DE2108276A1 - Process for the selective hydrogenation of butadiene in addition to monoolefins - Google Patents

Description

The invention relates to a method for selective Hydrogenation of butadiene in starting materials that have a a larger proportion of butene-1 and a smaller proportion of Contain butadiene, in the presence or absence of Butene-2.

The "British patent specification 1 110 826 describes the use of a sulphurized or sulphurized nickel carrier catalyst for the isomerization of ßuten-1 to Bufcen-2 in the counterv / kind of isobutene, where in. Eich κ hit ig butadiene, which optionally in the exit Hinateri.ui sn" .Iyold is, partially or fully hydrogenated v / ircu In many cases, however, it is desirable that ;; Geüe ^ te Buton-1, day in selectively hydrogenated! butene mixtures. Contains; 2ri io t, to be inherited unchanged.

It has now been found that butadiene, apart from a number of times, 10 parts per Iilion part is eliminated, while the isomerization of 1-butene to 10> ί or even more ? ⁿ _: _ ei * delimited int, if an auu Bulen-I and einci "wringt-n /iutaüierK.'icHK'e consisting of e; i starting material in üe ^ cnwa ·. ·! = oci'rr · Abv / e "Enhei" L from Buijon-2 under bestiiu.rton, p.cnau t: ir; -

r- ■ 109837/184 2 BADORieiNAL

Supported nickel catalyst is passed.

The invention accordingly provides a process for the selective hydrogenation of butadiene into a; Starting mixture, which contains a smaller proportion of butadiene and a greater proportion of butene-1, in the presence or absence of butene-2, while it is prevented that more than 10 / I of butene-1 is isomerized to butene-2. Las method is characterized in that the mixture together with hydrogen in a one ilenge of more than 3 piston ^f / o, based, leads to the Gesamtbutengehalt dos output ·· material over a supported nickel catalyst in which the nickel under the operating conditions as elementa

supply

res nickel is present, and that previously by sulphurising or sulphiding at a temperature below 100 G has been modified to recover a reaction product containing less than 10 parts per million of butadiene.

The sulfidation agent £ Uv the treatment of the nickel-supported catalyst in the process according to the invention consists of a) elemental sulfur, b) organic sulphurous compounds, c) H ₀ S, d) CSp and e) mixtures of 2v / ei or more of the aforementioned components (a ), (I))> (c) and (d).

The manufacture dor ;; Catalyst and its Aktiv.if ^j rur- · can be carried out by any known method. For example, the following three methods are suitable:

a) The catalyst can be applied by means of informa tion ruf ce n Traf ei, whereby a Kiekelaals,.:. B. i.'ickolniurat, dissolved in water and impregnated with the inert rna trr'.al nit ύ (- · ν solution. The carrier; 5th: ria !. is in the form of granules or pellets before that of d ^. Trägcrmaterini ground .- joformt, '"ve r can have as η New York Convention jode gcv.'ünnchte grain size i <acn dor Ir. .i nr fagnieri the catalyst is dried and is dot. η in e.'pe.r "

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'^ BAD ORIGfNAL

Form in which it can be stored for a long time without any disadvantageous change. To use the catalyst, it must be activated by heating it to decompose the salt. In the case of the nitrate, a temperature of about 500 Ms 55O ⁰ C is required for this. This converts the nickel into the oxide. The final activation by reduction to metallic nickel can be carried out in flowing hydrogen or hydrogen-containing gas at a temperature of 150 to 60O ⁰ G and under a pressure of 0 to 14 atm. The duration of treatment depends on the temperature. Typical conditions when using sepiolite as a catalyst support are 16 hours at 500 ^° C. and normal pressure. However, the sepiolite is not damaged if ^{it is heated to a temperature of 600 °} C. or slightly above.

