Self-sulfur-containing oil-soluble molybdenum-based catalyst as well as preparation method and application thereof

Abstract

The invention discloses a self-sulfur-containing oil-soluble molybdenum-based catalyst as well as a preparation method and application thereof, and belongs to the technical field of chemical catalysts. The catalyst is prepared by the following method: mixing a sulfur-containing organic ligand and polyol, adding a water carrying agent, and stirring for reaction; after the reaction is completed, standing for layering, and taking an upper-layer oil phase; adding a molybdenum source into the upper-layer oil phase, then adding an alkaline agent, and stirring for reaction; and after the reaction is finished, filtering and washing the product, and removing the water carrying agent to obtain the self-sulfur-containing oil-soluble molybdenum-based catalyst. The catalyst prepared by the invention contains sulfur, can be decomposed in situ to form an active phase MoS2 in the reaction process without adding any vulcanizing agent or utilizing sulfides in the raw materials, and has the advantages of high catalytic activity, wide raw material source, low cost, simple preparation process and easy operation.

Description

Technical Field

[0001] The present invention belongs to the technical field of chemical catalysts, and particularly relates to a sulfur-containing oil-soluble molybdenum-based catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] The slurry bed hydrogenation process using a dispersed catalyst has the advantages of strong raw material adaptability, no bed plugging, high conversion rate, etc. Using the slurry bed hydrogenation process as a platform technology can cleanly and efficiently convert inferior raw materials such as residue oil, coal tar, and coal / heavy oil into light fuels or chemical raw materials, and can also convert waste oils such as swill oil and gutter oil into hydrocarbon compounds that can replace fossil resources, such as biodiesel (HVO), sustainable aviation fuel (SAF), etc. The dispersed catalyst has no pore diffusion limitation, and the active sites of the catalyst are easier to approach the reactant molecules, with higher metal utilization. However, the dispersed catalyst and the waste oil pass through the reactor once, belonging to a disposable catalyst, and the addition amount needs to be strictly controlled to reduce the operation cost. Therefore, developing a highly active and low-cost dispersed catalyst is a key technical problem in the slurry bed hydrogenation process.

[0003] The dispersed catalyst can be divided into two types according to the type of precursor: water-soluble and oil-soluble. The precursors of water-soluble catalysts are generally inorganic salts of metals such as Fe, Ni, Mo, etc. Their prices are relatively cheap, but it is difficult to disperse them in the feedstock oil, resulting in low catalytic activity. The precursors of oil-soluble catalysts are mainly metal organic salts, which can be dissolved or evenly dispersed in the feedstock oil, with less dosage and high activity, and are ideal dispersed catalysts. Currently, the more commonly used oil-soluble catalysts mainly include naphthenates, fatty acid salts, organic amine salts, carbonyl salts, etc., such as nickel naphthenate, iron naphthenate, nickel oleate, cobalt oleate, molybdenum oleate, molybdenum hexacarbonyl, etc. Among them, the oil-soluble molybdenum-based catalyst has been widely used in the slurry bed hydrogenation process of heavy and inferior oil due to its excellent hydrogenation activity.

[0004] The active phase of the oil-soluble molybdenum-based catalyst is MoS2 formed by the sulfidation reaction of the precursor and the sulfur source. Currently, in industry, the method of in-situ sulfidation in the feedstock oil is generally used to obtain the active phase MoS2. For example, in the EST process, hydrogen at 500°C is used to quickly push the feedstock (residue oil) at 320°C and the catalyst precursor into the reactor, and the precursor reacts with the sulfur-containing compounds in the residue oil to form dispersed MoS2. Due to the complexity of the operating conditions and the composition of the residue oil, the sulfidation degree, structure, and particle size of the active phase cannot be effectively controlled, and it is difficult to ensure the high dispersion and high activity of the active phase. In addition, if the sulfur content in the raw material is not enough, an additional sulfurizing agent needs to be added to successfully complete the sulfidation to form MoS2.

