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CN116440930B - Catalyst used in methanol fuel modification and catalytic modification production process - Google Patents

Catalyst used in methanol fuel modification and catalytic modification production process Download PDF

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Publication number
CN116440930B
CN116440930B CN202310703013.4A CN202310703013A CN116440930B CN 116440930 B CN116440930 B CN 116440930B CN 202310703013 A CN202310703013 A CN 202310703013A CN 116440930 B CN116440930 B CN 116440930B
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methanol
catalyst
catalytic
modification
aggregate
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CN116440930A (en
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江含治
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Kunming Junfa New Energy Technology Co ltd
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Kunming Junfa New Energy Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/182—Phosphorus; Compounds thereof with silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/232—Carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to the technical field of chemical industry, in particular to a methanol fuel modified catalyst and a catalytic modification production process; the invention adopts two catalysts with different performances, wherein the catalysts are composed of aggregate and auxiliary materials, and the specific steps of the catalytic modification process are S1 pretreatment of methanol, S2 pretreatment of coal tar naphtha, S3 catalysis and S4 granulation; the invention changes the components of the methanol and the characteristics of the swelling rubber of the methanol through two catalysts and assistants with different performances, has short process flow, high yield, can realize zero emission, can be operated at low temperature and normal pressure, has high safety, has the octane number of a final product as high as 110-117, and solves a plurality of defects of methanol raw materials used as vehicle fuel.

Description

Catalyst used in methanol fuel modification and catalytic modification production process
Technical Field
The invention relates to the technical field of chemical industry, in particular to a methanol fuel modified catalyst and a catalytic modification production process.
Background
Along with the development of social economy, environmental pollution is more and more serious, and the shortage of petrochemical energy sources leads to more and more demands of alternative energy sources, and among a plurality of vehicle alternative fuels, the methanol fuel has the advantages of wide raw materials, mature technology, economy, feasibility, safety and reliability, is a novel alternative energy source suitable for national conditions of China, realizes large-scale industrialized popularization and application of the novel methanol fuel, and has important social and economic significance for adjusting the energy industry structure of China and reducing environmental pollution.
Although methanol can be directly mixed into gasoline to form methanol gasoline, the methanol gasoline has larger disadvantages: firstly, the heat value of the methanol is low, secondly, the water content in the mixed fuel has a great influence on the stability of the fuel, thirdly, when the methanol is used as the fuel, the methanol can absorb water from the air to stop the engine, and thirdly, the methanol has a corrosion effect on metals and a swelling effect on rubber.
As early as 70 in the twentieth century, the Mobil company developed ZSM-5 catalyst and technology for preparing gasoline from methanol, which developed the processes of different reactors of fixed bed, fluidized bed and tubular fixed bed successively. The methanol to gasoline generally adopts a two-stage conversion process, wherein the first stage is to prepare dimethyl ether by dehydration of methanol, and the mixture of dimethyl ether, unreacted methanol and water from the first stage enters a reactor filled with ZSM-5 catalyst from the second stage, and dry gas, liquefied gas and gasoline are generated under the acid catalysis of ZSM-5. The technological conditions are 250-350 deg.c and 3.0-5.OMPa, and the technological conditions are high temperature and high pressure, high construction investment and operation cost and high safety hidden trouble. Although this process has many drawbacks, it is gradually a viable trend to produce clean fuels for methanol modification, after which more and more research is being conducted on methanol modification.
