about 70 m /g, preferably 75 to lO0 m /g and catalytic activity for hydrogenation several times greater than the previously known nickel catalysts.
The massive nickel catalysts described in the aforesaid patents have proven to be active hydrogenation catalysts in laboratory and pilot plant runs when they are activated by reduction at 400C. However, there is a need to have such a catalyst that can be activated at lower temperatures than are normally obtainable in the commercial hydrogenation plant, which is in the range of approximately 200C.
It has been discovered that the presence of copper ions during the co-precipitation of the nickel and silica ions provides a catalyst which can be activated at lower temperatures than are normally required for nickel-containing hydrogenation eatalysts. Specifically, it has been found that by the incorporation of copper in a massive nickel catalyst during the co-precipitation provides a highly active hydrogenation catalyst which can be activated at temperatures of approximately 200C.
, In one preferred embodiment of the present invention, there is provided a copper promoted massive nickel catalyst which is capable of having a reduced nickel surface area ranging from about 55 to about 100 m /g as determined by hydrogen chemisorption after reduction, at 400&, and a B.E.T. total surface area ranging from about 150 to about 300 m /g which is prepared by a specific process described herein. The B.E.T. total surface area more preferably ranges from about 225 to about 300 m /g. The amount of copper in the catalyst ranges from about 2 wt. ~ to about lO wt. % and the amount of nickel ranges from about 25 wt. % to about 50 wt. %, said wt. % of copper and nickel being based on the total weight of the catalyst.

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According to the present invention, the copper promoted massive nickel catalysts are prepared by the steps comprising comingling a solution containing copper and nickel cations with another solution containing silicate anions and suspended solid porous particles under conditions of dilution r such that the amount of dissolved nickel in the comingled reaction solution is below 0.60 moles/liter, and thereafter coprecipitating the copper, nickel and silicate ions in aqueous solution onto the solid carrier particles followed by drying and calcining of the product.
In another aspect of the present invention there is provided a

10 process for hydrogenating organic compounds by contacting a hydrogenatable organic compound with hydrogen in the presence of a reduced copper promoted massive nickel-silica catalyst capable of having a reduced metal surface area ranging from about 55 to about 100 m /g as determined by hydrogen chemisorp-tion, after reduction at ~00 C, and a B.E.T. total surface area ranging from about 150 to about 300 m /g, and preferably from about 225 to about 300 m2/g.
In a preferred embodiment of this invention, the catalyst prepared according to the process of the invention contains from 2% to 10% by weight copper, has a nickel surface area of ahout 55 to about 100 m /g, total surface area of about 150 to about 300 m /g and sodium content of about 0.1 wt. % or 20 lower based on the total weight of active catalyst.
Unlike the prior art publications that show the addition of copper -to the surface of the nickel oxide, the copper must be added to these massive nickel systems during the precipitation stage through the use of separate solutions which are preferably aqueous in nature. In a first solution, there is dissolved a source of silicate anion and in a second solution, a source of nickel cation and copper cation. To achieve the preferred proportions of - 3a -J

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z nickel and copper men-tioned already herein, in the final catalyst, the amount of nickel in the copper-nickel solution is suitably from 5 to 60 grams per liter and the amount of copper is suit~bly from 0.2 to 12 grams per liter.
Slurried within the solution containing the silicate anion is a porous support, preferably a porous silica support such as kieselguhr. The two solutions are comingled by addition of the nickel-copper containing solution to the silicate solution over a period of approximately 5 to 40 minutes. By - 3b -~ o~

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1 comingling the two pre~iously prepared solutions, the 2 amount of dissolved nickel in the reaction mlxture is kept ~haf 15 3 exceedingly low~d~ ~i,_below 0.60 moles/liter ~JIl~Jo~
4 of aqueous mixture~ This ~Lr~4~~0f the dissolved nlckel ions is essen~ial in obtaining high nickel surface area 6 catalysts. Also, ~he addition should be made a~ a substan-7 tially constant rate accompanied by vigorous mixing to in-8 crease uniformity ~n ~he ¢a~alyst forma~ion. The mixt~lre 9 is then heated to its boiling point and a preeipitating agent is added. A commonly used pracipitating agent is

