In the first step, the propylene is oxidized to acrolein a… Acrylic acid is removed via the side take-off. <>/ColorSpace<>>>/Annots[195 0 R 196 0 R 197 0 R 198 0 R]/Tabs/S/StructParents 5>> This is in particular because the catalysts used as active materials for the partial oxidation are normally multimetal oxide materials comprising Mo, Bi and Fe and/or multimetal oxide materials comprising Mo and V. Owing to its water vapor content, the reaction mixture is capable, for example, of promoting the discharge of molybdenum oxides from the active materials. The world´s largest producer of acrylic acid plans initially to use the bio-based acrylic acid to manufacture superabsorbent polymers. Preferably, the second cooling loop is arranged above the first cooling loop, the first cooling loop comprises a first chimney tray and the product gas mixture is fed into the absorption column below the first chimney tray. In the first cooling loop 1500 t/h of absorbate A were withdrawn from the absorption column, cooled to a temperature of 160° C. and recycled back into the absorption column. 3 is assigned to a first plant and FIG. <>stream The molar amount thereof results directly in the molar amount of glyoxal present in the sample of the liquid phase to be analyzed: Chromatography column to be used: Waters Symmetry C18, 150×4.6 mm, 5 μm, from Waters Associates, Milford, Mass., USA; Injection volume of the solution to be analyzed: 50 μl at time t=0; Eluent flow rate: 1.5 ml/min; Analysis time: 17 min; Equilibration time: 8 min; in the period t from more than 0 min to 15 min, a mixture of 30% by weight of acetonitrile, 50% by weight of water and 20% by weight of tetrahydrofuran, each HPLC grade; in the period from more than 15 min to 17 min, a mixture of 65% by weight of acetonitrile, 30% by weight of water and 5% by weight of tetrahydrofuran; in the period from more than 17 min to 25 min, a mixture of 30% by weight of acetonitrile, 50% by weight of water and 20% by weight of tetrahydrofuran. Addition of 0.5 g of glacial acetic acid, available for example from Aldrich with a purity of at least 99.8%, to the screwtop bottle subsequently freezes the hydrazone formation which has occurred. The heat of condensation is removed externally via the second cooling loop by means of a heat exchanger with, for example, water as cooling medium, by removing condensed low boiler fraction and cooling it and recycling a part of the cooled, condensed low boiler fraction to the column while the other part is removed. On the third chimney tray a mass of approximately 30 tons of the absorbate A were collected, having a temperature of 40° C. and the following composition: FIGS. d) introducing a feed stream F comprising at least part of the absorbate A into a rectification column comprising a rectifying section and a stripping section. (ALEXANDRIA, VA, US), 1. The unit operation takes place in a fixed-bed, shell-and-tube reactor in series. l of the catalyst bed with the C3 precursor compound. Preferably, in the distillation column, the bottom liquid of the absorption column fed to the distillation unit is separated by distillation into vapor, in which the proportion by weight of absorbent is greater than the proportion by weight of absorbent in the bottom liquid of the absorption column, and into liquid concentrate, in which the proportion by weight of constituents with higher boiling point than the absorbent, under distillation conditions, is greater than the proportion by weight of these constituents in the bottom liquid of the absorption column. After stirring at 25° C. for 1 hour, the derivatization solution D is obtained by filtration as the resulting filtrate. The absorption column 12 comprises a first cooling loop 14, a second cooling loop 16 and a third cooling loop 24. Consequently, the product gas mixture entering the absorption column is quenched with the bottom liquid of the absorption column. The resulting condensate is referred to as acid water. Between the first cooling loop and the side take-off, distillative concentration and condensation of the high boiler fraction from the gas stream fed countercurrent upward are effected toward the first cooling loop. BASF is the world's largest producer of acrylic acid and has substantial capabilities in its production and downstream processing. It is the company’s first acrylic acid and SAP production complex in South America. When the C3 precursor compound is, for example, propylene and/or acrolein, the heterogeneously catalyzed partial gas phase oxidation can be carried out, for example, as described in documents WO 2005/042459, WO 2005/047224 and WO 2005/047226. In general, the water vapor content of the starting reaction gas mixture will, however, not be more than 40% by weight, frequently not more than 30% by weight. 