DE3012915A1 - METHOD FOR PRODUCING A CALCIUM BORPHOSPHATE CATALYST - Google Patents

Description

ZUR EbJHuTi) ILUWb EIWES KALZIUMBOfiIHOSPHATKATALYSiiTUBS

The present invention relates to the production of catalysts which are used, for example, in the production of isoprene from isobutylene and formaldehyde and in the dehydration of alcohols, and more precisely to a process for the production of fine calcium borophosphate catalyst for the cleavage of 1,2-dioxanes, especially 4,4 - Dime thy 1-1, J-Dioxanes (also called ΊΜΏ ) to isoprene.

A process is known for the production of phosphates II. Group, which are used as catalysts for the selective bond cleavage - O - G in the organic compounds, in particular for the splitting of 4,4-dimethyldioxane-1,2 to isoprene as well as for the dehydration of alcohols by the precipitation of neutral metal phosphates of the II group from water solutions their salts and water-soluble salts of phosphoric acid with subsequent secretion of the H ie -.erschlag it, the 'laundry and

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: -. Λ ::. '· Υ ^: τ OU 3012315

shaping the catalyst granulate from the paste obtained can be used (U.S. Patent 3,872,216).

The catalysts prepared by the above process are due to the low selectivity (78-82 mol%) and small Activity marked that the low barely speed of EMD throughput (0.7 h ~ ") and high operating temperature (approx.

O) conditional. The selectivity is related to the amount of isoprene formed, expressed in moles, and to the amount of converted DMD expressed in moles.

The selectivity value is determined by the composition and structure of the catalyst as well as by the working parameters of the Catalyst operation conditional ?.

As the selectivity increases, the amount of raw material required to obtain one unit of the finished product decreases (DMD). The insufficiently high selectivity of the catalyst produced by the known process causes the great raw material consumption for isoprene production, the is approx. 2.10-2.25 kg MD per 1 kg isoprene.

The activity of the catalysts depends on their acidity which is determined by the number and strength of the active centers, and can be characterized by the degree of DMD conversion * the.

The DMD conversion rate is expressed in percent Ratio of the amount of DMD converted to the total amount of DMD passed through Lot.

It is currently known a method by which the

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Calcium phosphate catalysts through the reaction of calcium and .Phosphoric acid salts in the water-ammonia medium, the secretion from the reaction mixture of the precipitate formed, through the washing, the drying and the thermal treatment of the Precipitation in the superheated steam or steam / air mixture be prepared at elevated temperatures (US-PS 384-6338).

The catalysts prepared by the process described show low activity.

In addition, the calcium phosphate catalysts obtained in the manner described have a low performance of 0.3 0.4 t of isoprene;) e 3 ^{m of the} catalyst per hour "is inherent.

The performance of a catalyst depends on its activity, selectivity and room speed of raw material supply.

In the known method mentioned, the thermal takes place Treatment of the catalyst at elevated temperatures, which requires the heat transfer medium to be overheated up to 650-800 ° C and leads to increased energy consumption of the process as well for the application of the special thermally stable materials for production of fieactors for catalyst recovery.

In addition, the above-mentioned, .Wise produced Catalyst has a relatively short life, which is equal to 250 h.

The service life of a catalytic converter depends on many parameters, including its composition and structure, Activity, operating temperature and coke deposition * Below the Coke deposition means coke formation on the catalyst

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gate surface in the DMD implementation. The coke deposit will as the ratio of the amount of coke deposited (in moles) to the amount of converted DMD (in moles), expressed as a percentage, certainly"

Apart from the advantages of using the known method produced calcium phosphate catalyst, was not an industrial production process of the DMD breakdown developed such a catalyst because no catalyst has been invented which has selectivity and stability necessary for production with the high turnover of the target product are sufficient

The invention is based on the object, through the changes in the process engineering manufacturing conditions an increase in the activity at low operating temperatures, the effectiveness and the selectivity as well as the service life of the Catalyst together with the reduction of coke deposits in the DMD conversion.

The task at hand is achieved by developing a procedure for the production of a calcium boron phosphate catalyst by the reaction between calcium salts and phosphoric acid salts in the water-ammonia medium with subsequent secretion the reaction mixture of the precipitate formed, its Forming, drying and thermal treatment at elevated temperatures in the presence of steam or steam / Inert gas-Ciemisch dissolved, in which according to the invention the thermal Treatment in the presence of water vapor / boric acid or water vapor / Boric acid / phosphoric acid mixture is carried out.

