WO2016172771A1

WO2016172771A1 - Method for producing hydrocarbon fuels from ethanol on apatite catalysts, method for producing said catalysts, thus obtained catalysts, and uses thereof

Info

Publication number: WO2016172771A1
Application number: PCT/BR2015/000200
Authority: WO
Inventors: Juan Jose LOVON-QUINTANA; Julie Caterine RODRIGUEZ-GUERRERO; Gustavo Paim VALENÇA
Original assignee: Universidade Estadual De Campinas - Unicamp
Priority date: 2015-04-30
Filing date: 2015-12-18
Publication date: 2016-11-03
Also published as: BR102015009832A2; BR102015009832B1

Abstract

This invention relates to a method for producing from ethanol a mixture of both oxygenated and non-oxygenated hydrocarbon fuels with a number of carbon atoms from C1 to C18, on apatite catalysts by heterogeneous catalysis in a single step in the gaseous phase and under atmospheric pressure, and to the synthesis of these catalysts. The aim of the invention is to provide alternative fuels to the existing fossil fuels (e.g. petrol, diesel and aviation fuels).

Description

PROCESS FOR PRODUCTION OF FUEL HYDROCARBONS FROM ETHANOL ON APATITA CATALYSTALS, PROCEDURE FOR OBTAINING THESE CATALYSTALS, SO OBTAINED CATALYSTALS, AND THEIR USES

FIELD OF INVENTION

[1] The present invention belongs to the field of biofuel production; specifically, the field of production of hydrocarbon fuels from ethanol.

BACKGROUND OF THE INVENTION

[2] In the last two decades to obtain fuel ^substitutes' fossil fuels and hydrocarbon synthesis; of interest to the petrochemical industry from (renewable) biomass ^" have drawn the attention of research centers around the world.

[3] Accordingly, there are several published works and patent documents related to the synthesis of materials (bioceramics, zeolites, mixed oxides, etc.) and the production of combustible hydrocarbons from ethanol.

[4] US 8,187,347 B2 describes a technology in which a Hydroxyapatite (HAP) -based catalyst was synthesized under a single experimental condition, synthesized at pH = 10 and calcined at 600 ° C for 2 hours. Subsequently, the catalyst powder was pelletized to particle sizes of ^'0.7 to ^1.4' mm, production of organic compounds from ethanol was carried out in two stages, comprising the reaction of ethanol on PAH catalysts and subsequent hydrogenation of the product in liquid phase. In this process combustible hydrocarbons having carbon number between C4 and C12 were obtained, with the purpose of of being applied as a substitute for automotive fossil fuels, named ^' biogasoline ^' .

(5] In the proposed invention, various apatite-type catalysts have been synthesized: PAH, Carbonate-Hydroxyapatite (CHAP) and Fluorapatite (FAP) which will henceforth be referred to as "apatite-type mass catalysts" and PAH-supported Lanthanum (La) catalysts ( PAH-supported Sodium (Na) (Na / PAH) which will hereinafter be referred to as "PAH-supported metal catalysts." Apatite-type mass catalysts were synthesized by chemical precipitation under different specific pH experimental conditions, between 8.5. and ^'11 and temperatures of calcination, ^"between -500 and 800 ° C. in the preparation of metal catalysts supported on PAH ions and Na ⁺ , and La ³⁺ were ^impregnated' in stoichiometric HAP (Ca / P ~ 1.67), varying the metal content from 3 to 12% w / w In addition, all catalysts were tested in the ethanol reaction over a wide temperature range, between 300 and 60 ° C, and W ratios / Ftanoi from 0.02 to 0.16 kg h mol ^'1 The catalysts were not pelletized since the catalytic tests were performed in a micro reactor and the hydrogenation process was not used. Under these experimental conditions a mixture of combustible, non-oxygenated and oxygenated hydrocarbons having carbon number between Cl to C18, preferably condensable combustible hydrocarbons having carbon number between C5 and C18 was obtained, ■ which have the potential, to be used as substitutes for existing fossil fuels (eg, gasoline, diesel, jet fuel), in addition to apresentarem- as an alternative source ^■ for obtaining base products from the petrochemical industry, preferably aromatics, olefins, higher alcohols, aldehydes, ethers, ketones, phenols and to a lesser extent dienes, paraffins and esters.

[6] In the technology described in PI0515805 hydroxyapatite was synthesized at pH 9 - 11 under nitrogen atmosphere, and calcined at a single temperature (600 ° C). In this range of ^'pH can be obtained various types of non - stoichiometric HAP with different ratios of Ca / P. Consequently, these catalysts will not always be able to play cs ^■ same reaction products.

[7] The invention dife.re It is proposed in the aforementioned document mainly using various catalysts apatite type mass flow ^'PAH, ^■ CHAP and FAP ,. . and. PAH supported metal catalysts: La ^' / HAP and Na / HAP for obtaining a mixture of oxygenated and non-oxygenated combustible hydrocarbons having a carbon number between Cl and Cl-8, preferably condensable combustible hydrocarbons having a number of atoms of carbon between C5 and Cl8 from ethanol-. Apatite-type mass catalysts were synthesized by chemical precipitation under different experimental conditions of pH (8.5 - 11) and calcination temperatures (500 - 800 ° C). In preparing the supported metal catalysts was PAH, the ions. La ³⁺ and Na ⁺ (3-12% w / w) were impregnated in stoichiometric PAH (Ca / P = 1.67). In addition, all catalysts were tested in the ethanol reaction at a wide range of temperatures, between 300 and 600 ° C, and W / FEtanoi ratios of 0.02 to 0.16 kg h mol ^"1. Therefore, for each specific reaction products were obtained and the reproducibility results ^' through replicate assays.

[8] CN1G1822992 describes a method for the synthesis of a PAH supported potassium oxide-metal fluoride (KF-MOx) catalyst (where M = · La, Al, Ca, Si or Mg) to obtain carbonate glycerin [C5H8O2] from glycerin [C3H8O3] and carbonate ^"dimethyl [CH3-CO-CH 3]. the PAH was prepared by chemical precipitation method and subsequently impregnated metals by humidity techniques incipient. For the synthesis of PAH calcium nitrate [Ca (NO3) 2.40¾] and ammonium acid phosphate [NH4H2PO4] were used.The pH was adjusted to a fixed 9-10 by the addition of aqueous ammonia solution. ] and the temperature was maintained at 70 ° C by heat bath. the products were washed, dried and calcined in ^■ temperature of 900 ° C. at this calcination temperature, sintering of the catalyst problems are significant.

[9] In the proposed invention a number of apatitic mass catalysts: -HAP, CHAP ■ and FAP were synthesized, and HAP-supported metal catalysts: La / HAP and Na / HAP were used in the process of obtaining atom-numbered combustible hydrocarbons. carbon dioxide from Cl to C18, preferably from condensable combustible hydrocarbons having carbon number from C5 to Cl8 from ethanol. In addition, the catalysts were synthesized at different specific pH values between 8, 5 and 11, and calcined at different temperatures between 500 and 800 ° C. _<

[10] The document RU ^'454 388 Cl 2. describes a technology in which H-ZS -5 (8%) / Ce203 (2%) type catalysts were prepared. ^' Catalysts have been used to reduce aromatic hidrocarbonetos- from a- mixture of ethanol ^'isobutanol (3: 1) at a temperature of 4Q0 ° C and pressures ranging from 0.1 to 5 MPa. As ^■ reaction products ^{■ they} obtained a wide range of hydrocarbons with carbon number between Cl and CIO. It is noteworthy that the catalysts prepared based on ZS-5 have acid characteristics that limit the production of high molecular weight hydrocarbons. Hydrocarbon production involves the use of a mixture of ethanol-isobutanol (3: 1).

[11] use 0 ^"·" apatite type catalysts, for presenting acidobásicas properties, favoring the production of high molecular weight hydrocarbons. In the present invention, for the production of hydrocarbon fuels ethanol was used as only- matter prima.-

[12] US 8,309,781 B2 describes a technology in which the catalysts were prepared based on ZSM-5 zeolites in the form of spheres with diameters ranging from 1.8 to 2.2 mm calcined at 600 ° C. The catalysts had a macroporous (0.12 - 0.18 ml / g) and mesoporous (0.28 - 0.35 ml / g) structure. Catalysts were used for the production of light olefins. The reaction was conducted in a ^{^'bed'} fixed with; 15 ml of catalyst. Prior to the catalytic tests the solids were activated in air flow at 550 ° C for 2 hours and the ethanol reaction conducted at 515 ° C at a pressure of 0.15 MPa. The reactor was fed with a mixture of 50% ethanol and 50% water at a rate of 20 g / h. After 2 hours of reaction, the conversion of ethanol was close to 100% and a yield of hydrocarbons (C3 - C6) between 70 and 88%.

[13] This technology presents as a technical problem that prepared ZSM-5-based catalysts have acid characteristics that limit the production of high molecular weight hydrocarbons. In addition, the catalytic tests were performed in. a single experimental condition.

[14] The proposed invention has the advantage of using thio catalysts. apatite with acidobasic properties that favor the production of high molecular weight hydrocarbons ■ To verify these properties in the present invention several apatite type catalysts were synthesized: KAP, CHAP and FAP under different conditions of pK (8,5 to 11) and temperatures calcination temperature (500 to 800 ° C). ^■ all solids had mesoporous structures. Reactions were carried out over a wide temperature range (300 to -600 ° C) and W / F _E ratios of 0.02 to 0.16 kg h mol ^_i . As a result, combustible hydrocarbons having carbon number between Cl and C18 were obtained. ,.

[15] The publication WY Zhou, M. Wang, WL Cheung, BC Guo, D.M ^' . Jia Synthesis of ^" carbonated ^■ hydroxyapatite nanospheres through nanoemulsion. J. -Mater. Sci-Mater. Med., V. 19, pp. 103-110, 2008, presents the synthesis of CHA biomaterials by chemical precipitation using microemulsi as medium. -acetate a acetone solution at pH 11, controlled by the addition of a NaOH solution.The resulting product was calcined at 900 ° C for 4 hours.The aim of this study was to obtain CHAP-based biomaterials prepared for applications. biomedical (eg, bone implants).

[16] the proposed invention, CHAP catalysts were synthesized by chemical precipitation using purely aqueous solutions. . Acetone was not used as a microemulsifying medium, or its release during the drying stage is difficult. CKAP catalysts were synthesized under different pH conditions (8.5; 9; 9.5; 1-0 and 10.5). The pH was controlled by addition of NH 4 OH. Use NaOH contaminate the product ^'end with Na ⁺ .- The catalysts were calcined at _500. 600, 700 and 800 ° C for 2 hours. The purpose of the present invention was the production of high molecular weight (C1-C18) combustible hydrocarbons.

[17] The publication T. Tsuchida, T. Yoshioka, S. Sakuma, T. Takeguchi, W. Ueda. Synthesis of Biogasoline from Ethanol over Hydroxyapatite Catalyst. Ind. Eng. Chem. Res. , v. 47, p. 1443-1452, 2008 discloses the synthesis of HAP catalysts by chemical precipitation at pH maintained between 9 and 10. The product was calcined at a temperature of 600 ° C. For the catalytic tests the powdered product was pelleted. obtaining particles with sizes between 0.7 and 1.4 mm. The solids were used for ethanol reaction, obtaining combustible hydrocarbons; (biogasoline) with number of carbon atoms between Cl and C10.

