DE2143608A1 - Process for the production of hydrogen-rich gas mixtures - Google Patents

Description

CHpJ.-lng. A.

Dr.-lng. \ j. KlnkefiHf O 1 / O £ η Q

Dr.'tog. W. Stockmak <L I H OOUO

Dr. w. not. W. Fiscfmr

4 *

- 37/9 * »

3? Oyo engineering

2-5 »j5-clioise _v Kasuaigaseki, Chiyoda-ku, Tokyo, Japan

Process for the production of hydrogen-rich gas genes

The invention relates to a method of production hydrogen-rich gas mixtures by catalytic steam reforming a feed of normally gaseous or liquid hydrocarbons Use of a silica-free catalyst.

In the production of hydrogen gas from hydrocarbons, that is, the conversion of normally liquid or gaseous hydrocarbons into low molecular weight products by cracking, two general processes have been widely used in this field: Λ) A process in which hydrocarbons are mixed with an oxidizing agent for partial oxidation will,

and
2) a process in which hydrocarbons and steam are heated together in a process known as steam reforming.

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The procedure 1) is applicable to a wide "range of Hydrogen charges. Applicable ranging from methane "to to distillation residue from mineral oils is enough. However, it has the clear disadvantage that it is practically pure oxygen required as the only practical oxidizing agent is.

Process 2) * is pure oxygen, albeit for cracking is not required, the area of the GftlenvJass.stoffmaterials severely limited. This is because the process is clearly sensitive to carbon deposition is. This tendency towards carbon deposition grows with it increasing molecular weight of the starting material and becomes particularly noticeable when using conventional nickel oxide catalysts. As a result, only hydrocarbons can low molecular weight used in method 2) and industrial use of hydrocarbons heavier than naphtha (light oil) was not feasible.

Another in hydrocarbon cracking to form The problem that emerges in the prior art is the poisoning effect of sulfur on the gas mixtures commonly used catalysts. This makes a desulfurization of the material used to a sulfur content less than about 0.2 ppm is required.

Steam reforming is an endothermic reaction and is desirably carried out at high temperatures. The conventional catalysts containing nickel oxide and alkali metal oxides as main constituents, however, have the disadvantage that at a high temperature, for example about 850 ^° C., this catalyst constituent with its refractory. Carrier reacts to form a solid solution and is therefore quickly inactivated.

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The invention provides a method for steam reforming various hydrocarbons without the above disadvantages.

A process for the gasification of fractions heavier than naphtha to find kerosene, light oil, etc., according to the steam reforming including an attempt was made to use such erections heavier than naphtha, and ee was found that the carbon deposition on the catalyst · generally was strong, and that the activity of the catalyst decreased rapidly under these circumstances.

In general, hydrocarbons become unstable. and your Z replacement points lower when the number of carbon atoms increases. As a result, heavy hydrocarbon cracking is possible at lower temperatures and some earlier Preliminary investigations into the cracking of these materials have been made carried out. The equilibrium composition in low temperature steam reforming contains methane to a large extent, and therefore unsuitable when higher purity hydrogen gas is desired. About that in addition, the deposition of carbonaceous material cannot be avoided.

As an example of previous research, it has been reported that the amount of methane is 31 »? ° / ° in a dry gas which is in a thermodynamic equilibrium state at 500 ⁰ C and 30 kg / cm overpressure, and the ratio of steam to carbon in the process is 3

The following examples are given to illustrate basic relationships. To show a steam regeneration reaction of hydrocarbons at a

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• Temperature above 800 C became a mixture of hydrocarbons and steam first passed through an externally heated hollow tube. The test conditions were as follows

added hydrocarbon

Amount of hydrocarbons

Mo! Ratio of steam to '
carbon

Beakti onst emp eratur
amount of gas generated

Composition of the generated gas (vol.%)

Gasification rate of carbon

Kuwait crude oil fractions with an end point of 170 ° C

6.94 g / min

4.0

1100 ⁰ C

23.2 Nl / min

H ₂ 65.5 i CH ₄ 9.6, CO 18.4 | CO ₂ 6.5f C ₂ H ₄ 0.1; C ^ K ₂ 0 »'

75.0 %

The results of the observations made during the place of the reaction made within the reaction zone are shown in FIG.

In Fig. 1, the distance between the inlet and the outlet of the reaction zone is shown on the abscissa at equal intervals and the carbon gasification rate in logarithmic scale is shown on the left ordinate. The change in the carbon gasification rate is shown in the figure by a broken line.

The one used here. Carbon gasification rate is as follows Are defined:

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Amount of carbon ^{in the} gas produced

Amount of carbon in supplied Hydrocarbons

In the same way, the selectivity is on the right oral nate shown on a logarithmic scale. The change in selectivity the gas-generating reaction for the respective components in the resulting gas mixture, which is made up of the K-dhienstoff in the supplied hydrocarbons is shown by the solid lines.

