Alkylated hydrogen-rich automotive fuel and method for its production

Abstract

The application discloses alkylated hydrogen-rich vehicle fuel and a preparation method thereof, the raw material of the alkylated hydrogen-rich vehicle fuel comprises methanol, hydrogen activation release aids, polyisobutylene succinimide and di-tert-butyl peroxide; the production process comprises the following steps: preparation of hydrogen activation release aids, preparation of a primary catalyst, heat treatment and alkylation reaction of methanol, primary catalysis and secondary catalysis of methanol derivatives; the hydrogen-rich fuel production is integrated into a three-stage series process of methanol alkylation, primary catalysis dehydration and deoxidation and secondary catalysis reforming, and the problems of long traditional process flow, high risk of high temperature and high pressure, and serious hydrogen loss are overcome; the decyl trimethyl ammonium bromide-ammonia borane nano microsphere aid is prepared, the cleaner and the antioxidant are integrated, the controllable hydrogen release at high temperature, the stable storage at normal temperature, the oxidation inhibition and the carbon deposition inhibition are realized, and the fuel performance is improved; the multi-element synergistic catalyst is prepared, the acid site is regulated, the metal is anchored and the pore channel is constructed, and the high methanol conversion is realized.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of clean fuel for vehicles and preparation technology, and particularly relates to an alkylated hydrogen-rich fuel for vehicles and a preparation method thereof. BACKGROUND

[0002] With the increasingly stringent environmental regulations and the demand for energy structure transformation, the traditional gasoline fuel has increasingly prominent problems of low combustion efficiency and large amount of pollutant emissions. Methanol, as a low-carbon raw material with a wide source and a high hydrogen content, which can be prepared from coal, natural gas and biomass, is regarded as one of the ideal raw materials for replacing vehicle fuel.

[0003] The current methanol modification technology for preparing light hydrocarbons has the following limitations: firstly, the catalyst performance is insufficient, the existing methanol alkylation catalysts are mainly single metal supported types, and have the problems of uneven distribution of active sites, high reaction temperature and high generation rate of by-products; secondly, the process complexity is high, and the catalytic hydrogenation process is needed, and a plurality of reaction equipment is required, so the process is long and the equipment investment cost is high; finally, the reaction needs high temperature and high pressure, and the corrosion and leakage risk coefficient of the equipment is high, although the methanol itself has a high hydrogen content, the hydrogen element is easily lost in the form of water in the existing preparation process, so that the hydrogen-carbon ratio of the final fuel is less than or equal to 1.5, and the advantages of high combustion efficiency and low emission of the hydrogen-rich fuel cannot be fully played.

[0004] Therefore, it is an urgent problem to be solved in the current industry to develop a vehicle fuel preparation technology based on methanol raw material, which can realize high-selectivity alkylation reaction and improve the hydrogen-rich characteristics and comprehensive performance of the fuel. SUMMARY

[0005] The present application aims at solving the problems in the prior art and provides an alkylated hydrogen-rich fuel for vehicles and a preparation method thereof.

[0006] In order to achieve the above-mentioned purpose, the present application adopts the following technical scheme:

[0007] The preparation method of the alkylated hydrogen-rich fuel for vehicles comprises the following steps:

[0008] S1, preparation of hydrogen activation release aid

[0009] A sodium hydroxide alkaline aqueous solution with a pH of 11 is prepared, 15% of ammonia borane in the total system is added, and the ammonia borane alkaline aqueous solution is dissolved by stirring, then the ammonia borane alkaline aqueous solution is added dropwise into an equal volume of decyl trimethyl ammonium bromide aqueous solution, and then the mixed solution is added dropwise into an equal volume of dodecane, emulsified at room temperature, separated, and dried overnight in a dynamic vacuum environment to obtain ammonia borane nanospheres, which are hydrogen activation release aids;

[0010] In an alkaline aqueous solution, the hydrolysis of ammonia borane is inhibited, and ammonia borane can exist stably. Water is used as a solvent, avoiding the toxicity and volatility of organic solvents, and providing a continuous phase for subsequent micelle formation. Decyl trimethyl ammonium bromide, as a cationic surfactant, has a molecular structure containing a hydrophilic head and a hydrophobic tail, and can form a reverse micelle structure. Ammonia borane is dissolved in the water core inside the reverse micelle. The size of the water core limits the growth of ammonia borane crystals. The smaller the water core space, the more inhibited the growth of ammonia borane particles. Finally, nanoscale particles are formed. Then, the mixed solution is dropped into dodecane. Dodecane is completely immiscible with water and the water phase is dispersed into small droplets. The decyl trimethyl ammonium bromide molecules form a monolayer on the surface of the droplets. The hydrophilic head is adsorbed on the surface of the ammonia borane crystal through electrostatic or coordination interaction. The hydrophobic tail interacts with the dodecane phase, preventing the diffusion of ammonia borane particles in the reverse micelle to the dodecane phase, and avoiding the agglomeration of adjacent ammonia borane particles. Each reverse micelle grows independently into a single nanosphere. During the separation operation, the ammonia borane nanospheres are in the water phase and are separated from dodecane. After the vacuum drying step, water and dodecane are further removed. The decyl trimethyl ammonium bromide micelles gradually shrink with the evaporation of the solvent, forming a rigid shell, and finally forming a nanosphere structure of decyl trimethyl ammonium bromide shell-ammonia borane core.

[0011] The ammonia borane nanospheres, polyisobutylene succinimide, and di-tert-butyl peroxide are ground and compounded. The decyl trimethyl ammonium cation on the surface of the ammonia borane nanospheres is combined with the succinimide group (-CONH-) in the polyisobutylene succinimide molecule through hydrogen bonding. The polyisobutylene segment extends outward and forms a three-dimensional barrier on the surface of the nanosphere. Adjacent microspheres cannot approach due to the steric hindrance of the hydrophobic chain, avoiding agglomeration. At the same time, polyisobutylene succinimide can adsorb trace amounts of metal impurities in the fuel, avoiding the catalysis of impurities on the hydrolysis of ammonia borane, and further improving the storage stability of the composite additive. Di-tert-butyl peroxide generates a tert-butoxy radical at a higher temperature, attacks the B-H bond in the core of the ammonia borane nanosphere, reduces the hydrogen release activation energy of ammonia borane through radical hydrogen abstraction, activates the hydrogen release of ammonia borane, and can also preferentially combine with fuel oxidation radicals to inhibit the further oxidation of fuel components, maintaining the stability of the fuel.

