PROCESS FOR PRODUCING A MULTIFUNCTIONAL PRODUCT AND THE DEVICE FOR APPLYING SAID PROCESS

Abstract

A process by which the raw material, a gas comprising mainly hydrogen, carbon monoxide and carbon dioxide, is introduced into a first reactor together with a catalyst, in which one or more reactions take place that produce methanol or dimethyl ether or both, which are then introduced into a second reactor adding oxygen and a catalyst and producing formaldehyde and a minority of dimethyl ether, and where there may be an excess of water, such water being extracted from the process and the remaining products being introduced into the third reactor with, optionally, an additive, and such raw material is exposed to catalysts and under an atmosphere at medium temperature and pressure, in order to produce three or four groups of chemical reactions that, after extracting most of the water that is generated as a residue during the process, produces as a result a liquid multifunctional product that can be used as a solvent, a foaming agent or an oxygenated fuel; said product, normally a fluid, comprises polyoxymethylene dimethyl ethers with molecular formula CH3O(CH2O)nCH3 wherein n has a value between 1 and 7.

Claims

1. PROCESS FOR PRODUCING A MULTIFUNCTIONAL PRODUCT, characterized in that it comprises. a prior phase of preparation of the raw material at a temperature between 200° and 300° C. and at a pressure between 18 and 60 bar, preferably between 30 and 50 bar and more preferably between 37 and 43 bar, the raw material being a gas comprising hydrogen, carbon monoxide and carbon dioxide.

1. A first phase, comprising the reactions caused by at least one of these two catalysts: a. A catalyst C1, preferably based on CuO/ZnO/Al2O3, thus giving rise to the first group of reactions comprising the reaction CO+2H2.fwdarw.CH3OH producing methanol. a. A catalyst C2, preferably based on aluminum oxide and CuO/ZnO/Al2O3, thus giving rise to the second group of reactions comprising the reaction 3CO+3H2.fwdarw.CH3OCH3+CO2, producing dimethyl ether.

2. A second phase in which at least one of the products resulting from the first phase passes into the second reactor and comprises the following sub-phases: i) Oxygen is injected into the products resulting from the first phase. ii) The products resulting from the first phase, together with the oxygen, come into contact with at least one catalyst C3, preferably based on at least one compound between aluminum oxide, molybdenum, vanadium and iron causing the third group of reactions. iii) After the third group of reactions formaldehyde is obtained, and as by-products hydrogen and the excess water that did not react. iv) Extraction, preferably by condensation, of the residual water.

3. A third phase in which the products resulting from the previous phase, mainly dimethyl ether and formaldehyde, pass into the third reactor and are subjected to reactive distillation. The products resulting from the previous phases, the unconverted synthesis gas and any by-products that have not previously been extracted from the productive system come into contact with at least one catalyst C4 that is a strong acid, preferably an ion exchange resin, that is inside the third reactor at a pressure of close to or less than 20 bar and a temperature of close to or less than 175° C., causing the fourth group of reactions and the production of polyoxymethylene dimethyl ethers or the multifunctional product.

4. In a fourth phase it comprises the output from the device of the multifunctional product together with any unconverted synthesis gas and the minority by-products that have not previously been extracted wherein the end products exit at a temperature between 150° and 200° C., preferably between 100° C. and 175° C. and at a pressure of less than 20 bar, preferably 17 bar, and the conversion of the synthesis gas into the multifunctional product, by weight, is of approximately 40% by weight and a maximum of 10% is methanol and a maximum of 8% is other liquid minority by-products (12) and wherein this fourth phase also comprises a process of separation of the multifunctional product from the synthesis gas and other unconverted products and any liquid minority by-products not previously extracted, which may be separated totally or partially, preferably by cooling.

5. An optional fifth phase wherein the liquid or gas products that come out of the third reactor together with the multifunctional product are recirculated and thus serve as raw material for a gasification process for the production of synthesis gas, or, once separated, may be used as a product for recycling in the device of the present invention.

2. PROCESS FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1, characterized in that: In the first phase the raw material, instead of coming into contact with C1 or C2, comes into contact with both catalysts C1 and C2 at the same time, generating the first and second group of reactions to produce methanol and dimethyl ether and also a reaction comprising 2CH3OH.fwdarw.CH3OCH3+H2O, thus producing more dimethyl ether and residual water, causing the side reaction CO+H2O.fwdarw.CO2+H2 producing hydrogen.

