DE3226616A1 - METHOD FOR PRODUCING HYDROCARBONS - Google Patents

Description

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ B.V. The Hague, Netherlands

"Process for the production of hydrocarbons.?

Claimed priority:

July 17, 19 81 - France - No. 8114008

The present invention relates to a process for the production of hydrocarbons from a mixture of carbon monoxide and hydrogen using a catalyst combination which one or more metal components with catalytic activity for the conversion of a H2 / CO mixture contains acyclic hydrocarbons and a carrier which, consists of a crystalline silicate zeolite, which in the dehydrated form has the following overall composition, expressed in moles of oxides, has:

(1.0 + 0.3) (R) ₂ .0. / A 2Ie ₃ O ₃ /.y(d SiO ₂ + e GeO ₂ ), where R = one or more mono- or divalent cations ( en) M = at least one trivalent metal

d + e = 1 and

η = the valence of R.

and the X-ray powder diagram, including those in Table A has contained lines.

Table A.

. 2Θ Relative intensity

7.8-8.2 strong

• 8.7-9.1 'medium

11.8-12.1 weak

12.4-12.7 weak

14.6-14.9 weak

15.4 - 15.7 weak

15.8-16.1. Weak

17.6-17.9 weak

19.2-19.5 ■ Poor

20.2-20.6 weak

20.7 - 21.1 'Weak

23.1 - 23.4 ■ Very strong

23.8-24.1. Very strong

2 4.2 - 24.8 strong

29.7-30.1 medium

The values contained in Table A have been determined using standard methods. Radiation: Cu-K, wavelength: 0.15418 nm. Θ = angle according to Bragg's law.

The full X-ray powder diagram of one in the invention Method of using silicate is given in Table B (radiation: Cu-K, wavelength: 0.15418 nm).

2Θ

Table B. Description of the shape Relative intensity the line (100th I / Ij Spicy 55 Spicy 36 shoulder 20th

• yr description of Relative intensity Shape of the line (100th I / Iq) Normal 7th normal 3 normal 4th normal 10 Wide 9 Wide 7th Wide 9 Wide 5 ■ - normal 6th normal 9 normal 10 normal 4th normal 8th Spicy 10O ⁺ ·. Spicy 45 Spicy 27 Wide 11th Wide 9 ■ normal 4th normal 7th Wide 11th normal 2 normal 4th normal 4th Wide 5 . Wide 4th Wide 9

45.30

⁺ I = intensity of the strong o in the powder diagram

most individual reflection.

θ = angle according to Bragg's law. "

Investigations by the applicant on this process have shown that it has two disadvantages. On the one hand, when using space velocities which are acceptable in practice, the converted amount of the H ₂ / CO mixture is not satisfactory. On the other hand, a product is obtained in the process which essentially consists of hydrocarbons with less than 5 carbon atoms in the molecule and too few hydrocarbons with 5 to 12 carbon atoms in the molecule.

Further investigations by the applicant into this process have shown that the disadvantages mentioned above can be countered by preparing the catalyst used by ion exchange, i.e. by bringing the feedstock into contact with a catalyst which contains one or more metal components ( n) with catalytic activity for converting an H ^ / CO mixture into acyclic hydrocarbons, the metal components preferably being iron, nickel, cobalt and ruthenium and this component (s) being incorporated into the crystalline zeolite by ion exchange. In this way it is achieved not only that a higher conversion rate of the H ₂ / C0 mixture is obtained when using space velocities which are acceptable in practice, but also that the reaction product consists mainly of hydrocarbons with 5 to 12 carbons in the molecule .

The present invention therefore relates to a process for the production of hydrocarbons from a mixture of carbon monoxide and hydrogen using a catalyst combination which has one or more metal components with catalytic activity for converting an H ₂ / CO mixture into acyclic hydrocarbons and contains a support which consists of a crystalline silicate zeolite which, in the dehydrated form, has the following overall composition, expressed in moles of the oxides: (1.0 + 0.3) (R) _{2 / n} 0. / a Me ₂ O ₃ /. y (d SiO ₂ + e GeO ₂₎ , where R = one or more mono- or divalent (.s) cation (s) Me = at least one trivalent metal 0 - £ a 61

d ^ 0.1

d + e = 1 and

η = the valence of R,

and its X-ray powder diagram, including those in table

which A reproduced lines contain , / characterized by

that the metal component (s) with the carrier by ion exchange, subsequent washing, drying and calcining has (have) been combined.

