Title of Invention

A PROCESS FOR THE PREPARATION OF AN ENVIRONMENT FRIENDLY CATALYST FOR LOW TEMPERATURE CONVERSION OF NITROBENZENE TO ANILLINE IN VAPOUR PHASE FIXED BED REACTORS.

Abstract

The invention relates to an environment friendly transition metal catalyst (free from hazardous chromium component) for low temperature conversion of nitrobenzene to aniline in vapour phase at about 140°C to 230°C, preferably 150°C to 220°C. The catalyst of the present invention contains oxide of the said metal promoted with the oxide or oxides of one or two elements, preferably oxide of one element of the lanthanide series and is supported on a composite support material in an optimized proportion of oxides of Group IIA, IIIA and IVA elements with improved total surface area & copper surface area, as well as an optimized proportion of binder, resulting in a more active and selective and stable catalyst suitable for commercial fixed bed reactor applications.

Full Text

FORM 2 THE PATENT ACT, 1970 (39 of 1970) AND THE PATENT RULES, 2003 COMPLETE SPECIFICATION (See Section 10, Rule 13) TITLE OF THE INVENTION: A process for the preparation of an environment friendly catalyst for low temperature conversion of nitrobenzene to aniline in vapour phase fixed bed reactors. PREAMBLE TO THE DESCRIPTION : COMPLETE SPECIFICATION The following specification particularly describes the invention and the manner in which it is to be performed. APPLICANT(S) (a) Name: (b) Nationality: (c) Address: M/s. HINDUSTAN ORGANIC CHEMICALS LIMITED Indian Mr. A. S. Didolkar, CMD 81, Maharshi Karve Road, MUMBAI-400 002, Maharashtra, India. M/s. SUD-CHEMIE INDIA PRIVATE LIMITED Indian Mrs. A. A. Lalljee, MD Edayar Industrial Development Area, P.O. Binanipuram, PIN- 683 503, Kerala, India 1 Introduction The invention relates to an environment friendly transition metal catalyst (free from hazardous chromium component) for low temperature conversion of nitrobenzene to aniline in vapour phase at about 140°C to 230°C, preferably 150°C to 220°C. The catalyst of the present invention contains oxide of the said metal promoted with the oxide or oxides of one or two elements, preferably oxide of one element of the lanthanide series and is supported on a composite support material in an optimized proportion of oxides of Group IIA, IIIA and IVA elements with improved total surface area & copper surface area, as well as an optimized proportion of binder, resulting in a more active, selective and stable catalyst suitable for commercial fixed bed reactor applications. Background of the Invention Catalysis has played a major role in last few decades, in the development of environmentally benign processes with improved economics. However demands for new catalytic systems focus on their disposal aspects too. The catalysts for the manufacture of aniline are known as copper chromite in the market. The presence of chromium (hexavalent chromium) has been found to be toxic to living organisms and a cause for pollution problems in waste waters. It is now recognized as a human carcinogen. Therefore we have already initiated work in green chemistry by way of development of chromium free catalyst and achieving further improvements in the same. Prior Art Catalytic hydrogenation of nitro compounds, particularly nitrobenzene to aniline has been a widely studied and published area. The available literature can be classified into the following: > Nickel / Zirconium based catalysts (US Patent No. US 6140539, 6680280, Japanese Patent No. JP 33177060); 2 > Noble metal catalysts & zeolite (US Patent No. US 6054617, 4265834, Europian Patent No. EP 458006, Chinese Patent No. CN 1861254 & CN 1803761 and Indian Patent No. IN 190552); > Copper based catalysts with or without additives (US Patent No. US 6049008, Chinese Patent No. CN 1768941, 1768930, Russian Patent No. RU 221745, 2102138). Commercial copper chromite catalysts for aniline manufacture have been referred to in European Patent No. EP 301853 as well as other literature; > A recent Chinese Patent (CN 1367040) describes hydrogenation with CeC>2 containing 2-16% copper, where the catalyst is prepared by precipitation of Cu and Ce salts with aqueous base solutions, followed by drying and cleaning. Our previous patent (IN 197777) revealed the development of a chrome free catalyst with high conversion of nitrobenzene in vapour phase (at about 150°C to 230°C) under the process conditions of commercial plants. The catalyst contains oxides of two elements of lanthanide series as promoter supported on a composite support comprising oxides of group II, Ml