[0012] S2, Preparation of a primary catalyst

[0013] In deionized water, add tetrapropyl ammonium bromide, stirring, then add pseudoboehmite, stirring for 30 min, finally add coarse-pore silica gel, continue stirring for 3 h to form a gel mixture, pre-crystallize at 100 ℃ for 18 h, crystallize at 170 ℃ for 12 h, cool, wash with water, filter until the pH of the filtrate is 7, dry, calcine at 550 ℃ for 4 h, mix with 1 mol / L NH4Cl solution at a mass ratio of 1:20, stir in a 90 ℃ water bath for 2 h, repeat 3 times, filter, dry, and calcine. Dissolve zinc nitrate and lanthanum nitrate by ultrasonic, add to the calcined porous zeolite, stir and ultrasonic for 5 min each time, stand at room temperature for 15 h, dry for 2 h, then put it into a dissolved diammonium hydrogen phosphate solution, stir in a 90 ℃ oil bath until the solution is evaporated, dry for 8 h, and calcine to obtain a primary catalyst;

[0014] Pseudoboehmite is dispersed in water, and Br - in tetrapropyl ammonium bromide has a weak interaction with Al-O bond, promoting the dissociation of Al-O bond, while the cation ((C4H9)3N + ) of tetrapropyl ammonium bromide is adsorbed on the surface of pseudoboehmite, reducing the energy of Al-O bond, so that Al 3+ exists in the form of [Al(OH)4] - in aqueous solution, avoiding Al(OH)3 precipitation:

[0015] AlOOH·nH2O+H2O+Br - →[Al(OH)4] - +H + +Br - +nH2O

[0016] [Al(OH)4] - releases OH - , attacking the silicon dioxide molecules on the surface of silica gel, gradually dissociating the skeleton to form monodentate or bidentate silicon hydroxyl groups, providing active sites for subsequent condensation:

[0017] SiO2+2H2O+OH - →[SiO(OH)3] - +H2O

[0018] [Al(OH)4] - generated by hydrolysis reacts with [SiO(OH)3] - to form Si-O-Al bonds, constructing a precursor gel, and the cation ((C4H9)3N + ) of tetrapropyl ammonium bromide is adsorbed on the surface of the silica-aluminum condensation product by electrostatic interaction, forming a complex micelle, and the micelles are aggregated by van der Waals force, finally forming a uniform gel, and the hydrophobic chain (C4H9 - ) of tetrapropyl ammonium bromide is oriented, providing spatial orientation for the subsequent ten-membered ring pore structure of the catalyst:

[0019] [SiO(OH)3] - +[Al(OH)4] - →(HO)3Si-O-Al(OH)3 2- +H2O

[0020] (HO)3Si-O-Al(OH)3 2- +n[SiO(OH)3] - →[Si n+1 AlO 3n+4 (OH) 3n+3 ] (n+2)- +nH2O

[0021] At 100℃, the slow diffusion of the silicon aluminum species in the micelles forms crystal nucleus, and tetrapropyl ammonium bromide inhibits the excessive growth of the crystal nucleus; at 170℃, the crystal nucleus grows, the Si-O-Al skeleton is gradually perfected, the ten-membered ring channel structure is formed, and the cations of tetrapropyl ammonium bromide are locked in the channel due to the space matching, thereby maintaining the stability of the crystal structure; in the calcination stage, when the temperature is increased to 200-300℃, the C-N bond of tetrapropyl ammonium bromide is broken to generate (C4H9)2NH, C4H8 and other intermediates; when the temperature is continuously increased to 400-550℃, the intermediates are completely oxidized into CO2, H2O and N2, which are removed from the micropores, leaving empty channels, and Na + still occupies the cation site outside the skeleton, at this time, the sodium ion acts as an exchange ion and has no activity; after NH4Cl impregnation, NH4 + diffuses into the catalyst channel driven by the concentration difference, and is electrostatically exchanged with Na + outside the skeleton, NH4 + is decomposed into NH3 and H + at 400℃ or above, H + forms a Si-OH-Al structure with AlO4 - of the catalyst skeleton, which is a B acid core active site for subsequent dehydration and deoxidation reactions;

[0022] Ultrasonic treatment destroys the aggregate state of zinc nitrate and lanthanum nitrate to form monodisperse metal ions, which are adsorbed on the negatively charged catalyst surface through electrostatic action or form coordination bonds with Si-OH, and are allowed to diffuse into the micropores for 15h at room temperature, after drying and calcination, the nitrate is decomposed into metal oxides, ZnO reacts with the B acid site (Si-OH-Al) to form a Zn 2+ -O-Al structure, which adjusts the acid strength, reduces the proportion of strong acid sites, and inhibits carbon deposition, and La2O3 covers part of the weak acid sites to further optimize the acid site distribution; when the diammonium hydrogen phosphate solution is impregnated, (NH4)2HPO4 is hydrolyzed into HPO4 2- , which reacts with Zn 2+La 3+ Forming soluble phosphate precursor, evenly dispersed on the surface of zeolite with water evaporation, after calcination, HPO4 2- Dehydration to form P2O5 species, reaction with ZnO, La2O3 to form Zn2P2O7, LaPO4 complex phase, which can anchor Zn 2+ La 3 + , prevent metal particles sintering, with the zeolite framework, reduce the number of strong acid sites, inhibit the excessive cracking of long-chain intermediates, block part of the micropore entrance, form the transition of microporous-mesoporous channels, improve the mass transfer efficiency;

[0023] S3, preparation of hydrogen-rich fuel for vehicles

[0024] The pretreated methanol is treated at 80-90℃ for 1-2h, which is converted into steam, and reacted with the activated molecular sieve under vacuum for 45min, isobutane gas is introduced for reaction, and 1-4% of polyisobutylene succinimide based on the total amount of the system is added, and the methanol alkylation is completed at room temperature for 1.5h. The activated primary catalyst is loaded in the catalytic column one, the air in the column is purged with nitrogen, and the methanol chain extension product is gradually transferred to the column. The temperature is increased to 180℃ at a rate of 10℃ / min, and the reaction is carried out in the second column. The ice water is loaded in the second column, and the liquid is separated to complete the primary catalysis. The Pt supported SAPO catalyst is loaded in the second column, hydrogen is introduced, the product in the second column is introduced, the temperature is increased to 250℃, and the reaction is carried out under the pressure of 2-3Mpa. The condenser is introduced to complete the secondary catalysis. 0.5-5% of hydrogen activation release aid and 0.5-3% of di-tert-butyl peroxide based on the total amount of the system are added, and the mixture is stirred uniformly to complete the preparation of hydrogen-rich fuel for vehicles.

