High-dispersed catalytic organic additive for refining coarse titanium tetrachloride and preparation method thereof

Abstract

This invention belongs to the field of refining titanium tetrachloride with organic additives, specifically relating to a method for preparing a highly dispersible catalytic organic additive for refining crude titanium tetrachloride. By mass, it comprises 450-550 parts of organic base oil; 45-110 parts of alkanes; 45-165 parts of aromatic oil; 45-220 parts of olefin oil; 10-40 parts of copper-supported graphene oxide; 20-50 parts of metal oxide; and 20-50 parts of metal chloride, prepared through a high-speed dispersion and gradient cooling process. This additive can efficiently reduce vanadium compounds in crude titanium tetrachloride. Even with a mass ratio of additive to crude titanium tetrachloride of 1:800, a vanadium content of 10 ppm can still be achieved, reducing the amount of organic matter used by more than 80% compared to existing technologies.

Description

Technical Field

[0001] This invention belongs to the field of refining titanium tetrachloride with organic additives, and specifically relates to a highly dispersed catalytic organic additive for refining crude titanium tetrachloride and its preparation method. Background Technology

[0002] High-purity titanium, with its low density, high strength, excellent corrosion resistance, and high-temperature stability, has become an indispensable key material in the aerospace field (such as engine blades and fuselage structural components). Titanium tetrachloride, as the core intermediate raw material for producing high-purity titanium, directly determines the mechanical properties and service reliability of the final titanium product. The production of aerospace-grade titanium materials requires that the purity of refined titanium tetrachloride reach above 99.95%, with vanadium impurities (mainly existing in the form of VOCl3 and VCl4) strictly controlled below 0.001%. Otherwise, it will lead to decreased toughness, shortened fatigue life, and serious engineering safety hazards.

[0003] In the refining process of crude titanium tetrachloride, the organic vanadium removal method has become the mainstream technology due to its mild reaction conditions and absence of secondary metal impurities (unlike the aluminum powder reduction method and copper wire replacement method). However, existing organic vanadium removal processes generally face the core problem of excessive addition of vanadium removal reagents: to meet the final vanadium content target, a large amount of organic vanadium removal reagents must be added to the crude titanium tetrachloride, which not only significantly increases production costs, but also causes high-boiling-point residues formed by unreacted organic matter in subsequent distillation processes, leading to distillation column blockage, shortened cleaning cycles, and seriously affecting production continuity.

[0004] Ultimately, the problem stems from the insufficient dispersibility of existing organic vanadium removal additives: traditional organic additives (such as single mineral oils and fatty acids) tend to agglomerate in liquid crude titanium tetrachloride, failing to form a uniformly dispersed system. This makes it difficult for the active carbon component in the additive to fully contact the vanadium impurities—only a few carbon components can participate in the core reaction of "vanadium ions being reduced to VCl3 precipitate," while most carbon components are not effectively utilized. Therefore, it is necessary to compensate for the insufficient reaction efficiency by "excessive addition of reagents," resulting in resource waste and cost burden.

[0005] Related studies have also confirmed this technical bottleneck: Yu Jing, Zhang Ping, Chen Tianxiang, et al., in "Research on the Process of Removing Vanadium from Crude Titanium Tetrachloride from Organic Matter" (Journal of Guizhou University of Technology: Natural Science Edition, 2008. 37 (2): 29-32), disclosed the mixing mass ratio of crude titanium tetrachloride and organic vanadium removal reagent and the corresponding vanadium content data, as shown in the table below:

[0006] Table 1. Relationship between reagent dosage and vanadium content as disclosed in the literature.

[0007]

[0008] The aforementioned literature discloses a high reagent dosage, which increases production costs. This is mainly because existing organic vanadium removal reagents fail to generate uniform, fine carbon particles, thus requiring an increase in the amount of organic vanadium removal reagent added to achieve the carbon content required for the vanadium removal reaction. Summary of the Invention

[0009] This invention aims to overcome the shortcomings of existing technologies by providing a highly dispersed catalytic organic additive for the refining of crude titanium tetrachloride. A further objective of this invention is to provide a method for preparing this highly dispersed catalytic organic additive for the refining of crude titanium tetrachloride. This method achieves high vanadium removal efficiency, requires less organic matter for vanadium removal, saves energy, exhibits good additive dispersibility, has low carbon utilization, and can meet vanadium removal requirements in a short time.

