CN116196927A - High-dispersion iron-based catalyst for hydrogenation liquefaction of solid hydrocarbon raw material and preparation method thereof - Google Patents
High-dispersion iron-based catalyst for hydrogenation liquefaction of solid hydrocarbon raw material and preparation method thereof Download PDFInfo
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- CN116196927A CN116196927A CN202310191517.2A CN202310191517A CN116196927A CN 116196927 A CN116196927 A CN 116196927A CN 202310191517 A CN202310191517 A CN 202310191517A CN 116196927 A CN116196927 A CN 116196927A
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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
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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Abstract
The invention discloses a high-dispersion iron-based catalyst for hydrogenation liquefaction of a solid hydrocarbon raw material and a preparation method thereof. The preparation method of the iron-based catalyst comprises the following steps: s1, preparing a solution of ferric salt and a solution of a precipitant, and respectively mixing with additives to obtain mixed slurry 1 and mixed slurry 2; s2, preheating working gas, and then introducing the preheated working gas into a suspension forming tower to form an upstream flow; s3, respectively passing the mixed slurry 1 and the solution of the precipitant and the mixed slurry 2 and the solution of the ferric salt through a pumping device to form reaction raw materials 1 and 2 with pressure; s4, feeding the pressurized reaction raw materials 1 and 2 into a suspension forming tower in the form of fog drops, spraying the fog drops into the upper space of the suspension forming tower in an opposite mode, carrying out impact mixing reaction on the pressurized reaction raw materials 1 and 2 to generate catalyst precursor fog drops, obtaining a suspension tower downlink material, carrying out cross flow contact with uplink air flow, and carrying out drying, roasting and/or activating processes to form catalyst powder. The catalyst powder prepared by the method can improve the hydro-conversion efficiency of the solid hydrocarbon raw material.
Description
Technical Field
The invention relates to a high-dispersion iron-based catalyst for hydrogenation liquefaction of a solid hydrocarbon raw material and a preparation method thereof, and belongs to the field of energy and chemical industry.
Background
The solid hydrocarbon feedstock is hydroliquefied, which is the process of producing liquefied oil (liquid fuel) from the solid hydrocarbon feedstock, and the key step is the hydroconversion of feedstock slurry (mixture of solid hydrocarbon feedstock, solvent oil and catalyst) in a reactor. Under the condition of hydrogenation reaction (high temperature, high pressure and catalysis), partial chemical bonds in the macromolecular structure of the solid hydrocarbon raw material are heated and cracked to generate free radicals; the free radicals combine with the active hydrogen atoms to form smaller molecular structures, including liquid fuel molecular structures; wherein the catalyst is one of the key factors affecting the coal liquefaction effect.
The solid hydrocarbon feedstock hydroliquefaction catalysts can be divided into three broad categories. The first is a noble metal catalyst, commonly used as cobalt (Co) -based, molybdenum (Mo) -based and nickel (Ni) -based catalysts. The catalyst has high catalytic activity, but is expensive, and is discharged along with waste residues, so that the catalyst has environmental pollution, difficult recovery and high cost. The second type of catalyst being a metal halide catalyst, e.g. ZnCl 2 And SnCl 2 Etc. The catalyst belongs to an acidic catalyst, has the capability of catalytic cracking, and has a strong corrosion effect on equipment. The third class of catalysts is iron-based catalysts. The iron-based catalyst, although not having the highest catalytic activity, is also apparent in its activity. And the price is low, the iron element has no pollution to the environment, no recovery is needed, and the catalyst has the most industrial prospect.
Iron-based catalysts are mainly derived from two approaches, one is natural and the other is chemical synthesis. Natural iron-containing ores (including pyrite, limonite and pyrrhotite) are not rare, but it is a major challenge to grind these iron-containing ores to ultrafine powders efficiently and with low consumption and to mix them highly with solid hydrocarbon feed powders to achieve uniform dispersion to achieve the desired catalytic activity. Furthermore, the chemical composition and structure of the iron-containing natural minerals themselves are often not the optimal active phase of the hydroliquefaction catalyst. When used, the addition amount is generally high, generally more than 3 wt.%.
