System for preparing coordination catalyst on line

Abstract

The utility model relates to a system for preparing a coordination catalyst on line. The system comprises an inert storage tank, a separation unit, a vacuum evaporation unit and a coordination catalyst preparation unit. According to the system disclosed by the invention, the oxidation catalyst precursor in the mixed catalyst precursor can be removed on line in an oxygen-free environment, so that the prepared target catalyst has multiple active components, high activity and good stability, and the reaction efficiency is high in the use process of subsequent reaction.

Description

Technical Field

[0001] The present invention belongs to the field of catalyst preparation, and in particular relates to an online system for preparing a coordination catalyst. Background Art

[0002] In industrial production, the use of catalysts greatly reduces the activation energy of the reaction, improves the reaction efficiency, and promotes industrial production. In the production of oil refining and chemical plants, both heterogeneous and homogeneous catalysts are widely used, such as solid catalysts of different shapes, solid powders of different sizes, microsphere catalysts, soluble oil-soluble / water-soluble catalysts, etc.

[0003] With the development of the refining industry, fine chemicals and synthetic oils have received more and more attention and development. The design of catalysts has become more and more complex. In addition to the role of different active metal centers, the different functional groups carried by the catalysts also play a vital role. When synthesizing certain types of coordination catalysts, due to their physical and chemical properties, transportation costs and other reasons, online preparation is often required in industrial production. However, when easily oxidized catalysts are prepared online, the raw materials may have been oxidized or oxidized during the preparation process, resulting in less active components in the final synthesized target catalyst, reduced reaction efficiency, and affecting the effective progress of subsequent reactions. Utility Model Content

[0004] The purpose of the present disclosure is to provide a system for online preparation of coordination catalysts. The system provided by the present disclosure can realize online preparation of target catalysts in an oxygen-free environment, and when the content of oxidative catalyst precursor in the mixed catalyst precursor is high, the oxidative catalyst precursor can be removed online, so that the prepared target catalyst has more active ingredients, high activity and good stability. In the process of use in subsequent reactions, the reaction efficiency can be improved and industrial production can be promoted.

[0005] In order to achieve the above object, the present disclosure provides a system for preparing a coordination catalyst online, the system comprising: an inert storage tank, a separation unit, a vacuum evaporation unit and a coordination catalyst preparation unit;

[0006] The inert storage tank comprises a material inlet, a first inert gas inlet and a material outlet;

[0007] The separation unit comprises a precursor mixed liquid inlet, a second inert gas inlet, a solid phase material outlet and an unoxidized catalyst precursor solution outlet; the material outlet of the inert storage tank is connected to the precursor mixed liquid inlet of the separation unit;

[0008] The vacuum evaporation unit comprises an unoxidized catalyst precursor solution inlet, an unoxidized catalyst precursor outlet and a solvent outlet; the unoxidized catalyst precursor solution outlet of the separation unit is connected to the unoxidized catalyst precursor solution inlet of the vacuum evaporation unit;

[0009] The coordination catalyst preparation unit comprises an unoxidized catalyst precursor inlet and a catalyst product outlet.

[0010] Optionally, the material inlet is arranged on the side wall of the inert storage tank, and the material inlet is connected to a material inlet pipeline; and an inlet pipeline valve is arranged on the material inlet pipeline.

[0011] Optionally, the system further comprises an online control unit, wherein the online control unit comprises a signal detection device disposed on the material inlet pipeline, and is used to detect a content signal of an oxidation catalyst in the material inlet pipeline.

[0012] Optionally, the online control unit further comprises a controller, which is respectively connected to the signal detection device and the inlet pipeline valve signal, and is used to receive the content signal and control the opening and closing of the inlet pipeline valve according to the content signal.

[0013] Optionally, the system further comprises a vacuum pump, wherein the vacuum pump comprises a circulating solvent inlet and a circulating solvent outlet;

[0014] The solvent outlet of the vacuum evaporation unit is communicated with the precursor mixed liquid inlet of the separation unit through the vacuum pump.

