DK160915B - PROCEDURES AND PLANTS FOR CRUSHING OF SLAUGHTER WORKS FROM STEEL PRODUCTION - Google Patents

Description

DK 160915 B

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The invention relates to a process for treating highly acidic cation exchange catalysts based on styrene / divinylbenzene copolymers.

In recent times, cation exchange catalysts are often used for environmentally friendly synthesis of organic chemistry catalyzed by acids. These are syntheses such as esterifications, ester cleavages, hydrolyses, condensations, hydrations as well as alkylations and acetylations of aromatic compounds.

10 They have the advantage over the use of liquid acids that the catalyst can easily be separated from the product and that there is no waste acid as in the usual homogeneous catalysis.

A prerequisite for the practical use of 15 solid cation exchangers instead of liquid acid is, besides sufficient selectivity and volume time yield, the thermal stability of the copolymers under the reaction conditions at each time.

Particularly thermostable are highly acidic styrene / divinylbenzene copolymers substituted in the nucleus by halogen used under temperature conditions within a range of 100 to 200 ° C for syntheses, catalyzed with acids such as for hydration of lower olefins or for alkylation reactions.

British Patent No. 1,393,594 describes the preparation of cation exchangers, substituted in the nucleus at least once with halogen, and their use as thermally stable catalysts for reactions in aqueous and anhydrous media at temperatures of between 100 and 200 has been pointed out. ° C.

In recent years, nuclear chlorinated and nuclear fluorinated highly acidic cation exchangers have attracted special attention as catalysts.

However, the core halogenated aromatic monomers used for the preparation, such as chlorostyrene or fluorostyrene, cannot or only to a disproportionately high level.

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2 price available on the market.

U.S. Patent Nos. 3,256,250 and 4,269,943 disclose processes for preparing core-halogenated highly acidic cation exchangers wherein, in the case of the first-mentioned patent / styrene / divinylbenzene copolymer, the sulfone is first sulfonated and then are chemochlorinated or core fluorinated or, in the case of the latter patent, are first chlorinated or core brominated and then sulfonated.

10 The nuclear halogenated highly acidic cation exchangers, in one way or another, are decomposed by use as catalysts during the first 200 to 300 hours of hydrogen halide and sulfuric acid. In the hydration of lower defines having from 3 to 5 C-15 atoms to form the corresponding alcohols, for example, preferably by the syntheses of isopropyl alcohol and sec-butyl alcohol, large amounts of chloro and sulfonic acid groups are removed from the chlorinated catalyst in the form of hydrochloric or sulfuric acid. In special steel reactors 20, such strong corrosion, pitting and stress corrosion are observed that the interior of the reactors and reactor linings are destroyed. At the same time, such a catalyst gains an activity loss of up to 50% and a portion of the catalyst matrix is destroyed.

The object of the invention is thus to provide a process which permits the use of highly acidic cation exchange catalysts based on styrene / divinylbenzene copolymers, in the nucleus substituted with halogen, in special steel reactors, and which excludes or loses activity loss and matrix destruction. within tolerable limits. The object of the invention is achieved by subjecting a precursor with deionized water at elevated temperature prior to its use as a catalyst, excluding oxygen and metal ions, to a highly acidic cation-substituted acidic cation exchanger.

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The pretreatment is preferably carried out at a temperature within a range of from ca. 100 to approx.

150 ° C and a pressure which enables the liquid phase treatment.

5 The pretreatment is conveniently done in an apparatus whose surfaces which are in contact with the highly acidic cation exchanger and the treatment liquid contain no iron, for example in appliances which are coated with enamel, glass, ceramic, teflon or other thermally stable synthetic substances. .

Preferably, the water is freed prior to its use for dissolved oxygen.

According to a particularly preferred embodiment, the pretreatment is carried out with a solution of 15 or more alcohols having from 1 to 4 C atoms, especially with 3 or 4 C atoms, in the deionized water, the alcohol solution being suitably containing from 0.5 to 20% by volume. , preferably from 1 to 10% by volume of the alcohol.

In particular, the pretreatment is carried out up to a cleavage rate of less than 25 mg of H2 SO4 / 1 catalyst times per hour and 7 mg of HCl / 1 catalyst times per hour.

It has been established that washing a nuclear chlorinated catalyst with demineralized water 25 at 100 to 150 ° C under pressure in a special steel container leads to a decrease in its mechanical stability. In that case, part of the catalyst has completely lost its mechanical stability due to depolymerization.

However, the washing of the catalyst with demineralized water is carried out at 100 to 150 ° C under pressure over approx. 400 hours in an enamelled container, the amount of cleavage of the chloro and sulphonic acid groups (SO 3 H) is then so low that the core chlorinated highly acidic cation exchanger can initially be used problemlessly as a catalyst.

