阅读说明：本技术 一种用于催化稠油减黏的催化剂的制备方法 (Preparation method of catalyst for catalyzing thickened oil viscosity reduction ) 是由 冯翔 林栋� 刘熠斌 陈小博 赵辉 金鑫 杨朝合 于 2019-04-10 设计创作，主要内容包括：本发明涉及一种催化稠油减黏领域,具体地说,涉及一种用于催化稠油减黏的催化剂的制备方法。所述的制备方法包括如下步骤：1)将分子筛与水混合,搅拌得到溶液1；2)将金属盐溶解在水中,搅拌得到溶液2；3)将溶液1与溶液2相互混合,并滴加油酸,搅拌,加热,得到混合溶液3；4)向混合溶液3中滴加碱溶液调节混合溶液pH值,老化后,离心,干燥得到催化剂；其中,步骤2)中所述的金属盐为铁盐或/和镍盐。本发明方法成功地将特定比表面积的金属铁/镍纳米颗粒以小尺寸形式均匀负载到分子筛表面,实现了对磁性纳米颗粒熟化倾向的抑制,所得的催化剂催化稠油减黏活性优异。(The invention relates to the field of thickened oil catalytic viscosity reduction, in particular to a preparation method of a catalyst for catalyzing thickened oil viscosity reduction. The preparation method comprises the following steps: 1) mixing a molecular sieve with water, and stirring to obtain a solution 1; 2) dissolving metal salt in water, and stirring to obtain a solution 2; 3) mixing the solution 1 and the solution 2 with each other, dripping oleic acid, stirring and heating to obtain a mixed solution 3; 4) dropwise adding an alkali solution into the mixed solution 3 to adjust the pH value of the mixed solution, aging, centrifuging, and drying to obtain a catalyst; wherein, the metal salt in the step 2) is ferric salt or/and nickel salt. The method successfully and uniformly loads the metallic iron/nickel nanoparticles with specific surface area on the surface of the molecular sieve in a small-size form, so that the aging tendency of the magnetic nanoparticles is inhibited, and the obtained catalyst has excellent viscosity-reducing activity in catalyzing thickened oil.)

1. The preparation method of the catalyst for catalyzing viscosity reduction of the heavy oil is characterized by comprising the following steps of:

1) mixing a molecular sieve with water, and stirring to obtain a solution 1;

2) dissolving metal salt in water, and stirring to obtain a solution 2;

3) mixing the solution 1 and the solution 2 with each other, dripping oleic acid, stirring and heating to obtain a mixed solution 3;

4) dropwise adding an alkali solution into the mixed solution 3 to adjust the pH value of the mixed solution, aging, centrifuging, and drying to obtain a catalyst;

wherein, the metal salt in the step 2) is ferric salt or/and nickel salt.

2. The method according to claim 1, wherein the iron salt is a mixture of a ferrous salt and a ferric salt; the nickel salt is divalent nickel salt.

3. The production method according to claim 2,

when the metal salt is ferric salt, the molar ratio of ferric ions, ferrous ions and oleic acid is 0.1-6: 1: 0.01-2, preferably 2.5: 1: 0.2; the mass ratio of the ferrous ions to the molecular sieve is more than zero and less than or equal to 0.5;

when the metal salt is a nickel salt, the mass ratio of the divalent nickel ions, the molecular sieve and the oleic acid is 0.05-0.5: 1: 0.02 to 10, preferably 0.2: 1: 0.2;

when the metal salt is a mixture of ferric salt and nickel salt, the molar ratio of ferric ions, ferrous ions and oleic acid is 0.1-6: 1: 0.5-6: 0.1-2, preferably 2: 1: 0.6: 1; the mass ratio of the ferrous ion to the molecular sieve is greater than zero and less than or equal to 0.5, preferably 0.28.

4. The method according to any one of claims 1 to 3, wherein the heating in step 3) is carried out to a temperature of 20 to 60 ℃;

specifically, the method comprises the following steps:

when the metal salt is ferric salt, the heating in the step 3) is heating to the temperature of 20-45 ℃, preferably 40 ℃;

when the metal salt is a nickel salt, the heating in step 3) is heating to a temperature of 25-60 ℃, preferably 50 ℃;

when the metal salt is a mixture of iron salt and nickel salt, the heating in step 3) is heating to a temperature of 25-60 ℃, preferably 50 ℃.

