CN116218564A - Application of iron-based catalyst in poor-quality/heavy-quality oil slurry bed hydrogenation upgrading - Google Patents

Abstract

The invention discloses an application of an iron-based catalyst in poor-quality/heavy-quality oil slurry bed hydrogenation upgrading. According to the invention, the precipitant, ferric salt and/or additive are oppositely sprayed into the suspension forming tower, and the raw materials are impacted and mixed to form catalyst precursor fogdrops, so that superfine high-dispersion powder is formed and used as the iron-based catalyst. The poor quality/heavy oil comprises crude geological heavy oil, by-product heavy oil in petroleum refining and processing processes, heavy oil and asphalt extracted from oil sand and oil shale, and by-product tar in heavy hydrocarbon raw material thermal processing processes. The catalyst phase can be effectively controlled by adjusting the temperature gradient and atmosphere in the tower, and the catalyst is in the optimal activity state when contacting with reactants (heavy/inferior oil) in the hydrogenation upgrading reaction process, so that the catalyst has better hydrogenation upgrading capability.

Description

Application of iron-based catalyst in poor-quality/heavy-quality oil slurry bed hydrogenation upgrading

Technical Field

The invention relates to an application of an iron-based catalyst in poor-quality/heavy-quality oil slurry bed hydrogenation upgrading, and belongs to the field of energy and chemical industry.

Background

At present, the world petroleum has a trend of heavy and poor quality, but the demand of the current society for heavy fuel oil is reduced year by year, and the market demand of the light fuel oil for chemical industry and the clean fuel oil for vehicles is increased day by day. The efficient utilization of the existing petroleum resources to ensure the supply of energy and chemical raw materials is an effective method. Therefore, in recent years, research for efficiently converting inferior/heavy oil into light oil has been paid attention to.

Poor/heavy oil is comprised of virgin geologic reservoir heavy oils (e.g., heavy oils, high viscosity crude oils, natural asphalts), petroleum refining and processing by-product heavy oils (e.g., atmospheric residuum, vacuum residuum, coker gas oils), and heavy oils and asphalts refined from oil sands and shale. The processing of the catalyst adopts a decarburization process or a hydrogenation process. The decarbonization process comprises solvent deasphalting, hot working and the like, and the method has strong raw material adaptability, but large solvent consumption and large energy consumption. The hydrogenation process is favorable for converting inferior/heavy oil into high added value products, reducing coke formation conversion, and the current research is mainly conducted on the hydrogenation process.

The reactor of the hydrogenation process comprises a fixed bed and a slurry bed. The fixed bed reactor is only suitable for poor quality/heavy oil with low heavy weight degree, if the heavy weight degree is too high, the reactor is easy to be blocked, the catalyst is easy to be deactivated, the equipment operation period is short and the catalyst replacement cost is high in actual production. The slurry bed reactor has the advantages of wide application range of raw materials, good mass and heat transfer effect in the reaction, flexible product distribution and the like, is more suitable for converting various inferior/heavy oil, and is widely studied at present.

The catalytic hydrogenation capacity of the catalyst used in the hydrogenation process is the key of the poor quality/heavy oil hydrogenation process technology. Slurry bed reactor catalysts can be currently classified into two broad categories, homogeneous and heterogeneous. The homogeneous catalyst is mainly an oil-soluble molybdenum-based catalyst, and has good performance, however, the preparation of the catalyst needs expensive organic ligands, so that the cost of the catalyst is high. Heterogeneous catalysts are solid powder-type catalysts, and are specifically classified into noble metal nickel molybdenum and inexpensive iron-based catalysts. The nickel-molybdenum-based catalyst has better performance than the iron-based catalyst, but has high price and difficult recovery and regeneration. The iron-based catalyst has low cost and can be used once without recovery and regeneration.

Iron-based catalysts come mainly from two pathways: firstly, natural world and secondly, chemical synthesis. Natural iron-containing ores (including pyrite, limonite, and pyrrhotite) are not rare, but how to grind these iron-containing ores to ultrafine powders efficiently and at low cost is a major challenge. Furthermore, the chemical composition and structure of the iron-containing natural minerals themselves are often not the optimal catalytically-active phase.

The micron or even nanometer specific phase iron-based product can be obtained by a chemical synthesis method, and is easy to realize high dispersion when being used for upgrading inferior/heavy oil hydrogen, so that the activity and the utilization rate of the catalyst are in the optimal state. In order to further optimize the catalyst preparation method, the metal dispersity is improved, and the catalyst preparation cost is reduced. The invention discloses a preparation method and application of an inferior/heavy oil slurry bed hydrogenation upgrading high-dispersion iron-based catalyst. The precipitant, ferric salt and/or additive are sprayed into the suspension forming tower oppositely, the raw materials are impacted and mixed to form catalyst precursor fog drops, the fog drops suspend and descend to contact with the ascending hot air flow in countercurrent, and the catalyst precursor fog drops undergo drying, roasting and/or activating processes in sequence, so that the catalyst powder with ultra-fine high-dispersion phase and required composition structure is formed. The particle size distribution of the catalyst powder is regulated and controlled by changing the number and caliber of the nozzles; the catalyst powder phase is controlled by adjusting the temperature gradient and atmosphere in the tower. The preparation method has the characteristics of simple preparation process, high raw material utilization rate and low water consumption, can effectively reduce the production cost of the catalyst, and the high-dispersion phase is beneficial to improving the hydrogenation quality improvement efficiency of the inferior/heavy oil.

