CN109897664B - Hydrotreating method for acid-containing crude oil - Google Patents
Hydrotreating method for acid-containing crude oil Download PDFInfo
- Publication number
- CN109897664B CN109897664B CN201711305427.2A CN201711305427A CN109897664B CN 109897664 B CN109897664 B CN 109897664B CN 201711305427 A CN201711305427 A CN 201711305427A CN 109897664 B CN109897664 B CN 109897664B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- crude oil
- acid
- upflow
- bed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrotreating method of acid-containing crude oil. The method comprises at least one upflow hydrogenation reactor and at least one hydrotreating catalyst is filled; the carrier of the hydrotreating catalyst is spherical with three-dimensional through pore channels, and the carrier is provided with seven through holes, including a middle through hole and side through holes, wherein the spherical outer diameter is 6.0-10.0 mm, the hole diameter of the middle through hole is 25-40% of the spherical outer diameter, and the hole diameter of the side through hole is 10-20% of the spherical outer diameter. The invention adopts a specific catalyst, has good hydrogenation deacidification performance, metal removing capacity, desulfurization, carbon residue and asphaltene conversion capacity, and long operation period of the device. Moreover, the method of the invention overcomes the problems of various catalysts, complicated loading and unloading, back mixing of different catalysts and the like in the existing upflow reactor.
Description
Technical Field
The invention relates to a hydrotreating method of acid-containing crude oil, in particular to a method for treating acid-containing crude oil by adopting an up-flow type hydrogenation process technology.
Background
Petroleum typically contains acid compounds, primarily in the form of naphthenic acids. The concentration or amount of acid in petroleum is expressed using the total acid number. The Total Acid Number (TAN) is the number of milligrams of potassium hydroxide (KOH) required to neutralize all of the acidic components of 1 gram of crude oil or petroleum fraction, expressed in mg KOH/g.
In the process of refining petroleum, naphthenic acid in the petroleum can directly react with iron to cause corrosion of oil refining equipment such as a heating furnace tube and the like; and the catalyst can also react with a protective film FeS on the oil refining equipment, so that the metal equipment is exposed on a new surface and is subjected to new corrosion. At present, common oil refining equipment can only process acid-containing hydrocarbon oil with the total acid value less than 0.3mgKOH/g, and when the total acid value in the acid-containing hydrocarbon oil exceeds 1mgKOH/g, the equipment is extremely corroded; when the total acid value reaches 0.5mgKOH/g, significant corrosion may occur to refinery equipment. Because of the corrosive nature of acid-containing crudes, refineries are generally reluctant to process crudes having acid numbers greater than 1 mgKOH/g.
Highly acidic crude oil is typically a poor quality, inexpensive crude oil, heavy and poor quality of which account for a large proportion of newly discovered and newly developed oil fields worldwide. In 2012, the global high acid crude oil yield exceeds 4 hundred million tons, accounting for 10% of the total crude oil yield. Also, the international crude oil market has a phenomenon that the supply and demand of high-acid crude oil are excessive, the price of the high-acid crude oil is generally low, and although the processing of the high-acid crude oil may cause a plurality of problems, the high-acid crude oil is pretreated by adopting an efficient and economic technical means, and the processing of the high-acid crude oil has good economic benefit.
In recent years, as crude oil resources are becoming heavier and higher in acid value and chemical or microbial oil recovery techniques are being widely used, the types and contents of metal ions in crude oil are increasing, and the contents of calcium ions therein are increasing. For example, the total acid value of the thickened oil of Liaohe in China is 2.10mgKOH/g, the calcium content is up to 284 mu g/g, the acid value of the Sudan mixed crude oil is 13.82mgKOH/g, and the calcium content can be up to 1600 mu g/g. The calcium content in most crude oil has a certain corresponding relation with the acid value, the acid value is increased, and the calcium content is also increased. Calcium in high acid crude oil exists mostly in the form of calcium naphthenate, which is easily soluble in oil but hardly soluble in water and cannot be removed in the desalting process. The current world crude market for acid-containing crude accounts for about 5% of the total global crude production annually, and also increases annually at a rate of 0.3%. Therefore, how to effectively treat the high-metal acid-containing crude oil is a major issue to be faced at present.
With the increase of the production amount of acid-containing crude oil, the problem of equipment corrosion caused by acid-containing hydrocarbon oil is receiving more and more attention. The deacidification method of the acid-containing hydrocarbon oil generally comprises physical adsorption, solvent extraction and chemical conversion, and the most common method is the chemical conversion method, such as pyrolysis, hydrogenation deacidification and the like.
Hydrogenation deacidification is a method for removing carboxyl by reaction of petroleum acid in acid-containing hydrocarbon oil and hydrogen to generate hydrocarbon and water. US5897769 firstly proposes using industrially produced small-pore hydrofining catalyst, at a reaction temperature of 200-370 ℃ and a liquid hourly space velocity of 0.1-10 h-1Under the conditions of 345-3450 kPa hydrogen partial pressure and 10-100 hydrogen-oil ratio, naphthenic acid with the relative molecular mass less than 450 in crude oil can be selectively removed, and the deacidification rate is highestCan reach 91.6 percent. US5910242 teaches that if the above hydrofining catalyst is presulfided or 4% mole fraction H is added to the hydrogen2S, the deacidification rate of naphthenic acid in crude oil can be improved.
The upflow reactor is characterized in that the oil-gas mixture is fed from the bottom of the reactor to pass through the upflow catalyst bed layer upwards, the liquid phase is continuous in the reactor, the gas phase passes through the reactor in a bubbling mode, the whole catalyst bed layer slightly expands, the deposits of metal, coke and the like can be uniformly deposited on the whole catalyst bed layer, the deposits are prevented from being concentrated on a certain part, the performance of all catalysts is well exerted, and the rapid increase of the pressure drop of the catalyst bed layer is slowed down. The technology can be used for deacidifying crude oil, but the problems of short operation period, quick catalyst inactivation and the like are caused by the fact that the front catalyst bed layer is easy to block due to the high iron-calcium content and solid particle content when the conventional upflow catalyst is adopted to process poor acid-containing crude oil.