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4 lysator, for example, for hydration of lower olefins having from 3 to 5 C atoms to form the corresponding alcohols. However, a higher proportion (about 50 mg / l of water) of organic sulfonic acids in the wash water suggests 5 pa of a reduced long-term stability of the catalyst.

* 1

It has now surprisingly been found that by conducting the pretreatment with the exclusion of oxygen and metal ions with demineralized water, and especially with a solution of C3 or C4 alcohols in the 10 deionized water, the thermal and mechanical stability of a strongly acidic cation exchanger, prepared by halogenation and subsequent sulfonation of a styrene / divinylbenzene matrix or in reverse, for more than 8000 hours. The use of one from 0.5 to 20%, preferably from 1 to 10% aqueous Cg or C2 alcohol, shortens the treatment time to demineralized water by 50%. In the derived alcoholic solution, less than 2 mg per ml can be detected. liter of oligomeric sulfonic acid fragments.

20

A core halogenated strong acid cation exchanger thus treated can be used both in the direct hydration of propylene to form isopropyl alcohol and in the hydration of n-butenes to sec-butyl alcohol at temperatures above 150 ° C in conventional special steel reactors without corrosion problems. Also, the catalyst activity remains virtually unchanged for more than 1000 hours.

A preferred embodiment of the pretreatment of core halogenated highly acidic cation exchangers is given in the drawing of FIG. 1. Here, demineralized water or the alcoholic solution is added via conduit 1 to the device 2, liberated by dissolution with dissolved oxygen nitrogen and then transported via conduit 4 by means of a pump 3 to the treatment vessel 5.

Thereby, it is both possible to pass the water or aqueous alcoholic solution through the treatment vessel 5 once, and then direct it away via line 8,

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and recirculating from 80 to 90% via conduits 7 and 4, and only gradually closing from 10 to 20% out of recirculation via conduit 8 as wastewater. The recycling is advantageous because of the otherwise high consumption of 5 demineralized water or the alcoholic solution, especially on a technical scale.

The following examples illustrate the invention.

For testing the catalysts pretreated according to the invention, these are used for the preparation of isopropyl alcohol (IPA) from propylene according to Example 9 of German Patent No. 2,233,967 or for the preparation of sec-butanol (SBA) from n-butenes according to Example 2 of German Patent No. 2,429,770.

15 Comparative Example

The FIG. The treatment container specified in 1 comprises a special steel tube 1.4571 with a length of 3.0 m and a diameter of 26 mm. For the temperature setting, the special steel pipe is fitted with a steam jacket. All connection pipes and pump 3 are made of the same material (1.4571). In this pretreatment apparatus of FIG. 1, 1000 ml of a cation exchanger containing 3.7 mval / g dry substance sulfonic acid and 5.5 mval / g dry substance chlorine are filled.

25 Via line 1, the about one liter of demineralized water, still containing residual oxygen, to the special steel pipe at the sump. Using steam heating, set a temperature of 155 ° C.

At the top of the special steel pipe, the pressure of 30 io bar contained in the pipe is released and the water flow which, due to the hydrolytic decomposition of the Cl - and SOgH groups contains hydrochloric and sulfuric acid, is cooled to 20 ° C.

The amounts of hydrochloric and sulfuric acid obtained are followed analytically. The values found in mg per 35 liters of catalyst and hour (mg / l of catalyst x hour) after the elapsed number of hours specified are compiled in Table I.

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Table I

after ... mg H ^ SO ^ mg HC1 mg org ♦ sulfonic acid hours 1 KAT x hour 1 CAT x hour 1 CAT x hour 4 190 1,030 1,350 5 24 · 60 175 850 72 45 80 800 120 35 29 580 240 29 12 550 360 21 6 530 10

Upon removal of the catalyst from the pretreatment apparatus, it is determined that approx. 20% of the catalyst has turned into a brown, transparent, seed-like product.

A study of the catalyst fraction that is not destroyed shows a 28% load on the residual capacity. Furthermore, the mechanical stability of the catalyst fraction which is not destroyed is greatly reduced. Using this catalyst for IPA synthesis by direct hydration of propylene, it achieves only approx. 50% of the expected 20 benefits.

Example 1

The test described in the comparative example is carried out under otherwise similar conditions in an apparatus in which the treatment vessel 5 consists of a 3 m long, internally enamelled tube with sheath and the connection lines and pump are made of Teflon.

The amounts of hydrochloric and sulfuric acid cleavage amounts found are summarized in Table II.