11 ammoniu~ blearbonateO

12 During the prepara~ion wa~er is added ~o maintain

13 a nearly c~nstant vo~ume so th~t water lost by evaporation

14 ls continually replacedO ~he aqueou~ mixture is kept at

15 its boiling point for a period of 1 to 5 hours, it is then

16 filtered and the resulting produet ~s washed repeatedly with 7 boiling wa~erO Next ~he catalys~ is dried and calcined in 18 an ogygen source~ The finished catalyst can then be charged 19 directly lnto ~he reaction vessel, w~hout act~vation, and ae~ivated in ~he reaetion veqsel wi~h a gaseous reductant, 21 usually flow~ng hydrogenO
22 As s~a~ed prev~ously, ~he oopper~nickel containing 23 solution and the sil~cate containing so7ution are comingled 24 under conditions of dilution sueh tha~ the amoun~ of dissolv-ed n~ckel ions in the resultant aqueous mixture is main 26 ~ained exceed;ngly low thereby providlng for a high nickel 27 surface area catalys~. Additionallys however9 it is essen-28 tial in preparing the eatalyst of ~h~s i~vention, that the 29 precipitation of the catalyst be m~de from dilu~e solutions, 30 i.eO the nickel-containing solution mu~t have a nickel con-~ 8 1 ~

1 centration no greater than l.O moles/liter and the other 2 solution a silicate ion concentration no greater than 0.35 3 moles/liter. The copper concentration is determined by the 4 desired amo~n* of copper in ~he catalyst. The most prefer-5 red solu~ion used in preparing the catalyst has no more than 6 0.75 moles/li~er of nickel and 0.26 moles/liter of silicate 7 ion. This is contrasted with a more concentrated precipi-8 tation in which the solution contains up to twice as much 9 eolute.
About 30 to 9O wt. percent of the total silica 11 content of the act~vated catalyst derives from precipitated 12 silicate ions. Preferably, however, 50 to 70 wt. percent of l3 the total silica eo~tent is derived from silicate ions.
14 The remaining steps in preparing and activating the catalyst are ldentical to those described above.
l6 In more detail, the instant invention pertains to

17 the production of an improved catalyst or hydrogenation.
l8 The catalyst may be used to hydrogenate aromatics as typi-19 fied by the hydrogenation of benzene to cyclohexane, the hydrogenation of aldehydes, both saturated and unsaturated 21 to the aloohols as in the well-known oxo process, the hydro-22 genation of the double bonds in edlble ats and oils as well 23 as other olefins both straight and branched chain, the hy-24 drogenation of aromatics in white oil base stocks to prod~ce 2~ high gr~de w~ite oil~ and the hydrogenakion of nitro com-26 pounds to amines. Indeed, olefins as used herein signify ..
27 J unsaturated compounds having at least one multiple bond and 28 cont~mplate polyunsaturated compounds as well.
29 To form the catalyst, nickel and copper, as well as the sllicate ions must be coprecipitated onto a porous .

1 solid particulate support, preferably a porous sllica parti-2 culate support Initially9 two distinct solutions are pre, 3 pared; in one of these solutions is a silicate ion source 4 such as alkali silicates, i eO sod~um and potassium sili-cates, sodium meta silicate, etc~, salicic acid or hydro-6 lyzed silicone hydrideO
7 A ~econd solution, containing a source of ~ickel 8 cation and copper ca~ion is also prepared; the source of 9 nickel cation may be any of the following: nickel nitrate, nickel chloride and nickel bromide. The source of copper 11 cation may be also copper nitrate, copper chloride and cop-12 per bromideO
13 Other sources o~ nickel cation and silicate anion . -14 may be utilized a~d will be obvious to one skilled in the art 16 Porous solid particles, preferably silica parti- :
17 cles, will be slurried in ~he silicate anion solution. In 8 particular, kieselguhr, inusor~al, diatomaceous, siliceous, 19 earth., silica or ~lumina would be the source of the porous particles. The concentration of the porous solid particles 21 can be expressed as percent of the total silica in the cata-22 lyst and should be from lO to 70 percent, preferably from 23 30 to 50 percent by weight~
24 The two solutions, one solution conta ming copper and nickel cations, the other containing the silicate anion 26 are comingled at a slow rate to e~fec~ maximum mixingc.
27 I'ypically, the nickel and copper nitrate sol~tion would be 28 added to a sodium meta silicate solutivn unifonmly over 29 approximately a 5 to 40 minute period, preferably lO to 30 minute perlod. The mix~ure is then heated to the boilin~

