DE1443678B - Process for the production of C deep 2 to C deep 4 olefin hydrocarbons - Google Patents

Description

3 4

Iron oxide added in an amount of 40 to 60%, based on the form of its oxides (e.g. chromic acid),

on the entire catalyst, contains, but you can also use salts, for example

brings. Chromium nitrate or sulfate, or molybdenum chloride.

The oxides of the metals of group VIlIb and the The relative proportions of metals of group VIIIb group VIb of the periodic table are together 5 and VIb are not critical, especially because those with iron oxide, usually in the form of salts or activity and selectivity easily by changing the Sulphides, which can be partially converted into oxides during firing at temperatures ranging from 150 to 600 ° C. Active material and carrier material. The metals of Group VIIIb converted are applied to the carrier. Before the catalyst used for selective hydrogenation can be used in amounts of about 5 to about 15 to 20 percent by weight (calculated as oxides and based on, the metal oxides on the support up to the total catalyst) are present, with a lower degree of oxidation or up to which preferably more nickel than cobalt is used, corresponding metals are reduced. The group VIb metal may be present in amounts of group VIIIb is preferably cobalt or nickel, 0.1 to 2 percent by weight (calculated as oxides and the group VIb metal is preferably 15 based on the total catalyst). Chromium or molybdenum; Usually nickel, The ^{carrier, composed of at least 85% of} SiO ₂ - cobalt, iron and chromium oxides in combination, can usually also be used in small amounts, although other combinations also use amounts (5 to 15%) of other oxides, such as titanium dioxide, are effective. Iron, alkali and alkaline earth oxides contain. A

The metals of group VIIIb are preferably ao catalyst, the 25 to 35 percent by weight of the carrier in the form of sulfates applied to the carrier. contains, has sufficient mechanical strength. The sulfates are converted into oxides when heated to about 150 to As iron oxide, which in amounts of about 40 to 510 ° C is only partially converted into oxides, so that 60 percent by weight, based on the total catalyst, still contains sulfur. Any iron oxides can be used as the lyser. B. ferric oxide, ferrous oxide, iron (II, sibel bound to the iron oxide. The sulfate determines III) oxide (Fe ₃ O ₄ ), iron sesquioxide (Fe ₂ O ₃ ), precipitates the temperature limit and contributes to the selectivity of the iron oxide, annealed iron vitriol and natural catalyst. Ores increase the temperature. When burning, these iron oxides undergo the exothermic hydrogenation reaction, so the sulphates (III) oxide is converted, which in the hydrogenation group is probably partly reduced to the sulphide group and partly to iron (II) oxide; the induced; As a catalyst poison, the latter inhibits the iron oxides given as well as other iron depletion reactions. If the reaction rate decreases, z. B. iron carbonates, which are converted into iron oxides during the digkeit, so also the temperature, and burning, the reduction of sulphate to sulphide ceases, which are therefore equivalent to each other, a complete inhibition of the hydrogenation reactions 35 The catalytically active material can be used as Mixture is prevented. of oxides or sulphides of metals of the group

The sulfur VIb and VIIIb used for temperature control, e.g. B. of iron, nickel and chromium can also be introduced in the form of sulfides. or iron, cobalt and chromium, or from others For example, cobalt and nickel sulfide can be used in combinations or in the form of a compound Instead of cobalt and nickel sulfate used 40 between the metal oxides and the metal sulfides will. Also hydrogen sulfide or organic or a mixture of two or more compound sulfur compounds there may be types of entrapment in the gas stream.

be performed, the hydrogen sulfide by In the selective hydrogenation, which, as above, the iron oxide is absorbed. The sulphides in the cata- specified, at a temperature of about 93 to lysator are partially oxidized to sulphates, and 45,316 ° C and a pressure of about 1.7 to 24 atmospheres the latter act in the manner described above when carried out, the Space velocity up to temperature controller. The sulfur content of the catalyst to 5000 parts by volume of gas per part by volume of catalyst and sators is usually 1 to 5, preferably 1.5 hours, the water vapor concentration can be up to 2.5 percent by weight. The desired amount of sulfur from 1 to 10 or more, preferably from 1 to 6, by volume in the finished catalyst depends on the amount of 5 % and the content of organic operating conditions under which the catalyst can be used up to sulfur compounds in the gas stream , away. At low temperatures and 100 ppm. The catalysts are poison-resistant pressures, for example at about 93 to 150 ° C and can be regenerated several times by oxidation with water vapor and 7 to 21 atmospheres, a sulfur content of 1 to 2.5 Ge air, without their weight percent desired, while at higher 55 you lose mechanical strength. Their activity and temperatures and pressures, for example at about selectivity, is in a wide space velocity-150 to 204 ° C and at about 21 to 35 atü, higher and temperature range high. They are preferred over sulfur contents in the range of 2.5 to 5%. Fluctuations in the sulfur content in the gas flow