5. The method according to claim 4, wherein in the step 4), the pH of the mixed solution is adjusted to 7 to 12;

specifically, the method comprises the following steps:

when the metal salt is ferric salt, in the step 4), adjusting the pH value of the mixed solution to 8-11, preferably adjusting the pH value of the mixed solution to 9;

when the metal salt is a nickel salt, in the step 4), adjusting the pH value of the mixed solution to 7-12, preferably adjusting the pH value of the mixed solution to 8.5;

when the metal salt is the mixture of iron salt and nickel salt, in the step 4), the pH value of the mixed solution is adjusted to 8-11, and preferably the pH value of the mixed solution is adjusted to 9.

6. The method according to any one of claims 1 to 5, wherein the molecular sieve is an artificially synthesized molecular sieve and/or a natural molecular sieve;

the preferable artificially synthesized molecular sieve is one or the mixture of more than two of ZSM-5, Y, beta or USY molecular sieves; more preferably, the artificially synthesized molecular sieve is ZSM-5 and/or USY;

the preferable natural molecular sieve is one or the mixture of more than two of clinoptilolite, heulandite or mordenite; more preferred natural molecular sieves are clinoptilolite and/or heulandite.

7. The preparation method according to any one of claims 2 to 6, wherein the ferrous salt is one or more of ferrous sulfate, ferrous nitrate, ferrous chloride or ferrous carbonate, preferably ferrous sulfate;

the ferric iron salt is one or more of ferric sulfate, ferric nitrate or ferric chloride, and preferably ferric sulfate.

8. The production method according to any one of claims 1 to 7, wherein in the step 4), the drying manner is ordinary forced air drying or vacuum drying, preferably vacuum drying; the drying temperature was 40 ℃.

9. The method according to any one of claims 1 to 7, wherein when the metal salt is a nickel salt or a mixture of iron and nickel salts, the drying in step 4) further comprises a roasting process.

10. The preparation method as claimed in claim 9, wherein in the calcination, the temperature rise rate is 1-10 ℃/min, the calcination temperature is 300-; preferably, the heating rate is 4-6 ℃/min, the roasting temperature is 350-.

Technical Field

The invention relates to the field of thickened oil catalytic viscosity reduction, in particular to a preparation method of a catalyst, and especially relates to a preparation method of a catalyst for thickened oil catalytic viscosity reduction.

Background

With the increasing global energy demand and the declining reserves of conventional oil, the production of heavy oil worldwide will continue to increase. Heavy oil accounts for at least 25% of the world's oil reserves, accounting for a large portion of the known hydrocarbon reserves. In fact, thirty countries around the world have established enormous reserves of heavy oil, with the united states, canada and venezuela occupying the largest proportion. Total global reserves of 5.6 trillion barrels (five times more than the traditional light oil 1.02 trillion barrels). However, heavy oil and bitumen are estimated at 4343 and 6507 barrels, respectively, based on the petroleum reserves available in the prior art (production and storage). Heavy oils are known to be rich in heavier organic compounds such as gums and asphaltenes. In fact, the precipitates in common heavy oils are rich in compounds of at least sixty carbon atoms. These mixtures result in high values for certain physicochemical properties, such as viscosity, boiling point and molecular weight. However, these physical properties can present significant recovery difficulties. For these reasons, the recovery rate in the global area is only in the range of 0.1-0.2.