[18] In the proposed invention, HAP catalysts were synthesized by chemical precipitation at different pH values (9; 9.5; - 10; - 10, 5 and 11.) and calcined at 500, 600, 700 and 800. ° C. The product was ground and sieved into particle sizes between 0.07 and 0.15 mm. Catalysts synthesized at pH = 10.5 and calcined at 70 ° C showed the highest yield for combustible hydrocarbons having carbon number between Cl and C18, preferably a ^' . condensable combustible hydrocarbons having a number of carbon atoms between C5 and C18. [19] The publication VF Tretyakov, YI Makarfi, KV Tretyakov, N ^.; A. Frantsuzova, RM Talyshinskii. The Catalytic Convention on Bioethanol to Hydrocarbon Fuel: A Review and Study. Catai. Ind., V. 2, no. 4, p. 402-420, 2010 presents the synthesis of HZSM-5 zeolites obtained from alkaline aluminosilicate gels using structure-forming additives such as hexamethylenediamine (TsKE-G), alcohol fractions (TsKE-AF) and X-oil (TsKE- XO). Subsequently, the zeolite surfaces were modified by impregnating Zn, Fe, Ga and Zr. The catalysts were used in the ethanol reaction at 400 ° C to obtain combustible hydrocarbons such as: benzene [CeHs], toluene [C6H5CH33, ethylbenzene [CsHio], meta / para / ortho-xylenes [CsHio], naphthenes [C _n H2n] and C5 -C8 hydrocarbons.

[20] The proposed invention is advantageous since the synthesis of apatite-type catalysts made by chemical precipitation is a simple route that does not require the use of structure-forming additives. In general, apatite-type catalysts are characterized by having acidobasic surface properties differing from H-ZS-5-type catalysts known for their acidic properties. The apatite-type catalysts provided by the present invention have shown high efficiency and, depending on the experimental conditions, between 50 and 400 products can be obtained between oxygenated and unoxygenated hydrocarbons having carbon number ranging from Cl to C18, preferably ₍ condensable combustible hydrocarbons). with number of carbon atoms between C5 and C18.

[21] The publication AK Talukdar, KG Bhattacharyya, S. Sivasanker. HZS-5 catalysed conversion of aqueous ethanol to hydrocarbons. Appl. Catal. , A, v. 148, p. 357-371, 1997 presents a work in which catalysts synthesized by hydrothermal methods with ratios SiO 2 / Al 2 O 3 = 40 and 206 were used. The catalysts were calcined at 500 ° C, ground and pelletized, obtaining particles with sizes between 1, 7 and 2.0 mm. In the catalytic tests combustible hydrocarbons between Cl and C6 were obtained.

[22] The proposed invention is advantageous since the synthesis of apatite-type catalysts made by chemical precipitation is a simple route. The catalysts were calcined at 500, 600, 700 and 800 ° C, presenting maximum yield to hydrocarbons ^: fuels in the calcined catalysts between 600 and 70 ° C. As already explained, the apatite-type catalysts provided by the present invention have been shown to be highly efficient and, depending on the experimental conditions, between 50 and 400 products between oxygenated and non-oxygenated hydrocarbons having carbon number ranging from Cl to C18, preferably condensable combustible hydrocarbons having a number of carbon atoms between C5 and Cl8.

[23] Finally, US2012 / 0277 67 describes a method for the production of acrylic acid from hydroxycarboxylic acid-derived biomass and / or its dehydration reaction derivative (eg, lactic acid [C3H6O3], ethyl lactate [C5H10O3]) using PAH, silica gel supported PAH and activated carbon supported PAH as a catalyst. The PAH was prepared by the autoclave hydrothermal method in the temperature range of 50 to 300 ° C by varying the pressure from 1x10 ⁵ to 1x10 'Pa in 14 hours; how raw materials were used phosphorus pentoxide [P2O5] and calcium nitrate [Ca (NO ₃ ) 2]. The pH was controlled by the addition of sodium hydroxide [NaOH]. PAHs with Ca / P molar ratios of 1.5, 1.6, 1.67 and 1.8 were prepared. Note that there is a lack of detail in the synthesis pH values of PAH in this document. On the other hand, the use of NaOH for the ^"pH control synthesis can cause contamination with Na ⁺ ions and hence change the catalytic properties of solids.

[24] The proposed invention differs principally in that the scope of the present invention is to produce a mixture of oxygenated and non-oxygenated combustible hydrocarbons having a carbon number of Cl to C18, preferably condensable combustible hydrocarbons having a carbon number. carbon atoms between C5 and C18. Several apatite catalysts (eg, HAP, CHAP, FAP, La / HAP and Na / HAP) were synthesized by chemical precipitation under different experimental conditions of pH (8.5 to 11) and calcination temperatures (500 to 800 ° Ç) . For synthesis pH control ammonium hydroxide [NH4OH] was used. In addition, ethanol reactions were carried out over a wide temperature range (300 to 600 ° C) and W / FE anoi ratios of 0.02 to 0.16 kg h mol ^"1 .

[25] As can be seen, in the present state of the art there are no processes involving the use of apatite-type mass catalysts (eg, HAP, CHAP, FAP) synthesized by chemical precipitation under different experimental pH conditions (8.5 - 11 ) and calcination temperatures (500 - 800 ° C) and HAP-supported metal catalysts (Na / HAP, La / HAP) ^' prepared from ion impregnation Na ⁺ and La ³⁺ (3 - 12%) in stoichiometric PAH (Ca / P = 1.67). In addition, all catalysts were tested in the ethanol reaction over a wide temperature range, between 300 and 600 ° C, and W / F _{Et year} ratios of 0.02 to 0.16 kg h mol ^"1 .

[26] Under these experimental conditions, in a single step heterogeneous gas phase catalysis and atmospheric pressure, as reaction products of ethanol, several mixtures of non-oxygenated and oxygenated hydrocarbons with varying number of carbon atoms were obtained. between C18 and C18, preferably condensable combustible hydrocarbons having a carbon atom number between C5 and C18, having great potential to be used as substitutes for existing fossil fuels (eg ^' , gasoline, diesel, aviation fuel), in addition to present as an alternative source for obtaining petrochemical industry base products, preferably aromatics, olefins, higher alcohols, aldehydes, ethers, ketones, phenols and to a lesser extent dienes, paraffins and esters.

[27] According to the present invention, the CHAP-based catalysts have the calorific value closest to the existing fossil fuels (eg gasoline and diesel) followed by stoichiometric HAP (Ca / P = 1.67), La / HAP and FAP. In the specific case of Na / HAP-based catalysts showed great potential for obtaining oxygenated hydrocarbons.

BRIEF DESCRIPTION OF THE INVENTION

[28] It is an object of the present invention to provide a process for obtaining apatite-type mass catalysts, wherein said catalysts comprise hydroxyapatite (PAH), carbonate hydroxyapatite (CHAP) and fluorapatite (FAP), the process for obtaining said catalyst comprises a precipitation reaction in basic medium, according to the following main steps:

a) Preparation of at least two precursor aqueous solutions under constant stirring and in a temperature range of 40 to · 60 ° C, a first solution being based on Ca ^{+ 2} ions, preferably a tetra calcium nitrate solution -hydrate [Ca (NO3) ₂ .4¾0], and a second solution is the basis of _. any ion selected from the group consisting of PCM ^{4 * 3} ions, CO ³ -2 ions and F ^" ions, preferably any solution selected from ammonium acid phosphate [(NH4) 2HPO4], ammonium bicarbonate [NH4 HCO33 and ammonium fluoride [NH4F ], respectively;

(b) controlled dropwise addition (0,5 - 1,0 ml / min) of the first aqueous precursor solution obtained in step a) to the second aqueous precursor solution obtained in step a);

(c) Keep the reaction medium obtained in step (b) under constant agitation for a temperature range of 40 to 80 ° C, preferably 50 to 60 ° C for at least 2 hours or until completion of the reaction. that the pH of the reaction medium must be kept to a specific value. In the synthesis of the PAH, CHAP and FAP catalysts, pH values between 8.5 and 11.0 are used. The variation in each specific pH value is maintained with a range of ± 0.2, preferably ± 0.1, by steady addition of a solution of ammonium hydroxide [NH ₄ 0H];

d) Cooling of the resulting medium obtained in step c) to ambient temperature and at rest for a period of 12 to 48 hours, preferably 18 to 24 hours.

e) Separation of the precipitate from the aqueous phase containing the unreacted ions, preferably by filtration and subsequent washing with DD water and ethanol, with the aid of a Buchner funnel, quantitative filter paper and a vacuum pump;

(f) Obtaining a moist paste with a moisture content between 70 and 90% w / w;

g) Drying the wet slurry obtained in step f) at a temperature of from 40 to 120 ° C, preferably from 70 to 80 ° C for a period of time from 8 to 24 hours, preferably from 12 to 16 hours. , in a static air greenhouse;

(h) grinding the dried material obtained in step (g);

(i) means for selecting the crushed material in step (h) in particulate matter of an average size of 0.07 to 0.15 mm, wherein the selection of said material comprises sieving in 100 mesh sieves;

j) Calcination of the material selected in step i) for a period of from 1 to 6 hours, preferably from 2 to 4 hours, within a temperature range of 500 to 800 ° C, wherein said calcination may be performed. performed in a static air muffle; in a thermostatized bath; in a heat exchanger; through. warm air flowing through an evaporated route; or by any means that guarantees heating under the operating conditions already mentioned.

^k) Obtaining the catalyst mass apatite type, with a specific surface area between 18 and 70 m ² ^gi, with a volume of pores between 0.1 and 0.5 m ³ gi, pore size between 17 and 43 nm and average crystallite size between 11 and 21 nm. Having a concentration of acidic sites between 1.0 and 2.9 pmolpyridine πτ ² and basic sites between 0.4 and 2.6 pmo lco2 nr ² , determined by the adsorption of pyridine [C5H5N] and carbon dioxide [CO2], respectively.

[29] Where:

- The main improved steps related to obtaining the HAP, CHAP and FAP catalysts are: the calcination temperature; pH used in the synthesis process of these solids; and the reaction conditions used for the production of combustible hydrocarbons (reaction temperature and W / F _E tanoi) ·

- HAP catalysts showed the highest yield for condensable combustible hydrocarbons (C5 - C18) under the following operating conditions: calcination temperature, 700 ° C; synthesis pH, 10.5; reaction temperature, 500 ° C; e, W / FEtanol, 0.04 kg h mol ^-1 ;

- CHAP catalysts showed the highest yield for condensable combustible hydrocarbons (C5 - C18) under the following operating conditions: calcination temperature, 600 ° C; synthesis pH, 10.0; reaction temperature, 500 ° C; e, W / F _E tanoi, 0.04 kg h mol ^-1 ;

- FAP catalysts presented the highest hydrocarbon yield, condensable fuels (C5 - C18) were obtained under the following operating conditions: calcination temperature, 700 ° C; synthesis pH, 10.0; reaction temperature, 450 ° C; and ΔEtanoi, 0.04 kg h mol ^-1 .

[30] It is a further object of the present invention the apatite-type mass catalysts obtained according to the process described above, wherein said catalysts comprise hydroxyapatite (HAP), carbonate hydroxyapatite (CHAP) and fluorapatite (FAP).

[31] For the purpose of the present invention, hydroxyapatite (PAH) means any PAH synthesized in the pH range 9 to 11, preferably at a pH of 10.5 with a range of ± 0.1 and calcined in the range. temperatures between 500 and 800 ° C, preferably at 700 ° C, maintaining a stoichiometric ratio Ca / P * 1.67, having among its main physical properties, preferably a surface area of 30 m ² g ^{~ 1} , size of crystallites of 19 nm and concentration of acidic and basic sites close to 1.6 ymolpyridine πτ ² and 1.7 pmolco2 nr ² , respectively.

