阅读说明：本技术 一种农药助剂用矿物油基础油及其制备方法 (Mineral oil base oil for pesticide adjuvant and preparation method thereof ) 是由 孙子强 高晶 慕巴沙·胡赛因 王朝红 叶凤娴 毛润乾 于 2021-08-13 设计创作，主要内容包括：本发明公开了一种农药助剂用矿物油基础油及其制备方法。以5号工业白油料经过润滑油加氢异构脱蜡装置的加氢异构脱蜡处理,得到农药助剂用矿物油基础油。本发明提供一种农药助剂用矿物油基础油的切割炼制方法,并综合矿物油理化性质指标、国家强制指标、重金属和持久性有机污染物含量等,明确了农药助剂用精炼矿物油的质量参数,包括常用理化指标、相对正构烷烃碳数与非磺化物含量、重金属含量、持久性有机污染物等。(The invention discloses mineral oil base oil for a pesticide adjuvant and a preparation method thereof. And (3) carrying out hydroisomerization dewaxing treatment on the No. 5 industrial white oil material by using a lubricating oil hydroisomerization dewaxing device to obtain the mineral oil base oil for the pesticide adjuvant. The invention provides a cutting and refining method of mineral oil base oil for a pesticide adjuvant, which integrates the physical and chemical property indexes of mineral oil, national mandatory indexes, contents of heavy metals and persistent organic pollutants and the like, and defines the quality parameters of the refined mineral oil for the pesticide adjuvant, wherein the quality parameters comprise common physical and chemical indexes, the carbon number of relative normal paraffins, the contents of non-sulfonated substances, the contents of heavy metals, persistent organic pollutants and the like.)

1. A preparation method of mineral oil base oil for a pesticide adjuvant is characterized in that a No. 5 industrial white oil material is subjected to hydroisomerization dewaxing treatment by a lubricating oil hydroisomerization dewaxing device to obtain the mineral oil base oil for the pesticide adjuvant.

2. The preparation method of claim 1, wherein the hydrogenation conditions of the hydroisomerization dewaxing treatment in the lubricant oil hydroisomerization dewaxing device are that the inlet pressure is 14.68MPa, the outlet pressure is 14.68MPa, the weighted average temperature is 210.7 ℃, the total temperature rise is 0.47 ℃, and the volume space velocity is 1.24/h; the isomerization reaction conditions are that the inlet hydrogen-oil ratio is 600, the inlet pressure is 15.09MPa, the outlet pressure is 14.77MPa, the weighted average temperature is 280.9 ℃, the total temperature rise is 43.1 ℃, and the volume space velocity is 1.06/h.

3. A mineral oil base oil for a pesticide adjuvant, which is prepared by the preparation method according to claim 1 or 2.

4. The mineral oil base oil for a pesticide adjuvant according to claim 3, characterized in that parameters of physical and chemical property indexes thereof are: the appearance is clear and transparent, the color is more than or equal to +25 (filtration), and the density is less than or equal to 840.0kg/m at 20 DEG C³Kinematic viscosity at 40 ℃ of 4.50-5.50mm²The pour point is less than or equal to minus 5 ℃, the open flash point is more than or equal to 120 ℃, and the sulfur content is less than or equal to 10 mg/kg.

5. The mineral oil base oil for a pesticide adjuvant according to claim 3, characterized in that the average carbon number of the normal paraffins is 15 to 20, the difference in carbon number range between the normal paraffins is not more than 8, and the non-sulfonated content is not less than 92.0%.

6. The mineral oil base oil for pesticide adjuvants according to claim 3, characterized in that the parameters of the heavy metal content index thereof are: hexavalent chromium is less than 1000mg/kg, cadmium is less than 100mg/kg, lead is less than 1000mg/kg, and mercury is less than 1000 mg/kg.

7. The mineral oil base oil for pesticide adjuvants according to claim 3, characterized in that the index parameters of persistent organic pollutants are: polybrominated biphenyls <1000mg/kg, polybrominated diphenyl ethers <1000 mg/kg.

The technical field is as follows:

the invention belongs to the field of mineral oil in petrochemical industry, and particularly relates to mineral oil base oil for a pesticide adjuvant and a preparation method thereof.

Background art:

and adding an emulsifier, a synergist, an antioxidant and other auxiliaries into the refined agricultural mineral oil base oil to obtain the mineral oil pesticide preparation. Safe mineral oil pesticides have extremely high requirements for base oils.