and IV elements in definite proportion. The catafyst of the present invention is a high pore-volume, high surface area catalyst, with optimized binder concentration, which exhibits very high conversion of nitrobenzene under the process condition of commercial plants and is highly selective for the conversion of nitrobenzene to aniline. Objective of the Invention The main objective of the present invention is to provide an improved hydrogenation catalyst for the hydrogenation of nitrobenzene to aniline with high activity and selectivity. This is achieved by improvements in the surface area and pore volume of the catalyst by optimizing the ratio of copper to oxides of silicon and calcium. 3 Improvement in the copper surface area of the catalyst, which also has effect on the catalyst activity and selectivity, is achieved by optimizing the atomic ratio of copper to rare earth oxide. Another objective of the present invention is to optimize the binder concentration in the catalyst with the required degree of strength to withstand the operating conditions, thus identifying the minimum required binder concentration, maintaining the desired level of porosity for the catalyst. Description of the Invention The present invention relates to a process for the preparation of transition metal catalyst for the conversion of nitrobenzene to aniline in the vapour phase in fixed bed reactors. According to this invention, the catalyst contains oxide of the said metal and is promoted with the oxide or oxides of one or two elements, preferably oxides of two elements of lanthanide series. In the practice of present invention, a combination of the oxides of two elements of the lanthanide series as promoters is preferred for better activity and selectivity of the catalyst. The said catalyst is supported on a composite support material comprising the oxides of Group IIA, IIIA and IVA elements in definite proportions. The aluminate of alkaline earth metal is used as a binder to impart proper mechanical strength to the catalyst particles. The shape of the catalyst particles of the present invention is cylindrical tablet of length 3 to 6 mm, preferably 4.7 to 5.2 mm and diameter 3 to 6 mm, preferably 4.7 to 5.2 mm. We herein disclose a process for the preparation of an environment friendly transition metal catalyst for low temperature conversion of nitrobenzene to aniline in the vapour phase, which catalyst contains oxide of the said metal which is promoted with the oxide or oxides of one or two elements, preferably oxides of two elements of the lanthanide series and is supported on a composite support 4 material comprising oxides of the Group IIA, IIIA and IV A elements, which is prepared by the process comprising the steps of: (i) precipitating the said metal from its salt solution as metal hydroxyl carbonate on the said support containing the oxide(s) of lanthanide element(s) at about 50°C -100°C and aging the precipitated material at about 60°C -80°C; (ii) cooling the precipitated material and washing the same with deionised water; (iii) drying the washed material at about 120°C - 250°C; (iv) calcining the dried material at about 300°C - 600°C, preferably at 400°C - 500°C; (v) mixing the calcined material with a suitable binder and a lubricant; (vi) granulating the resulting material to about 12-100 mesh size; (vii) tabletting the granulated material to catalyst particles of desired shape and size; (viii) finally calcining the tabletted material at about 400°C to 700°C, preferably at 450°C to 550°C to produce the finished product of desired higher mechanical strength. The transition metal salt used in the present invention is copper nitrate. The elements of the lanthanide series are lanthanum and cerium, the oxides of which are used in the mole ratio of 1:1. The Group IIA, IIIA and IVA elements are calcium, aluminium and silicon respectively. The composite support material contains oxides of the said elements having mole ratio of calcium oxide to alumina to silica of 2 to 4:1:2 to 5. The precipitation is carried out by adding metal nitrate solution to the solution of an alkali metal carbonate in the pH range of about 7 to 10 or by adding the solution of the alkali metal carbonate to metal nitrate solution in the pH range of about 2 to 7. 