阅读说明：本技术 一种超高粘度聚a-烯烃合成基础油的制备方法 (Preparation method of ultrahigh-viscosity poly-alpha-olefin synthetic base oil ) 是由 刘青才 刘中文 于 2021-08-23 设计创作，主要内容包括：本发明公开一种超高粘度聚a-烯烃合成基础油的制备方法,包括如下步骤：获取煤制费托a-烯烃100～170℃的馏份,进行含氧化合物杂质的去除处理,后在茂金属催化剂和助催化剂的条件下聚合,所得反应液经淬灭、脱除轻组份、精制后即得所述超高粘度聚a-烯烃合成基础油；其中,茂金属催化剂为Ph-(2)C(Cp-9-Flu)ZrCl-(2),助催化剂为B(C-(6)F-(5))-(3)和三异丁基铝。本发明有效利用了煤制费托a-烯烃100～170℃的馏份,成本低,其在茂金属催化剂Ph-(2)C(Cp-9-Flu)ZrCl-(2)和助催化剂B(C-(6)F-(5))-(3)、三异丁基铝的条件下聚合,制备的超高粘度聚a-烯烃合成基础油粘度大,分子量分布窄。(The invention discloses a preparation method of ultra-high viscosity poly-alpha-olefin synthetic base oil, which comprises the following steps: obtaining fractions of coal Fischer-Tropsch alpha-olefin at 100-170 ℃, removing oxygen-containing compound impurities, polymerizing under the conditions of a metallocene catalyst and a cocatalyst, quenching the obtained reaction liquid, removing light components, and refining to obtain the ultrahigh-viscosity polyal-olefin synthetic base oil; wherein the metallocene catalyst is Ph 2 C(Cp‑9‑Flu)ZrCl 2 The cocatalyst is B (C) 6 F 5 ) 3 And triisobutylaluminum. The invention effectively utilizes the fraction of the Fischer-Tropsch alpha-olefin prepared from coal at 100-170 ℃, has low cost, and has a low Ph value in the metallocene catalyst 2 C(Cp‑9‑Flu)ZrCl 2 And cocatalyst B (C) 6 F 5 ) 3 And triisobutylaluminum, and the prepared ultra-high viscosity poly-alpha-olefin synthetic base oil has high viscosity and narrow molecular weight distribution.)

1. A preparation method of ultra-high viscosity poly-a-olefin synthetic base oil is characterized by comprising the following steps:

1) obtaining a fraction of the Fischer-Tropsch alpha-olefin prepared from coal at 100-170 ℃;

2) removing oxygen-containing compound impurities from fractions of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃;

3) polymerizing a fraction of the coal Fischer-Tropsch alpha-olefin with oxygen-containing compound impurities removed at 100-170 ℃ under the conditions of a metallocene catalyst and a cocatalyst, quenching the obtained reaction liquid, removing light components, and refining to obtain the ultrahigh-viscosity polyal-olefin synthetic base oil; wherein the metallocene catalyst is Ph₂C(Cp-9-Flu)ZrCl₂The cocatalyst is B (C)₆F₅)₃And triisobutylaluminum.

2. The preparation method of the ultra-high viscosity polyalphaolefin synthetic base oil according to claim 1, wherein the operation of obtaining the fractions of the coal Fischer-Tropsch alpha-olefins at 100-170 ℃ in the step 1) is as follows: preparing coal Fischer-Tropsch light oil by a high-temperature Fischer-Tropsch method, distilling the coal Fischer-Tropsch light oil at normal pressure, removing fractions before 100 ℃, rectifying the tower bottom components again at normal pressure, and distilling out fractions before 170 ℃ to obtain the required fractions of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃, wherein the fractions are rich in C7-C9 alpha-olefin.

3. The method for preparing the ultra-high viscosity polyalphaolefin synthetic base oil according to claim 1, wherein the step 2) of removing the oxygen-containing compound impurities from the fraction of the coal Fischer-Tropsch alpha-olefins at 100 to 170 ℃ is as follows: drying the 5A molecular sieve and silica gel, taking out the dried product from the hot state in a nitrogen atmosphere, and cooling the product to room temperature according to a mass ratio of 1:1 filling the mixture into an adsorption column; adsorbing the fractions of the coal Fischer-Tropsch alpha-olefin obtained in the step 1) at 100-170 ℃ by an adsorption column, wherein the leaching amount is not more than 3 times of the silica gel filling amount.

