METHOD AND APPARATUS FOR THE PRODUCTION OF PERFORMIC ACID

Abstract

A catalytic distillation process, which when operated under vacuum conditions, makes possible the facilitation of peroxyacid chemistry under intrinsically safe conditions with superior efficiency compared to conventional technology. In particular, the process can be used for the production of performic acid (PFA) created from the chemical reaction of formic acid and hydrogen peroxide, while contacting one or more kinds of heterogeneous catalysts, immobilized in one or more regions of the reactor (i.e. within reaction zones within the column). Aqueous hydrogen peroxide and formic acid feed streams are directed to the catalytic distillation column. The products are separated from the reactants in situ from the distillation action within the column The process is made efficient by utilizing moisture tolerant catalyst materials which facilitate the chemical conversion of the reactants operating at or near stoichiometric amount and by operating the catalytic distillation reactor at or near 100% conversion and at an optimal reflux ratio which prevents the accumulation of water in the system while maximizing external mass transfer rates, catalyst wetting efficiency and energy efficiency.

Claims

1. A catalytic distillation process for production of performic acid, comprising: feeding aqueous solutions of formic acid and an oxidizing agent separately under controlled flow rates into a catalytic distillation column above one or more reaction zones located generally in the middle of the column, said one or more reaction zones including one or more heterogeneous catalysts immobilized in said one or more reaction zones; said column being operated at sub atmospheric pressure and preselected temperature such that the oxidizing agent and formic acid are introduced to the one or more reaction zones and undergo a reaction to produce performic acid and reaction by-products; wherein a performic acid enriched liquid product containing some unreacted oxidizing agent flows downwards into a stripping section located below the one or more reaction zones and wherein a vapour phase containing unreacted formic acid, some unreacted oxidizing agent and reaction by-products rise up through a rectification section located above the one or more reaction zones; and withdrawing the vapor phase containing unreacted formic acid, some unreacted oxidizing agent and reaction by-products from a condenser located at the top of the rectification section, and returning some or all of the condensed distillate back to the CD column as reflux and withdrawing the performic acid enriched liquid product from the bottom of the stripping section to create a performic acid rich bottoms product stream, optionally cooling the performic acid product and optionally storing the performic acid product.

2.-4. (canceled)

5. The catalytic distillation process according to claim 1, wherein the preselected temperature is in a range from about 0 to about 100° C.

6. The catalytic distillation process according to claim 1, wherein the preselected temperature in the reaction zone containing the catalyst is in a range from about 15° C. to about 60° C.

7. The catalytic distillation process according to claim 1, wherein the preselected temperature in the reaction zone containing the catalyst is in a range from about 20° C. to about 40° C.

8. The catalytic distillation process according to claim 1, wherein the oxidizing agent is hydrogen peroxide such that the hydrogen peroxide and formic acid mix in the one or more reaction zones and undergo the reaction (1) to produce performic acid and water as a reaction by product as follows ##STR00003##

9. The catalytic distillation process according to claims claim 1, wherein the oxidizing agent is a compound which can produce hydrogen peroxide in situ via its chemical reaction with other compounds present in the system or by interaction with the catalyst in the system.

10. The catalytic distillation process according to claim 1, wherein the heterogeneous catalyst is a cation exchange resin.

11.-13. (canceled)

14. The catalytic distillation process according to claim 1, wherein the heterogeneous catalyst comprises at least one metal oxide selected from the group Nb.sub.2O.sub.5, Al.sub.2O.sub.3, ZrO.sub.2, TiO.sub.2, Cr.sub.2O.sub.3, CrO.sub.3, WO.sub.3, W.sub.2O.sub.5, ZrW.sub.xO.sub.y (wherein x is 2 and y is 0.5 to 8) V.sub.2O.sub.5, BeO, MoO.sub.3, Fe.sub.2O.sub.3, Ga.sub.2O.sub.3, La.sub.2O.sub.3, ZnO and mixtures thereof.

15. The catalytic distillation process according to claim 1, wherein the heterogeneous catalyst contains a transition metal oxide with a transition metal selected from the group consisting of Fe, Ti, Zr, Hf, Sn and Si an Al and combinations thereof, and wherein the metal oxide has been treated by an acidic material, and wherein the acidic material is at least one of sulphate, tungstate and molybdate.

