CN111617757B

CN111617757B - Preparation method and application of hybrid suspension bed solution catalyst

Info

Publication number: CN111617757B
Application number: CN202010553353.XA
Authority: CN
Inventors: 柳云骐; 陈彦飞; 管泽坤; 潘原; 刘宾; 柴永明; 刘晨光
Original assignee: China University of Petroleum East China
Current assignee: China University of Petroleum East China
Priority date: 2020-06-17
Filing date: 2020-06-17
Publication date: 2023-01-24
Anticipated expiration: 2040-06-17
Also published as: CN111617757A

Abstract

The invention relates to a preparation method and application of a hybrid suspension bed solution catalyst, wherein the method comprises the following steps: dissolving metal salt in water under sufficient stirring; heating and dissolving the surfactant in the oil product under full stirring; and dropwise adding the water phase into the oil phase, fully stirring for reaction, standing for layering, and obtaining the hybrid suspension bed solution catalyst on the upper layer. According to the preparation method of the hybrid suspension bed solution catalyst, the solution catalyst is directly added during reaction, and the steps of separation, dispersion and the like of the catalyst are not needed, so that the oil solubility of the suspension bed hydrogenation catalyst is really realized. The method has the advantages of simple operation steps, small catalyst addition amount, simple preparation process, effective coke formation inhibition and particular suitability for the hydrogenation process of the poor-quality residual oil suspension bed with high sulfur, high nitrogen and high metal content.

Description

Preparation method and application of hybrid suspension bed solution catalyst

Technical Field

The invention belongs to the technical field of petrochemical industry, and particularly relates to a preparation method and application of a hybrid suspension bed solution catalyst.

Background

At present, with the continuous increase of international crude oil demand and the gradual decrease of producible high-quality crude oil, the proportion of heavy inferior crude oil with high sulfur, high nitrogen and high carbon residue tends to increase year by year in the global crude oil supply. Meanwhile, environmental protection regulations are increasingly strict, and the product quality standard is continuously upgraded, so that higher requirements are put forward on the refining and processing technology of heavy oil (especially heavy and poor residual oil). The large-scale industrialized fixed bed hydrogenation process has higher requirement on the quality of raw materials, and the suspension bed hydrocracking process adopts a hollow barrel structure with less or no internal components, so that the dispersed catalyst can also reduce the coking of a reactor to a great extent, has stronger raw material adaptability, and has flexible operation, simple process and high conversion rate. At present, many enterprises at home and abroad have developed relevant researches on the suspension bed hydrogenation process and have achieved certain results, such as VCC process developed by Veba company in germany, cannet process of the canadian mineral and technology center, HFC process in japan, HDH process of venezuela, EST process of ENI company in italy, and the like.

The key to the development of the heavy oil suspension bed hydrogenation process lies in the continuous progress of the high-quality hydrogenation catalyst. The catalyst used in the suspension bed hydrogenation process can be divided into heterogeneous catalyst and homogeneous catalyst, wherein the heterogeneous catalyst refers to solid powder catalyst, and the homogeneous catalyst can be divided into water-soluble catalyst and oil-soluble catalyst. The solid powder catalyst has low cost and simple process operation, but has large energy consumption and large using amount, and the tail oil contains a large amount of solid particles (catalyst and coke), so the treatment is difficult and the pollution is easy to cause. Although the catalytic activity of the water-soluble catalyst is higher than that of the solid powder catalyst, the dispersion process is complicated. Compared with the two catalysts, the oil-soluble catalyst has obvious advantages in the aspects of dispersion and hydrogenation coke inhibition performance, and has high dispersion degree, so that the oil-soluble catalyst becomes a hotspot for researching a heavy oil suspension bed hydrogenation process catalyst.

Chinese patent CN201410208927.4 discloses a sulfur-containing oil-soluble catalyst prepared by reacting sulfur-containing organic matter generated by reacting a multi-carbon alcohol with phosphorus pentasulfide with a neutral aqueous solution of molybdenum in the presence of an acidic cation exchange resin. Chinese patent 201710802071.7 discloses that an oil-soluble NiMo catalyst is prepared by reacting a sulfur-containing molybdenum source with an organic acid after filtering and drying to prepare a molybdenum-based precursor, reacting nickel salt with organic amine, filtering and washing to prepare a nickel-based precursor, and dissolving the nickel-based precursor and the nickel salt in an auxiliary dispersant. Chinese patent CN1362492A discloses a poor quality residual oil suspension bed hydrocracking oil soluble catalyst prepared by reacting N-benzoyl or N-aniline, chloroform and molybdenum salt. Chinese patent CN103349999A discloses that under the protection of nitrogen, molybdenum source, water, sodium sulfide, inorganic acid, etc. are used to prepare an oil-soluble molybdenum auto-sulfide catalyst. Although the catalyst prepared by the above patent shows excellent performance in hydrogenation reaction of heavy residual oil, the preparation steps of the catalyst are complicated, the catalyst is time-consuming and labor-consuming in separation, purification and dispersion, and great challenges are provided for energy conservation, emission reduction and cost reduction required in industrial production.