For the production of heavy underground oils, a number of methods have emerged, including thermal-operated viscosity reduction, microbial viscosity reduction, hydrothermal viscosity reduction, and other viscosity reduction methods. Among the thermally operated viscosity reductions, the steam method is most popular. However, this process is not economical. On the other hand, the in situ combustion method is to oxidize oil. However, problems have been reported with the formation of compounds such as sulfuric acid (e.g., sulfones) and carboxylic acid derivatives, which may increase viscosity and thereby reduce flowability. The microbial visbreaking process is to apply microbes and possible metabolites to the low temperature condition to improve the oil recovery ratio. The mechanism of action of the microorganisms is by altering the pH and viscosity of the oil, thereby promoting its flow. One major problem is that the microorganisms may be destroyed by the chemicals or the temperature of the reservoir. Likewise, it is not clear which microorganism provides the best activity in view of reservoir variations. An important alternative under consideration is the operating method known as "hydrothermal cracking", which involves breaking chemical bonds (such as carbon-sulfur bonds) in heavy oil at specific temperature and pressure conditions to increase the concentration of saturated and lighter aromatics. Currently, scientists have recognized that the use of catalysts increases the degree of chemical bond breaking and viscosity reduction. Thus, "catalytic hydrothermal cracking" requires the introduction of a suitable catalyst to effectively achieve viscosity reduction.

In catalyzing hydrothermal visbreaking, commonly used catalysts include solid acid catalysts, hydrophilic soluble catalysts, and other potential catalysts. Initially, salts of transition metals and organic compounds were the predominant catalysts. Solid acids and other super acids are then gradually rising. At the same time, it has also been found that the presence of the catalyst in catalytic hydrothermal visbreaking promotes the interaction between the catalyst and the heavy oil. The mechanism of action involves the breaking of carbon-carbon bonds as well as carbon-sulfur bonds and the production of reaction products rich in lower viscosity saturated hydrocarbons and lighter aromatics. The cleavage reaction of the carbon-carbon side chain can produce lighter alkanes. Complex carbon-oxygen, carbon-sulfur, and carbon-nitrogen bonds in colloids and asphaltenes can be attacked by the active sites (e.g., B acid sites) of the catalyst, resulting in the production of lighter aromatic alcohols such as phenols and carboxylic acids. Thus, the production and viscosity reduction of certain lighter reaction products is largely dependent on the initial composition of the heavy oil and the catalyst properties. For example, sulfonic acids interact with large amounts of hydrocarbon and non-hydrocarbon gums and asphaltenes in heavy oils, resulting in the production of saturated hydrocarbons, oxygenates (e.g., carboxylic acids, aromatic ethers and aromatic alcohols). However, in order to ensure the stability and the water-compatibility of the catalyst, it is necessary to modify with metals such as Cs and Pt or introduce SiO₂Or TiO₂And (3) a carrier. One of the main advantages of these compounds is that they can be regenerated and reused, thereby increasing the economic efficiency of the reaction.

Natural molecular sieve catalysts are well suited for hydrothermal cracking reactions due to their abundant recovery and unique structural and acidic properties. Unlike heteropolyacids and solid oxides, natural molecular sieves are distributed in large quantities in many parts of the world. Their development is economically feasible. And they are environmentally friendly and simple to process. Thus, both of these factors may make their promise as hydrothermal cracking catalysts even more promising. In addition, the Fe/Ni series metal load can effectively promote the experimental effect of the hydrothermal cracking reaction due to the low price and the unique electronic structure. In addition, because the oxides of ferroferric oxide and nickel oxide have magnetism, the magnetic separation and recovery are possible, and if the recovery is realized, the efficiency of industrial operation is greatly improved. However, the magnetic property also causes the agglomeration of the nanoparticles to be large, which is not favorable for improving the activity and stability. Therefore, there is an urgent need for a method for efficiently preparing a supported catalyst in which iron/nickel-based metals are uniformly distributed in small-sized particles on a molecular sieve and which is highly effective in catalyzing heavy oil viscosity reduction.

The present invention has been made in view of this situation.

Disclosure of Invention

The technical problem to be solved by the invention is to overcome the defects of the prior art, and provide a preparation method of a catalyst for catalyzing thickened oil viscosity reduction, in particular to a preparation method of a catalyst with iron/nickel metals uniformly distributed on a molecular sieve, which is used in the field of catalyzing thickened oil viscosity reduction.

