阅读说明：本技术 一种钇基油溶性高温抑钒剂及其制备方法 (Yttrium-based oil-soluble high-temperature vanadium inhibitor and preparation method thereof ) 是由 李辉 马庆功 李向阳 于 2020-06-30 设计创作，主要内容包括：本发明涉及一种钇基油溶性高温抑钒剂及其制备方法,该方法包括以下步骤：将50～90份磺酸、10～30份基础油、200～1000份溶剂、5～20份甲醇及30～50份氧化钇混合均匀,反应15min以上；将5-20份水、5-20份氨水加入步骤1)得到的产物中并通入CO<Sub>2</Sub>进行反应,在通入CO<Sub>2</Sub>20-60分钟后再次加入5-20水、5-20份氨水,继续反应30-60分钟,过滤,即可得到钇基油溶性高温抑钒剂。本发明的油溶性高温抑钒剂,以金属钇化合物为主体,具有出色的高温抑钒能力,优良的抗氧化能力,可使用在1200℃以上场合,此外,由于不含有镁化合物,从而避免了镁系抑钒剂产生胶凝及表面结皮的问题。(The invention relates to a yttrium-based oil-soluble high-temperature vanadium inhibitor and a preparation method thereof, wherein the method comprises the following steps: uniformly mixing 50-90 parts of sulfonic acid, 10-30 parts of base oil, 200-1000 parts of solvent, 5-20 parts of methanol and 30-50 parts of yttrium oxide, and reacting for more than 15 min; adding 5-20 parts of water and 5-20 parts of ammonia water into the product obtained in the step 1) and introducing CO 2 The reaction is carried out while introducing CO 2 And after 20-60 minutes, adding 5-20 parts of water and 5-20 parts of ammonia water again, continuing to react for 30-60 minutes, and filtering to obtain the yttrium-based oil-soluble high-temperature vanadium inhibitor. The oil-soluble high-temperature vanadium inhibitor takes a metal yttrium compound as a main body, has excellent high-temperature vanadium inhibiting capability and excellent oxidation resistance, can be used in the occasions with the temperature of more than 1200 ℃, and in addition, because the oil-soluble high-temperature vanadium inhibitor does not contain a magnesium compound, the problems of gelation and surface skinning of the magnesium vanadium inhibitor are avoided.)

1. The preparation method of the yttrium-based oil-soluble high-temperature vanadium inhibitor is characterized by comprising the following steps:

1) uniformly mixing 50-90 parts of sulfonic acid, 10-30 parts of base oil, 200-1000 parts of solvent, 5-20 parts of methanol and 30-50 parts of yttrium oxide, and carrying out acid-base reaction for more than 15 min;

2) adding 5-20 parts of water and 5-20 parts of ammonia water into the product obtained in the step 1) and introducing CO₂The reaction is carried out while introducing CO₂And after 20-60 minutes, adding 5-20 parts of water and 5-20 parts of ammonia water again, continuing to react for 30-60 minutes, and filtering to obtain the yttrium-based oil-soluble high-temperature vanadium inhibitor.

2. The method according to claim 1, wherein in step 1), the sulfonic acid is at least one selected from the group consisting of petroleum sulfonic acid, synthetic sulfonic acid, alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid.

3. The method according to claim 1, wherein in step 1), the base oil is a mineral oil having a kinematic viscosity of 10mm at 40 ℃²/s～200mm²/s。

4. The method of claim 1, wherein in step 1), the solvent is at least one selected from the group consisting of xylene, C9 heavy aromatics, octane, petroleum ether, kerosene, diesel oil, and gasoline.

5. The preparation method according to claim 1, wherein in the step 1), the reaction temperature is 20 to 80 ℃ and the reaction time is 10 to 60 min.

6. The method of claim 1, wherein in step 2), the CO is present₂The introduction rate of (a) is 100 to 160L/min/kg of sulfonic acid.

7. The method according to claim 1, wherein in the step 2), the reaction is a carbonation reaction, and the reaction temperature is 20 to 80 ℃.

8. The yttrium-based oil-soluble high-temperature vanadium inhibitor is characterized in that the yttrium content of the yttrium-based oil-soluble high-temperature vanadium inhibitor is 5-20 mg/kg.

9. The yttrium-based oil-soluble high-temperature vanadium inhibitor according to claim 8, wherein the yttrium content of the yttrium-based oil-soluble high-temperature vanadium inhibitor is 10 to 20 mg/kg.

10. The yttrium-based oil-soluble high-temperature vanadium inhibitor according to claim 8, wherein the yttrium-based oil-soluble high-temperature vanadium inhibitor is obtained by the method according to any one of claims 1 to 7.

Technical Field

The invention relates to the field of petroleum processing fuel additives, in particular to a yttrium-based oil-soluble high-temperature vanadium inhibitor for preventing vanadium corrosion and a preparation method thereof.