Disclosure of Invention

In view of the above defects of the existing oil-soluble catalyst, the invention aims to provide a preparation method and application of a hybrid suspension bed solution catalyst, which can overcome the defect of complicated preparation process in the prior art.

The principle on which the invention is based is as follows: the invention relates to a preparation method of a hybrid type suspension bed solution catalyst, which uses a liquid-liquid extraction reaction method, adopts a metalate to be dissolved in water under mechanical stirring, adopts a long-chain alkyl quaternary ammonium salt surfactant to be heated and dissolved in an oil product under mechanical stirring, the metalate and the oil product are fully mixed and reacted, the metalate is completely extracted and transferred from a water phase to an oil phase through reaction, and after the oil and the water are stood and layered, the organic-inorganic hybrid type suspension bed solution catalyst with a core-shell structure is obtained in an upper oil phase.

Based on the principle, the technical scheme of the invention is as follows:

the invention provides a preparation method of a hybrid suspension bed solution catalyst, which comprises the following steps:

s101: dissolving a main agent of metal acid salt in water under stirring to obtain a water phase; the main agent metalate is one or a combination of several of ammonium heptamolybdate, ammonium tetramolybdate, sodium heptamolybdate, ammonium tungstate, ammonium metatungstate and sodium tungstate;

s102: dissolving a surfactant in an oil product under full stirring to obtain an oil phase; the surfactant is a long-chain alkyl quaternary ammonium salt surfactant;

s103: and adding the water phase into the oil phase, fully stirring for reaction, standing for layering or centrifugally layering, and obtaining the hybrid suspension bed solution catalyst on the upper layer.

Further, the main agent metalate is dissolved in 20mL to 100mL of water per millimole in the step S101.

Further, the step S101 further includes an auxiliary agent metal acid salt, which is dissolved in water together with the main agent metal acid salt by stirring; the auxiliary agent metal acid salt is one or a combination of more of cobalt acetate, cobalt carbonate, cobalt nitrate, nickel carbonate and nickel nitrate; the molar ratio of metal in the main agent metal acid salt to metal in the auxiliary agent metal acid salt is 3:1-1:1. further, the main agent metallate and the auxiliary agent metallate are dissolved in 20mL to 100mL of water per millimole in the step S101.

Further, the long-chain alkyl quaternary ammonium salt surfactant at least comprises one or a combination of several of an anionic surfactant, a cationic surfactant and a zwitterionic surfactant. Further, in the anionic surfactant, the number of carbon atoms of the polycarboalkyl chain is 5 to 18, the number of the polycarboalkyl chain is 1 to 4, and dioctadecyldimethylammonium chloride is more preferable.

Further, the oil product is one or a combination of more of lubricating oil base oil, straight-run diesel oil, catalytic cracking diesel oil, coking diesel oil and liquid wax oil.

Further, in step S102, after the oil product is heated to 50 ℃ to 80 ℃, the surfactant is added into the oil product, the amount of the oil product is 50mL to 200mL (determined according to the solubility of the surfactant), and the amount of the long-chain alkyl quaternary ammonium salt surfactant is determined according to the total charge number of the metal ions in the main agent, namely, the total negative charge number of the long-chain alkylamine is consistent with the total positive charge number of the metal ions, so that the final product is electrically neutral.

Further, the step S103 includes the following steps:

s1031: at a temperature of 50-80 ℃, the water phase is added into the oil phase drop by drop at a speed of one drop per two seconds to two drops per second;

s1032: fully reacting under mechanical stirring for 1-5 h until the metal acid salt is completely extracted and transferred into an oil phase;

s1033: standing or centrifuging for layering, taking the upper oil phase, adding a drying agent for dewatering, and obtaining the solution catalyst.

The second invention provides a preparation method of the hybrid suspension bed solution catalyst obtained by the preparation method.

The third invention provides the application of the hybrid suspension bed solution catalyst in the suspension bed hydrogenation process; the application method comprises the steps of directly adding a certain volume of the solution catalyst into inferior heavy oil, and utilizing sulfur-containing compounds in the heavy oil to generate hydrogenation active components in situ in the reaction process, wherein the hydrogenation activity is excellent, and the dosage of the catalyst is 50-2000 mu g/g calculated by metal. The operating conditions of the suspension bed hydrogenation reactor are as follows: the reaction pressure is 5MPa to 25MPa, the reaction temperature is 380 ℃ to 480 ℃, and the volume space velocity is 0.2h ^-1 -1.5h ^-1 The volume ratio of hydrogen to oil is 200-1000.