The mineral oil in China has long use history and wide use range, but enterprises specially producing agricultural mineral oil base oil are lacked. Even diesel oil, waste engine oil and the like are used as agricultural mineral oil in a period of time, and serious threat is caused to the safety of agricultural products. In 1997, the American Gadders company provides high-standard agricultural mineral oil products for China for the first time, imported 98% mineral oil missible oil is adopted as 'D-C-TRON' in China, the appearance is light yellow, and then, oil with relatively high quality such as 150SN, No. 32 hydraulic oil and No. 46 transformer oil is adopted as base oil in the insect research institute of Guangdong province (the institute of animals of the academy of sciences of Guangdong province) in China, corresponding emulsifying agents are developed, 95% engine oil emulsion is developed, the quality of the agricultural mineral oil in China is improved, but the unsaturated degree of the base oil is still high, and the quality of a preparation product cannot compete with products of foreign companies.

The domestic mineral oil pesticide management is poor, firstly, the product quality standard of the pesticide is not established according to the product composition, characteristics and the like of the mineral oil, the indexes of mineral oil content, emulsion stability, acidity, moisture and the like are established only according to the general requirements of the quality standard of missible oil, and the mineral oil content is determined by adopting a gas chromatography method and selecting a plurality of representative peaks, so that the product composition cannot be really reflected. And secondly, the requirements on indexes, distillation ranges, specific gravity, pour points and the like of residues which are not sulfonated in engine oil and diesel oil are not provided. And thirdly, some enterprises use base oil without aromatic hydrocarbon removal as a raw material, and some enterprises directly purchase oil of a gas station for preparation processing, so that the product has high aromatic hydrocarbon content, is easy to cause environmental pollution and carcinogen residue, and has pesticide effect not meeting the international standard. And fourthly, safety information is lacked, because the engine oil missible oil is registered in China early, detailed information on toxicological, environment, residue and the like is not provided according to the current registration information requirements, the later registered products are mostly registered according to the same product, and the product quality cannot reach the international standard. And fifthly, the management is not classified, the mineral oil has a plurality of types (diesel oil, engine oil and mineral oil), the composition and quality difference is large, and the management is treated equally.

The 2008 department of agriculture promulgates a 1133 bulletin, which specifies that enterprises should select refined mineral oil and not use common petrochemical products to produce mineral oil pesticides, and specifies quality indexes of mineral oil base oil in detail, specifically including 3 quality indexes such as relative normal paraffin carbon number difference, relative normal paraffin average carbon number range and non-sulfonated substance content.

In 2018, China promulgates and implements national standard GB/T35108 plus 2017, specifies a method for measuring mineral oil in mineral oil pesticide, clearly specifies a method for measuring 3 parameter indexes of carbon number difference of mineral oil relative to normal paraffin, average carbon number range of relative normal paraffin and non-sulfonated substance content, and further regulates the quality of agricultural mineral oil products.

The inventor develops agricultural mineral oil base oil (nC 22 base oil for short) with the average carbon number of 22 for pesticides in 2017, measures related quality index parameters of the agricultural mineral oil base oil and establishes an enterprise standard. The invention develops mineral oil base oil for a pesticide adjuvant, and discloses quality parameters and a preparation method thereof.

The invention content is as follows:

the invention aims to provide a quality parameter of mineral oil base oil for a pesticide adjuvant and a preparation method thereof.

The mineral oil base oil for the pesticide adjuvant is prepared by the following method:

and (3) carrying out hydroisomerization dewaxing treatment on the No. 5 industrial white oil material by using a lubricating oil hydroisomerization dewaxing device to obtain the mineral oil base oil for the pesticide adjuvant.

Preferably, the hydrogenation conditions of the hydroisomerization dewaxing treatment by the lubricating oil hydroisomerization dewaxing device are that the inlet pressure is 14.68MPa, the outlet pressure is 14.68MPa, the weighted average temperature is 210.7 ℃, the total temperature rise is 0.47 ℃, and the volume space velocity is 1.24/h; the isomerization reaction conditions are that the inlet hydrogen-oil ratio is 600, the inlet pressure is 15.09MPa, the outlet pressure is 14.77MPa, the weighted average temperature is 280.9 ℃, the total temperature rise is 43.1 ℃, and the volume space velocity is 1.06/h.

The mineral oil base oil for the pesticide adjuvant has the parameters of physical and chemical property indexes as follows: the appearance is clear and transparent, the color is more than or equal to +25 (filtration), and the density is less than or equal to 840.0kg/m at 20 DEG C³Kinematic viscosity at 40 ℃ of 4.50-5.50mm²The pour point is less than or equal to minus 5 ℃, the open flash point is more than or equal to 120 ℃, and the sulfur content is less than or equal to 10 mg/kg.

