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    • 专利摘要:
    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 taking place one or more reactions by which methanol or dimethyl ether or both are obtained, being introduced into a second reactor by adding oxygen and a catalyst and formaldehyde and dimethyl ether being obtained, there being an excess of water being that the water is extracted from the process and the rest of the products are introduced into the third reactor with, optionally, an additive and they are exposed to catalysts under an environment of medium temperature and pressure, so that three or four groups of chemical reactions are produced that, after extracting most of the water generated as waste during the process, produce as a result a multifunctional liquid product that it can be used as a solvent, foaming agent or as an oxygenated fuel; said product, normally liquid, comprises poly-oxymethylene dimethyl ethers with molecular formula ch3 o (ch2 o)n ch3 where n has a value from 1 to 7. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2637949A1
    申请号:ES201630473
    申请日:2016-04-15
    公开日:2017-10-18
    发明作者:Mario ARAYA BRENES
    申请人:BLUEPLASMA POWER S L；BLUEPLASMA POWER SL；
    IPC主号:
    专利说明:

    DESCRIPTION

    PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT, DEVICE FOR APPLYING THIS PROCEDURE AND PRODUCT OBTAINED WITH THIS PROCEDURE 5

    The invention comprises: A) a process for obtaining a multifunctional product from raw material comprising oxygen, synthesis gas and an optional additive, B) a device for the application of the intended process, comprising at least three sequence reactors where maximum four four and at least three groups of reactions are produced, and C) the product finally obtained by this procedure.

    During the process, the raw material that is introduced into a first reactor comprises synthesis gas that mainly contains carbon monoxide and hydrogen, the raw material that is introduced into a second reactor mainly comprises oxygen, and the raw material that is introduced into a third reactor comprises an optional additive, and they are exposed to catalysts under an environment of medium temperature and pressure, so that three or four groups of chemical reactions are produced which, after extracting most of the water that is generated as waste during the process, they result in a multifunctional liquid product that can be used as a solvent, foaming agent or as an oxygenated fuel; said normally liquid product comprises poly-oxymethylene dimethyl ethers with molecular formula CH3O (CH2O) nCH3 wherein n has a value of 1 to 7. 25

    This product obtained together with its derivative by-products and which are also liquid at room temperature and atmospheric pressure, such as methanol, and traces of water among others, from now on it will be called multifunctional product and its fraction corresponding to by-products can be decreased , through a fractional distillation and its chemical stability can also be improved
    modifying its PH by incorporating and controlling the optional additive in the last group of reactions.

    BACKGROUND
     5
    The most economical conventional systems for converting the synthesis gas into a product with similar characteristics to the multifunctional product to which the present patent refers are by means of the by-products of the same synthesis gas: methanol and formaldehyde, or via dimethyl ether and formaldehyde.
     10
    The first way to produce a product similar to the multifunctional product referred to in this patent requires that the synthesis gas is first converted to methanol with pressures of approximately 60 bar and at temperatures approximately 250 degrees Celsius passing it several times through the same reactor, due to to that the water generated in the process limits the conversion of the synthesis gas to methanol. This modern process of producing low pressure methanol (LPM) was developed in the late 1960s.

    After methanol is produced, it is required to process it in a separate reactor and at near atmospheric pressure, to be dissociated into formaldehyde and hydrogen at a temperature of approximately 600 degrees Celsius using copper or silver 20 as catalysts, or it is oxidized with air to convert it to formaldehyde and water at 280 degrees Celsius using near atmospheric pressure.

    Finally, the formaldehyde produced is taken and reacted with methanol by raising its pressure to 20 bar and at an approximate temperature of 250 degrees Celsius in a reactive distillation process, using ion exchange resin as an acid catalyst and thus forming a product with similar characteristics to the multifunctional product.

    An example of this process is US Patent BP / AMOCO number US 30 6,160,186. However, this process loses efficiency when the synthesis gas, by generating water during methanol production, causes a percentage to be obtained.
    Minor conversion to methanol and therefore requires several passes through the reactor under a pressure of approximately 60 bar, and after each pass, this methanol needs to lose pressure and cool down to be able to extract the water generated in the process, since this acts as a limitation in the conversion; for the previous separation, a distillation process called in the English language 5 is generally used, such as "flash" distillation, which is carried out at a temperature and pressure lower than that required for methanol synthesis.

    Then to convert this methanol to formaldehyde, the methanol must be reheated generally with the presence of an oxidizing agent such as air, oxygen, water or CO2, and an appropriate catalyst. Once the methanol has been oxidized to formaldehyde, it must be cooled and stored in a stock that is separate from the process line and then recovered again from this stock, heated and injected at the same time as methanol, at a pressure of approximately 20 bar and a temperature near 180 degrees Celsius so that said products can react in a process known as reactive distillation, using ion exchange resin as a catalyst.

