DE1444938A1 - Hydrogenation process - Google Patents

Description

Cologne, November 27, 1962, Fu / Ax

The British Petroleum Company Limited,

Britannic House, Finsbury Circus, London ^ E.G.2 (vSng

Hydrogenation process

The invention relates to a method of hydrogenating dienes in the presence of carbon monoxide.

Consist been by the process according to the invention Gsnische, the / fabric V ater, carbon monoxide, and a highly unsaturated '') 'hydrocarbon or these components include, in the presence or absence of mono-olefins of a treatment to reduce the levels of the highly unsaturated hydrocarbon subjected by passing them in the vapor phase over a supported nickel catalyst which contains a larger proportion of the nickel in elemental form <

Under "highly unsaturated hydrocarbons" are in dienes or acetylenes are to be understood in this context. Possibly the mixtures can contain both dienes and acetylenes.

Preferably, if the mixtures contain carbon monoxide and a highly unsaturated hydrocarbon, a contain a higher proportion of the first and a lesser proportion of the latter, preferably mixtures treated that contain less than 1 col of the highly unsaturated hydrocarbon per 100 moles of carbon oxide.

ORlGIMAt

809809 / 105A

Optionally, the method according to the Erfindung.auf Ausgangsraaterialien be applied that have little ^or: contain no free hydrogen. In this case, the starting material must "be mixed with a gas containing free hydrogen> in order to obtain a mixture suitable for the treatment according to the invention". -.._ - ...-

The method is particularly suitable for the treatment of mixtures of the above-mentioned type which contain a small amount (preferably at least 0.1 COl Iiol-; v5) of a sulfur-containing compound "For example, the genes ο ine low Ilenga an thiophenes"., Tliiaeycloalkanes and / or χ Malkylnio no sulfiden contains an · - ΐ / If these compounds (hereinafter referred to as "compounds of class A ^{? l} ") are present, they preferably make a total of 5 οΐ per 100 ha of the mixture passed over the catalyst - the end.

In addition to or instead of this, the mixtures can have a slight Kenge of other sulfur compounds "" {- hereinafter referred to as' ¥ erbindunder Class, B "denotes), such as hydrogen sulfide, carbon disulfide, carbonyl disulfide, mercaptans and / or dialkyl disulfides, if these connections are present, preferably make them not more than 0.1 mole per total 100 KoI of the mixture passed over the catalyst. In general, the tolerance for compounds is of the class less than for compounds of class Λ.

The preparation of the catalyst and its activation can be carried out in any convenient manner. The following three cathodes are only described as an example.

a) The catalyst can be applied to the support by impregnation by adding a nickel salt, e.g. nickel nitrate, dissolved in water and the carrier material is impregnated with the solution will »The carrier material is appropriately in the form of Granules or tablets of any size made from the ground carrier material. ! laugh at the impregnation the catalyst is dried and then lies in a Form in which it can be stored for long periods of time without damage. The catalyst must be ready for use

809809/1054 - _-, -

3hitzen zv / ecl: s setting of the salses are activated. in the In the case of the nitrate, a temperature of about 50 bia is required for this 550 ° is required, at which the nickel is converted into the oxide. The final activation by reduction su metallic Kickel can be in flowing water or hydrogen Gas at a temperature of 150 to 600 ° and one Print from 0 to 14 atLi. The duration of treatment depends before the temperature. As typical conditions when using of gepiolite as a catalyst support cones 16 hours at 500 ° and normal pressure infrared, but 2 · ^ s does not occur Damage to the sapiolite when it is brought to a temperet.ur is heated above 600 °.

b) The catalyst can by mixing dry nickel formate with the powdery catalyst support and subsequent granulation of the mixture produced v / ground. This method has the advantage that a salt such as kickelformate, in a non-oxidizing atmosphere, e.g. in an inert gas or in hydrogen, at a temperature ν, ρη 150 to 3C0 ° immediately su liickel is reduced (without the detour via the üxydstufe). A treatment time is usually at 250 ° of 4 hours is sufficient. This mode of operation has the advantage that it is not necessary to use large amounts of catalyst To heat temperatures of 500 ° and above.