b) The catalyst can be prepared by grinding dry Ki e!: * .-] · formate, mixing with the ground catalyst support and tableting the mixture. Uieses manufacturing method has the advantage that a salt such as nickel formate in a non-oxidizing atmosphere, for example in an inert gas or Wasssrstoffstrom, preferably hydrogen, at a temperature of 250 to 400 ⁰ C for a period of 4 to 40 hours and a Raupistroranngsgeschv.'indigkeit of the gas from 50 to 1COG V / V / hr. is reduced immediately (without the Umv.'eg via the oxide state) to i-icbjl. The reaction pressure can be 0.7 to 70 a + g, but the normal pressure is preferably used. -

door to be heated from 500 ⁰ C and higher.

c) The catalyst can be prepared by a process in which the water-soluble Eoroplo, which is formed when the nickel formate is dissolved in Airnoniak: ·, -; ur ;; 'v-.u;.; - i: becomes'Diu' jGr V-ov. ^ ley. zerfti i It LcIi .; Krhi t: - 'c-, i :,,' oboj. ^ ic.Ci Hickelformiate is formed. Box Vc-rwemiut; · dl ^ _; , ·.:; . ., .-. · _:

109837/16 / ;?

BATH

soluble complex can be catalysts after the impregnation process are made from normally water-insoluble compounds such as nickel formate. For the production a catalyst according to this process, nickel formate is dissolved in ammonia solution and the solution is impregnated of granules or pellets of the carrier material used. The catalyst is then dried, whereupon the activation takes place according to the procedure described under (b).

After the reduction, the nickel catalyst must not come into contact with the air, otherwise it will oxidize spontaneously of nickel to nickel oxide can take place.

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

Suitable for treatment with a sulfur-containing material and for use in the method according to the invention Catalysts that contain nickel on diatomite or calcium carbonate as a carrier. A nitrogen-supported catalyst is preferred, which contains sepiolite as a carrier.

Sepiolite is a commercially available clay mineral that occurs naturally and can also be produced synthetically. It has the ideal formula II 31g _q S j ^ ₂ ° 3O ^ ^OH '1 o " ^6H 2 ° and is also known as meerschaum. Further details about sepiolite and its properties can be found in" Chemistry and Industry "of 16.11.1957, page 1492-1495.

Sepiolite has the advantage over other carriers, such as alumina, the advantage that no reaction during made for converting the nickel salt to the oxide heating of the catalyst of ^w ickelsa] zes takes place with the sepiolite and the final reduction at a lower temperature than for nickel -Aluminium oxide Katalyoatoren is necessary, can be carried out.

109837/1647 ?! ", <****.

When an elemental nickel-containing supported catalyst with a sulfur-containing compound at increased If the temperature is treated, the extent of sulphidation generally increases as long as sulphurous compounds are used be passed over the catalyst until finally a completely sulfurized catalyst is obtained will.

It has been found that certain classes of sulfur-containing compounds only undergo sulfidation up to one effect a limited degree. So if there is a certain degree of suIfidation is reached, this level is no longer significantly changed if further amounts of this sulfur-containing Connections can be used under the same conditions as before. In certain cases the Degree of sulfidation be essentially independent of the sulfidation conditions, so that the degree of sulfidation depends on the choice of the sulfur-containing compound and the sulfidation temperature.

The variable sulphidation conditions are the temperature, the pressure and the flow rate. The sulfiding agent is generally in the vapor phase used"

By using an organic sulfur compound which is only able to bring about a limited degree of sulphidation, it is possible to obtain a catalyst which is sulphurised uniformly on its surface. It would thus be possible to use a calculated amount of an organic sulfur compound for the sulfidation which does not have this property, but in this case the catalyst at the inlet end of the catalyst bed can be sulfurized to an undesirably high level. IL ^r s is possible, an average Sulfidiorur.f 3-grad reach zn, which corresponds to a required V.ert, jodoch the catalyst may partially; - * :, IIA and partially unUiraktiv No..

109Π37 / 1ΒΑ? _F.