[0015] Optionally, the precursor mixed liquid inlet of the separation unit is also connected to a first solvent inlet pipeline.

[0016] Optionally, the separation unit comprises a solvent separation tower; the type of the solvent separation tower is selected from a sieve plate tower, a packed tower or an extraction tower;

[0017] The precursor mixed liquid inlet is arranged at the upper part of the solvent separation tower; the second inert gas inlet is arranged at the lower part of the solvent separation tower; and the solid phase material outlet is arranged at the bottom of the solvent separation tower.

[0018] Optionally, the vacuum evaporation unit comprises a vacuum evaporator;

[0019] The unoxidized catalyst precursor solution inlet is arranged on the side wall of the vacuum evaporator; the solvent outlet is arranged on the top of the vacuum evaporator; and the unoxidized catalyst precursor outlet is arranged on the bottom of the vacuum evaporator.

[0020] Optionally, the coordination catalyst preparation unit comprises a coordination catalyst preparation tank;

[0021] The unoxidized catalyst precursor inlet is arranged at the upper part of the coordination catalyst preparation tank;

[0022] The coordination catalyst preparation unit further comprises a catalyst ligand and a metal compound inlet; the catalyst ligand and the metal compound inlet are arranged at the lower part of the coordination catalyst preparation tank;

[0023] The catalyst product outlet is arranged at the bottom of the coordination catalyst preparation tank.

[0024] Optionally, the system is further provided with a second solvent inlet pipeline; the second solvent inlet pipeline is connected to the unoxidized catalyst precursor inlet of the coordination catalyst preparation unit.

[0025] Through the above technical solution, the system disclosed in the present invention includes an inert storage tank, a separation unit, a vacuum evaporation unit and a coordination catalyst preparation unit. The system provided in the present invention can realize the online preparation of the target catalyst in an oxygen-free environment, and when the content of the oxidation catalyst precursor in the mixed catalyst precursor is high, the oxidation catalyst precursor can be removed online, so that the prepared target catalyst has more active components, high activity and good stability, and can improve the reaction efficiency and promote industrial production during the use of subsequent reactions.

[0026] Other features and advantages of the present disclosure will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] The accompanying drawings are used to provide a further understanding of the present disclosure and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present disclosure but do not constitute a limitation of the present disclosure. In the accompanying drawings:

[0028] Figure 1 This is a schematic diagram of a system for online preparation of a coordination catalyst according to Example 1 of the present disclosure.

[0029] Figure 2 NMR charts of the catalyst products prepared in Comparative Example 1(a) and Example 1(b) of the present disclosure.

[0030] Description of Reference Numerals

[0031] 1. Material inlet; 2. First inert gas inlet; 3. Material outlet; 4. Precursor mixed liquid inlet; 5. Second inert gas inlet; 6. Solid phase material outlet; 7. Unoxidized catalyst precursor solution outlet; 8. Unoxidized catalyst precursor solution inlet; 9. Unoxidized catalyst precursor outlet; 10. Solvent outlet; 11. Unoxidized catalyst precursor inlet; 12. Catalyst product outlet; 13. Circulating solvent inlet; 14. Circulating solvent outlet; 15. Catalyst ligand and metal compound inlet.

[0032] T1, inert storage tank; C1, solvent separation tower; F1, vacuum evaporator; P1, vacuum pump; T2, catalyst preparation tank.

[0033] S1, material inlet pipeline; S2, first solvent inlet pipeline; S3, second solvent inlet pipeline; S4, inlet pipeline valve. DETAILED DESCRIPTION

[0034] The specific implementation of the present disclosure is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described herein is only used to illustrate and explain the present disclosure, and is not used to limit the present disclosure.