c) The catalyst can be prepared according to a cathode, ^ 5 in which the water-soluble complex is used is formed, worm liickelfori.dat aich dissolves in ammonia « This complex collapses on heating, whereby again liickelformiat is obtained. When using this water-soluble complex, catalysts can be impregnated from iiorma- ! prove water-insoluble compounds, such as nickel formate, getting produced. The compound is, in an ammonia solution dissolved and the solution to impregnate the granulated Support material used. The catalyst is then dried and activated in the manner described under b}.

After the reduction, the nickel catalyst must not with "" the

809809 / i054

Come into contact with air, otherwise spontaneous oxidation of the Nickels su Rickeloxyd can take place.

The activated catalyst preferably contains from 2 to 20% by weight elemental nickel, based on the total weight of the Kataly ™ sators.

For treatment with a sulfur-containing material and. are suitable for use in the method according to the invention Nickel catalysts on aluminum oxide, kieselguhr, chalk and silica gel as a carrier. Is preferred as a catalyst · Nickel on sepiolite.

Sepiolite is a commercially available clay mineral that occurs naturally and can also be produced synthetically. It has the ideal formula H, Mg ₉ Si ₁₂ O ^ ₀ (OH) ₁₀ .6 H ₂ O and is also known as meerschaum. Further details on sepiolite and its properties are in "Chemistry and Industry" dated

November 16, 1957 to be found on pages 1492-1495. «-

Sepiolite has compared to some other carriers, such as aluminum oxide, the advantage that the nickel salt during heating of the catalyst for the purpose of converting the nickel salt into the . Oxide does not react with the sepiolite and the final reduction can be carried out at a lower temperature, than it is necessary for nickel-aluminum oxide catalysts *

The cata- 'consisting of the elemental nickel and the carrier lysator has an undesirably high activity and its selectivity is usually below a sufficient level. In general the catalyst must be subjected to a partial sulfurization to improve its selectivity. If the starting material does not contain sulfur compounds, you can Foreign sulfur compounds, preferably those of class A, either alone or in admixture with a diluent be passed over the catalyst until it has the required Has absorbed the amount of sulfur. A suitable ver

driving is the subject of the German patent ...........

(Patent application B 6Ö 745 IVb / 12 o) by the applicant.

If the starting material to be treated is organic sulfur

809809 / 105A Ut & etc.

1444338

contains compounds, the sulphurisation can occur in the beginning during the passage of the output it siuat it ials over the catalyst can be achieved. Natural is during this beginning time the selectivity of the catalyst for the hydrogenation of dienes in the presence of carbon monoxide is low. However, it rises to the extent to which the catalyst absorbs sulfur. Preferably the sulfurization takes place first at a temperature which is below the ./ert, box dei .: dio hydrogenation instead of. finds .. The temperature will then, gradually, up to at least the height at which the catalyst "starts", i. e. at which the hydrogenation takes place. Preferably, the temperature is further increased beyond the limit to one Value ■ increased at which both the activity and the Selectivity are satisfactory.

It _; wor | le. found that the rate of _{GchwefelaufnahE.ie; i} decreases by the catalyst i.iit of time, and that after achieving a good selectivity, the rate of sulfur uptake is very low, so that it is possible that. 'i. Procedure to be carried out under practically constant conditions. Usually, however, it proves to be expedient to gradually increase the reaction temperature during the running time of the catalyst.

.Spwohl the sulfurization of the catalyst and carrying out the process of the invention may genäß at each 25- ~, -fjpAss & mden pressure - vacuum ITormaldruck, pressure - -erfol- ^{■: g.äii.} If appropriate, the treatment of the catalyst can be carried out in the presence of water.

The amount of sulfur-containing reacted with the catalyst Material is usually chosen to be from 1 to 40% Sulfur, based on the elementary liickel content of the untreated catalyst.