    Another known way to produce a product similar to the multifunctional product is from synthesis gas and oxygen, less conventional than the first one, but with a majority conversion, is by converting the synthesis gas directly to dimethyl ether at a temperature close to 250 ° degrees Celsius and medium pressure: from 20 to 40 bar, then stored in a container at moderate pressure and room temperature, where it is extracted to be combined with formaldehyde taken from a source that contains it or generates it, to finally process both products , dimethyl ether and formaldehyde, heating them to a temperature of approximately 180 degrees Celsius and subjecting them to a pressure of about 20 bar, using ion exchange resin as a catalyst.

    This process requires producing the formaldehyde, generally obtained from methanol, with the drawbacks indicated in the first route, or taking it from other products that already contain the aldehyde but are more expensive; or in pure form, such is the case of tri-oxane, para-formaldehyde and formaldehyde in solution with methanol or water;
    This last way of obtaining formaldehyde to produce polyoxymethylene dimethyl ether is used by the process developed by BASF and reflected in US Patent No. 7,999,140 B2.

    The multifunctional product object of the present patent is useful as a solvent and also as a liquid fuel due to its characteristics and advantages, among which are:

    1. Low toxicity.
    2. It can be mixed in all proportions with gasoline or diesel. 10
    3. When the objective is to mix it with diesel, it can be adjusted to a different degree of viscosity and a different number of cetane.
    4. Maintains in a single liquid phase, mixtures of alcohol with hydrocarbons such as gasoline or diesel, even when there is water contamination.
    5. When mixed and combustion with hydrocarbons, the toxic levels of the emission of gases that come from the combustion of the hydrocarbon are lowered.
    6. It can be obtained from biomass or hydrocarbons.
    7. It is biodegradable.
    8. It acts as a carbon dioxide sink for generating less CO2 per unit of net energy obtained and because when used as a component in conventional fuels, its oxygen content is greater than 50%, with irrelevant impact negative in the power of the motor that is used.
    9. It can be complemented with other combustible components so that it can be used up to 100% in conventional engines without substantial modifications and obtaining competitive efficiency with respect to conventional fuels.
    10. Cleans carbon deposits and injectors from carbon and water.
    11. Work with current pumping systems at service stations.
     30
    In the current state of science there is no integrated procedure that manages to obtain the multifunctional product from only synthesis gas, oxygen and an additive
    optional, using the integration of known technologies, so that when interacting they are able to generate a surprising synergy characterized by:

    1. Achieve in a single pass a majority percentage of conversion to multifunctional product. 5
    2. To be able to keep the process working in a self-thermal and continuous way, at the expense of the thermal energy received from the partial oxidation of part of its raw materials and without causing greater expenditure on electrical energy, using almost all of it necessary to keep the process at moderate pressure. 10
    3. Avoid the need to store externally to the process line, the intermediate products of the procedure.
    4. Obtain a multifunctional product that, by properly applying the optional additive, can modify its PH and thus its physical-chemical characteristics so that, on the one hand, in the presence of acidic substances, it avoids the reversal of the 15 reactions that formed it; and on the other hand, when used as fuel, increase its sensitivity to detonation.

    The above four points is precisely what is achieved with the innovative procedure and device presented by this patent and described below. twenty

    DESCRIPTION OF THE INVENTION

    The invention relates to a process for obtaining a multifunctional product from a raw material comprising oxygen, synthesis gas, and an optional additive, also relates to the device for applying said process and also to the product finally obtained with said process. .

    1.- Regarding the procedure
     30
    In relation to the procedure, it should be noted that this is globally exothermic, since although it comprises some endothermic reactions, exothermic reactions release
    more thermal energy than endothermic reactions consume. In order for endothermic reactions to be maintained at the required temperature, this procedure includes the reuse of heat that exothermic reactions give off.
     5
    Therefore, the procedure is self-thermal without requiring external sources to give more heat than that used only once to start the procedure and in terms of electrical energy, its use is required to continuously maintain the pressure to the synthesis gas .
     10
    The procedure comprises at least three groups of reactions and a maximum of four groups of reactions.

    For this, the device that is part of this patent comprises at least three reactors in sequence: a first reactor, which can in turn comprise a main and an auxiliary reactor 15, in which at least one of the first two groups of reactions, a second reactor where the third group of reactions takes place and a third reactor where the fourth group of reactions takes place.

    Before starting the process itself, the raw material is prepared at a temperature between 200º and 300º and at a pressure between 18 and 60 bar, preferably between 30 and 50 bar and preferably between 37 and 43 bar, being that the Raw material is a gas that mainly comprises:
    to. Hydrogen
    b. Carbon monoxide 25
    C. Carbon dioxide.

    In a first phase, in the first reactor, which in turn comprises the main reactor and optionally an auxiliary one, at least one of the first two groups of reactions set forth below is produced. 30

    Synthesis gas composed mainly of hydrogen, carbon monoxide, enters the first reactor, at a temperature between 200º and 300º Celsius and at a pressure between 20 and 60 bar, preferably 40 bar, and contacts with at least one catalyst.
     5
    Depending on the composition of this catalyst, reactions of the first group to produce methanol or those of the second group to produce dimethyl ether can be caused.