Disclosure of Invention

The invention aims to provide an application of an iron-based catalyst in poor quality/heavy oil slurry bed hydrogenation upgrading, and can improve the hydrogenation upgrading efficiency of poor quality/heavy oil.

The present invention relates to poor quality/heavy oil including crude geologic reservoir heavy oil (e.g., heavy oil, high viscosity crude oil, natural asphalt), petroleum refining and processing by-product heavy oil (e.g., atmospheric residuum, vacuum residuum, coker gas oil), heavy oil and asphalt refined from oil sand and oil shale, and heavy hydrocarbon feedstock thermal processing (e.g., carbonization, liquefaction, gasification, coking) by-product tar.

The iron-based catalyst related by the invention is prepared according to 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 iron-based catalyst.

In the 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 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%.

In the step S1, the additive is at least one of pulverized coal, coal char, silica gel, pumice, diatomite, montmorillonite, kaolin, clay, silica sol, alumina sol, fly ash, coal 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 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 step S3, the mass ratio of the pressurized reaction raw material 1 to the pressurized reaction raw material 2 is 0.5-3: 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 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 the poor/heavy oil hydrogenation upgrading iron-based catalyst;

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.

Compared with the prior art, the method has the advantages that the precipitants, the ferric salt and/or the additives are oppositely sprayed into the suspension forming tower, the raw materials are impacted and mixed to form the catalyst precursor fogdrops, so that the superfine high-dispersion powder is formed, the superfine high-dispersion powder can be better dispersed in reactants (heavy/inferior oil), the stronger hydrogenation capability can be provided, and the higher oil yield is realized.

The catalyst phase can be effectively controlled by adjusting the temperature gradient and atmosphere in the tower, and the catalyst is in the optimal activity state when contacting with reactants (heavy/inferior oil) in the hydrogenation upgrading reaction process, so that the catalyst has better hydrogenation upgrading capability.

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.

In the following examples, the starting oil: the hydrogenation upgrading performance of the catalyst was evaluated for each of a (thick oil), B (vacuum residue) and C (coker wax oil), and the composition and properties of the feedstock 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 feedstock oil hydrodeoxygenation conditions and results for the catalysts obtained in the corresponding examples are given in table 2.

Comparative example 1: 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: 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 ammonia water to prepare 10wt.%

Ammonia water solution with concentration; 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 molding tower through a porous straight pipe type gas distributor 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 molding 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: 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 molding tower through a straight pipe baffle type gas distributor to form an upstream gas flow in the tower, carrying out countercurrent contact with a downstream material in the suspension molding 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: 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 through a tangential horn type gas distributor to form upward gas 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: 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 precipitant solution with the concentration of 20wt.% into the mixer, starting the 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 the suspension molding tower through a porous straight pipe type gas distributor to form an upward gas flow in the tower, carrying out countercurrent contact with a downward material in the suspension molding 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: 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 ℃ into a suspension forming tower from the bottom of the tower through a straight pipe baffle type gas distributor and a porous straight pipe type gas distributor to form an upward gas flow in the tower, carrying out countercurrent contact with a downward material of the suspension forming 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.

TABLE 1 Properties of raw oils A, B and C

TABLE 2 raw oil hydrodeoxygenation conditions and Main results for the catalysts obtained in examples 1-5

As can be seen from the data in Table 2, the invention adopts the heavy/inferior oil hydrogenation upgrading high dispersion iron-based catalyst, can improve the hydrogenation upgrading efficiency of the heavy/inferior oil, and has higher distillate oil yield of <520 ℃ and lower coking rate.

Claims (7)

1. An application of an iron-based catalyst in catalyzing poor/heavy oil slurry bed hydrogenation upgrading;

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 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 iron-based catalyst.

2. The use according to claim 1, characterized in that: the poor quality/heavy oil comprises crude geological heavy oil, by-product heavy oil in petroleum refining and processing processes, heavy oil and asphalt extracted from oil sand and oil shale, and by-product tar in heavy hydrocarbon raw material thermal processing processes.

3. Use according to claim 1 or 2, 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%.

4. A use according to any one of claims 1-3, 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.

5. The use according to any one of claims 1-4, 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 ℃.

6. The use according to any one of claims 1-5, characterized in that: 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.

7. The use according to any one of claims 1-6, 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 the poor/heavy oil hydrogenation upgrading iron-based catalyst;

and (3) recycling or evacuating the dust-removed tail gas after the catalyst fine powder is removed after tail gas purification treatment.