Composition for polyolefin catalyst, method for improving stability of titanium trichloride and application

Abstract

The invention relates to the field of catalysts, and discloses a composition for a polyolefin catalyst, the catalyst composition comprises a passivator and titanium trichloride, the dosage weight ratio of the titanium trichloride to the passivator is 1: (1.5-4), and the passivator is one or more of 5 # white oil, 7 # white oil, 10 # white oil, 15 # white oil, 32 # white oil and 68 # white oil. Through the passivator, the problem that hydrogen chloride and smoke are generated due to spontaneous combustion and deliquescence after titanium trichloride is aerated can be solved, the danger is reduced, meanwhile, the environment can be protected, long-distance transportation is facilitated, and the titanium trichloride and the passivator form suspension liquid, so that further harmless treatment is facilitated.

Description

Technical Field

[0001] The invention relates to the field of catalysts, and in particular to a composition for polyolefin catalysts, a method for improving the stability of titanium trichloride and applications thereof. Background Art

[0002] Titanium trichloride is dark purple crystals with a relative density of 2.64. It is unstable, has a melting point of 440°C, a boiling point of 660°C, is easily soluble in ethanol and hydrochloric acid, and is insoluble in ether and benzene. It is classified as a flammable solid, a self-igniting article, and a self-igniting article when wet. It is active in nature and can react with a variety of elements or compounds as a strong reducing agent. In industry, it is often used as a titration solution for azo dye analysis, for colorimetric determination of copper, iron, vanadium, etc. It can also be used as a reducing agent for tetravalent chromium and for the preparation of Ziegler-Natta catalysts for olefin polymerization. Since titanium trichloride has strong reducing properties, it will decompose immediately when it comes into contact with water and air to generate hydrogen chloride and titanium oxides, hydroxides, and chloride oxides. The dry powder can self-ignite when flowing in the air, so it must be kept dry and sealed during use and storage.

[0003] The Material Safety Data Sheet (MSDS) of titanium trichloride states that when titanium trichloride is handled, it must be handled in nitrogen. In the polyolefin catalyst production industry, titanium trichloride is also often packaged and stored as a raw material under nitrogen protection, but nitrogen is a gas with poor encapsulation. After exposure to air, titanium trichloride will spontaneously combust, producing hydrogen chloride and smoke, which is highly dangerous and has a great impact on the environment. Once materials are spilled or scrapped, it is difficult to dispose of them. Nitrogen protection is required throughout the process, which is not conducive to long-distance transfer and transportation. How to improve the stability and safety of titanium trichloride during use, storage and transfer is a technical problem that needs to be solved in this field. Summary of the invention

[0004] The purpose of the present invention is to provide a composition for polyolefin catalyst, a method for improving the stability of titanium trichloride and application thereof.

[0005] In order to achieve the above-mentioned object, the first aspect of the present invention provides a composition for a polyolefin catalyst, wherein the components of the catalyst composition include a passivator and titanium trichloride, the weight ratio of the titanium trichloride to the passivator is 1:1.5-4, and the passivator is one or more of 5# white oil, 7# white oil, 10# white oil, 15# white oil, 32# white oil and 68# white oil.

[0006] Preferably, the weight ratio of the titanium trichloride to the passivating agent is 1:2-3.5.

[0007] Preferably, the passivating agent is 32# white oil and / or 68# white oil.

[0008] The second aspect of the present invention provides a method for improving the stability of titanium trichloride, wherein the method includes the step of mixing titanium trichloride and a passivator, wherein the weight ratio of the titanium trichloride to the passivator is 1:1.5-4, and the passivator is one or more of 5# white oil, 7# white oil, 10# white oil, 15# white oil, 32# white oil and 68# white oil.

[0009] Preferably, the weight ratio of the titanium trichloride to the passivating agent is 1:2-3.5.

[0010] Preferably, the passivating agent is 32# white oil and / or 68# white oil.

[0011] Preferably, the mixing is carried out in a reaction kettle or a material barrel.

[0012] Preferably, the mixing is carried out in a reaction vessel.

[0013] Preferably, the mixing temperature is 15-80°C.

[0014] The third aspect of the present invention provides application of the method for improving the stability of titanium trichloride according to the second aspect of the present invention in preparing a polyolefin catalyst.