[32] For the purpose of the present invention, carbonate hydroxyapatite (CHAP) is any CHAP synthesized in the pH range 8.5 to 10.5, preferably at a pH of 10 with a range of ± 0.1 and calcined in the temperature range between 500 and 800 ° C, preferably at 600 ° C, having among its main physical properties, preferably a surface area of 40 m ² g ^_1 , crystallite size of 12 nm and concentration of acidic and non-acidic sites. around 2.3 umolpyridine nr ² and 1.9 pmolco2 nr ² , respectively,

[33] For the purpose of the present invention, fluorapatite (FAP) is any FAP synthesized in the pH range 9 to 11, preferably at a pH of 10 within a range of ± 0.1 and calcined in the temperature range between 500 and 800 ° C, preferably at 700 ° C, having among their main physical properties, preferably a surface area of 40 m ² g ^{~ 1} , crystallite size of 13 nm and concentration of acidic and basic sites close to 1, 9 ymolpyridine # ² and 1.4 pmolco2 # ² , respectively. [34] It is a further object of the present invention to provide a process for obtaining PAH supported metal catalysts, wherein _. said catalysts comprise PAH-supported Lanthanum (La) (La / PAH) and PAH-supported Sodium (Na) (Na / PAH), the process for obtaining said catalyst comprises the following main steps:

1) Preparation of an aqueous precursor solution based on any ion selected from La ^{+ 3} and Na ⁺ , preferably any solution selected from lanthanum nitrate hexahydrate [La (NO3) 3.6H2O] and sodium nitrate [NaNC> 3], wherein the molar concentrations of said solutions are in the range 0.04 to 0.20 mol ^Lt_1 and 0.27 to 1.24 mol ^Lt_1 , respectively,

(m) Insertion of hydroxyapatite (PAH) as obtained in step (k) into a rotary evaporator flask or any equipment capable of uniformly mixing the carrier with the precursor solution of the metal to be impregnated;

n) Addition of the precursor solution obtained in 1) in the system obtained in m);

o) Heating the system obtained in step n) in a thermostatized bath in a temperature range of between 60 and 90 ° C, preferably at 80 ° C, keeping the suspension under constant agitation between 50 and 100 RPM, preferably between 60 and 80 RPM, until complete removal of liquid solvent; P). Obtaining solid-wet product (70 to 90% w / w humidity);

(q) Oven drying in static air at a temperature range of 60 to 90 ° C, preferably 70 to 80 ° C for a period of time . from 8 to 24 hours, preferably 12 to 16 hours;

r) Crushing the solid obtained in step q);

s) Classification of crushed material in step r) by sieving in particle sizes between 0.07 and

0.15 mm;

(t) calcination of the material selected in step (s) in a static air muffle furnace for a period of time ranging from 6 to 12 hours, preferably from 6 to 8 hours, in a temperature range from 500 to 700 ° C; preferably between 600 and 650 ° C.

[35] Where:

- The main improved steps of said process are related to the type of support used; the metallic contents of lanthanum (La) and sodium (Na); the heat treatments performed on the hydroxyapatite supported (La / HAP) and supported sodium hydroxyapatite (Na / HAP) supported lanthanum catalysts; and, the reaction conditions used for the production of combustible hydrocarbons (reaction temperature e / Fetanoi). These data are unpublished in the literature.

- For both Na / HAP and La / HAP catalysts were used as support to stoichiometric hydroxyapatite which was synthesized in the

Í

following operating conditions: synthesis pH, 10.5; calcination temperature, 700 ° C.

- La / HAP catalysts showed the highest yield for condensable combustible hydrocarbons (C5 - C18) under the following operating conditions: metal content, 3% La; calcination temperature of La / HAP catalyst, 650 ° C; reaction temperature, 500 ° C; and W / F _Et Anoi, 0.04 kg mol h ^-1;

- Na / HAP catalysts presented the highest yield for condensable combustible hydrocarbons (C5 - C18) obtained under the following operating conditions: metallic content, 3% Na; calcination temperature of Na / HAP catalyst, 650 ° C; reaction temperature, 500 ° C; e, W / F _E tanoi, 0.04 kg h mol ^"1 .

- In the preparation of the La / HAP and Na / HAP catalysts, as precursors of the La ⁺³ and Na ⁺ ions, preference was given to hexahydrate [La (N0 ₃ ) 3.6H2O] and sodium nitrate [NaNOs], respectively.

- The metallic content of La and Na present in the La / PAH and Na / PAH catalysts varies between 3 and 12% (w / w).

[36] It is a further object of the present invention the PAH-supported metal catalysts obtained according to the process described above, wherein said catalysts comprise PAH-supported Lantlanium (La) and PA-supported Sodium (Na). PAH (Na / PAH).

[37] For the purpose of the present invention, PAH-supported Lanthanum (La) means any La / PAH having metallic contents of between 3 and 12% La (w / w), preferably with a metallic content of 3% La (w / w) and calcined in the temperature range between 600 and 650 ° C, preferably at 650 ° C, having among its main physical properties, preferably a surface area of 29 m ² g- ^x , size of crystallites 19 nm and the concentration of "acidic and basic sites near pmolpiridina 1.5 m ^-2 and 1, 7 pmolco2 m ^{~ 2,} respectively. [38.] For the purpose of the present invention, PAH-supported sodium (Na) (Na / PAH) means any Na / PAH having a metal content of between 3 and 12% Na (w / w), preferably with a metallic content. of 3% Na (w / w) and calcined in the temperature range between 600 and 650 ° C, preferably at 650 ° C, having among its main physical properties, preferably a surface area of 5 m ² g ^_1 , size of 21 nm crystallites and base site concentration near 1.2 pmolco2 m ^{~ 2} . Presenting complete absence of acid sites.

[39] It is a further object of the present invention to use the apatite type catalysts and PAH supported metal catalysts obtained according to the processes described above in processes for obtaining a mixture of combustible, non-oxygenated and oxygenated hydrocarbons with number of carbon atoms between Cl and C18. These catalysts can also be used to obtain petrochemical products, mainly aromatics, olefins, higher alcohols, aldehydes, ethers, ketones, phenols and to a lesser extent dienes, paraffins and esters.

[40] Finally, it is an object of the present invention to provide a process for obtaining a mixture of non-oxygenated and oxygenated combustible hydrocarbons having a number of carbon atoms between Cl and C18, preferably a mixture of condensable combustible hydrocarbons having an atom number. carbon dioxide from C5 to Cl8 from ethanol in a continuous gas-phase reaction flow system at atmospheric pressure and in a single step comprising the use of mass-type catalysts apatite and PAH supported metal catalysts and the following main steps:

i. Addition of any of the HAP-supported apatite or metallic mass-type catalysts obtained in the processes as described in steps (a - k) or (1 - t) in an o reactor, comprising catalyst thermal pretreatment, in gas flow (eg, nitrogen, helium, argon) in the reaction temperature range 300 to 600 ° C, preferably 400 to 500 ° C for a period of 1 to 4 hours, preferably 1 to 2 hours, wherein the catalyst mass to ethanol flow ratio (W / F _E tanoi) comprises 0.02 to 0.16 kg h mol ^-1 , preferably 0.04 kg h mol ^"1 ; ii. Evaporation of ethanol by bubbling an inert gas (eg, nitrogen, helium, argon) in absolute ethanol in an evaporator in the temperature range 40 to 84 ° C, preferably 56 to 72 ° C. generated on the evaporator is passed through a condenser kept at a temperature between 30 and 7 4 ° C, preferably between 46 and 62 ° C. Keeping the condenser at these temperatures the ethanol concentration varies between 10 and 75%;

iii. Usually the mixture ^'gas (vapor of ethanol / N ₂₎ to the reactor containing the catalyst at the reaction temperature. iv. Obtaining a mixture of Cl - C18 combustible hydrocarbons.

BRIEF DESCRIPTION OF DRAWINGS

[41] Figure 1 - Schematic diagram of the Reaction System being (a) gases: nitrogen (N ₂ ), oxygen (0 ₂ ), hydrogen (H ₂ ), helium (He) and synthetic air (20% 0 ₂ - 80% N ₂ ), with 99.999 % purity; (b) four valve flow controller; (c) ethanol evaporator; (d) temperature controlled condenser of ethanol; (e) ostatic bath; (f) 5 mm internal diameter U-tubular quartz reactor; (g) gas chromatograph with FID detector and DB1 column, J&W 125-106J: 300 ° C dimensions 60 mx 530 pm x 1 µm; (h) gas flow meter; (i) temperature controller with 3 J6 x 40 mm - 3 m thermocouples; (j) high pressure regulating valve; (k) pressure gauge; (1) needle valve; (m) 1/4 "and 1/8" stainless steel copper and gas pipe lines; (n) ceramic fiber insulation supporting up to 1000 ° C and aramid tapes; (o) valves and accessories.

[42] Figure 2 - Diffractograms of synthesized PAH catalysts a. pH 10,5 as a function of calcination temperature.

[43] Figure 3 - Diffractograms of CHAP catalysts synthesized at pH 10,0 as a function of calcination temperature.

[44] Figure 4 - Diffractograms of FAP catalysts synthesized at pH 9.0 as a function of calcination temperature.

[45] Figure 5 ^' - Diffractograms of La / HAP catalysts as a function of impregnated Lanthanum content.

[46] Figure 6 - Diffractograms of Na / PAH catalysts as a function of impregnated sodium content.

[47] Figure 7 - Ethanol conversion vs. catalyst type.

[48] Figure 8 - Product composition (including unreacted ethanol) vs. number of carbons depending on the type of catalyst.

[49] Figure 9 - Product composition (including ethanol unreacted) vs. catalyst type as a function of C1-C4 and C5-C18 hydrocarbon groups.

[50] Figure 10 - Composition (including unreacted ethanol) vs. organic functional groups depending on the type of catalyst

[51] Figure 11 - Composition (including unreacted ethanol) vs. type of catalyst as a function of oxygenated groups and non-oxygenated hydrocarbons.

[52] Figure ^'12 - Number of products obtained by the type of catalyst.

[53] Figure 13 - Lower calorific value (PCI) of combustible hydrocarbons ^* obtained from catalysts: (a) HAP - Hydroxyapatite; (b) CHAP - Carbonate hydroxyapatite; _and (c) FAP - Fluorapatite; (d) La / HAP - PAH-supported lanthanum; and (e) Na / HAP - PAH-supported sodium.

DETAILED DESCRIPTION OF THE INVENTION

[5] The present invention relates to a process for obtaining a mixture of non-oxygenated and oxygenated combustible hydrocarbons having carbon atoms between Cl and C18 from ethanol on apatite-type catalysts via heterogeneous catalysis. in one step, in gas phase and atmospheric pressure, as well as the synthesis of these catalysts. The products provided by the present invention are alternative fuels to ^■ existing fossil fuels (eg, gasoline, diesel, aviation fuel) and are an alternative source for obtaining petrochemical base products, preferably aromatics, olefins, alcohols. higher aldehydes, ethers, ketones, phenols and to a lesser extent dienes, paraffins and esters, which are obtained by a process comprising essentially the following steps:

(I) Synthesis of apatite-type mass catalysts such as: hydroxyapatite (HAP), carbonate hydroxyapatite (CHAP) and fluorapatite (FAP) by chemical precipitation techniques;

(II) Preparation of PAH-supported metal catalysts by excess solvent impregnation techniques on rotary evaporator of La ⁺³ (lanthanum) ions on PAH (La / HAP) and Na ⁺ (sodium) ions on PAH (Na / PAH);

(III) Production of combustible hydrocarbons (Cl - C18) from ethanol on the HAP, CHAP, FAP, La / HAP and Na / HAP catalysts.