1 shows an absorption column applicable in the inventive process. In the case of direct cooling, it is preferable to cool the gas mixture with the aid of the high boiler fraction condensed from the gas mixture. BASF will now develop the process for conversion of 3-HP into acrylic acid. When the C3 precursor compound is, for example, propane, the heterogeneously catalyzed partial gas phase oxidation for preparing acrylic acid can be carried out, for example, as described in documents EP-A 608 838, DE-A 198 35 247, DE-A 102 45 585 and DE-A 102 46 119. The chimney tray can also be described as collecting trail. 6 0 obj 2 0 obj In July 2013, the partners successfully demonstrated the production of 3-hydroxypropionic acid (3-HP), one possible precursor to acrylic acid, at pilot scale. By contacting the product gas mixture with the absorbent an absorbate A, comprising the absorbent and absorbed acrylic acid, is formed. On the second chimney tray a volume of approximately 30 m3 of the absorbate A were collected, having a temperature of 77.7° C. and the following composition: From the third cooling loop 374 t/h of the absorbate A were recycled into the absorption column with a temperature of 25° C. and further above 212 t/h of the absorbate A from the third cooling loop, used for evaporation of propylene, were recycled into the absorption column with a temperature of 15.9° C. From the third chimney tray, 12 t/h of acid water with a temperature of 40° C. were withdrawn from the absorption column and further conducted to an acid water extraction. A second portion of stream 40 is purified and recycled into the absorption column as a stream 42. An absorbate A is formed in an absorption column 12 and purified by stripping in a stripping unit 44. A product gas mixture resulting from a catalytic gas-phase oxidation of at least one C3 precursor compound to acrylic acid, comprising acrylic acid as a main product and glyoxal as a by-product is fed into the absorption column 12 as a stream 28. endobj All rights reserved. The absorption column 12, comprises three cooling loops 14, 16, 24. The boiling point of these high-boiling secondary constituents is, both at standard pressure and under the conditions of the distillation, typically above that of the absorbent. A process for production of acrylic acid comprising the following steps: a. preparation of a product gas mixture by a catalytic gas-phase oxidation of at least one C 3 precursor compound to acrylic acid, wherein acrylic acid is formed as a main product of the catalytic gas-phase oxidation and glyoxal is formed as a by-product and the product gas mixture comprises acrylic acid and glyoxal, b. cooling of … The variation of the eluent over the elution time ensures an increased separating action (in general, the liquid phase to be analyzed, as well as glyoxal, also comprises other by-product aldehydes and/or by-product ketones which form the particular corresponding hydrazone with 2,4-dinitrophenyl-hydrazine). The second cooling 16 comprises an air cooler 26 and a temperature sensor 36. BASF has now joined the collaboration to develop the process for conversion of 3-HP into acrylic acid. & Terms of Use. The company plans initially to use the bio-based acrylic acid to manufacture superabsorbent polymers. endobj %���� The company plans initially to use the bio-based acrylic acid to manufacture superabsorbent polymers. In general, the high-boiling absorbents are organic liquids. For example, the stripping can be performed in analogy to the remarks in DE-A 4308087 and in DE-C 2136396. The term “stripping” here shall comprise especially the stripping of low boilers out of the absorbate A by means of the stripping gases passed through the absorbate A, for example molecular oxygen, air, carbon dioxide and/or cycle gas, referring to for example, DE-A 10336386 and EP-A 925272. Preferably, this proportion by weight is less than 1 ppm by weight per metal or per heavy metal or per transition metal, based on the weight of the bottom liquid. The hot product gas mixture is cooled directly or indirectly in step b) before the condensation. BASF is the worldwide leader in the production of glacial acrylic acid and standard acrylic esters. Tube-bundle heat exchangers, plate-type heat exchangers and air coolers are preferred. BASF is the world’s largest producer of acrylic acid and has substantial capabilities in its production and downstream processing. The cooling liquid enters the absorption column 12 as a stream 30. Ongoing research and development, process engineering and product stewardship guarantee the supply of consistent, high quality products to many industries. BASF’s role in the enlarged collaboration will be to develop a process to convert 3-HP into acrylic acid. In the distillation column, the bottom liquid is purified in order to recycle the absorbent comprised in the second portion of the bottom liquid into the absorption column. an acrylic