Products of the same type of process, such as coal-to-gasoline, methyl tertiary butyl ether and paraffin produced by a Fischer-Tropsch process, have long process flow, large investment of fixed equipment, large occupied area and low yield, and can only receive 1 ton of the product only by about 2.4 to 3 tons of methanol raw materials, and more byproducts in the production process are easy to produce secondary pollution, and the comparison table is as follows:
some applicant filed some approximate patents in this field, for example, as follows:
the patent with the application number of 200910090727.2 and the patent name of "preparation method and device of finished methanol Fuel for vehicle" proposes a preparation method of modified methanol, wherein the raw material is "a. The main material is methanol, accounting for 85%; b. the auxiliary materials are the following 10 industrial grade materials: naphtha 5%; 3% of petroleum benzene; 1-3% of isobutene and 1% of isopropanol; 1 to 3 percent of isobutyraldehyde; 0.5% of secondary octanol; 0.5% of tertiary butanol; 0.5% of butenone; 0.3% of acetylacetone; 0.2% of phenylbutenone; the method comprises the steps of proportioning, preheating, catalyzing, condensing and mixing, and the method ensures that methanol is catalytically modified under milder process conditions and is converted into a mixture of various alcohols, ethers, esters, menstruum and other compounds, thereby overcoming the difficulties of low-temperature cold start such as high-temperature air resistance when the methanol is used as the fuel oil for vehicles,The method for preparing the methanol fuel for the large-scale vehicle has the advantages of low heat value, low dynamic performance, poor miscibility with gasoline, large limitation on the proportion of the substituted gasoline and the like. The patent uses additives to accomplish the dealdehyding, especially using ce 2 o 3, The cost is high, in addition, the patent solves the wall flow effect by adopting a far infrared radiation heating mode, in order to ensure that the combustion is sufficient, dimethoxy methane is added, the components are easy to gasify, and safety accidents are easy to occur, in addition, the patent also adopts P 2 O 5 The components have strong toxicity, are easy to cause pollution and have poor safety, and the electrochemical corrosion problem is not solved in the process.
Further, as the patent with application number 200610149663.5 and patent name of methanol modifier and application thereof, the methanol modifier is prepared from the following raw materials in parts by weight: 16-28 parts of lubricant, 10-30 parts of combustion improver, 4-8 parts of igniter, 6-12 parts of dehydrating agent, 4-8 parts of antiwear agent, 2-6 parts of antioxidant, 6-12 parts of cleaner, 2-4 parts of preservative, 4-8 parts of cetane number improver and 10-28 parts of phase solvent, wherein the lubricant is oleic acid; the combustion improver is butyl acetate; the ignition agent is petroleum ether; the dehydrating agent is nonylphenol polyoxyethylene ether; the antiwear agent is chlorinated paraffin: the cleaning agent is tetrachloroethylene; the preservative is benzotriazole; the cetane number improver is isooctyl nitrate; the phase solvent is n-butanol, octanol or their mixture. The methanol diesel oil produced by using the modifier reaches or is superior to the technical index of similar national standard diesel oil in terms of the physical and chemical properties. The methanol modifier is used for blending methanol diesel oil, the technology is eliminated, the technology can only be used as industrial fuel, and cannot be used for vehicles and engineering machinery, various additives used in the patent, such as oleic acid, can increase the flash point of methanol, chlorinated paraffin can increase the viscosity of methanol, but is easy to carbon, isooctyl nitrate can increase the cetane index of methanol, but the cetane index increased according to the content of the patent is less, in addition, the flash point of the patent is 38, the fire safety index does not reach the standard, the cetane number is lower, and mechanical knocking and working weakness can be caused.