3. PROCESS FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1, characterized in that only one of the products resulting from the first phase enters the second reactor, mainly dimethyl ether or methanol, causing the partial oxidation of part of the dimethyl ether or the methanol, via the reactions CH3OH+1/2O2.fwdarw.CH2O+H2O and CH3OCH3+O2.fwdarw.2CH2O+H2O, to produce formaldehyde and leaving as a by-product water that exits together with unconverted products.

4. PROCESS FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1, characterized in that all the products produced in the first group of reactions enter the second reactor simultaneously, mainly dimethyl ether and methanol to produce formaldehyde, causing the side reaction CH3OCH3+H2O.fwdarw.2CH2O+2H2 producing more formaldehyde and leaving as main by-products the unreacted excess water and hydrogen, together with other unconverted products.

5. PROCESS FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1 wherein the excess pressure lost by the resulting products between the first and the second phase may optionally be used to raise the pressure of the products passing through the second and third phase to reactors two and three.

6. PROCESS FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1 wherein at least one of the products from the first and second phase provides heat to the third reactor.

7. PROCESS FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1 wherein at least one of the products from the first and second phase provides heat to the raw materials entering the device.

8. PROCESS FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1 wherein the volatility, energy content, cetane number and vapor pressure of the multifunctional product produced are modified by varying the amount of aldehyde produced in the third group of reactions.

9. DEVICE FOR APPLYING THE PROCESS DISCLOSED, characterized in that comprises: 1. At least three reactors, a first, second and third, arranged in sequence wherein each reactor comprises: a. A plurality of pipes containing the relevant catalyst and through which the reagent product circulates. This plurality of pipes is contained within a covering element, all of this joined by a series of support elements. b. At least two chambers communicated with the exterior. 2. At least one compressor and at least two means of condensation. 3. Means to transfer heat from one reactor to another according to their requirements. 4. Means to collect or apply heat to the raw material entering the process. 5. Means for recovering pressure. 6. Means for measuring, automating and controlling flow, temperature and pressure according to the requirements of each reactor.

10. DEVICE FOR APPLYING THE PROCESS DISCLOSED according to claim 9, characterized in that the first reactor comprises a main reactor and an auxiliary reactor arranged in sequence, alternating or in parallel.

11. DEVICE FOR APPLYING THE PROCESS DISCLOSED according to claim 9, characterized in that the first reactor contains at least one catalyst from between C1 and C2, the second reactor contains catalyst C3 and the third reactor contains catalyst C4.

12. DEVICE FOR APPLYING THE PROCESS DISCLOSED according to claim 9, characterized in that the first reactor comprises catalysts Cl and C2 arranged one in the main reactor and the other in the auxiliary reactor.

13. DEVICE FOR APPLYING THE PROCESS DISCLOSED according to claim 9, characterized in that the first reactor comprises catalysts C1 and C2 mixed with one another.

14. DEVICE FOR APPLYING THE PROCESS DISCLOSED according to claim 9, characterized in that the covering element for the plurality of tubes is a jacket and the support elements are preferably flange disks with through holes through which the tubes receive or discharge the reagents.

15. DEVICE FOR APPLYING THE PROCESS DISCLOSED according to claim 9, characterized in that each reactor comprises at least two chambers, preferably each one on opposite ends in which said chambers comprise holes to receive or discharge mainly the reagents and holes communicated with the inside to receive or discharge the products that circulate within the tubes in the reactor.

16. DEVICE FOR APPLYING THE PROCESS DISCLOSED according to claim 9, characterized in that the second and third reactor are communicated with oxygen or air injectors.

17. PROCESS FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 2, characterized in that only one of the products resulting from the first phase enters the second reactor, mainly dimethyl ether or methanol, causing the partial oxidation of part of the dimethyl ether or the methanol, via the reactions CH3OH+1/2O2.fwdarw.CH2O+H2O and CH3OCH3+O2.fwdarw.2CH2O+H2O, to produce formaldehyde and leaving as a by-product water that exits together with unconverted products.

