JPS5819386A - Manufacture of hydrocarbon - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a method for producing hydrocarbons.

In particular, the present invention provides: (1) a method for producing hydrocarbons from a mixture of carbon monoxide and hydrogen using a catalyst composition, the catalyst composition converting a H2/CO mixture into an acyclic hydrocarbon; It contains seven or more metal components and a carrier that exhibit catalytic activity for the reaction of converting into , and when this carrier is in the form of a dehydrate, it has the following overall composition formula:

(/, 0±0-3) @) 2/n O/' NL
203 / y (d S s 02 + e Ge
0z ) (wherein R = /species or more heptavalent or divalent cations, M = at least 7 types of trivalent metals, 0xy≧/2, a>0., /e≧0, A crystalline material having a composition (indicated by the number of moles of oxide) represented by Table A 2θ relative strength 7, l? -1,28 1,7-9, / M/ /, ,
! i'-/, 2. ／w／
, 2.4Z −/ , 2.7
WllA otsu-/44ta Wl Yohiro-/3.7 Wl left 1-/
Otsu, /
WlZ Otsu-/'7. Ta
Wl・ri2-/9. ! W, 20
．． 2-20. Otsu W20, 7-
2 /, / W23, / -
23, + VS233-21A/
vs, 2! , Kono-IAI
, 8.2 Z 7-30. /
The values shown in Table A were determined by standard measurement methods (irradiation: Cu-K
: Wavelength: 0, / t ≠ / ♂nm) The symbols (Roman letters) shown in Table A represent the following meanings: VS = very strong; s = strong; M = moderate; W = weak; θ = An angle according to Nibragg's law.

Complete data of the X-ray powder diffraction images of seven examples of silicates that can be used in the process of the invention are shown in Table B (irradiation: Cu
-K: Wavelength: (1), /Jll-/fnm).

Table B g, o o s evening sp do, ri 0 3 otsu sp9, / 0
20 SR //, ri5 7 NL/2
．． j ,,5” 3NL/3.2G
4Z NL / 3.95 / ONL / lA 7 Tata
BD/Yoj Yu 7
BD / left ri j ta BD / 7.7
j j BD 79.3! Otsu
N.L.

, 2o, tl, o ta NI.

! 0. ? θ / ONL 2/,, r O≠ NT.

23, Ri! r ll-3sp 2≠≠0 27 SF 3 to 0 // BD. 26.70 ta
BD27, j 0 4L
NL,! 9.30 7 NL 2 'Z 90 / / BD3 /,,2
j 2 NL32.7 j 41-
NL3ku1l-OII-NL3A,03! ; BD 37,,t O≠ BD ≠! ;, 30 ta
BD*I9=strongest peak among the reflection peaks identified in this diffraction image.

The symbols listed in the “Shape of reflection peak” column in Table B represent the following meanings: sp = sharp peak; SR = shoulder (sh
NL=normal peak; BD=broad peak; θ=angle according to Nibragg's law.

As a result of the applicant's research on the method for producing the above-mentioned hydrocarbons, 1. This was found to have two drawbacks: The first drawback is that unsatisfactory results are obtained when the conversion reaction of the H2/CO mixture is carried out at the same space velocities as are commonly used in factories. One more
One disadvantage is that the method contains substantially more hydrocarbons having less than 5 carbon atoms in the molecule, while
Carbon atoms in molecules! A product containing only a small amount of -/2 hydrocarbons is obtained.

Furthermore, as a result of continuing research on the above-mentioned method, the applicant has now found that these two drawbacks can be improved by preparing the above-mentioned catalyst by a one-on exchange operation. The catalyst made in this way is H2/CO
It contains seven or more metal components that have catalytic activity for a reaction that converts a mixture into an acyclic hydrocarbon, and by bringing the raw material for this conversion reaction into contact with this catalyst, the above-mentioned Two disadvantages are improved and the conversion reaction can proceed as desired and advantageously. The metal component is preferably Fe, Ni, or C.

and Ru, and seven or more metal components can be introduced into the crystalline zeolite by an ion exchange operation. With this improvement, the conversion of the H2/Co mixture is even higher when the conversion reaction is carried out at the same space velocity as can be tolerated in a typical factory, and in addition, A reaction product containing a large amount of hydrocarbons having j-/2 carbon atoms is obtained.