[0010] To solve the above-mentioned technical problems, the present invention is implemented as follows:

[0011] A highly dispersible catalytic organic compound auxiliary for the refining of crude titanium tetrachloride, comprising, by weight:

[0012] 450-550 parts organic base oil;

[0013] Alkanes 45–110 parts;

[0014] Aromatic oil 45-165 parts;

[0015] 45-220 parts of olefin oil;

[0016] 10–40 parts of copper-loaded graphene oxide;

[0017] 20-50 parts of metal oxides;

[0018] 20-50 parts of metal chloride

[0019] Furthermore, the organic base oil is a mixed white oil composed of No. 5 white oil and No. 7 white oil in a mass ratio of 1 to 2:1.

[0020] Furthermore, the alkane is C 13 ~C 14 The isoparaffinic hydrocarbon is present in a mass ratio of 0.5 to 1:5 with the mixed white oil; the aromatic oil is A1004 aromatic oil, and the mass ratio of the aromatic oil to the mixed white oil is 0.5 to 1.5:5; the olefin oil is poly-α-olefin oil, and the mass ratio of the olefin oil to the mixed white oil is 0.5 to 2:5.

[0021] Further, the graphene is copper-loaded graphene oxide, and its mass ratio with the mixed white oil is 1-3:45-60; the metal oxide is Cu-hafnium oxide, and its mass ratio with the mixed white oil is 0.5-1:11; the metal chloride is aluminum chloride, and its mass ratio with the mixed white oil is 0.5-1:11.

[0022] Furthermore, the mass percentage of the mixed white oil in the additives is 45-55%.

[0023] The preparation method of the above-mentioned highly dispersed catalytic organic additive for the refining of crude titanium tetrachloride includes the following steps:

[0024] (1) Mix organic base oil, copper-loaded graphene oxide, metal oxide and metal chloride, and disperse at a high speed of 6000-10000 r / min for 160-240 min;

[0025] (2) Add alkanes to the mixture obtained in step (1) and ball mill at 40-60°C until the particle size is reached. 50nm;

[0026] (3) Heat the mixture obtained in step (2) to 80-100°C, add aromatic oil, stir, and then cool in a gradient.

[0027] (4) Heat the mixture obtained in step (3) to 90°C, add olefin oil, stir, and then cool in a gradient.

[0028] (5) Add copper-loaded graphene oxide to the mixture obtained in step (4), stir at a constant temperature and then cool.

[0029] Furthermore, the gradient cooling rate in steps (3) and (4) is 5℃ / 30min, and natural cooling is performed below 80℃.

[0030] The present invention also provides a method for refining crude titanium tetrachloride, wherein the above-mentioned auxiliary agent is mixed with crude titanium tetrachloride at a mass ratio of 1:200-800, stirred in a cold state for 90-120 min, and then distilled at 130-140℃.

[0031] Furthermore, when the mass ratio of the additive to crude titanium tetrachloride is 1:800, the vanadium content after purification is... 10ppm.

[0032] The present invention also provides the application of copper-loaded graphene oxide in catalytic organic catalytic additives, wherein the copper-loaded graphene oxide is used to catalytically crack the organic components in the refining of titanium tetrachloride, and the amount added is 6 to 8% of the total mass of the additives.