The micron or even nano specific phase iron-based product can be obtained by a chemical synthesis method, and is easy to realize when being used for the hydrogenation liquefaction of solid hydrocarbon raw materialsThe high dispersion of the catalyst on the inner and outer surfaces of the coal powder ensures that the activity and the utilization rate of the catalyst are in the optimal state. For the purpose of ultra-fine, high dispersion, freshly synthesized iron-based catalysts or their precursors are often highly dispersed in a solvent as colloids or nanoparticles, resulting in difficult solvent removal. The on-site loading or flocculation is a method developed for effectively removing the solvent and obtaining the superfine high-dispersion catalyst. Chinese patent application CN202210055408.3 discloses an acidic WO 3 -ZrO 2 The double-function catalyst with Fe, ni or Pd and other metals supported on the carrier utilizes the synergistic effect of the acid site and the metal site to promote the hydrocracking of waste plastics. Chinese patent application CN200310053377.5 discloses a supported iron-based catalyst and a process for its preparation, which process uses FeSO 4 The solution is an iron source, the coal powder is a carrier, the alkaline solution containing hydroxide ions is a precipitator, and the catalyst is prepared by stirring and mixing the alkaline solution containing active component gamma-FeOOH. Chinese patent application No. cn2016611041484. X discloses a biomass charcoal loaded Mo, W, fe or Ni metal catalyst for catalytic hydrogenation liquefaction of corn stalks, but the required reaction conditions are severe (about 400 ℃ and 20 MPa) due to the lower catalyst activity.
The conventional precipitation method used at present has the characteristics of multiple steps (precipitation, filtration, drying, roasting, or activation and forming) of catalyst preparation, uneven material contact, uneven texture structure of the obtained catalyst and low dispersity, and needs to be improved.
Disclosure of Invention
The invention aims to provide a solid hydrocarbon raw material hydrogenation liquefied iron-based catalyst and a preparation method thereof, and the prepared catalyst powder has the characteristics of uniform particle size, texture structure and dispersion degree, is easy to realize high dispersion in reaction slurry, and improves the hydrogenation conversion efficiency of the solid hydrocarbon raw material.
The preparation method of the solid hydrocarbon raw material hydrogenation liquefying iron-based catalyst provided by the invention comprises the following steps:
s1, preparing a solution of ferric salt and a solution of a precipitant, and respectively mixing with an additive to obtain mixed slurry 1 and mixed slurry 2;
s2, preheating working gas, and then introducing the preheated working gas into a suspension forming tower to form an upstream flow;
s3, forming a reaction raw material 1 under pressure and a reaction raw material 2 under pressure by a pumping device respectively from the mixed slurry 1 and the solution of the precipitant and the mixed slurry 2 and the solution of the ferric salt;
s4, feeding the pressurized reaction raw material 1 and the pressurized reaction raw material 2 into the suspension forming tower in the form of fog drops, oppositely spraying the fog drops into the upper space of the suspension forming tower, carrying out impact mixing reaction on the pressurized reaction raw material 1 and the pressurized reaction raw material 2 to generate catalyst precursor fog drops, obtaining a suspension tower downlink material, carrying out cross flow contact with the uplink air flow, and carrying out drying, roasting and/or activating processes to form catalyst powder serving as the solid hydrocarbon raw material hydrogenation liquefied iron-based catalyst.
In the above preparation method, in step S1, the iron salt is at least one of ferric sulfate, ferric chloride, ferric nitrate, ferrous sulfate, ferrous chloride, ferric acetate or ferrous acetate aqueous solution;
the precipitant is at least one of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium sulfide, potassium sulfide, calcium hydroxide and barium hydroxide;
preparing a solution of the iron salt and a solution of the bottoming agent by adopting water;
the concentration of the solution of the ferric salt is 10-35%, and the concentration of the solution of the precipitant is 10-35%.