5 In the practice of this invention, sodium carbonate is used as the preferred alkali metal carbonate. The addition of copper nitrate solution to the alkali metal carbonate or vice versa at a controlled slow rate with vigorous agitation is carried out to ensure that the precipitate is not getting agglomerated. Copper nitrate solution is prepared by dissolving the said nitrate in deionised water. Copper solution which is taken for precipitation contains between 30 and 100 grams of copper per litre, preferably between 70 and 90 grams per litre. Sodium carbonate solution is prepared by dissolving the said salt in deionised water. Sodium carbonate solution used for precipitation contains about 50-250 grams per litre, preferably 100 - 200 grams per litre of the said carbonate. According to this invention, a mixture of copper nitrate solution and the said promoters is added to a well-agitated solution of the alkali metal containing the said support material. Alternatively, the alkali metal solution and the mixture of copper nitrate solution, the said promoters and support material, are simultaneously added to boiling water. The pH of the mixture during precipitation is maintained at about 6 to 8. The temperature is maintained in the range of about 50° to 100°C, preferably at 60°C - 80°C. The precipitation is carried out over a period of 2 to 5 hours. The precipitated material is aged for a period of about 1-3 hours to improve crystallinity. The aging is carried out in the temperature range of about 60°C to 80°C. The slurry is then cooled to about 30°C - 35°C. Since the precipitation is carried out with excess of alkali metal carbonate than the stoichiometric requirement, the precipitate is to be thoroughly washed with deionised water to remove the alkali metal ions. Even the trace amount of alkali metal present in the catalyst is likely to reduce the dispersion of active phase, which reduces the performance of the catalyst remarkably. Therefore, the aged precipitate is washed with dionised water for about 3 to 10 times by filtration and reslurrying of the precipitated mass 6 to remove the alkali metal ions. The washed precipitate, which contains metal hydroxy carbonate and promoters on the composite support material, is decomposed to give metal oxide on the support containing promoters. Drying and calcinations of the washed precipitate are carried out in a precisely controlled slow heating rate to achieve maximum dispersion of active phase on the support. Controlled drying and calcinations can also lead to product with high surface area. The washed precipitate is dried at about 120°C- 250°C for about 3 to 12 hours and calcined at a temperature of about 300°C to 600°C, preferably at 400°C -500°C for about 2 to 6 hours. The programmed heating is carried out at a controlled rate of about 30°C to 100°C per hour, preferably 40°C to 60°C per hour. The aluminate of an alkaline earth metal is used as a binder and graphite is used as the lubricant. In the practice of this invention, the preferred alkaline earth metal used is calcium. The calcined mass is mixed with the said binder and the lubricant, and is ball-milled. Then the sample is granulated to 12 - 100 mesh size. Finally, the granulated sample is tabletted to form the cylindrical particles. The tabletted material is calcined at a temperature of about 400°C - 700°C preferably at 450°C - 550°C for about 2 to 6 hours. The catalyst according to the present invention is characterized by the copper oxide content of about 40 to 65% by weight and relatively higher copper surface area compared to reference sample of this present invention. The atomic ratio of copper to lanthanum to cerium is from about 45:2:1 to about 176:2:1, preferably in the range of 60:2:1 to 120:2:1. Surface area of the catalyst prepared by the method of the present invention is about 50-180 m2/g, preferably 130-180 with a total pore volume of about 0.2 to 0.35 ml/g. The side crushing strength of the catalyst particle is about 5 to 20 kg, preferably 6 to 10 kg. 7 The most preferred embodiments of the present invention are compared with a reference catalyst indicated in patent No. IN 197777 which is illustrated as Example - I. In the present invention, alumina / silica and calcium oxide were varied in 3 different preparations in the mofe ratio 1:5:5, 1:10:10, 1:10:20 and 0:1:1. Increasing the ratio of oxides of calcium and silica results in improvement in surface area and pore volume. The most preferred embodiment containing alumina/silica and calcium oxide in the mole ratio 1:20:20 showed relatively higher surface area and pore volume and this preferred embodiment is illustrated as Example - II of the present invention. The comparison example given in this present invention contains rare earth oxide having atomic ratio of copper to lanthanum to cerium as 77:2:1. The quantity of lanthanum plus cerium in the preferred embodiment, Example - II of this invention was replaced with the same quantity of cerium alone; i.e. the same weight ratio of copper to rare earth oxide, in a separate catalyst preparation where in evaluation of copper surface area indicated comparable results for lanthanum plus ceria catalyst as well as ceria alone containing catalyst. Further, optimization of cerium content as indicated in Example - III was derived on the basis of evaluation of copper surface area for a series of catalysts varying the atomic ratio of copper to cerium as 30:1, 60:1 and 120:1 and among these three preparations, copper surface area was found to be 10% relatively higher for the catalyst having copper to cerium atomic ratio of 60:1. The addition of binder which is a combination of oxides of aluminium and calcium, in the mole ratio 5:3, imparts extra mechanical strength to the catalyst to withstand severe operating conditions. The pore volume is adversely affected by increased mechanical strength. Hence a compromise between these two conflicting parameters is essential for the improved performance of the catalyst and therefore optimization of binder concentration was carried out for the formulation of the most preferred embodiment as indicated in Example - III of the present invention, varying weight percentage of binder in the finished catalyst as 8 10%, 5% and 2.5%; strength improved with increase in binder concentration whereas pore volume decreased with increase in binder concentration, catalyst having 5% binder concentration exhibited the desired strength and pore volume as indicated in Example - IV of the present invention. The catalyst is evaluated in the fixed bed in a mild steel/stainless steel single tube reactor, which is heated electrically by using a vertical tube furnace in which the reactor is fixed coaxially. The temperature of the tube furnace is controlled properly by using an automatic temperature controller. Alternatively, the catalyst is evaluated in the fixed bed in mild steel/stainless steel multi-tubular reactor which consists of about 2000 to 3000 tubes, in contact with circulating hot oil through a vertical jacket in which the said reactor is fixed coaxially. The volume of the catalyst used for evaluation in the said reactor is about 30 to 1290 ml. A desired volume of the catalyst is charged in the said reactor and is reduced by passing a mixture of nitrogen and hydrogen (with varying amounts of the latter from about 0.01 to 20% by volume) through the catalyst bed at a temperature of about 180°C - 220°C and a space velocity of about 1000 to 2200 hr'1 for about 8 to 168 hours. The catalyst is then evaluated in-situ by passing a mixture of nitrobenzene vapour and hydrogen through the catalyst bed at a temperature of about 140°C to 230°C, preferably at 150°C to 220°C and at a mole ratio (nitrobenzene : hydrogen) of 1:30 to 1:15, and a space velocity of about 1000-2100 hr"1. Nitrobenzene containing about 500-800 ppm of m-dinitrobenzene, produced by M/s Hindustan Organic Chemicals Limited, Rasayani has been used as feed stock for evaluation of the catalyst. Under the experimental condition employed, the catalyst of the present invention exhibits almost complete conversion of nitrobenzene which is indicated by the negligibly small amount of unreacted nitrobenzene ( 9 composition, surface area, pore volume and mechanical strength (side crushing strength) are determined by known methods. Examples I to IV are given for the preparation of the catalyst, inclusive of the reference catalyst and Examples V to VIII are given for the evaluation of the catalyst for the conversion of nitrobenzene to aniline in the vapour phase. The invention is described further with reference to the following examples. The examples are given only for illustration, which do not limit the scope of this invention. Example -1 Copper nitrate solution (35L, 7.2 % Cu), rare earth oxides (0.25 kg which contains lanthana and ceria in the mole ratio of 1:1) and the support material (1.6 kg containing AI203, SiO2 and CaO in the mole ratio of 1:2:2) are mixed and agitated well. Sodium carbonate solution (29L, 15%) and the above mixture are added simultaneously to boiling water under agitation maintaining the pH in the range of 6-8. The temperature is maintained at 60°C -80°C. The precipitate is aged for 2 hours and is cooled and filtered. It is washed five times by filtration and reslurrying, and is dried at 250°C for 3 hours. The dry powder is calcined at 450°C for 3 hrs. The dry powder which has got a bulk density of 0.98 Kg/litre, exhibits 13.0% loss on ignition at 540°C. The above powder is mixed with 0.30kg of the said binder and 0.050 kg of the said lubricant and mixmulloed with Dl water for 30 min and dried at 150°C for 4 hours. The dried sample was granulated to 12 x 100 mesh size, tabletted cylidricalshape 4.7 mm x 4.7 mm size and calcined at 450°C for 4 hrs. The finished product exhibits a surface area of 58 m2/g and a pore volume of 0.21 ml/g. The copper content in the catalyst is 48.73%. The atomic ratio of copper to lanthanum to cerium is 77:2:1. The catalyst which exhibits a side crushing strength of 18 kg has a bulk density of 1.4 kg/litre. 