If one considers the basic relationships, as shown in Fig. shown, you can see that the topmost one is interrupted Line representing the rate of carbon gasification decreasing to a point near the outlet of the reaction zone, and this suggests that the added hydrocarbons have not reacted with steam, but only thermally in Ethylene or acetylene have been cracked. If the residence time is extended to reduce the remaining hydrocarbons, the deposited amount of carbonaceous material increases.

This is clearly indicated by the curves showing the selectivities of acetylene and ethylene, as well as by the curves showing the selectivities of steam, carbon monoxide and. Show carbon dioxide in fig.

In the production of olefins by thermal cracking of hydrocarbons, a process is used in which the residence time in the reaction zone is short, around the Avoid deposition of carbon. Is the subject

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However, the production of hydrogen can reduce the residence time cannot be shortened without an increase in the quantity of unconverted materials or intermediate products caused.

Attempts to provide a gas generation process that is intermediate to the conventional catalytic steam reforming process and the usual, non-catalytic partial oxidation proceed from the standpoint of the diversity of the starting hydrocarbons and the reaction temperature is found that any significant increase in the rate of carbon gasification can not be achieved in a reaction that takes place in a reactor without a catalyst, as described above, is carried out.

On the basis of these results, surprisingly found that catalysts with known lower Activity can be used to utilize highly active and highly sensitive steam reforging catalysts or using a Vex * driving without a catalytic converter fc use to achieve previously unattainable results'. The invention achieves the desirable results of both Methods 1 and 2 above. It has been found that such catalysts can be selected as described below, and thus the principle of the method of the invention has been achieved.

The figures are graphic representations of Daiapfcracken encountered pactors.

The Pig. 1, 2 and 3 show the relationships between changes in carbon gas conversion rates more conventionally

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Hydrocarbon feeds under steam cracking conditions,. Conversion selectivity rates in relation to the gas components, and path length, i.e. dwell time in the re & ktionsjsone.

Fig. 4 is a graph showing the relationship between the rate of carbon gasification and the reaction temperature shows.

Pig. 5 is a graph showing the relationship between the carbon gasification rate and the Mo! ratio of steam to carbon shows.

Fig. 6 is a graph showing the relationship between the change in the rate of carbon gasification and the change in the carbon gasification rate Represents beryllium oxide content in the catalyst.

Fig. 7 is a diagram showing the relationship between the change the rate of carbon gasification and the change in calcium oxide content represents in the catalyst.

Fig. 8 is a graph showing the relationship between the change in the rate of carbon gasification and the change in the content of strontium oxide represents in the catalyst.

Further exemplary experiments illustrate further basic ones Connections.

A basic component of catalysts that are commonly used in Steam reforming the lighter hydrocarbons used is nickel oxide. However, not nickel oxide, but correspondingly the above principle aluminum oxide of high purity and high stability at high temperatures and with water molecules ▼ tolerable, was selected as a species for the method according to the invention. Nickel oxide is a so-called p-type semiconductor, obviously tends to

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Accelerated carbon deposition and poisoning by sulfur in an amount of 5 ppia or more. The following The experiment was designed to study the behavior of alumina in this regard ... ";

added hydrocarbon!

Amount of coal water emitted

Molar ratio of steam to Carbon:

Reaction stone temperature: Amount of evolved gas. Composition of the evolved gas (Vol.%):

Carbon gasification rate:

KinaB-Eohölfräkt'ionen with an upper boiling point of 290 ⁰ C

7.87 g / min - -

4.0 HOO ⁰ C 32.7 Hl / min

H ₂ 63.7; CH ₄ 9.0; CO 11.9; CO ₂ 15.4 95.2 %

The in this attempt in the reaction aone during the Results observed as the reaction proceeded are shown in FIG.

Then the same reaction was carried out in the presence of gamma aluminum oxide carried out under the following conditions:

supplied hydrocarbon;

Amount of hydrocarbons: reaction temperature Amount of evolved gas:

Composition of Evolved Gas (VIJ):

Carbon gasification rate

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Minas crude fractions with an upper boiling point of 290 ⁰ C 7.67 g / min 1100 C 37.1 ⁰ Hl / min H ₂ 69.4; CH ^ 2.4 ·,

CO 14, * 5t CO ₂ 13.7 95.0 %

■ \

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The observed in this experiment in the reaction zone progresses Heaktion results are shown j in FIG. ^7.

So far, the kataiytischeii effect at high temperature above 1000 ⁰ C negative .Erwartungen vrurden in general met with, and usually such a material in an atmosphere of high temperature was considered to be pure heat transfer medium. If one compares FIGS. 1, 2 and 3, it can clearly be seen that the different results in the case of the two Aluiuiniumo: <yde can reasonably only be ascribed to different catalytic effects and not only to pure heat transfer phenomena.