[55] The following steps (I) to (III) are described in more detail. ^■

I - Synthesis of apatite-type mass catalysts:

[56] The process proposed by the present invention is initiated by the synthesis of apatite-type catalysts such as hydroxyapatite (HAP), carbonate hydroxyapatite (CHAP) and fluorapatite (FAP).

[57] For this synthesis, it is important to select the raw materials and inputs used according to some criteria: (i) avoid the use of organic compounds to prevent the formation of semi-solid polymeric complexes and particle agglomerations during the drying process of the catalysts, which require prolonged heat treatments to be eliminated (eg, calcium fluoride, CaF ₂ ; triethyl phosphite, P (C ₂ H ₅ 0) 3); (ii) avoid the use of complex reagents with alkaline contaminants, halogenated, etc. (eg, anhydrous calcium chloride, CaCl2; cetyl trimethyl ammonium bromide, CTAB; potassium phosphate, K3PO4; disodium hydrogen phosphate, a2HP0 · I2H2O; sodium fluoride, NaF; monobasic potassium phosphate, KH2PO4); and (iii) avoid the use of inorganic raw materials with low water solubility (calcium oxide, CaO; calcium carbonate, CaCO3; calcium phosphate, Ca3 (P04) 2).

[58] Thus, in the present invention were screened as precursors of the calcium ions (Ca ^2+), phosphate (CP> 4 ^{+ 3),} carbonate (CO3- ²⁾ and fluorine ^(F-), preferably the nitrate tetrahydrate calcium [Ca (N0 ₃₎ 2 H ₂ 0], acid ammonium phosphate [(NH4) 2HPO4], ammonium bicarbonate [NH4HCO _3] fluoreto.de and ammonium [NH4 F], respectively.

[59] Synthesis of apatite catalysts (HAP, CHAP and FAP) was performed by a precipitation reaction in basic medium. The process begins by preparing an aqueous solution of the Ca ^{+ 2} ions precursor, previously heated to 40 to 60 ° C, under constant stirring. Then, in the ions Ca ^{4 "2} precursor solution, the aqueous solutions of the PC ⁺³ ions precursors to obtain PAH are added in a controlled manner, the PC ⁺³ and C0 ₃ ^{~ 2} ions precursors to obtain CHAP; and the precursor ions PCV ^'F ^~ ³ and for obtaining PAF. for the preparation of aqueous solutions of the precursors used is preferably distilled water and deionized (DD) with a conductivity between 0.5 and 1.3 pS.crrr ¹ at room temperature.

[60] During the reaction, the pH should be monitored to maintain the desired pH for each catalyst. For PAH and PAF catalysts pH values between 9.0 and 11.0 are used and for CHAP catalysts H values between 8, 5 and 10.5 are used. The pH range at each specific value is maintained within ± 0.2, preferably ± 0.1, by the constant addition of a hydroxide solution of ammonium [NHOH]. To aid the control of pH ⁴ is used an instrument (DIG ED pH meter) with a ^'two decimals sensitivity.

[61] After mixing the reagents, the reaction should be continued under constant stirring for about 2 hours at 40 to 80 ° C, preferably 50 to 60 ° C to complete the reaction.

[62] The resulting product should be cooled to room temperature and allowed to stand (aging time) between 12 and 48 hours, preferably between 18 and 24 hours. After the aging of the product, the solid precipitate is separated from the liquid containing the unreacted ions, preferably by filtration and subsequent washing with DD water and ethanol, with the aid of a Buchner funnel, quantitative filter paper and a pump. vacuum. Generally, the resulting wet paste has a moisture content of between 70 and 90% w / w. ^■

[63] The wet slurry is then oven dried in static air at 40 to 120 ° C, preferably 70 to 80 ° C for 8 to 24 hours, more preferably 12 to 16 hours. Alternatively, drying may be performed in a static air oven; in a tray dryer with hot air flowing through the damp paste; in a tunnel dryer; on a rotary evaporator, or in any medium that ensures drying ^' under the operating conditions already mentioned.

[64] Finally, the dried material is crushed, sorted by sieving into particle sizes. 0.07 to 0.15 mm and calcined in static air for 1 to 6 hours, preferably for 2 to 4 hours at temperatures between 500 and 800 ° C. Specific details for the synthesis of each of the catalysts proposed in this invention are shown in Examples 1 to 3. For each of the synthesized catalysts the specific surface area (BET), the average pore volume and size, the number of acidic sites were determined. and basic totals, the crystalline phase and the average size of the crystallites, as described in Examples 6 to 9.

II - Preparation of PAH supported metal catalysts

[65] In the preparation of La / HAP and Na / HAP catalysts, as precursors of the La ⁺³ and Na ⁺ ions, lanthanum nitrate hexahydrate was preferably selected.

[La (NO ₃ ) 3 · 6H 2 O] and sodium nitrate [NaNO 3], respectively. As a support, the synthesized hydroxyapatite (PAH) is used as described in Step I - Synthesis of the apatite mass catalysts. More specifically, PAH synthesized at pH = 10.5 ± 0.1 and calcined at 700 ° C is used. In this invention, the metallic content of La and Na present in the La / HAP and Na / HAP catalysts ranges from 3 to 12%.

(P / p) ·

[66] The preparation process begins by preparing the aqueous solutions of the La ^{+ 3} and Na ⁺ ions precursors at room temperature at the concentration required to obtain the desired metal content (3 to 12% w / w) in the La / HAP or Na / HAP catalysts. For the preparation of aqueous solutions, preferably DD water with conductivity between 0.5 and 1.3 pS.cnr ^{1 is used} . Then the holder (HAP) is placed inside the balloon of a rotary evaporator and the solution containing the metal precursor is added. Subsequently , the system is heated in a bath thermostatized at a temperature in the ^"range between 60 and 90 ° C, preferably at 80 ° C. Under these conditions, the suspension is maintained under constant stirring between 50 and 100 rpm, preferably between 60 and 80 RPM, until complete removal of the liquid solvent, indicated by the formation of a layer of solid-wet product (70 to 90% w / w moisture), detaching from the glass wall of the evaporator spinner flask. 60 to 90 minutes.

[67] After the impregnation process is completed, the sample is removed from the rotary evaporator, oven dried in static air at a temperature between 60 and 90 ° C, preferably between 70 and 80 ° C, for a time between 8 and 24 hours, preferably 12 to 16. hours Subsequently, the solid is ground, sorted by sieving into particle sizes between 0.07 and 0.15 mm, and calcined in a muffle in static air for 6 to 12 hours, preferably between 6 and 8 hours at 500 ° C. and 700 ° C, preferably between 600 and 650 ° C. More specific details for catalyst preparation via impregnation techniques in excess liquid by rotary evaporation are shown in Examples 4 and 5. For each of the prepared catalysts the specific surface area (BET), volume and average size were determined. pore size, the number of total acid and basic sites, the crystalline phase and the average size of the crystallites as described in Examples 6 to 9.

III - Production of high molecular weight hydrocarbons

^. [68] Catalysts prepared in Steps I and II of The present invention is characterized by bringing together the specific physicochemical properties for the production of combustible hydrocarbons (Cl - C18) from ethanol. For this it is used. a gas phase continuous flow reaction system at atmospheric pressure (Figure 1).

[69] For the production of combustible hydrocarbons (Cl - C18) from ethanol a catalyst mass and a N2 flux with a ratio / Fethane of between 0,02 and 0,16 kg h mol ^-1 , preferably 0.04 kg h mol ^-1 , comprising the catalyst heat pretreatment in the reaction temperature range 300 to 600 ° C, preferably 400 to 500 ° C, for a time of 1 to 4 hours, preferably 1 to 2 hours.

[70] Gas 2 is then bubbled into absolute ethanol in an evaporator in the temperature range 40 to 8 ° C, preferably 56 to 72 ° C. The vapor mixture of ethanol and 2 generated in the evaporator is passed through a condenser maintained at a temperature between 30 and 7 ° C, preferably between 46 and 62 ° C. Keeping the condenser at these temperatures the ethanol concentration varies between 10 and 75%. Subsequently, the gas mixture (ethanol vapor / N2) is sent to the reactor containing the catalyst at the reaction temperature.

[71] The resulting products were analyzed on an Agilent Technologies (Model 7890A) chromatograph equipped with a DB1 column (J&W 125-106J: 300 ° C). For product identification and chromatograph calibration, condensed samples on a cold trap at 0 ° C were analyzed on a Shimadzu GC / MS (GCMS-QP2010 Ultra). As reference 54 standard hydrocarbons (not oxygenated) with carbon atoms between Cl and C24, gaseous and liquid.

[72] Catalytic activity of the catalysts was assessed as a function of ethanol conversion. The ethanol conversion being defined as: CEtOH (%) = (Qconv / QEtOH) i

100, where Qconv 'is the molar amount of converted ethanol and QEtOH is the total molar amount of ethanol fed to the reactor. Product yield was defined as: PP (%) = (QP / QTP) 100, where QP is the number of moles of each product and QTP is the total amount of moles of reaction products present at the reactor outlet. This balance does not include moles of solid products such as small amounts of coke deposited on the surface of the catalysts.

[73] Some examples of embodiments involving steps I (Synthesis of apatite-type mass catalysts), II (Preparation of PAH-supported metal catalysts) and III (Fuel hydrocarbon production) are detailed above. described below.

Example 1 - Synthesis of Hydroxyapatite (PAH)

1.1. Preparation of Ca (NO ₃ ) 2 · 4H2O aqueous solution

[74] In a 50 ml flask were dissolved in 11.8074 g of Ca (N0 ₃₎ 2 H ₂ 0 (Merck product n ° 1.02121.0500, CAS No. 13477- 34-4, purity 99.9% ) in DD water (~ 1 S.cm ^-1 ) at 50 ° C, the volume was made up to the meniscus with DD water to give an aqueous reagent solution with a concentration of 1.0 M Ca (NO3 ) 2. H2O. The dissolution was totally transparent.

1.2. Preparation of the aqueous solution of (NH ^ HPO _s.?

^[ 75] In a 50 ml flask was dissolved 3.9617 g of (ΝΗ ₄ ) ₂ ΗΡ0 (Merck, product no. 1.02121.0500, CAS no. 13477-34-4, purity 99.9%) in DD water (~ 1 pS.crrr ¹ ) at a temperature of 50 ° C. The volume was made up to the meniscus with DD water to give an aqueous solution of the reagent with a concentration of 0.6 M (NH4) 2H PC. The solution was totally transparent.

1.3.HAP synthesis reaction

[76] the present invention obtained 5 different PAH catalysts, varying the pH of the reaction mixtures. The synthesis pH values used were 9.0, 9.5, 10.0, 10.5 and 11.0. All catalysts were synthesized from the aqueous solutions prepared in Examples 1.1 and 1.2. The pH control of the reaction mixtures was performed by the addition of an ammonium hydroxide solution (Merck, product no. 1054321000, CAS no. 1336-21-6, 25% purity) in the amount necessary to maintain the pH at the desired value.

[77]. The PAH synthesis process was initiated by placing the Ca (NO3) 2.4¾0 solution into a 500 ml three-necked flask and heated under constant stirring to 50 ° C in a thermostated water bath. Ammonium hydroxide was then added to the Ca (NO3) 2.4¾0 solution until the desired reaction pH was reached (e.g., pH = 10.5); then the solution of

(NH4) H PC was added at a rate of 1 ml / min. At the same time the ammonium hydroxide solution was added in the amount necessary to maintain the reaction pH.