[0035] like Figure 1 As shown, the first aspect of the present disclosure provides a system for preparing a coordination catalyst online, the system comprising: an inert storage tank T1, a separation unit C1, a vacuum evaporation unit F1 and a coordination catalyst preparation unit T2;

[0036] The inert storage tank T1 comprises a material inlet 1, a first inert gas inlet 2 and a material outlet 3;

[0037] The separation unit C1 includes a precursor mixed solution inlet 4, a second inert gas inlet 5, a solid phase material outlet 6 and an unoxidized catalyst precursor solution outlet 7; the material outlet 3 of the inert storage tank is connected to the precursor mixed solution inlet 4 of the separation unit C1;

[0038] The vacuum evaporation unit F1 includes an unoxidized catalyst precursor solution inlet 8, an unoxidized catalyst precursor outlet 9 and a solvent outlet 10; the unoxidized catalyst precursor solution outlet 7 of the separation unit C1 is connected to the unoxidized catalyst precursor solution inlet 8 of the vacuum evaporation unit F1;

[0039] The coordination catalyst preparation unit T2 includes an unoxidized catalyst precursor inlet 11 and a catalyst product outlet 12 .

[0040] The system provided by the present invention can realize online control to reduce the content of oxidation catalyst precursor in the catalyst precursor in an oxygen-free environment, and prepare a target catalyst with rich active ingredients, high activity and good stability, so that it can exhibit excellent performance during the use of subsequent reactions, improve reaction efficiency and promote industrial production.

[0041] In a specific implementation manner, the material inlet 1 is disposed on the side wall of the inert storage tank T1 , and the material inlet 1 is connected to a material inlet pipeline S1 ; an inlet pipeline valve S4 is disposed on the material inlet pipeline S1 .

[0042] In a specific embodiment, the system further comprises an online control unit, and the online control unit comprises a signal detection device disposed on the material inlet pipeline, for detecting a content signal of an oxidation catalyst in the material inlet pipeline S1.

[0043] In a specific embodiment, the online control unit further includes a controller, which is respectively connected to the signal detection device and the inlet pipeline valve signal, and is used to receive the content signal and control the opening and closing of the inlet pipeline valve according to the content signal.

[0044] In a specific embodiment, the system further comprises a vacuum pump P1, wherein the vacuum pump P1 comprises a circulating solvent inlet 13 and a circulating solvent outlet 14;

[0045] The solvent outlet 10 of the vacuum evaporation unit F1 is connected to the precursor mixed liquid inlet 4 of the separation unit C1 through the vacuum pump P1.

[0046] In a specific implementation manner, the precursor mixed liquid inlet 4 of the separation unit C1 is also connected to a first solvent inlet pipeline S2.

[0047] In a specific embodiment, the separation unit C1 comprises a solvent separation tower; the type of the solvent separation tower is selected from a sieve plate tower, a packed tower or an extraction tower;

[0048] The precursor mixed liquid inlet 4 is arranged at the upper part of the solvent separation tower; the second inert gas inlet 5 is arranged at the lower part of the solvent separation tower; and the solid phase material outlet 6 is arranged at the bottom of the solvent separation tower.

[0049] In a specific embodiment, the vacuum evaporation unit F1 includes a vacuum evaporator;

[0050] The unoxidized catalyst precursor solution inlet 8 is disposed on the side wall of the vacuum evaporator; the solvent outlet 10 is disposed on the top of the vacuum evaporator; and the unoxidized catalyst precursor outlet 9 is disposed on the bottom of the vacuum evaporator.

[0051] In a specific embodiment, the coordination catalyst preparation unit T2 comprises a coordination catalyst preparation tank;

[0052] The unoxidized catalyst precursor inlet 11 is disposed at the upper portion of the coordination catalyst preparation tank;

[0053] The coordination catalyst preparation unit further includes a catalyst ligand and metal compound inlet 15; the catalyst ligand and metal compound inlet 15 is arranged at the lower part of the coordination catalyst preparation tank;

[0054] The catalyst product outlet 12 is arranged at the bottom of the coordination catalyst preparation tank;

[0055] The coordination catalyst preparation tank is provided with a stirring device inside.

[0056] In a specific embodiment, the system is further provided with a second solvent inlet pipeline S3; the second solvent inlet pipeline S3 is connected to the unoxidized catalyst precursor inlet 11 of the coordination catalyst preparation unit T2.