In order to solve the technical problems, the invention adopts the following technical scheme:

a preparation method of a catalyst for catalyzing viscosity reduction of heavy oil is disclosed, wherein the preparation method comprises the following steps:

1) mixing a molecular sieve with water, and stirring to obtain a solution 1;

2) dissolving metal salt in water, and stirring to obtain a solution 2;

3) mixing the solution 1 and the solution 2 with each other, dripping oleic acid, stirring and heating to obtain a mixed solution 3;

4) dropwise adding an alkali solution into the mixed solution 3 to adjust the pH value of the mixed solution, aging, centrifuging, and drying to obtain a catalyst;

wherein, the metal salt in the step 2) is ferric salt or/and nickel salt.

Further, the ferric salt is the mixture of ferrous salt and ferric salt; the nickel salt is divalent nickel salt.

Specifically, the method comprises the following steps:

when the metal salt is ferric salt, the molar ratio of ferric ions, ferrous ions and oleic acid is 0.1-6: 1: 0.01-2, preferably 2.5: 1: 0.2; the mass ratio of the ferrous ions to the molecular sieve is more than zero and less than or equal to 0.5;

when the metal salt is a nickel salt, the mass ratio of the divalent nickel ions, the molecular sieve and the oleic acid is 0.05-0.5: 1: 0.02 to 10, preferably 0.2: 1: 0.2;

when the metal salt is a mixture of ferric salt and nickel salt, the molar ratio of ferric ions, ferrous ions and oleic acid is 0.1-6: 1: 0.5-6: 0.1-2, preferably 2: 1: 0.6: 1; the mass ratio of the ferrous ion to the molecular sieve is greater than zero and less than or equal to 0.5, preferably 0.28.

Further, in the step 3), the heating is carried out until the temperature is 20-60 ℃;

specifically, the method comprises the following steps:

when the metal salt is ferric salt, the heating in the step 3) is heating to the temperature of 20-45 ℃, preferably 40 ℃;

when the metal salt is a nickel salt, the heating in step 3) is heating to a temperature of 25-60 ℃, preferably 50 ℃;

when the metal salt is a mixture of iron salt and nickel salt, the heating in step 3) is heating to a temperature of 25-60 ℃, preferably 50 ℃.

Further, in the step 4), adjusting the pH value of the mixed solution to 7-12;

specifically, the method comprises the following steps:

when the metal salt is ferric salt, in the step 4), adjusting the pH value of the mixed solution to 8-11, preferably adjusting the pH value of the mixed solution to 9;

when the metal salt is a nickel salt, in the step 4), adjusting the pH value of the mixed solution to 7-12, preferably adjusting the pH value of the mixed solution to 8.5;

when the metal salt is the mixture of iron salt and nickel salt, in the step 4), the pH value of the mixed solution is adjusted to 8-11, and preferably the pH value of the mixed solution is adjusted to 9.

In the invention, the molecular sieve is an artificially synthesized molecular sieve and/or a natural molecular sieve;

the preferable artificially synthesized molecular sieve is one or the mixture of more than two of ZSM-5, Y, beta or USY molecular sieves; more preferably, the artificially synthesized molecular sieve is ZSM-5 and/or USY;

the preferable natural molecular sieve is one or the mixture of more than two of clinoptilolite, heulandite or mordenite; more preferred natural molecular sieves are clinoptilolite and/or heulandite.

In the invention, the ferrous salt is one or more of ferrous sulfate, ferrous nitrate, ferrous chloride or ferrous carbonate, and ferrous sulfate is preferred;

the ferric iron salt is one or more of ferric sulfate, ferric nitrate or ferric chloride, and preferably ferric sulfate.

In the invention, in the step 4), the drying mode is common air blast drying or vacuum drying, preferably vacuum drying; the drying temperature was 40 ℃.

Further, when the metal salt is nickel salt or the mixture of iron salt and nickel salt, the step 4) of drying also includes a roasting process.

Furthermore, in the roasting, the heating rate is 1-10 ℃/min, the roasting temperature is 300-; preferably, the heating rate is 4-6 ℃/min, the roasting temperature is 350-.

After adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:

according to the preparation method for uniformly distributing iron/nickel on the molecular sieve for efficiently catalyzing thickened oil viscosity reduction, the growth of iron/nickel nanoparticles is effectively controlled by controlling and regulating the pH value and the temperature of a solution and adding oleic acid, the uniform distribution of the iron/nickel nanoparticles is promoted and the growth of the ferroferric oxide nanoparticles is inhibited by effectively utilizing the interaction of metal of the molecular sieve and the iron/nickel nanoparticles and a carrier and the protection effect of the oleic acid, the iron/nickel nanoparticles with specific surface area are successfully and uniformly precipitated on the surface of the molecular sieve in a small-size form, the aging tendency of the magnetic nanoparticles is inhibited, and the obtained catalyst is excellent in viscosity reduction activity of catalyzing thickened oil.

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

Drawings

FIG. 1 is an XRD pattern of the catalyst prepared in example 5;

FIG. 2 is a HRTEM image of the catalyst prepared in example 5;

FIG. 3 is a HRTEM image of the catalyst prepared in example 6;

FIG. 4 is an XRD pattern of the catalyst prepared in comparative example 1;

FIG. 5 is a HRTEM image of the catalyst prepared in comparative example 1;

fig. 6 is an HRTEM of the catalyst prepared in comparative example 6.

It should be noted that the drawings and the description are not intended to limit the scope of the inventive concept in any way, but to illustrate it by a person skilled in the art with reference to specific embodiments.

Detailed Description

The catalyst preparation process of the present invention is described in further detail below. And do not limit the scope of the present application, which is defined by the claims. Certain disclosed specific details provide a thorough understanding of various disclosed embodiments. One skilled in the relevant art will recognize, however, that embodiments may be practiced without one or more of the specific details, with other materials, etc.

Unless the context requires otherwise, in the description and claims, the terms "comprise," comprises, "and" comprising "are to be construed in an open-ended, inclusive sense, i.e., as" including, but not limited to.

Reference in the specification to "an embodiment," "another embodiment," or "certain embodiments," etc., means that a particular described feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, "an embodiment," "another embodiment," or "certain embodiments" do not necessarily all refer to the same embodiments. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.

In the field of thickened oil catalytic viscosity reduction applied in the application, thickened oil refers to a high-viscosity oil product with the viscosity range of 1000-100000cp at 50 ℃.

Small-sized iron/nickel metal magnetic oxide nanoparticles in this application refers to metal oxide nanoparticles having a size of less than 20 nm.

The iron/nickel metal oxide having a specific surface area in the present application means that the specific surface area is in the range of 50-100m²Iron/nickel metal oxide per gram.

The molecular sieve in the application comprises an artificially synthesized molecular sieve and a natural molecular sieve; the artificially synthesized molecular sieve comprises one or more of ZSM-5, Y, beta or USY molecular sieve; the natural molecular sieve includes, for example, one or a mixture of two or more of clinoptilolite, heulandite and mordenite.

Ferrous salts in this application refer to salts containing ferrous ions; iron salt refers to salts containing ferric ions; the nickel salt refers to a salt containing divalent nickel ions; ferrous salts such as ferrous sulfate, ferrous nitrate, ferrous chloride or ferrous carbonate; ferric salts such as ferric sulfate, ferric nitrate, or ferric chloride; nickel salts such as nickel sulfate, nickel nitrate or nickel chloride; wherein, the ferrous salt used in the experiment in the application comprises one or two ferrous salts and a mixture of the two ferrous salts; the ferric iron salt used in the experiment in the application comprises one or two of the ferric iron salts and a mixture of the two; the nickel salt used in the experiment of the application comprises one or two of the nickel salts and the mixture of the nickel salts.

The reagent for adjusting the pH value is a sodium hydroxide solution, a potassium hydroxide solution or ammonia water.

The inventor of the application finds a preparation method for uniformly distributing small-size iron/nickel nanoparticles with specific surface area on a molecular sieve for efficiently catalyzing thickened oil viscosity reduction through extensive and intensive research, namely, the preparation method can effectively inhibit the growth of magnetic nanoparticles by utilizing the accurate adjustment of temperature and pH and combining the strong interaction of oleic acid and the molecular sieve and metal oxide nanoparticles, and simultaneously realizes the uniform distribution of the magnetic iron/nickel nanoparticles on the molecular sieve. On the basis of this, the present invention has been completed.