16. (canceled)

17. The catalytic distillation process according to claim 15, wherein the acidic material is selected from the group consisting of SO.sub.4/SnO.sub.2, SO.sub.4/ZrO.sub.2, SO.sub.4/HfO.sub.2, SO.sub.4/TiO.sub.2, SO.sub.4/Al.sub.2O.sub.3, SO.sub.4/Fe.sub.2O.sub.3, MoO.sub.3/ZrO.sub.2, SO.sub.4/SiO.sub.2, WO.sub.3/ZrO.sub.2, WO.sub.3/TiO.sub.2, WO.sub.3/Fe.sub.2O.sub.3, B.sub.2O.sub.3/ZrO.sub.2 and combinations thereof.

18. (canceled)

19. The catalytic distillation process according to claim 1, wherein the heterogeneous catalyst is an amphoteric material exhibiting basic sites.

20. The catalytic distillation process according to claim 1, wherein the catalyst is an amphoteric material exhibiting basic sites includes any one or combination of MgO, CeO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, Cr.sub.2O.sub.3, or is a basic anion exchange resin.

21.-24. (canceled)

25. A catalytic distillation process for production of performic acid, comprising: feeding aqueous solutions of formic acid and an oxidizing agent under controlled flow rates into a catalytic distillation column above one or more reaction zones located generally in the middle of the column, said one or more reaction zones including one or more heterogeneous catalysts immobilized in said one or more reactive zones; said column being operated at sub atmospheric pressure and preselected temperature such that the oxidizing agent and formic acid are introduced in the one or more reaction zones and undergo a reaction to produce performic acid and reaction by products; wherein performic acid enriched vapours flow upwards into a rectification section located above the one or more reaction zones and a liquid enriched in unreacted formic acid, unreacted oxidizing agent and reaction by products descend downwards through a stripping section located below the one or more reaction zones; and optionally withdrawing a proportion of the unreacted formic acid, unreacted oxidizing agent and reaction by products from a reboiler located at the bottom of the stripping section, and withdrawing some or all of the performic acid enriched product from a condenser located at the top of the rectification section to create a performic acid rich distillate product stream, for point of use application, optionally cooling the performic acid product and optionally storing the performic acid product.

26.-28. (canceled)

29. The catalytic distillation process according to claim 25, wherein the preselected temperature is in a range from about 0 to about 100° C.

30. The catalytic distillation process according to claim 25, wherein the preselected temperature in the reaction zone containing the catalyst is in a range from about 15° C. to about 60° C.

31. The catalytic distillation process according to claim 25, wherein the preselected temperature in the reaction zone containing the catalyst is in a range from about 20° C. to about 40° C.

32. The catalytic distillation process according to claim 25, wherein the oxidizing agent is hydrogen peroxide such that the hydrogen peroxide and formic acid mix in the one or more reaction zones and undergo the reaction (1) to produce performic acid and water as a reaction by product as follows ##STR00004##

33. The catalytic distillation process according to claim 25, wherein the oxidizing agent is a compound which can produce hydrogen peroxide in situ via its chemical reaction with other compounds present in the system or by interaction with the catalyst in the system

34. The catalytic distillation process according to claim 25, wherein the heterogeneous catalyst is a cation exchange resin.

35.-37. (canceled)

38. The catalytic distillation process according to claim 25, wherein the heterogeneous catalyst comprises at least one metal oxide selected from the group Nb.sub.2O.sub.5, Al.sub.2O.sub.3, ZrO.sub.2, TiO.sub.2, Cr.sub.2O.sub.3, CrO.sub.3, WO.sub.3, W.sub.2O.sub.5, ZrW.sub.xO.sub.y (wherein x is 2 and y is 0.5 to 8) V.sub.2O.sub.5, BeO, MoO.sub.3, Fe.sub.2O.sub.3, Ga.sub.2O.sub.3, La.sub.2O.sub.3, ZnO and mixtures thereof.

39. The catalytic distillation process according to claim 25, wherein the heterogeneous catalyst contains a transition metal oxide with a transition metal selected from the group consisting of Fe, Ti, Zr, Hf, Sn and Si an Al and combinations thereof, and wherein the metal oxide has been treated by an acidic material, and wherein the acidic material is at least one of sulphate, tungstate and molybdate.