[0005] Since the sulfur-containing oil-soluble molybdenum-based catalyst contains sulfur element itself, it does not need to add any sulfurizing agent and does not need to utilize the sulfide in the raw material, and can be decomposed in-situ during the reaction to form MoS2. Patent CN 112371139 A discloses that thio molybdates such as ammonium tetrathiomolybdate, sodium tetrathiomolybdate, ammonium dodecylthiotungstate, etc. react with C6-C 20 primary amines to successfully obtain self-sulfurizing oil-soluble molybdenum-based catalysts. Patent CN 112371138 A also uses thio molybdates to react with organic amines to prepare self-sulfurizing oil-soluble molybdenum-based catalysts. The sulfur source for preparing these self-sulfurizing oil-soluble molybdenum-based catalysts in the above-mentioned prior art comes from thio molybdates. However, the price of thio molybdates is expensive, resulting in a very high raw material cost of the catalyst. Therefore, it is necessary to develop a low-cost preparation technology for sulfur-containing oil-soluble molybdenum-based catalysts. Summary of the Invention

[0006] In order to reduce the preparation cost of the sulfur-containing oil-soluble molybdenum-based catalyst, the present invention provides a sulfur-containing oil-soluble molybdenum-based catalyst, which uses an organic ligand containing sulfur element as a raw material. It has a wide source and low cost, can be decomposed in-situ during the sulfidation process to form a MoS2 active phase, and due to the "reverse micelle" confinement effect of the ligand, the composition and structure of the formed active phase are controllable, the particle size is small, and the catalytic activity is high. It can effectively reduce the operation cost of slurry bed hydroprocessing of heavy and inferior oil raw materials such as residue oil, coal tar, coal / heavy oil, and waste grease.

[0007] The technical solution of the present invention is as follows:

[0008] The present invention provides a preparation method of a sulfur-containing oil-soluble molybdenum-based catalyst, comprising the following steps:

[0009] Mix a sulfur-containing organic ligand and a polyol, add a water-carrying agent, and stir to react; after the reaction is completed, let it stand for layering, and take the upper oil phase; add a molybdenum source to the upper oil phase, and then add a basic agent, and stir to react; after the reaction ends, filter and wash the product to remove the water-carrying agent to obtain a sulfur-containing oil-soluble molybdenum-based catalyst.

[0010] In the above preparation method, the molar ratio of the sulfur-containing organic ligand to the polyol is selected from 1:2 to 1:6; the mass fraction of the water-carrying agent in the total reaction materials is 10-30%; the molar ratio of molybdenum metal in the molybdenum source to the sulfur-containing ligand in the upper oil phase is selected from 1:2.5 to 1:4; the mass fraction of the basic agent in the molybdenum source is 1-10%.

[0011] In the above preparation method, the sulfur-containing organic ligand is selected from alkylbenzenesulfonic acid or alkylsulfonic acid. Specifically, it can be selected from one of dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, eicosylbenzenesulfonic acid, dodecylsulfonic acid, hexadecylsulfonic acid, octadecylsulfonic acid, and eicosylsulfonic acid.

[0012] In the above preparation method, the polyol is selected from one of glycerol, trimethylolpropane, pentaerythritol, diethanolamine, triethanolamine, and triisopropanolamine.

[0013] In the above preparation method, the water-carrying agent is selected from one of benzene, toluene, and xylene.

[0014] In the above preparation method, the molybdenum source is selected from one of molybdenum trioxide, ammonium molybdate, and sodium molybdate.

[0015] In the above preparation method, the alkaline agent is sodium hydroxide or potassium hydroxide.

[0016] In the above preparation method, the stirring reaction is selected from the following conditions: boiling under reflux for 3 to 10 h under stirring conditions.

[0017] The present invention provides a sulfur-containing oil-soluble molybdenum-based catalyst prepared by the above method.

[0018] The present invention provides the application of the above sulfur-containing oil-soluble molybdenum-based catalyst in the heavy and inferior oil slurry bed hydrogenation process.

[0019] The present invention provides a catalytic reaction method for the heavy and inferior oil slurry bed hydrogenation process, including the following steps:

[0020] The sulfur-containing oil-soluble molybdenum-based catalyst is added to the heavy and inferior oil raw material at a ratio of 100 to 2000 μg / g and mixed evenly; then the raw material oil mixed with the catalyst is mixed with fresh hydrogen and recycle hydrogen and then enters the heating furnace. After heating to 355 to 435 °C, it enters from the bottom of the slurry bed reactor and undergoes a hydrogenation reaction under the conditions of a reaction temperature of 360 to 440 °C, a reaction pressure of 8 to 20 MPa, a residence time of 0.2 to 1.5 h, and a hydrogen-oil volume ratio of (600 to 1200):1.