In the preparation method, in the step S1, the additive is at least one of pulverized coal, coal coke, silica gel, pumice, diatomite, montmorillonite, kaolin, clay, silica sol, alumina sol, fly ash, cinder, activated carbon, carbon nanotubes, zeolite, molecular sieve, natural ore, metal organic framework, alumina, oxide of the following metals and salts thereof;
titanium, zirconium, cerium, zinc, manganese, nickel, molybdenum and tungsten.
In the above preparation method, in step S2, the working gas is at least one of air, nitrogen, hydrogen sulfide, carbon monoxide and flue gas;
the working gas is introduced from the lower part of the suspension forming tower after being preheated;
the working gas is preheated to 300-600 ℃.
In the above preparation method, in step S3, the mass ratio of the pressurized reaction raw material 1 to the pressurized reaction raw material 2 is 0.5 to 3:1, a step of;
the atomizing device is a pressure type atomizing device, a centrifugal atomizing device, a pneumatic atomizing device or an ultrasonic atomizing device;
at least two atomization devices are oppositely arranged so that the sprayed mist drops meet in the same area;
controlling the diameter of the fog drops to be smaller than 1.2mm.
In the above preparation method, in step S3, the method further includes the following treatment steps for the dust-containing tail gas discharged from the gas outlet of the suspension forming tower:
removing catalyst fine powder entrained in the dust-containing tail gas through a tail gas dust removal system, wherein the catalyst fine powder is mixed with catalyst powder to be used as an iron-based catalyst for the hydrogenation liquefaction of the solid hydrocarbon raw material;
the tail gas dust removing system can be any device conventionally used in the field, such as one or more of single-stage or multi-stage cyclone dust removal, cloth bag dust removal and electric dust removal;
the dust-removing tail gas after the catalyst fine powder is removed is circularly utilized or emptied after tail gas purification treatment;
the following tail gas treatment devices can be adopted for treatment: one or more of a heat exchanger, a condensate recuperator, an absorber, or a catalytic combustion apparatus.
The solid hydrocarbon raw material hydrogenation liquefaction iron-based catalyst provided by the invention can be used for catalyzing the hydrogenation liquefaction of the solid hydrocarbon raw material;
the solid hydrocarbon raw materials are coal with different metamorphic degrees (such as lignite, bituminous coal and the like), biomass (such as crop wastes, plants, biological excreta and the like) and industrial and domestic wastes (such as waste tires, waste plastics and the like).
The preparation method provided by the invention has the advantages that the synthesis, drying, roasting and activation of the catalyst are finished in one step in the suspension forming tower, and the process route is short. The components are contacted in a collision way in a fogdrop form, so that efficient mixing and controllable forming are ensured; and (3) solid phase suspension drying and roasting to obtain the superfine high-dispersion catalyst.
According to the preparation method of the solid hydrocarbon raw material hydrogenation liquefying high-dispersion iron-based catalyst, raw materials are oppositely sprayed into a suspension forming tower, and ferric salt, a precipitator and/or an additive are impacted and mixed to form a catalyst precursor. Then, the suspension descends in the form of fog drops, and is in countercurrent contact with the ascending hot air flow, so that the axial temperature gradient of the suspension forming tower is formed. Suspending fog drops, and in the descending process, carrying out desolventizing, roasting and/or activating processes to generate catalyst powder with required particle size distribution and composition structure. Controlling the particle size distribution of the catalyst powder by adjusting the size of the fog drops; the catalyst powder phase is controlled by adjusting the temperature gradient and atmosphere in the tower. The invention has the characteristics of simple preparation process, high raw material utilization rate and low water consumption, and can effectively reduce the production cost of the catalyst. By means of the suspension fog drop state in the forming process, superfine high-dispersion phase is formed. The catalyst powder prepared by the method has the characteristics of uniform particle size, texture structure and dispersion degree, is easy to realize high dispersion in reaction slurry, and improves the hydro-conversion efficiency of solid hydrocarbon raw materials.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The preparation method of the high-dispersion iron-based catalyst for the hydrogenation liquefaction of the solid hydrocarbon raw material comprises the following steps:
