TH74365A - Industrial processes for the production of aromatic carbonates - Google Patents

Abstract

------ 31/01/2018 ------ (OCR) page 1 of number 1 page invention summary. It is the purpose of this invention to provide, for the case of aromatic production. Any carbonate containing aryl carbonate as a main product is continued by the use of aldyl-arylate. Carbonates, as a substrate, can be obtained through trans esterification. Between kylkyl carbonates And aromatic monohydroxy compounds, using a column of Continuous multi-stage distillation In the catalyst scale 1 there is, and the continuous casting of the substrate in Column of continuous multistage distillation, specific process Make diary-carbonate Can be manufactured with high selectivity And high productivity Stable for long periods of time on an industrial scale as at least 1 pressure / hour, although there are various offers With respect to the process for the production of aromatic carbonates using As a method of reactive distillation, these monkeys are at the laboratory level with smaller scales and short run times, and there is no public disclosure of specific processes or equipment. Make There can be mass production on an industrial scale at all. According to this invention, there was A specific column of multistage distillation, and a specific process is also provided. This allows chyearyl carbonate to be manufactured with high selectivity and stable high productivity for long periods of time on an industrial scale. Is not less than 1 pressure per hour From alkyl aryl carbonate ------------ It is the purpose of invention to prepare For the case of aromatic production Carbonates with diaryl carbonates as the main product By using alkyl aryl carbonate as the starting material, which can be obtained Through the reaction Transesterification between dialkyl carbonate and aromatic monohydroxy compounds by means of continuous multi-layer distillation columns with active catalyst and continuous feeding of the initial material. To Continuous multi-layer distillation column The specific process through which diaryl carbonate to be produced can have high selectivity stability and high production stability. It is a long period of time on industrial sizes of at least 1 t / h, although several proposals have been involved. Process for producing aromatic carbonate by means of Reactive distillation method All of these are small and lab scale. A brief and not entirely disclosed period of time regarding a specific process or device. That makes it possible to mass-produce on an industrial scale in accordance with this invention. Has been prepared Continuous multi-layer distillation column Specific and also have been prepared. The specific process that enables the manufactured diaryl carbonate can have high selectivity and highly stable production conditions. It is a long time on a scale of at least 1 ton per hour from alkylaryl carbonate.

Claims (31)

------31/01/2018------(OCR) Page 1 of 7 pages. Claims 1. A process for the continuous production of aromatic carbonates with diaryl carbonate as the main product, in which the process consists of the following steps: (i-a) Obtaining of a starting material consisting of alkylaryl carbonate through transesterification reaction between dialkyl carbonate with formula (8) described below and an aromatic monohydroxy compound with formula (9) below with the molar ratio of (i-b) The continuous forwarding of the starting material into a continuous multistage distillation column in which a catalyst is present; (ii) The reaction proceeds in the column to produce dialkyl carbonate and diaryl carbonate; (iii) The continuous extraction of the low-boiling reaction mixture containing the produced dialkyl carbonate from the upper part of the column in gaseous form, and the continuous extraction of the high-boiling reaction mixture containing diaryl carbonate from the lower part of the column in liquid form, and the continuous multistage distillation column is assembled. A structure consisting of a pair of plates ending above and below a cylindrical column of length L (cm) and inner diameter D (cm), with an inner section containing a certain number of steps, and incorporating a gas outlet channel with an inner diameter d (cm) at the top of the column or in the upper part of the column near the top, a liquid outlet channel