CN104560134A provides a method for processing acid-containing hydrocarbon oil, the acid-containing hydrocarbon oil is divided into two paths after being heated or heat exchanged to 160-220 ℃, wherein, the first path of acid-containing hydrocarbon oil is mixed with hydrogen and then enters a fluidized bed reactor, the second path of acid-containing hydrocarbon oil is mixed with circulating materials on-line replaced by the fluidized bed reactor and then enters the fluidized bed reactor through an inlet at the upper part of a reactor distributor, the first path of acid-containing hydrocarbon oil and the second path of acid-containing hydrocarbon oil are contacted with a catalyst for reaction, and gas and liquid products are obtained after reaction products are cooled and separated.
CN101240189A discloses a fixed bed hydrotreating method for acid-containing crude oil. The method is characterized in that the hydrogenation catalyst filled in the hydrogenation reactor at least comprises two or more catalyst bed layers, the upper catalyst bed layer is filled with a large-aperture hydrogenation protection catalyst, and the lower catalyst bed layer is filled with a double-peak-aperture hydrogenation catalyst. In the bimodal pore hydrogenation catalyst, the pore diameters are mainly concentrated in the range of 5-10 nm and 10-20 nm.
The catalytic hydrogenation deacidification method has the problems of poor raw material adaptability, easy coking and hardening at the top of a reactor when processing poor-quality high-acid and high-calcium poor-acid-containing crude oil, quick catalyst inactivation and greatly shortened device operation period.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a hydrotreating method of acid-containing crude oil, which adopts a specific catalyst and an up-flow hydrogenation process technology to treat the acid-containing crude oil, has good hydrogenation deacidification performance and capacity-removing metal capacity, simultaneously has certain desulfurization and carbon residue and asphaltene conversion capacities, high hydrogenation activity and long device running period. Moreover, the single-type catalyst can be applied to the upflow reactor, and the problems of multiple types of catalysts, complicated loading and unloading, back mixing of different types of catalysts and the like in the conventional upflow reactor are solved.
The invention provides a hydrotreating method of acid-containing crude oil, which comprises at least one upflow hydrogenation reactor, wherein the acid-containing crude oil and hydrogen enter the upflow hydrogenation reactor for hydrogenation reaction to obtain a product after hydrogenation deacidification; at least one hydrotreating catalyst is filled in the upflow hydrogenation reactor; the hydrotreating catalyst comprises a carrier and an active component, wherein the carrier is spherical and is provided with a three-dimensional through hole channel, the carrier is provided with seven through holes, the x-axis direction, the y-axis direction and the z-axis direction of the center of the sphere are respectively provided with one through hole, namely three middle through holes, the four side through holes which are parallel to the middle through holes in the same direction and distributed on two sides of the middle through holes are also arranged in two directions of the x-axis direction, the y-axis direction and the z-axis direction, the side through holes and the side through holes are mutually communicated with the middle through holes in the third direction, the spherical outer diameter is 6.0-10.0 mm, the hole diameter of the middle through hole is 25-40% of the spherical outer diameter, and the hole diameter of the side through holes is 10-20.
In the hydrotreating catalyst of the present invention, the through-hole may be in any shape, and is preferably a cylindrical through-hole.
In the hydrotreating catalyst of the invention, the active metal component includes a second metal component, i.e., a VIB group metal element, and a third metal component, i.e., a VIII group metal element.
The carrier of the hydrotreating catalyst of the invention is prepared from Al2O3-SiO2As a carrier, wherein SiO2The weight content is 20-50%, preferably 30-40%.
In the hydrotreating catalyst of the invention, the VIB group metal element as the active metal component is preferably Mo, and the VIII group metal element is preferably Ni and/or Co. Wherein, the content of the second metal component calculated by oxide is 1.0-10.0%, preferably 1.5-6.5%, the total content of the first metal component and the third metal component calculated by oxide is 3.0-10.0%, preferably 4.0-8.0%, the content of silicon oxide is 25.0-35.0%, the content of aluminum oxide is 55.0-65.0%, the molar ratio of the third metal component to the second metal component calculated by atom is 1.5: 1-4.5: 1.
in the hydrotreating catalyst of the present invention, the support preferably further contains a first metal component oxide, and the first metal component oxide is NiO. The first metal component oxide NiO and Al2O3Is 0.03: 1-0.13: 1, preferably 0.05: 1-0.11: 1.
the hydrotreating catalyst carrier of the invention has the following properties: the specific surface area is 100-200 m2The pore volume is more than 0.70mL/g, preferably 0.75-1.15 mL/g, the pore volume occupied by the pore diameter of 20-100 nm is 35-60% of the total pore volume, and the average pore diameter is more than 18nm, preferably 20-30 nm.
The preparation method of the hydrotreating catalyst comprises the following steps:
(1) adding an acidic peptizing agent into a silicon source for acidification treatment;
(2) adding pseudo-boehmite and a curing agent into the step (1) to prepare a paste material;
(3) adding the paste material obtained in the step (2) into a mould, and heating the mould containing the paste material for a certain time to solidify and form the paste material;
(4) removing the material in the step (3) from the mold, washing, drying and roasting to obtain a catalyst carrier;
(5) and (4) impregnating the carrier obtained in the step (4) with active metal components of the supported catalyst, and drying and roasting to obtain the hydrotreating catalyst.
In the preparation method of the hydrotreating catalyst according to the present invention, the first metal oxide is preferably introduced into the support, and the first metal source (nickel source) may be introduced in step (1) and/or step (2), and the preferred introduction method is as follows: adding a nickel source into the material obtained in the step (1), and dissolving the nickel source into the material. The nickel source can adopt soluble nickel salt, wherein the soluble nickel salt can be one or more of nickel nitrate, nickel sulfate and nickel chloride, and nickel nitrate is preferred.