(1) Preparing an iron salt solution and a precipitant solution;
(2) Uniformly mixing the additive with the ferric salt solution or the precipitant solution in the step (1) in a mixer to obtain mixed slurry;
(3) Forming a pressed material 1 and a pressed material 2 by the mixed slurry in the step (2) and the precipitator solution or the ferric salt solution in the step (1) through a pumping device;
(4) Feeding the pressurized material 1 and the pressurized material 2 in the step (3) into an atomization system, oppositely spraying into the upper space of a suspension forming tower, and carrying out impact mixing to form catalyst precursor fogdrops which are downward materials of the suspension tower;
(5) After the working gas is preheated, the working gas is introduced into a suspension forming tower to form an upstream flow in the tower;
(6) In the suspension forming tower, the downlink material in the step (4) is contacted with the uplink air flow in the step (5) to form an axial temperature gradient of the suspension forming tower;
(7) The downlink material in the step (4) contacts with the working air flow in the step (5) in the suspension downlink process, and undergoes the drying, roasting and/or vulcanization processes to form catalyst powder, and the catalyst powder falls at the bottom of the tower; carrying catalyst fine powder with the upward air flow to form dust-containing tail gas, and discharging from the top of the tower;
(8) Introducing the catalyst powder falling at the bottom of the tower in the step (7) into a product collecting device, and storing in an inert environment;
(9) Introducing the dust-containing tail gas in the step (7) into a tail gas dust removal system, and collecting catalyst fine powder to obtain dust-removing tail gas;
(10) And (3) introducing the dust-removing tail gas in the step (9) into a tail gas treatment device, and further purifying and recycling or evacuating.
In some preferred embodiments, the iron salt solution in step (1) comprises one or more combinations of iron sulfate, iron chloride, iron nitrate, ferrous sulfate, ferrous chloride, iron acetate, and an aqueous solution of ferrous acetate.
In some preferred embodiments, in step (1), the concentration of the iron salt solution is from 10 to 35wt.%.
In some preferred embodiments, in step (1), the precipitant is one or more of ammonia, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate, sodium sulfide, potassium sulfide, calcium hydroxide, and/or barium hydroxide.
In some preferred embodiments, in step (1), the concentration of the precipitant solution is 10 to 35wt.%.
In some preferred embodiments, in step (2), the additive is one or more combinations of coal fines, coal char, silica gel, pumice, diatomaceous earth, montmorillonite, kaolin, clay, silica sol, alumina sol, fly ash and cinder, activated carbon, carbon nanotubes, zeolite, molecular sieves, natural ores, metal organic frameworks, alumina, oxides of titanium/zirconium/cerium/zinc/manganese/nickel/molybdenum/tungsten, salts thereof, and the like.
In some preferred embodiments, in step (2), the mass ratio of the iron salt solution or the precipitant solution to the additive is from 2 to 4:1.
in some preferred embodiments, the mixed slurry formation in step (2) includes three types of:
firstly, adding an optional ferric salt solution or an optional precipitant solution into a mixer, starting a device, then adding an optional additive, and stirring for 0.1-3 h;
ii) adding optional additives into a mixer, starting a device, adding optional ferric salt solution or optional precipitant solution, and stirring for 0.1-3 h;
iii) starting the device, adding the optional ferric salt solution or the optional precipitant solution and the optional additive into the mixer at the same time, and stirring for 0.1-3 h.
In some preferred embodiments, in step (2), the mixer is any device conventionally used in the art, such as one or more combinations of a stirring mixer, a pipe mixer, a jet mixer, a forced circulation mixer, a static mixer, a kneader, a rotary kiln, and the like.
In some preferred embodiments, in step (4), the mass ratio of the ejection of the tape preform 1 and the ejection of the tape preform 2 is 0.5 to 3:1.
in some preferred embodiments, in step (4), the atomizer is any device conventionally used in the art, such as one or more combinations of pressure, centrifugal, pneumatic, and ultrasonic atomizers; further, at least 2 atomizers are arranged, and ejected mist drops are converged in the same area; still further, according to the material property, the caliber of the spray head is adjusted, and the diameter of the fog drops is controlled below 1.2mm.
