FR2509719A1 - PROCESS FOR PRODUCING HYDROCARBONS - Google Patents

Abstract

HYDROCARBON PRODUCTION PROCESS. PROCESS FOR THE PRODUCTION OF HYDROCARBONS FROM A MIXTURE OF CARBON MONOXIDE AND HYDROGEN, USING A COMBINATION OF CATALYSIS CONTAINING ONE OR MORE METAL COMPONENTS WITH CATALYTIC ACTIVITY FOR THE TRANSFORMATION OF A MIXTURE OF HCO AND HYDROCARBONS, A SUPPORT CONSTITUTE OF A CRYSTALLINE SILICATE ZEOLITH HAVING THE FOLLOWING OVERALL COMPOSITION IN DEHYDRATED FORM, EXPRESSED IN MOLES OF OXIDES: (1.0 0.3) (R) 2NO. A ME O Y (D SIO E GEO) OR R ONE OR MORE MONO- OR BIVALENT CATIONS, M AT LEAST ONE TRIVALENT METAL, O A 1; Y 12, D 0.1; E 0; D E 1, AND N THE VALENCE OF R; D E 1, AND N THE VALENCE OF R; AND HAVING AN X-RAY POWDER DIAGRAM SHOWING, AMONG OTHERS, THE REFLECTIONS GIVEN IN TABLE A, CHARACTERIZED IN THAT THE METAL COMPONENT (S) WAS (HAVE) BEEN COMBINED WITH THE SUPPORT BY EXCHANGE ION THEN BY WASHING, DRYING AND CALCINATION.

Description

i

  The present invention relates to a production process

  hydrocarbons from a mixture of carbon monoxide and hydrogen, using a combination of

  catalysts containing one or more metal components

  catalysts for the conversion of an H 2 / C O mixture to acyclic hydrocarbons and a support consisting of a crystalline silicate zeolite having

  dehydrated form, the following overall composition, ex-

  Molar winning oxide (1.0 0.3) (R) 2 / n O / a Me 203 /.

  y (d Si 02 + e Ge O 2), where R = one or more mono- or bivalent cations, M = at least one trivalent metal, 0 to 1 y> 12 d / 0.1 e O d + e = 1 , and n = the valence of R, and having an X-ray powder diagram showing, among others, the reflections given in Table A. 8.2 9.1 12.1 12.7 14.9, 7 16.1 17.9 19.5, 6 21.1 23.4 24.1 24.8, 1

Table A

  relative intensity SMWWWWWWWWW VS VS SM 7.8 8.7 11.8 12.4 14.6, 4, 8 17.6 19.2, 2, 7 23.1 23.8 24.2 29.7 The values given in Table A were determined according to conventional methods Radiation = Cu-K, wavelength: 0.15418 nm The letters of Table A used

  to indicate the relative intensities have the significant

  following: VS = very strong; S = strong; M = moderate;

  W = weak; O = angle according to Bragg's law.

  The complete x-ray powder diagram of a silicate for use in the process according to

  the invention is given in Table B (Radiation: Cu-K, lon-

wavelength: 0.15418 nm).

Table B

  Relative intensity description of the

(100 I / Io) reflection 8.00 8.90

9.10

11.95 12.55 13.25 13.95

14.75

, 55, 95 17.75 19.35

20,40

, 90 21.80 22.25 23.25

25.95

24.40, 90 26.70 27.50

29,30

  29,90 * SP SP SR NL NL NL NL BD BD BD BD NL NL NL NL SP SP SP BD BD NL NL BD

31.25 NL

32.75 4 NL

34.40 4 NL

36.05 5 BD

37.50 4 BD

, 30 9 BD

  * Io = intensity of the strongest separate reflection

in the diagram.

  The letters in Table B used to describe the reflections have the following meaning: SP = fine; SR = inflection; NL = normal; BD = large; O = angle according to

Bragg's law.

  In a research conducted by the Applicant on

  This process has proved to have two disadvantages.

  Firstly, when using flow rates acceptable in actual practice, the conversion of the H 2 / CO mixture is unsatisfactory. In addition, the process gives a product consisting essentially of hydrocarbons having less than 5 carbon atoms in the process. molecule and too little

hydrocarbons C to C 12.

  12 Another research carried out by the Applicant

  This process has shown that it is possible to

  mentioned above by preparing the catalyst

  used by ion exchange, that is to say by putting the

  in contact with a catalyst containing one or more metal components having a catalytic activity for

  the transformation of an H 2 / CO mixture into acyl hydrocarbons

  cliques, metallic components which are selected from

  in the group formed by Fe, Ni, Co and Ru, and which

  is / are deposited in the crystalline zeolite by

  In this way it is possible not only to obtain, by using flow rates acceptable in actual practice, a higher conversion of the H 2 / CO mixture, but also that the product of the reaction consists of

  predominantly in C 5 to C 12 hydrocarbons.