10 Example - II Copper nitrate solution (30L, 8.4% Cu), rare earth oxides (0.25 kg which contains lanthana and ceria in the mole ratio of 1:1) and the support material (1.6 kg containing Al203, SiO2 and CaO in the mole ration 1:20:20), are mixed and agitated well. Sodium carbonate solution (30L, 15%) and the above mixture are added simultaneously to boiling water under agitation. pH of the mixture during precipitation was 6-8 and the temperature was maintained at 70°C - 90°C. The precipited obtained is aged for 2 hours, cooled and filtered. The precursor thus obtained is processed to final finished catalyst as indicated in Example - I. The finished product exhibits a surface area of 150m2/g and a pore volume of 0.26 ml/gm. The catalyst which exhibits a side crushing strength of 12 kg and has a bulk density of 1.24 kg/litre. The percentage of Cu, rare earth oxide and support material is maintained identical to that in Example-). Example HI Copper nitrate solution (30L, 8.4% Cu), rare earth oxides (0.125 kg of ceria) and the support material (1.73 kg containing AI2O3, SiO2 and CaO in the mole ration 1:20:20) are mixed and agitated well. The precipation with sodium carbonate solution, washing, drying and further processing of this precursor to the final finish catalyst is carried out as indicated in Example - I. The finished product exhibits a surface area of 155 m2/g and a pore volume of 0.27 ml/gm. The catalyst exhibits a side crushing strength of 11 kg and has a bulk density of 1.23 kg/litre. The copper content in the catalyst is maintained same as in Example-I. Example - IV Copper nitrate solution (30L, 8.4% Cu), rare earth oxides (0.125 kg of ceria) and the support material (1.83 kg containing AI2O3, SiO2 and CaO in the mole 11 ration 1:20:20) are mixed and agitated well. The precipation with sodium carbonate solution, washing drying and further processing of this precursor to the final finish catalyst is carried out as indicated in Example -1, but with 0.2 kg binder. The finished product exhibits a surface area of 160 m2/g and a pore volume of 0.29 ml/gm. The catalyst which exhibits a side crushing strength of 8 kg has a bulk density of 1.15 kg/litre. Example V The catalyst of Example - I (30 ml) charged in a stainless steel single tube reactor was reduced at 200°C - 215°C by passing a mixture of nitrogen and hydrogen with varying amount of the latter from 1 to 10% by volume at a space velocity of 1090 - 1200 hr -1 for 10 hours. The hydrogenation of nitrobenzene to aniline was carried out in-situ by passing a mixture of nitrobenzene vapour and hydrogen at a temperature of 150°C - 155°C, a space velocity of 1200 hr-1 and a mole ratio (nitrobenzene : hydrogen ) of 1:20. The mixture of nitrobenzene vapour and hydrogen was passed through the catalyst bed for 20 hours under the reaction conditions as hereinbefore described. A sample of the hydrogenated mass collected after 20 hours, was analyzed. The results of analysis are as follows: Aniline 99.0 % PCHA 0.5 % Unreacted nitrobenzene 30 ppm Example - VI The experiment was carried out using the catalyst of Example - II in a similar manner under similar experimental conditions as described in Example - V. The results of analysis of the hydrogenated mass are as follows: 12 Aniline 99.4 % PCHA 0.6 % Unreacted nitrobenzene 20 ppm Example-VII The experiment was carried out using the catalyst of Example - III in a simitar manner under similar experimental conditions as described in Example - V. The results of analysis of the hydrogenated mass are as follows: Aniline 99.7 % PCHA 0.3 % Unreacted nitrobenzene 8 ppm Example-VIII The experiment was carried out using the catalyst of Example - IV in a similar manner under similar experimental conditions as described in Example - V. The results of analysis of the hydrogenated mass are as follows: Aniline 99.9 % PCHA 0.1 % Unreacted nitrobenzene 1.5 ppm 13 We claim 1. A process for the preparation of an environment friendly transition metal catalyst suitable for low