CS239938B2 - Catalyst on aluminium oxide base and its processing method - Google Patents

Abstract

Catalysts based on gamma alumina, consisting of gamma alumina stabilised by silica and containing oxides of bivalent or trivalent metals chosen from those of Group 2a and/or Group 8 and/or Group 3b and/or the Lanthanide Series, are disclosed. The catalysts are particularly active in isomerisation reactions.

Description

The present invention relates to an aluminum-α-oxide-based catalyst.

Aluminum (III) -alkolate catalysts are known, but they are too acidic for some, especially for isomerization of bonds.

In addition, their acidity is increased by treating the alumina with silica in order to increase its thermal stability, for example by the methods described in U.S. Pat.

On the other hand, stabilization by means of silicon dioxide is necessary in order to be able to regenerate alumina at high temperature without losing its activity.

We have now surprisingly found that it is possible on the one hand sinžit acidity of catalysts. Alumina to a level that is suitable for reaction spooívající in isomerization Weigh while on the other hand nesnnží thermal stability of ^Z to the j oxime ^d u ^ ftUnitému hundred liooannému oxide ^armchair EMI ^No make of p ^ ^p ales can he ^d dvojmocnáho ene oxide or a trivalent metal selected from the group zatainjící calcium, barium, lenthan, lanthsnidy and iron.

Katal Zátor ^y ^ .- based oxide hliniáého ^p ccording ^{characterized} in finding a composition odjjoo ^ aaíoí obecnámu formulas and А1, Оз. b SL0,. c Me _x O _y wherein ^Me x ° y wherein the oxide is at least one divalent or trivalent metal selected from the group consisting of calcium, barium, lanthene, lanthanides and iron, means moles of aluminum oxide, silica and oxide of formula Me _at 0, * y 'indexes. and £ are ^P ol vzdecHnám ratio defined relationship c> »b + B having a value in a value ranging from 0> 01 to 0.05 and a range from 0.020 to 0.250, the value of ratio (B + C) ', and

is from 0.01 to 9.0 and i is a number ranging from 0.7 to 0.1.

In the specific case of lanthanum, the optimum ratio between the amount of lanthanum and the amount of silica was found to correspond to the mooy ratio of ^ 8.03 00257 x moles of SiOg + 0.014, while in the case of calcium the optimum ratio between calcium oxide and silica CaO * 0.500 x moles SiOg + 0.030.

In the case of barium, the optimum ratio between barium oxide and silica is expressed in terms of mol BaO - 0.500 x moles SiOg + 0.020 and in the case of iron the optimum ratio between iron oxide and silicon dioxide is expressed in terms of ol F <2 ^O 3> ° » ² ^ ° ^x ® ° 1у ^Si0 2 ⁺ ° ^'18 ·

In these four particular cases, the silica content in moles and the ratio (b + c) / a has the aforementioned value ·

The catalyst of the invention is particularly useful for reactions involving isomerization of an olefinic bond, particularly for the isomerization of 2-butene to 1-butene.

The catalyst of the present invention is prepared by impregnating N-aluminum oxide stabilized by any of the processes described in the aforementioned U.S. patents with an aqueous solution of a metal salt or salts selected from the group consisting of divalent or trivalent metals of calcium, barium, lanthanum, lanthanide and Iron, preferably aqueous solutions of the nitrate or acetate of these metals.

The following examples are intended to illustrate the invention in more detail.

Example!

20 g of У-alumina with a specific surface area of 200 m ² / g are treated with 15 ml of an alcoholic solution containing 0.75 g of Dynasil A40 (40% ethyl orthosilicate solution).

The mixture was allowed to react at 50 ° C for 2 hours, decanted and steamed to hydrolyze the silanol groups; It is then dried and calcined at 500 ° C for 4 hours.

The material containing 1.5% silica was impregnated with 15 ml of an aqueous solution containing 5.90 g of lanthanum nitrate and the impregnated material was dried and calcined at 500 ° C for 4 hours.

The resulting substance consists of aluminum oxide stabilized with 1.5% silica and containing 10% lanthanum dioxide.

The catalyst is introduced into a trans-2-butene isomerization reactor at 470 ° C, at atmospheric pressure, at a hourly hourly space velocity of 6 h4. The catalyst is capable of conversion to 1-butene in which the isobutene content is only 140 ppm.