[0057] The present disclosure provides a method for preparing a coordination catalyst using the system provided by the present disclosure, wherein the method comprises:

[0058] S1, under an inert atmosphere, mixing a precursor raw material with a first solvent to obtain a precursor mixed solution 5;

[0059] S2. Under an inert atmosphere, the precursor mixture is sent to a solvent separation tower C1 for solid-liquid separation to obtain a first precursor solution containing dissolved unoxidized catalyst precursor and an oxidized catalyst precursor;

[0060] S3, sending the first precursor solution into a vacuum evaporator F1 to separate the first solvent to obtain an unoxidized catalyst precursor;

[0061] S4, mixing the unoxidized catalyst precursor with a second solvent to obtain a second precursor solution, and contacting the second precursor solution, the catalyst ligand and the metal compound in a catalyst preparation tank T2 to obtain a target catalyst;

[0062] The precursor raw material 1 includes an oxidized catalyst precursor and an unoxidized catalyst precursor, and the mass content of the oxidized catalyst precursor in the precursor raw material is 0.1 to 99%, preferably 0.1 to 1%.

[0063] In the present disclosure, when the signal detection device on the material inlet pipeline detects that the content signal of the oxidation catalyst in the material inlet pipeline S1 is lower than a preset threshold, the material can directly enter the coordination catalyst preparation unit for reaction.

[0064] In a specific implementation manner, Figure 1 As shown, the type of the mixed catalyst precursor includes one or more of phosphorus-containing compounds, nitrides and sulfides, preferably phosphorus-containing compounds.

[0065] In a specific implementation manner, Figure 1 As shown, the first solvent and the second solvent are independently selected from one or more of methanol, ethanol, propanol, isopropanol and diethyl ether, preferably ethanol and isopropanol.

[0066] In a specific implementation manner, Figure 1 As shown, the molar ratio of the mixed catalyst precursor to the first solvent is 1:(0.5-99), preferably 1:(1-10).

[0067] In a specific implementation manner, Figure 1 As shown, the molar ratio of the unoxidized catalyst precursor to the second solvent is 1:(0.5-99), preferably 1:(1-10).

[0068] In a specific implementation manner, Figure 1 As shown, the gas type of the inert atmosphere includes one or more of nitrogen, argon and helium, preferably nitrogen; the volume content of oxygen in the inert atmosphere is less than 1%; the pressure of the inert atmosphere is 0 to 99 MpaG, preferably 0 to 1 MpaG.

[0069] In a specific implementation manner, Figure 1 As shown, the metal types in the metal compound include one or more of Ni, Mo, Co, V, Au, Ag, Rh, Ru, Pd and Pt, preferably one or more of Ni, Mo, Rh and Ru.

[0070] In a specific implementation manner, Figure 1 As shown, the type of catalyst ligand is selected from one or more of phosphorus-containing compounds, nitrides and sulfides, preferably phosphorus-containing compounds.

[0071] In a specific implementation manner, Figure 1 As shown, the method further includes: the first solvent is evaporated by a vacuum pump to obtain a circulating solvent. In the above embodiment, the first solvent can be recycled in the process flow, so that the device can achieve long-term operation, extend the service life of the equipment, reduce process costs, and improve economic benefits.

[0072] In a specific embodiment, in step S3, the temperature of the vacuum evaporator F1 is 20-120°C, preferably 25-100°C, and the vacuum degree is 1-760 mmHg, preferably 5-50 mmHg;

[0073] In step S4, the conditions for preparing the catalyst in the catalyst preparation tank T2 include: a reaction temperature of 20 to 60° C., preferably 25 to 45° C., and a reaction time of 1 to 999 min, preferably 1 to 120 min.

[0074] The present disclosure is further illustrated below by way of examples, but the present disclosure is not limited thereby.