40. (canceled)

41. The catalytic distillation process according to claim 39, wherein the acidic material is selected from the group consisting of SO.sub.4/SnO.sub.2, SO.sub.4/ZrO.sub.2, SO.sub.4/HfO.sub.2, SO.sub.4/TiO.sub.2, SO.sub.4/Al.sub.2O.sub.3, SO.sub.4/Fe.sub.2O.sub.3, MoO.sub.3/ZrO.sub.2, SO.sub.4/SiO.sub.2, WO.sub.3/ZrO.sub.2, WO.sub.3/TiO.sub.2, WO.sub.3/Fe.sub.2O.sub.3, B.sub.2O.sub.3/ZrO.sub.2 and combinations thereof.

42. (canceled)

43. The catalytic distillation process according to claim 25, wherein the heterogeneous catalyst is an amphoteric material exhibiting basic sites.

44. The catalytic distillation process according to claim 43, wherein the amphoteric material exhibiting basic sites includes any one or combination of MgO, CeO.sub.2, Al.sub.2O.sub.3, Fe.sub.2O.sub.3, Cr.sub.2O.sub.3, or is a basic anion exchange resin.

45.-48. (canceled)

49. The catalytic distillation process according to claim 25, further comprising flowing a proportion of the performic acid rich distillate product stream into the top of the catalytic distillation column as liquid reflux.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Preferred embodiments of the invention will now be described, by way of example only, with reference to the drawings, in which:

[0032] FIG. 1 shows a schematic representation of a first embodiment a catalytic distillation process for the production of performic acid (PFA) and water (H.sub.2O) from hydrogen peroxide (H.sub.2O.sub.2) and formic acid (FA).

[0033] FIG. 2 shows a schematic representation of a second embodiment of a catalytic distillation process for the production of performic acid (PFA) and water (H.sub.2O) from hydrogen peroxide (H.sub.2O.sub.2) and formic acid (FA).

DETAILED DESCRIPTION

[0034] Various embodiments and aspects of the disclosure will be described with reference to details discussed below. The following description and drawings are illustrative of the disclosure and are not to be construed as limiting the disclosure. Numerous specific details are described to provide a thorough understanding of various embodiments of the present disclosure. However, in certain instances, well-known or conventional details are not described in order to provide a concise discussion of embodiments of the present disclosure.

[0035] The Figures may not be to scale and some features may be exaggerated or minimized to show details of particular elements while related elements may have been eliminated to prevent obscuring novel aspects. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention.

[0036] As used herein, the terms “comprises”, “comprising”, “includes” and “including” are to be construed as being inclusive and open ended, and not exclusive. Specifically, when used in this specification including claims, the terms “comprises”, “comprising”, “includes” and “including” and variations thereof mean the specified features, steps or components are included. These terms are not to be interpreted to exclude the presence of other features, steps or components.

[0037] As used herein, the term “exemplary” means “serving as an example, instance, or illustration,” and should not be construed as preferred or advantageous over other configurations disclosed herein.

[0038] As used herein, the terms “about” and “approximately” are meant to cover variations that may exist in the upper and lower limits of the ranges of values, such as variations in properties, parameters, and dimensions. Unless otherwise specified, the terms “about” and “approximately” mean plus or minus percent or less.

[0039] It is to be understood that unless otherwise specified, any specified range or group is as a shorthand way of referring to each and every member of a range or group individually, as well as each and every possible sub-range or sub-group encompassed therein and similarly with respect to any sub-ranges or sub-groups therein. Unless otherwise specified, the present disclosure relates to and explicitly incorporates each and every specific member and combination of sub-ranges or sub-groups.

[0040] As used herein, the term “on the order of”, when used in conjunction with a quantity or parameter, refers to a range spanning approximately one tenth to ten times the stated quantity or parameter.

[0041] A goal of the process disclosed herein is to obviate or mitigate at least one of the above-mentioned disadvantages of the prior art and to provide a novel element that obviates or mitigates at least one of the above-mentioned disadvantages of the prior art.