with an inner diameter ε (cm) at the bottom of the column or in the lower part of the column near the bottom, at least one inlet channel provided in the upper and/or middle section of the column below the gas outlet channel, and at least one... The inlet is provided in the lower part of the column above the fluid outlet, where (1) such length L (cm) corresponds to the following formula (1), page 2 of number 7, page 1500? Li 8000 (1), (2) such inner diameter W (cm) of the column corresponds to the following formula (2), 100 i D i 2000 (2), (3) the ratio of such length L (cm) to such inner diameter D (cm) of the column corresponds to the following formula (3), 2 i L/D i 40 (3), (4) such number of steps corresponds to the following formula (4), 10 Si T — 80 (4), (5) the ratio of such inner diameter D (cm) of the column to The ratio of the inner diameter d, (cm) of the gas outlet channel to the inner diameter d2 (cm) of the liquid outlet channel will correspond to the following formula (5), 2i D/d, Si 15 (5); and (6) the ratio of the inner diameter D (cm) of the column to the inner diameter d2 (cm) of the liquid outlet channel will correspond to the following formula (6), 5 i D/dj i 30 (6); formula (8) r'OCOOR1, where R1 represents an alkyl group with 1 to 10 carbon atoms, an alicyclic group with 3 to 10 carbon atoms, or an aralkyl group with 6 to 10 carbon atoms, formula (9) Ar'OH, where At' represents an aromatic group with 5 to 30 carbon atoms, and where the number of diaryls The amount of such carbonate produced shall not be less than 1 ton per hour. Page 3 of 7, where the scale Ar1 represents aromatic carbonates with 5 to 30 carbon atoms, and where the amount of such diaryl carbonate produced shall not be less than 1 ton per hour. 2. The process under claim 1, in which distillation shall be carried out concurrently in step (ii). 3. The process under claim 1 or 2, where scales d, and dj shall comply with the following formula (7): 1 d,/d2 6 (7) 4. Any of the processes under claims 1 through 3, in which L, D, L/D, t, D/d? And the D/d2 for the columns of the aforementioned continuous multistage distillation will correspond to the following formulas: 2000 R L, 6000 R, 150 R D, 1000 R, 3 R L/D, 30 R, 15 R, 60 R, 2.5 R D/d, 12 R, and 7 R D/d2, 25 R, respectively. 5. Which of the following processes of claims 1 through 4, in which L, D, L/D, R, D/d? And the D/d2 ratio for the column of continuous multistage distillation corresponds to the following formulas: 2500 R L R 5000, 200 R D R 800, 5 R L/D R 15, 20 R R 50, 3 R D/d, R 10, and 9 R D/d, R 20, respectively. 6. Which of the processes under claims 1 through 5, in which the column of such continuous multistage distillation is a packing distillation column? and trays as internal part 7. The process under claim 6, where the column of continuous multistage distillation is, i.e., a distillation column that has, as an internal part, packing in the upper part of the column, and trays in the lower part of the column. 8. The process under claim 6 or 7, where the said packing of the internal part is structural packing. 9. The process under claim 6 or 7, where the said tray of the internal part is a sieve tray with a sieve section and a downcomer section. Page 4 of 7. 10. The process under claim 6 or 7, where the said packing of the internal part is One or more types of structural packing, and such trays are mesh trays with a mesh section and a downcomer section. 11. The process under claim 8 or 10, in which such structural packing is at least one type selected from a group comprising Mellapak, Gempak, TECHNO-PAK, FLEXIPAC, Sulzer packing, Goodloe semi-pack, and Glitsch grid. 12. The process under claim 9 or 10, in which such mesh trays have 100 to 1000 slits/m² in the mesh section. 