4. The method of claim 1, wherein the Zr/ene molar ratio in the step 3) is 6 to 12 x 10^-5The molar ratio of Al to Zr is 60-150: 1, and the molar ratio of B to Zr is 1-5: 1.

5. The method of claim 4, wherein the Zr/ene molar ratio in the step 3) is 8 to 10 x 10^-5The molar ratio of Al to Zr is 70-110: 1, and the molar ratio of B to Zr is 1-3: 1.

6. The method for preparing the ultra-high viscosity polyal-olefin synthetic base oil according to claim 1, wherein the fraction of the coal Fischer-Tropsch alpha-olefin of 100 to 170 ℃ subjected to the oxygen-containing compound impurity removal treatment in the step 3) is polymerized under the conditions of the metallocene catalyst and the cocatalyst, and the polymerization operation is as follows: adding the fraction of the coal Fischer-Tropsch alpha-olefin subjected to oxygen-containing compound impurity removal treatment at 100-170 ℃ into a reactor subjected to oxygen removal and water removal, adding a part of triisobutylaluminum toluene solution, stirring and removing trace impurities and water in the fraction of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃, slowly dropwise adding the prepared catalyst into the fraction of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃ for starting reaction, and controlling the reaction temperature by adjusting the dropwise adding speed; after the end of the dropwise addition, the reaction temperature was again maintained for a certain period of time.

7. The method of claim 6, wherein triisobutane is used in the step of preparing the base oilThe concentration of the toluene solution of the aluminum base is 0.05 wt% -1 wt%, 1/4-1/3 dosage of triisobutyl aluminum is added when removing trace impurities and moisture in the fraction of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃, and the rest is added when preparing a catalyst; the catalyst configuration operation was as follows: weighing Ph₂C(Cp-9-Flu)ZrCl₂And B (C)₆F₅)₃Slowly dripping the residual toluene solution of triisobutyl aluminum, and sealing and storing the mixed solution for later use.

8. The method for preparing the ultra-high viscosity polyal-olefin synthetic base oil according to claim 6, wherein the reaction temperature is 40 to 110 ℃, the reaction time is 60 to 180min, and the reaction time comprises the time for dropping the catalyst.

9. The method for preparing the ultra-high viscosity polyal-olefin synthetic base oil according to claim 8, wherein the reaction temperature is 60 to 80 ℃, the reaction time is 90 to 150min, and the reaction time includes the time for dropping the catalyst.

10. The method for preparing the ultra-high viscosity polyal-olefin synthetic base oil according to claim 1, wherein the reaction solution obtained in the step 3) is quenched, subjected to light component removal, and refined as follows: transferring the obtained reaction liquid into a three-neck flask, dropwise adding 1-2 wt% of water based on the mass of the reaction liquid to stop reaction, then adding 1-2 wt% of clay based on the mass of a reaction product, uniformly stirring, heating the system to 220-230 ℃ in a reduced pressure state, maintaining for more than 0.5h to evaporate unreacted monomers and solvents, and filtering while hot to obtain a viscous substance, namely the ultrahigh-viscosity polyalpha-olefin synthetic base oil.

Technical Field

The invention relates to the technical field of preparation of poly-alpha-olefin synthetic base oil, in particular to a preparation method of ultra-high viscosity poly-alpha-olefin synthetic base oil.

Background

Poly a-olefin synthetic base oils are generally obtained by polymerizing a-olefins as a starting material under the action of a Lewis acid catalyst. Most of raw material alpha-olefin is prepared by ethylene oligomerization, and related reports are more. Domestic alpha-olefins are mostly dependent on importation.

In recent years, due to the development of coal-based oil, the coal-based oil prepared by the high-temperature Fischer-Tropsch process is found to contain a large amount of straight-chain alkane and straight-chain a-olefin, and is characterized in that the carbon number of the mixture is continuously distributed, and simultaneously, a small amount of isomeric hydrocarbon and oxygen-containing compounds (such as alcohol, aldehyde, acid and the like) are contained, so that the a-olefin resource can be fully utilized to prepare a product with high added value.

The reports of producing middle-low viscosity poly-a-olefin synthetic base oil by using a-olefin produced by an ethylene oligomerization method as a raw material are more, and the reports of synthesizing poly-a-olefin synthetic base oil, particularly ultra-high viscosity poly-a-olefin synthetic base oil by using metallocene as a catalyst and coal-made a-olefin as a raw material are not found.