[0075] Example 1

[0076] The system of this embodiment includes: an inert storage tank T1, a separation unit C1, a vacuum evaporation unit F1 and a coordination catalyst preparation unit T2;

[0077] The inert storage tank T1 comprises a material inlet 1, a first inert gas inlet 2 and a material outlet 3;

[0078] The separation unit C1 includes a precursor mixed solution inlet 4, a second inert gas inlet 5, a solid phase material outlet 6 and an unoxidized catalyst precursor solution outlet 7; the material outlet 3 of the inert storage tank is connected to the precursor mixed solution inlet 4 of the separation unit;

[0079] The vacuum evaporation unit F1 includes an unoxidized catalyst precursor solution inlet 8, an unoxidized catalyst precursor outlet 9 and a solvent outlet 10; the unoxidized catalyst precursor solution outlet 7 of the separation unit C1 is connected to the unoxidized catalyst precursor solution inlet 8 of the vacuum evaporation unit F1;

[0080] The coordination catalyst preparation unit T2 includes an unoxidized catalyst precursor inlet 11 and a catalyst product outlet 12 .

[0081] The method for preparing a coordination catalyst using the above system comprises the following specific steps:

[0082] a. The precursor raw material (100 kg / h) is fed into the inert storage tank T1 through the material inlet pipeline S1, mixed with ethanol (35 kg / h), and a precursor mixed liquid is obtained at the material outlet 1 of the inert storage tank T1;

[0083] b. Under an inert atmosphere, the precursor mixture in step a is sent to the solvent separation tower C1 through the precursor mixture inlet 4 for solid-liquid separation, and a first precursor solution (120 kg / h) containing dissolved unoxidized catalyst precursor is obtained from the unoxidized catalyst precursor solution outlet 7 of the solvent separation tower C1, and an oxidized catalyst precursor (about 15 kg / h) is obtained from the solid phase material outlet 6 of the solvent separation tower C1, wherein the inert atmosphere is nitrogen, the pressure is 0.8 MPaG, and the gas volume is 10 Nm 3 / h;

[0084] c. Send the first precursor solution in step b into the vacuum evaporator F1 through the unoxidized catalyst precursor solution inlet 8 to separate ethanol, and obtain the unoxidized catalyst precursor (about 85 kg / h) from the unoxidized catalyst precursor outlet 9 of the vacuum evaporator F1; send the ethanol into the vacuum pump P1 (20 mmHg) through the solvent outlet 10 for vacuum evaporation to obtain a circulating solvent;

[0085] d. Mix the unoxidized catalyst precursor in step c with methanol (21 kg / h) to obtain a second precursor solution, mix the second precursor solution, the catalyst ligand and the metal compound (the ligand is R-NH2; the metal compound is Pd-R), and send it into the coordination catalyst preparation tank T2 through the unoxidized catalyst precursor inlet 11, and obtain the catalyst product (106 kg / h) from the catalyst product outlet 12 of the coordination catalyst preparation tank T2.

[0086] Comparative Example 1

[0087] The catalyst product was prepared by adopting the method of Example 1, except that the inert gas protection in steps a and b was not performed.

[0088] Test Case

[0089] The catalyst products prepared in Example 1 and Comparative Example 1 were tested as follows:

[0090] FT-IR infrared spectra were measured using a common infrared spectrometer;

[0091] NMR detection was performed using a Bruker nuclear magnetic resonance spectrometer.

[0092] Table 1

[0093]

[0094]

[0095] According to the test results in Table 1, it can be seen that compared with the comparative example, the system provided by the present invention can realize the online preparation of catalyst products in an oxygen-free environment when preparing coordination catalysts. When the content of the oxidative catalyst precursor in the mixed catalyst precursor is high, the oxidative catalyst precursor can be removed online, so that the prepared catalyst product has a low oxide content, high active ingredients, high activity, and good stability. In the process of use in subsequent reactions, the catalytic effect is good, the reaction efficiency can be improved, and industrial production can be promoted.