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Table II

after ... mg H ^ SO ^ mg HC1 mg org, sulfonic acid hourly 1 CAT x hour 1 CAT x hour 1 CAT x hour 4 185 1,010 68 5 24 61 174 45 72 44 78 38 120 36 29 38 240 28 13 35 360 20 6 29 10

The catalyst / removal of the pre-treatment apparatus is completely non-degraded this time.

The use of this catalyst for SBA synthesis by direct hydration of n-butenes shows, however, in long-term experiments a diminished mechanical stability.

The catalyst only reaches approx. 85% of expected performance.

Example 2

The experiment described in Example 1 is repeated with the proviso that the demineralized water stream prior to delivery to the treatment vessel is liberated from dissolved oxygen by a nitrogen annealing via a frit. The following decomposition quantities are obtained:

Table III

after ... mg I ^ SO ^ mg HCl mg org. sulfonic acids hourly 1 CAT x hour 1 CAT x hour 1 CAT x hour 4 188 1,015 2.0 24 60 171 1.5 30 72 41 80 1.2 120 35 30 1.3 240 28 12 1.0 360 19 5 1 The catalyst thus treated is completely non-degraded and shows in long-term experiments in connection with the SBA synthesis with direct hydration of n-butenes

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for 8000 hours no appreciable reduction in mechanical stability.

Example 3 Example 2 is repeated with the proviso that instead of the water, free of dissolved oxygen, an aqueous solution is used, subjected to the same treatment containing 10% isopropyl alcohol.

Under otherwise similar conditions, the treatment time is reduced by half to 180 hours. The properties and activity of the treated catalyst are equal to the properties and activity of the catalyst obtained from Example 2, as determined by using this catalyst for the synthesis of SBA.

15

Example 4

Example 2 is repeated with the proviso that instead of the water, liberated from dissolved oxygen, an aqueous solution is used, subjected to the same treatment containing 1% SBA. After 180 hours, the amounts of sulfuric acid or hydrochloric acid obtained by hydrolytic decomposition have reached 2.22 mg / l of catalyst times per hour and 6 mg of HCl / liter of catalyst times per hour. The content of sulfonic acid fragments (organic sulfonic acids) is constantly below 2 mg / liter of catalyst times per hour. In the SBA synthesis, the catalyst exhibits the same good properties as the catalyst obtained in Example 3.

Example 5

Example 4 is repeated with the proviso that treatment with the same solution containing 1% SBA is started at 110 ° C and then the temperature is increased to 155 ° C. In addition, to minimize the aqueous solution formed, 90% of the solution is recycled and only 10% is gradually eliminated. The following decomposition quantities are obtained:

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Table IV mg org. sulfone after ... mg H ^ SO ^. mg HCl acids__Temp.

1 hour CAT 1 hour 1 CAT x hour 1 CAT x hour ° C.

5 4 54 302 1.5 110 24 35 95 1.1 120 72 38 71 1.2 148 100 37 62 1.4 155 120 34 40 1.4 155 10 160 29 17 1.2 155 200 22 9 1.0 155 210 21 6 1.1 155

The catalyst thus treated, in terms of its properties and activity, is equal to the catalysts obtained from Examples 3 and 4, which are similarly determined by the synthesis of IPA and SBA by directly hydrating the corresponding olefins.

Due to the total loss of sulfonic acid by the temperature program 20, this catalyst achieves longer service life by the alcohol syntheses by direct hydration, or by an alkylation synthesis.

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Claims (7)

A process for treating highly acidic cation exchange catalysts based on styrene / divinylbenzene copolymers, characterized in that prior to its use as a catalyst, excluding a highly acidic cation exchanger, it is subjected to the core substituted with halogen, a pretreatment with deionized water at elevated temperature, and · the pretreatment is carried out at a temperature within a range of approx. 100 to approx. 150 ° C, and a pressure allowing the liquid phase treatment. Process according to claim 1, characterized in that the pretreatment is carried out in an apparatus in which the materials in contact with the highly acidic cation exchanger and the treatment liquid contain no iron. Process according to one of Claims 1 or 2, characterized in that water is used which is previously liberated from dissolved oxygen. 4 C atoms. Process according to one of claims 1, 2 or 3, characterized in that the pretreatment is carried out with a solution of one or more alcohols having from 1 to 4 C atoms in the deionized water. Process according to claim 4, characterized in that a solution of an alcohol of 3 or 4 is used Process according to one of Claims 4 or 5, characterized in that an aqueous 30 alcohol solution containing from 0.5 to 20% by volume, preferably from 1 to 10% by volume of the alcohol, is used. Process according to one of Claims 1, 2, 3, 4, 5 or 6, characterized in that the treatment is carried out up to a decomposition amount of less than 25 mg of E mg HCl / liter catalyst times per hour.