Disclosure of Invention

The invention aims to provide a preparation method of ultra-high viscosity poly-a-olefin synthetic base oil, which aims to overcome the defects of the prior art.

The invention adopts the following technical scheme:

a preparation method of ultra-high viscosity poly-a-olefin synthetic base oil comprises the following steps:

1) obtaining a fraction of the Fischer-Tropsch alpha-olefin prepared from coal at 100-170 ℃;

2) removing oxygen-containing compound impurities from fractions of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃;

3) polymerizing a fraction of the coal Fischer-Tropsch alpha-olefin with oxygen-containing compound impurities removed at 100-170 ℃ under the conditions of a metallocene catalyst and a cocatalyst, quenching the obtained reaction liquid, removing light components, and refining to obtain the ultrahigh-viscosity polyal-olefin synthetic base oil; wherein the metallocene catalyst is Ph₂C(Cp-9-Flu)ZrCl₂The cocatalyst is B (C)₆F₅)₃And triisobutylaluminum.

Further, the operation of obtaining the fractions of the Fischer-Tropsch alpha-olefins made from coal at 100-170 ℃ in the step 1) is as follows: preparing coal Fischer-Tropsch light oil by a high-temperature Fischer-Tropsch method, distilling the coal Fischer-Tropsch light oil at normal pressure, removing fractions before 100 ℃, rectifying the tower bottom components again at normal pressure, and distilling out fractions before 170 ℃ to obtain the required fractions of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃, wherein the fractions are rich in C7-C9 alpha-olefin.

Further, the step 2) of removing oxygen-containing compound impurities from the fraction of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃ is as follows: drying the 5A molecular sieve and silica gel, taking out the dried product from the hot state in a nitrogen atmosphere, and cooling the product to room temperature according to a mass ratio of 1:1 filling the mixture into an adsorption column; adsorbing the fractions of the coal Fischer-Tropsch alpha-olefin obtained in the step 1) at 100-170 ℃ by an adsorption column, wherein the leaching amount is not more than 3 times of the silica gel filling amount.

Further, the Zr/alkene molar ratio in the step 3) is 6-12 multiplied by 10^-5The molar ratio of Al to Zr is 60-150: 1, and the molar ratio of B to Zr is 1-5: 1.

Further, the Zr/alkene molar ratio in the step 3) is 8-10 multiplied by 10^-5The molar ratio of Al to Zr is 70-110: 1, and the molar ratio of B to Zr is 1-3: 1.

Further, the polymerization operation of the fraction of the coal Fischer-Tropsch alpha-olefin subjected to the oxygen-containing compound impurity removal treatment in the step 3) at the temperature of 100-170 ℃ under the condition of the metallocene catalyst and the cocatalyst is as follows: adding the fraction of the coal Fischer-Tropsch alpha-olefin subjected to oxygen-containing compound impurity removal treatment at 100-170 ℃ into a reactor subjected to oxygen removal and water removal, adding a part of triisobutylaluminum toluene solution, stirring and removing trace impurities and water in the fraction of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃, slowly dropwise adding the prepared catalyst into the fraction of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃ for starting reaction, and controlling the reaction temperature by adjusting the dropwise adding speed; after the end of the dropwise addition, the reaction temperature was again maintained for a certain period of time.

Furthermore, the concentration of the toluene solution of triisobutylaluminum is 0.05 wt% -1 wt%, the amount of the triisobutylaluminum used in 1/4-1/3 is added when trace impurities and moisture in the fraction of coal Fischer-Tropsch alpha-olefin at 100-170 ℃ are removed, and the rest is added when a catalyst is prepared; catalyst deployment operations such asThe following: weighing Ph₂C(Cp-9-Flu)ZrCl₂And B (C)₆F₅)₃Slowly dripping the residual toluene solution of triisobutyl aluminum, and sealing and storing the mixed solution for later use.

Furthermore, the reaction temperature is 40-110 ℃, the reaction time is 60-180 min, and the reaction time comprises the time of dripping the catalyst.

Furthermore, the reaction temperature is 60-80 ℃, the reaction time is 90-150 min, and the reaction time comprises the time for dripping the catalyst.