[0025] The intermolecular hydrogen bond of dry methanol is destroyed at 80-90℃, which facilitates the subsequent reaction. Under the action of HFER molecular sieve, methanol and isobutane undergo alkylation reaction. Methanol or ethanol is adsorbed on the acid site and immediately converted into surface methoxy species, which belongs to carbonium ion intermediate. In the initial stage of the reaction, the polarized methyl attacks the primary C-H bond of isobutane to form a non-classical carbonium ion transition state. In the transition state, the central H atom forms a three-center two-electron bond with the polarized methyl carbon and the carbon of isobutane. The positive charge is delocalized on the two carbons. In the middle stage of the reaction, the C-H bond of the transition state breaks the C-O bond of the surface methoxy group, and a negative hydrogen transfer or alkylation reaction occurs to generate isopentane or neopentane. Due to the steric hindrance of the isobutyl group and the surface methoxy group, isopentane is mainly generated. The isobutyl carbonium ion is not stable and is prone to β-scission to generate propane and methyl carbonium ion, or deprotonation to generate isobutene, which can be activated with the surface methoxy group in the subsequent reaction.

[0026]

[0027] Table 1 Reaction one-pot product component table

[0028]

[0029] The catalytic column is filled with self-made primary catalyst, which is a porous silicoaluminate zeolite as a carrier, loaded with zinc, lanthanum and phosphorus elements. In the framework of the zeolite, both silicon and aluminum undergo sp 3 Hybridization, the hybrid orbitals are respectively composed of tetrahedrons, and each five tetrahedrons form a five-membered ring under the participation of oxygen bridge bonds, and eight five-membered rings share an edge to form a "connecting tetrahedron", which is the basic structural unit of the zeolite. The basic structural units share edges to form a chain structure, and the existence of oxygen bridges causes the chain structure to form a sheet according to a symmetrical relationship, and the secondary helix of the sheet forms a three-dimensional framework structure. The zeolite has two different channels, one is a straight-through channel with an elliptical cross-section, and the other is a Z-shaped channel with a circular cross-section. The two channels intersect with each other, and the unique three-dimensional intersecting channel structure can provide spatial restriction for shape-selective catalysis, and also provide more channels for the entry and exit of reactants and products, thereby controlling the carbon number of the product within the required range.

[0030] The Zn-La-P three elements in the catalyst complement each other through active sites, control the acid strength, and stabilize the structure, and cooperatively adapt to the chain extension demand of methanol. Zn provides L acid sites and cooperates with La to activate the C-H bond of isobutane, thereby reducing the bond energy and promoting the transfer of negative hydrogen. At the same time, La covers part of the weak acid sites to control the density of B acid sites to 0.3-0.5 mmol / g and the proportion of medium-strength acid sites to ≥80%, thereby avoiding excessive cracking caused by strong acid and generating C5 or less alkanes. P anchors Zn 2+ and La 3+ in the form of phosphate, prevents the agglomeration of metal ions, slightly reconstructs the pore channel of the molecular sieve to improve the connectivity between micropores and mesopores, and reduces the mass transfer resistance of methanol / isobutane. Under the combined action of the three, the methanol is efficiently generated into surface methoxy intermediates, and the isobutane is directionally alkylated, and the carbon chain is precisely chain-extended to C8-C9 oxygen-containing compounds, while the carbon deposition and side reactions are inhibited.

[0031] The remaining unreacted methanol undergoes a nucleophilic substitution reaction on the B acid sites of the catalyst to generate dimethyl ether by removing one molecule of water. The dimethyl ether or methanol continues to react with the acid sites to generate surface methoxy species. Through a series of complex carbonium ion or free radical mechanisms, the first C-C bond is formed to generate the initial olefin or aromatic hydrocarbon precursor. These substances act as co-catalysts, constantly reacting with methanol or dimethyl ether to methylate and crack them, like an assembly line, to continuously generate low-carbon olefins such as ethylene and propylene, and byproducts such as water, which is removed through ice water and 4A molecular sieve.

[0032] 2CH3OH→2CH3OCH3

[0033] CH3OCH3→ C2H4 + C3H6 + C4H8 + H2O

[0034] In the primary catalysis, isopentane gets a proton on the B acid site of the catalyst to form a tertiary pentyl carbocation, which breaks the C-C bond at the β position to form more stable isobutene and a smaller methyl carbocation, and also forms propylene and an ethyl carbation, the isobutene is protonated to form a tertiary butyl carbocation, and the carbocation further undergoes electrophilic addition with another molecule of isobutene to form C8 alkanes, and the generated olefins further undergo hydrogen transfer, alkylation, condensation and other reactions to form various substances shown in Table 2;

[0035]

[0036] Table 2 Primary catalysis product component table

[0037]

[0038] The generated water and alcohol ether substances are removed in the condenser, and other products enter the catalytic two-tower, and undergo catalytic reforming reaction under the Pt supported SAPO catalyst. On the acid sites of the catalyst, saturated alkanes form carbon cations, rearrange to form more stable structures, and hydrogen molecules dissociate and chemisorb on the metal active center, and H-H bonds are broken into two adsorbed hydrogen atoms. At the same time, olefins are coordinated and adsorbed on the metal center through double bond π electrons, weakening the π bond. Subsequently, one adsorbed hydrogen atom is transferred to one carbon atom of the olefin to form a semi-hydrogenated alkyl intermediate; another adsorbed hydrogen atom continues to transfer to the remaining carbon atom of the intermediate to complete hydrogenation to form an adsorbed saturated alkane, and finally the alkane desorbs from the metal surface into the gas phase, and the active site is regenerated. In order to tend to be thermodynamically stable, the carbon cation rapidly isomerizes, and then electrophilically attacks the double bond of other olefin molecules to undergo polymerization to form longer carbon cations, and the newly generated carbon cations again optimize the stability by rearrangement, and the degree of polymerization is precisely limited by the pore space of the modified molecular sieve, mainly generating C5-C11 carbon cations.

[0039] Table 3 Secondary catalysis product component table

[0040]

[0041] Preferably, the hydrogen activation release aid can controllably release high-activity hydrogen gas in the high-temperature and high-pressure environment of the engine cylinder, so that the combustion is faster and more complete; the cleaning dispersant (polyisobutylene succinimide) has a polar group at one end of the molecular structure, which can be firmly adsorbed on the surface of the carbon deposit and gum; the other end is a non-polar long chain, which can be dissolved in fuel to disperse the deposits into small particles and burn them out with the fuel; the antioxidant (di-tert-butyl peroxide) prevents the fuel from contacting oxygen to generate gum and acidic substances.

[0042] Preferably, in the preparation process of the primary catalyst, the mass ratio of tetrapropylammonium bromide, pseudoboehmite, coarse-pore silica gel and water is 2:0.5:10:100, the zinc loading in the primary catalyst is 1.2%, the lanthanum loading is 0.5%, and the phosphorus loading is 0.5%.