In some preferred embodiments, in step (5), the working gas is one or more of air, nitrogen, hydrogen sulfide, carbon monoxide, flue gas, and the hot gas inlet temperature is 300-600 ℃.
In some preferred embodiments, in step (8), the inert environment is an inert atmosphere, a water seal, a solvent oil seal, or a wax seal.
In some preferred embodiments, in step (9), the tail gas dust removal system is any device conventionally used in the art, such as one or more combinations of single or multi-stage cyclone dust removal, cloth bag dust removal, electric dust removal
In some preferred embodiments, in step (10), the tail gas treatment device is any device conventionally used in the art, such as one or a combination of more of a heat exchanger, a condensate recuperator, an absorber, or a catalytic combustion apparatus.
In some preferred embodiments, the solid hydrocarbon feedstock hydroliquefaction catalyst is used in hydroliquefaction processes of varying degrees of deterioration of coal (e.g., lignite, bituminous coal, etc.), biomass (e.g., crop waste, plants, biological excreta, etc.), and industrial and domestic waste (e.g., tires, waste plastics, etc.).
The technical solution of the present invention will be further described with reference to the following examples, however, it should be understood that the scope of the present invention is not limited to these examples.
Comparative example 1: preparation of catalyst D1
182.8kg of ferrous sulfate heptahydrate is added into 817.2kg of water to prepare a ferrous sulfate solution with the concentration of 10wt.% and 500kg of alumina is added to obtain mixed slurry; 300kg of water was added to 200kg of 25wt.% strength aqueous ammonia to prepare 10wt.% strength aqueous ammonia solution; and (3) pumping the mixed slurry and an ammonia water solution into an acid-base mixing kettle in parallel flow to obtain a precipitate slurry. Washing, filtering, drying and roasting the precipitate slurry to obtain the catalyst D1.
Example 1: preparation of catalyst C1
182.8kg of ferrous sulfate heptahydrate is added into 817.2kg of water to prepare a ferrous sulfate solution with the concentration of 10 wt.%; 300kg of water was added to 200kg of 25wt.% strength aqueous ammonia to prepare 10wt.% strength aqueous ammonia solution; adding 500kg of aluminum oxide into a stirring mixer, adding 1000kg of ferrous sulfate solution, starting a device, and mixing for 0.5h to obtain mixed slurry; feeding the mixed slurry and 10wt.% ammonia water solution into a pressure atomizer at the upper part of a suspension forming tower according to a preparation proportion by a pumping device, spraying the mixed slurry and 10wt.% ammonia water solution into the upper space of the suspension forming tower through opposite double nozzles (2.0 mm caliber) to form fog drops with the diameter of about 1mm, and carrying out impact mixing to form a descending material of the suspension forming tower; heating air to 300 ℃, feeding the air from the bottom of a suspension forming tower to form an upward air flow in the tower, enabling the upward air flow to be in countercurrent contact with a downward material in the suspension forming tower, and carrying out synthesis, drying and roasting processes to obtain a catalyst product (A1) and dust-containing tail gas at the bottom of the tower; introducing dust-containing tail gas into a secondary cyclone separation system at the top of the suspension forming tower, and collecting catalyst fine powder (B1) and dust-removing tail gas; and (3) introducing the dust-removed tail gas into a condensation recoverer, and recycling air after condensing steam. Catalysts A1 and B1 were homogeneously mixed to give catalyst C1, which was stored under nitrogen atmosphere.