[0042] Accordingly, the present disclosure provides a novel catalytic distillation process for the point of use production of PFA in high yield with the first embodiment as outlined in FIG. 1 and the second embodiment as outlined in FIG. 2. The reactor in FIG. 1 is a catalytic distillation reactor system, the concept of which is known to those skilled in the art. The reactor internals are comprised of either distillation media (packing) or trays depending on the scale of the process. Heterogeneous catalyst is immobilized in one or more reaction zones (020) within the column (010) in a manner known to those skilled in the art, for example as described by Taylor and Krishna (Chem. Eng. Sci., 2000, 55, 5183), such as in the form of catalyst pellets or extrudate, catalyst material retained within structured porous tubes, envelopes and structured packings, such as KATAPAK®-S(Sulzer Chemtech) or KATAMAX® (Koch-Glitsch), or within catalytic coatings deposited onto reactor internals or media. Reactants are continuously fed to the reactor system. In the case of the first embodiment shown in FIG. 1, aqueous solutions of hydrogen peroxide (H.sub.2O.sub.2) and formic acid (FA) are fed to the reactor separately and a PFA rich product stream is drawn from the bottoms product. In the case of the second embodiment shown in FIG. 2, the PFA rich product stream is drawn from the overhead distillate.

[0043] FIG. 1 illustrates the process flow for a catalytic distillation process for the production of PFA from formic acid (FA) and hydrogen peroxide. The catalytic distillation column (CD) (010) is comprised of 3 main sections. A reaction zone (020) which contains the immobilized catalyst noted above, a rectification section (030) located above the reaction zone (020) and a stripping section (050) located below the reaction zone (020). The stripping and rectification sections (050) and (030) do not contain catalyst but do contain distillation media such as Pall rings, Raschig rings or if the column (010) is sufficiently large, may contain other internals to promote heat and mass transfer such as sieve trays. Aqueous hydrogen peroxide and FA are fed to the catalytic distillation column separately at controlled flow rates. Without loss of generality, the embodiments of the systems and processes shown in FIGS. 1 and 2 show the feed streams of FA and H.sub.2O.sub.2 located near the reaction zone (020) for illustrative purpose. The precise locations can be chosen to optimize the outcome of the process. Within the CD column (010), liquid flows downward under the influence of gravity under conditions of trickle flow wetting and spreading over the distillation media and immobilized solid catalyst.

[0044] A vapour phase rises in the column and is condensed in the condenser (040). As the vapour rises in the column (010), the vapour phase becomes more concentrated with the volatile fractions in the rectification section (030); liquid that falls in the column (010) becomes increasingly enriched in the less volatile fractions. A reboiler (060) at the bottom of the column provides the energy to drive the distillation process, causing the product at the bottom of the column (010) to maintain a boiling condition.

[0045] A bottoms product can be recovered from the bottom of the column (010) and rapidly cooled with a heat exchanger (070). Similarly, an overhead distillate product stream can be drawn from the top of the column (010). Due to the ambiguity in the literature regarding the boiling point of PFA, two embodiments have been presented. In the first embodiment (FIG. 1), the PFA rich stream is recovered in the bottoms product, while in the second embodiment (FIG. 2), the PFA rich stream is produced in the overhead distillate. However, a proportion of the condensed distillate is refluxed to the catalytic distillation column. A vacuum pump (080) and control system (090) can be employed to control the pressure in the column (010), reducing it to sub atmospheric pressure by connection with the distillate head at the top of the column (010).

[0046] The process for production of performic acid using the apparatus of FIGS. 1 and 2 will now be described but it will be appreciated this method is exemplary and non-limiting. It will be understood that, the precise location of feed streams can be selected to optimize the process conditions and that a multiplicity of catalysts and reaction zones (020) may be employed. Within the column (010), a boiling liquid falls under the influence of gravity, in the low interaction regime of trickle flow wetting and spreading over the distillation media while a vapour phase rises in a counter-current fashion towards the top of the column (010). The presence of sieve trays or distillation media promote mass and heat transfer between these phases. When in the reaction zones (020) of the column (010), liquid and vapour phases contact the catalyst which facilitates the chemical conversion of formic acid and hydrogen peroxide to water and PFA.