In addition, as in the patent with application number 200810080300.X and patent name of "a methanol fuel catalytic modification production process", a methanol fuel catalytic modification production process is that the methanol fuel is flashed to obtain light components and heavy components, and at least one of them is put into a catalytic reactor for catalytic modification, and catalytic modification is carried out under the conditions of reaction space velocity of 200-2000 h1, reaction temperature of 200-500 ℃ and reaction pressure of 1-3 MPa; wherein, the catalyst used for the catalytic modification of the top light component is an Fe-based or Co-based catalyst used in the Fischer-Tropsch synthesis process, a catalyst used in the MTBE process of methanol and an aromatic alkylation catalyst; the catalyst used for catalytic modification of the heavy components at the bottom is an industrial catalytic cracking and catalytic reforming catalyst or a modified product thereof, and the catalytic modified methanol fuel is obtained after remixing. The methanol fuel comprises methanol gasoline, methanol diesel oil or methanol lubricating oil which are mixed according to any proportion. The invention changes the internal composition of the methanol fuel through catalytic reaction, reduces the saturated vapor pressure of the low-proportion methanol fuel, avoids the vapor lock phenomenon in the using process, solves the cold starting problem of the high-proportion methanol fuel in winter, improves the octane number of the methanol gasoline by 2 to 3, reduces the cetane number of the methanol diesel by 5 to 9, and improves the oil quality and the power attribute of the methanol fuel. The patent is operated under pressure, the safety is poor, meanwhile, the process involved in the patent has problems, the patent mixes methanol and 0# diesel oil according to the ratio of 9:1, the methanol and the 0# diesel oil cannot be uniformly mixed, the methanol and the 0# diesel oil are insoluble, the methanol and the 0# diesel oil can be mutually dissolved only under the condition of assisting in a cosolvent, but according to the principle of physical distillation, the mutual solubility of the methanol and the 0# diesel oil cannot be changed no matter whether pressurizing, heating or catalyzing is adopted, layering occurs, even if the methanol and the 0# diesel oil are mutually dissolved by using the cosolvent, reduction reaction can be generated once heating and distilling, and the scheme has problems in technical feasibility.
At present, the methanol fuel used as the motor vehicle has some defects which cannot be solved by the prior art, such as: (1) When the engine outputs the same power, the amount of the methanol combusted is 2.2 times of that of the gasoline according to the requirement of the equal heat value, so that the heat value required for completely vaporizing the fuel in the mixed gas when the methanol is combusted is about 8 times greater than that of the combusted gasoline, and the fuel consumption is increased; (2) Methanol has high vaporization latent heat and low vapor pressure, so that mixed gas is difficult to form and start, the temperature in a compression end cylinder is low, the flame retardant period of the mixed gas before ignition is prolonged, the compression work is reduced, and the air charging coefficient is possibly improved; (3) In the air inlet process, the temperature of the mixed gas is reduced, the density is increased due to the fact that the methanol absorbs heat in a gasification mode along with the air entering the air cylinder, atomization is poor, in the air inlet process, the gasification part is few, and compression consumption work is reduced; (4) The conductivity of methanol is higher than that of gasoline, and the methanol is easy to cause galvanic corrosion; (5) The methanol contains a large number of hydroxyl molecules and can absorb moisture in the air; (6) Methanol generates an intermediate product HCHO when combusted, and can be further oxidized to form formic acid HCOOH under certain conditions; (7) Methanol is single-chain alcohol, has larger molecules and lower atomization than gasoline, has lower combustion value, enters a cylinder body, is easy to cause a flame retardation period before ignition, and causes a wall flow effect, so that engine oil can be diluted, and a vehicle is caused to break down. In order to solve the above problems, technical development is required.
Disclosure of Invention
The invention aims to provide a convenient and efficient methanol modification method to solve seven problems in the background technology.
In order to achieve the above purpose, the invention adopts the following technical scheme: the catalyst used in the modification of the methanol fuel comprises a catalyst I and a catalyst II with different performances, wherein the two catalysts are composed of aggregate and auxiliary materials, and the catalyst I comprises the following components:
the catalyst-aggregate is sodium silicate, and the auxiliary materials comprise aluminum chloride, zinc chloride and phosphoric acid;
the catalyst two aggregate is one of diatomite or sodium silicate, and the auxiliary materials are copper oxide, iron powder, cobalt powder, sodium carbonate, calcium oxide and nickel oxide.