[0043] Preferably, in the preparation process of the hydrogen activation release aid, the mass fraction of decyltrimethylammonium bromide in the aqueous solution of decyltrimethylammonium bromide is 0.4%, and the volume ratio of water to dodecane in the preparation of the hydrogen activation release aid is 1:1.

[0044] Preferably, the pretreatment method of the methanol is as follows: industrial-grade methanol is adsorbed with 4A molecular sieves to remove water, and then filtered with 0.2 mu ceramic membranes; and isobutane gas also needs to be treated with 4A molecular sieves before use.

[0045] Preferably, the molecular sieve used in the primary catalyst is HFER molecular sieve, and the activation method is as follows: the purchased molecular sieve is immersed in 1 mol / L ammonium nitrate solution, stirred at 80 DEG C for 5h, centrifuged, filtered, washed with deionized water, and the process is repeated for 3 times, dried, and calcined at 470 DEG C under vacuum for 4h.

[0046] Preferably, the prepared hydrogen-rich fuel for vehicles is C5-C11 light hydrocarbon components, the properties of the composite aid added at the beginning are stable, mainly to prevent carbon deposition on the surface of the catalyst and enhance the service life of the catalyst, the di-tert-butyl peroxide added subsequently prevents the oxidation of the fuel itself, the hydrogen activation aid improves the energy density and optimizes the combustion performance of the fuel, and the prepared fuel can be used alone or added to gasoline in any proportion.

[0047] Compared with the prior art, the present application has the following advantages:

[0048] 1. The process for producing the hydrogen-rich fuel of the present application is methanol alkylation, primary catalyst dehydration and deoxidation and secondary catalyst reforming, which reduces equipment investment and land occupation, has milder reaction conditions, reduces equipment corrosion and safety hazards, and inhibits hydrogen loss through the hydrogen activation release aid, so that the hydrogen-carbon ratio of the fuel is increased to 1.8-2.2, the combustion efficiency and pollutant emission reduction effect are remarkable, the traditional methanol modification technology for producing light hydrocarbons relies on multi-stage reaction equipment, has a long process and requires high temperature and high pressure, not only has large equipment investment, but also has serious corrosion and leakage risks, and hydrogen is easily lost in the form of water, so that the hydrogen-carbon ratio of the fuel is ≤1.5, and it is difficult to play the advantages of hydrogen enrichment.

[0049] 2, The hydrogen-activated release nanometer microsphere aid with a decyl trimethyl ammonium bromide shell and an ammonia borane core is prepared, which realizes controllable hydrogen release under high temperature and high pressure environment of the engine, greatly improves the normal temperature storage stability, burns boron hydride elements to release more energy, and the fuel product is pollution-free, and the hydrogen-activated release nanometer microsphere aid is integrated with anti-oxidation, combustion-supporting, cleaning and dispersing functions, and the like, the di-tert-butyl peroxide can inhibit fuel oxidation and promote complete combustion, and the polyisobutylene succinimide can remove carbon on the surface of the engine and catalyst and protect ammonia borane from catalytic hydrolysis of impurities, so that the comprehensive performance of the fuel is improved.

[0050] 3, The primary catalyst prepared in the application realizes synergistic effect of Zn, La and P three elements, Zn and La accurately regulate acid site strength and distribution, so that the proportion of medium strength B acid site is greater than or equal to 80%, excessive cracking reaction is inhibited, P anchors metal ions in the form of composite phosphate to prevent agglomeration, and a micropore-mesopore transition channel is also constructed to improve mass transfer efficiency, so that the selectivity of methanol-isobutane alkylation is greater than or equal to 85%. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 The process flow chart for producing hydrogen-rich vehicle fuel of the application is shown in the figure;

[0052] Figure 2 The equipment connection diagram for producing hydrogen-rich vehicle fuel of the application is shown in the figure;

[0053] Figure 3 The structure schematic diagram of the hydrogen-activated release aid produced by the application is shown in the figure. DETAILED DESCRIPTION

[0054] The technical solutions in the embodiments of the application will be clearly and completely described below with reference to the drawings in the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments of the application.

[0055] Embodiment 1:

[0056] S1, Preparation of hydrogen-activated release aid

[0057] A sodium hydroxide alkaline aqueous solution with a pH of 11 is prepared, 15% of ammonia borane in the total system is added, and the ammonia borane alkaline aqueous solution is stirred and dissolved, then the ammonia borane alkaline aqueous solution is added dropwise into an equal volume of decyl trimethyl ammonium bromide aqueous solution, and then the mixed solution is added dropwise into an equal volume of dodecane, emulsified at room temperature, separated, and dried in a dynamic vacuum environment overnight to obtain ammonia borane nanometer microspheres, that is, the hydrogen-activated release aid;

[0058] S2, Preparation of primary catalyst

[0059] In deionized water, add tetrapropyl ammonium bromide in turn, stirring while adding, then add pseudoboehmite, stirring for 30 min, finally add coarse-pore silica gel, continue stirring for 3 h to form a gel mixture, pre-crystallize at 100℃ for 18 h, crystallize at 170℃ for 12 h, cool, wash with water, filter under suction until the pH of the filtrate is 7, dry, calcine at 550℃ for 4 h, mix with 1 mol / L NH4Cl solution at a mass ratio of 1:20, stir in a 90℃ water bath for 2 h, repeat 3 times, filter under suction, dry, and calcine; after ultrasonic dissolution of zinc nitrate and lanthanum nitrate, add the calcined porous zeolite, stir and ultrasonic for 5 min each time, stand at room temperature for 15 h, dry for 2 h, then put it into the dissolved diammonium hydrogen phosphate solution, stir in a 90℃ oil bath until the solution is evaporated to dryness, dry for 8 h, and calcine to obtain a primary catalyst;

[0060] S3, preparation of hydrogen-rich fuel for vehicles

[0061] The pretreated methanol is treated at 85℃ for 1.5 h, converted into steam, reacted with the activated molecular sieve under vacuum for 45 min, isobutane gas is introduced for reaction, 2.5% polyisobutylene succinimide based on the total system is added, and the methanol alkylation is completed at room temperature for 1.5 h. The activated primary catalyst is filled in the catalysis one column, the air in the column is purged with nitrogen, and the methanol chain extension product is gradually transferred to the column. The temperature is increased to 180℃ at a rate of 10℃ / min, and ice water is filled in the reaction two column. The primary catalysis is completed, and the Pt supported SAPO catalyst is filled in the catalysis two column. Hydrogen is introduced, the product in the reaction two column is introduced, the temperature is increased to 250℃, and the reaction is carried out under 2.5Mpa. The condenser is introduced, the secondary catalysis is completed, 0.5% hydrogen activation release aid and 1.5% di-tert-butyl peroxide based on the total system are added, and the stirring is uniform. The preparation of hydrogen-rich fuel for vehicles is completed.