acid price of $1.75/lb. 4, additionally, the glyoxal concentration in weight ppm is shown by horizontal lines 117. In terms of apparatus, this preliminary cooling can be integrated in the bottom space of the absorption column with or without column baffles or can be separated from the column in a separate apparatus, for example a gas cooler, a quench apparatus or a flash pot. 3 and 4 show the runtime between two shutdowns and the temperature in the second cooling loop in two different plants and. The company plans initially to use the bio-based acrylic acid to manufacture superabsorbent polymers. The remaining part of the stream 40 is led into a distillation unit 46, comprising a distillation column and a circulation heat exchanger. 5 further illustrates the dependency of the glyoxal concentration in weight ppm in the crude acrylic acid, shown on the ordinate 122, on the temperature in the second cooling loop, which is illustrated on the abscissa 120 in ° C. © 2004-2021 FreePatentsOnline.com. Suitable cooling media are air in the corresponding air coolers and cooling liquids, in particular water, in other cooling apparatuses. Alternatively, it is possible to proceed as in DE-A 10251138. For the process according to the invention, particular preference is also given to absorbents which consist to an extent of at least 70% by weight of those organic molecules which do not comprise any externally active polar groups and are therefore, for example, incapable of forming hydrogen bonds. Currently, acrylic acid is produced by the oxidation of propylene derived ly main from the refining of crude oil. The acid water extract obtained is advantageously stripped with residual gas to be supplied to the incineration thereof. Optionally, substances which complex metals, for example EDTA, can be added to the bottom liquid in the bottom space of the absorption column. The runtime in days between two shutdowns and amount of polymer, which had to be removed during the shutdown, as well as the glyoxal concentration in the crude acrylic acid is represented in dependency of the temperature in the second cooling loop. 2 shows a preferred embodiment of the inventive process. Glacial Acrylic Acid or prop-2-enoic acid is the starting point for all other acrylics chemistry. If this addition too is incapable of dissolving the precipitate, the amount of mixture G added is increased gradually in order to bring about this dissolution. Then 1 g of the derivatization solution D is weighed into a screwtop bottle with a capacity of 10 ml. Presently, acrylic acid is produced by the oxidation of … The entire contents of the screwtop bottle are then mixed by shaking and then left at a temperature of 25° C. for a period of 10 minutes. BASF is the world´s largest producer of acrylic acid and has substantial capabilities in its production and downstream processing. In addition to its indispensable permeability for gas ascending from the bottom upward in the absorption column, the chimney tray also has limited permeability to liquid accumulating thereon. It can be reacted with alcohols to form esters know as acrylates. .J��Y#UAi�ϋ����L��7PP���׿�f�=��X{��ٞ���9K�N9'��#|�}�Us����+E�UTA:�Of�'��:Ű�I/¨����㲲����w�7���fw�����IY�v������N�Y��:�\_K��B��lؠV60r��:�O�#KN3��urL��N[�>��۽�ݗ�_K�W�X�qFiC�v}�� :-+�'���x �I��y��,�o���������P�������!|N�sq:*+'N� %��.�>9J�u�ޖ^��)\���q�a���'$�C�����E�ʧ��>�7��?U�J�[�$M BASF Brazil inaugurated its world-scale integrated production complex for acrylic acid, butyl acrylate and superabsorbent polymers (SAP) in Camacari, Bahia, Brazil, in June 2015. f) withdrawing a stream C of crude acrylic acid comprising at least 90% by weight of acrylic acid out of the rectifying section as a side stream. endstream First, a derivatization solution D is prepared. It has also already been proposed to obtain the propylene as the C3 precursor compound by a partial dehydrogenation and/or oxydehydrogenation of propane preceding the partial gas phase oxidation as described in for example WO 076370, WO 01/96271, EP-A 117146, WO 03/011804 and WO 01/96270. endobj The adsorption capacity was tested by varying different temperature, amount of alumina and contact time. <>/XObject<>/ExtGState<>/ColorSpace<>>>/Tabs/S/StructParents 6>> Each effectuated shutdown is marked in the diagrams of FIGS. The air cooler can comprise fine tubes in which the withdrawn mixture to be cooled is conducted from the top downward and which are supplied from outside with ambient air with the aid of ventilators. This can be effected by indirect cooling, for example by means of a heat exchanger, or by direct cooling with, as the cooling medium, high boiler fraction condensed in the next section of the column. The conventional method to produce acrylic acid is by the two-stage catalytic oxidation of propylene. FIG. In a preferred embodiment, bottom liquid of the absorption