  The present application therefore relates to a method of

  the production of hydrocarbons from a mixture of carbon monoxide and hydrogen using a combination of catalysis containing one or more metal components having a catalytic activity for the conversion of an H 2 / CO mixture to acyclic hydrocarbons and a -

  port, consisting of a crystalline silicate zeolite a-

  in the dehydrated form the overall composition

  vante, expressed in moles of oxides:

(1.0 0.3) (R) 2 / n O / a Me 203 /.

  y (d Si O 2 + e Ge O 2), where R = one or more mono- or bivalent cations, Me = at least one trivalent metal i I o O y Y 7 / s 12, d 0.1, e 0 , d + e = 1, and n = the valence of R

  and having an X-ray powder diagram showing,

  other reflections given in Table A, characterized in that the (the) component (s) metal (s) has (have) been combined (s) with the support by ion exchange

  followed by washing, drying and calcination.

  In the process according to the invention, the product of

  part is a mixture H 2 / CO These mixtures H 2 / C O can be

  be conveniently prepared by steam gasification or

  partial combustion of a material containing carbon.

  Examples of such materials include wood, peat, lignite, bituminous coal, anthracite, coke, crude mineral oil and its fractions as well as

  tars and oils extracted from tar sands

  The steam gasification or partial combustion is preferably carried out at a temperature of 9001600 C and a pressure of 10-100 bar. In the process according to the invention, it is preferable to use an H 2 mixture. / CO with a higher H 2 / CO molar ratio

at 0.25 and below 6.

  The combinations of catalysis used in the

  according to the invention contain, in addition to catalytically active metal components for the synthesis of

  hydrocarbons, at least one crystalline silicate,

  These silicates are described in "Atlas of zeolite structure types" by WM Meier and DH Olson (1978), Polycrystal Book Service, Pittsburgh, Pa, and EM Flaninger, JM Bennet, RM. Grose, JP Cohen and JV Smith, Nature (London), 1978, 271, p 512 and by LV C. Rees, Proceedings of the Fifth International Conference

  on Zeolites ", (Naples), 2-6 June, 1980, p 562.

  As silicates particularly suitable for

  assigned according to the invention, mention must be made of "Silicalite"

  tallin mentioned in US Patent Application No. 4,061,724 and crystalline aluminosilicate ZSM-5, which is

  described in U.S. Patent Application No. 3,702,886.

  Other preferred supports for the catalyst

  in the process according to the invention are a

  crystalline iron (CIS) (described in the

  British Patent No. 1,555,928 and the United States patent application

  No. 4,208,305), a crystalline gallium silicate (US Patent Application No. 7,905,643), and a crystalline cobalt silicate (Netherlands Patent Application No.

8,101,543).

  In European patent application N 8 200 495 is described another crystalline silicate which is very suitable as a catalyst support in the process according to

  This silicate has the following composition

mole of oxides:

  p (0.9 + 0.3) M 2 / n O p (a X 203 b Y 203).

  If O 2 o M = H and / or an alkali metal and / or alkali metal

  earth; X = Rh, Cr and / or Sc; Y = Al, Fe and / or Ga; a = 0.5; b 0; a + b = 1; ## STR1 ## The catalyst combinations used in the process according to the invention contain one or more catalytically active components for the conversion.

  an H 2 / CO mixture of acyclic hydrocarbons.

  The catalyst components capable of converting an H 2 / CO mixture into especially acyclic hydrocarbons are known in the literature as Fischer-Tropsch catalysts. These catalyst components comprise one or more metals of the iron or ruthenium group together, possibly with one or more activators

  to increase activity and / or selectivity.

  Suitable lysers contain from 0.1 to 10% by weight of ruthenium and / or from 0.05 to 10% by weight of one or more iron group metals with one or more activators in an amount of 1 to 50% of the amount of iron group metals present on the catalyst as activators for

  catalysts according to the invention, a large number of

  The following may be mentioned as examples: alkali metals, alkaline earth metals, Group VIB metals (W, Mo, Cr), Ti, Zr Al, Si, As, V,

  Mn, Cu, Ag, Zn, Cd, Bi, Pb, Sn, Ce, Th and U It is pre-

  able to introduce one or more of these activators into

  Ion exchange support Combinations of activity

  very suitable for the iron catalyst component

  according to the invention consist of an alkali metal such as K, an easily reducible metal such as Cu or Ag and optionally a metal difficult to reduce, such as Al or

  Zn An example of a component of highly effective iron catalysis

  According to the invention, a catalyst component containing iron, potassium and copper in the crystalline silicate zeolite is used as the Si support. In the process according to the invention, an iron-containing catalyst component containing K is used as an activator. selectivity, a catalyst containing not more than 0.15 g of K per g of Fe is preferred, since it has been found that if higher concentrations of K are applied, the selectivity no longer increases while the stability decreases substantially. as a result of the carbon deposition on the catalyst The very appropriate activation combinations for the components

  cobalt catalysis for use according to the invention.