(eg, pH = 10.5 ± 0.1). Under these conditions a white precipitate of fine particles is suspended. At the end of (NH ₄ ) ₂ H PC solution addition, the pH was adjusted to the desired value (eg, 10.5) and kept at the reaction temperature under constant stirring for 120 hours. minutes

[78] 0 resulting reaction product was cooled until room temperature and maintained at rest for 24 hours. Subsequently the precipitate and the liquid containing the unreacted ions were separated by filtration and held · successive washes with filtered water and slurry DD ethanol using ^'.a Buchner funnel, quantitative filter paper and a vacuum pump. Thereafter, the resulting wet slurry was dried in a static air oven at 80 ° C for 12 hours. Finally, crushed and sorted by sieving into particle sizes between 0.07 and 0.15 mm.

1.4. Heat Treatments - HAP

[79] Catalysts obtained at pH = 9.0, 9.5, 10.0, 10.5 and 11.0 as described in Example 1.3 were calcined at 700 ° C. In addition, three catalysts synthesized at pH 10.5 were also calcined at temperatures of 500, 600 and 800 ° C.

[80] The calcination process of the PAH catalysts was performed in one: muffle in air. according to the program of temperatures and heating rates presented in Table 1. The final mass of products synthesized at different pH and calcination temperatures varies between 4.8 and 5.2 g.

Table 1. Calcination program.

Rate of

Temperature

N ° Time (min) heating

(° C) <

(° C / min)

1 25-250 * ^'110 2.0

2 250 - - 250 20 -

3,250 - TC 50 to 110 5.0

4 TC - - C 120 -

5 TC - - 50 * 260 2.5

TC: ^■ Temperature Calcination Example 2 - Synthesis of Carbonate Hydroxyapatite (CHAP)

2.1. Preparation of the aqueous (NH4) 2HP04 and NH4HCO3 solution [81] In a 100 ml flask 3.8851 g of

(NH ₄ ) ₂ HP04 (Merck, product no. 1.02121.0500, CAS no. 13477-34-4, purity 99.9%) and 0.3872 g of NH4HCO3 (Sigma Aldrich - Fluka, product no. 09830-500G , CAS No. 1066-33-7, purity 99%) in DD water (* 1 pS.cnr ¹ ) at 50 ° C, the volume was made up to the meniscus with DD water to give an aqueous solution of the reagents. with concentrations of 0.3 M (NH4) 2HPC 'and 0.3 M NH4HCO3. The solution was totally transparent.

2.2. CHAP synthesis reaction

[82] the present invention obtained 5 different CHAP catalysts, varying the pH of the reaction mixtures. The synthesis pH values used were 8.5, 9.0, 9.5, 10.0 and 10.5. All catalysts were synthesized from the aqueous solutions prepared in Examples 1.1 and 2.1. The synthesis process of the CHAP catalysts from the mixture of aqueous solutions of Ca (NO3) 2.4¾0 and (H4) 2HP0 + NH4 HCO3 follows the same mechanism described in Example 1.3.

2.3. thermal treatments - CHAP

[83] The catalysts obtained at pH = 8.5, 9.0, 9.5, 10.0, and 10.5 as described in Example 2.2 were calcined at a temperature of 600 ° C. In addition, three catalysts synthesized at pH 10.0 were calcined at temperatures of 500, 700 800 ° C. The heat treatment processes of the products were performed as described in Example 1.4.

Example 3 - Fluoroapatite Synthesis (FAP)

3.1. Preparation of aqueous solution (NH) 2HP04 E NH4 F

[84] In a 100 ml flask was dissolved 3.9699 g of (NH ₄ ) 2HP0 ₄ (Merck, product no. 1.02121.0500, CAS no. 13477-34- 4, 99.9% purity) and 0.3689g NH ₄ F (Merck, product no. 1011640250, CAS no. 12125-01-8, 100% purity) in DD water (* 1 pS.crrr ¹ ) at room temperature. At 50 ° C, the volume was completed to the meniscus with DD water to give an aqueous solution of the reagents with concentrations of 0.3 M (NH4) 2HP04 and 0.3 M NH4F. The solution was totally transparent.

3.2. FAP synthesis reaction ^f

[85] the present invention obtained five different PAF catalysts by varying the pH of the reaction mixtures. The synthesis pH values used were 9.0, 9.5, 10.0, 10.5 and 11.0. All catalysts were synthesized from the aqueous solutions prepared in Examples 1.1 and 3.1. The synthesis process of the PAF catalysts from the mixture of the aqueous solutions of Ca (NO3) 2.4 )0 and (NH4) 2HPC + NH ₄ F follows the same mechanism described in Example 1.3.

3.3. thermal treatments - FAP

[86] Catalysts obtained at pH = ^■ 9.0, 9.5, 10.0, 10.5 and 11.0 as described in Example 3.2 were calcined at 700 ° C. In addition, three catalysts synthesized at pH = 9.0 were calcined at temperatures of 500, 600 and 800 ° C. The heat treatment processes of the products were performed as described in Example 1.4.

Example 4 - Preparation of Hydroxyapatite Supported Lanthanum Catalysts (La / HAP)

.1. Preparation of aqueous solutions of La (NO3) 3.6H2O

[87] The present invention prepared three metal-supported La / HAP catalysts with metal contents of 3, 6 and 12% (w / w) in La. In 100 ml beakers, various aqueous solutions of La (NO ₃ ) 3.6¾0 were prepared. (Sigma-Aldrich, product No. 61520-100G-F, CAS No. 10277-43-7, 100% purity) in DD water (~ 1 pS.crrr ¹ ) at 50 ° C. The solvent volume and La (NO3) 3.6H2O and HAP masses for the different metal contents are shown in Table 2. The support mass and the precursor solution / support mass ratio have always been kept at 5 g and 5 ml / g. respectively

Table 2. Formulation for catalyst preparation

La / HAP. _

Concentration

La Massa content La (NO3) 3.6H2O

La (NO3) 3.6H2O

(%, W / W) (g) (molar)

3 0.4846 0.0448

61.0060 0.0929

12 2.1767 0.2011

PAH Lanthanum Impregnation

[88] As set out in Example 4.1, a total of three La / HAP catalysts with metal contents of 3, 6 and 12% La (w / w) were prepared. The PAH, synthesized as described in Example 1, was initially placed into the spinner flask and added to the La ^{+ 3} ions precursor solution at the required concentration (Table 2) to obtain the desired La content in La / HAP catalysts. . Thereafter, the suspension was heated in a thermostated bath at 80Â ° C and kept under constant stirring at 60 RPM until complete removal of the solvent, indicated by the formation of a layer of the dry solid peeling off the glass wall of the flask. evaporator route. After the impregnation process is completed, the samples are taken from the spin evaporator flask and thereafter the heat treatments described in Example 4.3 are continued. .3. Heat Treatments - La / ΗΆΡ

[89] The filtered material resulting from Example 4.2 was oven dried in static air at 80 ° C for 12 hours. Subsequently, the solid was crushed, sieved into particle sizes between 0.07 and 0.15 mm, and calcined in a muffle in static air for 7 hours at 650 ° C. The heating rate used in the calcination process is 5 ° C / min.

Example 5 - Preparation of Hydroxyapatite Supported Sodium Catalysts (NA / PAH)

5.1. Preparation of aqueous NaNCb solutions

[90] The present invention prepared three metal-supported Na / HAP catalysts with metal contents of 3, 6 and 12% (w / w) in Na. In 100 ml beakers, various aqueous solutions of NaNCb (Sigma-Aldrich, product no. S5506-250G, CAS no. 7631-99-4, purity 99.8%) in DD water ('1 pS.cnr ¹ ) were prepared. at a temperature of 50 ° C. The volume of solvent and the masses of NO3 and HAP for the different metal contents are shown in Table 3. The support mass and the precursor solution / support mass ratio were always kept at 5 g and 5 ml / g, respectively.

Table 3. Formulation for preparation of Na / HAP catalysts.

Bulk Content NaN0 ₃ NaNC Concentration

(%, W / W) (g) (molar)

3 0.5779 0.2720

61 1, 2067 0, 5679

12 2, 6463 1.2454

5.2. PAH sodium impregnation

[91] As set out in Example 5.1, in total they were Cooked three. Na / HAP catalysts with metal contents of 3, 6 and 12% Na {w / w}. The Na impregnation process from the aqueous NaN03 solutions (Table 3) on the synthesized PAH support as described in Example 1 was performed similarly to the procedure described in Example 4.2.

5.3. Heat Treatments - Na / HAP

[92] The filtered material resulting from Example 5.2 was heat treated in a similar manner as described in Example 4.3.

Example 6 - Catalyst Characterization: Textural Properties

[93] Textural properties such as surface area and average pore volume and pore size of the catalysts: HAP, CHAP, FAP, La / HAP and Na / HAP synthesized in Examples 1, 2, 3, 4 and 5, respectively, were determined from 2 to 77K adsorption analysis. Measurements were performed on a Micromeritics Instrument Corporation (ASAP 2020) apparatus. The gases used in the experiments were He (White Martins, 99.999% v / v) and N ₂ (White Martins, 99.999% v / v).

[94] Before adsorption analysis, ca. 0.5 g of sample from each catalyst was heated under vacuum (110-5 mmHg) at 350 ° C for 12 hours. Then, the samples were cooled to room temperature and the adsorption measurements from 2 to 77 K were started, following the standard procedure of the equipment. The specific surface area of the solids was determined by the Brunauer-Emmett-Teller (BET) equation through the adsorption isotherms obtained in the relative pressure range 0.07 <P / Po <0.30. The total pore volume was obtained from the amount of 2 adsorbed to a Relatively close to the unit pressure and mean pore diameter were determined by the Barrett-Joyner-Halenda (BJH) method from the N ₂ desorption isotherms. Results are presented in Table 4.

Table 4 Textural properties, crystallite size, acidic and basic site concentration of HAP, CHAP, FAP, La / HAP and Na / HAP catalysts.

FAP

synthesized as described in Examples .1, 2, 3, 4 and 5, respectively _; It ^was' determined by density basic sites ^■ CO ₂ adsorption analysis expressed in pmoles CO2 adsorbed per m ² of the solid surface. Measurements were performed on Micromeritics Instrument Corporation (ASAP 2020C) equipment available from FEQ / DEPro / UNICAMP The gases used in the experiments were He (White Martins, 99.999% v / v), N ₂ (White Martins, 99.999% v / v) and C0 ₂ (White Martins, 99.999% v / v).

[96] Prior to the adsorption measurements, approximately 0.5 g of sample was evacuated at 1x10 ^-5 mmHg at 400 ° C for 2 hours. The system temperature was then decreased under vacuum to the analysis temperature (37 ° C) and evacuated for 10 minutes to ensure temperature stabilization. In all cases, two isotherms were obtained with equilibrium pressures between 5 and 400 mmHg. The second isotherm was obtained after evacuation of the sample at the analysis temperature (37 ° C) for 15 minutes. The difference between the two isotherms and their subsequent zero pressure extrapolation allowed to determine the amount of gas irreversibly adsorbed in µmol of CO2 per unit mass of the sample. This result was later divided by the specific surface area of the solids, previously determined by adsorption at 2 to -196 ° C (Example 6). Results are presented in Table 4.

Example 8 - Characterization of catalysts: acid site density

[97] In the synthesized HAP, CHAP, FAP, La / HAP and Na / HAP catalysts as described in Examples 1, 2, 3, 4 and 5, respectively, the density of the acid sites was determined by Programmed Temperature Desorption analysis. (TPD) of pyridine (Sigma-Aldrich, product No. 270970, CAS No. 110-86-1, purity 99.8%), expressed in µmol pyridine adsorbed per m2 of solid surface. Measurements were performed on a Micromeritics Instrument Corporation (AutoChem II - 2920) device coupled to an MKS mass spectrometer (Cirrus LM99). As gas of drag was used He (White Martins, 99.999% v / v).