In the preparation method of the hydrotreating catalyst, the silicon source in the step (1) is one or more of water glass and silica sol, wherein the mass content of silicon in terms of silicon oxide is 20-40%, preferably 25-35%; the acid peptizing agent is one or more of nitric acid, formic acid, acetic acid and citric acid, preferably nitric acid, and the mass concentration of the acid peptizing agent is 55-75%, preferably 60-65%; the adding amount of the acidic peptizing agent is that the molar ratio of hydrogen ions to silicon dioxide is 1: 1.0-1: 1.5; the pH value of the silicon source after acidification treatment is 1.0-4.0, preferably 1.5-2.5.
In the preparation method of the hydrotreating catalyst, the dry weight of the pseudo-boehmite in the step (2) is more than 70 percent, and the pseudo-boehmite is converted into gamma-Al by high-temperature roasting2O3The latter properties are as follows: the pore volume is more than 0.95mL/g, the preferable pore volume is 0.95-1.2 mL/g, and the specific surface area is 270m2More than g, preferably the specific surface area is 270-330 m2(ii) in terms of/g. The curing agent is one or more of urea and organic ammonium salt. The organic ammonium salt is hexamethinetetrammonium. The addition amount of the curing agent is 1: 1.5-1: 2.0 in terms of the molar ratio of nitrogen atoms to silicon dioxide; the solid content of the prepared paste material is 25-45 percent, preferably 28-40 percent by weight of silicon dioxide and aluminum oxide, and the paste material has a plastic body with certain fluidity.
In the preparation method of the hydrotreating catalyst, the mold in the step (3) comprises a shell with a spherical cavity and a guide mold capable of forming a through passage, wherein the shell is made of rigid materials, and the external shape can be any shape, preferably a spherical symmetrical geometric shape and the like. The invention is illustrated by taking the case that the external shape is spherical, and the spherical shell can be composed of two identical hemispheres or four quarter spheres. The diameter of the spherical cavity can be adjusted according to the size of catalyst particles and can be 6.0-20.0 mm. The guide mold is made of heat or combustion removable material, such as graphite, wood, paper, paraffin or petroleum resin. The structure of the guide die is matched with a three-dimensional through hole channel in the carrier, namely the hole channel generated after the guide die is removed is a through hole.
In the preparation method of the hydrotreating catalyst, in the step (3), spherical shells of all parts are fixed with each other to form two complete hemispheroid cavities, a guide die capable of three-dimensionally penetrating a pore passage is placed into one hemispheroid cavity, a paste material is injected or pressed into the two hemispheroid cavities, and the two hemispheroids are combined to form a complete sphere and fixed after the whole cavity is filled.
In the preparation method of the hydrotreating catalyst, in the step (3), the heating temperature of the die for containing the paste material is 70-200 ℃, preferably 100-150 ℃, and the constant temperature time is 30-240 minutes, preferably 50-120 minutes, so that the material is cured.
In the preparation method of the hydrotreating catalyst, the mold is removed in the step (4), namely the lower shell is taken, and the pasty material is solidified and contracted and then automatically demolded because the pasty material in the mold releases alkaline gas after being heated. In the step (4), the washing is to wash the demolded spherical material to be neutral by using deionized water. The drying temperature is 100-150 ℃, and the drying time is 4-10 hours. The roasting temperature is 500-900 ℃, preferably 550-800 ℃, and the roasting time is 2-8 hours. The guide die is removed in the roasting process, three-dimensional through pore channels are left, and gas released in the roasting process of the guide die can also achieve the purpose of pore expansion of the catalyst carrier.
In the preparation method of the hydrotreating catalyst of the present invention, the drying and calcining conditions after the carrier is impregnated with the active metal component of the catalyst in the step (5) are as follows: drying at 100-150 ℃ for 4-10 hours, and roasting at 400-600 ℃ for 2-6 hours.
In the processing method of the acid-containing crude oil, at least one upflow hydrogenation reactor is adopted, and one or two upflow hydrogenation reactors are generally adopted. At least one hydrotreating catalyst of the invention, preferably at least two catalyst beds, are filled in the one upflow hydrogenation reactor, and each catalyst bed is filled with the same hydrotreating catalyst of the invention.
In the hydrotreating method of acid-containing crude oil, 2-5 catalyst beds are preferably arranged in the upflow reactor, and each catalyst bed preferably adopts the same hydrotreating catalyst. The height of each bed layer in the reactor can be properly adjusted. When two catalyst beds are arranged in one upflow reactor, the lower part is a first bed, and the upper part is a second bed, wherein the first bed accounts for 35-50% of the total filling volume of the catalyst in the upflow reactor, and the second bed accounts for 50-65% of the total filling volume of the catalyst in the upflow reactor. When the upflow reactor is provided with three catalyst beds, the lower part is a first bed layer, the middle part is a second bed layer, the upper part is a third bed layer, the first bed layer accounts for 20-30% of the total filling volume of the catalyst in the upflow reactor, the second bed layer accounts for 25-35% of the total filling volume of the catalyst in the upflow reactor, and the third bed layer accounts for 30-45% of the total filling volume of the catalyst in the upflow reactor. The bed height can be set to be the same or different according to different processing raw materials.
The invention provides a processing method of acid-containing crude oil, wherein the operating conditions adopted by an upflow hydrogenation reactor are as follows: the reaction temperature is 200-400 ℃, preferably 240-350 ℃; the hydrogen partial pressure is 3-20 MPa, preferably 5-15 MPa; the liquid hourly space velocity is 0.1-10 h-1Preferably 1 to 5 hours-1(ii) a The volume ratio of hydrogen to oil is 100-400, preferably 150-350.
The acid-containing crude oil can be high acid number crude oil, topped high acid crude oil or a mixture of the high acid number crude oil and heavy oil and/or residual oil, or a mixture of the high acid number crude oil and low acid number crude oil, and the total acid number of the acid-containing crude oil is more than 0.5mg KOH/g, and further more than 1.0mg KOH/g. The invention is especially suitable for treating inferior acid-containing crude oil with high metal content such as inferior high acid, high iron, high calcium and the like.