  An example of a very suitable cobalt catalyst component for use according to the invention is a catalyst containing an alkaline earth metal and a Th, U or Ce.

  cobalt, magnesium and thorium in the silicon zeolite

  crystalline class as a carrier Other components of

  Very suitable cobalt lyses for use according to the invention are the catalysts containing Co / Cr, Co / Zr, Co / Zn or Co / Mg in the crystalline silicate zeolite as a support. As very suitable activators for the nickel catalysis components to be used. according to the invention, mention should be made of Al, Mn, Th, W and U. In the process according to the invention, it is intended to use a combination of catalysis of which the catalyst component having Fischer-Tropsch activity. is iron, an iron catalysis component preferably containing an activation combination consisting of an alkali metal, an easily reducible metal such as copper or silver and optionally a metal that is difficult to reduce, such as aluminum or Zinc A very suitable iron catalysis component for the objective pursued here is an ion exchange catalyst containing iron, potassium and copper in the silicate zeolite.

  as a support If in the combination of cat-

  lysis, iron is used as a catalyst component having

  the desired Fischer-Tropsch activity, one conducts

  the process according to the invention at a temperature of

  250-3250 C and a pressure of 20-100 bar.

  If in the process according to the invention, it is

  It is preferred to use a catalysis combination where the catalytic component having Fischer-Tropsch activity is cobalt, a cobalt catalysis component is preferred.

  containing an activation combination consisting of a.

  alkaline earth metal and chromium, thorium, uranium or cerium. A cobalt catalyst very suitable for the present purpose is an ion exchange catalyst containing cobalt, magnesium and thorium in the

  crystalline silicate zeolite as support

  Highly suitable cobalt catalysts prepared by ion exchange are catalysts containing, besides cobalt, one of the elements chromium, titanium, zirconium and zinc in

  crystalline silicate zeolite as support.

  If in the combination of catalysis one uses co-

  balt as a catalyst with Fischer-Tropsch activity

  desired, the process is preferably carried out according to the

  vention at a temperature of 220-300 C and a pressure of

-100 bar.

  Catalysts which are very suitable for the process according to the invention are: a) catalysts containing from 0.05 to 10 parts by weight of iron and from 0.025 to 5 parts by weight of magnesium per parts by weight of crystalline silicate zeolite support

  and prepared by ion exchange of the support with one or more

  and then, by washing and drying the composition, calcining it at a temperature of 30 ° to 600 ° C. and reducing it. In particular, preference is given to catalysts containing, in addition to

  from 0.1 to 5 parts by weight of iron and from 0.05 to 2.5 parts by weight

  by weight of magnesium, 0.05 to 2.5 parts by weight

  of copper as a reduction promoter and from 0.1 to 1.5 par-

  by weight of potassium as selectivity promoter per 100 parts by weight of carrier and calcined at 400-500 ° C

and reduced to 250-450 C.

  b) catalysts containing 0.05 to 10 parts by weight of cobalt and 0.01 to 2.5 parts by weight of chromium for

  parts by weight of silica-crystalline zeolite support

  and by ion exchange of the support with one or more solutions of cobalt and chromium salts followed by washing and drying of the composition, calcination and reduction at a temperature of 300750 ° C. Catalysts containing in particular from 0.1 to 5 parts by weight of cobalt and from 0.05 to 1 part by weight of chromium, calcined at 300-700 o C and reduced to 300-700 WC; c) catalysts containing from 0.05 to 10 parts by weight of cobalt and from 0.01 to 2.5 parts by weight of zirconium, titanium or chromium per 100 parts by weight of crystalline silicate zeolite support and prepared by exchange of ions of a silicate support with one or more solutions of salts of cobalt and zirconium, titanium or chromium, then washing and drying of the composition, calcination at 350-700 WC and reduction at 200-7000 C.

  In the process according to the invention,

  catalysts which are prepared by ion exchange of the support, preferably with one or more aqueous solutions of ruthenium salts or iron group metals and activating salts, followed by washing with washing water, drying

and calcining the composition.