[0033] The core of this invention lies in constructing a highly dispersed, nanoscale stable catalytic organic compound catalytic agent system. Relying on the ternary synergistic catalytic mechanism of copper-loaded graphene oxide, Cu-hafnium oxide, and aluminum chloride, it efficiently catalyzes the decomposition of organic compounds under mild conditions to generate uniform nano-carbon particles, thereby improving carbon utilization and vanadium reduction efficiency and achieving deep vanadium removal at low dosage. Specifically, by customizing a mixed oil-based carrier system, constructing a synergistic catalytic network, and combining high-speed dispersion and gradient cooling, uniform composite and structural stability of each component at the nanoscale are achieved, reducing the decomposition activation energy and inhibiting carbon particle agglomeration.

[0034] Compared with the prior art, the present invention has the following characteristics:

[0035] 1. In the prior art, the mass ratio of crude titanium tetrachloride to organic vanadium removal reagent needs to be 83 to 100:1 to meet the vanadium content requirements, while the mass ratio of crude titanium tetrachloride to the additive of this invention can be increased to 800:1, and the amount of reagent used is only 1 / 8 to 1 / 10 of that in the prior art, directly reducing the raw material cost by more than 88%.

[0036] 2. Under the condition of a mass ratio of 800:1, the vanadium content in refined titanium tetrachloride can be stably controlled below 0.0006%, which meets the requirements for vanadium impurities in the production of aerospace-grade high-purity titanium, and the vanadium removal effect is comparable to that of existing technologies.

[0037] 3. The additives are uniformly dispersed in crude titanium tetrachloride, with a particle size of [missing information]. With a particle size of 80nm, a dispersion uniformity of ≥98%, and no obvious agglomeration, the contact area between activated carbon particles and vanadium impurities is increased by 3 to 5 times, and the carbon utilization rate is increased from less than 50% in the existing technology to more than 90%.

[0038] 4. Due to the reduced amount of reagents used, the amount of residue generated after distillation... The cleaning cycle of the distillation column was extended from 15 days in the existing technology to more than 60 days, reducing downtime losses and improving production efficiency.

[0039] This invention C 13 ~C 14 Isoparaffins can reduce the viscosity of the additive and improve its diffusion ability in crude titanium tetrachloride; Cu-hafnium oxide inhibits carbon particle agglomeration through steric hindrance. The synergy of these two substances allows the additive to form a stable dispersion system, avoiding the reaction dead zones of "local carbon excess and local carbon absence" found in existing technologies. The copper ions in copper-loaded graphene oxide, the copper doping sites in Cu-hafnium oxide, and the Lewis acid active centers of aluminum chloride can form a "ternary catalytic system," which can lower the activation energy for the cracking of alkanes, aromatic oils, and olefin oils, enabling them to rapidly crack and generate fine carbon particles (particle size...) at 50–60℃. (50nm), the carbon generation rate is more than 3 times higher than that of existing technologies. This invention utilizes the synergistic effect of highly active carbon generated from pyrolysis, the aromatic ring coordination of aromatic oils, and the reduction of unsaturated bonds in olefin oils to reduce V in crude titanium tetrachloride. 5+ (VOCl3, VCl4) are efficiently reduced to V 3+ (VCl3 precipitation); at the same time, the active carbon provided by the copper-loaded graphene oxide itself replenishes the reaction requirements, ensuring that the vanadium removal reaction is complete, without the need to make up for insufficient carbon by adding excessive reagents.

[0040] Compared with existing data, the mass ratio of the organic additive to crude titanium tetrachloride in this invention is reduced from 1:100 to 1:800. This indicates that the organic additive of this invention can promote the dispersion of base oil in titanium tetrachloride, making it easier to be catalytically cracked. Furthermore, the carbon generated by cracking reacts with the vanadium compounds in titanium tetrachloride through catalysis and reduction, making the compounded organic vanadium removal of this invention more efficient, improving the dispersion performance of base oil, reducing the amount of vanadium-removing organic matter used, and significantly reducing the production cost of enterprises.