In the processing method of the acid-containing crude oil, the crude oil needs to be pretreated before entering the upflow reactor, and the pretreatment process is the conventional processes of crude oil desalting, dehydration and the like to remove most of salt substances, water and the like in the crude oil.
In the method, the processing scheme of the product after hydrogenation deacidification can be determined according to the properties of the crude oil, the product requirement of the market, economic benefits, environmental protection requirements and other factors. The present invention recommends the treatment by one of the following methods, wherein the light fraction is generally referred to as gasoline and diesel oil fractions:
(1) and (3) carrying out gas-liquid separation on the product after hydrogenation and deacidification, and sending the obtained liquid-phase product to an atmospheric fractionation device to obtain light fraction and atmospheric residue. The atmospheric residue can be used as residue hydrotreating raw material to carry out deep hydrofining at higher temperature and pressure, and the separated hydrogenation residue can be used as downstream catalytic cracking feed;
(2) and (3) carrying out gas-liquid separation on the product after hydrogenation and deacidification, and sending the obtained liquid-phase product to a vacuum fractionation device for fractionation to obtain light fraction, vacuum gas oil and vacuum residual oil. The vacuum residue can be used as a coking feed, and partial sulfur and other impurities are removed by hydrogenation deacidification, so that high-value low-sulfur petroleum coke can be obtained.
Compared with the prior art, the invention has the advantages that:
1. the upflow type hydrotreatment reactor at least uses one hydrotreatment catalyst with unique appearance and pore structure, and has the characteristics of high mechanical strength and wear resistance as well as the following characteristics: (1) the device has good diffusion channels and reaction channels, can eliminate the influence of diffusion on the reaction, enables the reaction to be more efficient, and has better utilization effect of the catalyst; (2) the anti-coking and bed thermal stability are good; (3) the catalyst has good hydrogenation deacidification capability; (4) has good capacity of removing metal impurities and certain capacity of removing sulfur nitrogen and carbon residue impurities.
2. The method of the invention fills the hydrotreating catalyst with unique appearance and pore structure in the upflow hydrogenation reactor, which not only can remove a large amount of metal suspended matters such as iron, calcium and the like and carbon-deposited impurities and the like in the high-acid crude oil, but also can prevent heavy metal impurities such as nickel, vanadium and the like in the high-acid crude oil from blocking pores, and prolong the service life of the catalyst and the operation period of the device. In addition, the catalyst has certain hydrogenation capacity, and obtains good deacidification effect in a hydrogenation treatment environment.
3. By adopting the method, the same hydrotreating catalyst of the invention is preferably filled in the upflow hydrogenation reactor, because the material property is gradually improved along the direction of the reactant flow, the hydrogenation reaction is an exothermic reaction, the reaction temperature can be gradually increased, and the rear catalyst bed layer is in an environment with less hydrogen in the whole reaction process, the upflow catalyst with large aperture and low hydrogen consumption is favorable for the stability of the catalyst bed layer and the performance of the catalyst. In addition, the reaction temperature is gradually increased along the direction of the reactant flow, and if a catalyst with higher activity is adopted in a reaction zone with higher temperature, the partial hydrogen deficiency reaction of the bed layer is more easily caused, and the generation of hot spots of the bed layer and the fluctuation of the bed layer are easily caused. Therefore, the control of the catalyst activity can be used for the upflow reactor, so that the balance of the activity and the stability can be realized.
4. In the upflow hydrogenation reactor, although not as strongly backmixed as the material in the ebullated bed reactor. However, due to the flow direction characteristics of the material flow and the micro-expansion state of the catalyst bed, if different catalyst grading technologies are adopted in the same catalyst bed in the fixed bed hydrogenation technology, bed back-mixing and bed reaction fluctuation are easily caused, and the stable operation of the device is adversely affected.
5. The up-flow type hydrotreating catalyst has good iron and calcium capacity and metal removing capacity, and has the characteristics of long-period stable operation due to the fact that the catalyst has higher deacidification capacity and certain metal removing, desulfurization and carbon residue and asphaltene conversion capacities in addition to the optimized pore channel design and the optimized carrier structure of the catalyst. Particularly, a large amount of metal suspended matters such as iron, calcium and the like exist in the high-acid crude oil, and carbon-deposited impurities also exist, so that the effect is more remarkable.
Drawings
FIG. 1 is a schematic cross-sectional view of a process for preparing a residue hydrotreating catalyst support according to the present invention;
FIG. 2 is a schematic view of a hemispherical cavity mold for forming a mold shell;
FIG. 3 is a schematic view of a guide die for forming a through passage;
FIG. 4 is a schematic cross-sectional view of a catalyst support prepared;
the reference numerals are explained below:
1. a mold housing; 2. a pasty material; 3. a guide die capable of forming a through passage; 4. a hemispherical cavity; 5. a cylinder traversing the "cross"; 6. a large cross-shaped body in the middle; 7. a small cross-shaped body at two sides; 8. a through passage.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, which are not intended to limit the scope of the present invention. In the present invention, wt% is a mass fraction.
In the invention, the specific surface area, the pore volume, the pore diameter and the pore distribution are measured by adopting a low-temperature liquid nitrogen adsorption method.