Further, the first catalyst comprises, by mass, 80% -90% of aggregate, 5% -9% of aluminum chloride, 1% -5% of zinc chloride and 3% -7% of phosphoric acid, and the second catalyst comprises, by mass, 10% -18% of copper oxide, 20% -30% of iron powder, 0.3% -1.2% of cobalt powder, 6% -12% of sodium carbonate, 8% -15% of calcium oxide and 5% -10% of nickel oxide.
Further, the first catalyst comprises, by mass, 83% of aggregate, 7% of aluminum chloride, 3% of zinc chloride and 7% of phosphoric acid, and the second catalyst comprises, by mass, 26% of aggregate, 15% of copper oxide, 28% of iron powder, 0.6% of cobalt powder, 10% of sodium carbonate, 12.4% of calcium oxide and 8% of nickel oxide.
A catalytic modification production process of methanol fuel comprises the following steps:
s1, pretreatment of methanol: adding 0.1-0.7% of chain extender according to the mass of methanol, circularly stirring for 4h, and standing for 24-48 h for standby:
s2, pretreating coal tar naphtha: adding 1% -3% of boiling point reducing agent according to the coal tar naphtha, circularly stirring for 4 hours, and standing for 12 hours for standby;
s3, catalysis: after the pretreatment of methanol and coal tar naphtha is finished, uniformly mixing the treated methanol and the coal tar naphtha, catalyzing the mixture twice by using a catalyst I and a catalyst II respectively, and then entering a storage tank;
s4, granulating: and uniformly mixing the catalytic tailings and granulating.
Further, in the step S1, the chain extender is ethylene glycol.
Further, the boiling point reducing agent in the step S2 is composed of petroleum ether and pentane, wherein the weight ratio of petroleum ether to pentane is 7:3.
Further, the step S3 adopts double-tower catalysis, and comprises the following specific steps: after the pretreatment of methanol and coal tar naphtha is finished, the methanol and the coal tar naphtha enter a first reaction kettle through a feed hopper and a flow hopper, are heated to 58-62 degrees, enter a pipeline after vaporization, are heated to 120-150 degrees through a pipeline heating device in the pipeline, enter a first catalytic tower for alkylation, keep a vaporization state through a reboiler, enter a second reaction kettle through a magnetization device, the temperature of the vaporization state product is reduced to about 70 degrees, the second reaction kettle is heated to about 100 degrees again, then enter a second catalytic tower, are subjected to dechlorination in the second catalytic tower, are cooled to 70-80 degrees through a condensation device after etherification and oxygen absorption catalytic reaction, and enter a storage tank.
And further, after granulating in the step S4, dehydrating at the temperature of 70 ℃, heating to 300-350 ℃ and calcining for 4 hours to obtain a finished product.
Further, after the methanol and the coal tar naphtha are uniformly mixed, 8-10% of auxiliary agent is added according to the total amount of the methanol and the coal tar naphtha, and the auxiliary agent is tertiary butanol: isooctanol: isobutanol=50: 25:25 is prepared by uniformly mixing and catalyzing and distilling.
The beneficial technical effects of the invention are as follows:
(1) The invention has short process flow and high yield, 94% of the product can be obtained from 1 ton of methanol raw material, 6% of the kettle substrate is added with the auxiliary agent, and 95% of the diesel oil component can be obtained;
(2) The octane number of the final product of the process is up to 110-117, for example, the octane number can be added into national standard gasoline, so that the grade and standard of the national standard gasoline can be improved, and the emission standard of the national standard gasoline can be reduced;
(3) The process solves the defects of the methanol raw material used as the vehicle fuel, such as high conductivity of the methanol, easy electrochemical corrosion, air resistance caused by high steam pressure of the methanol, wall flow effect caused by difficult atomization of the methanol, dilution engine oil and the like;
(4) The process solves the problem that the tail gas contains formaldehyde through a product treated by the catalyst;
(5) The process changes the components of the methanol through two catalysts and assistants with different performances, and simultaneously changes the characteristics of swelling rubber of the methanol;
(6) The process can be operated at low temperature and normal pressure, the production is safe, and the reliability is improved;
(7) Through copper sheet corrosion test, the corrosiveness of the product produced by the process is equal to that of national standard gasoline.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a flow chart of the production process equipment of the present invention.