Example 2: preparation of catalyst C2
200kg of ferric chloride was added to 800kg of water to prepare a ferric chloride solution having a concentration of 20 wt.%; 150kg of sodium carbonate was added to 600kg of water to prepare a 20wt.% sodium carbonate solution; 1000kg of ferric chloride is added into a rotary kiln, 250kg of kaolin is added, a device is started, and mixing is carried out for 0.1h, so as to obtain mixed slurry; feeding the mixed slurry and a sodium carbonate solution with the concentration of 20wt.% into a centrifugal atomizer at the upper part of a suspension forming tower according to a preparation proportion by a pumping device, spraying the mixed slurry and the sodium carbonate solution into the upper space of the suspension forming tower through three opposite nozzles (1.4 mm caliber) to form 0.7mm fog drops, and carrying out impact mixing on the materials to form a descending material of the suspension forming tower; heating a 20% hydrogen sulfide/nitrogen mixed gas to 450 ℃, feeding the mixed gas from the bottom of a suspension forming tower to form an upward gas flow in the tower, carrying out countercurrent contact with a downward material in the suspension forming tower, and carrying out drying, roasting and activating processes to obtain a catalyst product (A2) and dust-containing tail gas at the bottom of the tower; introducing dust-containing tail gas into a cloth bag dust removal and separation system at the top of the suspension molding tower, and collecting catalyst fine powder (B2) and dust-removing tail gas; and (3) introducing the dust-removed tail gas into an alkali liquor absorption tower, purifying the tail gas and recycling the tail gas. Catalysts A2 and B2 were mixed homogeneously to give catalyst C2, which was stored in solvent oil.
Example 3: preparation of catalyst C3
350kg of iron acetate was added to 650kg of water to prepare an iron acetate solution having a concentration of 35 wt.%; 270kg of sodium hydroxide was added to 480kg of water to prepare a 35wt.% strength sodium hydroxide solution; starting the kneader, simultaneously adding 750kg of sodium hydroxide solution and 250kg of fly ash, and mixing for 1.5 hours to obtain mixed slurry; feeding the mixed slurry and 35wt.% ferric acetate solution into an ultrasonic atomizer at the upper part of a suspension forming tower according to a preparation proportion by a pumping device, spraying the mixed slurry and 35wt.% ferric acetate solution into the upper space of the suspension forming tower through four opposite nozzles (1.0 mm caliber) to form mist drops with the thickness of about 0.5mm, and carrying out impact mixing on the materials to form a descending material of the suspension forming tower; feeding flue gas with the temperature of 600 ℃ from the bottom of a suspension forming tower to form an upward air flow in the tower, carrying out countercurrent contact with downward materials in the suspension forming tower, and carrying out drying and roasting processes to obtain a catalyst product (A3) and dust-containing tail gas at the bottom of the tower; introducing dust-containing tail gas into a suspension molding tower top electric dust removing system, and collecting catalyst fine powder (B3) and dust-removing tail gas; and (3) sequentially introducing the dust-removing tail gas into a heat exchanger tower, purifying by an alkali liquor absorption tower, and then evacuating. And uniformly mixing the catalysts A3 and B3 to obtain a catalyst C3, and sealing the catalyst C3 in paraffin.
Example 4: preparation of catalyst C4
Adding 100kg of ferric nitrate and 100kg of ferric sulfate into 600kg of water to prepare an iron salt solution with the concentration of 25 wt%; adding 50kg of sodium sulfide and 50kg of sodium hydroxide to 400kg of water to prepare a precipitant solution with a concentration of 20 wt.%; adding 200kg of molecular sieve and 100kg of kaolin into a stirring mixer, adding 500kg of 20wt.% precipitant solution, starting a device, mixing for 3 hours, and adding the slurry into a mixer for mixing for 1 hour; feeding the obtained mixed slurry and 25wt.% ferric nitrate solution into a pneumatic atomizer at the upper part of a suspension forming tower according to a preparation proportion through a pumping device, spraying the mixed slurry and the 25wt.% ferric nitrate solution into the upper space of the suspension forming tower through opposite double nozzles (0.5 mm caliber) to form fog drops with the diameter of about 0.3mm, and carrying out impact mixing on the materials to form a descending material of the suspension forming tower; feeding nitrogen with the temperature of 500 ℃ from the bottom of a suspension forming tower to form an upward air flow in the tower, carrying out countercurrent contact with a downward material in the suspension forming tower, and carrying out drying and roasting processes to obtain a catalyst product (A4) and dust-containing tail gas at the bottom of the tower; the dust-containing tail gas is sequentially led into a suspension molding tower top secondary cyclone separation system and an electric dust removal system, and catalyst fine powder (B4) and dust-removing tail gas are collected; and (3) sequentially introducing the dust-removing tail gas into a heat exchanger and a condensation recoverer, and recycling nitrogen after recovering water vapor. Catalysts A4 and B4 were mixed homogeneously to give catalyst C4, which was stored in water.