[0062] Example 2:

[0063] S1, preparation of hydrogen activation release aid

[0064] A sodium hydroxide alkaline aqueous solution with pH of 11 is prepared, and 15% ammonia borane based on the total system is added and stirred and dissolved. The ammonia borane alkaline aqueous solution is added dropwise into an equal volume of decyltrimethylammonium bromide aqueous solution, and then the mixed solution is added dropwise into an equal volume of dodecane. Emulsification is carried out at room temperature, and the liquid is separated. The dynamic vacuum environment is dried overnight to obtain ammonia borane nanospheres, which is the hydrogen activation release aid.

[0065] S2, preparation of primary catalyst

[0066] In deionized water, add tetrapropyl ammonium bromide in turn, stirring while adding, then add pseudoboehmite, stirring for 30 min, finally add coarse-pore silica gel, continue stirring for 3 h to form a gel mixture, pre-crystallize at 100℃ for 18 h, crystallize at 170℃ for 12 h, cool, wash with water, suction filter until the pH of the filtrate is 7, dry, calcine at 550℃ for 4 h, mix with 1 mol / L NH4Cl solution at a mass ratio of 1:20, 90℃ water bath stirring for 2 h, repeat 3 times, suction filter, dry, calcine, dissolve zinc nitrate and lanthanum nitrate by ultrasonic, then add to the calcined porous zeolite, stirring and ultrasonic for 5 min each, stand at room temperature for 15 h, dry for 2 h, then put it into the dissolved diammonium hydrogen phosphate solution, 90℃ oil bath stirring until the solution is evaporated, dry for 8 h, calcine, finally obtain the primary catalyst;

[0067] S3, preparation of hydrogen-rich fuel for vehicles

[0068] The pretreated methanol is treated at 85℃ for 1.5 h, converted into steam, reacted with the activated molecular sieve under vacuum for 45 min, isobutane gas is introduced for reaction, 2.5% of polyisobutylene succinimide based on the total system is added, and the methanol alkylation is completed at room temperature for 1.5 h. The activated primary catalyst is filled in the catalysis one column, the air in the column is purged by nitrogen, and the methanol chain extension product is gradually transferred to the column. The temperature is increased to 180℃ at a rate of 10℃ / min, and ice water is filled in the reaction two column. The primary catalysis is completed, and the Pt supported SAPO catalyst is filled in the catalysis two column. Hydrogen is introduced, the product in the reaction two column is introduced, the temperature is increased to 250℃, and the reaction is carried out under 2.5Mpa. The condenser is introduced, the secondary catalysis is completed, 5% of hydrogen activation release aid and 1.5% of di-tert-butyl peroxide based on the total system are added, and the stirring is uniform. The preparation of hydrogen-rich fuel for vehicles is completed.

[0069] Example 3:

[0070] S1, preparation of hydrogen activation release aid

[0071] A sodium hydroxide alkaline aqueous solution with pH of 11 is prepared, and 15% of ammonia borane based on the total system is added and stirred and dissolved. The ammonia borane alkaline aqueous solution is added dropwise into an equal volume of decyltrimethylammonium bromide aqueous solution, and then the mixed solution is added dropwise into an equal volume of dodecane. Emulsification is carried out at room temperature, and the liquid is separated. The dynamic vacuum environment is dried overnight to obtain ammonia borane nanospheres, which is the hydrogen activation release aid.

[0072] S2, preparation of primary catalyst

[0073] In deionized water, add tetrapropyl ammonium bromide in turn, stirring while adding, then add pseudoboehmite, stirring for 30 min, finally add coarse-pore silica gel, continue stirring for 3 h to form a gel mixture, pre-crystallize at 100℃ for 18 h, crystallize at 170℃ for 12 h, cool, wash with water, filter under suction until the pH of the filtrate is 7, dry, calcine at 550℃ for 4 h, mix with 1 mol / L NH4Cl solution at a mass ratio of 1:20, stir in a 90℃ water bath for 2 h, repeat 3 times, filter under suction, dry, and calcine. Dissolve zinc nitrate and lanthanum nitrate by ultrasonic, add to the calcined porous zeolite, stir and ultrasonic for 5 min each time, stand at room temperature for 15 h, dry for 2 h, then put it into a solution of dissolved diammonium hydrogen phosphate, stir in a 90℃ oil bath until the solution is evaporated to dryness, dry for 8 h, and calcine. Finally, the primary catalyst is obtained.

[0074] S3, Preparation of hydrogen-rich fuel for vehicles

[0075] The pretreated methanol is treated at 85℃ for 1.5 h, converted into steam, reacted with the activated molecular sieve under vacuum for 45 min, isobutane gas is introduced for reaction, 2.5% of polyisobutylene succinimide based on the total system is added, and the methanol alkylation is completed at room temperature for 1.5 h. The activated primary catalyst is filled in the catalysis one column, the air in the column is purged with nitrogen, and the methanol chain extension product is gradually transferred to the column. The temperature is increased to 180℃ at a rate of 10℃ / min, the reaction two kettle is filled with ice water, and the primary catalysis is completed. The Pt supported SAPO catalyst is filled in the catalysis two column, hydrogen is introduced, the product in the reaction two kettle is introduced, the temperature is increased to 250℃, and the reaction is carried out under 2.5Mpa. The condenser is introduced, the secondary catalysis is completed, 3% of hydrogen activation release aid and 1.5% of di-tert-butyl peroxide based on the total system are added, and the preparation of hydrogen-rich fuel for vehicles is completed.

[0076] Comparative example 1:

[0077] S1, Preparation of hydrogen activation release aid

[0078] A sodium hydroxide alkaline aqueous solution with pH of 11 is prepared, 15% of ammonia borane based on the total system is added, and stirred and dissolved. The ammonia borane alkaline aqueous solution is added dropwise into an equal volume of decyltrimethylammonium bromide aqueous solution, and then the mixed solution is added dropwise into an equal volume of dodecane. Emulsification is carried out at room temperature, and the solution is dried under dynamic vacuum overnight to obtain ammonia borane nanospheres, which is the hydrogen activation release aid.