[0096] The preferred embodiments of the present disclosure are described in detail above in conjunction with the accompanying drawings; however, the present disclosure is not limited to the specific details in the above embodiments. Within the technical concept of the present disclosure, a variety of simple modifications can be made to the technical solution of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0097] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0098] In addition, various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A system for preparing a coordination catalyst online, characterized in that: The system comprises: an inert storage tank (T1), a separation unit (C1), a vacuum evaporation unit (F1) and a coordination catalyst preparation unit (T2); The inert storage tank (T1) comprises a material inlet (1), a first inert gas inlet (2) and a material outlet (3); The separation unit (C1) comprises a precursor mixed liquid inlet (4), a second inert gas inlet (5), a solid phase material outlet (6) and an unoxidized catalyst precursor solution outlet (7); the material outlet (3) of the inert storage tank is connected to the precursor mixed liquid inlet (4) of the separation unit (C1); The vacuum evaporation unit (F1) comprises an unoxidized catalyst precursor solution inlet (8), an unoxidized catalyst precursor outlet (9) and a solvent outlet (10); the unoxidized catalyst precursor solution outlet (7) of the separation unit (C1) is connected to the unoxidized catalyst precursor solution inlet (8) of the vacuum evaporation unit (F1); The coordination catalyst preparation unit (T2) comprises an unoxidized catalyst precursor inlet (11) and a catalyst product outlet (12).

2. The system according to claim 1, characterized in that The material inlet (1) is arranged on the side wall of the inert storage tank (T1), and the material inlet (1) is connected to a material inlet pipeline (S1); an inlet pipeline valve (S4) is arranged on the material inlet pipeline (S1).

3. The system according to claim 2, characterized in that The system further comprises an online control unit, which comprises a signal detection device arranged on the material inlet pipeline and used for detecting a content signal of an oxidation catalyst in the material inlet pipeline (S1).

4. The system according to claim 3, characterized in that The online control unit further comprises a controller, which is respectively connected to the signal detection device and the inlet pipeline valve signal, and is used for receiving the content signal and controlling the opening and closing of the inlet pipeline valve according to the content signal.

5. The system according to claim 1, characterized in that The system further comprises a vacuum pump (P1), wherein the vacuum pump (P1) comprises a circulating solvent inlet (13) and a circulating solvent outlet (14); The solvent outlet (10) of the vacuum evaporation unit (F1) is connected to the precursor mixed liquid inlet (4) of the separation unit (C1) through the vacuum pump (P1).

6. The system according to claim 1, characterized in that The precursor mixed liquid inlet (4) of the separation unit (C1) is also connected to a first solvent inlet pipeline (S2).

7. The system according to claim 1, characterized in that The separation unit (C1) comprises a solvent separation tower; the type of the solvent separation tower is selected from a sieve plate tower, a packed tower or an extraction tower; The precursor mixed liquid inlet (4) is arranged at the upper part of the solvent separation tower; the second inert gas inlet (5) is arranged at the lower part of the solvent separation tower; and the solid phase material outlet (6) is arranged at the bottom of the solvent separation tower.

8. The system according to claim 1, characterized in that The vacuum evaporation unit (F1) comprises a vacuum evaporator; The unoxidized catalyst precursor solution inlet (8) is arranged on the side wall of the vacuum evaporator; the solvent outlet (10) is arranged on the top of the vacuum evaporator; and the unoxidized catalyst precursor outlet (9) is arranged on the bottom of the vacuum evaporator.

9. The system according to claim 1, characterized in that The coordination catalyst preparation unit (T2) comprises a coordination catalyst preparation tank; The unoxidized catalyst precursor inlet (11) is arranged at the upper part of the coordination catalyst preparation tank; The coordination catalyst preparation unit further comprises a catalyst ligand and metal compound inlet (15); the catalyst ligand and metal compound inlet (15) is arranged at the lower part of the coordination catalyst preparation tank; The catalyst product outlet (12) is arranged at the bottom of the coordination catalyst preparation tank.

10. The system according to claim 1, characterized in that The system is also provided with a second solvent inlet pipeline (S3); the second solvent inlet pipeline (S3) is connected to the unoxidized catalyst precursor inlet (11) of the coordination catalyst preparation unit (T2).

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