The invention therefore provides a method for producing hydrocarbons from a mixture of carbon monoxide and hydrogen using a catalyst composition, the catalyst composition converting a H2/co mixture into an acyclic hydrocarbon. It contains seven or more metal components exhibiting catalytic activity for the reaction and a carrier, and when the carrier is in the form of a dehydrate, it has the following total composition formula 0 formula %) ( where R=7 or more heptavalent or covalent cations, M=at least 7 trivalent metals, Q<, a<hy≧72, d>0., /, e>0.

d-)-e = valence of H) (indicated by the number of moles of oxide), and shows an X-ray powder diffraction image particularly including the reflection peaks listed in Table A In the method for producing a hydrocarbon made of crystalline silicate-based zeolite, the seven or more metal components described above are the carrier.

The present invention relates to a method characterized in that the bonding is performed by an ion exchange operation and subsequent washing, drying, and calcination operations.

The starting material used in the process of the invention is a H2/CO mixture. This rich H2/CO mixture is most preferably produced by a steam sifting or partial combustion operation of carbon-containing material.

Examples of carbon-containing materials include: wood, beets, lignite, bituminous coal, anthracite, coke, crude oil and its fractions, tar, tar sands extracted oil, bituminous sierre. This steam gasification operation and partial combustion operation are preferably carried out at a temperature of 900-7400°C and a pressure of 10-700 par. In the method of the present invention, a moiety of H2/CO is used.

Le ratio is 0.2! It is preferable to use as a raw material a H2/CO mixture larger than , but smaller than .

The catalyst composition used in the method of the present invention contains at least seven types of crystalline silicates in addition to the metal component exhibiting catalytic activity for hydrocarbon synthesis reactions, and the silicate contains pentasil family (pentagil)
It is preferable that it is a crystalline silicate belonging to group ). This silicate is described, for example, in the following literature: "Atlas of Zeolites, Strafucha, Tides", W. M. Mayer and H.
Olson (ed., Cl971), Polycrystal, Books, Services, Pittsburgh, 4th edition: E, M.
, Franinzoyer, J.M., Pennett, R.M., Grodzuk, J.P., Cohen, J.;

V. Smith, Nature (London), 1971, vol. 277, p. 3;/2; L,'/,C,! J
-S, ``Proceedins of the Figures, International Conference, on Zeolites'' (Nables), June 2010, 1! Sun-Oto Sun, page 562.

A particularly suitable silicate for the process of the invention is crystalline silicalite (U.S. Pat. No. 1A0-1).
No. 72 specification), O and crystalline aluminosilicate Z
SM-Y (U.S. Pat. No. 3.702.1fg). Other catalyst supports suitable for use in the process of the invention are crystalline iron silicate (CIS) (UK Patent No. 1, 201.303; U.S. Pat. No. 201.303); Crystalline gallium silicate (Dutch patent application no. 7)
crystalline cobalt silicate (
Dutch Patent Application No. 110/! ≠ Specification No. 3).

Furthermore, the crystalline silicates described in European Patent Application No. Go, Zooll-J are also very suitable for use as catalyst supports in the process of the invention.

This silicate has a composition (expressed in moles of oxide) expressed by the following formula.

p(0,9±0.3)M2/n00p(aX203.b
Y2o3), 5io2(・In the above formula, M=H and/or alkali metal and/or alkaline earth metal, X=Rh, Cr and/or Sc; Y=AI, Fe and/or Ga; a′2( 1), j:b≧0: a −1−b = /
:() < p </; n = valence of M).

The catalyst composition used in the process of the present invention contains seven or more metal components that exhibit catalytic activity for the conversion reaction of H2/CO mixtures to acyclic hydrocarbons.