[0041] This invention achieves the core objectives of high vanadium removal efficiency, low organic reagent usage, and strong dispersion stability through the synergistic compounding of specific components. This meets the stringent requirements for titanium tetrachloride purity (≥99.95%) in the production of aerospace-grade high-purity titanium, while simultaneously reducing raw material costs and improving the continuity of the distillation process. The organic base oil in this invention is white oil, with alkane, aromatic, and olefin oils as additives. Copper-loaded graphene oxide, metal oxides, and metal chlorides catalyze the cracking of organic matter, and the copper-loaded graphene oxide also provides carbon for the reaction. Based on the above formulation, in the crude titanium tetrachloride refining process, a test was conducted with crude titanium tetrachloride and organic additives at a mass ratio of 800:1. Compared to ratios disclosed in existing technical literature, the same vanadium removal effect was achieved. This is because titanium tetrachloride and the added metal oxides and chlorides catalyze alkanes, alkenes, and aromatics, rapidly and fully cracking and generating carbon, preventing agglomeration. This allows for a more uniform reaction with vanadium compounds in titanium tetrachloride, enabling the vanadium compounds in refined titanium tetrachloride to quickly and efficiently reach the standard content, thereby reducing industrial costs. In the titanium tetrachloride refining process of this invention, the organic additives enable titanium tetrachloride to have a highly dispersible vanadium removal effect, thus reducing the initial addition amount of organic vanadium removal reagents and achieving the goal of reducing industrial costs. The additives of this invention can efficiently reduce vanadium compounds in crude titanium tetrachloride; even when the mass ratio of the additive to crude titanium tetrachloride is 1:800, the vanadium content can still be achieved. The concentration is 10 ppm, reducing the amount of organic matter used by more than 80% compared to existing technologies. The synergistic mechanism of highly dispersed carrier and three-way catalysis proposed in this invention fundamentally solves the problems of uneven dispersion and low carbon utilization of traditional additives, achieving an order-of-magnitude reduction in additive usage, and has significant technological breakthrough and industrial application value. Attached Figure Description

[0042] Figure 1 XRD pattern of the residue;

[0043] Figure 2 The infrared spectrum of the residue;

[0044] Figure 3 Thermogravimetric curve of the residue;

[0045] Figure 4 SEM images of alumina-coated titanium dioxide composite graphene material. Detailed Implementation

[0046] The present invention will now be described in detail through specific embodiments. These embodiments are provided to enable a more thorough understanding of the invention and to fully convey the scope of the invention to those skilled in the art. As used throughout the specification and claims, the terms "comprising" or "including" are open-ended and are interpreted as "comprising but not limited to". The following description is a preferred embodiment for carrying out the invention; however, this description is intended to illustrate the general principles of the specification and is not intended to limit the scope of the invention. The scope of protection of the invention is determined by the appended claims. Unless otherwise specified, all reagents and materials used in the present invention are commercially available.

[0047] The highly dispersed catalytic organic additives for the refining of crude titanium tetrachloride of this invention include organic base oils, alkanes, aromatic oils, olefin oils, graphene, metal oxides, and metal chlorides.

[0048] In the above-mentioned method for preparing a highly dispersed catalytic organic additive for refining crude titanium tetrachloride, the organic base oil is a mixed white oil obtained by mixing No. 5 white oil and No. 7 white oil in a ratio of 1 to 2:1, and its mass percentage in the organic additive is 45 to 55%.

[0049] In the above-mentioned method for preparing a highly dispersed catalytic organic additive for the refining of crude titanium tetrachloride, the alkane is C14-244-32 ... 13 ~C 14 Isoalkanes; the C 13 ~C 14 The mass ratio of isoparaffins to mixed white oil is 0.5 to 1:5.

[0050] In the above-mentioned method for preparing a highly dispersed catalytic organic additive for refining crude titanium tetrachloride, the aromatic oil is A1004 aromatic oil; the mass ratio of the A1004 aromatic oil to the mixed white oil is 0.5 to 1.5:5.

[0051] In the above-mentioned method for preparing a highly dispersed catalytic organic additive for refining crude titanium tetrachloride, the olefin oil is a polyalphaolefin oil; the mass ratio of the polyalphaolefin oil to the mixed white oil is 0.5 to 2:5.