The device comprises a feed hopper A, a feed hopper B, a flow hopper 3, a first reaction kettle 4, a pipeline heating device 5, a first catalytic tower 6, a reboiler 7, a magnetization device 8, a second reaction kettle 9, a condensing device 10, a second catalytic tower 11 and a storage tank 12.
Description of the embodiments
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples
The catalyst used in the modification of the methanol fuel comprises a catalyst I and a catalyst II with different performances, wherein the two catalysts are composed of aggregate and auxiliary materials, and the catalyst I comprises the following components:
the catalyst comprises 80 mass percent of aggregate sodium silicate, 9 mass percent of auxiliary material aluminum chloride, 4 mass percent of zinc chloride and 7 mass percent of phosphoric acid;
the catalyst comprises 20% of aggregate diatomite, 18% of auxiliary materials of cupric oxide, 30% of iron powder, 1.2% of cobalt powder, 12% of sodium carbonate, 13.8% of calcium oxide and 5% of nickel oxide.
All of the above raw materials are commercially available raw materials.
Examples
The catalyst used in the modification of the methanol fuel comprises a catalyst I and a catalyst II with different performances, wherein the two catalysts are composed of aggregate and auxiliary materials, and the catalyst I comprises the following components:
the catalyst comprises 90% of aggregate sodium silicate, 5% of auxiliary material aluminum chloride, 1% of zinc chloride and 4% of phosphoric acid according to the mass percentage;
the catalyst comprises 30% of aggregate diatomite, 10% of auxiliary materials copper oxide, 28.7% of iron powder, 0.3% of cobalt powder, 6% of sodium carbonate, 15% of calcium oxide and 10% of nickel oxide.
All of the above raw materials are commercially available raw materials.
Examples
The catalyst used in the modification of the methanol fuel comprises a catalyst I and a catalyst II with different performances, wherein the two catalysts are composed of aggregate and auxiliary materials, and the catalyst I comprises the following components:
the catalyst comprises 85% of aggregate sodium silicate, 7% of auxiliary materials aluminum chloride, 5% of zinc chloride and 3% of phosphoric acid according to the mass percentage;
the catalyst comprises 28% of diatomite aggregate, 17% of copper oxide, 20% of iron powder, 1% of cobalt powder, 12% of sodium carbonate, 12% of calcium oxide and 10% of nickel oxide.
All of the above raw materials are commercially available raw materials.
Examples
The catalyst used in the modification of the methanol fuel comprises a catalyst I and a catalyst II with different performances, wherein the two catalysts are composed of aggregate and auxiliary materials, and the catalyst I comprises the following components:
the catalyst comprises 88 mass percent of aggregate sodium silicate, 8 mass percent of auxiliary material aluminum chloride, 2 mass percent of zinc chloride and 2 mass percent of phosphoric acid;
the catalyst comprises 26% of diatomite aggregate, 16% of copper oxide, 29% of iron powder, 0.5% of cobalt powder, 10.5% of sodium carbonate, 8% of calcium oxide and 10% of nickel oxide.
All of the above raw materials are commercially available raw materials.
Examples
The catalyst used in the modification of the methanol fuel comprises a catalyst I and a catalyst II with different performances, wherein the two catalysts are composed of aggregate and auxiliary materials, and the catalyst I comprises the following components:
the catalyst comprises 83% of aggregate sodium silicate, 7% of auxiliary materials aluminum chloride, 3% of zinc chloride and 7% of phosphoric acid according to the mass percentage;
the catalyst comprises 26% of aggregate diatomite, 15% of auxiliary materials copper oxide, 28% of iron powder, 0.6% of cobalt powder, 10% of sodium carbonate, 12.4% of calcium oxide and 8% of nickel oxide.