    If the catalyst is to produce methanol, the preferred compound is based on CuO / ZnO / Al2O3 which we will call C1 here, and this accelerates the main reaction of the first group: CO + 2H2 → CH3OH.

    If the catalyst is to produce dimethyl ether, the preferred compound is based on CuO / ZnO / Al2O3 and alumina, which here we will call C2 and accelerates the main reaction of the second group: 3CO + 3H2 → CH3OCH3 + CO2. fifteen

    When the first two groups of reactions occur simultaneously during the procedure, the catalysts corresponding to each of these two groups of reactions can be arranged in sequence, in parallel or both mixed in any proportion, and the following reaction occurs: 2CH3OH → CH3OCH3 + H2O and the residual water of this reaction, is used as raw material to form more hydrogen, through the side reaction: CO + H2O → CO2 + H2, thus avoiding having excess water between the reactants, which means reducing the main limitation in the conversion of the synthesis gas to dimethyl ether and methanol.
     25
    As discussed, the first reactor may comprise a main and an auxiliary reactor.

    In an embodiment where the first reactor comprises a main and an auxiliary reactor, the two reaction groups can be produced separately in such a way that each reactor, main or auxiliary, contains only one type of these two
    catalysts, and the main and auxiliary reactors may be arranged in sequence, alternately, in parallel or in combined forms of these arrangements.

    In the event that this first reactor comprises a main reactor and an auxiliary reactor to carry out the two reaction groups and both the main and auxiliary reactor 5 contain catalysts C1 and C2 in mixed form, these reactors, main and auxiliary, also they may be arranged in sequence, alternately, in parallel or in combination with these arrangements.

    In a second phase, the products resulting from the first phase, usually dimethyl ether and methanol, enter the second reactor of the device, where oxygen is added, and contact C3 catalysts that favor the production of formaldehyde by partial oxidation of a part of the dimethyl ether or methanol, by the following reactions: CH3OH + 1 / 2O2 → CH2O + H2O and CH3OCH3 + O2 → 2CH2O + H2O; and also favor the reaction 2CH3OH → 15 CH3OCH3 + H2O obtaining dimethyl ether as a minor product.

    If both products enter this second reactor then side reactions such as the following occur: CH3OCH3 + H2O → 2CH2O + 2H2 thus producing more formaldehyde and leaving as excess by-products the excess water that did not react and hydrogen.

    The preferred catalysts for these reactions, which we will call C3 here, are based on at least two metals or compounds of the group: alumina, molybdenum oxide, vanadium and iron. 25

    The wastewater, by-product of the third group of reactions that occurs within the second reactor, is preferably condensed at the end of this reactor or in a separate condenser and extracted outside the process, before the products that run through it, are discharged into the third reactor preferably at the pressure and temperature not higher than those leaving the second reactor, and this to start the fourth and last group of reactions, in order to obtain the multifunctional product.
    During the fourth group of reactions, the aldehyde molecules are incorporated into the dimethyl ether molecules by aldolic reactions, to reinforce the formulation of the multifunctional product in aldehyde, a process by which, in this product, its volatility can be adjusted, point of inflammation, vapor pressure and energy content, according to the specific needs of the market where it will be placed. 5

    In the third reactor it is where the main intermediate products, dimethyl ether and formaldehyde, together with the unconverted synthesis gas and some minor by-products, undergo reactive distillation and come into contact with at least one type of strongly acid catalyst where the Preferred is an ion exchange resin, which we will call C4 here.

    In the third reactor, the optional additive can be incorporated, which preferably comprises an amine to alkalize and modify the pH of the multifunctional product, in order to prevent the reactions of this group from reversing and permanently sensitizing the multifunctional product to the detonation when used in internal combustion engines.

    As for the amine referred to in the preceding paragraph, the preferred is ethylenediamine and the second preferred is 2-dimethylaminoethylazide, and preferably, this optional additive 20 can be incorporated into the process diluted in at least one diluent group of the following group: i) a alcohol of 1 to 4 carbon atoms doped with nitromethane and ii) dibutyl ether doped with propylene glycol monomethyl ether.

    Then the multifunctional product together with part of the unconverted synthesis gas and the minor by-products, leave the device so that, if desired, by means of fractional distillation, they can be partially or totally separated.

    In relation to the optional additive, this preferably comprises at least one amine where the preferred is ethylenediamine and the second preferred is 2-dimethylaminoethylazide. 30

    When used for combustion purposes, this optional additive may be diluted in an alcohol of 1 to 4 carbon atoms, preferably doped with nitromethane and / or diluted in dibutyl ether preferably doped with propylene glycol monomethyl ether, to increase the sensitivity power to the detonation, which gives the amine to the multifunctional product. 5

    One of the characteristics of this procedure is that between the first and the second phase the pressure of the products resulting from the first phase is reduced, preferably by two thirds and the excess excess pressure between the first and the second phase is destined to rise the pressure of the products that run between the third and fourth phases.