18. PROCESS FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 2, characterized in that all the products produced in the first group of reactions enter the second reactor simultaneously, mainly dimethyl ether and methanol to produce formaldehyde, causing the side reaction CH3OCH3+H2O.fwdarw.2CH2O+2H2 producing more formaldehyde and leaving as main by-products the unreacted excess water and hydrogen, together with other unconverted products.

Description

BRIEF DESCRIPTION OF FIG. 1

[0081] FIG. 1 shows a diagram of the process of the invention and the preferred catalysts that can be used, and should not be considered the only one but instead a mere descriptive example showing the device with a first reactor (1) comprising a main reactor (2) and an auxiliary reactor (3), a second reactor (4) and a third reactor (5).

[0082] In this case, the first group of reactions takes place in the main reactor (2) of the first reactor (1), the second group of reactions takes place in the auxiliary reactor (3) of the first reactor (1), the third group of reactions takes place in the second reactor (4), and the fourth group of reactions takes place in the third reactor (5).

[0083] Before the materials enter the first reactor they have passed through a compressor (6) and a heat exchanger (7).

[0084] An oxygen injector (8) is associated with the second reactor (4) and an injector of the optional additive (9) is associated with the third reactor (5).

[0085] After the third group of reactions and before the fourth group of reactions the residual water (10) is extracted from the process by the action of a condenser (13)

[0086] After the fourth group of reactions the multifunctional product (11) and the unconverted synthesis gas and any minority by-products (12) are extracted from the process.

[0087] Within the circuit there are at least two interconnections throttle/relief valves that are responsible for discharging any excess of product without affecting the environment and without the end production or quality of the multifunctional product being substantially affected.

[0088] These interconnections are a first interconnection (15) located between the main reactor (2) and the second reactor (4) and a second interconnection (14) located between the auxiliary reactor (3) and the third reactor (5).

DESCRIPTION OF AN EMBODIMENT OF THE INVENTION

[0089] We shall now describe an embodiment of the invention that is not unique but merely intended as an example.

[0090] The synthesis gas is compressed to 40 bar with the compressor (6) and it is then heated to 280° C. in the heat exchanger (7) in order to then enter the first reactor (1) via its main reactor (2) and its auxiliary reactor (3), which may be arranged in sequence or in parallel.

[0091] According to one possible embodiment, the synthesis gas enters in parallel to the main reactor (2) and the auxiliary reactor (3) of the first reactor (1). These reactors house catalysts C1 and C2 respectively, and both work at 280° C. and a pressure of 40 bar.

[0092] In the main reactor (2) of the first reactor (1) takes place the first group of reactions to produce mainly the methanol, which then enters the auxiliary reactor (3) together with the gas that did not react and other by-products from the first group of reactions. All the products that circulate through the main reactor (2) enter the auxiliary reactor (3) that contains catalyst C2, with the gas that did not react in the main reactor (2) to produce mainly dimethyl ether via the second group of reactions.

[0093] The dimethyl ether and the methanol, each in conjunction with their respective raw materials that did not react and the respective by-products derived from their respective reactions, such as carbon dioxide, methyl formate and carbonic acid, together with the oxygen and the optional additive injected from outside the device, all enter the second reactor (4) at the same temperature at which the products leave the auxiliary reactor (3) and at a reduced pressure so that, via the third group of reactions, the methanol may mainly be oxidized to formaldehyde, under the presence of catalyst C3. The oxygen is injected by an oxygen injector (8) comprising an orifice that communicates the outside with the inside of the second reactor (4) as shown in FIG. 1.

[0094] All products that circulate through the second reactor (4) are exposed to catalyst C3 to produce mainly formaldehyde and they pass through a condenser, preferably under pressure, to extract the residual water (10), preferably via a condenser (13) that is outside the device.

[0095] The products that exit the second reactor (4) and enter the third reactor (5) together with the optional additive that is injected from the outside by an additive injector (9), pass in contact with catalyst C4 in a temperature scenario of approximately 170° C. and a pressure of close to 20 bar, to generate the reactions of the fourth group, in which the multifunctional product (11) is mainly produced. This third reactor produces, as well as the multifunctional product, a minority or traces of: water, methanol, carbonic acid, formic acid, acetic acid, carbon dioxide, methyl formate and formaldehyde; other products also exit in gas form, from the raw material that was not converted, such as carbon monoxide, methane, hydrogen, oxygen and hydrocarbon traces, which we shall call minority by-products (12).