[98] For this analysis between 0.1 and 0.5 g of sample were used. Previously the samples were oven dried in static air at a temperature of 120 ° C for 12 hours. They were then glued into a quartz reactor on the equipment and pretreated in a 25 ml.min ^-1 He flow at 150 ° C for 60 minutes. Subsequently, TPD measurements were performed in the temperature range 150 to 500 ° C, with a heating rate of 10 ° C min ^'1 . By mass spectroscopy the pyridine fragments corresponding to the molecular masses of 26, 39, 52 and 79 were monitored. The results are presented in Table 4.

Example 9 - Characterization of catalysts: determination of crystalline phase and average size of crystallites

[99] The synthesized HAP, CHAP, FAP, La / HAP and Na / HAP catalysts as described in Examples 1, 2, 3, 4 and 5, respectively, determined the crystalline phase of the solids by the light diffraction technique. X. Measurements were performed on a Philips Analytical device (model X 'Pert PW3050). The diffractograms were obtained in the scanning range (2Θ) from 20 to 50 °, with 0.02 ° step and 1.8 s step time, with CuK wavelength = 0.15456 nm, intensity 40 kV and the current of 40 mA. The analyses. Diffractograms were performed using the Philips PC-APD v. 4.0d. The estimation of the average crystallite size was performed from the highest intensity peak of the X-ray diffratrogram using the Scherrer equation. The diffractograms of the catalysts prepared under different conditions of calcination temperature and _P H of Synthesis are shown in Figures 2 to 6 and the average size of the crystallites are shown in Table.

Example 10 - Production of combustible hydrocarbons on HAP catalysts

[100] PAH catalysts obtained with different synthesis pH values and calcination temperatures as described in Example 1 were tested in the ethanol reaction in phase. gas pressure and atmospheric pressure under various reaction temperature (TR) conditions and W / FEtanoi ratios as a function of reaction time. Reaction conditions and results obtained on HAP catalysts are presented in Tables 5, 6, 7 and 8.

[101] Production of combustible hydrocarbons (Cl - C18) from ethanol was initiated by placing 0.7 g of HAP catalyst in the reaction system quartz reactor (Figure 1) and pretreated to the desired reaction temperature ( eg, 500 ° C) for 1 hour under continuous flow of 2 (23 ml min ^-1 ). Then absolute ethanol was bubbled with N 2 (23 ml min ^-1 ) in an evaporator at 56.3 ° C. The mixture of ethanol vapor and N2 gas was passed in a saturator maintaining the temperature of 46.3 ° C. Under these conditions, the equilibrium concentration of ethanol was 25% v / v. Subsequently, the gas mixture (ethanol vapor / N2) was sent to the reactor. Total reaction time was ^¾ 7 hours. For each catalytic test, a total of 5 samples were performed for chromatographic analysis, and the first sample was performed 30 minutes after the reaction started.

[102] Depending on catalyst synthesis characteristics and reaction conditions used in tests Catalytic catalysts were obtained between 50 and 400 products, including oxygenated and non-oxygenated hydrocarbons, consisting mainly of aromatics, dienes, olefins, paraffins, alcohols, aldehydes, esters, ethers, ketones, phenols.

[103] The highest yield of condensable combustible hydrocarbons (C5 - C18) was obtained under the following operating conditions: calcination temperature, 700 ° C; synthesis pH, 10.5; reaction temperature, 500 ° C; and ΔEtanoi, 0.04 kg h mol ^-1 . Table 10 shows the composition of the gaseous product, including unreacted ethanol, at the reactor outlet. Figures 7 to 12 show the highest yield of combustible hydrocarbons obtained from the catalysts developed in this invention.

Example 11 - Production of combustible hydrocarbons on CHAP catalysts

[104] CHAP catalysts obtained with different synthesis pH values and calcination temperatures as described in Example 2 were tested in the ethanol reaction, gas phase and atmospheric pressure under various reaction temperature (RT) and W / FEtanoi ratios as a function of reaction time. The process of producing fuel hydrocarbons (Cl - C18) from ethanol is similar to that described in Example 10. The reaction conditions and results obtained on CHAP catalysts are presented in Tables 5, 6, 7 and 8.

[105] The highest yield of condensable combustible hydrocarbons (C5 - C18) was obtained under the following operating conditions: calcination temperature, 600 ° C; synthesis pH, 10.0; reaction temperature, 500 ° C; e, W / F _E tanoi, 0.04 kg h mol " ^11. Table 11 shows the composition of the gaseous product, ^" including unreacted ethanol, at the reactor outlet. Figures 7 through 12 show the highest yield of combustible hydrocarbons obtained from the catalysts developed in this invention.

Example 12 - Production of Combustible Hydrocarbons on FAP Catalysts

[106] FAP catalysts obtained with different synthesis pH values and calcination temperatures as described in Example 3 were tested for the ethanol, phase: gas reaction and atmospheric pressure under various reaction temperature (RT) conditions. and W / F _E tanoi ratios as a function of reaction time. The process of producing fuel hydrocarbons (Cl - C18) from ethanol is similar to that described in Example 10. The reaction conditions and the results obtained on the FAP catalysts are presented in Tables 5, 6, 7 and 8.

[107] The highest yield for condensable combustible hydrocarbons (C5 - C18) was obtained under the following operating conditions: calcination temperature, 700 ° C; synthesis pH, 10.0; reaction temperature, 450 ° C; e, W / FEtanoi, 0.04 kg h mol ^"1. Table 12 shows the composition of the gaseous product, including unreacted ethanol, at the reactor outlet. Figures 7 to 12 show the highest yield for combustible hydrocarbons. obtained from the catalysts developed in this invention.

Example 13 - Production of combustible hydrocarbons on La / HAP catalysts

[108] In this invention, La / HAP catalysts obtained with different La contents, as described in Example 4, were tested in the gas phase ethanol reaction and pressure. atmospheric conditions under various reaction temperature (TR) conditions and ratios / F _E tanoi as a function of reaction time. The process of producing fuel hydrocarbons (Cl - C18) from ethanol is similar to that described in Example 10. The reaction conditions and the results obtained on the La / HAP catalysts are presented in Tables 6, 7 and 9.

[109] The highest yield of condensable combustible hydrocarbons (C5 - C18) was obtained under the following operating conditions: metallic content, 3% La; calcination temperature of La / HAP catalyst, 650 ° C; reaction temperature, 500 ° C; e, F _E tanoi, 0.04 kg h mol ^-1 . Table 13 shows the composition of the gaseous product, including unreacted ethanol, at the reactor outlet. Figures 7 to 12 show the highest yield of combustible hydrocarbons obtained from the catalysts developed in this invention.

Example 14 - Production of combustible hydrocarbons on Na / HAP catalysts

[110] Na / HAP catalysts obtained with different Na contents, as described in Example 5, were tested in the ethanol reaction, gas phase and atmospheric pressure under various reaction temperature (RT) conditions and W / W ratios. Fetanoi _f as a function of reaction time. The process of producing fuel hydrocarbons (Cl - C18) from ethanol is similar to that described in Example 10. The reaction conditions and the results obtained on the La / HAP catalysts are presented in Tables 6, 7 and 9.

[111] The highest yield of condensable combustible hydrocarbons (C5 - C18) was obtained under the following operating conditions: metallic content, 3% Na; calcination temperature of Na / HAP catalyst, 650 ° C; reaction temperature, 500 ° C; and, W / FEtanoi, 0.04 kg h mol ^"1. Table 14 shows the composition of the gaseous product, including unreacted ethanol, at the outlet of the reactor. Figures 7 to 12 show the highest yield for combustible hydrocarbons. obtained from the catalysts developed in this invention.

Example 15 - Determination of the calorific value of combustible hydrocarbons

[112] The catalyst products that showed the highest yield of condensable combustible hydrocarbons (C5 - C18) as described in Examples 10, 11, 12, 13 and 14 were condensed on a cold trap at 0 ° C. Condensed products at room temperature separate into two phases except that obtained with Na / HAP catalysts. Then, by decanting techniques, the oily part of the samples were separated and the calorific value determined in them.

[113] The calorific value was determined according to ASTM D240 - Standard Test Method for Heat of Combustion of. Liquid Hydrocarbon Fuels by Bomb Calorimeter, in an IKA equipment (Mod. C180). Benzoic Acid, PCI 26427 J / g, Max Error 0.02%) was used as standard. Standard (IKA c723, ID No. 3243000, PCI 26427 J / g, Max Error 0.02%). The results are shown in Figure 13.

Table 5. Yield as a function of calcination temperature.

YIELD (%)

TR: reaction temperature

Table 6. Yield against reaction temperature.

YIELD (%)

TC: calcination temperature

Table 7. Yield against W / FEtanoi.

YIELD (%)

RT: reaction temperature; TC: apatite calcination temperature; TCM: Calcination temperature of metal-supported catalyst

Table 8. Yield as a function of synthesis pH.

YIELD (%)

RT: reaction temperature; TC: apatite calcination temperature

Table 9 Yield as a function of supported metal content.

YIELD (%)

Table 11. Composition of the product obtained over CHAP catalyst (pH: 10.0; calcination temperature: 600 ° C; reaction temperature: 500 ° C) including unreacted ethanol.

Table 12. Composition of the product obtained over FAP catalyst (pH: 10.0; calcination temperature: 700 ° C; reaction temperature: 450 ° C) including unreacted ethanol.

Table 13. Product composition obtained on La / HAP catalyst (La content: 3% w / w; calcination temperature: 650 ° C; reaction temperature: 500 ° C) including unreacted ethanol.

Table 14. Composition of the product obtained over Na / HAP catalyst (Na content: 3% w / w; calcination temperature: 650 ° C; reaction temperature: 500 ° C) including unreacted ethanol.

Dienos 0.25 0, 02 0, 50 0, 00 0, 02 0, 18 0, 09 1.05

[114] While the invention has been fully described, it is obvious to ^'those skilled in the art that various changes and modifications may be made without seeking design improvements that these changes are not covered by the scope of the invention.

Claims

1. Process for obtaining apatite-type mass catalysts comprising the following steps:

(a) Preparation of at least two precursor aqueous solutions under constant stirring at a temperature range of 40 to 60 ° C, the first of which being a Ca ^{+ 2} ions based solution, preferably a tetrahydrochloric calcium nitrate solution. [Ca (NO3) 2.4 )0], and a second solution is the basis of any ion selected from the group consisting of ions P0 ⁺³ , ions CO ₃ ^"2 and ions F ^~ , preferably any solution selected from ammonium acid phosphate [ (NH 1) 2HPO 4], ammonium bicarbonate [NH HCO 3] and ammonium fluoride [NH 4 F], respectively;

(b) controlled addition of the first aqueous precursor solution obtained in step a) to the second aqueous precursor solution obtained in step a); c) Keep the reaction medium obtained in step b) under constant stirring, in a temperature range of 40 to 100 ° C. 80 ° C until completion of the reaction, and within a pH range of 8.5 to 11.0;

(d) cooling the resultant medium obtained in step (c) to ambient temperature (~ 25 ° C) and at rest for a period of time between 12 and 48 hours;

e) Separating the precipitate from the aqueous phase containing the unreacted ions;

f) Obtaining a wet paste;

(g) Drying the wet slurry in step (f) at a temperature of 40 to 120 ° C for a period of time of 8 to 24 ° C. hours;

(h) grinding the dried material obtained in step (g); (i) Means for separating the comminuted material in step (h) are particles with an average size of 0.07 to 0.15 mm;

(j) calcination of the material selected in step (i) for a period of from 1 to 6 hours over a temperature range of from 500 to 800 ° C;

(k) Apatite - type mass catalyst with a specific surface area of between 18 and 70 m ² g ^-1 , pore volume between 0,1 and 0,5 m ³ g ^-1 , pore size 17 and. 43 nm and average crystallite size between 11 and 21 nm, with a concentration of acid sites between 1.0 and 2.9 pmo l pyridine m ^{~ 2} and basic sites between 0.4 and 2.6 pmolco2 m ^{~ 2} .