[0021] In the above catalytic reaction method for the heavy and inferior oil slurry bed hydrogenation process, the heavy and inferior oil is selected from one or more of residue oil, coal tar, and waste grease.

[0022] The beneficial effects of the present invention are as follows:

[0023] The present invention uses a sulfur-containing organic ligand as a raw material to prepare a sulfur-containing oil-soluble molybdenum-based catalyst. Among them, the sulfur-containing organic ligand has a wide source and low cost, so as to reduce the preparation cost of the sulfur-containing oil-soluble molybdenum-based catalyst.

[0024] Since the catalyst prepared by the present invention contains sulfur itself, in the catalytic reaction of heavy and inferior oils, no sulfurizing agent needs to be added, nor is it necessary to utilize the sulfides in the raw materials. Instead, the active phase MoS2 can be formed by in-situ decomposition during the reaction process, promoting the efficient progress of the catalytic reaction.

[0025] In addition, during the sulfurization process of the sulfur-containing catalyst of the present invention, the formation of the active phase MoS2 is not affected by the sulfur content of the raw materials and their compositional structures such as the forms of sulfides. By utilizing the "reverse micelle" confinement effect of the oil-soluble ligand, the agglomeration of the active phase during the formation process can be restricted, and the controllable construction of the sulfurized compositional structure and particle size of the active phase can be achieved.

[0026] The catalyst of the present invention has good dissolution and dispersion properties in heavy and inferior oil raw materials, high catalytic activity, high light oil yield, and low coke yield.

[0027] In summary, the self-sulfur-containing oil-soluble molybdenum-based catalyst prepared by the present invention is a dispersed catalyst with controllable structure, high activity, and low cost, which can further improve the technical economy of the slurry bed hydrogenation process. Detailed implementation mode

[0028] In the present invention, taking the sulfur-containing organic ligand as alkylbenzene sulfonic acid and the polyol as glycerol as an example, the molecular structure of the prepared self-sulfur-containing oil-soluble molybdenum-based catalyst is shown as follows:

[0029]

[0030] Taking the sulfur-containing organic ligand as alkyl sulfonic acid and the polyol as glycerol as an example, the molecular structure of the prepared self-sulfur-containing oil-soluble molybdenum-based catalyst is shown as follows:

[0031]

[0032] Among them, n = 11 - 19.

[0033] Other materials used in the present invention, unless otherwise stated, can be obtained through commercial channels. Other terms used in the present invention, unless otherwise explained, generally have the meanings commonly understood by those of ordinary skill in the art. The present invention will be further described in detail below with reference to specific examples and data. The following examples are only for illustrating the present invention and do not limit the scope of the present invention in any way.

[0034] Example 1

[0035] To prepare a self-sulfur-containing oil-soluble molybdenum-based catalyst, the steps are as follows:

[0036] Charge 326.5 g of dodecylbenzenesulfonic acid (1 mol) and 184.2 g of glycerol (2 mol) into a reaction kettle, add 153.2 g of toluene (accounting for 30%), boil and reflux for 6 h under stirring conditions. After the reaction, let it stand for liquid separation, take the upper oil phase, add 57.6 g of molybdenum trioxide (0.4 mol) to the upper oil phase, and then add 5.7 g of potassium hydroxide (accounting for 10%). Continue to boil and reflux for 8 h under stirring conditions. After the reaction, filter and wash the product, and finally distill off toluene to obtain a sulfur-containing oil-soluble molybdenum-based catalyst. The molybdenum content is 8.4% detected by ICP.