After heat treatment at 1000 ° C for 24 hours, the catalyst has a specific surface area of 113 m ² / g · The catalyst does not discard any activity after 40 reaction cycles (total 332 hours) and 40 regeneration cycles (total 152 hours) · * Regeneration is performed at temperature 540 ° C.

Example 2

As described in Example 1, a catalyst is prepared comprising 1.5% silica and 2.5% oxi ^d u in ^P enatého on hHnitém. Calcium is not released from deserts of an aqueous solution (15 ml) of calcium nitrate (2.40 g).

Drying and kalcinece the ^P ET performed at 500 ° C for 4 hours.

The catalyst was introduced into a tris-2-butene isomerization reactor carried out at ⁴⁷⁰ ° C at atmospheric mass at a space ^{speed of} 6 h ^-1 . The catalyst is capable of conversion to 1-butene in which the isobutene content is only 150 ppm.

After heat treatment at 1000 ° C for 24 hours, the catalyst has a specific surface area.

183 m ^ / g · Catalyst does not show any loss of activity after 40 reaction cycles (total 332 hours) and 40 regeneration cycles (total 152 hours).

The regeneration is carried out at a temperature of 540 ° C.

Example 3 p

20 g of aluminum oxide having a specific surface area of 200 mVg are treated with 15 m. Of an alcoholic solution containing 0.75 g of a 40% ethyl acetate solution.

The mixture is allowed to react at 50 ° C, decaned and treated with steam to hydrolyze the silanol groups. It is then dried and calcined at 500 ° C for 4 hours.

The substance thus obtained containing 1.5% of silica is impregnated with 2.57 g of laothaoite nitrate.

A substance consisting of aluminum oxide stabilized with 1.5% silica and containing 5% of laotanol oxide was obtained. The catalyst is introduced into a reactor in which trans -butane isomerization is carried out.

The experimental data are shown in Table 1 together with the surface area values of the substances subjected to a 24-hour heat treatment at 1000 ° C.

EXAMPLE 4 g of the silica stabilizer alumina prepared according to Example 3 was not swollen with an aqueous solution of laotanitane. The material obtained contained alumina and 1.5% silica and 7.5% lithium oxide.

P Clearance

An aluminum oxide catalyst is prepared as described above which is stabilized with 1.5% silica and moodfied with 10% laothaolttho.

EXAMPLE 6 Alumina (6 g) was not impregnated with the alcoholic solution of rtl orthoaleate as described in Example 3 to give a substance which, after steam treatment and elsewhere, contained 3.8% of silica.

The formed substance is then added to the required amount of lanahaoit nitrate solution to introduce 5% laothoxide.

The catalyst obtained in this way contains 3.8% silica and 5.0% lanthanum oxide on alumina.

Catalytic efficacy tests were carried out on the substance.

Example 7.

A catalyst comprising 3.8% silica and 7.5% lanthanum oxide on alumina was prepared as described in Example 6.

Example 8

A catalyst comprising 3.8% silica and 10.0% lanthanum oxide on corrugated oxide was prepared as described in Example 6.

Example. 9

The catalyst described in Example 6 was used to prepare a catalyst comprising 8% silica and 5% lanthanum oxide on the L2O4 oxide.

He did

A catalyst containing 8% silica and 7.5% oxide on silica was prepared as described in Example 6.

Example 1 a d 11

By the method described in ^{1 of} Example 6, the reaction was carried out. to prepare a catalyst comprising 8% silica and 10.0% lanthanum oxide on the oxide.

Example 12

Caused as described. In the example 6. A catalyst containing 8% silica and 15.0% lanthanum oxide per liter is prepared. aluminum oxide.

Example 13.

Alumina Modified · 3.8% Oxide. The silica prepared as described in Example 8 is impregnated with an aqueous solution. the rare earth metal acetate in an amount such that the resulting catalyst contains 10% of the rare earth metal oxide. .

The data presented in Table 2 shows the extent to which the behavior of pure lanthanum and the rare earth mixture is identical.

Example

A catalyst comprising 1.5% of silica and 2.5% of calcium oxide on the oxide is prepared as described above. Calcium is introduced analogously to lanthaine via a calcium nitrate solution.

The data are listed in Table 2.

Example 15

A catalyst comprising 1.5% silica and 5.0% calcium oxide on alumina was prepared as described in Example 14.

Example 16

A catalyst containing 1.5% silica and 7.5% calcium oxide on alumina was prepared as described in Example 14.

