Preparation method of a novel heavy-duty environmental protection plasticizer material

Abstract

The present invention discloses a preparation method of a novel heavy environmental protection plasticizer material. The preparation method of the environmental protection plasticizer material is as follows: S1: The raw material oil is stored in the warehouse for inspection, the content of high-aromatic hydrocarbon oil in the raw material oil is measured, and the number of distillation times is determined according to the content of polycyclic aromatic hydrocarbons; S2: Heat treatment, the high-aromatic hydrocarbon oil inspected and stored in the warehouse is heat-treated, and the heating temperature is 85-110 °C; S3: Filtering to remove slag, the raw material oil is filtered to remove particulate impurities in the raw material oil; S4: High-temperature distillation, the high-temperature distillation is a single distillation, and the distillation is carried out using a distillation column. The distillation column is divided into three distillation stages; S5: Formulation blending, the heavy-phase solvent and the light-phase solvent obtained by high-temperature distillation in S4 are respectively subjected to formulation blending; S6: Secondary distillation, the blended heavy-phase solvent and light-phase solvent are independently subjected to secondary distillation; S7: Outgoing inspection. According to the different contents of polycyclic aromatic hydrocarbons in the raw material oil, the present invention can carry out cyclic distillation treatment to obtain high-aromatic hydrocarbon oil with a low content of polycyclic aromatic hydrocarbons.

Description

Technical Field

[0001] The present invention relates to the technical field of chemical production, and specifically to a preparation method of a new type of heavy environmental protection plasticizer material. Background Art

[0002] Aromatic oil is a commonly used plasticizer in the rubber softening process. It has excellent compatibility with general rubbers and can endow rubbers with excellent processing performance and physical and mechanical properties. It is widely used in large-scale rubber products such as tires, conveyor belts, and rubber hoses. The existing production method of aromatic oil is to heat the residue oil or vacuum residue oil in the petroleum refining process, filter out the residue, perform high-temperature distillation, conduct physical and chemical tests, formulate and blend, and store in the warehouse after passing the inspection. The produced aromatic oil has a relatively high content of polycyclic aromatic hydrocarbons, and such compounds have carcinogenicity, mutagenicity, and toxicity to the reproductive system.

[0003] After a large amount of retrieval, it is found that the prior art: the publication number is CN109627457B, which discloses a method for uniform dispersion of high-aromatic oil, belonging to the technical field of styrene-butadiene rubber production. Its characteristics are that the dispersion steps are as follows: 1) Measure and reserve high-aromatic oil and demineralized water in a mass ratio of 1:0.7 - 1.2; 2) Mix the high-aromatic oil and 35% - 50% of the total amount of demineralized water, and then blow in steam to heat up to 120°C - 180°C; 3) After the material enters the emulsifier and is stirred for 5 - 10 s, the output mixed liquid is diluted with the remaining demineralized water to reach the available dispersion degree. The present invention no longer uses emulsifiers, reduces the cost of additives, reduces energy consumption, simplifies the on-site process, and achieves the same process conditions.

[0004] To sum up, in the production process of the existing high-aromatic oil, due to the ineffective reduction of polycyclic aromatic hydrocarbons in the primary distillation, the light-phase and heavy-phase solvents after distillation treatment still contain a relatively high content of polycyclic aromatic hydrocarbons, so that the high-aromatic oil cannot be put into use. Summary of the Invention

[0005] The purpose of the present invention is to provide a preparation method of a new type of heavy environmental protection plasticizer material to solve the problems raised in the above background art.

[0006] To achieve the above purpose, the present invention provides the following technical solution: A preparation method of a new type of heavy environmental protection plasticizer material, and the preparation method of the environmental protection plasticizer material is as follows:

[0007] S1: Incoming inspection of raw material oil;

[0008] S2: Heat treatment;

[0009] S3: Filter out residue;

[0010] S4: High-temperature distillation;

[0011] S5: Formulation and blending;

[0012] S6: Secondary distillation;

[0013] S7: Outgoing inspection.