The metals of group VIb can be in the form of men insensitive, with the operating temperature aqueous solutions applied to the carrier 60 need not be changed to avoid fluctuations will. It can balance salts such as cobalt nitrate and the sulfur content. You have im Chloride, as well as nickel nitrate and acetate used in contrast to other catalysts for the selective but if these salts are preferably hydrogenated, they have the advantage that their activity is combined equivalent amount of sulfate to the desired diminishes when the operating temperature vermin-sulfur content to obtain. This can be done by the same 65, and vice versa.

early addition of sulfuric acid or sodium sulfate The iron oxide in the catalysts has a large

can be achieved. Affinity for sulfur and carbon monoxide.

Chromium and molybdenum are expedient in are these compounds in the supplied gas stream

present in excess, then they are absorbed by the iron oxide; in the opposite case will be they are given off by the iron oxide.

The iron oxide serves primarily as a carrier material for the metals of group VIIIb and VIb, but also has a catalytic effect, albeit with a low level of activity. That's why you can get the content Catalyst metals (nickel, cobalt, chromium and molybdenum) degrade and still maintain an active catalyst. The iron oxide serves as a diluent and in this way gives the Catalysts show great selectivity for the hydrogenation of acetylenes. For example, reduce the catalysts according to the invention butadiene to butene, whereas the usual catalysts for the Selective hydrogenation to reduce butadiene to butane.

The silica serving as the internal support preferably has a surface area of less than 10 m ² / g. As a result of the low surface area of the silicon dioxide and the iron oxide, the formation of polymers is prevented, which extends the operating time between two regenerations. The usual forms of finely divided silicon dioxide, such as diatomaceous earth, colloidal silicon dioxide and kieselguhr, are suitable.

The catalyst masses are pressed into pellets, tablets or other forms, stränggepreßt or granulated and then at about 150-540 ⁰ C to 15 hours, preferably at about 480 to 510 ° C for about 8 hours, fired. 5

Before they are used, the catalysts are activated in a gas stream containing 2 to 20% hydrogen for 2 to 16 hours at about 230 to 450 ^° C., the cobalt, nickel, chromium and molybdenum compounds being partially reduced to the corresponding catalyst metals .

A catalyst which is preferably used contains 25 to 35 percent by weight of silicon dioxide with a surface area of less than 5 m ² / g, 40 to 60 percent by weight of iron (III) oxide, 1.5 to 15 percent by weight of nickel sulfate, 0.25 to 3.5 percent by weight of cobalt sulfate , 0.1 to 2 percent by weight chromium oxide, 2 to 10 percent by weight colloidal silica and 1 to 5 percent by weight sulfur.

In the examples below, the preparation of the catalysts used according to the invention and their effect in the selective hydrogenation of olefin gas streams explained.

example 1

A catalyst containing 8.9% NiSO ₄ , 1.6% CoSO ₄ , 52.0% Fe ₂ O ₃ and 0.11% Cr ₂ O ₃ in a mixture with silicon dioxide as the support material is prepared as follows:

102 parts of silica (Standard Filter CeI, Johns Manville Company), 150 parts of iron oxide (Fe ₂ O ₃ , Williams No. 1085), 41.1 parts of nickel sulfate hexahydrate, 8.7 parts of cobalt sulfate heptahydrate and 0.9 parts of chromic acid Thoroughly mixed together and processed into a paste after adding 30 parts of colloidal silicon dioxide (Ludox, 30% SiO ₂ ) and 250 parts of water. The paste is dried at about 116 ° C. for 16 hours, powdered and forced through a sieve with a mesh size of about 2 mm. An appropriate amount of graphite is added to the dried mixture as a lubricant to form the material into cylinders

ao with the dimensions 6.4 x 6.4 mm. After molding, the cylinders are first ^{dried for 16 hours at about 110 °} C. and then further dried according to the following scheme:

1 hour at about 15O ⁰ C
1 hour at about 230 ° C
ί Would be at around 340 ^° C
8 hours at about 51O ⁰ C

The catalyst produced in this way has a surface area of 26 m ² / g. It gives excellent results over a wide temperature and space velocity range when cleaning a gas stream with a high olefin content. By adding organic sulfur to the gas introduced, the catalyst activity can be influenced only slightly or not at all.

Said catalyst shows good selectivity and activity in the purification of an ethylene-rich gas stream at temperatures of 150 to 230 ⁰ C and at space velocities of 1200 to 4800.

Table I shows the mode of operation of the catalyst in the selective hydrogenation of acetylene in one.

Ethylene gas flow under a pressure of about 7 atü The gas flow consists of 34.0% methane, 32.3 °, Ethylene, 32.4% hydrogen, 1.1% propylene and 0.20% acetylene.