In the process according to the invention, the starting material is an H ₂ / CO mixture. Such H / CO mixtures can very suitably be produced by steam gasification or partial combustion of a carbonaceous material. Such materials are, for example, wood, peat, lignite, bituminous coal, anthracite, coke, crude mineral oil and fractions thereof, as well as tars and oils extracted from tar sand and bituminous shale. The vapor gasification or partial combustion takes place preferably at a temperature of 900 to 1600 ° C. and a pressure of 10 to 100 bar. The method according to the invention is preferably based on an H / CO mixture with a molar ratio of H ₂ : CO of more than 0.25 and less than 6.

The catalyst combinations used in the process according to the invention contain in addition to metal components with catalytic activity for hydrocarbon synthesis at least a crystalline silicate, which preferably belongs to the "Pentasil" group of crystalline silicates. These silicates are in "Atlas of zeolite structure Types" by W.M. Meier and D.H. Olson (1978), Polycrystal Book Service, Pittsburgh, Pa.,

as well as .- ■

by E.M. Flaninger, J.M. Bennet, R.M. Grose, J.P. Cohen and J.V. Smith, "Nature * (London), 1978, 271, p. 512, and through

in
LVC Rees, Proceedings of the Fifth International Conference on Zeolites, (Naples) June 2-6, 1980, p. 562.

3226ϋΊ6

A particularly suitable silicate for the process according to the invention is the crystalline "silicalite" mentioned in US Pat. No. 4,061,724 and the crystalline aluminosilicate ZSM-5 described in US Pat. No. 3,702,886. Other preferred supports for the catalyst to be used in the process of the present invention are a crystalline iron silicate (CIS) (which is described in British Patent No. 1,555,928 and U.S. Patent No. 4,208,305), a crystalline gallium silicate (Dutch Patent application _{79O5643) and a} crystalline cobalt silicate (Dutch patent application No. 8101543).

In the European patent application no. 80200495 another crystalline silicate is described, which as a catalyst support is very suitable in the method according to the invention. This silicate has the following composition, expressed as follows Moles of oxides:

ρ (0.9 + 0.3) M _{2 / n} Op (aX ₂ 0 ₃ .bY ₂ 0 ₃ ) .Si0 ₂ , where M = H and / or alkali and / or alkaline earth metal, X = Rh, Cr and / or Sc

Y -Al ₁ Fe and / or Ga

a ^ 0.5; b ^ O; a + b = 1

0 ^ pZI; η = the valence of M.

The catalyst combinations used in the process according to the invention contain one or more metal components with catalytic activity for converting an H ₂ / CO mixture into acyclic hydrocarbons. ■

Catalyst components which have the ability _{to convert an H 2} / CQ mixture into essentially acyclic hydrocarbons are known in the relevant literature as Fischer-Tropsch catalysts. Such catalyst components contain one or more metal (s) of the iron group or ruthenium, optionally together with. one or more promoters) to increase the activity and / or selectivity. Suitable catalysts contain 0.1 to 10 percent by weight

-Tt-

Ruthenium and / or 0.05 to 10 percent by weight of one or several iron group metals together with one or more promoters in an amount of 1 to 50% of that in the catalyst amount of iron group metals present. Suitable promoters for the catalysts according to the invention are a variety of elements, for example alkali metals, alkaline earth metals, metals of group VIB (W, Mo, Cr), Ti, Sr, Al, Si, As, V, Mn, Cu, Ag, 2n, Cd, Bi, Pb /, Sn, Ce, Th and U. One or more of these promoters are preferred to the wearer incorporated by ion exchange. Very suitable promoter combinations for the iron catalyst component used in the present invention consist of an alkali metal, for example K, an easily reducible metal, for example Cu or Ag, as well as, if necessary, a metal that is difficult to reduce, for example Al or Zn. A very suitable iron catalyst component to be used according to the invention is a Catalyst component containing iron, potassium and copper in the crystalline silicate zeolite as a carrier. Will be in that Process according to the invention uses an iron catalyst component which contains potassium as a selectivity promoter, so preference is given to a catalyst which contains no more than 0.15 g of potassium per g of iron, as has been found is that when higher potassium concentrations are used, the selectivity does not increase any further, while the stability substantially decreases due to the deposition of carbon on the catalyst. Very suitable promoter combinations for According to the invention to be used cobalt catalyst components consist of an alkaline earth metal and thorium, or uranium Cerium.