Process according to Claim 1, characterized in that the controlled addition of step b) is preferably performed dropwise at a flow rate of 0.5 to 1.0 ml / min).

Process according to Claim 1, characterized in that the temperature range of step c) is preferably between 50 and 60 ° C.

4. Process according to claim 1, characterized by the fact that when the second solution of step a ) is the base P0 ^~ ions, the pH in step c) should be maintained in a range ^'of between 9.0 and 11.0, preferably between 10.3 and 10.7, more preferably at pH 10.5; and the calcination temperature of step j) preferably comprises 700 ° C.

Process according to Claim 1, characterized in that when the second solution of step a) is based on C0 ₃ ^{~ 2} ions, the pH of step c) must be kept at a range from 8.5 to 10.5, preferably from 9.8 to 10.2, more preferably at pH 10; and the calcination temperature of step j) preferably comprises 600 ° C.

Process according to Claim 1, characterized in that when the second solution of step a) is based on ions F ^" , the pH of step c) must be kept within a range of 9.0 to 11, preferably between 9.8 and 10.2, more preferably at pH 10, and the calcination temperature of step j) preferably comprising 700 ° C.

Process according to any one of claims 1, 3-6, characterized in that the pH of step c) is preferably maintained by the constant addition of an ammonium hydroxide solution [NH 4 OH].

Process according to Claim 1, characterized in that the rest period of step d) preferably comprises 18 to 24 hours.

Process according to Claim 1, characterized in that the separation of the precipitate from the aqueous phase of step e) comprises filtrations and subsequent washings with deionized water and ethanol, preferably under vacuum.

Process according to Claim 1, characterized in that the wet paste obtained in step f) has a moisture content of between 70 and 90% w / w.

11. Process according to. claim 1, characterized in that the drying of step g) is preferably carried out at a temperature of from 70 to 80 ° C for a period of time from 12 to 16 hours.

Process according to Claims 1 and 11, characterized in that the drying of step g) can be carried out in a static air oven; in a tray dryer with hot air flowing through the damp paste; on a tunnel dryer; in a rotary evaporator, or in any medium that guarantees drying under the operating conditions set forth in any one of claims 1 and 11.

Process according to Claim 1, characterized in that the means for selecting the material of step i) comprises sieving.

Process according to Claim -13, characterized in that the sieving is carried out in 100 mesh sieves.

Process according to Claim 1, characterized in that the calcination of step j} takes place over a preferred time range of 2 to 4 hours.

Process according to Claim 1, characterized in that the calcination of step j) can be performed in a static air muffle; in a thermostatized bath; in a heat exchanger; through hot air flowing through an evaporator spinner; or by any means that guarantees heating under the operating conditions set forth in any one of claims 1 and 15.

17. Apatite-type mass catalysts, characterized in that they comprise a specific surface area of between 20 and 60 m ² ^g_1 , pore volume between 0.1 and 0.5 m ³ g ^_i , pore size between 20 and 50 nm, and average crystallite size between 10 and 20 nm, with an acid site concentration between 1.0 and 3.0 ymolpyridine m ^{~ 2} and a basic site concentration between 0.5 and 2.5 pmolco2 m ^{~ 2} ; and are obtained according to the steps described in claims 1 to 16.

Use of apatite-type mass catalysts as defined in claim 17, characterized in that they are for application as process catalysts in their mass form for applications where the acid-base properties of solids are determinant for obtaining products which preferably involve the formation of CH and / or C-0 bonds from renewable sources such as ethanol, for the purpose of producing high molecular weight hydrocarbon fuels to replace fossil fuels and for the production of oxygenated and non-hydrogenated hydrocarbons. oxygenates useful for the petrochemical industry; and as an oxide support for the production of supported metal catalysts for specific catalytic applications.

19. Catalyst mass type hydroxyapatite (HAP), characterized in that it comprises specific surface area between 18 and ^'57 m ² g ^_1, pore volume comprised between 0.1 and 0.5 m ³ g ^-1, pore size between 17 and 34 nm and an average crystallite size between 16 and 21 nm with a concentration of acidic sites ranging from 1.0 to 2.9 pmolpyridine m ^{~ 2} and a concentration of basic sites ranging from 0.6 to 1.7 mol2 m ^-2 .

Hydroxyapatite-type mass catalyst (PAH) according to Claim 19, characterized in that it preferably comprises a specific surface area of 30 m ² g ^_1 , pore volume 0.2 m ³ g ^_1 , pore size. 33 nm, and mean crystallite size 19 nm, with an acid site concentration of 1.6 pmolpyridine m ^{~ 2} and a basic site concentration of 1.7 molco2 m ^{~ 2} .

Use of hydroxyapatite-type mass catalysts (PAHs) as defined in any one of claims 19 and 20, characterized in that they are for application as a process catalyst for the production of a mixture of high molecular weight combustible hydrocarbons from ethanol, with a number of carbon atoms between Cl and C18 and a lower calorific value> 39 MJ kg ^-1 , aiming to replace fossil fuels; as a process catalyst for hydrocarbon production oxygenated and non-oxygenated for the petrochemical industry, preferably for the production of aromatics, olefins, higher alcohols, ketones and phenols; and as oxide support for production of metal catalysts supported as HAP-supported lanthanum (La / HAP) and HAP-supported sodium (Na / HAP).

22. Catalyst type mass carbonate-hydroxyapatite (CHAP), characterized in that it comprises specific surface area between 25 and 70 m ² g ^_1, pore volume comprised between 0.3 and 0.5 m ³ g ^-1 size pores comprised between 23 and 41 nm, and average crystallite size between 11 and 20 nm, with a concentration of acid sites between 1.8 and 2.6 pmolpyridine m ^-2 and a concentration of basic sites between 1, 3 and 2.6 pmolco2 m ^{~ 2} .

Carbonate hydroxyapatite-type mass catalyst (CHAP) according to Claim 22, characterized in that it preferably comprises a specific surface area of 40 m ² g ^{* 1} , a pore volume of 0,4 m ³ g ^-i. , pore size 37 nm, and mean crystallite size 12 nm, with an acid site concentration of 2,3 pmolpidine m ^{~ 2} and a basic site concentration of 1,9 pmolco2 nr ² .

Use of the carbonate hydroxyapatite (CHAP) type catalysts as defined in any one of claims 22 and 23, characterized in that they are for application as a process catalyst for the production of a mixture of high molecular weight combustible hydrocarbons at from ethanol, with a number of carbon atoms between Cl and C18 and a lower calorific value> 41 MJ kg ^-1 , aiming to replace fossil fuels; and as a process catalyst for producing oxygenated and non-oxygenated hydrocarbons specific to the petrochemical industry, preferably for obtaining aromatics, olefins, higher alcohols, and ketones.

25. Fluorapatite-type mass catalyst (PAF) characterized in that it comprises a specific surface area of between 18 and 61 m ² ^g_1 , pore volume between 0.2 and 0.5 m ³ g ^_1 , pore size between 28 and 43 nm, and average crystallite size between 10 and 14 nm, with an acid site concentration between 1.9 and 2.4 pmolpyridine m ^-2 and a basic site concentration between 0.4 and 1.4 ymolco2 m ^~ .

Fluorapatite-type mass catalyst (FAP) according to Claim 25, characterized in that it preferably comprises a specific surface area of 40 m ² g ^_1 , pore volume 0.4 m ³ g ^_1 , pore size. 38 nm, and average crystallite size of 13 nm, with an acid site concentration of 1.9 nmolpyridine m ^{~ 2} and a basic site concentration of 1.4 pmolco2 nr ² .

Use of fluorapatite-type mass catalysts (FAP) as defined in any one of claims 25 and 26, characterized in that it is to be for application as a process catalyst for the production of a mixture of high molecular weight hydrocarbons. from ethanol, with a number of carbon atoms between Cl and C18 and a lower calorific value> 38 MJ kg ^-1 , aiming to replace fossil fuels; and as a catalyst for producing oxygenated and non-oxygenated hydrocarbons specific to the petrochemical industry, preferably for obtaining aromatics, olefins, higher alcohols, and ketones.

A process for obtaining PAH-supported metal catalysts comprising the following steps:

1) Preparation of an aqueous precursor solution based on any ion selected from La ^{+ 3} and Na ⁺ ; ^: m) Insertion of hydroxyapatite (PAH) as obtained in step k) into equipment capable of generating a uniform mixture of the support with the precursor solution of the metal to be impregnated; n) Addition of the precursor solution obtained in 1) in the system obtained in m);

o) Heating the system obtained in step n), keeping the suspension under constant agitation until complete removal of the liquid solvent;

p) Obtaining solid-wet product;

(q) drying the product obtained in step (p) at a temperature range of 60 to 90 ° C for a period of time of 8 to 24 hours;

r) Crushing the solid obtained in step q);

s) Means for selecting the crushed material in step r) in particles - with an average size of 0.07 to 0.15 mm;

t) Calcination of the material selected in step s) for a period of time ranging from 6 to 12 hours in a temperature range from 500 to 700 ° C.

A process according to claim 28, characterized in that the aqueous solution of step 1) is preferably selected from lanthanum nitrate hexahydrate [La (NO ₃ ) 3.6H ₂ O] and sodium nitrate [Na 03] -.

Process according to Claims 28 and 29, characterized in that the molar concentrations of the solutions are in the range 0.04 and 0.20 mol / L and 0.27 to 1.24 mol / L. L, respectively.

Process according to claim 28, characterized in that the equipment of step m) comprises a rotary evaporator.

Process according to Claim 28, characterized in that the heating of step o) ^' is carried out in a temperature range of from 6 ° to 90 ° C, the suspension being kept under constant stirring from 50 ° to 100 rpm until complete, removal of liquid solvent. ^'

33. Proceedings of _; The method according to claim 28 or 32, characterized in that the heating of step o) is preferably carried out at a temperature of 80 ° C while the suspension is kept under constant agitation at 60 to 80 rpm _. J

34. Process of; according to any of the claims

t,

28, 32 e.33, characterized by the fact that the heating of step a ) can ^'be performed in a thermostated bath; in a heat exchanger; through hot air flowing through an evaporated route; or by any means ensuring ^'heating under operational conditions established in any one of claims 28, 32 or 33.

35. The method _of: claim 28, characterized by the fact that the solid-moist product obtained in step p) has humidity between 70 and 90% w / w. ^:

A process according to the claim _. 28, characterized in that the drying of step q) is carried out over a temperature range of 60 to 90 ° C over a period _. between 8 and 24 hours.

37. Process according to claim 28, characterized by the fact that the secagem- ^'step q) is carried out preferably in a- ■ temperature range between 70 and 80 ° C. for a period of time ranging from 12 to 18 hours.

38. ^_Process': according to any one of claims 28, 36 and 37, characterized in that the drying step q) can be performed in static air in an oven; in. a tray dryer with air. hot flowing through the solid-humic product; in a dryer ^'type tunnel; on an evaporator, - or any. drying means guaranteeing the operating conditions ^"set in. any of claims 28, 36 and 37.

39. Procedure,. Claim 28, characterized in that the means for selecting the material of step (s) comprises sieving. :

Process, in accordance with claim 39, characterized in that the screening is carried out on 100 mesh sieves. -. · ■ '

Process according to claim 28, characterized in that the calcination of step ^: t) is carried out for a period of time between 6 ^' and. -12 hours over a temperature range of 500 to 700 ° C.