    On the other hand, the outgoing products of the first and second phase give heat to the third reactor, to the incoming raw materials to the device or to the optional additive that enters the device through the additive injector. fifteen

    For this, the device has means to recover heat and pressure.

    The recovery of pressure and heat makes the procedure largely self-sufficient energy. twenty

    2.- Regarding the device:

    As for the device, and notwithstanding the foregoing, it comprises at least three reactors connected in sequence where at least three of the four groups of 25 main reactions occur, to be used continuously and making the intermediate products pass from one to another without requiring external storage to the process.

    Of these three reactors, at least one first reactor, which may comprise a main and an auxiliary reactor, is for the first two reaction groups, at least a second second reactor for the third reaction group, at least one third reactor for the Fourth group of reactions.
    The first reactor contains at least one catalyst between C1 and C2, the second reactor contains the catalyst C3 and the third reactor contains the catalyst C4.

    All these reactors comprise a tube bundle, within which the catalysts are located and that is where the reactant products run. 5

    The tube bundle of each reactor is covered by a jacket that rests on at least two supports, preferably four, which can be discs / flanges.

    In a preferred embodiment, with four discs / flanges, two at one end and two at another of the 10 bundle of tubes, the outermost discs / flanges function as reactor covers. While between the innermost discs / flanges and those that work as covers, they form chambers that collect products that come out or enter the tube bundle.

    The outermost flanged discs, those that function as reactor covers, are used to introduce or extract certain materials from the process such as raw materials, oxygen, water, additives or final product.

    The introduction or extraction of these materials is carried out by means of holes that connect the interior with the exterior of the aforementioned chambers. twenty

    Each reactor comprises at least two chambers, preferably each one at its opposite ends where such chambers comprise orifices to mainly receive or discharge the reactants and orifices communicated with the interior to receive or discharge the products that flow inside the tubes in the reactor. . 25

    The second and third reactor are communicated with oxygen and additive injectors respectively.

    The tubes of the tube bundle of each reactor are attached to the discs / flanges adjacent to the chambers, preferably with welding, pressure or thread, and said discs / flanges have a past hole for each tube of the tube bundle.
    The device comprises a direct means and an indirect means for transferring heat from the main groups of exothermic reactions to the group of endothermic reactions, which can occur together.

    The different means that the device has to transmit this heat from the 5 exothermic reactions to the endothermic can be direct, indirect or a combination of both,

    The direct medium is via recirculation of the product itself resulting from the exothermic reactions of the first, second and third group of reactions, through the conduit in which the endothermic reactions occur, directly causing heat exchange and transmitting it to the endothermic reactions through said resulting product.

    The indirect medium is via recirculation of the product itself resulting from the exothermic reactions of the first, second and third group of reactions, through the conduit in which the endothermic reactions occur, indirectly causing heat exchange and transmitting it to the endothermic reactions by means of a fluid that does not chemically intervene in the process.
     twenty
    We will call here a combined medium, the medium that uses the direct and indirect means to transmit heat. The excess heat can optionally be transferred with the different means mentioned above: direct, indirect or combined.

    3.- Differentiating factor of the resulting product when used as fuel 25

    The resulting multifunctional product applying the optional additive, when used in internal combustion engines, has the characteristic of having a PH greater than 7, which makes it an alkaline product and high detonation sensitivity, factors that are positive and differentiators to be used as a component in 30 engine fuels that work by internal combustion.

    BRIEF EXPLANATION OF FIGURE 1

    FIGURE 1 shows, a scheme of the process object of the present and of the preferred catalysts usable, without having to be taken as a single but as a mere descriptive example where the device with a first reactor (1) comprising a main reactor is appreciated (2) and another auxiliary (3), a second reactor (4) and a third reactor (5).

    In this case, the first group of reactions occurs in the main reactor (2) of the first reactor (1) and the second group of reactions in the auxiliary reactor (3) of the first reactor 10 (1), the third group of reactions has place in the second reactor (4) and the fourth group of reactions in the third reactor (5).

    Prior to the matter entering the first reactor, it has passed through a compressor (6) and a heat exchanger (7) 15

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

    After the third group of reactions and before the fourth group of reactions, the wastewater (10) is extracted from the process by the action of a condenser (13)

    After the fourth group of reactions, the multifunctional product (11) and unconverted synthesis gas and minor by-products (12) are extracted from the process
     25
    Within the circuit there are at least two interconnections with stop / relief valves whose function is to discharge excess product without affecting the environment and without substantially affecting the production or final quality of the multifunctional product.
     30

    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 A WAY TO CARRY OUT THE INVENTION 5

    We proceed here to present a way of carrying out the invention that is not unique without merely exemplifying.

    The synthesis gas is compressed at 40 bar with the compressor (6) and then heat 10 to 280 degrees is provided in the heat exchanger (7) to then enter the first reactor (1), its main reactor (2) and to the auxiliary (3) that can be in sequence or in parallel.