An example of a very suitable cobalt catalyst component to be used in accordance with the process of the invention is a catalyst containing cobalt, magnesium and thorium in the crystalline silicate zeolite as a carrier. Further cobalt catalyst components to be used by the process according to the invention are catalysts that use Co / Cr, Co / Zr, Co / Zn or Co / Mg in the crystalline silicate zeolite as a carrier contain. Very suitable promoters for nickel catalyst components to be used in the process according to the invention

'IV

are aluminum, manganese, thorium, tungsten and uranium.

If a catalyst combination is to be used in the process according to the invention, in which the catalyst component with Fischer-Tropsch activity is iron, an iron catalyst component is preferably used which contains a promoter combination which consists 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 catalyst component for the present purpose is a catalyst which has been prepared by ion exchange and which contains iron, potassium and copper in the crystalline silicate zeolite as carriers. If iron is used as a catalyst component with the required Fischer-Tropsch activity in the catalyst combination, the process according to the invention is preferably carried out at a temperature of;
100 bar carried out.

a temperature of 250 to 325 ° C and a pressure of 20 to

Should a catalyst combination in the process according to the invention be used in which the catalyst component with the required Fischer-Tropsch activity is cobalt, see above For example, preference is given to a cobalt catalyst component which contains a promoter combination composed of an alkaline earth metal and chromium, thorium, uranium or cerium.

A cobalt catalyst that is very suitable for the present purpose is a catalyst produced by ion exchange, which contains cobalt, magnesium and thorium in the crystalline silicate zeolite as carriers. Others by ion exchange manufactured, very suitable cobalt catalysts are catalysts, which in addition to cobalt one of the elements chromium, titanium, zirconium and zinc in the crystalline silicate zeolite as Carrier included.

Used in the catalyst combination with cobalt as a catalyst the required Fischer-Tropsch activity is used, the inventive method is preferably used in a

3226b

Temperature from 220 to 300 ° C and a pressure from 10 to 100 carried out in cash.

Catalysts which are very suitable for the process according to the invention are

a) Catalysts containing 0.05 to 10 parts by weight of iron and 0.025 to 5 parts by weight of magnesium per 100 parts by weight of crystalline Contain silicate zeolite carriers and by ion exchange of the carrier with one or more solutions) of iron and magnesium salts, then washing and drying the Composition, calcining at a temperature of 300 to 600 C. and reducing. The special one Preference is given to those catalysts which contain 0.1 to 5 parts by weight of iron and 0.05 to 2.5 parts by weight Magnesium 0.05 to 2.5 parts by weight of copper as a reduction promoter and 0.1 to 1.5 parts by weight. Potassium as a selectivity promoter contain 100 parts by weight of carrier and have been calcined at 400 to 500 ° C and reduced at 250 to 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 per 100 parts by weight of crystalline silicate zeolite support and by ion exchange of the support with one or more solutions) of cobalt and chromium salts, subsequent washing and drying of the Composition, calcining and reducing at a temperature of 300 to 750 ° C have been prepared. Particular preference is given to catalysts which contain 0.1 to 5 parts by weight of cobalt and: ö _f 05, to 1 part by weight of chromium and an additional 1 to 5 parts by weight of potassium as a selectivity promoter - and which are both calcined at a temperature of 300 to 700.degree as well as have been reduced.

c) catalysts containing 0.05 to 10 parts by weight of cobalt and 0.01 to 2.5 parts by weight of zirconium, titanium or chromium per 100 parts by weight Contain crystalline silicate zeolite carrier and by ion exchange of a silicate carrier with one or more aqueous solutions) made of cobalt and zirconium, titanium or Chromium salts, subsequent washing and drying of the

3226Ö1Ö

»» ■ ·· w ■ »♦ w w ·« W

settlement, calcining at 350 to 700 ° C and reducing at 200 to 700 ° C have been produced.

j In the process according to the invention, catalysts are used

*, applied by ion exchange of the carrier, preferably

ι with one or more aqueous. Solutions) of ruthenium al ζ (en)

f or salts of metals of the iron group and salts of pro-

/ engines, subsequent washing with washing water, drying

; and calcining the composition.

V ■ ·

I The suitability of crystalline metal silicates for ionic

i exchange is well known. In the case of the crystalline metal

The electrovalence of the metal is in the silicates

'", Structure due to the inclusion of a cation in the crystal in

I balance. The cation is generally an alkali metal,

I * for example sodium or potassium. The cations of either

1 synthetic or naturally occurring aluminosilicates can

Sf. be exchanged for mono- or polyvalent cations, which

ί before a suitable physical size and configuration

I point to the intnacrystalline cavities in the silicate

I structure to be able to penetrate. The original cation can

I can be replaced by another cation, for example by

I a hydrogen ion or an ammonium ion. In general, can

I any suitable acid or salt solution, such as a sulphate or Ni !