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point and copreclpltation of copper nickel and sll:Lcate Lons must be completed. Thls may be effected by various methods known ln the art, but it is most preferred that the copreclpitatlon of copper, nlckel and silicate ions in aqueous solution containing the solid carrier particles ; be completed by addltion oE a water soluble alkaline precipitating com-pound such as ammonium bicarbonate. The alkaline ammonium precipitants are most suitable for minimizing the amount of alkali metal residue which has to be removed by washing to avoid poisoning action on the finished catalyst. In some instances, the potassium precipitants may be used where the potassium acts as a promoter rather than as a poison.
The salts of the metal are preferably the water-soluble compounds, e.g. nitrates, chlorides, formates or oxalates. The preferred catalytic metal is nickel but other catalytic metals may be used; these metals include cobalt and iron.
Following the precipitation, the mixture is maintained at the boiling point for about 1 to 5 bours, then it is filtered and washed 4 times with boiling water. Precipitated catalyst is then dried by heating for about 1 to 5 hours àt a temperature of 90 to 200C. It is;then calcined by heating in the presence of an oxygen-containing gas or air to a temper-ature in the range of 300 to 450C. for a period of 2 to 8 hours, preferably 3 to 5 hours.
After the calcining is completed, the catalyst must be reduced in order ; to activate it. Reduction is carried out in the presence of a reducing gas which is preferably hydrogen. Hydrogen is passed over the catalyst at am-bient temperature at a rate of 5 l/hr/gm catalyst to 100 ~ ,, ~,, ,:~: , :

85i8~L2 l/hr/gm catalyst, preferably 10 l/hr/gm to 30 l/hr/gm and then the temp-erature is raised to a range from 75C. to 400C, preferably 80 to 250C.
The reduction is preferably carried out a~ter the catalyst has been loaded into the reaction vessel, where the hydrogenation will be carried out, which may be either batch or continuous, the nature of the reactor will be obvious to one skilled in the art.
The resulting catalyst preferably is capable of having a nickel surface area ranging from about 55 to 100 m2/g as determined by hydrogen chemisorption, after Eeduction at 40QC, and a B.E.T. total surface area ranging from about 150 to about 300 m2/g. Also, the catalyst preferably contains about 0.1 wt. % or less of sodium and preferably from 25 wt. % to about 50 wt.% of nickel.
One particularly useful hydrogenation is the conversion of benzene to cyclohexane.
Another useful hydrogenation is the conversion of aromatics in white spirits to yield high quality solvents. The upgrading of white spirits by the process of this invention is an improvement in the treatment of such materials.
Another useful improved hydrogenation is the conversion of olefins in paraffin solvents such as denoneinizer bottoms and deoctenizer overheads.
The cDnditions for the hydrogenation reactions which have been discussed vary widely and are well known to those skilled in the art; broadly the following conditions may be utilized: temperatures - 75-400C; pressure 1 atm.- 12,000 psig; feed rate 0.2-100 v/hrlv;
H2 rate of 2,000- 10,000 SCF/B.
The oxo process is the addition of carbon monoxide and hydrogen t~ alkene~ in order to produce alcohols, aldehydes and other oxygenated organic compounds. Typical ~ -8-~L~858~LZ