All of the above raw materials are commercially available raw materials.
Examples
A catalytic modification production process of methanol fuel comprises the following steps:
s1, pretreatment of methanol: adding 0.1-0.7% of chain extender according to the mass of methanol, circularly stirring for 4h, standing for 24-48 h for standby, stirring for 4h to ensure that the methanol and the chain extender are completely mutually dissolved and fully combined for reaction, and standing for 24-48 h to ensure that the quality of a product is affected if the reaction is not in place and the trace inorganic salt and alkylation contained in the methanol are separated and precipitated, so that pure long-chain methanol is obtained, wherein the chain extender is ethylene glycol;
s2, pretreating coal tar naphtha: adding 1% -3% of boiling point reducing agent according to coal tar naphtha, circularly stirring for 4 hours, and standing for 12 hours for standby, wherein the boiling point reducing agent consists of petroleum ether and pentane, and the weight ratio of petroleum ether to pentane is 7:3;
s3, catalysis: after the pretreatment of methanol and coal tar naphtha is finished, the pretreated methanol and coal tar naphtha are treated according to the pretreatment of methanol: pretreating coal tar naphtha= (7-8), namely uniformly mixing the raw materials in the ratio of (3-2), feeding the mixture into a first reaction kettle through a feed hopper and a flow hopper, heating the mixture to 58-62 degrees, feeding the mixture into a pipeline after vaporization, heating the mixture to 120-150 degrees in the pipeline through a pipeline heating device, feeding the mixture into a first catalytic tower for alkylation, reacting the mixture through a first catalyst, keeping the vaporized state through a reboiler, feeding the vaporized state product into a second reaction kettle through a magnetization device, reducing the temperature to about 70 degrees at the moment, heating the second reaction kettle to about 100 degrees again, feeding the second catalytic tower, performing dechlorination through a second catalyst, etherifying and oxygen-absorbing catalytic reaction, reducing the temperature to 70-80 degrees through a condensing device, and feeding the cooled product into a storage tank; the catalyst I comprises, by mass, 80% -90% of aggregate, 5% -9% of aluminum chloride, 1% -5% of zinc chloride and 3% -7% of phosphoric acid, and the catalyst II comprises, by mass, 20% -30% of aggregate, 10% -18% of copper oxide, 20% -30% of iron powder, 0.3% -1.2% of cobalt powder, 6% -12% of sodium carbonate, 8% -15% of calcium oxide and 5% -10% of nickel oxide;
s4, granulating: and (3) uniformly mixing and granulating the tailings treated in the step (S3), dehydrating at 70 ℃ and then heating to 300-350 ℃ for calcination for 4 hours to obtain the finished product.
Examples
A catalytic modification production process of methanol fuel comprises the following steps:
s1, pretreatment of methanol: adding 0.1-0.7% of chain extender according to the mass of methanol, circularly stirring for 4h, standing for 24-48 h for standby, stirring for 4h to ensure that the methanol and the chain extender are completely mutually dissolved and fully combined for reaction, and standing for 24-48 h to ensure that the quality of a product is affected if the reaction is not in place and the trace inorganic salt and alkylation contained in the methanol are separated and precipitated, so that pure long-chain methanol is obtained, wherein the chain extender is ethylene glycol;
s2, pretreating coal tar naphtha: adding 1% -3% of boiling point reducing agent according to coal tar naphtha, circularly stirring for 4 hours, and standing for 12 hours for standby, wherein the boiling point reducing agent consists of petroleum ether and pentane, and the weight ratio of petroleum ether to pentane is 7:3;
s3, catalysis: after the pretreatment of methanol and coal tar naphtha is finished, the pretreated methanol and coal tar naphtha are treated according to the pretreatment of methanol: after the pretreated coal tar naphtha= (7-8) and the pretreated coal tar naphtha= (3-2) are uniformly mixed, 8-10% of auxiliary agent is added according to the total amount of the pretreated coal tar naphtha= (7-8), and the auxiliary agent is tertiary butanol: isooctanol: isobutanol=50: 25:25, the mixture and the auxiliary agent enter a first reaction kettle through a feed hopper and a flow hopper, are heated to 58-62 degrees, enter a pipeline after being gasified, are heated to 120-150 degrees through a pipeline heating device in the pipeline, enter a first catalytic tower for alkylation, react through a first catalyst, keep a gasified state through a reboiler, enter a second reaction kettle through a magnetization device, at the moment, the temperature is reduced to about 70 degrees, the second reaction kettle is heated to about 100 degrees again, enter a second catalytic tower, are dechlorinated through a second catalyst, are cooled to 70-80 degrees through a condensation device after etherification and oxygen absorption catalytic reaction, and enter a storage tank; the catalyst I comprises, by mass, 80% -90% of aggregate, 5% -9% of aluminum chloride, 1% -5% of zinc chloride and 3% -7% of phosphoric acid, and the catalyst II comprises, by mass, 20% -30% of aggregate, 10% -18% of copper oxide, 20% -30% of iron powder, 0.3% -1.2% of cobalt powder, 6% -12% of sodium carbonate, 8% -15% of calcium oxide and 5% -10% of nickel oxide;