[0047] The more volatile components rise towards the top of the column, becoming more concentrated in the rectification section (030) and most concentrated in the overhead distillate leaving the condenser (040). A proportion of the distillate stream is returned to the column as reflux, while some of this stream may be drawn from the reactor as a distillate product. In the first embodiment (FIG. 1) PFA, is presumed to be less volatile, and will become more concentrated in the stripping section (050) of the column and most concentrated reboiler (060) from which the bottoms product is drawn. The bottoms product can be cooled using a heat exchanger (070). In the second embodiment (FIG. 2) PFA is presumed to be more volatile and therefore become more concentrated in the overhead distillate, producing a PFA rich product stream. Thus, a continuous and concentrated PFA rich stream can be produced for on site, point of use generation as a disinfectant. The concentration of PFA in the bottoms or distillate product streams and the rate of its production can be controlled by the mass flow rate of reactants as well as by adjusting the reflux ratio of the catalytic distillation reactor as well as the product mass flow rates including the distillate and bottoms product streams.

[0048] Formic acid has a normal boiling point of 100.8° C. Although the normal boiling point of hydrogen peroxide is 150° C., in aqueous systems, water will form non-ideal mixtures with hydrogen peroxide, due to hydrogen bonding, resulting in bubble points which range from 105 to 114° C., for mixtures ranging from 27 to 50 wt % H.sub.2O.sub.2 respectively. The normal boiling point of PFA cannot be measured experimentally but has been estimated to be 127.5±23° C. based on numerical calculations (see ref. 13). Thus, PFA appears to be significantly less volatile than the reactants (formic acid and hydrogen peroxide) and the other by-product (water), which suggests separation of PFA from the reactants by distillation is possible. In the first embodiment (FIG. 1) it is assumed due to its low volatility, that PFA will substantially concentrate in the reboiler creating a PFA rich bottoms product stream and be present to a much lesser extent or not at all in the overhead distillate stream. Since the bubble point of a H.sub.2O.sub.2/H.sub.2O mixture increases with increasing concentration of H.sub.2O.sub.2, the current inventors realized that the efficacy of the separation of PFA from the mixture, (if PFA is presumed to have a normal boiling point of 127° C.), via catalytic distillation can be improved by operating the reactor under conditions where the catalytic conversion of H.sub.2O.sub.2 is close to 100%, by using H.sub.2O.sub.2 either as the limiting reagent or in stochiometric amount with formic acid or not significantly in stoichiometric excess of the formic acid and by operating the reactor at sufficiently low space velocity to ensure the catalytic conversion of hydrogen peroxide is close to 100%. Thus, the relative volatility of PFA and the remaining constituents will be sufficiently high to affect its purification by distillation.

[0049] Although the boiling point of PFA has been estimated to be 127° C. by computational methods, this contradicts the boiling point trends observed for peracids of experimentally verified boiling points whereby the boiling point of the peracid is typically lower than the parent acid. Based on these observations, a second embodiment (FIG. 2) is contemplated by the inventors where the boiling point of PFA is less than FA, and therefore is the most volatile constituent in the process and will substantially concentrate in the overhead distillate stream and to a much lesser extent or not at all in the bottoms product stream.

[0050] Thus, it will be appreciated that in the embodiment of FIG. 1, the majority of the PFA is taken from the bottom of the column there may be smaller amounts of PFA in the top of the column and the same goes for the embodiment of FIG. 2, the majority of the product is taken from the top of the column but there may be smaller amounts located in the bottom of the column.

[0051] In a catalytic distillation process, there are insufficient degrees of freedom to independently specify temperature and pressure. The boiling point of the mixture depends on its composition and the system pressure. Since the composition of the liquid changes throughout the column, there is a temperature gradient in the column being a maximum in the reboiler at the bottom of the column and a minimum at the condenser at the top of the column. Due to the energetic and unstable nature of PFA, operating a catalytic distillation reactor at a temperature near the normal boiling point of water to produce a concentrated boiling PFA product near the normal boiling point of PFA is neither technically feasible nor advisable for producing concentrated solutions of PFA. However, the current inventors discovered that by operating the catalytic distillation column under sub atmospheric conditions by connecting a vacuum pump (100) to the distillate head at the condenser to reduce the overall system pressure to a range from about 27 to about 29 in Hg, the temperature in the reaction zone can be reduced to temperatures below 40° C., providing advantageous conditions to facilitate the production of PFA while minimizing undesirable consecutive reactions, such as the decomposition of PFA into carbon dioxide. Similarly, the PFA product, can be maintained at a relatively low temperature and (optionally) rapidly quenched by a heat exchanger when drawn from the reactor.