alkenes which may be utilized in the process are those having 2 to 20 carbon atoms; conditions for oxo would be temperatures of 70 to 1~5C;
hydrogen to hydrocarbon mol ratio of 0.5 to 10.0 pressure of 100 to 1000 psig.
The product of such a carbonylation process generally consist6 of aldehydes, acetals~ unsaturated oxygenated materials and the like which require hydrofinishlng in a second or further hydrogenation stage.
It is to the treatment of the aldehyde product, in particular, that the present invention applies.
Hydeogenation conditions in this further reaction stage follow those generally employed in the first stage.
SPECIFIC EMBODIMENTS
Example 1 Catalyst A was prepared as follows: 8.75 gm. of Cu(NO3)2.3H20 and 112 gm. of Ni(N03)2.6H20 were dissolved i71 500 ml of distilled water, then 38 gm. of Na2Si03.9H20 was dissolved in another 500 ml of water and 5 gm.
of acid washed kieselguhr was slurried in this second solution. The second solution with the kieselguhr slurried therein was stirred vigorously while the first solution containing the copper and nickel salts was added at a uniform rate over a 20 minute period. This mixture was then heated to the boiling point and 80 gm. of NH4HCO3 was added at a uniform rate ; over a 20 minute period. The mixture was kept at the boiling point for 3 hours while stirring continued. It was then filtered and washed 5 times with boiling water, each wash consisting of 500 ml of water. The filter-cake was then dried at 120C and calcined in air for ~ hours at 400C.
The reduced nickel surface area of Catalyst A was determined by hydrogen chemisorption at 400C to be 62.0 m /g.
Ca~alyst B was prepared in the same manner as _9_ 58~;~

Catalyst A with the exception that there was no copper added. Catalyst B had a reduced nickel surface area of 65 m2/g as determined by hydrogen chemisorption after reduction at 400C and a B.E.T. total surface area of 292 m2!g.
Table I demonstrates the data from thermogravemetric analysis experiments which are presented for two massive nickel catalysts, one with 5% copper (Catalyst A) added during the precipitation step and the other (Catalyst B) without any copper added. The Table shows that the copper-containing catalyst starts to reduce significantly at about 200C lower than the catalyst without copper. It also shows that Catalyst A is substantially reduced at temperatures that can be reached in commercial hydrogenation plants whereas Catalyst B does not start to reduce signi-flcantly below about 350C.
Example 2 The data in Table II compares two catalysts for the hydro-genation of benzene. They are Catalyst A and a catalyst made by the same procedure as Catalyst A (Catalyst E) but there was no copper used in the preparation. The catalysts were pre-reduced and stabilized then re-reduced in the reactor at 204C. This temperature is not adequate to activate the catalyst that does not contain copper and it can be seen that the converslon of benzene to cyclohexane is much greater over the copper containing catalyst.

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TABLE I
CATALYST A CATALYST B

Extent of Reduction Based on reductive and nonreductive thermogravemetric Temperature analysis 100C 19% 1~%
150C 22% 17%
200C 32% 18%
250C 50% 18%
10 300C 72% 19%

350C 100% 21%
400C 100% 33%
450C 100% 57%
TABLE II

CATALYST A CATALYST B
5 % CoppPr No Cop~er Conversion of benzene30.5% 15%
to cyclohexane after 1 hour on stream Run Conditions: Temp. 100C
Press. 1 atm.
s.v. 25 W/HrlW
H2/C6H6 50 mol ratio Example_3 Catalyst C, which was prepared in the same manner as Catalyst A of E~ample 2, was tested and compared with Catalyst B in a manner designed to simulate conditions used in solvent hydrogenation.
Catalyst C had a reduced nickel surface area of 65.4 m2¦g as determined by hydrogen chemisorption after reduction at 400DC and a B.E.T. total 30~ surface area of 275 m2/g. The feed was 15% benzene in cyclohexane and the pressure was 70 psig. The data in Table III shows that Catalyst C can be activated under cond~tions used in the plant and has high activity wh~reas the catalyst without copper (Ca~alys~ B) shows almost no acti~i~y.