BADORJÖINAL

For the purposes of the invention, the sulfur-containing Connections classified as follows:

Class Αϊ thiophenes, thiocycloalkanes with at least

4 carbon atoms in the ring and dialkyl monosulfides.

Class B: Sulphurous compounds that are not used for

Belong to class A (e.g. mercaptans or dialkyl

disulfide), elemental sulfur, hydrogen sulfide and carbon disulfide.

As already mentioned, the compounds of class A cause only limited sulfidation. These connections, which are used alone or in a mixture, are used for the modification of the method according to the invention The carrier catalysts used are preferred.

A preferred class of organic sulfur compounds for the preparation of the catalyst form the Tetrahydrothiophenes. Tetrahydrothiophene is particularly preferred itself. As already mentioned, it has been found that these compounds are the nickel catalyst up to a to a satisfactory extent, i.e. without excessive sulphide formation, are able to sulphide, even if they are in excess the amount used to introduce the required amount of sulfur is preferred Tetrahydrothiophenes with 4 to 10 carbon atoms in the molecule.

Another class of suitable organic sulfur compounds are the mercaptans. In general, however, excessive sulfidation of the catalyst takes place if, when elemental sulfur, H ₀ S, CSp or organic sulfur compounds which do not belong to the compounds of class A are used, an excess of these materials over the amount which is to react with a smaller part of the mickeys required sulfur, - *: - contains, is used. Pol use of this iULer'ia.l i.au ViO r de η nie in Nilgerne Lnen in about «mohr al: 3 den« tod-io-

109837/1642 ^, "WH". '

metric quantities used for the sulphidation of the required part of the nickel present in the catalyst.

A preferred method for treating the reduced supported nickel catalyst "is that it with an excess of thiophene at a temperature in the range of 0 to 100 ⁰ C, preferably 25 to 80 ⁰ C, in flowing hydrogen at a space velocity of 50 to 500 V / V / The treatment can be carried out at any pressure, i.e. under reduced pressure, normal pressure or overpressure. Preferably, a pressure in the range from 0 to 3.5 atmospheres or worked about it

Normal pressure is particularly preferred.

The amount of the sulfur-containing material reacted with the catalyst is chosen so that the treated catalyst has a sulfur / nickel atomic ratio of 0.01 to 0.4. When using a sepiolite as a carrier which the nickel has been applied by impregnation with an ammoniacal nickel formate solution the sulfur treated catalyst preferably has a sulfur / nickel atomic ratio in the range of 0.05 to 0.25.

The selective hydrogenation can take place at a temperature in -

Range from 0 to 300 ° C., preferably 25 to 100 ° C., and carried out under reduced pressure, normal pressure or elevated pressure will. The pressure is preferably in the range from 0 to 7 atmospheres, in particular 3.5 to 6.3 atmospheres.

The room flow velocity related to the liquid state the use of butene is preferably in the range from 1 to 10 V / V / hour.

The selective hydrogenation can be carried out under liquid phase or vapor phase conditions. Preferably

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the steam phase is used. The process can also be carried out in the presence or absence of a diluent be performed. Gaseous saturated solvents are suitable as diluents for working in the vapor phase Hydrocarbons such as butane and inert gases such as nitrogen. As a diluent for operation in the Saturated hydrocarbons and inert gases are suitable for the liquid phase.

example 1 A. Preparation and activation of the catalyst

A catalyst containing 10% by weight of nickel on sepiolite was prepared by reducing Niokelammoniuraformiat on sepiolite in hydrogen (room flow rate 200 V / V / 3td.) At 30O ⁰ C for 24 hours.

B. Sulphidation of the catalyst

The catalyst containing reduced nickel on sepiolite was treated with tetrahydrothiophene (0.05 g / g catalyst / Hour) in hydrogen (main flow velocity. 200 V / V / hour) sulphurized for 24 hours.