    According to one possible embodiment, the synthesis gas enters parallel to the main (2) and auxiliary (15) reactor of the first reactor (1), these reactors house the catalyst C1 and C2 respectively, and both work at 280 degrees Celsius and 40 bar pressure.

    In the main reactor (2) of the first reactor (1) the first group of reactions 20 occurs to form mainly methanol which then enters the auxiliary reactor (3) together with the unreacted gas and other by-products derived from the first group of reactions. All products that run in the main reactor (2) enter the auxiliary reactor (3) that contains the catalyst C2, with the gas that did not react in the main reactor (2), to produce mainly dimethyl ether by means of the second group of reactions.

    Dimethyl ether and methanol, each together with the 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, plus oxygen and the optional additive that they are injected from outside the device, they all enter the second reactor (4) under the same temperature at which the products of the auxiliary reactor (3) leave
    and at a reduced pressure so that, through the third group of reactions, methanol can be oxidized primarily to formaldehyde, in the presence of the C3 catalyst. The oxygen is injected by an oxygen injector (8) comprising a hole that communicates the outside with the inside of the second reactor (4) as indicated in Figure 1. 5

    All products that run in the second reactor (4) are exposed to catalyst C3 to produce mainly formaldehyde and pass through a condenser, preferably under pressure, to extract residual water (10), preferably by means of a condenser (13) which Be out of the device. 10

    Products that leave 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), come into contact with the catalyst C4 in a temperature scenario of approximately 170 degrees Celsius and a pressure close to 20 bar, to generate the reactions 15 of the fourth group, in which the multifunctional product (11) is produced in the majority. In addition to this third reactor, a multifunctional product also comes out in minority or trace forms: water, methanol, carbonic acid, formic acid, acetic acid, carbon dioxide, methyl formate and formaldehyde; other products also come out in the form of gas, coming from the raw material that could not be converted, such as 20 carbon monoxide, methane, hydrogen, oxygen and traces of hydrocarbons which we will call minority by-products (12).

    There are two interconnections with stop / relief valves shown in Figure 1. Both serve to discharge excess product without substantially affecting the production or final quality of the MULTIFUNCTIONAL product.

    The interconnections are a first interconnection (15) of the main reactor (2) to the second reactor (4) and the other a second interconnection (14) of the auxiliary reactor (3) to the third reactor (5) 30

    While the different reaction groups occur, the outgoing products of the first reactor (1), comprising its main (2) and auxiliary reactors (3) and the second reactor (4) give heat to the third reactor (5), indirectly Through a non-volatile liquid that circulates between the jacket and the bundle of tubes that contain the reactors, using a thermal power plant and the excess heat can optionally be applied to the 5 incoming raw materials to the device and to the optional additive that can enter the device by the additive injector (9).

    Finally, if desired, the multifunctional product (11) leaving the third reactor (5) can be separated into its different components, by means of a distillation, where fractional type distillation is preferred.

    Liquid or gaseous products leaving the R4 reactor together with the poly-oxymethylene dimethyl ethers, can optionally be recirculated and serve as raw material to a gasification process for the production of synthesis gas. fifteen

    In another exemplary embodiment of the invention, the synthesis gas is compressed at 40 bar with the compressor (6) and then heat is supplied up to 280 degrees in the heat exchanger (7) to then enter the main reactor (2) and to the auxiliary (3) those that can be in sequence or in parallel, where in the main reactor this synthesis gas comes into contact with the catalyst C1 and in the auxiliary reactor (3) comes into contact with the catalyst C2. As a result, a group of reactions is produced in each reactor where the products resulting from the main and auxiliary reactor are mainly methanol and dimethyl ether respectively, obtaining a weight conversion greater than 40% of the synthesis gas used. 25

    The products of the main (2) and 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 is produced ether, all enter the second reactor (4) at a temperature and pressure not higher than that of the main and auxiliary reactor 30 and have contact with the catalyst C3 which favors the partial oxidation of methanol and dimethyl ether to formaldehyde, thus generating by-products
    liquids, mainly: water, carbon dioxide, methyl formate, carbonic acid and methanol. Also present during this oxidation process are 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. 5

    The products of the main (2) and auxiliary reactors (3) both leave at 280 degrees and 34 bar pressure which is preferably reduced to 12 bar, and enter the second reactor (4) where the C3 catalyst is housed and added with an oxygen injector (8) either pure oxygen or a compound containing it. 10

    In this second reactor (4) methanol is almost completely oxidized to formaldehyde resulting in water as a byproduct, also part of the dimethyl ether is oxidized in a smaller proportion to formaldehyde, resulting in water as a byproduct.
     fifteen
    At the end of the second reactor (4), all the products that run pass through a condenser (13) that is preferably located at the final end of the second reactor (4) although it can be external, so that mainly the wastewater (10) Produced as a byproduct in the second reactor (4) is condensed and extracted outside the production system. twenty

    The outgoing products of the condenser apart from those that were extracted from the production system, together with the optional additive, enter the third reactor (5) that houses the C4 catalyst that is at a pressure close to 20 bar and a temperature of 175º degrees Celsius, and produces the fourth group of reactions that mainly produce 25 multifunctional product. The final products leave between 150º and 200º, preferably between 100º and 175º and at a pressure between 15 and 20 bar, preferably at 17 bar and the conversion of the synthesis gas to the multifunctional product is approximately 40% of its weight and a maximum 10% methanol and 8% maximum of other minor by-products (12) liquids. 30

    The remaining percentage is of products that were not converted to MULTIFUNCTIONAL product and come out in the form of gas, along with those that failed to react and that are separated from the multifunctional product by cooling.