42. Process according to any one of claims 28 is ^'41, characterized in that the calcination step .t) ^■ being preferably carried out by' a period of time between 6 and · 8.horas in a temperature range between 600 and 6 ^'50 ° C.

43. Process according to any one ^'of claims 28, 41 and 42, characterized in that the calcination step t) can be performed in static air in an oven; in a thermostatized bath; in a heat exchanger; through hot air - flowing through an evaporator spinner; or by any means which ensures heating in operating conditions ^"set forth in any one of ^claims' 28, 41 and 42.

4 Metal catalysts supported on PAH, characterized by the fact -de comprise metal content in a range between 3 and ^'12% (w / w), specific surface area of between 2:29 nv-g ^-1 average crystallite .tamanho understood 'between _. 19:21 nm with a concentration of acid sites ^¾ between 0 and 1.5 pmolpiridina ^'rrr ^2' and ■ a concentration of basic sites between 1.2 and 4.6. pmolco ² m ^-2 ; and are obtained according to the ^steps' described in claims 28-43.

45. Metal Catalysts supported on PAH according to claim 44, characterized by the fact comprise ^■ catalysts selected from among La / HAP and Na / PAH.

HAP-supported metal catalysts according to claim 45, characterized in that it preferably comprises a metal content of 3% w / w.

47. Using PAH-supported metal catalysts, ■

i

as defined in any one of claims 44 to 46, characterized in that they are for. application as process catalysts; for applications in which the acid-base properties of the solid · are instrumental in obtaining ^{'.preferencialmente} products that involve the formation of CH bonds and / or CO from renewable sources such as ethanol ;, in hydrocarbon production ^processes: fuel high molecular weight os for replacing fuels, ^'fossil origin and / or for the production of oxygenated hydrocarbons and non - oxygen ^■ useful in petrochemical industry.

48. PAH-supported metal catalyst comprising Lanthanum ^: (PA) supported on PAH, with metal content in a range from 3 to 12% La (w / w), specific surface area between 21 and 29 m ² g ^~ ¹ , average crystallite size between 19 and 21 nm, with an acid site concentration between 1.4 and 1.5 pmolpyridine m ^-2 and a basic site concentration between 1.6 and 1.7 ymolco2 m ^{~ 2} . ·

PAH-supported metal catalyst according to Claim 48, characterized in that it preferably comprises a metal content of 3 La (w / w), a specific surface area of 29 m ² g- ¹ , an average size of ^{crystallites'} of 19 nm at a concentration of acid sites molpiridina nr ² 1.5. and a basic site concentration of 1.7 pmolco2 rrr ² . <-

HAP-supported metal catalyst according to any one of claims 48 and 49, characterized in that it is La / HAP. ^'

Use of the PAH-supported metal catalyst as defined in any one of claims 48 to 5Q, characterized in that it is intended for application as a process catalyst for the production of a hydrocarbon mixture; Fuel high ^'molecular weight from ethanol with the number of carbon atoms between ^Cl- and C18 and power - lower calorific value> 39 MJ kg ^-1 order to replace ^the'. fuels of _. fossil origin; and as catalyst ^"process for the production of non - oxygenated hydrocarbons and oxygenated specific for the petrochemical industry, preferably for obtaining aromatics, olefins, alcohols" upper, ethers and ketones.

52. PAH-supported metal catalyst, characterized in that it comprises PAH-supported sodium (Na), with a metal content in the range 3 to 12% La (w / w), specific surface area of 2 to 5 m ² g ^{~ 1} , average size of crystallites between -19 and 21 nm, a concentration of basic sites between 1.2 and 4.6 mol / m ² and no acid sites.

53. PAH supported metal catalyst according .com to claim 52, characterized in that it comprises, preferably, ^■ metal content 3% Na (w / w), specific surface area ^"5m ² g ^_1, medium - sized of 21 nm crystallites; with a concentration a basic site concentration of 1.2 umolcc »rrr ² . _ ^■

54. HAP supported metal catalyst according to any of the. claims 52 and 53, characterized in that it is Na / PAH.

55. Use of PAH-supported metal catalyst as per

defined in any one of claims 52 to 5, characterized in that f t. be for the application as catalytic 'process for ^producing' a mixture of hydrocarbons; specific oxygenates for the petrochemical industry, preferably to obtain higher alcohols, aldehydes and ketones.

Process for obtaining combustible hydrocarbons characterized in that it is made from ethanol on at least one apatite-type catalyst selected from the group comprised of apatite-type mass catalysts as defined in any one of claims 17, 19 and 19. , 20, 22, 23, 25 ie 26; and PAH-supported metal catalysts as described in any of claims A 'Ã, 45, 46, 48, 49, 50, 52, 53, 54; and comprises a continuous flow reaction system in gas phase and under pressure ^{"atmospheric.}

57. Combustible hydrocarbons characterized in that said combustible hydrocarbons comprise unoxygenated and oxygenated hydrocarbons having a number of carbon atoms between Cl and C18.

Combustible hydrocarbons according to claim 53, characterized in that they comprise _. preferably condensable combustible hydrocarbons having a carbon number of from C5 to C18,

A process for obtaining combustible hydrocarbons comprising apatite catalysts selected from the group comprised of apatite mass catalysts as defined in any one of claims 17, 19, 20, 22, 23, 25- and 26; and PAH supported metal catalysts as described in any one of the claims _. 44, 45, 46, 48, 49, 50, 52, 53, 54; and the following steps: i. Addition of the apatite catalyst, the mass of said catalyst being a function of the W / FEtanoi ratio in a reactor having structural characteristics capable of operating at a temperature of 800 ° C or more and at a pressure of up to 2 atmospheres;

ii. Subjecting said catalyst to a continuous flow of an inert gas;

iii. Ethanol evaporation;

iv. Sending the gas mixture produced in step iii) to the reactor of step i) containing the catalyst at the reaction temperature;

v. Obtaining a mixture of Cl - C18 combustible hydrocarbons.

Process for obtaining combustible hydrocarbons according to claim 59, characterized in that the addition of step i), expressed as a function of the W / FEtanoi ratio, comprises from 0,02 to 0,16 kg hrnol ^-1 .

61. The process for obtaining combustible hydrocarbons according to claim 60, wherein the addition of step i), expressed as a function of the W / F _E ratio, preferably comprises 0.04 kg h mol ^{". 1} .

Process for obtaining combustible hydrocarbons according to claim 59, characterized in that the reactor of step i) comprises a quartz reactor.

63. The process for obtaining combustible hydrocarbons according to claim 59, characterized in that the continuous flow of step ii) preferably comprises N _{2 (} the inert gas flow being a function of the ratio W / F _E tanoi). according to claims 55 and 56, within a reaction temperature range of 300 to 600 ° C.

64. Process for obtaining combustible hydrocarbons according to claim 59, characterized in that that the evaporation of step iii) comprises an inert gas bubbling in ethanol, absolute anol, and a- mixture of ethanol vapor and inert gas is passed ^'through a condenser.

65. A method for obtaining hydrocarbons fuels, according ^to:; any one of claims 59 to 64, characterized by the fact that the evaporation of step iii) is carried out in a ^'evaporator. ^"

66. Process for obtaining. combustible hydrocarbons according to any one of claims 59, 64 and 65, characterized in that the bubbling of the inert gas is carried out in absolute ethanol while maintaining the evaporator in a temperature range of 40 to 84 ° C, wherein the vapor mixture of ethanol and N 2 generated in the evaporator is passed through; of a condenser maintained at a temperature of 30 to 74 ° C.

Process for obtaining combustible hydrocarbons according to any one of claims 59, 64-65, characterized in that the ethanol concentration is in the range of 10 to 75%.

68. Combustible hydrocarbons, characterized in that they comprise a mixture of unoxygenated and oxygenated hydrocarbons having a number of carbon atoms between Cl and C18 and a lower calorific value between 31,9 and 41,3 MJ kg- ¹ , preferably between 37.7 ^" and 41.3 MJ kg ^-1 ; and are obtained according to the steps described in claims 59 to 67.

69. Combustible hydrocarbons according to. to claim 66, characterized in that they comprise, preferably, a mixture of non - oxygenated hydrocarbons and oxygenated .com ^'number of carbon atoms between _C5. and C18.

70. Use of hydrocarbon fuels ^■ as defined in claim 69, characterized by being applied as substitutes for fossil fuels and as a source for obtaining specific products for the petrochemical industry (eg, aromatics, dienes, olefins, paraffins, alcohols, aldehydes, ethers, ketones, phenols).

71. A process for obtaining combustible hydrocarbons comprising apatite catalysts selected from the group consisting of apatite mass catalysts and PAH supported metal catalysts; and the following steps:

i. Preparation of apatite-type mass catalysts, said preparation comprising the following sub-steps:

The. Preparation of at least two aqueous precursor solutions, the first of which is Ca ^{+ 2} ions, and a second solution is the basis of any ion selected from the group consisting of P04 ⁺³ ions, CO3 ^"2 ions and F ions. ^~ ;

B. Controlled addition of the first aqueous precursor solution obtained in step a) to the second aqueous precursor solution obtained in step a);

ç. Means for allowing completion of the reaction in the reaction medium obtained in step b);

d. Cooling of the resulting medium obtained in step c) to room temperature and at rest; and. Separation of precipitate from aqueous phase containing unreacted ions;

f. Obtaining a wet paste;

g. Drying the wet paste in step f);

H. Grinding of the dried material obtained in step g); i. Means for selecting the shredded material in step h) by particle size;

j. Calcination of the material selected in step i); k. Obtaining apatite-type mass catalyst, said catalyst comprising any one selected from hydroxyapatite-type mass catalyst (PAH); carbonate hydroxyapatite mass catalyst (CHAP); and fluorapatite mass catalyst (FAP);

Alternatively, preparation of HAP-supported metal catalysts from hydroxyapatite-type (HAP) mass catalysts, as obtained in step k), and comprising the following sub-steps:

1) Preparation of an aqueous precursor solution based on any ion selected from La ^{+ 3} and Na ⁺ ; (m) Insertion of the hydroxyapatite mass catalyst (PAH) as obtained in step (k) into equipment capable of generating a uniform mixture of the support with the precursor solution of the metal to be impregnated;

p) Obtaining a solid-wet product;

q) Drying of the solid-wet product obtained in step

P ⁾ ;

r) Grinding the dry material obtained in step q); (s) means for selecting the ground material in step h) by particle size; t) Calcination of the material selected in step s); (u) Obtaining metal catalyst supported on

PAH;

Addition of any apatite-type catalyst selected from the group comprised of hydroxyapatite-type mass catalyst (PAH); type mass catalyst carbonate hydroxyapatite (CHAP); type catalyst mass f1 ^'uorapatita (PAF); and PAH supported metal catalyst in a reactor, the mass of said catalyst being a function of the W / FEtanoi ratio,

iv. Subjecting said catalyst to a continuous flow of an inert gas;

v. Evaporation of absolute ethanol;

saw. Sending the gas mixture produced in step v) to the reactor of step iii) containing the catalyst at the reaction temperature;

vii. Obtaining a mixture of combustible hydrocarbons

Cl - C18.

Combustible hydrocarbons, characterized in that it is obtainable by the process of obtaining combustible hydrocarbons as defined in claim 71.

Use of the combustible hydrocarbon as defined in claim 72, characterized in that it is applied as a substitute for fossil fuels.

Use of the combustible hydrocarbon as defined in claim 72, characterized in that it is in the preparation of products specific to the petrochemical industry (e.g., aromatics, dienes, olefins, paraffins, alcohols, aldehydes, these, ethers, ketones, phenols).