Further, quenching the reaction liquid obtained in the step 3), removing light components, and refining the reaction liquid as follows: transferring the obtained reaction liquid into a three-neck flask, dropwise adding 1-2 wt% of water based on the mass of the reaction liquid to stop reaction, then adding 1-2 wt% of clay based on the mass of a reaction product, uniformly stirring, heating the system to 220-230 ℃ in a reduced pressure state, maintaining for more than 0.5h to evaporate unreacted monomers and solvents, and filtering while hot to obtain a viscous substance, namely the ultrahigh-viscosity polyalpha-olefin synthetic base oil.

The invention has the beneficial effects that:

1. the distillate of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃ is basically not used, and is mostly saturated and hydrogenated into naphtha. The invention effectively utilizes the fraction of the Fischer-Tropsch alpha-olefin prepared from coal at 100-170 ℃, has low cost, and has a low Ph value in the metallocene catalyst₂C(Cp-9-Flu)ZrCl₂And cocatalyst B (C)₆F₅)₃And triisobutylaluminum, and the prepared ultra-high viscosity poly-alpha-olefin synthetic base oil has high viscosity and narrow molecular weight distribution.

2. The invention selects Ph₂C(Cp-9-Flu)ZrCl₂Being a metallocene catalyst, B (C)₆F₅)₃Triisobutyl aluminum is used as a cocatalyst, the catalyst and the cocatalyst have high activity, and can quickly reach higher conversion rate at lower temperature, thereby improving the production efficiency. Metallocene catalyst Ph₂C(Cp-9-Flu)ZrCl₂High catalytic activity, controllable structure, main catalyst, triisobutyl aluminum and B (C)₆F₅)₃Is a cocatalyst, triisobutylaluminum cocatalysisThe agent is the same as alkyl aluminoxane in reaction principle, but the property is more stable than alkyl aluminoxane, the cost is low, and simultaneously the agent is used as an impurity scavenger of olefin raw materials by utilizing the characteristic of high activity; b (C)₆F₅)₃Is cheap and stable.

Detailed Description

The present invention will be further explained with reference to examples. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.

The poly-a-olefin synthetic base oils are classified by kinematic viscosity at 100 ℃ (KV100), typically 10mm²The low-viscosity poly-alpha-olefin synthetic base oil has the viscosity of 40-300 mm below s²The s is high-viscosity poly-alpha-olefin synthetic base oil and is 600mm²The base oil is synthesized by ultra-high viscosity poly alpha-olefin above s.

The following embodiment takes coal-made olefin as a raw material, which is a fraction of Fischer-Tropsch alpha-olefin made from coal at 100-170 ℃, and the preparation method specifically comprises the following steps:

1) and obtaining the fraction of the Fischer-Tropsch alpha-olefin prepared from coal at 100-170 DEG C

Preparing coal Fischer-Tropsch light oil by a high-temperature Fischer-Tropsch method, distilling the coal Fischer-Tropsch light oil at normal pressure, removing fractions before 100 ℃, rectifying the tower bottom components again at normal pressure, and distilling out fractions before 170 ℃ to obtain the required fractions of the coal Fischer-Tropsch alpha-olefin at 100-170 ℃, wherein the fractions are rich in C7-C9 alpha-olefin.

2) Removing oxygen-containing compound impurities from fractions of coal Fischer-Tropsch alpha-olefins at 100-170 DEG C

Placing the 5A molecular sieve and the silica gel in an oven to dry for more than 4 hours at 160 ℃, taking out the dried product while the product is hot, cooling the product to room temperature under the nitrogen atmosphere, and filling the product into an adsorption column according to the mass ratio of 1: 1. Adsorbing the fractions of the coal Fischer-Tropsch alpha-olefin obtained in the step 1) at 100-170 ℃ by an adsorption column, wherein the leaching amount is not more than 3 times of the silica gel filling amount.

3) And identifying the components of the fractions of the Fischer-Tropsch alpha-olefins (100-170 ℃) prepared from coal and subjected to the removal treatment of the oxygen-containing compound impurities

The fraction of the coal Fischer-Tropsch alpha olefin at 100-170 ℃ is mainly a C7/C8/C9 fraction, wherein the ratio of C7/C8/C9 olefin is about 65%, and the rest is C7/C8/C9 alkane.

The coal-to-olefin content is calculated by taking the average carbon number olefin as a mole number to calculate the catalyst amount.