Carrying out the thermal treatment on this

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Way allows the production of calcium borophosphate catalyst which is stable at low operating temperatures (equal to or below 3CX) ⁰ O),

• It is ^{recommended to carry out the thermal treatment at} a boric acid concentration of 0.01-0.8 ^ ew.%,

which allows the production of a calcium borophosphate catalyst, which has a high activity at the low operating temperatures «

It is preferred the thermal treatment in the presence of

• π ^ / τ> , j n with a / boric acid concentration

water vapor / boric acid- ^ emiscn / of 0.02 uew.%

to perform

The best results can be achieved when carrying out the thermal treatment with the specified amount of boric acid.

Ea is also useful, the thermal treatment under Molar ratio of boric and phosphoric acid 0.1-10: 1.

The increase in the stability of potassium borophosphate catalyst is at the stated molar ratio of boron and phosphate acids achieved.

It is preferred here to carry out the thermal treatment with the equimole ratio of boric and phosphoric acid.

The best stability results can be obtained under the equimole ratio boric and phosphoric acid can be achieved.

Jtüs is to be recommended, the vi / echael effect of the calcium salts and Phosphoric acid salts in the water-ammonia medium under molar ratio

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nis the output bicomponent en 1.5: 1 to be carried out.

The interaction of the components mentioned under the conditions described above leaves a calcium borophosphate catalyst obtained with the low coke deposit.

It is recommended to check the interaction between calcium folds and phosphoric acid salts in the water-ammonia medium at a molar ratio of the starting components corresponding to 1.5-5.0 : 1 to carry out and the reaction mixture formed to be treated with the jfh & phosporic acid solution until the pH value is 5.0-7.0.

The above-mentioned ranges of the starting component ratio and ensure the pH value of the heating mixture the production of a calcium boron phosphate catalyst with the required structure and composition,

It is preferable to use the reaction mixture with the phosphoric acid solution to be treated up to the pH value 5 »5-6.0.

The implementation of the process for the preparation of calcium borophosphate catalyst under the above-mentioned conditions allows a catalyst with high selectivity (87.2-88 mol.%) And increased activity at low operating temperatures of 30O ⁰ C or below 300 ^o G, low coke deposition and high ötability maintained, the DMD conversion level remains practically constant within 100 h.

The stated and other objects and novel features of the present invention are set out in the attached claims determined and the iSrfindung is when considering the subsequent

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following detailed description of their implementation examples clarified in more detail.

The method of making the calcium borophosphate catalyst is realized in the following way »

As starting reagents, the solutions of calcium salts, z. B, of calcium chloride, and those of phosphoric acid salts, for example, of diammonium phosphate, disodium phosphate and others. The solution of Phpaphorsäuresalz is added before the WLchsel _WiXkUn-0 with the calcium salt solution is a solution of ammonia for the purpose of adjusting the pH value.

The calcium salt and phosphoric acid salt solutions are placed in a container gradually poured with continuous stirring the resulting suspension. The interaction will carried out at a molar ratio of calcium salts and phosphoric acid salts 1.5: 1. The reciprocal effect is also at, molar ratio the output components of 1.5 · »· 5> Οί1», preferably 2.5: 1 possible »In this ball the feaction mixture formed with the solution of phosphoric acid down to the pH value 5fO-7fO, preferably 5 »5-6» O treated.

The above-mentioned ranges and the proportions of the calcium and phosphoric acid salts and the range of the The pH of the reaction mixture ensures the required Structure and composition of the obtained calcium boron phosphate catalyst,

The leather flip formed is passed through the filter or through any other known process apart from calcination

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Salt anion washed free with distilled water, granulated according to the known experience and ^{dried at a temperature of 110 140 0} C, the calcium phosphate obtained being obtained, which is then introduced into a reactor.

The reactor is a resin tube with a diameter of 20-26 mm. It is placed in an electric furnace and the im The catalyst located in the reactor is heated at 400-6Q0 ° C with steam treated with the addition of boric acid or a mixture of boric and phosphoric acids.

In the preparation of the calcium borophosphate catalyst without processing the reaction mixture with phosphoric acid solution the thermal treatment is preferably carried out at 400.degree.

If the manufacturing process of a calcium boron phosphate catalyst includes a stage of treatment of the suspension with phosphoric acid down to the pH value of 5.0-?, 0 , the thermal

o see treatment preferably at 450 C.

The thermal treatment can also be carried out with steam with the addition of inert gas, in particular nitrogen, argon, etc. will.