A remarkably significant finding in the cases in where -aluminum oxide or γ-aluminum oxide was used in the reaction zone, is that, surprisingly. no carbon deposition at all on the catalyst surface took place. If the reaction is stopped to examine the catalyst, it is found that its The surface is clean and pure white in color, except for the inlet portion of the catalyst layer. .

Is silica built into aluminum oxide as an incidental impurity, and the concentration of the impurity increases, carbon deposition begins to occur on the surface of the catalyst. With a silicon dioxide content of about 10 wt. $ 6, the catalyst surface cannot must be kept clean and is covered with a carbon deposit within a short time.

A similar deposition also occurs when other al3 silicon dioxide, such as oxides of the elements of the IV. group of the periodic table and heavy metal oxides

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Impurities are introduced in amounts over 10 % .

Regarding these facts described above it can be seen that one of the characteristics of alumina in its newly discovered catalytic effect on acceleration 4 «? Reaction of hydrocarbons, especially of carbonaceous materials with There is steam.

Gasification of crude oil in the presence of aluminum oxide has been done, and the following have been good ones Results obtained:

added hydrocarbon: Kuwait crude oil Group »with an upper one
Boiling point below 100 ⁰ C: 10.27% by weight Naphtha: _12.58 " Kerosene and light oil: 25.89 " Lubricating oil: 29.90 " Asphalt: 20.85 " Hydrocarbon amount: 8.44 g / min Fetch ratio of steam to
Carbon i 4.0 Reaction temperature; 1100 ⁰ C Developed gas volume: 34.4 Nl / min Composition of the develop
th gas (vol.%) ' H ₂ 64.7; CH ^ 9.4; CO 12.3 J CO ₂ 13.8 Carbon gasification rate 90.3 %

Relationships between the reaction temperature to a Factor influencing the catalytic action of alumina and the rate of carbon gasification, and also between the col ratio of steam to carbon as a factor,

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which influences the catalytic reaction, and the gasification process in experiments are shown in FIGS. 4 and 5, respectively.

The influence of the reaction temperature is considerable and good results are achieved at temperatures above 1000 ^° C. In addition, the influence of the ratio of steam to carbon is relatively small.

The results obtained in one attempt! the-· shows the influence of sulfur, which, as a catalyst poison, leads to difficulties, are listed below:

added hydrocarbon: Kuwait crude oil fractions,

upper boiling point?

Composition (wt.%): Amount of hydrocarbons

Steam to carbon pick ratio

Reaction stone temperature developed gas volume Composition of the evolved gas (vol.%)

Carbon gasification rate

A fraction with a relatively high sulfur content of 4,300 ppm was used in the experiment, but ee was used no influence and no change in the catalyst used Aluminum oxide found. . ".. '" .- ·' ■

The above investigations show that aluminum oxide, used alone *, for the gasification of carbonaceous materials at temperatures above 1000 ^° C. and in particular

315 ^c > c. I, 2; CO ₂ 13.8 C 85, , 78 | H 14.07 * S 0.43 % 7.56 g / min 4.1 1100 ⁰ C 32.1 Nl / min H ₂ 64.0; CH ₄ 10.8J co r 95.9

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For the gasification of hydrocarbons with 20 % distillation residue oil, such as crude oils, with a high carbon gasification rate of over 90% . It has also been found that catalysts composed of several components, e.g. B. aluminum oxide and other ketone oxides, especially basic metal oxides, are suitable for obtaining additional, industrially advantageous results. In experiments described below, it was found that substantial Kohlenstoffabscheidung- in the gasification of hydrocarbons, in particular ψ of heavy hydrocarbon en with Rückstandsölßn, does not occur, · when catalysts are of aluminum oxide and beryllium oxide, calcium oxide and / or strontium oxide used as a main second components, and that the gasification reaction proceeds smoothly at a temperature slightly below that used when using alumina alone.

Catalysts used in the present invention include sintered products from aluminum oxide and one or more of the oxides beryllium oxide, calcium oxide and strontium oxide.

Although the special effect of each individual component

»The catalyst compositions obtained by combining these components has not yet been determined, oxides of alkaline earth metals such as beryllium oxide, Calcium oxide and strontium oxide have their own properties for controlling the dehydrogenation reactions of hydrocarbons to prevent thermal polymerisation.