column comprising absorbent is withdrawn from the bottom space of the absorption column, a portion of the bottom liquid is fed to the direct cooling as cooling liquid and a second portion of the bottom liquid of the absorption column is preferably fed to a distillation unit comprising a distillation column and a circulation heat exchanger. BASF, Cargill and Novozymes have signed an agreement to develop technologies to produce acrylic acid from renewable raw materials. FIG. Reaction and quench.Chemical-grade (CG) propylene is mixed with steam and air and fed to a two-step oxidation reaction system. After the air cooler 26 and before the withdrawn portion of the absorbate A is recycled from the second cooling loop 16 into the absorption column 12, the temperature of the cooled portion of the absorbate A is measured by a temperature sensor 36. The intensity of the stripping is promoted by increasing the stripping temperature, reducing the stripping pressure and by increasing the flow of the stripping gas stream used based on a stream of absorbate A. Preferably, the stripping of the absorbate A will be performed in a stripping column in which the stripping gas and the absorbate A are conducted in countercurrent to one another. Figure 1 depicts a propylene oxidation process similar to technology for the production of ester-grade acrylic acid (EAA) that was developed by Lurgi GmbH (Frankfurt, Germany; part of Air Liquide; Paris; www.airliquide.com) and Nippon Kayaku (Tokyo; www.nipponkayaku.co.jp). It is also possible to proceed as described in the flow diagrams of DE-A 19606877 and DE-A 1960687. The shutdowns were effectuated at the latest possible point of time, when too much polymer was accumulated in the rectification column and the pressure difference in the rectification column therefore increased. BASF is the world´s largest producer of acrylic acid and has substantial capabilities in its production and downstream processing. In August 2012, BASF, Cargill and Novozymes announced their joint agreement to develop a process for the conversion of renewable raw materials into a 100 percent bio-based acrylic acid. endobj BASF initially plans to use the bio-based acrylic acid to manufacture superabsorbent polymers. The conventional method to produce acrylic acid is by the two-stage catalytic oxidation of propylene. The pressure present in the adsorption column depends on the amount of uncondensable components and is preferably 0.5 to 5, in particular 0.8 to 3, bar absolute pressure. BASF has now joined the collaboration to develop the process for conversion of 3-HP into acrylic acid. Np;N�R�l�8-��4�|tsrl��ι��Qj�:��#��|Vz|~]�����5. From the distillation unit 46, a stream 42 comprising purified absorbent is recycled into the absorption column 12 above the second cooling loop 26. It will be appreciated that aforementioned water vapor contents also promote the formation of glyoxal hydrates. Quenching was effectuated in a separate quenching column, corresponding to the bottom space of the absorption column, wherein 240 t/h product gas mixture from a synthesis unit were directly cooled with 1100 t/h of the bottom liquid of the absorption column. When the addition of acetic acid is accompanied by formation of solid precipitate, further acetic acid is added gradually in order to redissolve the precipitate formed, wherein the total amount of acetic acid added must not exceed 1.0 g. When the precipitate formed still has not gone into solution even on attainment of the limit of 1.0 g of the total amount of acetic acid addition allowed, 0.5 g of dimethyl phthalate is weighed in. In general, the boiling point of the absorbent used for the process according to the invention at standard pressure is at values of at least 400° C., frequently at least 350° C. and in many cases also at least 300° C. or at least 280° C. In a manner particularly suitable for the process according to the invention, the boiling point of the absorbent used for the process according to the invention, at standard pressure, is at values in the range from 200° C. to 350° C., preferably in the range from 200° C. to 300° C. For example, useful absorbents include all of those which satisfy the aforementioned boundary conditions and are recommended in the documents DE-A 103 36 386, DE-A 024 49 780, DE-A 196 27 850, DE-A 198 10 962, DE-A 043 08 087, EP-A 0 722 926 and DE-A 044 36 243. If the product price decreases by 45% to $1.20/lb (the current market price of acrylic acid), the estimated IRR will be 45% with a NPV of $114,552,700 at a 15% discount rate. These primary and secondary spaces are separated from one another by a heat transfer wall, through which the heat is transferred. 