[0052] In the above-mentioned method for preparing a highly dispersed catalytic organic additive for the refining of crude titanium tetrachloride, the graphene is copper-loaded graphene oxide (Cu-RGO), and its mass ratio with the mixed white oil in the compounded organic matter is 1-3:45-60.

[0053] In the above-mentioned method for preparing a highly dispersed catalytic organic additive for the refining of crude titanium tetrachloride, the metal oxide is Cu-hafnium oxide; the mass ratio of Cu-hafnium oxide to mixed white oil is 0.5 to 1:11.

[0054] In the above-mentioned method for preparing a highly dispersed catalytic organic additive for the refining of crude titanium tetrachloride, the metal chloride is aluminum chloride (AlCl3); the mass ratio of aluminum chloride to mixed white oil is 0.5 to 1:11.

[0055] Example 1

[0056] (1) Mix the mixed white oil with Cu-RGO, Cu-hafnium oxide and AlCl3 in a ratio of 46:1:1:1, place them in a sealed high-speed disperser, and stir for 160 min at a speed of 8000 r / min to obtain mixture A;

[0057] (2) Heat the mixture A obtained in step (1) at a temperature of 40°C, and mix the mixture with C. 13 ~C 14 Add C at a ratio of 49:10 for isoparaffins. 13 ~C 14 Isoparaffins were subjected to a heat-insulating circulating ball milling process to achieve a powder particle size of 50 nm, resulting in mixture B.

[0058] (3) Heat the mixture B obtained in step (2) to 80°C, add A1004 aromatic oil at a ratio of 59:14 between the mixture and A1004 aromatic oil, and stir at 100r / min for 30min; cool in a gradient above 80°C at a cooling rate of 5°C / 30min, and cool naturally to room temperature below 80°C.

[0059] (4) Heat the mixture obtained in step (3) to 90°C, add polyalphaolefin oil at a ratio of 73:20, and stir at 120 r / min for 30 min; cool in a gradient above 80°C at a cooling rate of 5°C / 30 min, and cool naturally to room temperature below 80°C.

[0060] (5) Add Cu-RGO to the mixture obtained in step (4) at a ratio of 93:7 between the mixture and Cu-RGO. After adjusting to the required carbon form ratio, stir at a constant temperature for 80 minutes and let it stand and cool to room temperature to obtain the target product, crude titanium tetrachloride refining highly dispersed catalytic organic auxiliaries.

[0061] Example 2

[0062] (1) Mix the mixed white oil with Cu-RGO, Cu-hafnium oxide and AlCl3 in a ratio of 50:1:2.5:2.5, place it in a sealed high-speed disperser, and stir for 160 min at a speed of 8000 r / min to obtain mixture A;

[0063] (2) Heat the mixture A obtained in step (1) at a temperature of 40°C, and mix the mixture with C. 13 ~C 14 Add C in a 7:1 ratio of isoparaffins 13 ~C 14 Isoparaffins were subjected to a heat-insulating circulating ball milling process to achieve a powder particle size of 50 nm, resulting in mixture B.

[0064] (3) Heat the mixture B obtained in step (2) to 80°C, add A1004 aromatic oil at a ratio of 16:3 to the mixture, and stir at 100r / min for 30min; cool in a gradient above 80°C at a cooling rate of 5°C / 30min, and cool naturally to room temperature below 80°C.

[0065] (4) Heat the mixture obtained in step (3) to 90°C, add polyalphaolefin oil at a ratio of 38:9, and stir at 120 r / min for 30 min; cool in a gradient above 80°C at a cooling rate of 5°C / 30 min, and cool naturally to room temperature below 80°C.

[0066] (5) Add Cu-RGO to the mixture obtained in step (4) at a ratio of 47:3 between the mixture and Cu-RGO. After adjusting to the required carbon form ratio, stir at a constant temperature for 80 minutes and let it stand and cool to room temperature to obtain the target product, a highly dispersed catalytic organic additive for the refining of crude titanium tetrachloride.