Aluminum oxide accelerates the reaction of hydrocarbons with steam. If the catalysts are sintered or crystallized, aluminum oxide becomes with the alkaline earth metal oxides mainly in a spinel-like structure for elevation

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the mechanical strength of the shaped catalysts firmly connected «i

According to a theory expressed in the past , catalysts, as mentioned above, should be ^{inactivated at temperatures above 600 °} C. and only act as a heat transfer medium, since the hydrogen ion concentration on the surface of the catalyst is rapidly reduced. However, it is believed that the surprising effect of the above-described catalysts for controlling the dehydrogenation reaction of hydrocarbons to prevent carbon deposition is based on the action of the electrons of the outer shells of the atoms that form the catalysts, and that the electrons of the outer shells of the Catalysts are easily activated at high temperature. Hence the effect of the catalysts while preventing carbon deposition. remarkable at a high temperature. ". ·

The compositions of the method according to the invention Catalysts used are characterized in that the ability of E. alkaline earth metal oxides to deposit carbon to prevent, is decreased with increasing amount of aluminum oxide. Therefore, the content should be Alkaline earth metal oxide at least 10% by weight * and consequently the The aluminum oxide content should not exceed 90% by weight.

Furthermore, the range of the catalyst content of the optional calcium oxide constituent is 10-60% by weight, that of beryllium oxide 20-60% by weight and that of strontium oxide 20-60% by weight. In ternary or quaternary mixtures, the beryllium oxide content can be reduced to 6% if the content of the other optional components is as above.

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'In the present process a Reektion & tesiperatur 8 ^ 0 ⁰ C eats suitable und.kann about 1QOO ⁰ C even _t' up to 1100 ⁰ G * are the event "that raw materials are used with one, high content of heavy hydrocarbons, is a relatively high texture within this range is preferably used, and on the other hand, in the case of a high content of light hydrocarbons, a relatively low temperature "is preferably used. ... · _.

The fringing speed of the stream of reactants in the process according to the invention lies.im. Range from 1000 5000 / h. The steam to carbon molar ratio can be from 2 to 10.

The reaction can take place under atmospheric pressure or above be performed. The operating pressure is not critical and can be any pressure between atmospheric pressure and 300 at be. "■

In the reaction according to the invention can reactors with at least one fixed catalyst bed, moving bed or Spouted bed can be used.

The heat of reaction can either be generated by an external heating system be fed, in which the reactor is heated from the outside by a heat exchange wall, or by a so-called internal heating system, in which a suitable amount of oxygen or oxygen-rich air is supplied to the reactor is supplied, and in which the heat generated by partial oxidation of the raw materials is used.

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There "is no particular influence of impurities such as for example sulfur as contained in the raw materials supplied, as will be explained below. thats why There is a restriction on the composition of the raw materials within the range normally found in royal oil materials occurring areas necessary.

The invention includes the reforming of heavy oils such as crude oils as well as ITaphtha, kerosene or light oil fractions from these crude oils and mixtures of body oils and crude oils. The light oils contain 6 to 8 carbon atoms, such as heptanes, octanes and the like.

If oil is used for the feed, such as, for example, crude oils with a content of residual starting oils, the reaction should be ^{carried out at a temperature above 950 °} C. in order to avoid carbon deposits. In general, eutectic crystals of alumina and alkaline earth metal oxides are stable and durable enough for a long time at such a high temperature.

In general, heavy oils have high sulfur contents, and in the running of the invention, Kuwait crude oil with a particularly high sulfur content was used as a raw material, but no sulfur compound formed on the catalyst and no reduction in the activity of the catalyst was observed.

Beryllium oxide is relatively expensive, and can therefore be minimal set for economic reasons, its content in the catalyst. However, after tests with various compositions, it was found that the presence of free beryllium dioxide in the catalyst in addition to the

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Beryllium oxide, which is a crystalline eutectic, "in preventing carbon deposition in the Steam reforming reaction is quite effective.

In the binary system of beryllium oxide and aluminum oxide, crystalline BeO.Al ₂ O is produced relatively easily. The beryllium oxide content of the catalyst should be at least 20% by weight, preferably above 50% by weight.

Beryllium Oxide "has the following characteristic advantages, although, as mentioned above, it is expensive.

First, the carbon separation is prevented by beryl ruin oxide even at a relatively low temperature. _t

Pur the case that calcium oxide-alumina catalyst, as explained below is used, a reaction temperature of I050 is - 1 100 ⁰ C is necessary, in order to prevent carbon deposition during steam reforming of Kuwait Hohöl. On the other hand, a Berylliunoxyd-alumina catalyst used, occurs even when K _e action temperatures of 950 - 1050 ⁰ C no carbon deposition, a.

Second, the important property of thermal conductivity of beryllium oxide is extremely high, and so is thermal conductivity of the Berylliuraoxyd-containing catalyst high.