    Then, it is convenient to separate the poly-oxymethylene dimethyl ether from the unwanted liquid by-products 5 which the multifunctional product entails, where the separated liquid by-products together with the other gaseous products leaving the third reactor can optionally be used, in the synthesis gas production process, in preheating raw materials and optional additives.
     10
    The volatility, level of energy content, cetane number and vapor pressure of the multifunctional product obtained is modified by varying the amount of aldehyde produced in the third group of reactions.

    The nebulizing effect on the internal combustion chambers and the octane of the multifunctional product 15 when used together with conventional fuels is altered by modifying the amount of diluent "i" or "ii" of the optional additive in the third phase.

    权利要求:
    Claims (46)
    [1]

    1.- PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT, characterized in that it comprises:
     5
    A previous phase of preparation of the raw material at a temperature between 200º and 300º and at a pressure between 18 and 60 bar, preferably between 30 and 50 bar and preferably between 37 and 43 bar, the raw material being a gas comprising hydrogen , carbon monoxide and carbon dioxide.
     10
    1.- A first phase, which includes the reactions caused by at least one of these two catalysts:
    A catalyst, C1, preferably based on CuO / ZnO / Al2O3 taking place the first group of reactions. fifteen
    A catalyst, C2, preferably based on alumina and CuO / ZnO / Al2O3 taking place the second group of reactions.

    [2]
    2.- A second phase in which at least one of the products resulting from the first phase passes to 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 oxygen, come into contact with at least one catalyst, C3, preferably based on at least one compound of alumina, molybdenum oxide, vanadium and iron, the third occurring reaction group
    iii) After the third group of reactions, hydrogen is obtained as a byproduct and the excess water that did not react.

    [3]
    3.- A third phase in which the products resulting from the previous phase, mainly 30 dimethyl ether and formaldehyde, pass to the third reactor and undergo a reactive distillation, since this phase comprises the following sub-phases:
    i) Extraction, preferably by condensation, of wastewater.
    ii) The products resulting from the previous phases, the unconverted synthesis gas and by-products not previously extracted outside the production system, come into contact with at least one strongly acidic C4 catalyst, preferably ion exchange resin 5 taking place the fourth group of reactions and to obtain the multifunctional product.

    [4]
    4.- In a fourth phase it comprises the output of the device of the multifunctional product together with the unconverted synthesis gas and minor by-products not previously extracted 10.

    [2]
    2. PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim one characterized in that the first group of reactions comprises the reaction the reaction CO + 2H2 → CH3OH obtaining methanol. fifteen

    [3]
    3. PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim one characterized in that the second group of reactions comprises the reaction 3CO + 3H2 → CH3OCH3 + CO2 obtaining dimethyl ether.
     twenty
    [4]
    4. PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim one characterized in that the raw material comes into contact with the catalyst C1 and C2 at the same time generating a reaction comprising 2CH3OH → CH3OCH3 + H2O obtaining dimethyl ether and residual water causing the lateral reaction CO + H2O → CO2 + H2 obtaining hydrogen. 25

    [5]
    5. PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to the first claim characterized in that only one of the products resulting from the first phase, mainly dimethyl ether or methanol, enters the second reactor, with partial oxidation of a part of the dimethyl ether taking place. or of methanol, 30 by the reactions CH3OH + 1 / 2O2 → CH2O + H2O and CH3OCH3 + O2 → 2CH2O + H2O.

    [6]
    6. PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to the first claim characterized in that the products obtained in the first group of reactions, mainly dimethyl ether and methanol, enter the second reactor, with the side reaction CH3OCH3 + H2O → 2CH2O + 2H2 leaving as its main by-products the excess water that did not react and hydrogen.

    [7]
    7. PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1 characterized in that in the third phase the products obtained in the previous phases plus the unconverted synthesis gas and by-products 10 not previously extracted outside the production system, come into contact with at least one strongly acid catalyst, preferably ion exchange resin resulting in polyoxymethylene dimethyl ethers, and if the additive were incorporated, said product would possess a neutral PH or greater than 7.
     fifteen
    [8]
    8. PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to the preceding claim, characterized in that the third phase further comprises the injection of an additive comprising at least one amine where the preferred is ethylenediamine and the second preferred is 2-dimethylaminoethylazide.
     twenty
    [9]
    9.- PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to the preceding claim characterized in that the optional additive is incorporated into the process diluted in at least one diluent group of the following group: i) an alcohol of 1 to 4 carbon atoms preferably doped with nitromethane and ii) dibutyl ether doped preferably with propylene glycol monomethyl ether, obtaining polyoxymethylene dimethyl ethers with a neutral PH or greater than 7.