[0052] Solid acid catalysts exhibiting either Bronsted and or Lewis acid sites can be immobilized in the reaction zone, in a manner as described previously and known to those skilled in the art, and used to facilitate the production of PFA from formic acid and hydrogen peroxide. Acidic cation exchange resins, such as Amberlyst® 15 and other cation exchange resins could be used to catalyze the reaction (see ref. 14). Other particularly useful catalysts include Nb.sub.2O.sub.5/X where X denotes a ceramic catalyst carrier substrate such as a metal oxide like SiO.sub.2, Al.sub.2O.sub.3, and so on. Generally, solid acid catalysts described by Tanabe can potentially be used to affect the catalytic conversion of formic acid and hydrogen peroxide to PFA and water (see ref. 15). Some reactions that are solid acid catalyzed, can also be catalyzed by solid basic catalysts although the fundamental reaction mechanisms will be different. However, from an industrial perspective, acid catalysts are typically more robust and preferred.

[0053] The use of an immobilized heterogeneous catalyst offers significant advantages over the use of homogeneous catalysts described previously in the prior art. For example, the use of liquid mineral acid catalysts like sulphuric acid can cause corrosion issues to equipment and piping. In addition, the homogeneous acid catalysts are residual in the product and can destabilize PFA accelerating its degradation to oxygen, carbon dioxide and water unless neutralized. The use of homogeneous acid catalysts requires that the catalyst be a consumable reagent as separation and recovery of the homogeneous catalyst would not be economically viable. In contrast, solid catalysts (heterogeneous catalysts) immobilized in a reactor are fixed in place and not be residual in the product. The rapid separation of the product stream from the catalyst reaction significantly minimizes undesirable consecutive reactions and obviates the need for neutralization of the product stream or recovery of the homogeneous catalyst.

[0054] The solid catalyst used in the catalytic distillation process does not become consumed or lost in the product stream, which is a distinct advantage over the conventional technology. Heterogeneous catalysts may be regenerated in place after some period of operation to restore its functionality. Eventually, heterogeneous catalysts are replaced, typically after several years. It has been reported that the continuous distillation action in a catalytic distillation process, helps reduce catalyst poisoning, thereby greatly extending the viable catalyst life (see ref. 16).

[0055] A significant advantage and the distinguishing feature of catalytic distillation, from which it gains its greatest utility is the ability to simultaneously conduct chemical reaction and product purification in a single unit operation. The continuous removal of product from the reaction zone by the distillation action, keeps the product concentration at the boundary layer near the catalyst surface very low compared to the very high reactant concentration. This is known to shift the chemical equilibrium in favour of product formation in accordance with Le Chate̊liers Principle circumventing the thermodynamic equilibrium conversion constraint. It has been proven experimentally and is known to those skilled in the art, that chemical conversions as high as 100% for otherwise equilibrium limited reactions can be achieved using catalytic distillation (see refs. 17, 18). Thus, the use of catalytic distillation to produce PFA will enable product yield in excess of the theoretical equilibrium conversion, which is a distinct advantage over the conventional technology described in the prior art. The rapid removal of products from the reactant zone is also known to greatly minimize the occurrence of undesirable consecutive reactions, such as the decomposition of PFA and result in a concentrated PFA product whose concentration is adjustable as desired by the operator of the process.

[0056] The strongly exothermic reaction associated with PFA production as well as the instability of PFA are significant challenges for conventional technology. The proposed process disclosed herein, using catalytic distillation, offers a unique advantage in this regard. Since the reaction occurs in a boiling medium, the reaction temperature will remain constant, providing more precise control over the chemical reaction. All of the reaction heat generated is efficiently converted to drive the distillation process and thereby reduce energy consumption requirements. Furthermore, heat transfer efficiency is maximized in a boiling medium. The fact that the heat of reaction is absorbed by the boiling liquid provides a significant advantage in terms of safety, since the temperature of a boiling liquid will not increase further due to the addition of energy. Thus, hot spot formation and thermal runaway chemical reactions can be prevented in the instance of a significant exotherm or other unexpectedly large release of energy in the system. This is particularly advantageous for the production of energetic and highly oxygenated species like peracid compounds, including PFA. In fact, the potential for runaway reactions has been identified as a significant safety risk for the conventional technology used to produce PFA, wherein PFA is produced in a batch or semi-batch reactor; Leveneur et al. (Ref. 19) conducted a thermal safety assessment of the production of PFA using a semi-batch reactor and advise that the criticality of the reaction is class 5 based on Stoessel classification and that a continuous flow system is recommended instead of a batch system for industrial production. Thus, the proposed invention using catalytic distillation technology obviates this critical deficiency of the state of the art by providing a continuous flow system and by mitigating the potential for hot spots and thermal runaway by conducting the reaction in a boiling medium.