Catalyst components exhibiting catalytic activity for conversion reactions that convert H2/CO mixtures primarily into acyclic hydrocarbons are known as Fischer-Tropsch catalysts and are described in the literature. The catalyst component includes seven or more iron group metals or ruthenium, and optionally contains seven or more cocatalysts (those that can enhance catalytic activity and/or selectivity). It is. A suitable catalyst is ruthenium 0. / -/ 0% by weight and/or 7 or more iron group metals 0.0 j-/
0% by weight and, together with these metals, contains 7 or more cocatalysts/-30% (based on the amount of iron group metals present in the catalyst). A large number of elements can be advantageously used as cocatalysts in the catalyst reservoir used in the present invention. Examples of these elements include: alkali metals, alkaline earth metals, Part VI
Group B metals (W, Mo, Cr), Ti, Zr,
Aj, St,, All XV% Mn% Cu
%Ag SZn % Cd % Old, Pb) 5nXC
e, Th) U.

Preferably, seven or more of these cocatalysts are introduced into the support by an ion exchange operation.

Very suitable cocatalysts (or cocatalyst combinations) for the iron-containing catalyst components used in this invention include alkali metals (
a readily reducible metal (e.g. Cu or Ag), and optionally a less reducible metal (e.g. A) or Zn). Iron-containing catalyst components which can be used very advantageously in the present invention are catalyst components containing iron, potassium and copper present in a crystalline silicate zeolite as support. In the method of the present invention, when a catalyst having an iron-containing catalyst component containing K is used as a cocatalyst for improving selectivity, this
/ ,! K per i' is 0. /j g of catalyst is preferred. This is because even if a larger amount of K is added, no further improvement in selectivity will be achieved, and furthermore, the stability of the catalyst will be substantially reduced due to the deposition of carbon on the catalyst. A very suitable cocatalyst combination for the cobalt-containing catalyst component used in the present invention is a combination of an alkaline earth metal with Th, U or Ce. Examples of catalysts containing cobalt-containing catalyst components that can be used very advantageously in the present invention include cobalt present in a crystalline silicate-based zeolite as a support.

Examples include catalysts containing magnesium and thorium. Other specific examples of catalysts containing co-Glut-containing catalyst components that can be used very advantageously in the present invention include Co/Cr in a crystalline silicate-based zeolite as a support;
Co/Zr, Co/Zn ′i! or Co/Mg
Examples include catalysts containing. Very suitable cocatalysts for the nickel-containing catalysts used in the present invention are A, M
n, Th + W and U.

If it is desired to use a catalyst composition containing iron as a catalyst component with Fischer-Tropsch activity in the process of the invention, an alkali metal, a readily reducible metal (e.g. copper or silver), and an optional In particular, it is preferable to select and use iron-containing catalyst components that include a combination of cocatalysts consisting of metals that are difficult to reduce, such as aluminum or zinc. Catalysts containing iron-containing catalyst components which are very suitable for this purpose are those prepared by incorporating iron, potassium and copper in a crystalline silicate zeolite as a support by means of an ion exchange operation. When a catalyst composition prepared using iron as the catalyst component having a given Fischer-Trozosch activity is used in the process of the invention, the process can be carried out at a temperature of 2! ;0-32j℃
, pressure, 20-100 par.

If it is desired to use in the process of the invention a catalyst composition having a cobalt catalyst as catalyst component with a defined Fischer-Trobsch activity, the catalyst composition may consist of an alkaline earth metal and chromium, thorium, uranium or cerium. Preference is given to using catalyst compositions having a cobalt-containing catalyst component that includes a combination of promoters.

Cobalt catalysts which are very suitable for this purpose are those made by incorporating cobalt, magnesium and thorium by ion exchange operations in crystalline silicate zeolites as a support. Another very suitable cobalt catalyst is a crystalline silicate zeolite as a support which, in addition to cobalt, also contains seven elements of chromium, titanium, zolconium and zinc by an ion exchange operation.
Let's make it 9 times a day.