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TABLE I-LI

S.V. % C H % Conversion ~ W/Hr/S 6 6 of the C6H6 Catalyst C 200 18.8 -0- 100 5% Cu Catalyst B 202 18.8 14.9 0.7 no CU

Run Conditions : Press. 70 pslg., H2 to Hydrocarbon 10.5 mole ratio Feed, 15% benzene in cyclohexane Example 4 -A fur~her illustration of the low ~emperature activation of this catalyst is given in Table IV where we show the active nickel surface area for two catalysts, with and without copper, which were obtained after reduction at 200C. Catalyst D was prepared in the same manner as Catalyst B of Example 1. (Ca~alyst C had a reduced nickel surface area of 65.4 m2/g and Catalyst D had a reduced nickel surface area of 64.3 m /g, both as determined by hydrogen chemisorption after ~ reduction at 400C).

TABLE IV

CATALYST C CATALYST D
5% Cu No copper Active nickel 34.1 3.9 surface area m2/gm catalyst Therefore, the new copper-nickel-silica catalyst dis-closed in this example can be charged lnto the hydrogenation plant without undergoing the customary pre-reduction and stabilization steps that are required for the commercial hydrogenation catalysts now being used. It is clearly shown that the catalyst containlng the copper is easily reduced and develops a substantial active nickel surface area whereas the catalyst without copper does not reduce nor develop an active nickel surface area to any significant extent.

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This experiment was run to show the importance of adding the copper during the precipitation of the catalyst. In Catalyst A
(as prepared in Example 1), the copper was coprecipitated with the nickel, as taught in the instant patent application. Catalyst F was prepared by impregnating copper on the dried but uncalcined powder used to make Catalyst B. Specifically, Catalyst F was prepared by impregnating 6.85 grams of the powder with 4.8 ml of an aqueous solution of Cu(N03)2.3H)20 of proper concentration to give 5% copper on the reduced catalyst. The catalyst was then dried at 230F and calcined 4 hours at 750F. The results are shown in Table V.
TABLE V
CATALYST A CATALYST F

Percent Extent of Reduction Based on Total Loss in H~ at 700~C
Temp., C
O O O ,~

150 2~ 16 These results demonstrate the crlticality in coprecipitating the Cu and Ni with the silicate anion as opposed to adding them to the surface of the NiO as taught in the prior art.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for making a copper-promoted nickel-silica catalyst, comprising the following steps:

(a) uniformly comingling an aqueous slurry containing silicate anions and solid porous carrier particles with a solution containing nickel and copper cations, the amount of nickel metal in the copper-nickel solution being sufficient to provide an amount of about 25 to about 50 wt. % in the catalyst and the amount of copper being sufficient to provide an amount of about 2 to about 10 wt. % in the catalyst, both based on total weight of catalyst, under conditions of dilution such that the amount of dissolved nickel in the comingled reaction solution is below 0.60 moles/liter;
(b) heating the comingled reaction mixture;
(c) adding a precipitating agent to coprecipitate the copper, nickel and silicate ions onto said solid porous carrier particles; and (d) drying the product of step (c) and calcining it at a tempera-ture of 300 - 450°C.

2. The process of claim 1 wherein the catalyst is capable of having a reduced nickel surface area ranging from about 55 to about 100 m2/g, as determined by hydrogen chemisorption, after reduction at 400°C.

3. The process of claim 1 wherein the amount of copper in the copper-nickel solution ranges from about 0.2 to 12 grams per liter.

4. The process of claim 1 wherein the amount of nickel in the copper-nickel solution ranges from about 5 to about 60 grams per liter.