    [10]
    10. PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1 characterized in that between the first and the second phase the pressure of the products resulting from the first phase is reduced, preferably by two thirds.

    [11]
    11.- PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to the preceding claim characterized in that the excess of excess pressure between the first and the second phase is intended to increase the pressure of the products that run between the third and fourth phase.
     5
    [12]
    12. PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1 characterized in that the outgoing products of the first and second phase give heat to the third reactor.

    [13]
    13.- PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT 10 according to claim 1 characterized in that the outgoing products of the first and second phase give heat to the raw materials entering the device.

    [14]
    14.- PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1 characterized in that the outgoing products of the first and second phase yield optional additive heat that enters the device through the additive injector (9).

    [15]
    15.- PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1 characterized in that the catalyst C4 is located inside the third reactor at a pressure close to or below 20 bar and a temperature near or below 175 degrees Celsius.

    [16]
    16.- PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1 characterized in that in the fourth phase the final products 25 leave at a temperature between 150º and 200º, preferably between 100º and 175º and at a pressure between 15 and 20 bar of pressure, preferably at 17 bar pressure and the conversion of the synthesis gas to the multifunctional product, by weight, is approximately 40% and a maximum of 10% is methanol and a maximum of 8% is from other minor by-products (12) liquids. 30

    [17]
    17.- PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1, characterized in that the fourth phase also comprises a process of separation of the multifunctional product with respect to the synthesis gas and other unconverted products and the minority liquid by-products not previously extracted, being able to be totally or partially separated, preferably by cooling.

    [18]
    18.- PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT according to claim 1 characterized in that the liquid or gaseous products leaving the third reactor together with the multifunctional product are recirculated serving 10 as raw material to a gasification process for the production of gas from synthesis, or, once separated, can enter as a product to be recycled in the device of the present invention

    [19]
    19.- PROCEDURE FOR THE PRODUCTION OF A MULTIFUNCTIONAL PRODUCT 15 according to claim 1 characterized in that the liquid or gaseous products leaving the third reactor together with the multifunctional product are recycled serving as a product to be recycled in the device of the present invention

    [20]
    20.- PROCEDURE FOR OBTAINING A MULTIFUNCTIONAL PRODUCT 20 according to claim 7, characterized in that the volatility, energy content level, cetane number and vapor pressure of the multifunctional product obtained is modified by varying the amount of aldehyde produced in the third group of reactions.
     25
    [21]
    21.- PROCEDURE FOR OBTAINING A MULTIFUNCTIONAL PRODUCT according to claim 8, characterized in that the level of detonation sensitivity and its stability or degree of resistance to the reversal of its reactions in the presence of acidic substances of the multifunctional product, is altered modifying the amount of the optional additive and type of diluent incorporated in the fourth reaction group. 30

    [22]
    22.- PROCEDURE FOR OBTAINING A MULTIFUNCTIONAL PRODUCT according to claim 9 characterized in that the nebulizing effect in the internal combustion chambers and the octane when used together with conventional fuels is altered by modifying the amount of diluent "i" of the optional additive.
     5
    [23]
    23.- PROCEDURE FOR OBTAINING A MULTIFUNCTIONAL PRODUCT according to claim 9, characterized in that the nebulizing effect in the internal combustion chambers and the emission gases from their combustion when used together with conventional fuels is altered by means of the diluent control “ ii ”of the optional additive. 10

    [24]
    24.- DEVICE FOR APPLYING THE EXPOSED PROCEDURE characterized in that it comprises:
    1. At least three reactors, first, second and third, arranged in sequence where each reactor comprises:
    to. A plurality of tubes containing the appropriate catalyst and where the reactant product flows. This plurality of tubes is contained within a cover element, all supported by a series of support elements.
    b. At least two cameras connected to the outside. twenty
    [2]
    2. At least one compressor and at least two condensing means.
    [3]
    3. Means to transfer heat from one reactor to another according to your needs.
    [4]
    4. Means to collect or apply heat to the raw material entering the process.
    [5]
    5. Pressure recovery means.
    [6]
    6. Means of measurement, automation and control of flows, temperature and pressure, 25 according to the needs of each reactor.

    [25]
    25.- DEVICE FOR APPLYING THE EXPOSED PROCEDURE according to the preceding claim characterized in that the first reactor comprises a main reactor and an auxiliary reactor arranged sequentially, alternately or in parallel. 30

    [26]
    26.- DEVICE FOR APPLYING THE EXPOSED PROCEDURE according to the preceding claim characterized in that the first reactor contains at least one catalyst between C1 and C2, the second reactor contains the catalyst C3 and the third reactor contains the catalyst C4.
     5
    [27]
    27.- DEVICE FOR APPLYING THE EXPOSED PROCEDURE according to claim 24 characterized in that the first reactor comprises catalysts C1 and C2 separately arranged one in the main reactor and another in the auxiliary.