s4, granulating: and (3) uniformly mixing and granulating the tailings treated in the step (S3), dehydrating at 70 ℃ and then heating to 300-350 ℃ for calcination for 4 hours to obtain the finished product.
The invention adopts normal pressure distillation, the production safety is enhanced, through two different physical catalysts, the linear methanol is changed into multiple chain type through methanol modification, the 1 carbon is changed into 4-5 carbon, the continuous two times of reactive distillation, formaldehyde removal, etherification, high frequency electronic cutting and magnetization cutting are carried out, so that the methanol molecules are thinned, the combustion value is improved, the 7975-8100 kcal/kg is reached, and the octane number is about 117. The invention realizes aldehyde removal through catalytic modification, and the invention solves the wall flow effect by cutting and thinning molecules through high-frequency electrons and a magnetic field and heating at the same time, improves combustibility, ensures that fuel can be fully combusted, reduces oil consumption, reduces conductivity in the process and solves the problem of galvanic corrosion.
The oxygen content of the methanol is as high as 50-54, and the purpose of methanol modification is to solve the problem that the oxygen content in the methanol is too high, so that an oxygen sensor on the vehicle reacts in the using process of the vehicle, and a mechanical fault lamp of an instrument panel is lightened. The invention adopts catalytic oxygen absorption to reduce the oxygen content of methanol to 25-30, thus solving the problem that a mechanical fault lamp is lighted in the using process of the vehicle and simultaneously achieving the effect of clean exhaust emission.
The catalytic modified vehicular methanol fuel produced according to the formulation of example 1 according to the preparation process of example 6 prepared 50-50 finished gasoline samples, and tested for quality and composition, as follows:
table 1:
table 2:
the product produced by the process of example 7 of the present invention was sampled and tested using a calorimeter from the company Hejirime heating value instruments, inc., as follows:
the invention has short process flow and high yield, 94% of the product can be obtained from 1 ton of methanol raw material, 6% of the kettle substrate is added with the auxiliary agent, and 95% of the diesel oil component can be obtained;
the octane number of the final product of the process is up to 110-117 as measured by an octane number measuring instrument, for example, the octane number measuring instrument is doped into national standard gasoline, so that the grade and standard of the national standard gasoline can be improved, and the emission standard of the national standard gasoline can be reduced;
the process solves the problem that the tail gas contains formaldehyde through a product treated by the catalyst; the formaldehyde content of the product after combustion is measured to be 0 by adopting an Interscan4160 formaldehyde analyzer in the United states;
the process changes the components of the methanol through two catalysts and assistants with different performances, and simultaneously changes the characteristics of swelling rubber of the methanol;
through copper sheet corrosion test, the corrosiveness of the product produced by the process is equal to that of national standard gasoline,
the foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (7)

1. The catalyst used in the modification of the methanol fuel is characterized by comprising a catalyst I and a catalyst II with different performances, wherein the two catalysts are composed of aggregate and auxiliary materials, and the catalyst I and the catalyst II are prepared from the following components:
the catalyst I comprises 80-90% of aggregate, 5-9% of aluminum chloride, 1-5% of zinc chloride and 3-7% of phosphoric acid according to the mass percentage content;
the catalyst II aggregate is one of diatomite or sodium silicate, and the auxiliary materials are copper oxide, iron powder, cobalt powder, sodium carbonate, calcium oxide and nickel oxide, wherein the catalyst II comprises, by mass, 20% -30% of aggregate, 10% -18% of copper oxide, 20% -30% of iron powder, 0.3% -1.2% of cobalt powder, 6% -12% of sodium carbonate, 8% -15% of calcium oxide and 5% -10% of nickel oxide.