13. The process under either claim 9, 10, or 12, in which the cross-sectional area... 14. The process under claim 10, in which the structural packing is at least one type selected from the group comprising Mellapak, Gempak, TECHNO-PAK, FLEXIPAC, Sulzer packing, Goodloe packing and Glitsch grid, the sieve tray shall have 100 to 1000 holes/m² in the mesh section, and the face area per hole of the sieve tray shall be in the range of 0.5 to 5 cm². 15. The process under any of claims 1 to 14, which is used to pack aromatic carbonates. Such a column shall contain a halogen concentration of no more than 0.1 ppm. 16. A continuous multistage distillation column for reaction and distillation operations, which is characterized in such that the column shall consist of: a cylindrical body with length L (cm) and inner diameter D (cm); end plates arranged above and below the body; an inner section containing a number of stages inside the body; a gas outlet with an inner diameter d (cm) and which is arranged on the end plate at the top of the column or in the upper part of the column near it; Page 5 of 7 pages; a liquid outlet with an inner diameter (cm) and which is arranged on the end plate at the bottom of the column or in the lower part of the column near it; at least one inlet arranged in the upper and/or middle part of the column below the gas outlet; and at least one inlet channel is provided in the lower part of the column above the outlet channel of the liquid, and (1) such length L (cm) shall correspond to the following formula (1), 1500^L^8000(1), (2) such inner diameter D (cm) of the column shall correspond to the following formula (2), 100^D^2000(2), (3) the ratio of such length L (cm) to such inner diameter D (cm) of the column shall correspond to the following formula (3), 2 g L/D g 40(3), (4) such number of steps shall correspond to the following formula (4), 10^T i 80(4), (5) the ratio of such inner diameter D (cm) of the column to The inner diameter d, (cm) of the gas outlet channel will correspond to the following formula (5), 3 ^D/d,^15 (5), and (6). The ratio of the inner diameter D(cm) of the column to the inner diameter d2(cm) of the liquid outlet channel will correspond to the following formula (6), 5 g D/d2 30 (6). Page 6 of 7 of 17. The column of continuous multistage distillation according to claim 16, where d, and will correspond to the following formula (7) 1 r d,/d2 r 6 (7). 18. The column of continuous multistage distillation according to claim 16 or 17, where L, D, L/D, t, D/d? The D/d2 ratio for a continuous multistage distillation column shall correspond to the following formulas: 2500 r L r 5000, 200 r D r 800, 5 r L/D r 15, 20 r r 50, 3 r D/d r 10, and 9 r D/d2 r 20, respectively. 19. A continuous multistage distillation column under any of the claims 16 through 18, in which the column is a distillation column with packing and trays as internal components. 20. A continuous multistage distillation column under claim 19, in which the column is a distillation column with packing and trays as internal components. The following is a continuous multistage distillation column: 21. A continuous multistage distillation column under claim 19 or 20, where the internal packing is structural packing. 22. A continuous multistage distillation column under claim 19 or 20, where the internal packing is a sieve tray with a sieve section and a downcomer section. 23. A continuous multistage distillation column under claim 19 or 20, where the internal packing is one or more types of structural packing, and the tray is a sieve tray with a sieve section. 24. A column of continuous multistage distillation pursuant to claim 21 or 23, in which the packing structure is at least one of the selected types from the group of Mellapak, Gempak, TECHNO-PAK, FLEXIPAC, Sulzer packing, Goodloe packing and Glitsch packing. 25. A column of continuous multistage distillation pursuant to claim 22 or 23, in which the sieve trays have 100 to 1000 slits/m² on page 7 of 7 pages. 26. A column of continuous multistage distillation pursuant to any of the claims 22, 23 or 25, in which the cross-sectional area of the sieve trays is in the range of 0.5 to 5 cm². 27. A column of continuous multistage distillation pursuant to claim 23, in which the packing structure... The structure in question is at least one type selected from a group comprising Mellapak, Gempak, TECHNO-PAK, FLEXIPAC, Sulzer packing, Goodloe packing, and Glitsch grids. These grid trays will have 100 to 1000 holes/m² in the grid section, and the grid mesh cross-sectional area will range from 0.5 to 5 centimeters². 