Example 17

A catalyst comprising 3.8% silica and 2.5% calcium oxide on alumina was prepared as described in Example 14.

Example 18

The catalyst described in Example 14 prepared a catalyst containing 3.8% silica and 5.0% calcium oxide and hemi-oxide.

Example 19

A catalyst containing 3.8% silica and 7.5% calcium oxide on alumina was prepared as described in Example 14.

Example 20

A catalyst containing 1.5% silica and 4.0% barium oxide on alumina was prepared as described in Example 14 (the barium was introduced analogously to calcium using a barium nitrate solution).

The relevant data are shown in Table 3.

Example 21

A catalyst containing 1.5% silica and 8.0% barium oxide on silica was prepared as described in Example 20.

Example 22 '

A catalyst containing 3.8% silica and 4.0% barium oxide on alumina was prepared as described in Example 20.

Example 23

A catalyst containing 3.8% of silica and 8.0% of barium oxide on aluminum oxide was prepared as described in Example 20.

Example 24

The catalyst described in Example 20 prepared a catalyst containing 3.8% silica and 3.5% strontium oxide on silica.

The results shown in Table 3 show that strontium behaves in a similar manner to calcium and barium.

Example 25

A catalyst containing 1.5% silica and 2.5% iron oxide (% by weight) not silica is prepared as described above (the iron is introduced in the form of an aqueous solution of iron nitrate). The results are shown in Table 4.

Example 26

The catalyst described in Example 25 was used to prepare a catalyst containing 1.5% Umoonotonic silica with 3.8% Umoonotonic Iron Oxide on Ulintec®.

Example 27

The process described in Example 25 provides a catalyst comprising 1.5% hrnoonoot silica and 5.0% hrnoonoot iron oxide on alumina.

Example 28

By the method described in Example 25, a catalyst of 3,8 3.8% of a mono-monosilic silica and 2.5% of an hour-old iron oxide of alumina was prepared.

Example 29

As described in Example 25 to prepare a catalyst content of 3.8% compounding UmoonootníUo oxide · ^ ITEU creams and ^{3% 8-lezitéto} Umoonootníto oxide on γ-aluminum oxide.

Example 30

A catalyst comprising 3.8% of a mono-monosilic silica and 5.0% of an iron-alumina-oxide was used as described in Example 25.

Example 31

The catalyst described in Example 25 was prepared with a catalyst containing 5.0% evening-silica and 2.5% Umoothniotic iron oxide on γ-Ulinnéo o -oxide.

He said a 32

The catalyst described in Example 25 was used to prepare a catalyst comprising 5.0% UMO and 3.8% UMO on aluminum oxide.

Example 33

A catalyst comprising 5.0% Umoonootic silica and 5.0% Umoonootic iron oxide and U-oxide was prepared as described in Example 25.

Example 34

The catalyst described in Example 25 was prepared with a catalyst containing 5.0% Umoonotonic silica and 7.5% Umoonotonic iron oxide on Ulinnéo f -oxide.

θ

Table 1

Isomerization of trens-2-totene to 1-butane

Relative temperature: 470 ° C, absolute to 0.1 MPa, mass hourly space velocity 6 h ""

Catalyst Obseh La ^ O ^ (wt.%)

Content Si0- Specific surface after (% by weight) 24 h annealing at

000 ° C ( ⁿ / g)

Iaobutene content in reaction products (linear butanes are always present in amounts corresponding to thermodynamic equilibrium at reaction temperature)

Example 3 5.0 1.5 154 990 ppn Example 4 7.5 1.5 134 490 ppm Example 5 10.0 1.5 113 140 ppn Example 6 5.0 3.8 164 0.35 « Example 7 7.5 3.8 163 0,145 » Example 8 10.0 3.8 139 330 ppn Example 9 5.0 8.0 188 0,7 * Example 10 7.5 8.0 170 1,4 » Example 11 10.0 8.0 155 1 500 ppn Example 12 15.0 8.0 145 200 ppn Example 13 10.0 3.8 143 380 ppn

^(Fox ° ^of TXID ^of RP ^and earth cnýc ^h)

Note: Examples 5, 8, 9, 11, 12, 13 clearly show that when operating outside the range of the invention, 1-butene with an isobutene content below the maximum permissible threshold (0.1 wt.% Based on to 1-butene)