Example 5: preparation of catalyst C5
Adding 100kg of ferric sulfate into 400kg of water to prepare a ferric sulfate solution with the concentration of 20 wt%; 200kg of ammonia carbonate was added to 800kg of water to prepare an ammonia carbonate solution of 20wt.% concentration; starting a device, namely introducing 200kg of coal dust and 500kg of 20wt.% ferric sulfate solution into a pipeline mixer, and mixing for 0.1h to obtain mixed slurry; the mixed slurry and the ammonium carbonate solution with the concentration of 20wt.% are respectively sent into a centrifugal atomizer and a pressure atomizer at the upper part of a suspension forming tower through a pumping device, and are sprayed into the upper space of the suspension forming tower through four opposite nozzles (1.0 mm caliber) to form fog drops with the diameter of about 0.7mm, and the materials are impacted and mixed to form the descending materials of the suspension forming tower; feeding 10% carbon monoxide/hydrogen with the temperature of 350 ℃ from the bottom of a suspension molding tower to form an upward airflow in the tower, carrying out countercurrent contact with a downward material of the suspension molding tower, and carrying out drying and roasting processes to obtain a catalyst product (A5) and dust-containing tail gas at the bottom of the tower; introducing dust-containing tail gas into a secondary cyclone separation system at the top of the suspension forming tower, and collecting catalyst fine powder (B5) and dust-removing tail gas; and (3) introducing the dust-removed tail gas into an absorption tower, purifying and recycling. And uniformly mixing the catalysts A5 and B5 to obtain a catalyst C5, and sealing the catalyst C5 in solvent oil.
Application example 1 catalytic solid Hydrocarbon feedstock Hydroliquefaction
The catalysts prepared in comparative examples and examples 1 to 5 of the present invention catalyze solid hydrocarbon raw materials a (lignite)/B (straw)/C (waste plastics), and the properties of the raw materials are shown in table 1.
The reaction conditions are as follows: the pressure is 3-6 MPa, the temperature is 400-450 ℃, the residence time is 30-240 min, the simple substance S/Fe=1/1, and the catalyst addition amount is 1-3% (mass fraction) Fe daf 。
The conditions and results of the individual catalysts for the hydroliquefaction of the solid hydrocarbon feedstock are shown in table 2.
TABLE 1 Properties of several solid Hydrocarbon feedstocks
TABLE 2 Hydroliquefaction conditions and results for several solid hydrocarbon feedstocks for the catalysts obtained in examples 1-5
As can be seen from the data in Table 2, the high-dispersion iron-based catalyst for the hydrogenation liquefaction of the solid hydrocarbon raw material provided by the invention is easy to realize high dispersion in reaction slurry, improves the hydrogenation conversion rate of the solid hydrocarbon raw material, has higher oil yield, and has a simple preparation process, and the production cost of the catalyst can be effectively reduced.