1. The process for the production of aromatic carbonates, with diaryl carbonate as the main product, from starting materials consisting of alkyl aryl carbonate, which can be obtained by transesterification reaction between dialkyl carbonate and aromatic monohydroxy compounds, consists of (i) the continuous feeding of such starting materials into a continuous multistage distillation column containing a catalyst; (ii) the operation of the reaction in such column to produce dialkyl carbonate and diaryl carbonate; and (iii) the continuous extraction of the low-boiling point reaction mixture, containing the dialkyl carbonate produced from the top of the column in gaseous form, and the extraction of the high-boiling point reaction mixture, containing diaryl carbonate, from the bottom of the column in liquid form. The continuous multistage distillation column consists of a structure with a pair of final plates above and below a cylindrical body of length L (cm) and inner diameter D (cm), which has an inner core containing n layers and a gas outlet. A liquid outlet with a diameter d1 (cm) is located at the top of the column, or in the upper part of the column near the top; a liquid outlet with a diameter d2 (cm) is located at the bottom of the column, or in the lower part of the column near the bottom; at least one inlet is provided in the upper and/or middle section of the column below the gas outlet; and at least one inlet is provided in the lower section of the column above the gas outlet. The liquid outlet is where (1) the length L (cm) is such that it satisfies the following formula (1): 1500 less than or equal to L less than or equal to 8000 (1); (2) the inner diameter D (cm) of the column is such that it satisfies the following formula (2): 100 less than or equal to D less than or equal to 2000 (2); (3) the ratio of the length L (cm) to the inner diameter D (cm) of the column is such that it satisfies the following formula (3): 2 less than or equal to L/D less than or equal to 40 (3); (4) the number of layers n is such that it satisfies the following formula (4): 10 less than or equal to n less than or equal to 80 (4); (5) the ratio of the inner diameter D (cm) of the column to the inner diameter d1 (cm) of the gas outlet is such that it satisfies the following formula (5): 2 less than or equal to D/d1. Less than or equal to 15 (5) and (6), the ratio of the inner diameter D (cm) of the column to the inner diameter d2 (cm) of the liquid outlet is given by the formula (6) as follows: 5 less than or equal to D/d2 less than or equal to 30 (6). 2. The process under claim 1 in which distillation is carried out concurrently in step (ii) as mentioned above. 3. The process under claim 1 or 2 where the quantity of aromatic carbonates, with diaryl carbonate as the primary product, is continuously produced and the quantity of such diaryl carbonate produced is not less than 1 ton per hour. 4. In the process for the production of aromatic carbonates with diaryl carbonate as the primary product, where aromatic carbonates with diaryl carbonate as the primary product are continuously produced by continuously feeding alkyl aryl carbonate as the starting material through transesterification reactions between dialkyl carbonate and aromatic monohydroxy compounds into a catalytic multistage distillation column, the reaction and distillation are carried out simultaneously in the column. A low-boiling point reaction mixture containing dialkyl carbonate produced from the top of the column is continuously extracted in gaseous form. A high-boiling point reaction mixture containing at least one alkyl aryl carbonate produced from the bottom of the column is continuously extracted in gaseous form. A high-boiling point reaction mixture containing alkyl aryl carbonate from the bottom of the column is continuously extracted in liquid form. The continuous multistage distillation column consists of a structure containing... A pair of end plates, one above and one below, is a cylindrical body of length L (cm) and inner diameter D (cm), which contains an inner layer of n layers and includes a gas outlet with an inner diameter d1 (cm) at the top of the column or in the upper section near the top, and a liquid outlet with an inner diameter d2 (cm) at the bottom of the column or in the lower section near the bottom. At least one inlet is provided in either the upper and/or middle section of the column. The gas outlet and at least one inlet are provided in the lower section of the column above the liquid outlet where (1) such length L (cm) satisfies the following formula (1): 1500 ≤ L ≤ 8000 (1); (2) such inner diameter D (cm) of the column satisfies the following formula (2): 100 ≤ D ≤ 2000 (2); (3) such ratio of such length L (cm) to such inner diameter D (cm) of the column satisfies the following formula (3): 2 ≤ L/D ≤ 40 (3); (4) such number of such layers n1 satisfies the following formula (4): 10 ≤ n ≤ 80 (4); (5) such ratio of such inner diameter D (cm) of the column to such inner diameter d1 (cm) of the gas outlet satisfies the following formula (5): 2 Less than or equal to D/d1 less than or equal to 15 (5) and (6) The ratio of the inner diameter D (cm) of the column to the inner diameter d2 (cm) of the liquid outlet is given by the formula (6) as follows: 5 less than or equal to D/d2 less than or equal to 30 (6) 5. The process pursuant to claim paragraph 4, where the production quantity of diary carbonate is not less than 1 ton per hour. 6. The process under any one of the claims 1 through 5 where d1 and d2 satisfy the formula (7) as follows: 1 less than or equal to d1/d2 less than or equal to 6 (7) 7. Any process under any of the claims 1 through 6 where L, D, L/D, n, D/d1, and D/d2 for the continuous multistage distillation column are satisfied by the following formulas; 2000 less than or equal to L less than or equal to 6000, 150 less than or equal to D less than or equal to 1000, 3 less than or equal to L/D less than or equal to 30, 15 less than or equal to n less than or equal to 60, 2.5 less than or equal to D/d1 less than or equal to 12, and 7 less than or equal to D/d2 less than or equal to 25, respectively. 8. Any process under any of the claims 1 through 7 where L, D, L/D, n, D/d1, and D/d2 for a continuous multistage distillation column are satisfied by the following formulas; 2500 less than or equal to L less than or equal to 5000, 200 less than or equal to D less than or equal to 800, 5 less than or equal to L/D less than or equal to 15, 20 less than or equal to n less than or equal to 50, 3 less than or equal to D/d1 less than or equal to 10, and 9 less than or equal to D/d2 less than or equal to 20, respectively, and 9. Any of the processes described in Claims 1 through 8 where each of the aforementioned continuous multistage distillation columns is a distillation column containing packing and trays as internal material. 10. The process under claim 9 where a continuous multistage distillation column is a distillation column in which the packing in the upper part of the column and the trays in the lower part of the column are the internal parts. 11. The process under any one of the claims of Claim 9 or 10 where such contents within are structured contents. 12. The process pursuant to claim 9 or 10 where the said tray is an inner tray with a mesh screen, which has a mesh section and an inlet section underneath. 13. The process under claim 9 or 10 where such packing of the interior is a packing that is structured into one or more pieces, and such tray is a sieve tray which has a sieve section and an inlet section below. 14. The process under Claim 11 or 13 where at least one of the structured containers is selected from a pool comprising Mellapak, Gempak, TECHNO-PAK, FLEXI-PAK, Sulzer container, Goodroll container and Glitchgrid. 15. The process under any of the claims 12 to 13 where such sieve tray has 100 to 1000 holes/cm² in the sieve portion. 16. The process under any of the claims in Clauses 12, 13 or 15 where the cross-sectional area per hole of such sieve is between 0.5 and 5 cm². 17. The process pursuant to claim 13 shall be carried out where at least one of the structured packings is selected from a group comprising Mellapak, Gempak, TECHNO-PAK, FLEXI-PAK, Sulzer packing, Goodrool packing and Glitchgrid packing. The auxiliary sieve trays shall have 100 to 1000 holes/cm² in the sieve section and the cross-sectional area per hole of such sieve shall be in the range of 0.5 to 5 cm². 18. Aromatic carbonates containing no more than 0.1 ppm of halogen, produced by a process in compliance with one of the claims 1 through 17. 