[0079] S2, Preparation of primary catalyst

[0080] In deionized water, add tetrapropyl ammonium bromide in turn, stirring while adding, then add pseudoboehmite, stir for 30 min, finally add coarse-pore silica gel, continue stirring for 3 h to form a gel mixture, pre-crystallize at 100 ℃ for 18 h, crystallize at 170 ℃ for 12 h, cool, wash with water, suction filter until the pH of the filtrate is 7, dry, calcine at 550 ℃ for 4 h, mix with 1 mol / L NH4Cl solution at a mass ratio of 1:20, stir in a 90 ℃ water bath for 2 h, repeat 3 times, suction filter, dry, and calcine. Dissolve zinc nitrate and lanthanum nitrate by ultrasonic, add to the calcined porous zeolite, stir and ultrasonic for 5 min each time, stand at room temperature for 15 h, dry for 2 h, then put it into a solution of dissolved diammonium hydrogen phosphate, stir in a 90 ℃ oil bath until the solution is evaporated to dryness, dry for 8 h, and calcine to obtain a primary catalyst;

[0081] S3. Preparation of hydrogen-rich fuel for vehicles

[0082] The pretreated methanol is treated at 85 ℃ for 1.5 h, converted into steam, reacted with the activated molecular sieve under vacuum for 45 min, and isobutane gas is introduced for reaction, and 2.5% of polyisobutylene succinimide based on the total system is added, and the methanol alkylation is completed at room temperature for 1.5 h. The activated primary catalyst is filled in a catalytic column one, the air in the column is purged with nitrogen, and the methanol chain extension product is gradually transferred to the column. The temperature is increased to 180 ℃ at a rate of 10 ℃ / min, and ice water is filled in a reaction column two to separate the liquid. The primary catalysis is completed. The Pt supported SAPO catalyst is filled in a catalytic column two, hydrogen is introduced, the product in the reaction column two is introduced, the temperature is increased to 250 ℃, and the reaction is carried out under 2.5 MPa. A condenser is introduced, the secondary catalysis is completed, 7% of hydrogen activation release aid and 1.5% of di-tert-butyl peroxide based on the total system are added, and stirring is uniform. The preparation of the hydrogen-rich fuel for vehicles is completed.

[0083] Comparative Example 2

[0084] Compared with Example 3, no hydrogen activation release aid is added to the fuel.

[0085] Comparative Example 3

[0086] Compared with Example 3, ammonia borane is directly added to the fuel.

[0087] Comparative Example 4

[0088] Compared with Example 3, no anti-oxidation and corrosion agent di-tert-butyl peroxide is added to the fuel.

[0089] Comparative Example 5

[0090] Compared with Example 3, no clean dispersant polyisobutylene succinimide is added to the fuel.

[0091] Comparative Example 6

[0092] Compared with Example 3, the self-made primary catalyst is used for primary catalysis and secondary catalysis.

[0093] Performance test:

[0094] According to the standards and detection methods of GB / T 6536-2010 "Determination of Distillation Characteristics of Petroleum Products", GB / T 1884-2000 "Laboratory Determination of Density of Crude Oil and Liquid Petroleum Products", GB / T 503-2016 "Determination of Octane Number of Gasoline by Motor Method", GB18352.6-2016 "Light-Duty Vehicle Emission Limit Values and Measurement Methods (China Phase VI)", and GB / T 5096-2017 "Copper Strip Corrosion Test Method for Petroleum Products", the distillation range, density, octane number, combustion emission, corrosion resistance and other performances of the hydrogen-rich vehicle fuel produced in each group are determined.

[0095] Table 4 Performance test data of hydrogen-rich vehicle fuel produced in each group

[0096]

[0097] Figure 1 and Figure 2 respectively are the process flow chart and equipment connection chart for producing hydrogen-rich vehicle fuel of the present application. The present application adopts a three-stage series process of methanol alkylation, primary catalytic dehydration and deoxidation, and secondary catalytic reforming. The pretreated methanol (dehydrated by 4A molecular sieve and filtered by ceramic membrane) is vaporized at 80-90℃, reacts with activated HFER molecular sieve and isobutane in a vacuum environment, and polyisobutylene succinimide (cleaning dispersant) is added synchronously. The alkylation reaction of the surface methoxy species generated by methanol and isobutane completes the chain extension of carbon chain, laying the foundation for the carbon skeleton of subsequent light hydrocarbon generation. Then, the chain extension product enters the catalytic one tower filled with primary catalyst, and is heated to 180℃ at a rate of 10℃ / min. Under the synergistic action of medium-strength B acid sites and metal sites in the catalyst, the oxygen-containing groups such as hydroxyl and ether bond in the product are removed, while excessive cracking is inhibited. The ice water in the second reactor further separates the unremoved water and a small amount of alcohol ether. Finally, the intermediate product enters the catalytic two tower filled with Pt supported SAPO catalyst, and is subjected to directional reforming to C5-C11 light hydrocarbon at 250℃, 2-3MPa and in a hydrogen atmosphere through the hydrogenation activity of Pt metal sites and the isomerization / shape-selective action of SAPO acid sites. Hydrogen activation release aid and di-tert-butyl peroxide are finally added to complete the preparation of hydrogen-rich vehicle fuel. The three-stage process is closely linked, realizing the continuousness of "chain extension-deoxidation-refining", reducing equipment occupation and material loss.

[0098] Figure 3 is the structural schematic diagram of hydrogen activation release aid produced by the present application. The hydrophilic head of the outer decyltrimethylammonium bromide (CH3)3N +) and electrostatic double action with the N-H bond of the core ammonia borane, which not only fixes the ammonia borane crystal to avoid its migration, but also does not destroy the B-H bond, ensuring the stability of the core at room temperature. The hydrogen-activated release aid of the core-shell structure is stored stably at room temperature and releases hydrogen controllably at high temperature, thereby affecting the distillation range, octane value and combustion emission characteristics of the fuel.

[0099] For the content change of the hydrogen-activated release aid in Examples 1, 2, 3 and Comparative Examples 1, 2, no hydrogen-activated release aid is added in Comparative Example 2. In Example 1, the low amount of aid added can be uniformly dispersed in the light hydrocarbon component, but the amount of hydrogen released during engine combustion is limited, and the active hydrogen released can only partially supplement the consumption of H during the combustion process, and the oxidation of C atoms still has a local insufficient phenomenon, and the hydrogen-carbon ratio of the fuel is improved by a small amount, resulting in suboptimal combustion efficiency and emission reduction effect; at the same time, the low concentration of the aid has weak ability to capture oxidative radicals during fuel storage, and although the amount of microglial generated is small, it is still higher than that of Example 3, which indirectly affects the stability of the octane value. In Example 2, the amount of aid added is increased, the amount of hydrogen released during combustion is increased, and active hydrogen can more fully participate in C-C bond breaking and oxidation reactions, promoting the complete conversion of C atoms to CO2, and the hydrogen-carbon ratio is improved more than in Example 1, and the combustion emissions are further optimized; and the aid's ability to capture oxidative radicals is enhanced, the fuel storage stability is improved, and the octane value is less affected by gum. However, an excess of hydrogen-activated release aid can destroy the uniformity of the fuel system, affect oil line delivery and fuel injection atomization, and excessive aid combustion can cause local hydrogen enrichment of the mixture, exacerbate CO, NO x emissions, so the CO, NO x emissions of Example 2 in Table 4 are higher than those of Example 1, so it can also cause backfiring of the exhaust pipe, damage engine components due to residual borides, and excessive addition beyond the performance improvement threshold, so there is no gain in octane value and other indicators, so the amount of aid added in Example 3 is optimal: on the one hand, the amount of hydrogen released during combustion is completely matched with the amount of H required for fuel combustion, and active hydrogen not only promotes the complete oxidation of C atoms, but also reduces the peak combustion temperature, inhibits the generation of NO , and the emission reduction effect is optimal; on the other hand, the concentration of the aid is sufficient to form a "dispersion-antioxidant" double protection, which not only avoids the agglomeration of the aid itself to affect the uniformity of the fuel, but also efficiently captures oxidative radicals to prevent gum formation, while not introducing excess impurities, ensuring that the octane value and distillation range remain in an optimal state.