The mineral oil base oil for the pesticide adjuvant has the average carbon number of 15-20 relative to normal alkane, the carbon number range difference of less than or equal to 8 relative to normal alkane and the non-sulfonated content of more than or equal to 92.0 percent.

The mineral oil base oil for the pesticide adjuvant has the following heavy metal content indexes: hexavalent chromium (Cr (VI)) <1000mg/kg, cadmium (Cd) <100mg/kg, lead (Pb) <1000mg/kg, mercury (Hg) <1000 mg/kg.

The mineral oil base oil for the pesticide adjuvant has the following index parameters of persistent organic pollutants: polybrominated biphenyls <1000mg/kg, polybrominated diphenyl ethers <1000 mg/kg.

The invention provides a cutting and refining method of mineral oil base oil for a pesticide adjuvant, which integrates the physical and chemical property indexes of mineral oil, national mandatory indexes, contents of heavy metals and persistent organic pollutants and the like, and defines the quality parameters of the refined mineral oil for the pesticide adjuvant, wherein the quality parameters comprise common physical and chemical indexes, the carbon number of relative normal paraffins, the contents of non-sulfonated substances, the contents of heavy metals, persistent organic pollutants and the like.

The specific implementation mode is as follows:

the following examples are further illustrative of the present invention and are not intended to be limiting thereof. The protection scope of the present invention shall be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.

Example 1:

the mineral oil base oil for the pesticide adjuvant is obtained by the hydrogenation isodewaxing treatment of a lubricating oil hydrogenation isodewaxing device on the No. 5 industrial white oil, wherein the hydrogenation conditions of the lubricating oil hydrogenation isodewaxing device are that the inlet pressure is 14.68MPa, the outlet pressure is 14.68MPa, the weighted average temperature is 210.7 ℃, the total temperature rise is 0.47 ℃, and the volume airspeed is 1.24/h. The isomerization reaction conditions are that the inlet hydrogen-oil ratio is 600, the inlet pressure is 15.09MPa, the outlet pressure is 14.77MPa, the weighted average temperature is 280.9 ℃, the total temperature rise is 43.1 ℃, and the volume space velocity is 1.06/h.

Example 2:

the common physical and chemical indexes of the mineral oil base oil for the pesticide auxiliary agent comprise 7 indexes such as appearance, color, density, kinematic viscosity, flash point, pour point, sulfur content and the like. The parameters are as follows:

(1) the appearance is required to be clear and transparent;

(2) the color aspect is required to be not less than +25 (filtration);

(3) the density varies with the change of the environmental temperature, so the detection temperature is indicated when the measurement is carried out, and the measurement value is generally subject to the condition of 20 ℃. The density of various agricultural mineral oils under flag of Orchex company, Sunspray company and SK company in Korea in the United states is 846-863 kg/m³China petrochemical nC₂₂The base oil density was 828.8kg/m 3. The present invention recognizes that there may be variations in the measured value of the density, but it is required that the refined mineral oil for agricultural chemical adjuvant of the present invention has a density of not more than 840kg/m at 20 ℃³。

(4) Kinematic viscosity refers to the fluidity of oils and also reflects the relative molecular mass of the hydrocarbon molecules contained in the base oil, low viscosity oils contain hydrocarbons with low average relative molecular mass, and high viscosity oils have correspondingly high molecular mass. Within a certain range, agricultural mineral oil with high viscosity characteristics can exhibit better control effect, but too high viscosity may remain on plants for too long to affect photosynthesis. On the contrary, the insecticidal effect is poor when the viscosity is too low. The viscosity measurement is also related to the measurement temperature, and a change in temperature will result in a change in the viscosity parameter, typically based on the measurement at 40 ℃. The reference range of kinematic viscosity of the refined mineral oil for the pesticide auxiliary agent at 40 ℃ is 4.50-5.50mm²/s。

(5) The pour point and the flash point respectively represent the stability and the safety of the base oil at low temperature and high temperature, and have different requirements aiming at the agricultural mineral oil with different purposes, the pour point reference value of the refined mineral oil for the pesticide adjuvant measured in the invention is not higher than-5 ℃, and the flash point reference value is not lower than 120 ℃.