    [28]
    28.- DEVICE FOR APPLYING THE EXPOSED PROCEDURE according to claim 10 24 characterized in that the first reactor comprises catalysts C1 and C2 mixed together.

    [29]
    29.- DEVICE FOR APPLYING THE EXPOSED PROCEDURE according to claim 24 characterized in that the covering element of the plurality of 15 tubes is a jacket and the elements that support it are preferably flanged discs with holes passed from one side to the other, where the tubes receive or discharge the reactants.

    [ 30]
     30.- DEVICE FOR APPLYING THE EXPOSED PROCEDURE according to claim 24 characterized in that each reactor comprises at least two chambers, preferably each one at its opposite ends where said chambers comprise orifices to receive or discharge mainly the reactants and orifices communicated with the interior to receive or unload the products that run inside the tubes in the reactor. 25

    [31]
    31.- DEVICE FOR APPLYING THE EXPOSED PROCEDURE according to the preceding claim characterized in that the second and third reactor are communicated with oxygen and additive injectors respectively.
     30
    [32]
    32.- MULTIFUNCTIONAL PRODUCT obtained by the method claimed in claims 1 to 23 characterized in that it comprises poly-oxymethylene dimethyl ethers with molecular formula CH3O (CH2O) nCH3 wherein n has a value of 1 to 7.

    [33]
    33.- MULTIFUNCTIONAL PRODUCT obtained by the method claimed in claims 1 to 23 characterized in that it comprises unpolished poly-oxymethylene dimethyl ethers, that is with all or part of the liquid by-products derived from the process, and if the optional one has been used additive, with its diluents if any.

    [34]
    34.- MULTIFUNCTIONAL PRODUCT obtained by the method claimed in claims 1 to 23 characterized in that it comprises purified poly-oxymethylene dimethyl ethers, having previously separated all or a majority of the liquid by-products derived from the process, and if the optional one has been used additive, separating all or a majority of this optional additive and its diluents if any. fifteen

    [35]
    35.- MULTIFUNCTIONAL PRODUCT obtained by the method claimed in claims 1 to 23 characterized in that the volatility, energy content level, cetane number and vapor pressure of the multifunctional product obtained is adjustable by controlling the amount of aldehyde produced in the third third group of reactions.

    [36]
    36.- MULTIFUNCTIONAL PRODUCT obtained by the method claimed in claims 1 to 23 characterized in that the level of detonation sensitivity and its stability or degree of resistance to the reversal of its reactions in the presence of acidic substances of the multifunctional product is Adjustable by controlling the optional additive and type of diluent incorporated in the fourth reaction group.

    [37]
    37.- MULTIFUNCTIONAL PRODUCT obtained by the method claimed in claims 1 to 23 characterized in that the nebulizing effect in the internal combustion chambers and the octane when used together with conventional fuels is adjustable by controlling the diluent "i" of the optional additive.
    [38]
    38.- MULTIFUNCTIONAL PRODUCT obtained by the method claimed in claims 1 to 23 characterized in that the nebulizing effect in the internal combustion chambers and the emission gases from their combustion when used together with conventional fuels is adjustable by controlling the diluent "ii" of the optional additive. 5
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    同族专利:
    公开号 | 公开日
    ES2637949B1|2018-07-27|
    ES2831862T3|2021-06-09|
    JP6877226B2|2021-05-26|
    BR102017007842A2|2017-10-31|
    US20170297989A1|2017-10-19|
    JP2018021006A|2018-02-08|
    DK3231788T3|2020-11-16|
    EP3231788B1|2020-08-12|
    US10106478B2|2018-10-23|
    EP3231788A1|2017-10-18|
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    EP0038138A1|1980-04-02|1981-10-21|Mobil Oil Corporation|Gasification of solid carbonaceous material for use in a turbine-generator power installation|
    US6166266A|1998-11-12|2000-12-26|Bp Amoco Corporation|Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of dimethyl ether with formaldehyde formed by oxidation of methanol|
    US20050154226A1|2004-01-08|2005-07-14|The Regents Of The University Of California|Oxidation of methanol and/or dimethyl ether using supported molybdenum-containing heteropolyacid catalysts|
    US20080216390A1|2005-06-29|2008-09-11|Basf Aktiengesellschaft|Biodiesel Fuel Mixture Containing Polyoxymethylene Dialkyl Ether|
    US20030171534A1|1998-11-12|2003-09-11|Hagen Gary P.|Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of formaldehyde formed by oxy-dehydrogenation of dimethyl ether|
    WO2000029364A1|1998-11-12|2000-05-25|Bp Amoco Corporation|Preparation of polyoxymethylene dimethyl ethers by reaction of dimethylether with formaldehyde over heterogeneous catalysts|CN109557964B|2018-12-27|2020-09-29|南通江天化学股份有限公司|Distributed control system of high-concentration formaldehyde production line|
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