C. Response

A mixture containing 43 to 47% butane, 20 to 26% butene-1, 25 to 33% butene-2 and 0.3 to 0.5% butadiene was passed in separate preliminary tests over three nickel-on-sepiolite-containing catalysts, the sulfided at various temperatures under the conditions set out in the table below. IHf. The feed to the reactor and the product were analyzed periodically. The butadicne content of the product leaving the reactor and the iaomerized Ar: to.Il of the butene-1, calculated as the percentage of the butene-1 content of the input material fed to the reactor, are shown in Table 1 below called. Among the applied; No increase in the butane level was determined in the course of the dilution.

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BATH ORIGINAL

attempt SuIfidlerunss-
temperature, C Set Dr u OK Table 1 Molar ratio product analyzes 100 lot
V / Y / hr, * atü Reaction nis Hp / butene Butadiene,
ppm isomerized
Butene-1,
G-ew. - ^c / o (a) 100 2.5 4, 9 temperature, 9.0 20th 24 (D) 70 2.5 4, 9 77 9.0 10 29 (c) 70 3.5 6, 3 79 5.3 10 10.5- - * (a) 60 6.1 4, 9 70 2.5 100 3.1 O
co (e) 60 4.0 6, 7th 64 6.2 10 10.5 00 Cf) 60 5.5, ■ - 5, 6th 62 8.5 10 5.6 do U) 5.5 5, 6th 63 7.5 100 1.0 ι *> *
σ »
P * 64

* be in Plüssi ^ condition

Experiments (a), (b), (d) and (g) do not illustrate the method according to FIG
Invention and are included for comparison purposes only.

O OO N)

- ίο -

The example shows that low suIf idation steratures increase the selectivity of the catalyst utul large quantities and low hydrogen content Limit isomerization of butene-1 and the efficiency of butadiene removal. Low usage quantities and a high hydrogen content favor the isomerization of butene-1 and the removal of the butadiene. By carefully choosing the sulfidation temperature, des Hydrogen content of the feed and the feed the butadiene is down to less than 10 ppm removed, while the isomerization of 1-butene to 10; - or even less limited.

Example 2

In the manner described in Example 1, a catalyst was prepared, activated and sulphurised. The suIfidation temperature was 60 ° C. The feed material mentioned in Example 1 was passed over the catalyst. The reaction conditions were adjusted so that the product leaving the reactor, if possible, contained less than 10 ppm of butadiene. The. ^: Settings and corrections were made each time because the reactor was able to process different input quantities every day and, on the other hand, the decrease in the activity of the catalyst was to be counteracted. The addition of the product leaving the reactor is given in Table 2 below.

The analyzes show that by changing the real conditions to the V ^ .Lae described in Example 1, a product which contains less than 10 pp ;: _s butadiene and 90 dtrs of butene contained in the basic material 1 ^enthi: 1 ', was erhi'.lten. The values in the table show that more than 10/5 of the butene-1 was isolated from one company to the next , since '; however you i.vh corresponding And ·; t: υ ng der ': i: ·: "i ί ri ^ j-.ifi ■ _- ;; r; this portion then below 10 / ί ί."i;. ::: ki, became.

103 8 37/1642 _ßAD original

Table 2
■ 2cmOera "turoro £ raniniierunp to extend the life of the catalyst

Running time. Hours. 18th 6th 198 ί 12. 3.5 14.5 | Γ.26 244 I 292 5.0 7.5 331 I 361 427 I 452 477 501 597 669 Ren Ittionsbed in? Un «en 4.2 <5 <5 0 4.5 <5 Lr uc ic, atü > 5, 6 - «- > «? 1 > ■ 7 <- > Space flow velocity,
di £ k: eit (in plus -6-6.3- * " V / V / ota. 4.5 4.5 4.5 4.5 4.5 5.0 5.0 5.0 5.0 5.0 5.0 '.hydrogen, col-% 6th 5.4 5.6 5.6 5.4 5.4 4.8 4.8 4.8 4.9 4.2 4.9 ■ lerriprature, ⁰ C 4.0 72 72 80 84 Interest rate material ■ r > Euten — 1 I 14, [Total n-butenesJ 48.4- <5 ■ Butadiene, weight-? " 5.6 - «- -0.5 4.6 5.0 11.3 9.6 rutcn-1 isomerized. ', 9 3.2 7.4 9.0 11.6 <10 <1Ο <10 <20 Butadiene * ρρπι <ιο <5 <10 <10 <10