The following table shows the thermal conductivity of beryllium oxide and other oxides at 1000 ⁰ C (Kcal./mh ⁰ C):

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BeO Al ₀ O ₇ GaO SiO ^ MgO 16.56 5.04 6.12 4.32 5.76

approximately

So the thermal conductivity of beryllium oxide eats / three times as high as the other oxides listed. "''

When performing an endothermic "reaction" at high Temperature as in steam reforming using an external heating system, it is economical It is very important to maintain a low temperature on the heated surfaces of the reactor. Therefore, catalysts containing beryllium oxide are industrially advantageous because they have low reaction temperatures and, moreover, lower temperatures of the heated surface of the reactor and consequently also of the Allow heat source.

It has also been found that carbon deposition in the gasification of hydrocarbons and in particular heavy hydrocarbons containing residual oil can be switched off very substantially if catalysts, which use aluminum oxide and calcium oxide as the main constituents may be used, and the crystalline eutectic form is desirable.

Various compositions of calcium oxide and aluminum oxide were experimentally prepared and by X-ray diffraction investigated, whereby it was found that the calcium oxide content should be below 60% by weight in order to be "sufficient

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- 16 - ^:

mechanical strength for the use of the catalyst. If the calcium oxide content is above 60% by weight, it becomes free Calcium oxide is formed and tends to be powdery.

Eg it has already been stated above that the crystalline Eutectic of calcium oxide and aluminum oxide and that crystalline eutectic of beryllium oxide and aluminum oxide accelerate the cracking or reforming of hydrocarbons, particularly heavy hydrocarbons and also during the reaction the carbon separation impede. It was also found that strontium oxide has a similar, very effective effect, and that an effective catalytic effect by introducing Strontium oxide and aluminum oxide in the crystalline eutectic Form can be achieved.

Conversion of stonium oxide into shaped bodies is common practice posed considerable difficulties, but it has been found that when using a strontium oxide catalyst used in powder form or in a suitably shaped porra its catalytic effect, in particular the carbon deposition preventing effect, with the of beryllium oxide is comparable.

Compared with catalysts containing calcium oxide, catalysts containing beryllium oxide show good properties to prevent carbon deposition during cracking or reforming at lower temperatures, and their behavior in this regard is the same as that of PlaLalyzers containing strontium oxide.

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Me current cost of strontium oxide is around a string of beryllium oxide, and the discovery the fact that strontium oxide is essentially the same catalytic properties in the invention Process is therefore quite important industrially.

The sulfur content of heavy hydrocarbons is bcXarinterra.-eat high and try using

Kuvait crude oil With a special, high sulfur content- ' were carried out according to the invention, including the poisoning Effect of sulfur on the catalyst according to the invention ~ to finish. Neither the building of sulfur compounds a \ if the catalytic converters still have a reduction in efficiency the catalysts have been observed.

Further features, details and advantages of the invention result from the following description of exemplary embodiments.

In the following examples the reactor used was a tubular reactor 1000 mm long and 50 mm inner diameter, were filled into the catalyst body of 10 mm in length and 10 mm in diameter.

The tubular reactor was placed in an electric furnace and aufheist.

Kuwait crude oils in the following examples have the following properties:

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BATH ORIGINAL

85.08 0 21 * 43608 12.50 5. . ' 0.8532 (20/4 ⁰ C) 2.93 O '' C - • 0 H «= 0 S β Q ⁰ C 33.0 90.5 145, 189 253, 321, 357, 364,

specific weight elemental analysis (wt.%)

ASTM distillation IBP 10 % 20 % 30 % 40 % 50.% • '60 % / O / σ

The rough velocity of the flow of reaction coinpones im'Reaktor was 2000 h in the following examples.

The invention also encompasses the use of in the following Examples of substances not listed as fillers or binders.

example 1

Mixtures of Berylliumoxydpulver and alumina powder in the following four different ratios were mixed with water, molded, and calcined with heating at I300 ⁰ C for several hours to BeO / AlPO to obtain catalysts.

Using such catalysts, h-heptane was steam reformed, the following results were obtained:

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BeO-
salary
(Gew #) Reaction
tereperatui
( ⁰ C) Steam ■
Coals
Otoff
(MoI-
mated) Composition of the developed
Celtic gas (vol.%) co co ₂ CH ₄ C ₂ H ₄ Coal
material-
Parting
manure 10 900 5.0 H ₂ 6.2 19.5 15, α 2.5 + 10 1000 5.0 ■ 56.8 7.5 19.8 11.0 - + 20th 900 5.0 59.5 6.0 19.0 17.2 2.5 no 20th 1000 5.0 55.2 7.2 19.7 12.5 - no 50 900 5.0 60.5 5.8 19.1 ie, 5 2.5 • no 40 900 5.0 54.0 5.2 19.2 19.0 2.5 no 54.2

If BeO / AlgO ^ catalysts are used, a BeO content of 20% by weight and above preferred