2. The catalyst for methanol fuel modification according to claim 1, wherein the first catalyst comprises, by mass, 83% of aggregate, 7% of aluminum chloride, 3% of zinc chloride and 7% of phosphoric acid, and the second catalyst comprises, by mass, 26% of aggregate, 15% of copper oxide, 28% of iron powder, 0.6% of cobalt powder, 10% of sodium carbonate, 12.4% of calcium oxide and 8% of nickel oxide.
3. A process for the catalytic modification of a methanol fuel containing the catalyst according to any one of claims 1 to 2, characterized by comprising the steps of:
s1, pretreatment of methanol: adding 0.1-0.7% of chain extender according to the mass of methanol, circularly stirring for 4h, and standing for 24-48 h for standby;
s2, pretreating coal tar naphtha: adding 1% -3% of boiling point reducing agent according to the coal tar naphtha, circularly stirring for 4 hours, and standing for 12 hours for standby;
s3, catalysis: after the pretreatment of methanol and coal tar naphtha is finished, the pretreated methanol and coal tar naphtha are treated according to the pretreatment of methanol: uniformly mixing the pretreated coal tar naphtha= (7-8) ((3-2)), heating to 58-62 ℃ by a feed hopper and a flow hopper, vaporizing, then entering a pipeline, heating to 120-150 ℃ by a pipeline heating device in the pipeline, then entering a first catalytic tower for alkylation, keeping a vaporized state by a reboiler, enabling a vaporized state product to enter a second reaction kettle by a magnetization device, reducing the temperature to about 70 ℃, re-heating to about 100 ℃, then entering a second catalytic tower, dechlorinating in the second catalytic tower, etherifying, oxygen-absorbing catalytic reaction, reducing the temperature to 70-80 ℃ by a condensation device, and entering a storage tank;
s4, granulating: and uniformly mixing the catalytic tailings and granulating.
4. The catalytic modification process for producing methanol fuel according to claim 3, wherein the chain extender in the step S1 is ethylene glycol.
5. A process for the catalytic modification of a methanol fuel according to claim 3, wherein the boiling point reducing agent in step S2 is composed of petroleum ether and pentane in a weight ratio of 7:3.
6. The catalytic modification process for producing methanol fuel according to claim 3, wherein after pelleting in step S4, dehydration is performed at 70 ℃, and then calcination is performed for 4 hours after heating to 300 ℃ to 350 ℃ to obtain the finished product.
7. The catalytic modification production process of methanol fuel according to any one of claims 3 to 6, wherein after methanol and coal tar naphtha are uniformly mixed, 8 to 10 percent of auxiliary agent is added according to the total amount of the methanol and the coal tar naphtha, and the auxiliary agent is tertiary butanol: isooctanol: isobutanol=50: 25:25 is prepared by uniformly mixing and catalyzing and distilling.
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