temperature conversion of nitrobenzene to aniline in the vapour phase, which catalyst contains oxide of the said metal, which is promoted with the oxide or oxides of one or two elements(s), preferably oxides of one element of the lanthanide series and is supported on a composite support material comprising oxides of the Group HA, IIIA and 1VA elements with improved total surface area, copper surface area and pore volume, by optimization of support and binder concentration, for the process, comprising of the steps of: (i) precipitating the said metal from its salt solution as metal hydroxycarbonate on the said support containing oxide(s) of the lanthanide eiement(s) at about 50°C - 100°C and aging the precipitated material at about 60°C - 80°C; (ii) cooling the precipitated material and washing the same with deionised water; (iii) drying the washed material at about 120°C - 250°C; (iv) calcining the dried material at about 300°C - 600°C, preferably at 400°C - 500°C; (v) mixing the calcined material with a suitable binder and a lubricant; (vi) granulating the resulting material to about 12-100 mesh size; (vii) tabletting the granulated matenal to catalyst particles of desired shape and size; (viii) finally calcining the tabletted material at about 400°C - 700°C, preferably at 450°C - 550°C to produce the finished product of desired mechanical strength. 2. A process as claimed in claim 1, wherein the transition metal is copper. 14 3. A process as claimed in claim 1, wherein the lanthanide elements are lanthanum and cerium, most preferably cerium. 4. A process as claimed in claim 1, wherein the group IIA, IIIA and IVA elements are calcium, aluminum and silicon respectively. 5. A process as claimed in claim 1, wherein the metal salt used in step (i) is copper nitrate. 6. A process as claimed in claim 1, wherein step (i), the precipitation is carried out over a period of about 2 to 5 hours. 7. A process as claimed in claim 1, wherein step (i), the precipitated material is aged for a period of about 1 to 3 hour(s). 8. A process as claimed in claim 1, wherein step (ii), the precipitated material is cooled to about 30°C to 35°C. 9. A process as claimed in claim 1, wherein in step (ii), the washing is carried out with deionised water for about 3 to 10 times by filtration and reslurrying of the precipitated mass. 10. A process as claimed in claim 1, wherein in step (iii), the drying is carried out for about 3 to 12 hours. 11. A process as claimed in claim 1, wherein in step (iv), the calcination is carried out for 2 to 6 hours. 12. A process as claimed in claim 1, wherein in step (v), the binder and the lubricant used are calcium aluminate and graphite respectively. 13. A process as claimed in claim 1, wherein in step (vii), the desired length of said tablet is about 3 to 6 mm, preferably 4.7 to 5.2 mm and the desired diameter is about 3 to 6 mm, preferably 4.7 to 5.2 mm. 14. A process as claimed in claim 1, wherein in step (viii), the calcination of the tabletted material is carried out for about 2 to 6 hours. 15. A process as claimed in claim 1 to 14, wherein the mole ratio of support material (Al203, SiO2 and CuO) varies from 1:2:2 to 1:20:20. 15 16. A process as claimed in claims 1 to 15, wherein the side crushing strength of the catalyst particle is 9 to 18 kg. 17. A process as claimed in claims 1 to 16, wherein the surface area and the pore volume of the finished product are 50-180 m2/g and 0.20 - 0.34 ml/g respectively. 18. A process as claimed in claims 1 to 17, wherein the atomic ratio of copper to lanthanum to cerium is from about 45:2:1 to 176:2:1. 19. A process as claimed in claims 1 to 18, wherein the atomic ratio of copper to cerium is from about 30:1 to 120:1, where in ceria is lone promoter. 20. A process as claimed in claims 1 to 19, wherein the percentage conversion of nitrobenzene is from 99.35 to 99.9%. 21. A process as claimed in claims 1 to 20, wherein the PCHA is reduced to about 0.1%. 22. A process as claimed in claims 1 to 21, wherein the un-reacted nitrobenzene is reduced to trace level. 23. A process for the preparation of an environment friendly transition metal catalyst for low temperature conversion of nitrobenzene to aniline in the vapour phase as described substantially hereinbefore with reference to the Examples- I to VIII. Dated this day of 2008 For and on behalf of Hindustan Organic Chemicals Limited (ARVIND SHRIRAM DIDOLKAR) CHAIRMAN & MANAGING DIRECTOR For and on behalf of Sud-Chemie India Private Limited (ARSHIA ALTAF LALLJEE) MANAGING DIRECTOR 16

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