Example 2 *

Kuwait crude oil was steam reformed using the same catalyst as in Example 1, with the following results were achieved:

BeO-
salary
(Wt.%) Reaction
temperature
( ⁰ C) Steam/
Coals
material
(MoI-
mate _T ) Composition of the developed
Celtic gas (Vol.?a) CO co ₂ CH ₄ C ₂ H ₄ Coal
BtOff-
Parting
manure 50
50
50 950
1000
1050 4.0
4.0
4.0 H ₂ 5.2
7.6
16.1 19.5
19.5
19.0 20.8
17.0
9.8 1.5
0.5 small amount
docile
no
no 55.0
54.5
55.2

Was Angev a fieaktionstemperatur of 950 ⁰ C in the above experiments / andt, the deposition was a very small Kenge carbon from raw materials high Kohlenstoffgehaltß

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as observed for example Kuwait-Hohöl.

Example 3

Kuwait crude oil was steam reformed using the catalyst used in Example 2 (ie BeO / Al _o 0, with a BeO content of 30% by weight) under a pressure of 30 kp / cu with the following results:

BeO
salary
[Weight ^) Seaction
temperature
C ⁰ C) Steam/
Coals
material
(MoI-
mated) Composition of the dev
Celtic gas- (Vol./j) 00 co ₂ ^. Kphlen-
Material-
Adsehei-
dunf, 30th 1050 4.0 ^Ä 2 12.1 13.2 18.0 no 57.2

Fig. 6 is a graph showing the relationship between the change in the rate of carbon gasification and the change in beryllium content in a catalyst.

Example 4

Fig. 7 shows the results of an experiment to dump reforming a light fraction of Kuwait crude oil in the presence of a calcium oxide / aluminum oxide analyzer. Operating conditions and catalyst compositions in the experiment were as follows:

Properties of the crude oil fraction:

End point 360 ⁰ C spec. weight 0.7835 Operating conditions: temperature 1000 ⁰ C pressure Atuo spherical pressure

H ₂ O / C (Mo! Ratio) 4

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Catalytic converter replacement

Al ₀ O, CrO Other inorganic

* "' Material

99.0 0 1.0 85.0 13.3 1.7 78.1 20.0 1 * 9 72.9 25.0 2.1 60.4 37.1 2.5 47.3 50.0 2.7 37.4 59.9 2.7

1 2

6 7

Pig. 7 shows that a calcium oxide content of over 10 wt.? ^, Preferably in the range from 20 "to 60 wt. 56, is effective in preventing carbon deposition.

When investigating the sulfur resistance of the invention Catalysts have found many favorable properties of the catalysts as shown below «

As shown in the following examples, the oil reforming of crude oils even with a content of 1 to 3 wt / »sulfur can be carried out with practically no reduction in the catalyst activities. It has been found that sulfur compounds of both aluminum and calcium, ie, Al ₂ S, and CaS, are unstable at high temperature, especially in the presence of steam, and that although sulfur is converted to hydrogen sulfide in the crude oils, neither CaS nor Al ^ S arises.

An examination of the sulfur content of the catalysts by means of X-ray fluorescence after their use in the

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OR & JNAL INSPECTED

Examples showed that practically no sulfur atom was present was.

Examples of steam reforming "where according to the invention Catalysts used are given below for further illustration.

Example 5

A tfaphtha faction was steam reformed. The Zusasnaensetzung the catalyst, raw material, products and carbon capture were as follows:

Catalyst composition (

Al O 4.7 Z

CaO 50.0

other inorganic.

Materials . 2 ,? . . ^: , -

Properties of the crude oil (Kuwait crude oil fraction): upper boiling point 180 ⁰ C spec. Weight . 0.7413 Elemental Analysis (wt. #) C «85.24; Y H = 14.74

S = tracks

Yield based on ■.

the hollow oil (volume) 24.2%. !

Operating conditions! '· I - ■' ^Λ fV ^ y & X

Temperature 950 ⁰ C; Pressure atmospheric pressure "■■ · '-' '· H _o 0 / C (molar ratio) 4 Space velocity 2200 h

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Composition of the reaction product., J (mol- / 0 * H ₂ - 56.6 CO = 8.4 CO ₂ - 18.0 CII ₄ - 17.0

Carbon deposition on the catalyst is not avoided observed.

Example 6

Steam reforming of another hollow oil was made using of the same catalyst as in Example 5, the following results being obtained:

Properties of crude oil (Kuwait crude oil fraction) s

upper boiling point 'JE> 0 ⁰ C • epez. Weight 0.7035 Blementarenalysis (weight #) C «85.34

. ■ '- ■■ / ■■ · ^H - 13> 86 ■ ^··: -'V,

Yield based on the crude oil (volume)

S - 1 , 26 61 % 1000 ⁰ C

Operating conditions: temperature

"Brück atmospheric pressure

H ₂ O / C (molar ratio) 4 Eftum speed 2 300 h "* ¹ :

Composition of the reaction product (Holverhälnti *) i H ₂ «59.5 CO - 10.5 CO ₂ - 16.6 CH ^ - 13.4

Carbon deposition on the catalyst was not observed.