The water vapor is with the Raumgeschwindijkeit 1.0 2.0 h supplied. The boric acid content in the steam is 0.01-0.8% by weight, preferably 0.02% by weight,

If the thermal treatment of the catalyst in the presence If a boron and phosphoric acid mixture is made, the boric acid content in the steam is Qi, 00i-0.02% by weight, preferably 0.02% by weight and the phosphoric acid content 0.0015-0.03% by weight, preferably 0.003% by weight.

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During the treatment, the molar ratio of boric and phosphoric acid should be kept in the range 0.1-10: 1 _f preferably 1: 1 «

The treatment time is 2-50 hours, preferably 20-30 hours.

The calcium borophosphate catalyst obtained has the following properties / DMD conversion within 100 operating hours remains practically constant (90%), the selectivity is 87 »5-88 mol% j the coke deposit - below 1 mol%,

Below are typical examples that identify specific Illustrating aspects of the invention and expressing its characteristics and advantages as clearly as possible. Example 1 ^ 1

As a starting component for the production of the starting calcium " phosphate catalyst one takes 1.78 l of an aqueous calcium chloride solution (calcium chloride content is 101.892 g per 1 Liters) and 1.608 liters of an aqueous diammonium phosphate solution (diammonium phosphate content is 51 »08 g per 1 liter), whereby the latter an ammonia solution (152.15 g per 1 liter) based on the ratio of 2.35 moles of ammonia per 1 mole of diammonium phosphine is admitted. The starting components are placed in a feed container poured gradually · The molar ratio of calcium chloride and diammonium phosphate is 2.5: 1 · The pouring together the solution takes place within 2 hours with the continuous stretching of the resulting reaction mixture, that represents a suspension that. pH of the reaction mixture is 9 »Q ± 0.05. The suspension is 150 ml of the

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Phosphoric acid with a concentration of 281.26 g of ßeaktionsgemisches added to 5 »75 per 1 liter to reduce the pH · The formed precipitate is

Filtration of the & e action mixture separated, dried by the Ohlorion with the distilled ^w ater washed, granulated in a press and at the temperature 120 C "

24 cm of the starting calcium phosphate catalyst are in A reactor consisting of a quartz tube with a diameter of 20-26 mm is inserted · The .reactor is placed in an .electric furnace · The starting calcium phosphate catalyst is used treated with steam within 20 hours at a temperature of 450 C with the addition of 0.01% by weight of boric acid

The catalyst is used in the DMD cleavage in a steam atmosphere checked with subsequent generation, which from The deposited coke is burned off every 2 hours of operation.

The DMD cleavage process is the average

ο
Operating temperature of 280 C and atmospheric pressure carried out within 2 hours. DMD is applied at a rate of 24 cm / h

3 and water - conveyed in an amount of 48 cm / h what the Space velocity the DMD throughput of 1.0 h and the IM D dilution with steam in a ratio of 1: 2.

A regeneration cycle follows the contact cycle Temperature 425 C with the addition of 48 cm of water and 16800 cm Air. The test of the catalyst lasts 100 hours.

The catalyst is then using Cras liquid chromatography analyzed. The deposited coke beam

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is determined according to the known procedure «

The test results are shown in Table 1 below listed "

Example 2.

The starting calcium phosphate catalyst is based on the im Example 1 produced in the manner described «The produced Calcium asphate catalyst is used with water vapor within 20 hours at the temperature 4 ° C with the addition of 0.8 Ciew.% treated by boric acid. Testing of the produced calcium borophosphate catalyst runs as in example 1.

The test results are in the 'i' table below cited.

Example 3

The starting calcium phosphate catalyst is based on the example 1 and described in Example 2 manner. The calcium phosphate catalyst produced is steamed within 20 hours at the temperature 450 0 with addition treated by 0.02 Uew.% of boric acid.

Testing of the produced calcium borophosphate catalyst runs as in example 1.

The test results are shown in Table 1 below cited.

Example 4

The external calcium phosphate catalyst is based on the in the examples. 1 »2 described way produced« The calcium phosphate catalyst produced is called »Kasser-

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steam within 20 hours at the temperature 450 C with addition of 0.02% by weight boric acid and nitrogen in an amount of 4800 cnr / h, which is a space velocity of nitrogen addition of 200 h ~ * corresponds to treated. Examination of the manufactured Calcium borophosphate catalyst proceeds as in Examples 1, 2.

The test results are shown in Table 1 below cited.

Example 5

The starting calcium phosphate catalyst is based on the im Example 1 described manner prepared. The calcium phosphate catalyst produced is treated with steam inside

half past 20 hours at the temperature ^ 50 C with the addition of 0.02

3% by weight boric acid and air in an amount of 4800 cm, which is a Space velocity corresponds to the addition of air of 200 h ".