[0037] Example 2

[0038] The steps for preparing a sulfur-containing oil-soluble molybdenum-based catalyst are as follows:

[0039] Charge 250.4 g of dodecylsulfonic acid (1 mol) and 816.9 g of pentaerythritol (6 mol) into a reaction kettle, add 106.7 g of xylene (accounting for 10%), boil and reflux for 3 h under stirring conditions. After the reaction, let it stand for liquid separation, take the upper oil phase, add 36.0 g of molybdenum trioxide (0.25 mol) to the upper oil phase, and then add 0.4 g of potassium hydroxide (accounting for 1%). Continue to boil and reflux for 10 h under stirring conditions. After the reaction, filter and wash the product, and finally distill off xylene to obtain a sulfur-containing oil-soluble molybdenum-based catalyst. The molybdenum content is 5.8% detected by ICP.

[0040] Example 3

[0041] The steps for preparing a sulfur-containing oil-soluble molybdenum-based catalyst are as follows:

[0042] Charge 438.5 g of eicosylbenzenesulfonic acid (1 mol) and 536.7 g of trimethylolpropane (4 mol) into a reaction kettle, add 195.0 g of benzene (accounting for 20%), boil and reflux for 7 h under stirring conditions. After the reaction, let it stand for liquid separation, take the upper oil phase, add 78.4 g of ammonium molybdate (0.4 mol) to the upper oil phase, and then add 3.9 g of sodium hydroxide (accounting for 5%). Continue to boil and reflux for 9 h under stirring conditions. After the reaction, filter and wash the product, and finally distill off benzene to obtain a sulfur-containing oil-soluble molybdenum-based catalyst. The molybdenum content is 6.5% detected by ICP.

[0043] Example 4

[0044] The steps for preparing a sulfur-containing oil-soluble molybdenum-based catalyst are as follows:

[0045] Charge 362.4 g of docosylsulfonic acid (1 mol) and 420.5 g of diethanolamine (4 mol) into a reaction kettle, add 156.6 g of toluene (accounting for 20%), boil and reflux for 7.5 h under stirring. After the reaction, let it stand for stratification, take the upper oil phase, add 61.8 g of sodium molybdate (0.3 mol) to the upper oil phase, then add 2.5 g of sodium hydroxide (accounting for 4%), and continue to boil and reflux for 8.5 h under stirring. After the reaction, filter and wash the product, and finally distill off toluene to obtain a sulfur-containing oil-soluble molybdenum-based catalyst. The molybdenum content detected by ICP is 5.8%.

[0046] Example 5

[0047] The steps for preparing a sulfur-containing oil-soluble molybdenum-based catalyst are as follows:

[0048] Charge 306.4 g of cetylsulfonic acid (1 mol) and 447.6 g of triethanolamine (3 mol) into a reaction kettle, add 113.1 g of xylene (accounting for 15%), boil and reflux for 8 h under stirring. After the reaction, let it stand for stratification, take the upper oil phase, add 43.2 g of molybdenum trioxide (0.3 mol) to the upper oil phase, then add 0.9 g of potassium hydroxide (accounting for 2%), and continue to boil and reflux for 10 h under stirring. After the reaction, filter and wash the product, and finally distill off xylene to obtain a sulfur-containing oil-soluble molybdenum-based catalyst. The molybdenum content detected by ICP is 6.6%.

[0049] Example 6

[0050] The steps for preparing a sulfur-containing oil-soluble molybdenum-based catalyst are as follows:

[0051] Charge 354.5 g of tetradecylbenzenesulfonic acid (1 mol) and 573.8 g of triisopropanolamine (3 mol) into a reaction kettle, add 139.2 g of toluene (accounting for 15%), boil and reflux for 10 h under stirring. After the reaction, let it stand for stratification, take the upper oil phase, add 43.2 g of molybdenum trioxide (0.3 mol) to the upper oil phase, then add 2.6 g of potassium hydroxide (accounting for 6%), and continue to boil and reflux for 8 h under stirring. After the reaction, filter and wash the product, and finally distill off toluene to obtain a sulfur-containing oil-soluble molybdenum-based catalyst. The molybdenum content detected by ICP is 5.0%.