As shown in fig. 1 to 4, when preparing a residual oil hydrotreating catalyst support according to the present invention, the mold comprises a mold housing 1 (see fig. 1) having a spherical cavity and a guide mold 3 (see fig. 1) capable of forming a through passage. The invention is illustrated by the outer shape being spherical, the spherical shell may be composed of two identical hemispheres. Diameter of the spherical cavity is D1(see FIG. 1). The guide mold is made of heat or combustion removable material, such as graphite, wood, paper, paraffin or petroleum resin. The structure of the guide die is matched with a three-dimensional through hole in the carrier, and the guide die comprises a cylinder 5 crossing the cross, a large cross body 6 in the middle and small cross bodies 7 at two sides (see figure 3), wherein the cylinder 5 crossing the cross and the large cross body in the middleThe cross-shaped body 6 has a diameter d1The diameter of the small cross-shaped bodies 7 on both sides is d2See in particular fig. 1. The resulting channels after removal of the guide die are through channels 8. In the method, firstly, spherical shells of all parts are mutually fixed to form two complete hemispheroid cavities 4 (see figure 2), a guide die with a pore passage capable of being communicated in a three-dimensional mode is placed into one hemispheroid cavity 4, the pasty material 2 is pressed into the two hemispheroid cavities 4, and the two hemispheroids are combined to form a complete sphere and fixed after the whole cavity is filled. The guide films form mutually perpendicular carrier through channels 8, as shown in fig. 4.
The properties of the acid-containing crude oil feedstocks used in the examples and comparative examples are shown in Table 3, and the properties of the hydrotreating catalysts used are shown in tables 1 and 2.
Example 1
Weighing 400g of water glass with the silicon oxide content of 30 wt%, adding the water glass into a beaker, starting a stirring device, slowly adding 150g of nitric acid solution with the mass concentration of 62% into the beaker, then adding 42.9g of nickel nitrate, stirring and dissolving the mixture until the pH value of the water glass solution in the beaker is 2.0, and then adding 385.3g of pseudo-boehmite (with the properties as follows: the pore volume is 1.05mL/g, and the specific surface area is 306 m) into the solution270 wt% of dry basis), adding 35g of curing agent urea after uniformly stirring, adding deionized water after the urea is completely dissolved, and enabling the materials in the beaker to be in a paste shape with certain fluidity and the solid content of the materials calculated by silicon dioxide and aluminum oxide to be 33%.
The pasty material is pressed into two identical hemispheres with spherical cavities. Wherein a guide die is placed in one hemisphere, and the guide die is made of wood. The structure of the guide die is that a cylinder is arranged in the directions of an x axis, a y axis and a z axis passing through the center of a sphere, the length of the cylinder is the diameter of the spherical cavity, two cylinders are arranged in the directions of the x axis and the y axis respectively, the two cylinders are respectively arranged at the half part of the radius of the spherical cavity, and the length of the cylinder is the diameter of the spherical crown at the half part of the radius of the spherical cavity.
The pasty material is pressed into the two hemispheroidal cavities, and the two hemispheroids are combined together to form a complete sphere and fixed after the whole cavity is filled with the pasty material.
Heating a mould containing the paste material to 120 ℃, keeping the temperature for 60 minutes, releasing ammonia gas after the paste material in the mould is heated to enable the paste material to be solidified and contracted, then automatically demoulding to form spherical gel, washing the spherical gel to be neutral by deionized water, drying for 5 hours at 120 ℃, and roasting for 3 hours at 750 ℃ to obtain the spherical catalyst carrier A. Wherein the obtained catalyst carrier A had an outer diameter of about 7.0mm, a middle through-hole diameter of about 1.9mm and a side through-hole diameter of about 1.3 mm.
Soaking the carrier A in Mo-Ni-P solution, drying at 120 deg.c for 6 hr, and roasting at 500 deg.c for 3 hr to obtain the catalyst ACThe catalyst properties are shown in Table 1.
Example 2
The preparation was carried out as in example 1 except that the solid content in terms of silica and alumina was 35%, and the mold was changed to increase the diameters of the cavity and the cylinder, and catalyst carrier B and catalyst B were preparedCThe properties are shown in Table 1. Wherein the obtained catalyst carrier B had an outer diameter of about 9.5mm, a middle through-hole diameter of about 3.0mm and a side through-hole diameter of about 1.6 mm.
Example 3
The procedure is as in example 1, except that nickel nitrate is not added, catalyst support C and catalyst C are preparedCThe properties are shown in Table 1. Wherein the obtained catalyst carrier C had an outer diameter of about 7.0mm, a middle through-hole diameter of about 1.9mm and a side through-hole diameter of about 1.3 mm.
Comparative example 1
Weighing 400g of water glass with the silicon oxide content of 30 wt%, adding the water glass into a beaker, starting a stirring device, slowly adding 150g of nitric acid solution with the mass concentration of 62% into the beaker, then adding 42.9g of nickel nitrate, stirring and dissolving the mixture until the pH value of the water glass solution in the beaker is 2.0, and then adding 385.3g of pseudo-boehmite (with the properties as follows: the pore volume is 1.05mL/g, and the specific surface area is 306 m) into the solution270 wt% of dry basis), adding 35g of curing agent urea after uniformly stirring, adding deionized water after the urea is completely dissolved, and enabling the materials in the beaker to be in a paste shape with certain fluidity and the solid content of the materials calculated by silicon dioxide and aluminum oxide to be 33%.
The paste material is pressed into two rigid body molds with hemispherical hollow structures with the same diameter, the diameter of the spherical cavity is the same as that of the spherical cavity of the mold used in the embodiment 1, and the two hemispheres are combined together to form a complete sphere and fixed after the whole cavity is filled.
Heating a mould containing the paste material to 120 ℃, keeping the temperature for 60 minutes, releasing ammonia gas after the paste material in the mould is heated to enable the paste material to be solidified and contracted, then automatically demoulding to form spherical gel, washing the spherical gel to be neutral by deionized water, drying for 5 hours at 120 ℃, and roasting for 3 hours at 750 ℃ to obtain the spherical catalyst carrier D of the comparative example, wherein the outer diameter of the obtained catalyst carrier D is about 7.0 mm.
The carrier D was impregnated with a Mo-Ni-P solution, dried at 120 ℃ for 6 hours, and calcined at 500 ℃ for 3 hours to obtain the catalyst D of this comparative exampleCThe catalyst properties are shown in Table 1.