  The ion exchange capacity of crystalline metal silicates is well known In crystalline metal silicates, the electrovalence of the metal in the structure

  is balanced by the inclusion of a cation in the crystal.

  The cation is mostly an alkali metal, as

  sodium or potassium Cations of aluminosilica-

  Synthetic or natural can be exchanged for mono or polyvalent cations of appropriate physical size and configuration to diffuse into the intracrystalline passages in the silicate structure. The original cation may be replaced by another. cation, for example by a hydrogen ion or by a

  ammonium ion In general we can use any

  the appropriate acid or salt solution such as a sulphate or nitrate as cation source to be exchanged in the silicate.

  The theoretical exchange capacity of the crystalline silicate

  tallin is represented by the number of equivalents of

  such as sodium ions, which balance the electricity

  crystalline silicate trunceutrality The ability to

  varies according to the particular type of sieve involved.

  In practice, all the silicate cations are not

  are replaced by the desired cations, so that the effective exchange capacity is often somewhat

  less than the theoretical exchange capacity.

  This type of exchange depends on factors such as the type of

  put, the cations of the sieve, the cations to exchange, the type

  solvent (water, alcohol) and the temperature of the exchange.

  It is clear that there is a limit to the amount of catalytically active metal that can be introduced by exchange

of ions in the crystalline silicate.

  The exchange of ions is preferably carried out at a time

  between 20 and 2001 C.

  After the ion exchange step, the solution is removed.

  the ion exchange of zeolite containing the metal

  talytically active agent which is exchanged therein, for example by filtration. The zeolite is then washed, preferably with

  the ion exchange solvent, to remove the metal does not

  if not reacted and the washing liquid is removed, for example by filtration The zeolite cake

  from which the washing liquid has been removed contains

  about 50% solids With or without other adjustments

  of the solvent content, the zeolite can be

  If desired, one or more extrusion binders and / or adjuvants can be added. The zeolite can then be dried, and the shaped catalyst is calcined at a temperature between about 300.degree.

  about 6001 C, to form the ready-to-use catalyst.

  In the preparation of catalysts, metals can

  can be deposited on the support in one or more steps.

  Between the separated ion exchange steps the material can be dried for the preparation of catalysts with a

  high metal content, it may be necessary to

  to a multi-step technique The salts of the iron group metals and the salts of the activators can be deposited on the support separately from

  different solutions or together from a solution.

  In the process according to the invention, the intention is

  to transform as much as possible of the pre-

  in the hydrocarbon feedstock on a catalyst con-

  holding one or more catalytically active metal components for the conversion of an H 2 / CO mixture into hydrocarbons, metal components which are selected from

  the group consisting of iron, cobalt, nickel and

  For this purpose it is practical that the molal ratio

  re H 2 / CO in the load of at least 1.0 and preferably

1.25-2.25.

  The process according to the invention can be conducted very conveniently by passing the feed up or down through a vertically mounted reactor containing a fixed catalyst bed or passing the feeds.

  gaseous upwardly through a fluid catalyst bed.

  The process can also be carried out using a suspension of the catalyst or the catalyst combination in a hydrocarbon oil. The process is preferably carried out under the following conditions:

  125-3500 C and in particular 175-275 WC and a press

  1-150 bar and in particular 5-100 bar.

  The invention will now be clarified with reference to the following examples

Example 1

  The crystalline aluminosilicate ZSM-5 is prepared according to

  the recipe described in U.S. Patent No. 3,702,886.

  The silicate obtained is first transferred into the amine form.

  ion exchange with a 2N solution of NH 4 NO 3, the ammonium form of ZSN-5 is ion-exchanged with an aqueous solution of Ru C 13 (5% by weight) for 48 hours. The catalyst is then washed with water, dried and calcined for 2 hours at 500 ° C. with atmospheric pressure and reduced for 2 hours at 280 ° C. with H 2 The catalyst obtained has the following composition: 1.7 Ru / 66 Si O 2 / l A 1203 (parts by weight) is passed over this catalyst.

  gaseous mixture consisting of H 2 and CO (H 2 C O = 1) in

  with the following conditions: Hourly gas flow: 1000 liters (NTP) / 1 h Pressure: 20 bar

Temperature: 260 C.

  The conversion of H 2 + CO to hydrocarbons is 0% by weight. The spatio-temporal yield is 67 g of hydrocarbons per liter of catalyst volume per hour. The selectivity is given in the following table:

C 1 + C 2: 4% by weight.

C 3 + C 4: 16% by weight.

C 5 C 12: 78% by weight.

C 13 -C 19: 1.5% by weight.

C 20 +: 0.5% by weight.