[0052] Example 7

[0053] The steps for preparing a sulfur-containing oil-soluble molybdenum-based catalyst are as follows:

[0054] Charge 382.5 g of cetylbenzenesulfonic acid (1 mol) and 276.3 g of glycerol (3 mol) into a reaction kettle, add 131.7 g of toluene (accounting for 20%), boil and reflux for 9.5 h under stirring conditions. After the reaction, let it stand and separate layers, take the upper oil phase, add 43.2 g of molybdenum trioxide (0.3 mol) to the upper oil phase, then add 2.2 g of potassium hydroxide (accounting for 5%), and continue to boil and reflux for 9 h under stirring conditions. After the reaction, filter and wash the product, and finally distill off toluene to obtain a sulfur-containing oil-soluble molybdenum-based catalyst. The molybdenum content is detected by ICP to be 5.7%.

[0055] Example 8

[0056] Prepare a sulfur-containing oil-soluble molybdenum-based catalyst, and the steps are as follows:

[0057] Charge 306.4 g of hexadecylsulfonic acid (1 mol) and 276.3 g of glycerol (3 mol) into a reaction kettle, add 116.5 g of toluene (accounting for 20%), boil and reflux for 9 h under stirring conditions. After the reaction, let it stand and separate layers, take the upper oil phase, add 58.8 g of ammonium molybdate (0.3 mol) to the upper oil phase, then add 1.8 g of potassium hydroxide (accounting for 3%), and continue to boil and reflux for 9.5 h under stirring conditions. After the reaction, filter and wash the product, and finally distill off toluene to obtain a sulfur-containing oil-soluble molybdenum-based catalyst. The molybdenum content is detected by ICP to be 6.7%.

[0058] Example 9

[0059] Prepare a sulfur-containing oil-soluble molybdenum-based catalyst, and the steps are as follows:

[0060] Charge 334.4 g of octadecylsulfonic acid (1 mol) and 447.6 g of triethanolamine (3 mol) into a reaction kettle, add 117.3 g of toluene (accounting for 15%), boil and reflux for 8.5 h under stirring conditions. After the reaction, let it stand and separate layers, take the upper oil phase, add 43.2 g of molybdenum trioxide (0.3 mol) to the upper oil phase, then add 2.2 g of sodium hydroxide (accounting for 5%), and continue to boil and reflux for 9.5 h under stirring conditions. After the reaction, filter and wash the product, and finally distill off toluene to obtain a sulfur-containing oil-soluble molybdenum-based catalyst. The molybdenum content is detected by ICP to be 5.6%.

[0061] Example 10

[0062] Prepare a sulfur-containing oil-soluble molybdenum-based catalyst, and the steps are as follows:

[0063] Charge 326.5 g of dodecylbenzenesulfonic acid (1 mol) and 447.6 g of triethanolamine (3 mol) into a reaction kettle, add 117.3 g of toluene (accounting for 15%), boil and reflux for 9 h under stirring conditions. After the reaction, let it stand for stratification, take the upper oil phase, add 58.8 g of ammonium molybdate (0.3 mol) to the upper oil phase, and then add 2.4 g of potassium hydroxide (accounting for 4%). Continue to boil and reflux for 10 h under stirring conditions. After the reaction, filter and wash the product, and finally distill out toluene to obtain a sulfur-containing oil-soluble molybdenum-based catalyst. The molybdenum content detected by ICP is 5.7%.

[0064] I. Heavy and inferior oil catalytic test

[0065] The sulfur-containing oil-soluble molybdenum-based catalysts prepared in Examples 1 to 10 are respectively denoted as catalysts C1 to C10.

[0066] Add the above catalysts to the heavy and inferior oil raw materials (residue, coal tar, waste oil) at a ratio of 100 - 2000 μg / g, and stir and mix evenly. After mixing the raw material oil with the catalyst with fresh hydrogen and recycle hydrogen, enter a heating furnace, heat to 355 - 435 °C and then enter from the bottom of a slurry bed reactor, and carry out a hydrogenation reaction under the conditions of a reaction temperature of 360 - 440 °C, a reaction pressure of 8 - 20 MPa, a residence time of 0.2 - 1.5 h, and a hydrogen-oil volume ratio of (600 - 1200):1.