Table I.

Treatment temperature space Added
Amount of sulfur Hydrogenation
\ j / "Vrt fil ^ finpii Starting
mixture (ppm) QtLUCr "
(Hours) ⁰ C speed as COS
(ppm) VUIl WICHUCIl
(Mole percent) 2300 End product 2 177 1200 0 1.0 2300 0 5 177 2400 0 0.4 2300 0 7th 232 2400 0 0.4 2300 0 23 232 1200 0 0.8 2300 0 26th 232 3600 0 0.2 2300 0 29 177 3600 0 0.2 2300 16 31 150 2400 0 0.8 2300 24 34 232 4800 0 0.0 2300 20th 36 *) 232 2400 5.3 0.0 2300 6th 40 232 1200 5.3 0.0 2300 0 56 177 1200 5.3 0.0 6th

*) New Ausgarigsgas: 32.4% methane, 32.3% ethylene. 32.4% hydrogen, 1.1% propylene, 1.6% carbon monoxide, 0.2% acetylene and 5.3 ppm sulfur (as carbon oxysulphide).

Example 2

Table II
Operating conditions

Space velocity 2500

Inlet temperature 204 ° C

Outlet temperature 208 ⁰ C pressure 16.1 atü

Components

Acetylene, C ₂ H ₂

Monoalkylacetylenes, RC ₂ H

Propadien

Sulfur, total

Ethylene

Propylene

butane

Isobutane

Butene-1 + isobutene

trans-butene-2

cis-butene-2

1,3-butadiene

Volume concentration

Starting mixture

0.45% 300ppm

0.13%

27.6%

6.6%

lOOppm

lOOppm

0.38% 0.05% 0.05% 0.98%

End product

10 ppm

45 ppm

185 ppm

27.6%

6.5%

200ppm

lOOppm

0.45%

0.36% 0.17% 0.41%

A catalyst containing 7.67% NiSO ₄ , 1.81% CoSO ₄ , 51.65% Fe ₂ O ₃ and 0.50% Cr ₂ O ₃ in a mixture with silicon dioxide as a carrier is prepared as follows:

110 parts of silicon dioxide (standard filter CeI), 200 parts of iron oxide (Williams No. 1085), 50 parts of nickel sulfate hexahydrate, 12.5 parts of cobalt sulfate heptahydrate and 1.3 parts of chromic acid are thoroughly mixed with one another and, after adding 80 parts of colloidal silicon dioxide (Nalcoag, 50% SiO ₂ ) and 90 parts of water processed into a paste. The paste is then extruded and cut into pieces that are about 6.4 mm in diameter and about 6.4 to 12.8 mm in length. After molding, the extruded material is dried and fired according to the following scheme:

1 hour at about 15O ⁰ C
1 hour at about 23O ⁰ C
1 hour at about 34O ⁰ C
8 hours at around 510 ° C.

Table II shows the values obtained after 120tägigem continuous operation with this catalyst in ^a 5 äthylenreichen gas stream.

The above values show that C ₂ H _{8 is} almost completely removed. The propadiene and methylacetylene content was reduced from 1600 to 230 ppm. The propylene and ethylene content remained practically unchanged. About 58% of the butadiene present was hydrogenated to butene.

Example 3

A catalyst prepared according to Example 2 is reduced for 4 hours at about 340 ⁰ C in a wasserstofihaltigen gas stream and then tested in a äthylenreichen gas stream having the following composition on its activity.

20th

nd parts Volume percentage H ₂ 8.9 CH ₄ 29.4 C ₂ H ₄ 30.2 C ₂ H ₆ 9.0 C ₃ H ₆ 14.5 C ₂ H ₈ 1.0 C ₂ H ₂ 0.18 N ₂ 5.7 CO 300 ppm O ₂ 100 ppm Total sulfur 3 ppm

30th

35 Operating Conditions

Inlet temperature ^{120 0 C}

Space velocity 3000
Pressure 17 atm

Table ΠΙ contains the analysis values for the gaseous starting material and the end product according to 62 hours of continuous operation.

Table III

40

45 components

C ₂ H ₄
C ₃ H ₆
C ₂ H ₂

Volume concentration
Starting material end product

30.2%

14.5%

1800 ppm

30.2%
14.5%
7 ppm

The above values illustrate the excellent selectivity of this catalyst, as can be seen from almost complete removal of acetylene and negligible loss of unsaturated gases results from the hydrogenation.