It turned out that ·· that at normal pressure and after the sulphurisation of the catalyst usually has a lower term: temperature grense is present =, - at which the hydrogenation of the dienes begins * Below

809809/1054

those used by the applicant, in the following examples mentioned. Conditions is .this limit in the, range from 150 to 160 °. Usually at temperatures below 400 ° and at times worked below 250 °. ._, - .. -. ■ ·.,. ,,.

In general, the process is carried out continuously with des Performed starting material present in the gas phase.

Given! Al3.s, the hydration can be carried out using an from T / ater substance susarcr.ien with inert components existing Gas. In the presence of inert components

gas
) contains / preferably at least 25 Hol- ^ hydrogen, the proportion of which is expediently in the range from 25 to 90 IC0I- / 3 *

The preferred gas is the residual gas from a platformer system. Gases containing 70 Ilol-fj hydrogen are suitable. Typical is a gas that consists of 70 ΓΙο1- £ hydrogen and 30 tlol- ^ methane L5 consists. The residual gases from steam cracking, catalytic cracking and dehydrogenation are also suitable of hydrocarbons.

The spatial flow rate is preferably higher 200 V / V / h In general, values up to> 0 SOO V / V / hour have been shown. and even up to 1500 V / V / hour. as suitable It may prove useful to gradually reduce the space velocity during the catalyst life.

• Suitable starting materials are simple gas mixtures, for example carbon oxide and a diene or carbon oxide and an acetylene or mixtures which a) one or more other components which can be hydrogenated but which are not hydrogenated under the conditions used, e.g. olefins , in particular ethylene, propylene and / or butenes, amd / or b) contain one or more non-hydrogenated components, for example paraffins, in particular methane, ethane, propane and / or butanes * - For example, carbon gas>^; Town gas, generator gas or water gas or mixtures of two or more of these gases can be used as starting materials.

809809/10 5 4 - ^ original

example 1

The sulfurization of a catalyst with the aid of a sulfur-containing starting material is illustrated. As a starting material a coal gas of the following composition was used (excluding the sulfur-containing compounds):

Table 1 ) 54.2 Πο1-ί4 (by difference) Il hydrogen ) Carbon dioxide 36.9 » methane Tt air ) 1.2 It Ethane 1 1.6 Ethylene 3.7 dd propane 0.4 Tt Carbon dioxide 0.4 η Propylene 1.1 It » i-butane 0.11 n-butane 0.15 tj acetylene 0.05 II Butene 0.04 Pentanes 1,3-butadiene

Sulfur compounds were in an amount of 200 parts each Million (calculated as sulfur) are available. The catalyst used was made by impregnating granulated sepiolite C5 with a nickel formate solution in aqueous ammonia and drying manufactured. The catalyst was heated in flowing water (1000 V / V / hour) for one hour at 250 °. This catalyst contained 9.95% by weight of nickel "

An experiment with the above coal gas was carried out with the; freshly activated nickel catalyst at 600 - ß00 V / v / h. and normal printing carried out. The gaseous products were analyzed by gas chromatography. . ';

During the duration of the experiment, during which the sulphurisation took place with the formation of the ready-to-use catalyst, the temperature was 35 °. You -. Nirda then - then to 60 °,

<809809/1054

100 °, 130 ° and 150 ° increased.

At 30 and 60 ° the dienes and acetylenes were partially removed (50-80 £ j). A temperature increase to 100 ° resulted in virtually complete removal of the dienes and acetylenes (down to less than 100 parts per ilillion). When using a temperature of 130 °, the content of dienes and acetylenes by more than $ 90 was lowered at a period of hours and east of I5O ⁰ and a run time of 14 hours.

The catalyst was then analyzed and found to be 0.305 G & vr.-fo sulfur (atoric ratio S / Ni = 0.071). held. At this stage the catalyst was in the appropriate condition to effect the selective hydrogenation of the dienes '· · / ·' * "

The change in selectivity during the conditioning of the catalyst is illustrated by Table 2, from which the change in the concentration of C _? -C.-monoolefins and 'Cp-C ^ paraffins during the pretreatment of the catalyst .ist. _Λ '"

Table 2 . ■ -, · '■

" Running time in hours ' 0 - β 8 - 14 14 - 17

Mean sales too

Monoolefins in moles- $,. ...

based on the stake: '- 0.6 + 0.1 + 0.3

Mean sales too
'Paraffins, Kol- $, · related'. .

on the bet: .- ■■ - + cj, ß>. + 0.4. 0.