[0067] Example 3

[0068] (1) Mix the mixed white oil with Cu-RGO, Cu-hafnium oxide and AlCl3 in a ratio of 54:1:4:4, place them in a sealed high-speed disperser, and stir for 160 min at a speed of 8000 r / min to obtain mixture A;

[0069] (2) Heat the mixture A obtained in step (1) at a temperature of 40°C, and mix the mixture with C. 13 ~C 14 Add C in a 63:6 ratio of isoparaffins. 13 ~C 14 Isoparaffins were subjected to a heat-insulating circulating ball milling process to achieve a powder particle size of 50 nm, resulting in mixture B.

[0070] (3) Heat the mixture B obtained in step (2) to 80°C, add A1004 aromatic oil at a ratio of 69:10 between the mixture and A1004 aromatic oil, and stir at 100r / min for 30min; cool in a gradient above 80°C at a cooling rate of 5°C / 30min, and cool naturally to room temperature below 80°C.

[0071] (4) Heat the mixture obtained in step (3) to 90°C, add polyalphaolefin oil at a ratio of 79:16, and stir at 120 r / min for 30 min; cool in a gradient above 80°C at a cooling rate of 5°C / 30 min, and cool naturally to room temperature below 80°C.

[0072] (5) Add Cu-RGO to the mixture obtained in step (4) at a ratio of 19:1 between the mixture and Cu-RGO. After adjusting to the required carbon form ratio, stir at a constant temperature for 80 minutes and cool to room temperature to obtain the target product, crude titanium tetrachloride refining highly dispersed catalytic organic additive.

[0073] Comparative Example 1

[0074] (1) Mix the mixed white oil with Cu-hafnium oxide and AlCl3 in a ratio of 27:1:1, place it in a sealed high-speed disperser, and stir for 160 min at a speed of 8000 r / min to obtain mixture A;

[0075] (2) Heat the mixture A obtained in step (1) at a temperature of 40°C, and mix the mixture with C. 13 ~C 14 Add C in a ratio of 29:4 for isoparaffins. 13 ~C 14 Isoparaffins were subjected to a heat-insulating circulating ball milling process to achieve a powder particle size of 50 nm, resulting in mixture B.

[0076] (3) Heat the mixture B obtained in step (2) to 80°C, add A1004 aromatic oil at a ratio of 33:7, and stir at 100r / min for 30min; cool in a gradient above 80°C at a cooling rate of 5°C / 30min, and cool naturally to room temperature below 80°C.

[0077] (4) Heat the mixture obtained in step (3) to 90°C, add polyalphaolefin oil at a ratio of 4:1 to the mixture, and stir at 120 r / min for 30 min; cool in a gradient above 80°C at a rate of 5°C / 30 min, and cool naturally to room temperature below 80°C to obtain the target product, crude titanium tetrachloride refining highly dispersed catalytic organic additive.

[0078] Comparative Example 2

[0079] (1) Mix the mixed white oil with Cu-RGO, Cu-hafnium oxide and AlCl3 in a ratio of 50:1:1:1, place them in a sealed high-speed disperser, and stir for 160 min at a speed of 8000 r / min to obtain mixture A;

[0080] (2) Heat the mixture A obtained in step (1) at a temperature of 40°C, and mix the mixture with C. 13 ~C 14 Add C in a ratio of 53:8 for isoparaffins. 13 ~C 14 Isoparaffins were subjected to a heat-insulating circulating ball milling process to achieve a powder particle size of 50 nm, resulting in mixture B.

[0081] (3) Heat the mixture B obtained in step (2) to 80°C, add A1004 aromatic oil at a ratio of 61:12 between the mixture and A1004 aromatic oil, and stir at 100r / min for 30min; cool in a gradient above 80°C at a cooling rate of 5°C / 30min, and cool naturally to room temperature below 80°C.

[0082] (4) Heat the mixture obtained in step (3) to 90°C, add polyalphaolefin oil at a ratio of 73:16, and stir at 120 r / min for 30 min; cool in a gradient above 80°C at a cooling rate of 5°C / 30 min, and cool naturally to room temperature below 80°C.