Example 4
High-acid raw materials (properties are shown in a table 3) and hydrogen enter an upflow hydrogenation reactor and contact with a hydrogenation catalyst to carry out hydrogenation reaction. Wherein hydrogenation catalysts A are respectively adoptedC、BC、CC、DCThe operating conditions were as follows: the reaction temperature is 300 ℃, the reaction pressure is 10.0MPa, the volume ratio of hydrogen to oil is 300, and the liquid hour volume (LHSV) is 1.2h-1The properties of the product obtained by the reaction are shown in Table 4.
Example 5
High acid raw material (properties shown in table 3) and hydrogen enter an upflow hydrogenation reactor to be contacted with a hydrogenation catalyst for hydrogenation reaction, wherein the hydrogenation catalyst A is adoptedCTwo catalyst bed layers are adopted, the volume ratio is 1:1, the reaction temperature is 260 ℃, 280 ℃, 300 ℃ and 350 ℃, the reaction pressure is 10.0MPa, the volume ratio of hydrogen to oil is 300, and the liquid hour volume (LHSV) is 1.2h-1The properties of the product obtained by the reaction are shown in Table 5.
Comparative example 2
Hydrogenation catalyst A in comparison with example 5CReplacement by hydrogenation catalyst DCAnd obtaining hydrogenated oil. The properties of the resulting oil are shown in Table 6.
Comparative example 3
The difference from example 5 is the double bed catalyst used in the upflow hydrogenation reactor, in which the lower part is packed with FZC10UH and the upper part is packed with FZC11 UH. Wherein, FZC10UH belongs to a conventional upflow demetallization catalyst, FZC11UH belongs to an upflow desulfurization catalyst, the reaction temperature is 260 ℃, 280 ℃, 300 ℃ and 350 ℃, the reaction pressure is 10.0MPa, the volume ratio of hydrogen to oil is 300, and the volume in Liquid (LHSV) is 1.2h-1The catalyst properties are shown in Table 2 and the properties of the product obtained by the reaction are shown in Table 7.
TABLE 1 Properties of catalysts prepared in examples and comparative examples
| Catalyst support numbering | Carrier A | Carrier B | Carrier C | Carrier D |
| Pore volume, mL/g | 0.782 | 0.781 | 0.781 | 0.771 |
| Specific surface area, m2/g | 140 | 141 | 143 | 146 |
| Average pore diameter, nm | 22.3 | 22.2 | 21.9 | 21.1 |
| Hole distribution,% | ||||
| <8.0nm | 0.6 | 0.6 | 0.5 | 1.0 |
| 8-20nm | 62.5 | 62.2 | 62.7 | 63.5 |
| >20.0nm | 36.9 | 37.2 | 36.8 | 35.5 |
| Catalyst numbering | Catalyst AC | Catalyst BC | Catalyst CC | Catalyst DC |
| Metal content% | ||||
| MoO3 | 8.6 | 8.5 | 8.6 | 8.6 |
| NiO | 4.4 | 4.4 | 2.4 | 4.4 |
| Lateral pressure strength, N/grain | 41 | 46 | 34 | 88 |
TABLE 2 Properties of the hydrogenation catalysts used in the comparative examples
| Catalyst brand | FZC-10U | FZC-11U |
| Function(s) | Demetallization catalyst | Desulfurization catalyst |
| Particle shape | Spherical shape | Spherical shape |
| Outer diameter of the granule mm | 2.9 | 2.9 |
| Strength, N.mm-1 | 32 | 30 |
| Specific surface area, m2/g | 110 | 148 |
| Wear rate, wt% | 0.3 | 0.4 |
| Metal content, wt.% | ||
| MoO3 | 5.2 | 10.8 |
| NiO | 1.2 | 2.4 |
TABLE 3 Properties of highly sour crude oils
TABLE 4 Properties of the products obtained by the hydrogenation
| Catalyst numbering | Catalyst AC | Catalyst BC | Catalyst CC | Catalyst DC |
| Total acid value of mgKOH/g | 0.06 | 0.05 | 0.05 | 0.11 |
| Sulfur, wt.% | 0.25 | 0.26 | 0.22 | 0.42 |
| Nitrogen,. mu.g/g | 3130 | 3142 | 3145 | 3256 |
| Iron,. mu.g/g | 3.56 | 2.24 | 3.33 | 7.32 |
| Calcium, μ g/g | 5.60 | 4.60 | 5.05 | 7.75 |
| Nickel + vanadium, μ g/g | 12.50 | 11.79 | 12.13 | 16.50 |
TABLE 5 catalyst A prepared using example 1CProperties of the product obtained under different operating conditions
| Reaction temperature of | 260 | 280 | 300 | 350 |
| Total acid value of mgKOH/g | 0.18 | 0.12 | 0.06 | 0.04 |
| Sulfur, wt.% | 0.62 | 0.46 | 0.25 | 0.12 |
| Nitrogen,. mu.g/g | 3359 | 3248 | 3130 | 2774 |
| Iron,. mu.g/g | 13.30 | 8.6 | 3.56 | 2.25 |
| Calcium, μ g/g | 15.68 | 12.2 | 5.6 | 1.22 |
| Nickel + vanadium, μ g/g | 22.6 | 17.1 | 12.5 | 5.8 |
TABLE 6 catalyst D prepared by comparative example 1CProperties of the product obtained under different operating conditions
| Reaction temperature of | 260 | 280 | 300 | 350 |
| Total acid value of mgKOH/g | 0.28 | 0.23 | 0.11 | 0.07 |
| Sulfur, m% | 0.65 | 0.52 | 0.42 | 0.26 |
| Nitrogen,. mu.g/g | 3410 | 3363 | 3256 | 3061 |
| Iron,. mu.g/g | 17.30 | 12.55 | 7.32 | 3.40 |
| Calcium, μ g/g | 16.30 | 12.55 | 7.75 | 3.11 |
| Nickel + vanadium, μ g/g | 23.2 | 19.1 | 16.5 | 8.8 |
The results in tables 5 and 6 show that the hydrotreating catalyst A of the present invention is used at 260-350 ℃ and 10.0MPaCThe naphthenic acid removal effect is obviously better than that of the catalyst D of the comparative exampleC. Because the calcium content in the raw oil reaches up to 45.6 mu g/g and the iron content also reaches up to 27.2 mu g/g, the catalyst A of the invention is adoptedCThe effect of removing metallic impurities such as calcium, iron and the like is better than that of the catalyst D of the comparative exampleCThe problems of coking and hardening at the top of the reactor are effectively avoided, and the running period of the device is prolonged. And from the test result, the catalyst has higher performance of removing sulfur and nitrogen impurities, and reduces the difficulty of subsequent processing of the raw oil.