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Although the fraction used with- a content of 1.26 Gew.?o sulfur as raw material "is, no influence was recognized by sulfur. It was found no change in the catalyst used.

Example 7

Kuwait crude oil has been steam reformed using the same catalyst as in Example 5, with the following Results obtained were:

Operating conditions:

Temperature 1100 ⁰ G

Atmospheric pressure

H 0 / C (WolverhUlntis) M-

2 _1

Space velocity 2400 h

Composition of the reaction product (KqI- ^) H ₂ - 65.6 CO = 12.8 CO ₂ = 16.1 CH ₄ = 5.5

No carbon deposition was observed on the catalyst. Although the parliamentary group with a salary of. 2.93 wt. 56 sulfur was used as the raw material , no influence of sulfur was observed. A change in the catalyst used was not found.

Example 8

Steam reforming was carried out using the same catalyst as in Example 5 under the same conditions as

oei ο

carried out in example 7, but a pressure of 30 kp / cn , the following results being obtained:

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Operating conditions:
temperature
pressure

H ₂ O / C (Holverhälntis)
EauKjje speed

1050 ° C 50 kp / cir. ²

-1

2000 II

Addition of the reaction products (Iiol-%) Ii ₂ = i> ö, 1 CO = 11.3 CO ₂ = 13.4 CH ₄ - 17.2

No carbon deposits were found on the catalyst. Although the fraction with a content of 2.93 wt.? When sulfur was used as a raw material, no influence of sulfur was found. A change in the used Catalyst was not found.

Example 9

A mixture of Berylliuraoxyd, calcium hydroxide and aluminum hydroxide was mixed with water, molded, and calcined by heating at 1300 ⁰ C for several hours, to obtain a BeO-CaO ^ ALPO catalyst.

Using the catalyst, n-heptane and Kuwait crude oil were steam reformed with the following results •became:

The catalyst composition (% by weight) was as follows: BeO »7.5 CaO- 32.0 Al ₃ O ₅ » 59.0

Raw material action
temperature
(° c) steam
Coals
material
(MoIr.
mated) Composition of the developed
Celtic gas (vol .-%) CO CO ₂ CH ^ ' C ₂ H ₄ n-heptane 900 5 H ₂ 5.5 19.5 21.0 3.0 Kuwait crude oil ·. 950 4th 55.0 5.1 19.5 20.2 1.5 Kuwait crude oil 1000 4th 55.7 9.2 18.0 15.8 0.5 Kuwait crude oil 1050 4 ' 56.5 15.4 16.0 10.5 - 58.5

209811/1693

Example 10

A mixture of Berylliumcxyd, Strontiumcarbonai and Aluiriniumhydroxyd was mixed with water, shaped and ^{calcined by heating to 1300 0} C for several hours in order to get a BeO-SrO-

to obtain.

Using the catalyst became n-heptane and Kuwait crude oil steam reformed, achieving the following results became:

The catalyst composition (% by weight) was as follows:

BeO = 6.4 SrO = 30.8 Al ₂ O 3 ⁼ , 5 CO CO 2 21. CpH ^ Raw material Reaction
fc temperature Steam/
Coals
material
(MoI-
mated) = 62.5 ,1 4.2 19th , 0 19- 3.1 900 3 , 5 5.5 19th , 0 14, 1 4 n-heptane 950 4- , 2 9.8 18th , 0 10, 0.1 Kuwait crude oil 1000 4th 15.8 16 , 0 4- - Kuwait crude oil 1050 4th , 2 Kuwait crude oil "O Composition of the developed
Celtic gas (Vol .- #) 6th H ₂ 0 52 55 57 58

Example 11

Mixtures of strontium carbonate, aluminum hydroxide and calcium hydroxide in the following three conditions have been mixed with water, molded, and calcined with heating at I300 ⁰ C for several hours to obtain SrO-Al ₂ O ₇ CaO catalysts.