When a catalyst composition containing cobalt as a catalyst component with a given Fischer-Trozosch activity is used in the process of the invention, the process can be carried out at temperatures of 220-30°C.
Preference is given to carrying out at 0° C. and pressure/0-700 bar.

Examples of catalysts that are highly suitable for use in the process of the invention include:

(,) An ion-exchange operation is carried out on a crystalline silicate-based zeolite support using seven or more solutions of iron salts and magnesium salts, the resulting composition is washed and dried, and then it is , 0 j −/0 parts by weight and 0.023-5 parts by weight of magnesium (per 100 parts by weight of crystalline silicate zeolite support) [0.0 parts by weight of iron]. /- parts by weight and magnesium 0.0
j −,2,j In addition to the overlapping part, copper O and OS as reduction co-catalysts ~2.5 parts by weight, potassium as selectivity improving co-catalysts 0. / - /, j parts by weight (per 100 parts by weight of support) and produced by calcining at ≠oo-soo °C and carrying out a reduction operation at 1.2.3-0-≠50 °C. Particularly preferred].

Φ) An ion exchange operation is performed on the crystalline silicate-based zeolite support using seven or more solutions of cobalt salts and chromium salts, and the resulting composition is washed, dried, calcined, and then Cobalt 0.01 produced by performing a reduction operation at a temperature of -730°C
-10 parts by weight of chromium and 0.0/-,2,! parts by weight (per 100 parts by weight of crystalline silicate-based zeolite support) of a catalyst [copal] containing 0./-5 parts by weight and 0.0/-,2,! parts of chromium. 0 j −/part by weight and calcined at a temperature of 300 to 700° C., 3o.

Particularly preferred are catalysts produced by carrying out a reduction operation at a temperature of -700°C].

(c) Performing an ion exchange operation on the crystalline silicate-based zeolite support using a solution of seven or more salts of cobalt, zolconium, titanium, or chromium, and washing the resulting composition.

Dry, 3! ;0-. Calcinate at 700'ClIC,
Copal is then produced by performing a reduction operation at 200-700°C. Oj −/0 parts by weight and 0.07-2 parts by weight of zirconium, titanium or chromium
．． 5 parts by weight (crystalline silicate zeolite carrier 10O
(per part by weight).

The catalyst used in the process of the invention is obtained by subjecting the carrier to an ion exchange operation, preferably using an aqueous solution of one or more ruthenium salts or salts of iron group metals and salts of the promoter. A catalyst prepared by subsequently washing the product or composition with wash water, drying, and calcining.

It is well known that crystalline metal silicates, or silicates, have ion exchange capabilities. In a crystalline metal silicate, the valence (ELEC) of the metal in its structure can be kept in balance by including all the cations in the crystal.

This cation is usually an alkali metal cation such as sodium or potassium. The cations present in synthetic or natural aluminosilicates can be exchanged with heptavalent or multivalent ions having suitable physical dimensions and structures that allow them to diffuse into the 'intracrystalline channels' in the crystal structure. The cations present can be exchanged with other cations, such as hydrogen ions or ammonium ions. Generally, a solution of a suitable acid or salt (e.g. sulphate or nitrate) is the source of cations to be introduced into the silicate by an ion exchange operation. Can be used as

The theoretical ion exchange ability of a crystalline silicate can be expressed by the number (equivalent value) of cations such as sodium that can be introduced to keep the crystalline silicate electrically neutral. The ion exchange capacity varies depending on the particular type of sieve contained therein.In reality, not all the cations present in the silicate can be exchanged for the desired cation, and therefore the actual ion exchange The value of the effective ion exchange capacity is often a value somewhat smaller than the theoretical value of the ion exchange capacity. It will vary depending on various factors such as t-on, the type of solvent (water, alcohol, etc.), the temperature at which the ion exchange is carried out, etc. Obviously, the catalytic activity obtained by introducing into the crystalline silicate by the ion exchange reaction will vary. There are limits to the amount of metals that can be introduced.

Preferably, this ion exchange operation is carried out at a temperature within the range of 20-200°C.