TABLE 7 Properties of the product obtained by the hydrogenation reaction using the catalyst of comparative example 3
| Reaction temperature of | 260 | 280 | 300 | 350 |
| Total acid value of mgKOH/g | 0.33 | 0.27 | 0.15 | 0.08 |
| Sulfur, m% | 0.72 | 0.55 | 0.50 | 0.31 |
| Nitrogen,. mu.g/g | 3467 | 3412 | 3323 | 3155 |
| Iron,. mu.g/g | 18.80 | 15.3 | 9.62 | 4.40 |
| Calcium, μ g/g | 19.61 | 14.25 | 7.98 | 5.32 |
| Nickel + vanadium, μ g/g | 25.35 | 21.54 | 18.78 | 12.72 |
Example 6
In comparison with example 5, the catalyst A of example 1 was used at a reaction temperature of 300 ℃ under otherwise unchanged conditionsCAnd comparative example 1 catalyst DCThe catalyst stability was examined using the same feed oil, and the results are shown in Table 8 below.
TABLE 8 catalyst stability test results
| Catalyst AC | Catalyst DC | |
| Run time (sky) | Total acid value (mgKOH/g) | Total acid value (mgKOH/g) |
| 10 | 0.06 | 0.11 |
| 50 | 0.06 | 0.12 |
| 80 | 0.07 | 0.15 |
| 100 | 0.07 | 0.18 |
| 120 | 0.07 | 0.20 |
| 150 | 0.08 | 0.21 |
From the examination of the long-time operation period in Table 8, it can be seen that the catalyst system of the present invention has stable deacidification activity, and the acid value of the product is greatly reduced to less than 0.10mgKOH/g by hydrotreating the raw oil, so as to achieve the purpose of the present invention. And no significant coking was observed from the discharged catalyst. While the catalyst of the comparative example has poor deacidification stability, and the acid value of the hydrogenated product is increased to 0.21mgKOH/g by 150 days.
Claims (20)
1. A hydrotreating method for acid-containing crude oil comprises at least one upflow hydrogenation reactor, wherein the acid-containing crude oil and hydrogen enter the upflow hydrogenation reactor for hydrogenation reaction to obtain a product after hydrogenation deacidification; at least one hydrotreating catalyst is filled in the upflow hydrogenation reactor; the hydrotreating catalyst comprises a carrier and an active component, wherein the carrier is spherical and is provided with a three-dimensional through hole channel, the carrier is provided with seven through holes, the x-axis direction, the y-axis direction and the z-axis direction of the center of the sphere are respectively provided with one through hole, namely three middle through holes, the two directions of the x-axis direction, the y-axis direction and the z-axis direction are also provided with four side through holes which are parallel to the middle through holes in the same direction and distributed on two sides of the middle through holes, the side through holes and the side through holes are mutually communicated with the middle through holes in the third direction, the spherical outer diameter is 6.0-10.0 mm, the hole diameter of the middle through hole is 25-40% of the spherical outer diameter, and the hole diameter of the side through holes is 10-20;
the properties of the vector are as follows: the specific surface area is 100-200 m2The pore volume is more than 0.70mL/g, the pore volume occupied by the pore diameter of 20-100 nm is 35-60% of the total pore volume, and the average pore diameter is more than 18 nm.
2. The method of claim 1, wherein the through-holes are cylindrical through-holes in the hydroprocessing catalyst.
3. The method of claim 1, wherein the hydrotreating catalyst is supported on Al2O3-SiO2As a carrier, wherein SiO2The weight content is 20-50%.
4. The method of claim 1, wherein the hydrotreating catalyst is supported on Al2O3-SiO2As a carrier, wherein SiO2The weight content is 30-40%.
5. The method of claim 3, further comprising a first metal component oxide in the support, wherein the first metal component oxide is NiO.
6. The method of claim 5, wherein the first metal component oxides NiO and Al2O3Is 0.03: 1-0.13: 1.
7. the method of claim 6, wherein the first metal component oxides NiO and Al2O3Is 0.05: 1-0.11: 1.
8. the method of any one of claims 1 to 7, wherein the vector has the following properties: the pore volume is 0.75-1.15 mL/g, and the average pore diameter is 20-30 nm.
9. The process of claim 5 wherein the active metal component of the hydrotreating catalyst comprises a second metal component which is an element of a group VIB metal and a third metal component which is an element of a group VIII metal.
10. The method of claim 9 wherein the group vib metal element is Mo and the group viii metal element is Ni and/or Co.
11. The process of claim 9 wherein the hydrotreating catalyst has a second metal component content, calculated as oxide, of from 1.0% to 10.0%, a total content of the first metal component and the third metal component, calculated as oxide, of from 3.0% to 10.0%, a content of silica of from 25.0% to 35.0%, a content of alumina of from 55.0% to 65.0%, and a molar ratio, calculated as atoms, of the third metal component to the second metal component of from 1.5: 1-4.5: 1.
12. the process of claim 11 wherein the hydrotreating catalyst has a second metal component content, calculated as oxide, of from 1.5% to 6.5% and a total content of the first metal component and the third metal component, calculated as oxide, of from 4.0% to 8.0%, based on the weight of the catalyst.
13. The process of claim 1 wherein there are at least two catalyst beds in said one upflow hydrogenation reactor and each catalyst bed is loaded with the same said hydrotreating catalyst.
14. The method of claim 13, wherein said one upflow hydrogenation reactor is provided with 2 to 5 catalyst beds, each catalyst bed using the same hydrotreating catalyst.