209 552/535

Claims (1)

1 2 Catalyst, the acetylene content is in the treated claim: mixture between 90 and 100 ppm. Furthermore, from the German patent specification 869 200 Process for the production of C ₂ - to C ₄ - a process for hydrogenation, dehydrogenation, re-olefin hydrocarbons with the removal of 5 formation and cleavage of hydrocarbons acetylene and monoalkylacetylenes from gas known, in which a catalyst is used, which flow in addition to the said olefin carbon carrier by mixing a 'water glass hydrogen and acetylenes excess water solution with a metal salt solution, z. B. contain an iron, by selective hydrogenation with salt solution, in the presence of acidic substances her-HiIfe a catalyst made of inert support io was made. This patent specification does not contain any evidence on which an oxide of a metal in a selective hydrogenation of acetylene group VIIIb and an oxide of a metal of hydrocarbons, and which is applied from the waterglass group VIb of the periodic table, solution precipitated silicon dioxide should be a carrier at a temperature of about 93 to 316 ⁰ C and with a relatively high surface area, which could give a pressure of about 1.7 to 24 atmospheres, thereby giving rise to polymer formation, characterized in that the gas flow is finally in the German Auslegeschrift with a catalyst that has a porous supported catalyst for the hy-85% composed of SiO ₂ carrier with continuous desulphurization of sulphurous carbons with a surface area of not more than about 50 m ² / g hydrogen, which is described as active hydrogenation in an amount of 25 to 35% and iron oxide 20 component oxides and / or sulfides of at least an amount of 40 to 60%> based on the two metals of the iron group (preferably nickel total catalyst, contains, in contact and cobalt) and of molybdenum on a support , brings. like clay, silica activated clay or a silica-alumina cracking catalyst. r ■ 25 There is no indication that this supported catalyst suitable for the selective hydrogenation of acetylene hydrocarbons. Since it is a Because of the relatively poor stability of the porous support, its surface appears Triple bond acetylenic hydrocarbons can be relatively high. in an olefin-containing gas mixture lighter than olefin 30 The invention is based on the object of small hydrocarbons are selectively hydrogenated when quantities of acetylenes in olefin gas mixtures are in opposition Catalyst with a specific activity waits to hydrogenate a catalyst in such a way that the reversal that hydrogenation of acetylene at high space velocity is more practical Much greater speed than with olefins table runs completely until the acetylene content allowed. However, the problem becomes difficult when 35 is a few parts per million (ppm), where only small amounts of acetylene are present in the gas mixture but, on the other hand, also in mixtures, the largest are and if the acetylene part completely hydrogenated consist of olefins, these only proportionally must be without the olefin content are substantially slightly hydrogenated. Furthermore, the should be reduced will, e.g. B. for the production of a turned catalyst only a relatively low synthesis gas mixture. For example, gas-based polymerization of olefins and proportionally mixed for the production of polyethylene, which in the relatively small amount of carbon deposits can be seen made up of olefins and hydrogen, I'm calling. Furthermore, the catalyst used should be a generally not more than about 25 parts acetylene, a relatively long duration of action, a good idea Contains a million parts of the mixture. Mixtures with resistance to temperature surges, a high higher acetylene concentrations are suitable for the 45 mechanical strength even after long use Polymerization does not. and high resistance to poisoning In the USA patent specification 3 003 008 a carbon oxide is possessed, and it is said to have its activity and drive for the selective hydrogenation of acetylenes in selectivity even in olefin gas mixtures with a presence of olefinic gases, the unsaturated relatively high content of organic sulfur ₄ containing hydrocarbons. Don't lose 50 fei for this. Finally, the suitable catalysts used should contain the oxides of the catalyst and can easily be generated from cobalt and molybdenum, nickel and chromium, even after prolonged use. of nickel and molybdenum, cobalt sulfide, nickel- The subject of the invention is a method for sulfide or molybdenum sulfide, preferably inert carriers such as aluminum oxide which are permanent _{on the recovery of C 2} - to C _{4 -olefin hydrocarbons.} Over 55, with removal of acetylene and monoalkyl, the surface quality of these catalysts acetylenes from gas streams; no information is found on the other than those mentioned. With such a ka- olefinic hydrocarbons and acetylenes excess analyzer, the acetylene content of the hydrogen to be cleared will indeed be contained, by means of selective hydrogenating gas at a temperature of about -230 ° C., a pressure of about 25 atmospheres and with the aid of a catalyst made from an inert carrier a space material on which an oxide of a metal of the group velocity of 2000 parts by volume of gas mixture per VIIIb and an oxide of a metal of the group VIb by volume of catalyst and hour of 0.7% is applied to the periodic table, at a Tem-12 ppm reduced, but about 70% of the temperature of about 93 to 316 ° C and a pressure of butadiene are lost. If the temperature is lowered to about 1.7 to 24 atmospheres, which is characterized by this, to about 216 ° C. and the space velocity is increased by the gas flow being increased to 2700 with a catalyst, butadiene no longer works at least 85% of SiO _{2 lost} together, but the acetylene content after the catalyst with a surface area of no more sator increases to 580 ppm. Other than about 50 m ² / g in an amount of 25 to 35% and