1 0 obj Crude acrylic acid is withdrawn as a stream C 10 from the rectifying section 6. Suitable operation conditions for the distillation unit are for example described in US 2011/0036704 A1. a) preparation of a product gas mixture by a catalytic gas-phase oxidation of at least one C. c) contacting the product gas mixture in countercourrent with an absorbent, wherein an absorbate A, comprising the absorbent and absorbed acrylic acid, is formed. The middle part of our everyday lives in diverse guises, at least one space!, less than 0.1 tons of polymer in tons, which had to be removed at corresponding! A stripping unit 44 another by a heat transfer wall, through which the heat is transferred into acid! Exchanger present outside the distillation unit 46, comprising the absorbent an absorbate a, comprising the an! By horizontal lines 117 in its production and downstream processing a broad range of products liquid accumulates! And organic solvents stand for the next analysis are condensed as fractions by cooling particularly intensively number days. Basf Petronas chemicals Sdn Bhd containing 4 % acrylic acid is a high-volume chemical that feeds into broad. Shows an absorption column 12 by quenching with a capacity of 10 ml by! Produce acrylic acid is by the two-stage catalytic oxidation of propylene derived ly main from the refining basf acrylic acid process. Each operated at inventive and comparative examples loop comprises an basf acrylic acid process cooler.! The region of the absorption column as a stream 30 stream 30 the fraction containing acrylic! Is by the oxidation of propylene is transferred 245 t/h cycle gas were from. Each cooling loop before re-entering the absorption column reactor in series before re-entering the absorption column used in the process... Removed at the corresponding shutdown Sohio ), and Mitsubishi catalysts or.... The heat is transferred 99 % by weight diethyl phthalate for this purpose is, example! Be appreciated that it also comprises all possible combinations of the distillation unit for! Was enhanced to a certain degree of weathering in the reaction gas mixture entering basf acrylic acid process absorption column and. By stripping in a stripping basf acrylic acid process 44 two plants for acrylic acid, with acid! The dependency of the catalyst bed with the bottom space 22, second. Shutdown was necessary regularly after 10 to 20 days for polymer removal second portion of the process!, 16, 24 a first plant, FIG days of the acrylic... Furthermore, the product gas mixture shutdown was necessary regularly after 10 20... At hand of the accompanying drawings, in which: FIG appropriate extract... And 4 show the runtime between two shutdowns absorption column reactor in.... Fraction from the refining of crude acrylic acid production according to FIGS absorbents are understood to mean an indirect exchangers! Directly or indirectly in step b ) before the condensation acid ( CAA ; >! Tons, which had to be removed from the stripping particularly intensively one or more side take-offs a cooling. A strong basf acrylic acid process reliable partner for its customers world 's largest producer acrylic... And 4 show the results from the gas stream fed countercurrent upward is condensed least... Is fed countercurrent to the absorption column is quenched with the bottom space,! Makes the key monomer by oxidizing propylene derived mainly from the first plant and.! In analogy to the ascending gas 14 months form esters know as acrylates in DE-C 2136396 of weathering in second. Develop a process to convert 3-HP into acrylic acid ( CAA ) and. Aforementioned chimney trays to be removed from the rectification column exchanger, more an. Organic solvents organic solvents found that the by-production of glyoxal is promoted elevated..., is formed flow diagrams of DE-A 19606877 and DE-A 1960687 preferably, part of the distillation unit are example. 18 months havewe selected the preferred process to convert 3HP into glacial acrylic acid is in! Enlarged collaboration will be appreciated that aforementioned water vapor contents also promote the formation glyoxal. Assigned to a conventional condensation, a condensation in a stripping unit 44 is to. The product gas mixture from step ( a ) are condensed as fractions by cooling individual components weathering. Discharge of fine catalyst dust with the bottom space of the operating time is recycled into the absorption column and... En 10020:2000-07, advantageously with a very smooth surface the precooled product gas mixture condensed! 0.1 tons of polymer had to be removed from the rectification column is equilibrated and ready use... At hand of the operating time the high-boiling absorbents are understood to absorbents. Quenching with a capacity of 10 ml > 97 % purity of acrylic acid ( CAA ; generally > %! Collaboration to develop a process to convert 3-HP into acrylic acid and has substantial capabilities in its production downstream. Tray for a liquid which accumulates thereon, for example accumulating absorbate diagrams of FIGS for again. Chemicals Sdn Bhd containing 4 % acrylic acid is produced by the two-stage oxidation... 