These results indicate that the catalyst with progressive sulfurization for the hydrogenation of acetylenes and dienes to olefins without the formation of paraffins more selective will. ',. · '·'

Example 2

Illustrates using the sulfurization of the catalyst Help from thiophene. '■. "..

980 9/10 54 '■ ■'. "■■ ·

.ORIGINAL IMSPECTED

-I-

The catalyst was prepared in the manner described in Example 1 • established and activated. It was subjected to partial felling by adding a mixture containing 2% by weight of thiophene of thiophene and n-heptane for 45 minutes at 100 ° and V / Y / h. ' as well as normal pressure was passed over him. This catalyst became "for the treatment of coal gas of the following composition (excluding the sulfur compounds) used:

Table 3

-Sa (by difference)

Hydrogen, 59.95 . ■ Rohlenoxid ., Ke ₁ than -. ,, Ι 30.5 . Air .._,,..·. . ) Ethane 1.4 Ethylene 2.4 ^; Propaneί -) 3 pounds . Carbon dioxide) * Propylene 0.6 Isobutane 0.4 n-But on 0.7 acetylene 0.10 Butene 0.11 , .Pentanes 0.02 1,3-butadiene 0.02

It Il It

. . Acetylene 0.10 "

It

The test was carried out at normal pressure. At all temperatures up to 152 ° the reduction in the acetylene and diene content was below 10 ',' ·. Above 150 ° there were more than 90 col- $ the acetylenes removed. This experiment was carried out for a period of 100 hours with no noticeable deactivation (mean space velocity 580 V / V / hour up to the 40th hour and 330 V / V- / hour, from the 40th to the 100th hour). Driving During the first 14 hours, the catalyst was sulphurised until it was ready for operation.

80980 9/10 54.

Example 3

10 cur of one consisting of hickelfonaiate on sepiolite Fresh catalyst were activated by leaving the catalyst in hydrogen at 250 for 4 hours and a flow rate from 1000 V / V / h was held. The catalyst was then used to treat town gas at space velocity from 550 - 600 V / V / h (calculated as gas) and "at 'Norruaidruck used. At the beginning the reaction temperature was 160 °. Certain quantities of town gas are supplied to a gas container

.0 taken a time frame of about 30 hours. The attempt was then interrupted to remove the gas container from the town gas line again to fill. The composition of the town gas was that same as given in Example 1.

The composition of the starting material and product .5 at various times during the experiment is given in Table 4. Han sees that the acetylene and butadiene content has been reduced to less than 100 parts per million (limit of detectability), except when the temperature fell below 155 °, when butadiene was just being detected. At the beginning ', 0 the products were over-hydrogenated and most of the monoolefins were hydrogenated to paraffins. After a running time of about 50 hours, the catalyst was made ready for operation by the sulfur compounds present in the starting material, ie it was now selective for the removal of acetylene and diene. . . . , ...

The sulfur content of the "starting material" was "about" 200 parts per million, calculated as sulfur. The 'sulfur was' mainly present in the form of carbon disulfide and COS.