[0096] There are two interconnections with throttle/relief valves that are shown in FIG. 1. Both serve to discharge excess product without substantially affecting the production or end quality of the MULTIFUNCTIONAL product.

[0097] The interconnections are a first interconnection (15) from the main reactor (2) to the second reactor (4) and a second interconnection (14) from the auxiliary reactor (3) to the third reactor (5)

[0098] Whilst the different groups of reactions occur, the products from the first reactor (1), comprising its main (2) and auxiliary (3) reactors and from the second reactor (4) provide heat to the third reactor (5) indirectly via a non-volatile liquid that circulates between the jacket and the pipe bank containing the reactors, using a heat exchange, and the excess heat can optionally be applied to the raw materials entering the device and to the optional additive that may enter the device via the additive injector (9).

[0099] Finally, if so desired, the multifunctional product (11) that exits the third reactor (5) may be separated into its different components via a distillation, where fractional distillation is preferred.

[0100] The liquid or gas products that exit reactor R4 together with the polyoxymethylene dimethyl ethers, may optionally be recirculated and serve as a raw material for a gasification process for the production of synthesis gas.

[0101] In another example of an embodiment of the invention, the synthesis gas is compressed to 40 bar with the compressor (6) and is then heated to 280° C. in the heat exchanger (7) to then enter the main reactor (2) and the auxiliary reactor (3) which may be arranged in sequence or in parallel, where in the main reactor this synthesis gas comes in contact with catalyst Cl and in the auxiliary reactor (3) it comes in contact with catalyst C2. As a result a group of reactions occurs in each reactor wherein the end products of the main reactor and the auxiliary reactor are mainly methanol and dimethyl ether respectively, obtaining a weight conversion of more than 40% of the synthesis gas used.

[0102] The products of the main reactor (2) and the auxiliary reactor (3) where in the main reactor (2) the first group of reactions occurs and methanol is produced and where in the auxiliary reactor (3) the second group of reactions occurs and dimethyl ether is produced, all enter the second reactor (4) at a temperature and pressure no greater than those of the main reactor and the auxiliary reactor and they come in contact with catalyst C3 which favors the partial oxidation of the methanol and the dimethyl ether into formaldehyde, therefore generating liquid by-products, mainly: water, carbon dioxide, methyl formate, carbonic acid and methanol. Also present during this oxidation process are the gaseous by-products of the synthesis gas and part of the synthesis gas that did not react in the main (2) and auxiliary (3) reactors, mainly: hydrogen, carbon monoxide, carbon dioxide and nitrogen infiltrated with oxygen and raw materials.

[0103] The products of the main (2) and auxiliary (3) reactors both exit at 280° C. and 34 bar of pressure, which is preferably reduced to 12 bar, and then enter the second reactor (4) that houses the catalyst C3 and either pure oxygen or a compound containing oxygen is added with an oxygen injector (8).

[0104] In this second reactor (4) the methanol oxidizes almost entirely to formaldehyde, producing water as a by-product; part of the dimethyl ether also oxidizes in a lower proportion to formaldehyde, producing water as a by-product.

[0105] At the end of the second reactor (4) all the products circulating pass through a condenser (13) that is preferably on the end of the second reactor (4), although it could be external, so that mainly the residual water (10) produced as a by-product in the second reactor (4) condenses and can be extracted from the productive system.

[0106] The products coming out of the condenser apart from those extracted from the productive system, together with the optional additive, enter the third reactor (5) that contains catalyst C4 which is at a pressure of close to 20 bar and a temperature of 175° C., and produces the full group of reactions at mainly produce the multifunctional product with a conversion of the synthesis gas of more than 40%.

[0107] The end products exit at approximately 175° C. and 17 bar of pressure, and the conversion of the synthesis gas to the multifunctional product, by weight, is of approximately 40%, and at most 10% is methanol and at most 8% is other minority liquid by-products (12). The remaining percentage is of products that were not converted to the multifunctional product and exit as gases, together with those that did not manage to react and which are separated from the multifunctional product by cooling.

[0108] It is then convenient to separate the polyoxymethylene dimethyl ether from the undesired liquid by-products carried with the multifunctional product, wherein the liquid by-products separated together with the other gas products that exit from the third reactor may optionally be used in the production process for synthesis gas, in preheating raw materials and optional additives.