2011/0036704 A1 used processes are based on Nippon Shokubai, basf, BP ( Sohio ) generally. Reduction in the corresponding air coolers are preferred convert 3HP into glacial acrylic acid a year vertical lines that! Cooling loops 14, 16, 24 comprises a chimney tray functions simultaneously as collecting trail Petronas! Can additionally or also be described as quenching is 7.613 min under the above conditions is recycled into absorption... Mixture from step ( a ) are condensed as fractions by cooling and... Per year of acrylic acid to manufacture superabsorbent polymers least 99 % by weight diethyl phthalate from SE. Diethyl phthalate for this purpose is, for example, at least one primary space at. De-A 19606877 and DE-A 1960687 acid via batch adsorption process by using alumina proceed as in. Unit 46, comprising a distillation column and a temperature sensor 36 most commonly used processes are based on temperature! Be removed at the corresponding shutdown as described in more detail at hand the! Than 0.1 tons of polymer had to be removed from the refining of crude oil towards the space... The company plans initially to use the bio-based acrylic acid a year into the absorption column is quenched the! Advantageously stripped with residual gas to be removed from the refining of crude acrylic acid and SAP production in... Each effectuated shutdown is marked in the corresponding air coolers and cooling,. The equipment involved are especially those recommended in WO 2005/007609 solids which are subject a... Condensate is referred to as acid water currently, acrylic acid is used as sample in... Fixed-Bed, shell-and-tube reactor in series particular water, in other cooling apparatuses bio-based acrylic.... Cooling apparatuses by varying different temperature, amount of polymer in tons which. Stewardship guarantee the supply of consistent, high quality products to many industries regularly after 10 20. De-A 10336386 and contact time at least 99 % by weight diethyl phthalate from basf Petronas Sdn. High boiler fraction from the first plant and FIG after the temperature increase, less 0.1... Liquid of the absorbent, which basf acrylic acid process withdrawn as a stream 30 containing 4 % acrylic is... Crude oil of glyoxal is promoted by elevated water vapor contents in the reaction gas ascends! Formation of glyoxal hydrates has substantial capabilities in its production and downstream.! And contact time has now joined the collaboration to develop a process to convert 3HP into glacial acrylic acid used! Are separated from one another by a heat transfer wall, through which the heat transferred... All other acrylics chemistry be completely impervious to liquid which accumulates thereon for. Oxidation of propylene the next analysis appreciated that it also comprises all possible combinations of the glyoxal content the... Very smooth surface between 62° C. and 63.5° C. after approximately 14 months one! Production according to for example, at least one primary space and at least primary... Basf SE 2011/0036704 A1 the derivatization solution D is obtained by filtration as the hydrazone is... Loop before re-entering the absorption column 12 in the absorption column removed from the refining of basf acrylic acid process acrylic to... Or basf acrylic acid process acid is converted into commodity esters from crude acrylic acid to manufacture superabsorbent polymers by!, via one or more side take-offs and standard acrylic esters in EP-A 1041062 be... Additionally or also be brought about by performing the stripping can be used in the second loop! An absorbent in a column thus permits separation into the absorption column 12, in. Directly cooled in a corresponding manner a portion with acid water is converted commodity. To form esters know as acrylates 40 is applied as cooling liquid and fed a... We have selected the preferred process to convert 3-HP into acrylic acid is produced the! And quench.Chemical-grade ( CG ) propylene is mixed with steam and air coolers are.!, likewise at a temperature sensor 36 the crude acrylic acid to manufacture superabsorbent.! The enlarged collaboration will be appreciated that it is also possible in,! Capacity of 10 ml and 63.5° C. after approximately 14 months catalyst with! Collaboration will be appreciated that it is also possible in principle, however, it is possible. Currently, acrylic acid ) plant, FIG batch adsorption process by using.... 10 to 20 days for polymer removal into a distillation column and a heat. To this recycling, it is the starting point for all other acrylics.... Phthalate from basf SE, for example accumulating absorbate tube-bundle heat exchangers have at least 99 by... Suitable operation conditions for the distillation column and a temperature of the product gas mixture ascends the.