Preferred Embodiments of the Process

[0057] The sizing of the reactor including the amount of catalyst required in the catalyst zones is dependent on the production requirements including the required throughput, the concentration of PFA in the desired product stream and the nature of the catalyst selected for the process.

[0058] The reaction temperature will be governed by the system pressure. The ideal reaction temperature is dependent on the nature of the catalyst used which governs the reaction kinetics. The operator designs and configures the process to ensure excessive temperatures are not achieved and that excessive concentrations are not achieved which can create potentially explosive or detonable mixtures, depending on the desired concentration of PFA in the PFA rich product stream. The catalytic distillation process should be carried out at a system pressure ranging from about 0.1 to about 14.7 psia. More preferably, the catalytic distillation should be carried out at a system pressure ranging from about 0.1 to about 3 psia. Most preferably, the catalytic distillation process should be carried out at a system pressure ranging from about 0.3 to about 1.1 psia.

[0059] Due to the ambiguity in the science regarding the boiling point of PFA, two process embodiments are disclosed. In the first embodiment (FIG. 1), an overhead distillate stream may optionally be drawn to facilitate the removal of water from the system to prevent its accumulation. The reflux ratio is defined as the mass of distillate returned to the column to the mass of distillate recovered as an overhead product. The column may be operated at total reflux (i.e. 100% of distillate returned to the column). More preferably, the column may be operated at a reflux ratio ranging from 20% to 99.9% (distillate returned to the column) and most preferably the column may be operated at a reflux ratio ranging from 90% to 99%.

[0060] In the second embodiment (FIG. 2), which presumes that PFA is the most volatile compound, a PFA rich overhead distillate product can be recovered while some proportion of the PFA rich distillate is returned to the CD column as reflux. A bottoms product may be drawn. The reflux rate of the overhead distillate may be optimized to ensure maximum energy efficiency while achieving the target PFA production rates and concentrations as well as target liquid flow rates within the column to ensure adequate catalyst wetting efficiency and promote mass and heat transfer. The reflux rate may range from 0% (no reflux) to 99.9% (returned to column). More preferably, the reflux rate may range from 20 to 97%, most preferably the reflux rate ranges from 50 to 90%.

[0061] The catalyst is preferably a solid having significant surface acidity preferably with a Hammet acidity (H.sub.0) less than 0. The catalyst used should be a strongly acidic cation exchange resin, preferably Amberlyst-15. Most preferably the catalyst is a moisture tolerant Nb.sub.2O.sub.5/SiO.sub.2 catalyst, either provided in the form of a catalytic coating applied directly onto distillation media or more having the Nb.sub.2O.sub.5 grafted onto a SiO.sub.2 carrier shaped in the form of a distillation packing, like a Raschig ring and whereby the Nb.sub.2O.sub.5 has strong Bronsted acidity and its loading is equivalent to one monolayer coverage on the SiO.sub.2 catalyst carrier.

[0062] While PFA is unstable and is typically used in situ provided by a point of use generator on site, it is not typically stored. It spontaneously decomposes usually over 12 h, but storage in a surge tank containing the PFA product is possible to ensure continuous provision of the PFA rich stream to the end use application during temporary process disruptions.

[0063] The reactor is operated in a manner which ensures that hydrogen peroxide (H.sub.2O.sub.2) is not in substantial stoichiometric excess of formic acid (FA). The stoichiometric ratio of H.sub.2O.sub.2:FA can range from about 100 to about 1. More preferably, the stoichiometric ratio of H.sub.2O.sub.2:FA can range from about 2 to about 1, most preferably the stoichiometric ratio of H.sub.2O.sub.2:FA should range from about 1.20 to about 1.

[0064] The specific embodiments described above have been shown by way of example, and it should be understood that these embodiments may be susceptible to various modifications and alternative forms. It should be further understood that the claims are not intended to be limited to the particular forms disclosed, but rather to cover all modifications, equivalents, and alternatives falling within the spirit and scope of this disclosure.

REFERENCES

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