After the ion exchange step is completed, the ion exchange solution is removed by filtration or the like from the zeolite containing the catalytically active metal introduced in this ion exchange operation. The zeolite is then washed, preferably with an ion exchange solvent, to remove unreacted metals. The wash is then removed by filtration or the like. The zeolite cake after washing away generally contains about 100 g of solids. After adjusting the solvent content of the zeolite, the zeolite can be shaped into shaped bodies of desired dimensions without shredding or adjustment. If desired, seven or more binders and/or extrusion aids can be added. The zeolite can then be dried and the zeolite or shaped catalyst calcined at a temperature of about 300-600 DEG C., thereby yielding the final finished catalyst.

During the preparation of the catalyst, the metal can be deposited onto the support and/or by a multi-stage operation. It is also possible to dry the catalyst-forming material (ie, the support) between one ion exchange step and the next. In the case of production of catalysts with high metal content,
It may be necessary to use multi-step manufacturing techniques. Both the iron group metal salt and the cocatalyst salt can be deposited on the support using separate solutions, or they can be
It can be deposited on the carrier using only seven solutions dissolved together.

The purpose of the process of the invention is to use a metal component selected from the group consisting of iron, cobalt, nickel and ruthenium as the metal component exhibiting catalytic activity for the conversion reaction of H2/Co mixtures into hydrocarbons. The aim is to convert as much CO in the raw material as possible into hydrocarbons in the presence of a catalyst containing seven or more types. For this purpose, the molar ratio of H2/CO in the feedstock is at least /,
0, preferably /, , 2 j or! , 2j is better.

When carrying out the process of the invention, it is very important to pass the feedstock up or down through a vertical reactor containing a fixed catalyst bed, or to pass the gaseous feedstock up through a fluidized bed. It is advantageous for The process of the invention can also be carried out using a suspension of a catalyst or catalyst composition suspended in a hydrocarbon oil. The process is preferably carried out under the following conditions: temperature/20° C., in particular I7.3-275° C.; pressure/200 g, especially 100 par.

EXAMPLES In order to more specifically illustrate the present invention, Examples are shown below.

Example/Crystalline Aluminosiliter) ZSM-j is disclosed in U.S. Patent No. 3.702. G,! i' Manufactured according to the recipe described in the specification. The obtained silicate was first subjected to 1. ! N
It was converted into ammonium type by ion exchange operation using -NH4NO3 solution. This ammonium type ZSM -j was subjected to an ion exchange operation using an aqueous solution (concentration 5% by weight) of RuC to ll-,! There was a long wait. The resulting catalyst was washed with water, dried and calcined for 2 hours in the presence of air at atmospheric pressure at 210°C.
The mixture was reduced with H2 for 2 hours under a pressure cracker.

The composition of the catalyst thus obtained was as follows.

/, 7 Ru /Otsu18102// hi2o3 (parts by weight) A gas mixture consisting of H2 and CO (H2/CO=/) was passed over this catalyst under the following conditions.

Space velocity of gas per 7 hours: / 0001CNTp
)I1. h.

Pressure crab, 20 pearls Temperature: 2 O℃ The conversion rate from this 'H2+Co' to hydrocarbons is 20
．． It was 0% by weight. The space-time yield was 67 g (
hydrocarbon) 11 (catalyst) 7 o'clock.

The selection rate is shown in the table below.

”-1+C2: 4’ 1wt.

C3+C4:/Otsu 1wt.

C6CI2 Near g % wt.

C13C19: /, j% wt.

Cro+: OJ% wt.

As is clear from the table above, the yield of desired hydrocarbons (Cs-Cs2) with boiling points in the gasoline boiling range is much higher than the yields of hydrocarbons with boiling points lower or higher than this preferred range. Ta.

The condensed liquid phase contains aromatic hydrocarbons (aromatics) at lA0
The amount of durene present was only a trace amount.