Table 2

Isomerization of trans-2-butene to 1-butene

Reaction P ^of dι .mu.m ^alkyl: 470 ° C, Melting absolute pressure of ^0.1 M? E ^ hmotootttní dlrnová space velocity 6 ~ ^h '

Catalyst

CeQ content SiO content (% by weight) (% by weight)

Specific surface pt h annealing at 1000 ° C (· ² / β)

Isobutene content in reaction products (linear butanes are always present in amounts predominantly temodynaic equilibrium at reaction heatW [ppi]

Example 14 2.5 1.5 183 150 Example 15 5.0 1.5 147 270 Example 16 7.5 1.5 136 300 Example 17 2.5 3.8 185 450 Example 18. 5.0 3.8 155 250 Example 19 7.5 3.8 150 150

All catalysts of Examples 3 to 18 were subjected to aging tests with a total of 332 cycles of reaction cycles and 40 regenerative cycles (152 cycles). Regeneration was performed at .aptotf 540 ®C ·

2.3993θ

Table 3

Isomerization of trans-2-butene to 1-butene

Reaction conditions: temperature 470 ° C, absolute pressure 0.1 MPa, mass hourly space velocity 6 h "

Catalyst

BaO content SiO ₂ content (% by weight) (% by weight)

Specific surface after 24 h annealing at 1000 ° C (m ² / g)

Isobutene content in reaction products (linear butenes are always present in amounts corresponding to thermodynamic equilibrium at reaction heat W [pp »j

Example 20 4.0 1.5 192 260 Example 21 8.0 1.5. 151 130 Example 22 4.0 3.8 189 470 Example 23 8.0 3.8 154 230 Example 24 3.5% (SrO) 3.8 185 280

Table 4

Isomerization of trans-2-butene to 1-butene

Reaction conditions: temperature 470 ° C, absolute pressure 0.1 MPa, mass hourly space velocity 6 h * l

Catalyst Fe ₂ Oj content (% by weight) SiO ₂ content (wt.%) Specific surface after 24 h annealing at 1000 ° C (m ² / g) Isobutene content in reaction products (linear butenes are always present in amounts corresponding to thermodynamic equilibrium © at reaction temperature) example 25 2.5 1.5 161 1100 ppm example 26 3.8 1.5 129 430 ppm example 27 Mar: 5.0 1.5 130 200 ppm example 28 2.5 3.8 158 0.41% example 29 3.8 3.8 165 0.21% example 30 5.0 3.8 141 420 ppm

SUBJECT OF THE INVENTION

Claims (5)

1. A catalyst based on aluminum oxide, characterized in TIA having the composition corresponding to the formula and A1 ₂ O _3rd b SiO ₂ . c Me _x O _y where It is an oxide of at least one divalent or trivalent metal selected from the group consisting of calcium, barium, lanthanum, lanthanides and iron, δ, b and ε are moles of alumina, silica and oxides of general interest Me _x 0 _y , ^xy . are together in the mutual ratio defined by the relation c ² n ^{b +} · В where В has a value in the range of 0.01 to 0.05 and J1 has a value in the range of 0.020 to 0.250, where the value of the ratio ⁽ c + · c) a it is in the range of 0.01 to 9.0 and £ is a number in the range of 0.7 to 0.1. A catalyst as claimed in claim 1, wherein the oxide of formula MexOy is lanthro trioxide and the ratio between moles of Laithai trioxide in moles and mica of silicon dioxide in moles in the catalyst is equivalent to mole ba ₂ O _3. 2 0.057 moles of SiO 2, + 0.014 with a silica content ranging from 0.000 to 0.050 mol. . 3. The catalyst of claim 1, wherein the oxide of the formula ΟΟ je is ferric iron and the ratio between moles of ferric oxide and moles of silica in moles of the catalyst corresponds to moles of ≥ 03-0.090. moles of S @ + + 0.018, the silicon ot content being in the range of 0.000 to 0.050 mol. 4. A catalyst according to claim 1, vyžMauujcí by • the Mex Oy oxide of the formula _Y is a calcium oxide and a ratio of yield! the amount of calcium oxide in moles and the amount of silica in moles in the catalyst corresponds to a CaO mole & 5. The catalyst of claim 1, wherein the oxide of formula (I) is boron oxide and the ratio between moles of barium oxide and moles of silica in moles in the catalyst corresponds to. •. ¹ mole BeO - 0.500 · mol SiO0 + 0.000, the silicon dioxide content ranging from 0.000 to 0.050 mol.