According to the preparation method of the hybrid suspension bed solution catalyst, the solution catalyst is directly added during reaction, the hydrogenation active site with extremely small particles is generated in situ in the reactor, the steps of catalyst separation, thermal decomposition, heating or mechanical stirring dispersion and the like are not needed, the production cost is greatly saved, and the oil solubility of the suspension bed hydrogenation catalyst is really realized. The catalyst is extremely convenient to use, small in addition amount, excellent in dispersity at the reaction temperature, simple in preparation process, capable of effectively inhibiting coke formation and particularly suitable for the high-sulfur, high-nitrogen and high-metal poor-quality residual oil suspended bed hydrogenation process while the operation steps are simplified.

Detailed Description

The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.

Example 1

A preparation method of a hybrid Mo-based solution catalyst comprises the following steps:

1.236g ammonium molybdate tetrahydrate is weighed, 50mL deionized water is added, and the mixture is stirred for 10min by a rotor to be completely dissolved.

3.519g of dioctadecyl dimethyl ammonium chloride is weighed, 100mL of white oil (lubricating oil base oil) is added, a rotor is added, the temperature is raised to 80 ℃, and stirring is carried out for 20min, so that the mixture is completely dissolved.

And (2) dropwise adding the aqueous solution into the white oil solution under the stirring condition of 80 ℃, reacting for 2 hours, cooling at room temperature, standing for layering, taking out the upper layer white oil solution, adding a calcium oxide drying agent for dewatering, and obtaining 100mL of the Mo-based solution catalyst.

Example 2

A preparation method of a hybrid W-based solution catalyst comprises the following steps:

1.319g of sodium tungstate dihydrate is weighed, 50mL of deionized water is added, and the mixture is added into a rotor and stirred for 10min to be completely dissolved.

Weighing 4.692g of dioctadecyldimethylammonium chloride, adding 100mL of white oil (lubricant base oil), adding a rotor, heating to 80 ℃, and stirring for 20min to completely dissolve.

And (2) dropwise adding the aqueous solution into the white oil solution under the stirring condition of 80 ℃, reacting for 2 hours, cooling at room temperature, standing for layering, taking out the upper white oil solution, adding a calcium oxide drying agent, and removing water to obtain 100mL of the W-based solution catalyst.

Example 3

A preparation method of a hybrid CoMo-based solution catalyst comprises the following steps:

1.236g of ammonium molybdate tetrahydrate and 0.747g of cobalt acetate tetrahydrate are weighed, 50mL of deionized water is added, and a rotor is added for stirring for 10min to ensure complete dissolution.

And dropwise adding the aqueous solution into the white oil solution under the stirring condition of 80 ℃, reacting for 2 hours, cooling at room temperature, standing for layering, taking out the upper white oil solution, adding a calcium oxide drying agent, and removing water to obtain 100mL of a CoMo-based solution catalyst.

Example 4

A preparation method of a hybrid NiW-based solution catalyst comprises the following steps:

1.319g of sodium tungstate dihydrate and 0.526g of nickel sulfate hexahydrate are weighed, 50mL of deionized water is added, and a rotor is added for stirring for 10min so as to be completely dissolved.

Weighing 4.692g of dioctadecyldimethylammonium chloride, adding 100mL of white oil (lubricant base oil), adding into a rotor, heating to 80 ℃, and stirring for 20min to completely dissolve.

And (3) dropwise adding the aqueous solution into the white oil solution under the stirring condition of 80 ℃, reacting for 2 hours, cooling at room temperature, standing for layering, taking out the upper white oil solution, adding a calcium oxide drying agent, and removing water to obtain 100mL of the NiW-based solution catalyst.

The hybrid solution catalyst can be used for a high-sulfur high-metal high-carbon residue poor heavy oil suspended bed hydrocracking process, and the using method comprises the steps of directly adding a certain volume of the solution catalyst into poor heavy oil, generating a hydrogenation active component in situ by utilizing a sulfur-containing compound in the heavy oil in the reaction process, wherein the hydrogenation activity is excellent, and the using amount of the catalyst is 50-2000 mu g/g calculated by metal. The operating conditions of the suspension bed hydrogenation reactor are as follows: the reaction pressure is 5MPa to 25MPa, the reaction temperature is 380 ℃ to 480 ℃, and the volume space velocity is 0.2h ^-1 -1.5h ^-1 The volume ratio of hydrogen to oil is 200-1000.