Testing of the produced calcium borophosphate catalyst runs as in example 1.

The examination results are shown in the following table 1 listed ·

Example 6

The starting calcium phosphate catalyst is prepared in the manner described in Example 1. The manufactured Calcium borophosphate catalyst is treated with steam for 20 hours at the temperature 400 C with the addition of 0, Q2 eiew.% Boric acid.

The calcium borophosphate catalyst produced is tested as in Example 1.

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The test results are in the table below cited.

Example 7

The starting calcium phosphate catalyst is prepared in the manner described in Example 1. The calcium phosphate calcium analyzer produced is treated with steam within 20 hours at the temperature 600 ^° C. with the addition of 0.02% by weight boric acid.

The calcium borophosphate catalyst produced is tested as in Example 1.

The test results are in the table below cited.

Example 8

The starting calcium phosphate catalyst is prepared in the manner described in Example 1. The Kalziumphosphfctkatalysator produced is treated with Waseerdampf within 20 hours at the temperature of 450 ⁰ C by adding 0.002

oew.% boric acid and O ₁ OOJ oew. # phosphoric acid.

Testing of the calcium borophosphate catalyst produced runs as in example 1

The test results are shown in Table 1 below listed ·

Example 9

The starting calcium phosphate catalyst is based on the im Example 1 described manner prepared. The calcium phosphate catalyst produced is treated with V »asserdarapf within

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half past 20 hours at the temperature 4OO ° C with the addition of 0.002% boric acid and 0.002% phosphoric acid »

Testing of the produced calcium borophosphate catalyst runs as in example 1.

The test results are in the table below 1 listed,

Example 10

The starting calcium phosphate catalyst is based on the im Example 1 described manner prepared. The calcium phosphate catalyst produced is treated with steam inside of 20 hours at the temperature 600 ° C with the addition of

0.002 (each% boric acid and 0.003% phosphoric acid.

The calcium borophosphate catalyst produced is tested as in Example 1.

The test results are in the table below 1 listed.

Example 11

The starting calcium phosphate catalyst is based on the im Example 1 described manner prepared. The calcium phosphate catalyst produced is treated with steam inside of 20 hours at the temperature 450 ° 0 with the addition of 0.02% by weight boric acid and 0.0OJ sew.% Phosphoric acid.

The calcium borophosphate catalyst produced is tested as in Example 1. _v

The test results are in the table below 1 listed,

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Example 12

The starting calcium phosphate catalyst is prepared in the manner described in Example 1. The calcium phosphate catalyst produced is treated with steam inside

o half of 20 seconds at the temperature 450 C with the addition of

0.002 izew,% boric acid and 0.03 ^ ew.Sfc phosphoric acid

Testing of the produced calcium borophosphate catalyst runs as in example 1.

The test results are in the table below 1 listed,

Example 12

The starting calcium phosphate catalyst is based on the im Example 1 described manner prepared. The calcium phosphate catalyst produced is treated with steam inside

o half of 20 hours at the temperature 4-50 C with addition of 0.002Grew,% boric acid and 0.0OJ% by weight phosphoric acid and Nitrogen in the amount of 4800 cm, which is an iiaum velocity corresponds to the addition of nitrogen for 200 h.

The calcium borophosphate catalyst produced is tested as in Example 1.

The test results are shown in Table 1 below cited,

Example 14

The calcium phosphate catalyst is based on the im Example 1 described manner prepared. The calcium phosphate catalyst produced is treated with steam inside

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half of 20 hours at the temperature 450 G with addition from 0.0 to 2% by weight boric acid and 0.005% by weight phosphoric acid and air

in an amount of 4800 cm, which is the speed of the

-1
Air addition of 200 h corresponds.

Testing of the produced calcium borophosphate catalyst runs as in example 1.

The test results are shown in Table 1 below cited,

Example 15

1.18 to 1 as a starting reagents for preparing a catalyst takes a Kalziumchlaridlßsung (calcium chloride content 99.8 g.pro 1 liter) and 2.0 liter of disodium phosphate (Dina triumphosphatgehalt 50 _f 21 g of salt per 1 liter). An ammonia solution with a concentration of 10 g / l is added to the disodium phosphate solution immediately before the reaction, based on the ratio of 1.5 mol of ammonia per 1 mol of disodium phosphate. The calcium chloride solution and the disodium phosphate solution are gradually poured into a feed container over the course of 2 hours while continuously stirring the resulting suspension. The interaction takes place unuej? the constant volume ratio of the solution, which ensures the molar ratio of calcium chloride and disodium phosphate 1.5 «1t °, the pH of the suspension is 9.0 ^ 0.05 Washed off distilled water, granulated and dried at the temperature 120 ⁰ G, the calcium phosphate catalyst produced

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sator is treated with steam within 20 hours at the '! temperature 400 ⁰ C with the addition of 0.02 "iew.% boric acid.