Background

In order to control the cost of raw materials and utilize low-value fractions, heavy components such as residual oil, slurry oil, asphalt and the like can be used as partial or all fuels of a gas turbine, a gasification furnace, an oil-fired boiler and an internal combustion engine. The heavy fraction can enrich various metal elements in the crude oil in the form of naphthenate, porphyrin compound and the like, such as nickel, vanadium, calcium, iron and the like, and bring adverse effects on the utilization process of oxidation combustion, particularly the negative effect of vanadium. Vanadium pentoxide with the melting point of about 670 ℃ is generated by vanadium elements with different forms under the condition of strong oxidation, the high-temperature interval of the combustion chamber and the hot channel of the utilization mode is different from 900 ℃ to 1500 ℃, and the subsequent heat flow can be cooled; vanadium pentoxide is easy to change phase under the condition of lower than 670 ℃, and is adhered to the surfaces of hot channels such as an impeller, a combustion chamber wall, a waste heat boiler, a cylinder and the like in a molten state; vanadium pentoxide is a strong acid oxide, easily causes molten salt corrosion of the equipment body, can form low-melting-point complex salt with elements such as iron, sodium, calcium and the like in the raw materials, and even erodes a nickel-containing substrate in the equipment body, thereby bringing potential safety hazards, shortening the service life of the equipment and reducing the utilization efficiency.

The vanadium corrosion under the above-mentioned occasion can be dealt with by adding vanadium inhibitor into fuel, its principle is that vanadium inhibitor and vanadic anhydride form high-melting point compound, pass the hot channel in the solid phase form, avoid the molten salt corrosion. The vanadium inhibitor is divided into water-soluble and oil-soluble agents, wherein the water-soluble agent is inconvenient to use and limited in effect due to uneven mixing, easy to absorb moisture and form a skin, needs a separate spraying facility and the like, and is gradually eliminated by the oil-soluble vanadium inhibitor. The oil-soluble vanadium inhibitor mainly comprises two types of magnesium and yttrium according to the composition: magnesium vanadate (Mg)₃V₂O₈) Has a melting point of 1124 ℃ and Yttrium Vanadate (YVO)₄) The melting point of the yttrium-based vanadium inhibitor is as high as 1800 ℃, so that the yttrium-based vanadium inhibitor can be applied at higher temperature and also adapts to the trend that the working temperature of a turbine is increased from 700-1100 ℃ to 1100-1380 ℃; the magnesium vanadium inhibitor can form 3MgO-V theoretically when the molar ratio of magnesium to vanadium is 3:2₂O₅High melting point compound, but considering that magnesium is previously combined with sodium sulfate in heavy oil and that MgO-V may be formed when magnesium is insufficient₂O₅、2MgO-V₂O₅When the risk of low-melting-point substances is equal, the magnesium-based vanadium inhibitor is generally added in an excessive amount according to the magnesium/vanadium mass ratio of 3:1 in practical application, and redundant magnesium substancesThe material can be MgO or MgSO₄The form is deposited and the scale recovery force is removed by stopping the water washing and the like.

The magnesium-based oil-soluble vanadium inhibitor can be prepared by dispersing a magnesium-containing compound into a colloid system, and metal oxide is generally refined in a wetting and grinding-aid manner and then is assisted by a surfactant to be stably dispersed in a hydrocarbon system; the prior art also provides a compound vanadium inhibitor prepared by organic magnesium salt and mixed rare earth organic matters, which takes mixed rare earth oxide as a raw material, has uncontrollable content of effective components and is possible to introduce other metal heteroatoms; the technology also proposes that the yttrium acid ester containing 4-12 carbon atoms is chelated with 2, 4-pentadiene to prepare the oil-soluble yttrium-based vanadium inhibitor, wherein the high-purity yttrium acid ester has high valence and is not easy to obtain.

Disclosure of Invention

In view of the above, the main object of the present invention is to provide an yttrium-based oil-soluble high-temperature vanadium inhibitor and a preparation method thereof, wherein the yttrium-based oil-soluble high-temperature vanadium inhibitor has the advantages of uniform system dispersion, convenient and easy addition, controllable and easily adjustable dosage.

The purpose and the technical problem of the invention are realized by adopting the following technical scheme. The preparation method of the yttrium-based oil-soluble high-temperature vanadium inhibitor provided by the invention comprises the following steps:

1) uniformly mixing 50-90 parts of sulfonic acid, 10-30 parts of base oil, 200-1000 parts of solvent, 5-20 parts of methanol and 30-50 parts of yttrium oxide, and carrying out acid-base reaction for more than 15 min;

2) adding 5-20 parts of water and 5-20 parts of ammonia water into the product obtained in the step 1) and introducing CO₂The reaction is carried out while introducing CO₂And after 20-60 minutes, adding 5-20 parts of water and 5-20 parts of ammonia water again, continuing to react for 30-60 minutes, and filtering to obtain the yttrium-based oil-soluble high-temperature vanadium inhibitor.