[0015] The technical personnel of the present invention have found in a large number of studies that the technical solution proposed by the present invention can achieve stable treatment of titanium trichloride, which not only avoids the harsh nitrogen protection conditions required for titanium trichloride packaging and transfer, but also avoids decomposition and environmental pollution caused by exposure to air, reduces the probability of generating hydrogen chloride and smoke, and protects the environment while reducing the danger. In addition, due to the poor volatility of white oil, it is more conducive to long-distance transportation. In addition, titanium trichloride and the passivator form a suspension, and the suspension has good fluidity, which is convenient for further harmless disposal. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is a diagram showing the addition of a passivating agent to titanium trichloride in Example 1.

[0017] Figure 2 This is a diagram after adding a passivating agent to titanium trichloride in Example 1 and stirring.

[0018] Figure 3 This is the water-encountering diagram of titanium trichloride after passivation in Example 1. DETAILED DESCRIPTION

[0019] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0020] According to a first aspect of the present invention, a composition for a polyolefin catalyst is provided, wherein the components of the catalyst composition include a passivator and titanium trichloride, the weight ratio of the titanium trichloride to the passivator is 1:1.5-4, and the passivator is one or more of 5# white oil, 7# white oil, 10# white oil, 15# white oil, 32# white oil and 68# white oil.

[0021] At present, nitrogen is often used to protect titanium trichloride in the field of polyolefin catalyst production to avoid spontaneous combustion after exposure to air and dangerous accidents, but the entire transportation process needs to be protected by nitrogen, which is not conducive to long-distance transfer and transportation. The passivating agent of the present invention can achieve long-distance transfer and transportation, and can effectively reduce the reaction activity and danger of titanium trichloride after exposure to air, so that the stability of titanium trichloride is increased to facilitate further disposal.

[0022] According to the present invention, the amount of the passivator can be selected according to the amount of the titanium trichloride. In order to more effectively encapsulate the titanium trichloride, the weight ratio of the titanium trichloride to the passivator is preferably 1:2-3.5.

[0023] According to the present invention, in order to make it have low viscosity at low temperature, good fluidity, high flash point and good safety, the passivating agent is 32# white oil and / or 68# white oil.

[0024] In the present invention, by selecting a specific passivator and the weight ratio of titanium trichloride and the passivator provided by the present invention, the passivator can effectively wrap the titanium trichloride to achieve the effect of safe transportation and long-distance transportation.

[0025] According to a second aspect of the present invention, a method for improving the stability of titanium trichloride in a catalyst is provided, wherein the weight ratio of the titanium trichloride to the passivator is 1:1.5-4, and the passivator is one or more of 5# white oil, 7# white oil, 10# white oil, 15# white oil, 32# white oil and 68# white oil.

[0026] When only nitrogen protection is used, titanium trichloride cannot be completely wrapped, resulting in spontaneous combustion after exposure, generating hydrogen chloride and smoke, which is highly dangerous and has a greater impact on the environment. Once materials are spilled or scrapped, the difficulty of disposal is also relatively large, and nitrogen protection is required throughout the process, which is not conducive to long-distance transfer and transportation. The passivator of the present invention can solve the problem of titanium trichloride being unable to be completely wrapped, can effectively reduce its exposure rate, reduce the probability of generating hydrogen chloride and smoke, reduce the danger while protecting the environment, and is conducive to long-distance transportation, and titanium trichloride and the passivator form a suspension, the suspension has good fluidity, and is convenient for further harmless disposal.

[0027] According to the present invention, the amount of the passivator can be selected according to the amount of the titanium trichloride. In order to more effectively encapsulate the titanium trichloride, the weight ratio of the titanium trichloride to the passivator is 1:2-3.5.

[0028] In the present invention, when the concentration of titanium trichloride is too low, the white oil consumption is high and the economic efficiency is poor; when the concentration of titanium trichloride is too high, the suspension has poor fluidity and is inconvenient for further disposal. Therefore, in the suspension of titanium trichloride and passivating agent, the mass fraction of titanium trichloride is preferably 20-40%.

[0029] According to the present invention, in order to make it have low viscosity at low temperature, good fluidity, high flash point and good safety, the passivating agent is 32# white oil and / or 68# white oil.

[0030] According to the present invention, there is no particular limitation on the equipment used for mixing, and the mixing can be performed in a mixing equipment commonly used in the art. Preferably, the mixing is performed in a reaction kettle or a material barrel.

[0031] According to the present invention, in order to achieve a better mixing degree of titanium trichloride and the passivating agent without residual powdery materials, more preferably, the mixing is carried out in a reaction kettle.