  According to this table-we can see that the yield in

  desired hydrocarbons boiling in the boiling range

  Gasoline (C 5-C 12) is very high compared to boiling below and above the preferred range. The condensed liquid phase contains 40% by weight

  aromatic, and there are only traces of durene.

  Comparative Experiment 1 ZSM-5 is prepared as described in Example 1. It is impregnated with an aqueous solution of ruthenium chloride, dried, calcined for 2 hours at 500 ° C. in air and reduced. for 2 h at 280 C with hydrogen at a

  pressure of 4 bar to obtain a catalyst having the

  position: 1.7 Ru / 66 Si 02/1 to 1203 (parts by weight) Using this catalyst under the conditions described in

  Example 1, hydrocarbons are formed from a mixture of

  gaseous mixture H 2 CO (H 2 / CO = 1) The conversion is 13% by weight The spatio-temporal yield is 26 g of hydrocarbons per liter of catalyst per hour. The selectivity is:

C 1 + C 2: 25% by weight.

C 3 + C 4: 40% by weight.

C 5 C 12: 35% by weight.

C 13 C 19: 0% by weight.

C 20 +: 0% by weight.

  This gives a lower result in terms of

  components of the gasoline type (C 5 C 12).

  there are no aromatics in the product.

  Example 2 Crystalline silica is prepared according to the silicalite recipe described in column 6 of US Pat.

4,061,724.

  The crystalline silica obtained is first transferred

  in the ammonium form by ion exchange with a solution

  2 N NH 4 NO 3 The ammonium form is subjected to

  exchange of ions with an aqueous solution of Co ((NH 3) 6 N 03) 2

  (at 15% by weight) for 24 hours.

  The catalyst is then washed with water, dried,

  it is calcined for 2 hours at 500 ° C. and subjected to a

  24 h with hydrogen at 575 C and 1 bar abs.

  This catalyst has the following composition: 100 Si O 2.

2.5 Co (parts by weight).

  This catalyst is passed through a mixture H 2 / CO (CH 2 / CO = 1) by applying the following conditions: Hourly gaseous flow: 1000 liters (NTP / 1 h) Pressure: 20 bar

Temperature: 260 C.

  The conversion of H 2 + CO into hydrocarbons is 51% by weight The spatio-temporal yield is 112 g

  of hydrocarbons per liter of catalyst per hour.

  The selectivity is given in the following table:

C 1 + C 2: 16%

C 3 + C 4: 15%

C 5 C 12: 58%

C 13 C 19: 8%

C 20 +: 3%

Claims (6)

  1) Process for producing hydrocarbons from a mixture of carbon monoxide and hydrogen, using   a combination of catalysis containing one or more compounds   catalytically active metallic additives for the conversion of an H 2 / CO mixture into acyclic hydrocarbons and a support consisting of a crystalline silicate zeolite   having in dehydrated form the overall composition   v, expressed in moles of oxides (1.0 + 0.3) (R) 2 / n O / a Me 2 O 3 / y (d Si O 2 + e Ge O 2), where R = one or more mono cations or bivalent M = at least one trivalent metal 0 to 1 y 12, d 0.1 e O d + e = 1, and n = the valence of R d + e = 1, and N = the valence of R   and having an X-ray powder diagram showing,   other reflections given in Table A, characterized in that the (the) component (s) metal (s) is (have) been combined (s) with the support by ion exchange and then   by washing, drying and calcining.   2) Process as claimed in claim 1, characterized in that it is conducted at a temperature of   -400 C and a pressure of 1-150 bar.   3) Process as claimed in claims 1   or 2, characterized in that the catalyst contains iron, nickel, cobalt and / or ruthenium as metal component (s). 4) A method as claimed in any one of   preceding claims, characterized in that the cata-   lyser contains one or more members of the group "Pen- heap of crystalline silicates.   ) Process as claimed in one or more of the   preceding claims, characterized in that the cata-   lyser contains ZSM-5 and / or silicalite.   6) Process as claimed in one or more of the   preceding claims, characterized in that the cata-   The lysate contains from 0.05 to 10% by weight of one or more   iron group metals introduced by ion exchange.   7) A method as claimed in one or more of the   preceding claims, characterized in that the cata-   The lysate contains one or more activator (s) in an amount of 1 to 50% by weight of the amount of iron group metals. 8) A process as claimed in one or more of the   preceding claims, characterized in that   The catalyst contains from 0.1 to 10% by weight of ruthenium.   9) A method as claimed in claim 1,   as described above with special reference to the examples   ples. ) Hydrocarbons, as obtained by the process as claimed in one or more of the preceding claims.