II. entered, can be used as a source of cations, which are included in the.

I Silicate should be replaced.

The theoretical exchangeability of the crystalline silicate is represented by the number of cation equivalents, e.g. B. Sodium ions, which bring the electroneutral act of the crystalline silicate into equilibrium. The exchangeability varies, depending on the type of ^{molecule used:} 5fi ^{: L} ^ e ^ · In practice, not all cations contained in the silicate are readily replaced by the desired cations, so that the effective exchangeability is often somewhat below the theoretical exchangeability . The extent of the exchange depends on. Facto-

¹ ren how the type of used? ^1st cfen in * the sieve-

retained cations, the cations to be exchanged, the type of

Solvent (water, alcohol) and the exchange temperature away. Obviously, the amount of catalytically active metal is subject to that in the crystalline silicate by an ion exchange can be built in, a restriction.

The ion exchange is preferably carried out at one temperature in the range of 20 to 200 ° C.

Following the ion exchange step, the ion exchange solution from the zeolite. removed, which contains the exchanged in these catalytically active metal, for example by filtering. The zeolite is then washed, preferably with the ion exchange solvent, to remove any unreacted Remove metal, and also the washing liquid is removed, for example by filtration. The zeolite cake from which the washing liquid has been removed, ■ generally has a solids content of about 50%. The zeolite can then be used with or without further adjustment the solvent content can be brought to the desired size. If necessary, one or more binding

• ι. *. -, Ji, extrusion aids. ,, "",. ., medium and / or. can be added. The zeolite can then be dried and the shaped catalyst calcined at a temperature of about 300 to about 600 ° C to obtain the final catalyst.

For the preparation of the catalysts, the metals can be deposited on the support in one or more steps. The material can be dried between the individual ion exchange steps. For the production of catalysis * For doors with a high metal content, multi-step technology may be required will. The salts of the metals of the iron group and the salts of the promoters can be separated from several on the support Solutions or can be deposited together from a single solution.

3226b16

According to the process according to the invention, as large a proportion as possible of the carbon monoxide present in the feedstock is to be converted into hydrocarbons over a catalyst which has one or more metal components with catalytic activity for converting an H ₂ / CO mixture into hydrocarbons, the metal components being iron, Are cobalt, nickel and ruthenium. For this purpose the molar ratio of H_: CO of the feed is suitably at least 1.0 and preferably from 1.25 to 2.25.

The process according to the invention can very suitably be carried out in such a way that the feedstock is increased or down through a vertically arranged reactor which contains a fixed bed of the catalyst, or else that the gaseous feed is passed up through a fluidized catalyst bed leads. The process can also be carried out so that a suspension of the catalyst or the catalyst combination used in a hydrocarbon oil. The process is preferably carried out under the following conditions: a temperature of 125 to 350 ° C, in particular from 175 to 275 ° C, and a pressure from 1 to 150 bar and in particular from 5 to 100 bar.

The invention will now be explained with the aid of the following examples.

Example 1 .

The crystalline aluminosilicate ZSM-5 was prepared according to US Pat. No. 3,702,886. The resulting silicate was first converted into the ammonium form by ion exchange with a 2N Nil .NO solution. The ammonium form of ZSM-5 was ion-exchanged with an aqueous solution of RuCl ₀ (5 percent by weight) for 4 b hours.

•% with water,

Then the catalyst / was washed, dried and one Subjected to calcination with air at 500 ° C. for 2 hours using normal pressure and then for 2 hours

32Z6616

at 2 80 ° C and using a pressure of 4 bar with H ₂ . The resulting catalyst had the following composition:

1.7 Ru / 66 SiO ₂ / l Al ₃ O ₃ (parts by weight), a _{gas mixture consisting of H 3} and CO (H ₂ / C0 = 1) was passed over this catalyst under the following conditions:

Space velocity of the gas / h: 1000 1 (NTD) / L. h pressure: 20 bar
Temperature: 260 ° C

mixture

The converted amount of H ₂ + CO to hydrocarbons was 20 _f 0 weight percent. The yield at the space velocity used was 67 g of hydrocarbons per liter of catalyst volume / h.