Taking the four hybrid solution catalysts in examples 1, 2, 3 and 4, taking Qingdao refined vacuum residue as a raw material (properties are shown in Table 1), and in a high-pressure automatic reaction kettle, the reaction temperature is 430 ℃, the initial hydrogen pressure is 6MPa, and the catalyst dosage is respectively: the single metal catalyst is 500 mug/g (calculated by metal mass), the double metal catalyst is 300 mug/g (calculated by main agent metal mass), and the reaction time is 1h. The results of the vacuum residue hydrocracking evaluation of the different hybrid type solution catalysts under the specified conditions are shown in table 2.

TABLE 1 Qingdao refinery vacuum residuum Properties

TABLE 2 results of vacuum residuum hydrocracking evaluation

As can be seen from the data in Table 2, the reaction temperature is 430 ℃, the initial hydrogen pressure is 6MPa, the vacuum residue undergoes the hydrocracking reaction without a catalyst, most or long-chain heavy oil molecules are deeply cracked to generate small-molecule hydrocarbon gases, or macromolecular radicals are polymerized with each other to form severe coke, and the wall coke reaches 17.14wt%. After the hybrid solution catalyst is added, the catalyst dissociates hydrogen molecules to generate a large amount of hydrogen radicals, alkyl radicals generated by thermal cracking are sealed in time, deep cracking of alkyl chains is prevented, excessive polymerization of macromolecular radicals is prevented, gasoline and diesel fractions are produced as much as possible, simultaneously, the coke inhibiting effect is obvious, and the wall coke is reduced from 17% to about 3%. The hydrogenation coke inhibiting effect of the Mo-based solution catalyst is better than that of the W-based solution catalyst, and the hydrogen activating effect of the element Mo is more remarkable; the hydrogenation coke-inhibiting effect of the bimetal solution catalyst is stronger than that of a single metal catalyst, probably because a synergistic effect occurs between the bimetal, and a CoMoS active phase or a NiWS active phase is generated, so that the catalyst can better play a medium role in combining hydrogen free radicals and alkyl free radicals.

Therefore, the hybrid solution catalyst prepared by the invention has excellent hydrogenation performance, is particularly suitable for a suspension bed hydrogenation process of poor heavy oil with high sulfur, high metal and high carbon residue, and the preparation method has certain universality on preparation raw materials.

In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims

1. A preparation method of a hybrid suspension bed solution catalyst is characterized by comprising the following steps:

s101: dissolving a main agent of metal acid salt in water under stirring to obtain a water phase; the main agent metallate is one or a combination of several of ammonium heptamolybdate, ammonium tetramolybdate, sodium heptamolybdate, ammonium tungstate, ammonium metatungstate and sodium tungstate;

s103: adding the water phase into the oil phase, fully stirring for reaction, standing for layering or centrifugally layering, and obtaining a hybrid suspension bed solution catalyst on the upper layer;

the step S101 also comprises an auxiliary agent metal acid salt which is stirred and dissolved in water together with the main agent metal acid salt; the auxiliary agent metal acid salt is one or a combination of more of cobalt acetate, cobalt carbonate, cobalt nitrate, nickel carbonate and nickel nitrate; the molar ratio of the metal in the main agent metal acid salt to the metal in the auxiliary agent metal acid salt is 3:1-1:1;

the long-chain alkyl quaternary ammonium salt surfactant at least comprises one or a combination of more of an anionic surfactant, a cationic surfactant and a zwitterionic surfactant;

the oil product is one or a combination of more of lubricating oil base oil, straight-run diesel oil, catalytic cracking diesel oil, coking diesel oil and liquid wax oil;

in the step S102, after the oil product is heated to 50-80 ℃, the surfactant is added into the oil product, the addition amount of the long-chain alkyl quaternary amine salt surfactant is determined according to the total charge number of metal ions in the main agent metal acid salt, namely the total negative charge number of the long-chain alkyl amine is consistent with the total positive charge number of the metal ions, so that the final product is electrically neutral;

the step S103 includes the steps of:

s1031: adding the water phase into the oil phase dropwise at a temperature of 50-80 ℃ at a speed of one drop per second to two drops per second;

s1033: standing or centrifuging for layering, taking the upper oil phase, and adding a drying agent for dewatering to obtain the solution catalyst.

2. The method for preparing the hybrid suspension bed solution catalyst according to claim 1, wherein in the anionic surfactant, the number of the carbon atoms in the multi-carbon alkyl chain is 5-18, and the number of the multi-carbon alkyl chain is 1-4.

3. The method for preparing the hybrid suspension bed solution catalyst according to claim 1, wherein the main agent metalate is dissolved in 20-100 mL water per millimole in step S101.

4. The method for preparing the hybrid suspension bed solution catalyst according to claim 1, wherein the main agent metalate and the auxiliary agent metalate are dissolved in 20mL to 100mL of water per millimole in step S101.

5. Use of the hybrid suspension bed solution catalyst of any of claims 1-4 in a suspension bed hydrogenation process.