5. The process of claim 1 wherein the precipitating agent is ammonium bicarbonate.

6. The process of claim 1 including the step of reducing said catalyst at a temperature ranging from 75 - 400°C.

7. The process of claim 6 including the step of reducing said catalyst at a temperature ranging from 80 - 250°C.

8. A process for preparing a copper-promoted nickel-silica catalyst having a B.E.T. total surface area ranging from about 150 to about 300 m2/g, comprising the steps:
(a) uniformly comingling a first aqueous slurry containing silicate anions and solid porous carrier particles with a second solution containing nickel and copper cations, the amount of nickel metal in the copper-nickel solution is sufficient to provide an amount of about 25 to about 50 wt. % in the catalyst, and the amount of copper being sufficient to provide an amount of about 2 to about 10 wt. % in the catalyst, both based on total weight of catalyst, under conditions of dilution such that the amount of dissolved nickel in the comingled solution is below 0.60 moles/liter;
(b) heating the comingled reaction mixture to its boiling point;
(c) adding a water-soluble alkaline precipitating agent to co-precipitate the copper, nickel and silicate ions onto said solid porous carrier particles; and (d) drying the product of step (c) and calcining it at a tempera-ture of 300 - 450°C.

9. The process of claim 8 wherein the catalyst is capable of having a reduced nickel surface area ranging from about 55 to about 100 m2/g, as determined by hydrogen chemisorption, after reduction at 400°C.

10. The process of claim 9 wherein the amount of copper in the nickel-copper solution ranges from about 0.2 to 12 grams per liter.

11. The process of claim 10 wherein the amount of nickel in the nickel-copper solution ranges from about 5 to about 60 grams per liter.

12. The process of claim 9 wherein the precipitating agent is ammonium bicarbonate.

13. The process of claim 9 including the step of reducing said catalyst at a temperature ranging from 75 - 400°C.

14. The process of claim 13 including the step of reducing said catalyst at a temperature ranging from 80 - 250°C.

15. The process of claim 9 wherein the solid porous carrier parti-cles are of the group of kieselguhr, infusorial earth, diatomaceous earth, siliceous earth, silica and alumina.

16. The process of claim 9 wherein the solid porous carrier parti-cles are kieselguhr.

17. The process of claim 16 wherein the concentration of porous solid particles ranges from about 10 to about 70 wt. % of total silica in the catalyst.

18. The process of claim 17 wherein the concentration of porous solid particles ranges from about 30 to about 50 wt. % based on total silica in the catalyst.

19. The copper-promoted nickel-silica catalyst prepared by the process of claim 1, 2 or 3.

20. The copper-promoted nickel-silica catalyst prepared by the process of claim 4, 5 or 7.

21. The copper-promoted nickel-silica catalyst prepared by the process of claim 8, 9 or 10.

22. The copper-promoted nickel-silica catalyst prepared by the process of claim 11, 12 or 14.

23. The copper-promoted nickel-silica catalyst prepared by the process of claim 15, 16 or 17.

24. A process for hydrogenating organic compounds which comprises contacting at least one hydrogenatable organic compound with hydrogen in the presence of a reduced copper-promoted nickel-silica catalyst prepared by the process of claim 1 and being capable of having an active nickel surface area ranging from about 55 m2/g to about 100 m2/g as determined by hydrogen chemisorption, after reduction at 400°C, and a B.E.T. total surface area ranging from about 150 m2/g to about 300 m2/g, wherein said catalyst contains from about 2 to about 10 wt. % copper, and from about 25 to about 50 wt. % nickel, said wt. % of copper and nickel being based on the total weight of the catalyst.

25. The process of claim 24 wherein the catalyst contains about 0.1 wt. % or less sodium based on the total weight of the active catalyst.

26. The process of claim 24 wherein said catalyst contains porous solid particles comprising kieselguhr.

27. The process of claim 24 wherein said hydrogenation is conducted at a temperature ranging from about 75 to about 450°C, at a pressure ranging from about 1 atmosphere to about 12,000 psig, at a space viscosity feed rate ranging from about 0.2 to about 100 V/Hr/V and at a H2 rate ranging from about 2,000 to about 10,000 SCF/B.

28. The process of claim 24 wherein at least one of the organic com-pounds is benzene.

29. The process of claim 24 wherein at least one of the organic compounds is an aldehyde.

30. The process of claim 24 wherein the organic compounds include a mixture of a paraffin and at least one olefin.