19. A continuous multistage distillation column for reaction and distillation operations, consisting of a cylindrical body section of length L (cm) and inner diameter D (cm); a pair of end plates provided above and below the body section; an inner section of the body section with n layers; a gas outlet, with inner diameter d1 (cm), and which is provided on the end plates at the top of the column or in the upper part of the column near them; a liquid outlet, with inner diameter d2 (cm), and which is provided on the end plates at the bottom of the column or in the lower part of the column near them; at least one inlet is provided in the upper and/or middle section of the column below the gas outlet; and at least one inlet is provided in the lower section of the column. Above the liquid outlet, where (1) such length L (cm) satisfies the following formula (1): 1500 less than or equal to L less than or equal to 8000 (1); (2) such inner diameter D (cm) of the column satisfies the following formula (2): 100 less than or equal to D less than or equal to 2000 (2); (3) such ratio of such length L (cm) to such inner diameter D (cm) of the column satisfies the following formula (3): 2 less than or equal to L/D less than or equal to 40 (3); (4) such number of such layers n satisfies the following formula (4): 10 less than or equal to n less than or equal to 80 (4); (5) such ratio of such inner diameter D (cm) of the column to such inner diameter d1 (cm) of the gas outlet satisfies the following formula (5): 2 less than or equal to D/d1 less than or equal to 15. (5) and (6) the ratio of the inner diameter D (cm) of the column to the inner diameter d2 (cm) of the liquid outlet is given by the formula (6) as follows: 5 less than or equal to D/d2 less than or equal to 30 (6) 20. A continuous multistage distillation column pursuant to claim 19 where d1 and d2 satisfy the formula (7) as follows: 1 less than or equal to d1/d2 less than or equal to 6 (7). 21. A continuous multistage distillation column pursuant to claim 19 or 20 where L, D, L/D, n, D/d1, and D/d2 for such continuous multistage distillation column are in accordance with the following formulas; 2000 ≤ or equal to L ≤ or equal to 6000, 150 ≤ or equal to D ≤ or equal to 1000, 3 ≤ or equal to L/D ≤ or equal to 30, 15 ≤ or equal to n ≤ or equal to 60, 2.5 ≤ or equal to D/d1 ≤ or equal to 12, and 7 ≤ or equal to D/d2 ≤ or equal to 25, respectively. 22. A continuous multistage distillation column pursuant to any of the claims 19 through 21 where L, D, L/D, n, D/d1, and D/d2 for the continuous multistage distillation column are satisfied by the following formulas; 2500 ≤ L ≤ 5000, 200 ≤ D ≤ 800, 5 ≤ L/D ≤ 15, 20 ≤ n ≤ 50, 3 ≤ D/d1 ≤ 10, and 9 ≤ D/d2 ≤ 20, respectively. 23. A continuous multistage distillation column pursuant to any of the claims 19 to 22, where such continuous multistage distillation column is a distillation column containing packing and trays as the contents. 24. A continuous multistage distillation column in accordance with claim 23, where the continuous multistage distillation column is a distillation column in which the packing in the upper part of the column and the tray in the lower part of the column are the internal parts. 25. A continuous multistage distillation column pursuant to claim 23 or 24 where the contents of the internal structure are structured. 26. A continuous multistage distillation column pursuant to claim 23 or 24, in which such trays contain internal sieve trays with a sieve section and an inlet section below. 27. A continuous multistage distillation column pursuant to claim 23 or 24, in which such packing of the interior is a packing that is made up of one or more structures, and such trays are sieve trays which contain a sieve section and an inlet section below. 28. A continuous multistage distillation column pursuant to claim 25 or 27, where at least one of the structured packings is selected from a pool comprising Mellapak, Gempak, TECHNO-PAK, FLEXI-PAK, Sulzer packing, Goodroll packing, and Glitchgrid packing. 29. Continuous multistage distillation columns pursuant to claims 26 to 27, where such sieves have 100 to 1000 holes/cm² in the sieve portion. 30. A continuous multistage distillation column pursuant to any of the claims in Clauses 26, 27, or 29, where the cross-sectional area per pore of such sieves is in the range of 0.5 to 5 cm². 31. Continuous multistage distillation column pursuant to claim 27, where at least one of the packing structures is selected from the group comprising Mellapak, Gempak, TECHNO-PAK, FLEXI-PAK, Sulzer packing, Goodroll packing and Glitchgrid packing. The auxiliary sieves have 100 to 1000 holes/cm² in the sieve section and the cross-sectional area per hole of such sieves is in the range of 0.5 to 5 cm².