(6) The sulfur content reflects the environmental safety of mineral oil, and sulfides increase the difficulty of biodegradation in the environment, so that high-quality agricultural mineral oil requires the lower the sulfur content, the better. The reference value of the sulfur content of the refined mineral oil for the pesticide auxiliary agent measured in the invention is not higher than 10 mg/kg.

Example 3:

the mineral oil base oil for the pesticide adjuvant comprises 3 indexes of average carbon number of relative normal paraffin, carbon number range of relative normal paraffin and non-sulfonated substance content.

The average carbon number of the relative n-alkanes and the carbon number range of the relative n-alkanes indicate insecticidal effects and environmental safety. The average carbon number of the relative normal paraffin of the insecticidal mineral oil is 21-24. If used as a pesticide adjuvant, the average carbon number of the pesticide adjuvant relative to normal alkanes can be different. The average carbon number reference value of the relative normal paraffin of the refined mineral oil for the pesticide adjuvant measured in the invention is 15-20.

The relative normal paraffin carbon number range difference is not more than 8, and too large difference indicates that the mineral oil has too dispersed carbon number, and mineral oil with too high and too low molecular weight exist simultaneously and the proportion may be large. The polymer mineral oil increases the risk of phytotoxicity, and the low molecules affect the insect prevention effect, so the lower the carbon number difference of the high-quality mineral oil is, the better the carbon number difference is.

The non-acid-absorbed substances in the agricultural mineral oil are non-sulfonate substances, and the content of the non-sulfonate substances represents the safety of the mineral oil to crops. The national standard index is not less than 92%, and the reference value of the non-sulfonated substance content of the refined mineral oil for the pesticide auxiliary agent measured by the invention is not less than 92%.

Example 4:

the heavy metal content indexes of the mineral oil base oil for the pesticide adjuvant comprise 4 items of hexavalent chromium (Cr (VI)), cadmium (Cd), lead (Pb) and mercury (Hg):

the heavy metal content reflects the safety to the environment. The invention refers to the requirement of electronic industry standard, 4 indexes respectively do not exceed 1000mg/kg, 100mg/kg, 1000mg/kg and 1000 mg/kg.

Example 5:

the indexes of the persistent organic pollutants of the mineral oil base oil for the pesticide adjuvant are as follows:

polybrominated biphenyls and polybrominated diphenyl ethers have a particularly long residual period in the environment, can accumulate in biological and human adipose tissues, disturb the thyroid system of mammals in adulthood and development stages, and have chronic toxicity to reproductive systems. The invention refers to the electronic industry standard, and the evaluation index requirement is not higher than 1000 mg/kg.

Example 6:

the quality parameters and the determination method of the refined mineral oil base oil for the pesticide adjuvant are summarized.

TABLE 1 index parameters of refined mineral oil for pesticide adjuvant and determination method thereof

Example 7:

the base oil prepared by the preparation method of the present invention was sampled and examined according to example 6. The sample is sent to a research center of mineral oil pesticide engineering technology in Guangdong province for detection of common physicochemical indexes, relative normal paraffin carbon number range difference (namely, carbon number distribution of 10-90 percent of fraction), relative normal paraffin average carbon number (namely, average carbon number of 50 percent of fraction), non-sulfonated substance content, heavy metal content, persistent organic pollutants and the like. The result shows that all indexes of the mineral oil for the pesticide adjuvant accord with the relevant standards, the color of the mineral oil is more than or equal to +30 (filtration), and the density at 20 ℃ is 818.5kg/m³Kinematic viscosity at 40 ℃ of 4.73mm²(s, pour point-18 deg.C, open flash point 170 deg.C, sulfur content 0.93mg/kg, average carbon number of 17 relative to normal paraffin, difference in carbon number range of 5 relative to normal paraffin, non-sulfonated content 98.7%, hexavalent chromium (Cr (VI)) not detected<10mg/kg), no cadmium (Cd) detected (C<2mg/kg), no lead (Pb) was detected(<2mg/kg), mercury (Hg) was not detected: (Hg)<2mg/kg), no polybrominated biphenyls were detected (<0.005%), polybrominated diphenyl ether was not detected (<0.005％)。

TABLE 2 measurement results of refined mineral oil for agricultural chemical adjuvant of the present invention

Example 8:

the mineral oil base oil for the pesticide adjuvant is used as the pesticide adjuvant and is mixed with the abamectin according to the following indexes:

the mineral oil base oil for the pesticide adjuvant is 20-40% in mixing proportion by mass, and can replace the original adjuvant toluene and xylene. The mineral oil base oil for the pesticide adjuvant is mixed with the abamectin to form stable missible oil after mixing.