[0100] The hydrogen release amount in the combustion stage is sufficient, but the excess additive destroys the uniformity of the fuel system: part of the additive particles cannot be completely dispersed, forming a small aggregate state, and the hydrogen release in the aggregation area is too concentrated during combustion, causing local mixed gas "H excess, C deficiency", which in turn causes low-carbon hydrocarbons to be discharged without being fully oxidized, resulting in a rebound in CO emissions; at the same time, the hydrophobic shell of the excess additive easily adsorbs trace amounts of heavy hydrocarbon components during fuel storage, causing the 90% distillation temperature to rise slightly, and the excess additive molecules may interact weakly with trace amounts of olefins in light hydrocarbons, slightly reducing the octane number. Example 2 does not add a hydrogen-activated additive, and the fuel combustion stage has no additional H supplement, relying entirely on the hydrogen-carbon ratio of light hydrocarbons: C atoms are not fully oxidized, and CO production is significantly higher than in the examples; and the lack of additive capture of oxidation radicals increases the amount of gum generated during storage, not only causing the octane number to drop, but also forming carbon deposits during combustion, indirectly affecting the distillation range stability, and without active hydrogen to suppress the combustion peak temperature, NO emissions are also the highest among all groups, completely unable to meet the demand for high-efficiency emission reduction.

[0101] In Example 3, the fuel directly adds ammonia borane, and does not use the form of ammonia borane nanomicrospheres. Compared with Example 3, first in terms of storage stability, the uncoated ammonia borane has a large contact area with trace amounts of water, metal impurities, and the like in the fuel, and is prone to hydrolysis, causing the ammonia borane to decompose prematurely and fail to effectively release hydrogen gas in the high-temperature and high-pressure environment of the engine. From the combustion mechanism, the direct addition of ammonia borane is difficult to disperse uniformly, and during combustion, the local ammonia borane concentration is too high or too low, causing uneven hydrogen release and affecting the stability of combustion. In areas with too high a local hydrogen concentration, the hydrogen content in the mixed gas is too high, causing incomplete combustion and increasing carbon monoxide emissions; while in areas with too low a hydrogen concentration, hydrocarbons cannot fully utilize hydrogen to assist combustion, also causing incomplete combustion, thereby increasing carbon monoxide and nitrogen oxide emissions. Furthermore, the non-uniformly dispersed ammonia borane may also produce some solid particle residues during combustion, affecting the normal operation of the engine, causing the octane number to drop, and the distillation range to deteriorate due to incomplete combustion and impurities.

[0102] In Comparative Example 4, the fuel was not added with antioxidant di-tert-butyl peroxide. During storage, compared with Example 3, the fuel was more prone to oxidation reaction with oxygen to generate gum and acidic substances. From the chemical reaction mechanism, the unsaturated hydrocarbons and other components in the fuel will gradually undergo free radical chain reaction under the action of oxygen to form intermediate products such as peroxide, and finally convert into gum. The generation of gum will adhere to the surface of engine parts, affect the normal operation of the engine, cause incomplete combustion, and increase carbon monoxide emissions. At the same time, acidic substances will have a corrosive effect on metal parts such as copper sheets, causing the copper sheet corrosion level to rise. During combustion, the gum produced by oxidation will change the combustion performance of the fuel, resulting in a decrease in octane rating, a decrease in combustion stability and efficiency, and an increase in nitrogen oxide emissions. The distillation range will also be affected by the presence of gum and changes in combustion.

[0103] In Comparative Example 5, the fuel was not added with clean dispersant polyisobutylene succinimide. During engine operation, compared with Example 3, the carbon deposits and gum deposits in the fuel could not be effectively dispersed. The formation of carbon deposits and gum is mainly due to incomplete combustion and polymerization of some components in the fuel during combustion. Without clean dispersants, these deposits will adhere to the surfaces of key engine components such as fuel injectors, spark plugs, and valves. From the impact mechanism, carbon deposits on fuel injectors will cause uneven fuel injection, resulting in unstable air-fuel mixture concentration, incomplete combustion, and increased carbon monoxide and nitrogen oxide emissions. Carbon deposits on spark plugs will affect the ignition performance and further reduce combustion efficiency, leading to a decrease in octane rating. Carbon deposits on valves will affect the sealing of the valves, causing increased energy loss during combustion, which will also lead to incomplete combustion and affect the distillation range. In addition, carbon deposits and gum will also change the flow characteristics of the fuel in the engine, indirectly affecting the combustion process and performance indicators of the fuel.

[0104] The fuel in Comparative Example 6 uses a self-prepared primary catalyst for primary catalysis and secondary catalysis, while Example 3 uses a Pt-loaded SAPO catalyst for secondary catalysis and a primary catalyst for primary catalysis. The primary catalysis mainly involves cracking, deoxidation and other reactions, and the secondary catalysis mainly involves catalytic reforming. The primary catalyst prepared by the application is a Zn, La and P synergistically loaded silico-aluminate catalyst. Alkanes or alkenes form carbon ions on the catalyst, which can not only perform cracking, deoxidation and other reactions, but also perform molecular rearrangement. In the secondary catalysis stage, compared with Example 3, the primary catalyst in Comparative Example 6 lacks Pt metal active centers and cannot efficiently dissociate hydrogen molecules, resulting in difficulty in activating hydrogen and providing sufficient active hydrogen atoms for the hydrogenation reaction of alkenes. This makes it difficult for alkenes to be fully hydrogenated to form alkanes, and a large amount of alkenes will undergo polymerization reactions at the acid sites of the catalyst to form heavy hydrocarbons, resulting in a wide distillation range, especially a significant increase in the 90% distillation temperature. At the same time, due to the lack of hydrogenation of Pt, the generation of coke cannot be effectively inhibited, and the coke adheres to the surface of the catalyst, reducing the activity of the catalyst and further affecting the catalytic effect, making the combustion incomplete, increasing the emission of carbon monoxide and nitrogen oxides. Moreover, the primary catalyst has weak isomerization effect on alkanes, and cannot effectively increase the content of isomeric alkanes in the fuel like the Pt-loaded SAPO catalyst, resulting in a decrease in octane number and a decrease in the anti-knock performance of the fuel.