[0083] (5) Add Cu-RGO to the mixture obtained in step (4) at a ratio of 89:11 between the mixture and Cu-RGO. After adjusting to the required carbon form ratio, stir at a constant temperature for 80 minutes and let it stand and cool to room temperature to obtain the target product, crude titanium tetrachloride refining highly dispersed catalytic organic auxiliaries.

[0084] Table 1 lists the physical properties of each component in the compounded organic compound, as follows:

[0085] Table 1. Physical properties of each component in the compounded organic compound

[0086] Appearance <![CDATA[Density (g / cm 3 ).]]> refractive index Flash point (°C) <![CDATA[Kinematic viscosity (40 °C / mm 2 / s)]]> <![CDATA[Kinematic viscosity (100 °C / mm 2 / s)]]> 5# White Oil liquid 0.8331 1.465 110 4.60 2.00 7# White Oil liquid 0.8312 1.312 100 6.90 2.28 Alkanes liquid 0.7566 1.429 80.5 1.62 - Aromatic oils liquid 0.9074 1.575 180 35.08 4.80 Olefin oil liquid 0.8000 1.450 160 5.10 1.80 graphene powder 0.9810 - - - - Hafnium oxide (Cu) powder 9.3200 - - - - <![CDATA[AlCl3]]> powder 2.4400 - - - -

[0087] Table 2 shows the organic components, physical properties, and efficacy evaluation of the compounded products. The evaluation methods in Table 2 are as follows:

[0088] Measure 200 ml of crude carbon tetrachloride, add 1 ml of the compound oil from the example, and stir under cold conditions for 90–120 min. Then, distill at 130–140 °C, collect the refined titanium sample, and perform vanadium content and colorimetric analysis. The test results show that the vanadium content is less than 1 ppm and the colorimetric content is less than 5 mg K₂Cr₂O₇ / L. -1 It was a qualified product at the time.

[0089] The evaluation results show that the amount of copper-loaded graphene oxide added significantly affects the vanadium removal effect. When the amount of copper-loaded graphene oxide added is 6-8 wt.%, the vanadium removal effect is optimal and the color is best due to the synergistic and efficient catalytic dispersion of copper-loaded graphene oxide with metal oxides and metal chlorides. When no copper-loaded graphene oxide is added, the lack of copper leads to a decrease in the catalytic cracking effect of metal oxides and metal chlorides on alkanes, resulting in a reduction in the amount of charged particles generated, affecting the coke production rate, and causing poor vanadium removal effect. When excessive copper-loaded graphene oxide is added, the large amount of graphene leads to uneven dispersion and agglomeration, reducing the catalytic contact area and resulting in poor vanadium removal effect.

[0090] Table 2. Organic components, physical properties, and efficacy evaluation of the compound.

[0091]

[0092] Crude carbon tetrachloride containing 197 ppm vanadium was mixed with organic compounds prepared in the above-mentioned optimal ratio at mass ratios of 200:1, 400:1, 600:1, and 800:1, respectively, and then cold-stirred for 90–120 min. The mixtures were then distilled at 130–140 °C, and the refined titanium samples were collected and their vanadium content determined. Next, crude titanium tetrachloride was mixed with an additive at a mass ratio of 200:1 to conduct a titanium tetrachloride purification experiment. The refined titanium samples were collected and their vanadium content determined.

[0093] The collected titanium samples were analyzed, and the experimental results are shown in Table 3.

[0094] Table 3. Vanadium content results in refined titanium during vanadium removal test.

[0095] sample 200:1 (ppm) 400:1 (ppm) 600:1 (ppm) 800:1 (ppm) Example 1 ＜1 ＜1 ＜1 10 Example 2 ＜1 ＜1 ＜1 15 Example 3 ＜1 ＜1 3 20 control sample 20 - - -

[0096] As can be seen from the examples and control samples, when achieving the same vanadium removal efficiency, the highly dispersed catalytic organic additive for crude titanium tetrachloride refining provided by the present invention can effectively reduce the initial addition amount of organic vanadium removal reagent (200:1 to 800:1), thereby achieving the goal of reducing industrial costs.