* 5 = 0 to 5 ppm; 10 = 5 to 10 ppm; 20 = 10 to 20 ppm

Claims (1)

- 12 claims . Process for the selective hydrogenation of butadiene in a starting mixture which contains a smaller proportion of butadiene and a larger proportion of butene-1, in the presence or absence of butene-2, with an isomerization of butene-1 to butene-2 of more than 10 % of butene-1 is prevented, characterized in that the mixture is passed together with hydrogen in an amount of more than 3 mol £, based on the total butene content of the starting material, over a supported nickel catalyst in which the nickel under the working conditions is elementary Nickel is present and the catalyst is modified by sulphidation at a temperature of less than 100 ° C, thereby obtaining a reaction product which contains less than 10 parts of butadiene per million parts. 2. The method according to claim 1, characterized in that a catalyst is used, from 2 to 0 wt -.% Of elemental nickel, based on the total weight of the catalyst. J5. Method according to claim 1, characterized in that that the catalyst carrier used is kieselguhr, calcium carbonate or, in particular, sepiolite b. ¹ I. The method according to claims 1 to 3, characterized in that the supported nickel catalyst by treatment with 109837 / 1RA? a) elemental sulfur, b) organic sulfur compounds, c) hydrogen sulfide, d) carbon disulfide or e) sulfided with mixtures of 2 or more compounds from a), b), c) and / or d) or. has been sulphurized. 5. The method according to claim 4, characterized in that that the supported nickel catalyst by treatment with thiophene, thiocycloalkane] * with at least | 4 carbon atoms in the ring, in particular a tetrahydrothiophene, or dialkyl monosulfides sulphurized has been. 6. The method according to claim 5> characterized in that the supported nickel catalyst by treatment with tetrahydrothiophenes having 4 to 10 carbon atoms has been sulphurized in the molecule, especially with tetrahydrothiophene. 7. Process according to claims 1 to 6, characterized in that the sulphurization of the catalyst in g a temperature of about 0 to 100 ° C, in particular ™ from about 25 to 8o ° C, - in a hydrogen stream a space flow rate of 50 to 500 V / V / hour over a period of 6 to 50 hours has been carried out. 8. The method according to claims 1 to 7 *, characterized in that that a catalyst is used which has a sulfur-nickel atomic ratio of 0.01 0.4 has. 109837/1642 9 «Method according to claim 1 to 8, characterized in that draws that the selective hydrogenation at a temperature of about 0 to 300 ° C, in particular about 25 to 100 ° C. Io. Method according to Claims 1 to 9 *, characterized in that that the selective hydrogenation at a pressure of about 0 to 7 atmospheres, in particular about 3.5 up to 6.3 atmospheres. 11. The method according to claims 1 to lo, characterized in that that the space flow velocity of the butene feed mixture, based on the liquid state, is about 1 to 10 V / V / hr. 12. The method according to claims 1 to 11, characterized in that that the process in the gas phase, especially in the presence of a diluent, performs. 13- method according to claim 12, characterized in, that the diluent used is gaseous, saturated hydrocarbons or inert gases. 14. The method according to claims 1 to 11, characterized in, that the process is carried out in the Plüssigphase in the presence of a diluent. 15. The method according to claim 14, characterized in that the diluent is saturated hydrocarbons or inert gases are used. 109837/1642