[0105] The above description is only a preferred specific embodiment of the application, but the protection scope of the application is not limited thereto. Any person skilled in the art can make equivalent replacements or changes to the technical solutions and inventive concepts of the application within the technical scope disclosed by the application, which should be covered within the protection scope of the application.

Claims

1. An alkylated hydrogen-rich vehicle fuel, characterized in that, Includes the following components by weight percentage: C5-C11 light hydrocarbon components: 90-96%; Hydrogen activation and release aid: 0.5-5%; Polyisobutylene succinimide: 1-4%; Di-tert-butyl peroxide: 0.5-3%; The C5-C11 light hydrocarbon component is a product obtained by alkylation of methanol, followed by separation under the catalysis of a primary catalyst and a secondary catalyst, with a light hydrocarbon yield of 96%. The preparation steps of the primary catalyst are as follows: Tetrapropylammonium bromide was added sequentially to deionized water while stirring. Then, boehmite was added and stirred for 30 min. Finally, coarse-porous silica gel was added and stirred continuously for 3 h to form a gel mixture. The mixture was pre-crystallized at 100℃ for 18 h and crystallized at 170℃ for 12 h. After cooling, the mixture was washed with water and filtered until the pH of the filtrate was 7. The mixture was dried and calcined at 550℃ for 4 h. It was then mixed with 1 mol / L NH4Cl solution at a mass ratio of 1:20 and stirred in a water bath at 90℃ for 2 h. This process was repeated 3 times. The mixture was then filtered, dried, and calcined. Zinc nitrate and lanthanum nitrate were dissolved by ultrasonication and then added to the calcined porous zeolite. The mixture was stirred and ultrasonicated for 5 min each. The mixture was allowed to stand at room temperature for 15 h and dried for 2 h. The mixture was then placed in a solution of dissolved diammonium hydrogen phosphate and stirred in an oil bath at 90℃ until the solution evaporated to dryness. The mixture was dried for 8 h and calcined to obtain the first-stage catalyst. The secondary catalyst is a Pt-supported SAPO catalyst; The preparation steps of the hydrogen activation and release aid are as follows: Prepare an alkaline aqueous solution of sodium hydroxide with a pH of 11, then add 15% of ammonia borane to the system and stir to dissolve. Add the ammonia borane alkaline aqueous solution dropwise to an equal volume of decyltrimethylammonium bromide aqueous solution, and then add the mixed solution dropwise to an equal volume of dodecane. Emulsify at room temperature, separate the layers, and dry overnight under dynamic vacuum to obtain ammonia borane nanospheres, which are hydrogen activation and release aids.

2. The alkylated hydrogen-rich vehicle fuel according to claim 1, characterized in that, The alkylation process of methanol uses HFER molecular sieves as a catalyst.

3. The alkylated hydrogen-rich vehicle fuel according to claim 1, characterized in that, In the preparation of the primary catalyst, the mass ratio of tetrapropylammonium bromide, pseudoboehmite, coarse-porous silica gel and water is 2:0.5:10:

100. The primary catalyst has a zinc loading of 1.2%, a lanthanum loading of 0.5%, and a phosphorus loading of 0.5%.

4. An alkylated hydrogen-rich vehicle fuel according to claim 1, characterized in that, In the preparation of the hydrogen activation and release aid, the mass fraction of decyltrimethylammonium bromide in the aqueous solution of decyltrimethylammonium bromide is 0.4%, and the volume ratio of water to dodecane in the preparation of the hydrogen activation and release aid is 1:

1.

5. A method for preparing an alkylated hydrogen-rich vehicle fuel according to any one of claims 1-4, characterized in that, Includes the following steps: S1, Heat treatment and alkylation reaction of methanol Pretreated methanol was treated at 80-90℃ for 1-2 hours to convert it into vapor. The vapor was then reacted with activated molecular sieves under vacuum for 45 minutes. Isobutane gas was introduced to react with the vapor, and polyisobutylene succinimide (1-4% of the total amount of the system) was added. The reaction was carried out at room temperature for 1.5 hours to complete the alkylation of methanol. S2, methanol derivative primary catalysis The activated primary catalyst is packed into the first catalytic column. The air in the column is purged with nitrogen. The product in step S1 is gradually transferred into the column. The temperature is increased to 180°C at 10°C / min. Ice water is contained in the second reaction vessel. The liquid is separated to complete the first catalysis. S3, methanol derivative secondary catalysis The second catalytic tower is filled with Pt-supported SAPO catalyst. Hydrogen gas is introduced, along with the product from the second reaction vessel. The temperature is raised to 250°C, and the reaction is carried out at 2-3 MPa. The mixture is then introduced into a condenser to complete the secondary catalysis. 0.5-5% of hydrogen activation and release agent and 0.5-3% of di-tert-butyl peroxide are added to the system and stirred until homogeneous, thus completing the preparation of hydrogen-rich vehicle fuel.

6. The method for preparing an alkylated hydrogen-rich vehicle fuel according to claim 5, characterized in that, The pretreated methanol preparation process is as follows: industrial-grade methanol is adsorbed with water using a 4A molecular sieve, and then filtered using a 0.2μm ceramic membrane. Isobutane gas also needs to be treated with a 4A molecular sieve before use.

7. The method for preparing an alkylated hydrogen-rich vehicle fuel according to claim 5, characterized in that, The molecular sieve in S1 is an HFER molecular sieve, and its activation method is as follows: the purchased molecular sieve is impregnated with 1 mol / L ammonium nitrate solution, stirred at 80°C for 5 hours, centrifuged, filtered, rinsed with deionized water, and this process is repeated 3 times. After drying, it is calcined at 470°C under vacuum for 4 hours.

8. The method for preparing an alkylated hydrogen-rich vehicle fuel according to claim 5, characterized in that, The primary catalytic product in S2 is treated with 4A molecular sieve before entering the secondary catalytic tower.

9. The method for preparing an alkylated hydrogen-rich vehicle fuel according to claim 5, characterized in that, The hydrogen-rich vehicle fuel obtained in S3 can be used alone or mixed with gasoline in any proportion as fuel.

Images