15. The method of claim 1 or 14, wherein when two catalyst beds are provided in said one upflow hydrogenation reactor, the lower portion is the first bed and the upper portion is the second bed, wherein the first bed comprises 35% to 50% of the total catalyst loading volume in the upflow reactor and the second bed comprises 50% to 65% of the total catalyst loading volume in the upflow reactor.
16. The method of claim 1 or 14, wherein when three catalyst beds are provided in the one upflow hydrogenation reactor, the lower portion is the first bed, the middle portion is the second bed, and the upper portion is the third bed, the first bed is 20% to 30% of the total catalyst loading volume in the upflow reactor, the second bed is 25% to 35% of the total catalyst loading volume in the upflow reactor, and the third bed is 30% to 45% of the total catalyst loading volume in the upflow reactor.
17. The process of claim 1 wherein the upflow hydrogenation reactor is operated under the following conditions: the reaction temperature is 200-400 ℃; the hydrogen partial pressure is 3-20 MPa; the liquid hourly space velocity is 0.1-10 h-1(ii) a The volume ratio of the hydrogen to the oil is 100-400.
18. The process of claim 1 wherein the upflow hydrogenation reactor is operated under the following conditions: the reaction temperature is 240-350 ℃; the hydrogen partial pressure is 5-15 MPa; the liquid hourly space velocity is 1-5 h-1(ii) a The volume ratio of hydrogen to oil is 150-350.
19. The method of claim 1, wherein the acid-containing crude oil is one or more of high acid value crude oil, topped high acid crude oil, a mixture of high acid value crude oil and heavy oil and/or residual oil, and a mixture of high acid value crude oil and low acid value crude oil, and the total acid value of the acid-containing crude oil is more than 0.5mg KOH/g.
20. The method of claim 19, wherein the acid-containing crude oil has a total acid number greater than 1.0mg KOH/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711305427.2A CN109897664B (en) | 2017-12-11 | 2017-12-11 | Hydrotreating method for acid-containing crude oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711305427.2A CN109897664B (en) | 2017-12-11 | 2017-12-11 | Hydrotreating method for acid-containing crude oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109897664A CN109897664A (en) | 2019-06-18 |
| CN109897664B true CN109897664B (en) | 2021-04-06 |
Family
ID=66941927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711305427.2A Active CN109897664B (en) | 2017-12-11 | 2017-12-11 | Hydrotreating method for acid-containing crude oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109897664B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745892A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Residual oil hydrotreating method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314733A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Hydrogenation depickling method for high-metal acid containing primary oil |
| CN101684414A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Hydrotreating method of high-acid and high-calcium crude oil |
| CN106457227A (en) * | 2016-09-20 | 2017-02-22 | 高化学技术株式会社 | Catalyst carrier and catalyst comprising the same |
-
2017
- 2017-12-11 CN CN201711305427.2A patent/CN109897664B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314733A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Hydrogenation depickling method for high-metal acid containing primary oil |
| CN101684414A (en) * | 2008-09-27 | 2010-03-31 | 中国石油化工股份有限公司 | Hydrotreating method of high-acid and high-calcium crude oil |
| CN106457227A (en) * | 2016-09-20 | 2017-02-22 | 高化学技术株式会社 | Catalyst carrier and catalyst comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109897664A (en) | 2019-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109894155B (en) | Catalyst carrier and catalyst for residual oil hydrotreatment and preparation method thereof | |
| CN111100680A (en) | Catalyst grading method and residual oil hydrotreating method | |
| CN109897664B (en) | Hydrotreating method for acid-containing crude oil | |
| CN103740404A (en) | High-nitrogen high-aromatic hydrocarbon hydrogenation modification method | |
| CN109897669B (en) | Hydrotreating method for acid-containing crude oil | |
| CN109897668B (en) | Processing method of acid-containing crude oil | |
| CN111100676A (en) | Catalyst grading method and application thereof in residual oil hydrotreating method | |
| JP4969754B2 (en) | Hydrodesulfurization method for gas oil fraction and reactor for hydrodesulfurization | |
| CN109894156B (en) | Residual oil hydrotreating catalyst carrier, catalyst and preparation method thereof | |
| CN103289734A (en) | Combined hydrogenation treatment technology of high-metal high-sulfur high-nitrogen inferior heavy oil by use of catalyst | |
| CN111100675A (en) | Process for treating heavy hydrocarbon feedstocks using upflow reactors | |
| CN111100693A (en) | Process for hydroprocessing heavy hydrocarbon feedstocks | |
| CN109897667B (en) | Method for processing heavy hydrocarbon raw material by adopting up-flow reactor | |
| CN109897665B (en) | Process for treating heavy hydrocarbon feedstocks using upflow reactors | |
| CN111097547A (en) | Residual oil hydrotreating catalyst carrier, catalyst and preparation method thereof | |
| CN109897670B (en) | Heavy hydrocarbon raw material hydrotreating method | |
| CN109897666B (en) | Method for treating heavy hydrocarbon raw material by adopting up-flow reactor | |
| CN109894107B (en) | Catalyst carrier and catalyst for residual oil hydrotreatment and preparation method thereof | |
| CN111100673A (en) | Process for hydroprocessing heavy hydrocarbon feedstocks using upflow reactors | |
| CN111097545A (en) | Catalyst carrier and catalyst for residual oil hydrotreating and preparation method thereof | |
| CN111100678A (en) | Method for hydrotreating residual oil by using up-flow reactor | |
| CN111100672A (en) | Method for hydrotreating heavy hydrocarbon raw material by adopting up-flow reactor | |
| CN111100677A (en) | Method for processing heavy hydrocarbon raw material by adopting up-flow reactor | |
| CN103965960A (en) | Technology for preparing diesel oil and naphtha through heavy oil hydrogenation | |
| CN111100694A (en) | Heavy hydrocarbon raw material hydrotreating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230930 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TR01 | Transfer of patent right |