[0032] According to the present invention, in order to ensure that the passivating agent has fluidity during the preparation process, the mixing temperature is preferably 15-80°C.

[0033] According to a third aspect of the present invention, there is provided application of the method for stabilizing titanium trichloride according to the second aspect of the present invention in preparing a polyolefin catalyst.

[0034] The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.

[0035] Example 1

[0036] Heat 60kg of 68# white oil to 50℃ in a reactor; use a 200L iron barrel to pack 40kg of titanium trichloride, add 60kg of 50℃ 68# white oil, shake and roll 10 times, and take samples to find that the mixture is uniform, the titanium trichloride is moistened by the white oil, and the air exposure property is stable, without sour smell and smoke.

[0037] Figure 1 is a diagram of adding a passivating agent to titanium trichloride in Example 1, Figure 2 This is a diagram of titanium trichloride in Example 1 after adding a passivating agent and stirring. Figure 3 This is the water diagram of titanium trichloride after passivation in Example 1. Figures 1 to 3 As shown, after adding 68# white oil, even if titanium trichloride meets water, it will not produce smoke and sour smell because it mixes with the passivating agent.

[0038] Example 2

[0039] Use a 200L iron barrel to pack 40kg of titanium trichloride, add 60kg of 15℃ 68# white oil, shake and roll 10 times, and take samples to find that the mixture is uniform, the titanium trichloride is moistened by the white oil, the air-exposure property is stable, there is no sour smell or smoke, and even if the titanium trichloride meets water, it will not produce smoke or sour smell.

[0040] Example 3

[0041] A synthesis kettle was used to pack 100 kg of titanium trichloride, add 200 kg of 68# white oil, control the kettle temperature at 45°C, control the stirring speed at 40 rpm, stir for 10 minutes, and take samples to find that the mixture was uniform, the titanium trichloride was moistened by the white oil, the air-exposure property was stable, there was no sour smell or smoke, and even if the titanium trichloride came into contact with water, no smoke or sour smell was generated.

[0042] Example 4

[0043] A synthesis kettle was used to pack 100 kg of titanium trichloride, add 200 kg of 32# white oil, control the kettle temperature at 25°C, control the stirring speed at 40 rpm, stir for 10 minutes, and take samples to find that the mixture was uniform, the titanium trichloride was moistened by the white oil, the air-exposure property was stable, there was no sour smell or smoke, and even if the titanium trichloride came into contact with water, no smoke or sour smell was generated.

[0044] Comparative Example 1

[0045] Use a 200L iron barrel to pack 40kg of titanium trichloride, add 60kg of 100# white oil at 15℃, shake and roll it 10 times. Sampling shows that the titanium trichloride and 100# white oil are not mixed evenly, and there is agglomeration of titanium trichloride powder. The inside of the agglomerate is not moistened and wrapped by 100# white oil, and there is still sour smell and smoke after exposure to air.

[0046] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A composition for a polyolefin catalyst, characterized in that: The components of the catalyst composition include a passivator and titanium trichloride, the weight ratio of the titanium trichloride to the passivator is 1:1.5-4, and the passivator is one or more of 5# white oil, 7# white oil, 10# white oil, 15# white oil, 32# white oil and 68# white oil.

2. The composition for polyolefin catalyst according to claim 1, wherein The weight ratio of the titanium trichloride to the passivating agent is 1:2-3.

5.

3. The composition for polyolefin catalyst according to claim 1, wherein The passivating agent is 32# white oil and / or 68# white oil.

4. A method for improving the stability of titanium trichloride, characterized in that: The method comprises the step of mixing titanium trichloride and a passivator, wherein the weight ratio of the titanium trichloride to the passivator is 1:1.5-4, and the passivator is one or more of 5# white oil, 7# white oil, 10# white oil, 15# white oil, 32# white oil and 68# white oil.

5. The method according to claim 4, wherein: The weight ratio of the titanium trichloride to the passivating agent is 1:2-3.

5.

6. The method according to claim 4, wherein: The passivating agent is 32# white oil and / or 68# white oil.

7. The method according to claim 4, wherein: The mixing is carried out in a reaction kettle or a material barrel.

8. The method according to claim 7, wherein: The mixing is carried out in a reaction vessel.

9. The method according to claim 4, wherein: The mixing temperature is 15-80°C.

10. Use of the method according to any one of claims 5 to 9 in preparing a polyolefin catalyst.

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