[0097] It is understood that the above specific description of the present invention is only for illustrating the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention to achieve the same technical effect; as long as the use needs are met, they are all within the protection scope of the present invention.

Claims

1. A highly dispersed catalytic organic compound auxiliary agent for the refining of crude titanium tetrachloride, characterized in that, By weight, it contains: 450-550 parts organic base oil; Alkanes 45–110 parts; Aromatic oil 45-165 parts; 45-220 parts of olefin oil; 10–40 parts of copper-loaded graphene oxide; 20-50 parts of metal oxides; 20-50 parts of metal chloride.

2. The highly dispersed catalytic organic compound auxiliary agent for the refining of crude titanium tetrachloride according to claim 1, characterized in that, The organic base oil is a blend of No. 5 white oil and No. 7 white oil in a mass ratio of 1 to 2:

1.

3. The highly dispersed catalytic organic compound auxiliary agent for the refining of crude titanium tetrachloride according to claim 2, characterized in that: The alkane is C 13 ~C 14 The isoparaffinic hydrocarbon is present in a mass ratio of 0.5 to 1:5 with the mixed white oil; the aromatic oil is A1004 aromatic oil, and the mass ratio of the aromatic oil to the mixed white oil is 0.5 to 1.5:5; the olefin oil is poly-α-olefin oil, and the mass ratio of the olefin oil to the mixed white oil is 0.5 to 2:

5.

4. The highly dispersed catalytic organic compound auxiliary agent for the refining of crude titanium tetrachloride according to claim 3, characterized in that: The graphene is copper-loaded graphene oxide, and its mass ratio with the mixed white oil is 1-3:45-60; the metal oxide is Cu-hafnium oxide, and its mass ratio with the mixed white oil is 0.5-1:11; the metal chloride is aluminum chloride, and its mass ratio with the mixed white oil is 0.5-1:

11.

5. The highly dispersed catalytic organic compound auxiliary agent for the refining of crude titanium tetrachloride according to claim 2, characterized in that: The mass percentage of the mixed white oil in the additives is 45-55%.

6. A method for preparing the highly dispersed catalytic organic auxiliary agent for the refining of crude titanium tetrachloride as described in claim 4, characterized in that, Includes the following steps: (1) Mix organic base oil, copper-loaded graphene oxide, Cu-hafnium oxide and aluminum chloride, and disperse at a high speed of 6000-10000 r / min for 160-240 min; (2) Add alkanes to the mixture obtained in step (1) and ball mill at 40-60°C until the particle size is reached. 50nm; (3) Heat the mixture obtained in step (2) to 80-100°C, add aromatic oil, stir, and then cool in a gradient. (4) Heat the mixture obtained in step (3) to 90°C, add olefin oil, stir, and then cool in a gradient. (5) Add copper-loaded graphene oxide to the mixture obtained in step (4), stir at a constant temperature and then cool.

7. The method for preparing the highly dispersed catalytic organic auxiliary agent for the refining of crude titanium tetrachloride according to claim 6, characterized in that: The gradient cooling rate in steps (3) and (4) is 5℃ / 30min, and natural cooling is performed below 80℃.

8. A method for refining crude titanium tetrachloride, characterized in that: The additives described in claims 1 to 5 are mixed with crude titanium tetrachloride at a mass ratio of 1:200 to 800, stirred in a cold state for 90 to 120 minutes, and then distilled at 130 to 140°C.

9. The method for refining crude titanium tetrachloride according to claim 8, characterized in that: When the mass ratio of the additive to crude titanium tetrachloride is 1:800, the vanadium content after purification is... 10ppm.

10. The application of copper-loaded graphene oxide in catalytic organic catalytic agents, characterized in that: The organic components used in the catalytic cracking and refining of titanium tetrachloride are added at a rate of 6-8% of the total mass of the additives.

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