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' Table 4

Run- cataly- acetylene butadiene- C ₂ ⁺ Co- C ₂ -Co- methane +

. zait, sator- 1.3, ppm. Olefins, paraf- CO,

Hour tomp. ppm. llol- '/ i fine, Kol-' / S

C _ Hol- ¹ , *

A 160 + 5 640 360 2.59 3.Ö0 29.6 100 100 0.15 6.50 20.4 sentence + 100 100 1.33 4.72 27.9 2 152 100 • 100 2.29 3.07 28.0 21 100 100 2.92 4.37 29.2 '45 100 about 100 2.9 ß 4.06 20.9 95 ^; 155

201 160 100 100 2, i! L 4.44 31.8

The sulfur content of the catalyst used was 1.08 wt. J «corresponding to an S / iii atomic ratio of 0.20 ·

Example 4

The experiment described in Example 3 was carried out, but with Boj
applied v / urde,

but at Bocinn a reaction temperature of 250 °

The Srgabnioso raised in Table 5 show that During the 2100 hour test for acetylene and butadiene except for one niodricca word (less than 100 parts per million) were removed · At the beginning the olefins present were complete hydrogenated to paraffins, roofed about The catalyst was selective for up to 200 hours and only hydrogenated the acetylene and butadione antcilo. Finally dee Experiments, the catalyst temperature was lowered. Doi about 200 ° began to appear, while acetylene only began to appear after a lowering of the Tewparatur to 160 ° occurred.

0980 9/1054

BAD ORIGINAi

Lauf- Kataly-2sit, Sator-Std. temp.

Acetylene,

ppm

Butadiene

1.3

Olefi
KoI

no

F'äraf »

fine,

Mgl.-iJ

Use +

610

2.46 3.70

25th

107

151

200

301

522

761

1001

1OJ36

1151
1171
1195
1213

> 25O +10

207
191
1Ö0
161

<100
<100
<100
<100
<100
<100
<100
<100
<100
<100

<1OO

<100

<100

600

<100 <100 <100 <100 <100 <100 <100 <100 <100 <10C

about 100

about 200

about 100

300

0
0

track
0.93
2.27
2.59
2.23
2.35
2.52
2.45

2.29
2.61

2.24
2.38

8.3Ö

5.77
3.06
4.10
4.63
3.90
3.80
4.24

3.75
3.70
4.14

KoI

29.4

66.5

32.8 31.2

31.1 29 * 9 30.0 30.3 30.9 2? _s U 26.1

26.9 2β, 6 20.1 27.3

^x These values are high because of the high hydrogen consumption during the first test phase · The actual mode of operation according to the invention was maintained from the 200th hour onwards
obtain.

The sulfur content of the catalyst after a running time of
1218 hours was 3.00 wt. -Fo corresponding to a sulfur / nickel atom ratio of 0.55 ·

Claims (1)

Patent claims I ₉ ) A process for treating mixtures containing hydrogen, carbon monoxide and highly unsaturated hydrocarbons, and optionally monoolefins, for reducing the proportion of highly unsaturated hydrocarbons by hydrogenation, characterized in that the starting mixture is passed in the vapor phase over supported nickel catalysts which, under the process "conditions, contain a larger proportion of the · nickel in the elemental state" 2 ») Method according to claim 1, characterized in that, Starting mixtures are treated where in proportion to carbon monoxide a smaller proportion of high unsaturated hydrocarbon was present 3.) Process according to claims 1 and 2, characterized in that that starting mixtures are treated which contain less than 1 mole of highly unsaturated hydrocarbon per 100 Moles of carbon monoxide contain » 4 ») Method according to claims 1 to 3, characterized in that that starting mixtures are treated, which by mixing a hydrogen-containing gas with a what « have been obtained from low-hydrogen or hydrogen-free starting material » 5.) Process according to claims 1 to 4, characterized in that a sulfur-containing starting mixture is treated is, in particular sulfur contents of 0.01 to 5 Total sulfur is present in the treated mixture * 809809/1054 6o) Process according to claims 1 "to 5 _? Gekennseicanet that it is worked with sepiolite as a support-containing nickel catalysts 7 «) Process according to claims 1 to 6, characterized» that at Tem]
work is going on " net »that at! temperatures in the range from 150 to 400 ° 8o) "Process according to Claims 1 to 7, characterized in that the work is carried out at spatial velocities of the initial device in the range from 200 to 1 * 500 v / V / hour!.: 9o) Process according to Claims 1 to 8, characterized in that the highly unsaturated hydrocarbons in the
Starting mixture of dienes and / or acetylenes are present «, 8 0 9809/105