[0067] The properties of the heavy and inferior oil raw materials are shown in Table 1:

[0068] Table 1 Basic indicators of heavy and inferior oil raw materials

[0069]

[0070]

[0071] The conditions and reaction results of the slurry bed hydrogenation reaction are shown in Table 2:

[0072] Table 2 Reaction conditions and reaction results of the slurry bed hydrogenation process

[0073]

[0074]

[0075] As can be seen from Table 2, when using residue as the raw material, when the catalyst addition amount is 200 - 1000 μg·g -1 , the unreacted residue (vacuum tail oil) is less than 24%, that is, the residue conversion rate exceeds 75%, and the coke yield is lower than 0.7%. Especially when the catalyst addition amount is 1000 μg·g -1When the carbon deposition rate is 0%. When using coal tar as the raw material, when the catalyst addition amount is 500 μg·g -1 When the coal tar conversion rate exceeds 90% and the carbon deposition rate is lower than 0.6%. When using waste oil as the raw material, when the catalyst addition amount is 500 μg·g -1 When the unreacted waste oil (>360°C fraction) is less than 2.1%, that is, the conversion rate of waste oil is about 98%, and the biodiesel yield exceeds 83%.

[0076] As described above, it is only a preferred embodiment of the present invention, and it is not a limitation of the present invention in other forms. Any person skilled in the art may use the disclosed technical content to make changes or modifications into equivalent embodiments with equivalent changes. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the technical solution content of the present invention still belong to the protection scope of the technical solution of the present invention.

Claims

1. A preparation method of a sulfur-containing oil-soluble molybdenum-based catalyst, characterized in that, It includes the following steps: Mix a sulfur-containing organic ligand and a polyol, add a water-carrying agent, and stir for reaction; after the reaction is completed, let it stand for layering, and take the upper oil phase; add a molybdenum source to the upper oil phase, then add an alkaline agent, and stir for reaction; after the reaction ends, filter and wash the product to remove the water-carrying agent to obtain a sulfur-containing oil-soluble molybdenum-based catalyst.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the sulfur-containing organic ligand to the polyol is selected from 1:2 to 1:6; the mass fraction of the water-carrying agent in the total reaction materials is 10-30%; the molar ratio of molybdenum metal in the molybdenum source to the sulfur-containing ligand in the upper oil phase is selected from 1:2.5 to 1:4; the mass fraction of the alkaline agent in the molybdenum source is 1-10%.

3. The preparation method according to claim 1, characterized in that, The sulfur-containing organic ligand is selected from alkylbenzenesulfonic acid or alkylsulfonic acid. Specifically, it can be selected from one of dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, eicosylbenzenesulfonic acid, dodecylsulfonic acid, hexadecylsulfonic acid, octadecylsulfonic acid, and eicosylsulfonic acid.

4. The preparation method according to claim 1, wherein The polyol is selected from one of glycerol, trimethylolpropane, pentaerythritol, diethanolamine, triethanolamine, and triisopropanolamine.

5. The preparation method according to claim 1, characterized in that, The water-carrying agent is selected from one of benzene, toluene, and xylene.

6. The preparation method according to claim 1, wherein The molybdenum source is selected from one of molybdenum trioxide, ammonium molybdate, and sodium molybdate.

7. The preparation method according to claim 1, wherein The alkaline agent is sodium hydroxide or potassium hydroxide.

8. A sulfur-containing oil-soluble molybdenum-based catalyst prepared by the method according to any one of claims 1 to 7.

9. Use of the sulfur-containing oil-soluble molybdenum-based catalyst according to claim 8 in a heavy and inferior oil slurry bed hydrogenation process.

10. A catalytic reaction method for a heavy and inferior slurry bed hydroprocessing process, characterized in that, It includes the following steps: Add the sulfur-containing oil-soluble molybdenum-based catalyst according to claim 8 to the heavy and inferior oil raw material at a ratio of 100-2000 μg / g, and mix evenly; then mix the raw material oil mixed with the catalyst with fresh hydrogen and recycle hydrogen and enter a heating furnace, heat to 355-435 °C and then enter from the bottom of the slurry bed reactor, and carry out a hydrogenation reaction under the conditions of a reaction temperature of 360-440 °C, a reaction pressure of 8-20 MPa, a residence time of 0.2-1.5 h, and a hydrogen-oil volume ratio of (600-1200):1.

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