The test of the calcium borophosphate catalyst produced is carried out as in Example 1

The test results are in the table below 1 listed,

Example 16

The Austjang calcium phosphate catalyst is applied to the im Example 15 described «/ prepared.

The calcium phosphate catalyst produced is treated with steam for 20 hours at that temperature 400 ° C with the addition of 0.02% by weight boric acid and 0.003% by weight Phosphoric acid,

Testing of the produced calcium borophosphate catalyst runs as in example 1.

The test results are in the table below 1 listed.

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Table 1
of the catalyst tests in the IMD fcipalt process

Operating temperatur:

Tree speed of EMD throughput:

MD dilution with HO:

280 ° G

1 h 1: 2

Characteristics catalysts loud

of the examples

Cycles MK 'IÄD conversion efficiency, % selectivity, mol% coke deposit, mol%

1 50 1 86.9 85.0 89.9 87.3 87.6 87.5 0 * 77 0.61 0.97

1 50 1 50 1

86.0 90.0 86.5 90.1 86.2 90.2

87.6 87.4- 87.7 87.3 87.7 87.5

0.67 0.95 0.64 0.99 0.65 0.98

50 1 ,1 50 86.3 90 , 2 86.3 87.7 87 99 87.6 0.62 0, 0.66

Table 1
(Continuation)

!? ' 8 9 10 11 12 13 14 15 16

5p 1 50 1 50 1 50 1 50 1 50 1 50 1 50 1 50 1 50

79.6 90.1 89.8 90.3 89.9 83.182.7 90.0 89.3 89.9 89.1 90.2 89.8 90.1 89.9 35.1 29.6 35, 2 34 ·, 2

ί ί ■ ^y

i?, 5 "8 ^, 8 87.5 88.0 87.3 87.7 87.5 87.7 87.5 87.7 87.4 87.7 87.4 87.9 87.4 8ö, 0 84.8 84.8 85.0 85.0

^; .48 0.36 0.72 .0.54 0.92 0.56 0.43 0.33 0.81 0.62 0.82 0.63 0.81 0.55 0.83 0.52 0, 18 0.13 0.16 0.12

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Claims (1)

VEKi ¹ AHREN FOR THE PRODUCTION OF A CAMUMORPHOSPHATE CATALYSATOB Claims 1 · Method of making a calcium borophosphate catalyst by the reaction between calcium and phosphoric acid 'salts in the water-ammonia medium, the secretion from the reaction mixture of the precipitate formed, its shaping, drying and thermal treatment at elevated temperatures in the presence of steam or steam / inert gas chamber, characterized in that the thermal treatment in the presence of steam / boric acid mixture or Steam / boron and phosphoric acid mixture takes place. 2 · The method according to claim 1, characterized in that the thermal treatment in the presence λ « * χ. / · * η * Ι ³ · * ^e 4 ⁿ em boric acid _{content ηΛ} „ _o of water vapor / boric acid mixture / of o, 01-0.8 % By weight occurs 5. The method according to claim 2, characterized in that the thermal treatment in the presence with a boric acid content of water vapor / boric acid mixture / of 0.02% by weight he follows. 4 «The method according to claim 1, characterized in that the thermal treatment under molar ratio of boric and phosphoric acid 0.1-10: 1 takes place » 3. The method according to claim 4, characterized in that the thermal treatment takes place under the equimole ratio of boric and phosphoric acid, 6, method according to claim 1, characterized in that the reaction between calcium salts and ORIGINAL INSPECTED Phosphoric acid s al ζ en in the water-ammonia medium under mol- ratio of the starting components 1.5: 1 expires. 7 · The method according to claim 1, characterized in that the reaction between calcium salts and Phosphoric acid salts in the water-ammonia medium with a molar ratio of the initial components 1.5-5 »O: 1 and that Reaction mixture with phosphoric acid solution to pH 5 »0-7.0 "is treated · 8. The method according to claim 7 _t, characterized in that the reaction mixture is treated with phosphoric acid solution to pH 5.5-6 »0. 130041/0628 [copy