The selectivity is given in the table below:

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 ₃₀ +: 0.5% by weight. From this table it can be seen that the yield of the desired _{hydrocarbons boiling in the gasoline range (C 5} -C ₁₂ ) is very high compared to those boiling below or above the preferred range.

The condensed liquid phase contained 40 percent by weight of aromatics and only traces of durol.

Comparative experiment 1 ■

- Zeolite
The ZSM-5 was manufactured according to Example 1. It was impregnated with an aqueous solution of ruthenium chloride, dried, calcined in air at 500 ° C. for 2 hours and reduced with hydrogen for 2 hours at 280 ° C. and under a pressure of 4 bar to obtain a catalyst which had the following composition : 1.7 Ru / 66 SiO "/ l Al_0_ (parts by weight). Using this catalyst under the conditions described in Example 1 were made from a

-JX-

II ,, / CO-G as mixture (H_ / CO = 1) hydrocarbons produced. The amount converted was 13 percent by weight. The yield at the space velocity used was 26 g of hydrocarbon per liter of catalyst / h. The selectivity was:
C. + C ₂ : 25% by weight
C ₃ + C.: 40% by weight
C ₅ - C ₁₂ : 35% by weight
C ₁₃ - C _1g : 0% by weight
C ₂₀ + ■: 0% by weight.

As for the yield of gasoline components (C ₁ - - C ₁ ~), a poor result was obtained. In addition, the product did not contain any aromatics.

Example2 /

It became a crystalline silicalite. according to column 6 of the US. U.S. Patent No. 4,061,724.

The crystalline silicalite obtained was first converted into the Anunoni to form by ion exchange with a 2N NH.NO_ solution. The ammonium form was ion-exchanged with an aqueous solution of Co (NH ₃ ) r (NO ₃ ) ₂ (15% by weight) for 24 hours.

The catalyst was then washed with water, dried, calcined for 2 hours at 500 ° C. and for 2 4 hours with Hydrogen at 575 ° C. and 1 bar abs. reduced.

This catalyst had the following composition: 100 SiO ₂ .2.5 Co (parts by weight).

_{An H 2} / CO mixture (H ₂ / CO = 1) was passed over this catalyst under the following conditions:

Space velocity of the gas: 1000 1 (NTD) / l * h)

3226G16

Pressure: 20 bar
Temperaturei 260 ° C

in hydrocarbons

The / converted amount of the H ^ + CO mixture was 51 percent by weight. The yield at the space velocity used was 112 g of hydrocarbons per liter Catalyst / h.

The selectivity is given in the table below:

C ₁ + C ₂ : T6 C ₃ + f ¹
^ 4 15th ^C 5 ~ P.
^C 12 ' 58 ^C 13 - ^c ₁₉ ^: 8th ^C 20 +: 3

Claims (8)

Patent claims 1. A process for the production of hydrocarbons from a mixture of carbon monoxide and hydrogen using a catalyst combination which contains one or more metal components with catalytic activity for the conversion of an H ₂ / CO mixture into acyclic hydrocarbons and a carrier, consisting of a crystalline silicate ze ο Ii then, which in the dehydrated form has the following overall composition, expressed in moles of the oxides:
(1.0 + 0.3) (R) ₂ , 0. / a Me ₂ O ₃ / y (d SiO ₂ + e GeO ₃ ), where R = one or more mono- or divalent cations ) M = at least one trivalent metal 12th d + e = 1 and η = the valence of R, and its X-ray powder diagram, among other things, in the Table A shows the lines, characterized in that the metal component (n) bonded to the support by ion exchange followed by washing, drying and calcining has been (are). 2. The method according to claim 1, characterized in that this at a temperature of 125 to 400 ° C and one Pressure of 1 to 150 bar is carried out. 3. The method according to claim 1 or 2, characterized in that the catalyst contains bisene, nickel, cobalt and / or ruthenium as metal component (s). 4, method according to one or more of the preceding Claims, characterized in that the catalyst at least contains a crystalline silicate of the "Pentasil" group. 5. The method according to one or more of the preceding claims, characterized in that the catalyst contains ZSM-5 and / or silicalite. 6. The method according to one or more of the preceding claims, characterized in that the catalyst is 0.05 to 10 percent by weight of one or more metals of the iron group contains which / have been incorporated by ion exchange. 7. The method according to one or more of the preceding claims, characterized in that the catalyst has one or more promoters in an amount of 1 to 50 percent by weight the proportion of metals in the iron group. 8. The method according to one or more of the preceding claims, characterized in that the catalyst contains 0.1 to 10 percent by weight ruthenium.