The following comparative example, which uses 1-decene as the starting material, was prepared by oligomerizing ethylene using commercially available 1-decene, and also required removal of the oxygenate impurities, with a rinse amount of not more than 10 times the amount of silica gel loading, as in step 2) above.

The following comparative and example catalysts were prepared as follows: before the polymerization experiment, the metallocene catalyst Ph was weighed₂C(Cp-9-Flu)ZrCl₂And an organic boride B (C)₆F₅)₃A toluene solution of triisobutylaluminum in an amount of 0.1 wt% of 3/4 was slowly added dropwise, and the mixture was sealed and stored for further use.

Comparative example 1

Using 1-decene as raw material, Ph₂C(Cp-9-Flu)ZrCl₂Being a metallocene catalyst, B (C)₆F₅)₃And triisobutylaluminum as cocatalyst in a Zr/ene molar ratio of 9 x 10^－51, the molar ratio of Al to Zr is 100:1, the molar ratio of B to Zr is 1.5:1, the reaction temperature is 60 ℃, and the reaction time is 120min (including the catalyst dropping time).

The specific operation is as follows:

adding 1-decene into a reactor after deoxygenation and dehydration, adding 0.1 wt% of triisobutyl aluminum toluene solution in an amount of 1/4, stirring to remove trace impurities and water in the 1-decene, slowly dripping the prepared catalyst into the 1-decene to start reaction, and controlling the reaction temperature by adjusting the dripping speed. After the end of the dropwise addition, the reaction temperature was again maintained for a certain period of time. Transferring the obtained reaction solution into a three-neck flask, dropwise adding 1-2 wt% of water (based on the mass of the reaction solution) to stop the reaction, then adding 1-2 wt% of clay (based on the mass of a reaction product), uniformly stirring, heating the system to 220-230 ℃ under a reduced pressure state, maintaining for 0.5h to evaporate unreacted monomers and solvents, and filtering while hot to obtain a viscous substance, namely a polymerization product: ultra-high viscosity poly-a-olefin synthetic base oils.

The olefin conversion of the product of comparative example 1 was 78.61%, KV100 was 4530mm²(ii)/s, weight average molecular weight Mw of 62565, molecular weight distribution of 1.7714.

Example 1

The rest is the same as the comparative example 1, using coal olefin as raw material.

The olefin conversion of the product of example 1 was 88.73% and KV100 was 4095mm²(ii)/s, weight average molecular weight Mw of 58032, molecular weight distribution of 1.8175.

Comparative example 2

Zr/ene molar ratio 10 x 10^－51, the rest is the same as the comparative example 1.

The olefin conversion of the product of comparative example 2 was 93.60%, KV100 was 3684mm²(ii)/s, weight average molecular weight Mw of 52390, molecular weight distribution of 1.8508.

Example 2

The rest is the same as the comparative example 2 with coal olefin as the raw material.

The olefin conversion of the product of example 2 was 93.20%, KV100 was 3489mm²(ii)/s, weight average molecular weight Mw of 47365 and molecular weight distribution of 1.8788.

Comparative example 3

The Al/Zr molar ratio was 80:1, otherwise the same as in comparative example 2.

The olefin conversion of the product of comparative example 3 was 90.27%, KV100 was 4530mm²(ii)/s, weight average molecular weight Mw of 68104 and molecular weight distribution 1.8469.

Example 3

The rest is the same as the comparative example 3, using coal-made olefin as raw material.

Example 3 product olefin conversion 92.40% KV100 4314mm²(ii)/s, weight average molecular weight Mw of 54943, molecular weight distribution of 1.8428.

Comparative example 4

The Al/Zr molar ratio was 90:1, otherwise the same as in comparative example 2.

Comparative example 4 the product olefin conversion was 93.60%, KV100 was 3684mm²(ii)/s, weight average molecular weight Mw of 51868 and molecular weight distribution of 1.8508.

Example 4

The same as in comparative example 4 except that coal-derived olefins were used as the starting materials.

The olefin conversion of the product of example 4 was 91.67%, KV100 was 3393mm²(ii)/s, weight average molecular weight Mw of 48978 and molecular weight distribution 1.8502.

Example 5

The reaction temperature was 80 ℃ as in example 2.

The olefin conversion of the product of example 5 was 94.06%, KV100 was 2063mm²(ii)/s, weight average molecular weight Mw of 40268 and molecular weight distribution of 1.8933.