Claims (9)
1. The preparation method of the solid hydrocarbon raw material hydrogenation liquefying iron-based catalyst comprises the following steps:
s1, preparing a solution of ferric salt and a solution of a precipitant, and respectively mixing with an additive to obtain mixed slurry 1 and mixed slurry 2;
s2, preheating working gas, and then introducing the preheated working gas into a suspension forming tower to form an upstream flow;
s3, forming a reaction raw material 1 under pressure and a reaction raw material 2 under pressure by a pumping device respectively from the mixed slurry 1 and the solution of the precipitant and the mixed slurry 2 and the solution of the ferric salt;
s4, feeding the pressurized reaction raw material 1 and the pressurized reaction raw material 2 into the suspension forming tower in the form of fog drops, oppositely spraying the fog drops into the upper space of the suspension forming tower, carrying out impact mixing reaction on the pressurized reaction raw material 1 and the pressurized reaction raw material 2 to generate catalyst precursor fog drops, obtaining a suspension tower downlink material, carrying out cross flow contact with the uplink air flow, and carrying out drying, roasting and/or activating processes to form catalyst powder serving as the solid hydrocarbon raw material hydrogenation liquefied iron-based catalyst.
2. The method of manufacturing according to claim 1, characterized in that: in the step S1, the ferric salt is at least one of ferric sulfate, ferric chloride, ferric nitrate, ferrous sulfate, ferrous chloride, ferric acetate or ferrous acetate water solution;
the precipitant is at least one of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate, ammonium bicarbonate, sodium sulfide, potassium sulfide, calcium hydroxide and barium hydroxide;
preparing a solution of the iron salt and a solution of the bottoming agent by adopting water;
the concentration of the solution of the ferric salt is 10-35%, and the concentration of the solution of the precipitant is 10-35%.
3. The preparation method according to claim 1 or 2, characterized in that: in the step S1, the additive is at least one of pulverized coal, coal coke, silica gel, pumice, diatomite, montmorillonite, kaolin, clay, silica sol, alumina sol, fly ash, coal cinder, activated carbon, carbon nano tubes, zeolite, molecular sieve, natural ore, metal organic framework, alumina, oxide of the following metals and salts thereof;
titanium, zirconium, cerium, zinc, manganese, nickel, molybdenum and tungsten.
4. A production method according to any one of claims 1 to 3, characterized in that: in step S2, the working gas is at least one of air, nitrogen, hydrogen sulfide, carbon monoxide and flue gas;
the working gas is introduced from the lower part of the suspension forming tower after being preheated;
the working gas is preheated to 300-600 ℃.
5. The method according to any one of claims 1 to 4, wherein: in step S3, the mass ratio of the pressurized reaction raw material 1 to the pressurized reaction raw material 2 is 0.5 to 3:1, a step of;
the atomizing device is a pressure type atomizing device, a centrifugal atomizing device, a pneumatic atomizing device or an ultrasonic atomizing device;
at least two atomization devices are oppositely arranged so that the sprayed mist drops meet in the same area;
controlling the diameter of the fog drops to be smaller than 1.2mm.
6. The production method according to any one of claims 1 to 5, characterized in that: in step S3, the method further includes the following treatment steps for the dust-containing tail gas discharged from the gas outlet of the suspension forming tower:
removing catalyst fine powder entrained in the dust-containing tail gas through a tail gas dust removal system, wherein the catalyst fine powder is mixed with catalyst powder to be used as an iron-based catalyst for the hydrogenation liquefaction of the solid hydrocarbon raw material;
and (3) recycling or evacuating the dust-removed tail gas after the catalyst fine powder is removed after tail gas purification treatment.
7. An iron-based catalyst for the hydroliquefaction of a solid hydrocarbon feedstock prepared by the process of any one of claims 1-6.
8. The use of the iron-based catalyst for the hydroliquefaction of a solid hydrocarbon feedstock according to claim 7 for catalyzing the hydroliquefaction of a solid hydrocarbon feedstock.
9. The use according to claim 8, characterized in that: the solid hydrocarbon raw materials are coal, biomass, industrial waste and domestic waste.
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|---|---|---|---|
| CN202310191517.2A CN116196927A (en) | 2023-03-02 | 2023-03-02 | High-dispersion iron-based catalyst for hydrogenation liquefaction of solid hydrocarbon raw material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310191517.2A CN116196927A (en) | 2023-03-02 | 2023-03-02 | High-dispersion iron-based catalyst for hydrogenation liquefaction of solid hydrocarbon raw material and preparation method thereof |
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