The purpose and the technical problem of the invention are further realized by adopting the following technical scheme.

Further, in the preparation method of the yttrium-based oil-soluble high-temperature vanadium inhibitor, in step 1), the sulfonic acid is at least one selected from petroleum sulfonic acid, synthetic sulfonic acid, alkyl benzene sulfonic acid and alkyl naphthalene sulfonic acid.

Further, in the preparation method of the yttrium-based oil-soluble high-temperature vanadium inhibitor, in the step 1), the base oil is mineral oil, and the viscosity of the mineral oil at 40 ℃ is 10mm²/s～200mm²/s。

Further, in the preparation method of the yttrium-based oil-soluble high-temperature vanadium inhibitor, in step 1), the solvent is at least one selected from xylene, C9 heavy aromatics, octane, petroleum ether, kerosene, diesel oil and gasoline.

Further, in the preparation method of the yttrium-based oil-soluble high-temperature vanadium inhibitor, in the step 1), the reaction temperature is 20-80 ℃, and the reaction time is 10-60 min.

Further, in the preparation method of the yttrium-based oil-soluble high-temperature vanadium inhibitor, wherein in the step 2), the CO₂The introduction rate of (a) is 100 to 160L/min/kg of sulfonic acid.

Further, in the preparation method of the yttrium-based oil-soluble high-temperature vanadium inhibitor, in the step 2), the reaction is a carbonation reaction, and the reaction temperature is 20-80 ℃.

The object and technical problems of the present invention can be achieved by the following technical solutions. According to the yttrium-based oil-soluble high-temperature vanadium inhibitor provided by the invention, the yttrium content of the yttrium-based oil-soluble high-temperature vanadium inhibitor is 5-20 mg/kg.

Further, in the yttrium-based oil-soluble high-temperature vanadium inhibitor, the yttrium content of the yttrium-based oil-soluble high-temperature vanadium inhibitor is 10-20 mg/kg.

Further, in the yttrium-based oil-soluble high-temperature vanadium inhibitor, the density of the yttrium-based oil-soluble high-temperature vanadium inhibitor at 20 ℃ reaches 0.9-1.0g/cm³The flash point is more than or equal to 70 ℃, and the kinematic viscosity at 100 ℃ is 62-67mm/s²Mechanical impurities<0.05％。

Further, in the yttrium-based oil-soluble high-temperature vanadium inhibitor, the yttrium-based oil-soluble high-temperature vanadium inhibitor is prepared by the method.

By the technical scheme, the invention at least has the following advantages:

the yttrium-based oil-soluble high-temperature vanadium inhibitor prepared by the invention takes the oil-soluble pure compound of metal yttrium as an effective component, can be used in the occasions that the maximum temperature of a hot channel is more than 1200 ℃ and less than 1800 ℃, and the maximum allowable temperature of the traditional magnesium-based vanadium inhibitor is less than 1100 ℃; because the oil-soluble high-temperature vanadium inhibitor does not contain magnesium compounds and is dispersed in a non-colloid manner, the problems of gelatinization and surface skinning in the storage, transportation and use processes are avoided; the yttrium-based oil-soluble high-temperature vanadium inhibitor obtained by the preparation method can accurately control the content of the effective components, is beneficial to being added according to the vanadium content in the raw materials in proportion, improves the economy and avoids the side effect of excessive addition; the yttrium-based oil-soluble high-temperature vanadium inhibitor obtained by the preparation method belongs to a complete oil-soluble formula, a molecular system is uniformly dispersed, and the side effects of non-uniform dispersion of a colloid system and inclusion of solid and organic impurities are avoided; the yttrium-based oil-soluble high-temperature vanadium inhibitor has high base number neutralization capacity, and is very effective to independent vanadium corrosion and corrosion of coexistence of sodium and sulfur, so that the trouble that the magnesium-based vanadium inhibitor is easily interfered by sodium and sulfur and is excessively added is avoided.

Detailed Description

The present invention will be described in further detail with reference to examples.

The following materials or reagents, unless otherwise specified, were all purchased.

The invention provides a preparation method of a yttrium-based oil-soluble high-temperature vanadium inhibitor, which comprises the following steps:

1) uniformly mixing 50-90 parts of sulfonic acid, 10-30 parts of base oil, 200-1000 parts of solvent, 5-20 parts of methanol and 30-50 parts of yttrium oxide, and carrying out acid-base reaction for more than 15 min;

2) adding 5-20 parts of water and 5-20 parts of ammonia water into the product obtained in the step 1) and introducing CO₂The reaction is carried out while introducing CO₂And after 20-60 minutes, adding 5-20 parts of water and 5-20 parts of ammonia water again, continuing to react for 30-60 minutes, and filtering to obtain the yttrium-based oil-soluble high-temperature vanadium inhibitor.