Using the catalysts were made n-heptane and Kuwait crude oil steam reformed, the following results being obtained became:

20981 1/1593

Raw material relationship
CrGW. ¹ / ''
SrO Al ₀ O, 45 CaO Reaction -
temperature
( ⁰ C) steam
Coals
material Together
developed G
(Vol.-fc) CO CO ₂ ^G 2 21.0 3 r n-heptane 40 900 (MoI-
mated) H ₂ 3.5 19.7 21.5 3 ^H 4 n-heptane 10 35 45 900 3 52.7 3.8 19.5 23.2 , 2 n-heptane 20th 40 40 900 3 52.2 3.2 19.7 19.0 1 , 2 Kuwait-
Sohöl 30th 40 35 950 3 51.0 4.8 19.5 17.0 O Kuwait-
crude oil 20th 40 40 1000 4- 55.0 8.0 19.6 10.2 , 6 Kuwait-
Crude oil · 20th 40 1050 4th 54.5 16.0 17.6 , 7 20th 40 4th 56.0 Lg des
rases mm CH ₄

A slight carbon deposition was only observed for the steam reforming of Kuwait crude oil at 950 ^° C. in this example.

Example 12

Using a catalyst of the composition 36.2 wt.% SrO, 35.5 wt.% Al ₂ O ₅ , 19.5 wt.% CaO and 8.7 Gev BeO, Kuwait crude oil was steam reformed under increased pressure, the following Results obtained:

Reaction pressure reaction temperature

Steam / carbon ratio

Gas composition (Col-%)

30 kgf / cm ^£
1050 ⁰ C

₂ = 56.3 CO = 12.0

1.30 CH ₄

The reaction was continued for 24 hours, but no carbon deposition was observed.

-Patent claims-

209811/1693

Claims (16)

30 "2U3608 claims 1. Process for the production of hydrogen-free gas mixtures by catalytic steam reforming a Charging normally gaseous or liquid hydrocarbons, characterized by that the feed together with steam in the presence of a reforming catalyst made of practically silica-free Aluminum dioxide, which optionally contains 10 to 60% by weight at least one silicon dioxide-free alkaline earth oxide ε of the group of beryllium oxide, calcium oxide and strontium oxide may contain ,, heated. 2. The method according to claim 1 for the production of a vacserstoffreiche Gas mixture by catalytic cracking of hydrocarbons that are present in gas or liquid form at room temperature under atmospheric pressure, in the presence of steam under atmospheric or increased pressure, thereby marked, that a reaction temperature above 850 C is applied and a calcined product of aluminum oxide and at least one of the oxides beryllium oxide, calcium oxide and strontium oxide is used as a catalyst. 3. The method according to claim 1 or 2, characterized in that a sintered product is used as the catalyst from aluminum oxide and alkaline earth oxide is used. 4. The method according to any one of claims 1 to 3, characterized in that an aluminum oxide-beryllium oxide mixture is used as the catalyst is used· 209811/1583 2U3608 5- The method according to any one of claims 1 to 3 »thereby characterized in that an aluminum oxide-calcium oxide mixture is used as the catalyst. 6. The method according to at least one of claims 1 "to 5» characterized in that the catalyst used is an aluminum oxide-beryllium oxide-calcium oxide mixture is used. *. 7- method according to any one of claims 1 to .3, characterized characterized in that a catalyst Aluminum oxide-strontium oxide-calcium oxide mixture used will. 8. The method according to at least one of claims 1 to * 7 » characterized in that as a charge a light crude fraction is used, particularly a Kuwait crude fraction. 9. The method according to claim 8, characterized in that heptane is used as the charge will, 10. The method according to claim 8 or 9 _t, characterized in that a mixture of crude oil and light oil is used as the charge. 11. The method according to at least one of claims 1 to 4 _: and / or 8 to 10, characterized in that a Kuwait crude oil is used as the charge and a binary composition of aluminum oxide and 20 to 40% by weight of beryllium oxide is used as the catalyst . 209811/1593 21 * 3608 12. The method according to at least one of claims 1 to 3 and / or 5 to 10, thereby. marked, that as a feed a Kuwait crude oil and as a catalyst a binary composition of aluminum oxide and 20 to 60% by weight of calcium oxide used vnxd. 13. Process according to at least one of claims 1 to 5 and / or 6 to 10, characterized in that the feed is a Kuwait crude oil and "the catalyst (1) is a composition of aluminum oyster, t _# (2), 20 to 60 wt .% At least one of the oxides calcium oxide and strontium oxide and (3) 6 to 60% by weight beryllium oxide is used. 14. The method according to at least one of claims 1 to 3 and / or 7 "to 10, characterized in that that as a feed a Kuwait crude oil and as a catalyst a ternary composition of aluminum oxide, 20 to 60 wt.% Strontium oxide and 10 to 60 wt.% Calcium oxide is used. 15. The method according to at least one of claims 1 to 10, characterized in that one of ψ of the crystalline eutectics calcium oxide / aluminum oxide, Beryllium oxide / aluminum oxide and strontium oxide / aluminum oxide containing catalyst is used. 16. The method at least according to claim 3 »characterized in that a sintered composition of aluminum oxide and containing at least one of the oxides beryllium oxide, calcium oxide and strontium oxide Catalyst is used. 209811/1593 Blank page