ZSM-j was produced in the same manner as in Comparative Experiment/Example/. This was impregnated with an aqueous solution of ruthenium chloride, dried, calcined in the air at OO℃ for 2 hours, and then reduced using hydrogen at a temperature of 210℃ for 2 hours under the pressure of a Hiroshima pearl. A catalyst having the following composition was prepared: /, 7Ru/Otsu 5102//Ano, 03 (parts by weight). Using this catalyst, H2/
An operation was performed to generate hydrocarbons from a CO gas mixture (H2/CO=/). The conversion rate at this time was 73% by weight. The space-time yield is x gc hydrocarbons)
/l (catalyst) at 7 o'clock. The selection rate is shown in the table below.

Cl10C2: 2! ;%wL- Ca + C4: '10% wt.

C,s　C1z: 33%wt.

C13C19: 0%wt.

C20+: 0% wt.

As mentioned above, poor results were obtained regarding the yield of the gasoline component (Cs'-Ct□). Furthermore, there were no aromatics present in this product.

Example 2 U.S. Patent No. ≠, 01. Crystalline silica was produced according to the recipe for silicalite described in Column B of Specification No. 7.21I-.

The obtained crystalline silica was first heated to 1.2N”-NT (4N
It was converted to ammonium type by ion exchange operation using O5 solution. Next, an aqueous solution of Co(NH3)6(No3)2 (concentration/
An ion exchange operation was carried out for 2≠ hours.

The resulting catalyst was then washed with water, dried and dried in the evening.

Calcination was carried out for 2 hours at 0.degree. C. and the reduction operation with hydrogen was carried out for 2≠ hours at a temperature of Taffeta 0.degree. C. and pressure/abs-.

The composition of this catalyst was as follows' / 0(1)
S i O2.2, Co (parts by weight) H2/CO mixture (H2/CO=/)
was passed under the following conditions.

/ Space velocity of gas over time: 1000iCNTpA,
h) Pressure crab, 20 Parr temperature: 2 O℃ The conversion rate of IH2+CO# to hydrocarbons was 57% by weight. Space-time yield is //29 (hydrocarbons)
/IIc catalyst) at 7 o'clock.

The selection rate is shown in the table below.

C1+C2:/Otsuchi C5+C4: /j section C5+C12: Yugchi C13-C79: Dochi C2o+23% Agent's name: Kawahara 1) - Ho

Claims (8)

[Claims] (1) A method of producing hydrocarbons from a mixture of carbon monoxide and hydrogen using a catalyst composition, wherein the catalyst composition is used in a reaction that converts a H2/CO mixture to an acyclic hydrocarbon. It contains one or more metal components and a carrier that exhibits catalytic activity toward R=one or more monovalent or divalent cations, M=at least 7 trivalent metals, 0×a≧/λ, d≧0.7, e>θ, a+e=han= consisting of a crystalline silicate-based zeolite having a composition (indicated by the number of moles of oxide) as shown in (the valence of H) and exhibiting an X-ray powder diffraction pattern including the reflection peaks listed in Table A. A method for producing hydrocarbons, characterized in that the seven or more metal components described above are bonded to the carrier by an ion exchange operation and subsequent washing, drying, and calcination operations. how to. (2) The method according to claim 1, characterized in that the method is carried out at a temperature i, zs=:≠OO°C and a pressure /-/20°C. (3) The method according to claim 1 or 2, wherein the catalyst contains iron, nickel, cobalt and/or ruthenium as a metal component. (4) The method according to any one of claims 1 to 3, wherein the catalyst contains seven or more types of silicates belonging to the intasil group of crystalline silicates. (5) Method 0 according to any one of claims 1 to ≠, wherein the catalyst contains ZSM-j and/or silicalite. (6) Claims 1 to 5, characterized in that the catalyst contains o, os-io weight percent of seven or more types of iron metals introduced by ion exchange operation. The method described in any of the above. (7) The catalyst contains 7 or more cocatalysts/-
7. The method according to any one of claims 1 to 6, wherein the method contains 0% by weight (based on the weight of iron group metals). (8) The catalyst absorbs 0.0% ruthenium. 8. The method according to any one of claims 1 to 7, characterized in that the method includes a weight ratio of /-70.