[0014] Preferably, in S1 of the preparation method based on the environmentally friendly plasticizer material: The raw material oil is high-aromatic oil. Before storage, the polycyclic aromatic hydrocarbons in the high-aromatic oil are measured, and the high-aromatic oil with a polycyclic aromatic hydrocarbon content of less than 10% is selected for treatment.

[0015] Preferably, in S1 of the preparation method based on the environmentally friendly plasticizer material:

[0016] Measure the content of high-aromatic oil in the raw material oil, and determine the number of distillations according to the polycyclic aromatic hydrocarbon content. When the polycyclic aromatic hydrocarbon content is less than 10%, perform one high-temperature distillation;

[0017] When the polycyclic aromatic hydrocarbon content is greater than 10% and less than 20%, perform secondary distillation;

[0018] When the polycyclic aromatic hydrocarbon content is greater than 20%, perform cyclic distillation according to the excess ratio, and measure the polycyclic aromatic hydrocarbon content again after cyclic distillation.

[0019] Preferably, in S2 of the preparation method based on the environmentally friendly plasticizer material: Heat the high-aromatic oil inspected and stored in the warehouse, and the heating temperature is 85 - 110 °C, which is used to improve the fluidity of the raw material oil and facilitate subsequent filtration treatment.

[0020] Preferably, in S3 of the preparation method based on the environmentally friendly plasticizer material: Filter the raw material oil to remove particulate impurities in the raw material oil. During the filtration process, keep the raw material oil at a temperature of 90 - 95 °C to accelerate the filtration efficiency of the raw material oil;

[0021] For the filtration of the raw material oil, use a silica gel filter paper with a pore size of 0.2 - 0.5 mm to separate the particulate impurities in the raw material oil.

[0022] Preferably, in S4 of the preparation method based on the environmentally friendly plasticizer material:

[0023] The high-temperature distillation is a single distillation. The distillation is carried out using a distillation column. The distillation column is divided into three distillation stages. The first stage is the top of the column, with a temperature of 210 - 235 °C; the second stage is the middle of the column, with a temperature of 185 - 200 °C; the third stage is the bottom of the column, with a temperature of 160 - 175 °C; the pressure in the column is controlled at 6 - 10 MPa.

[0024] Preferably, in S4 of the preparation method based on the environmentally friendly plasticizer material:

[0025] For the feedstock oil with the polycyclic aromatic hydrocarbon (PAH) content greater than 10% in the feedstock oil, the PAH content is measured in the light-phase solvent obtained by distillation. If the PAH content is greater than 5%, it is subjected to a secondary distillation with the heavy-phase solvent.

[0026] Preferably, in S5 of the preparation method of the environmentally friendly plasticizer material:

[0027] The heavy-phase solvent and the light-phase solvent obtained by high-temperature distillation in S4 are respectively subjected to formulation blending, and the addition ratio of the blending solvent is adjusted according to the PAH content in the heavy-phase solvent and the light-phase solvent;

[0028] The total addition ratio of the blending solvent in the heavy-phase solution is 5 - 7%; the total weight ratio of the blending solvent added in the light-phase solution is 2 - 3%.

[0029] Preferably, in S5 of the preparation method of the environmentally friendly plasticizer material:

[0030] The components of the blending solvent are: nitrobenzene 20%, dimethylformamide 30%, sulfolane 35%, furfural 10%, dimethyl sulfoxide 5%.

[0031] Preferably, in S6 of the preparation method of the environmentally friendly plasticizer material:

[0032] The blended heavy-phase solvent and light-phase solvent are independently subjected to a secondary distillation. The secondary distillation temperature of the heavy-phase solvent is controlled at 230 - 280 °C at the top of the column, 190 - 220 °C in the middle of the column, and 170 - 185 °C at the bottom of the column, and the pressure is 7.5 MPa;

[0033] The secondary distillation temperature of the light-phase solvent is controlled at 240 - 298 °C at the top of the column, 195 - 230 °C in the middle of the column, and 180 - 190 °C at the bottom of the column, and the pressure is 8.0 MPa;

[0034] The PAH content in the solvents after the secondary distillation of the heavy-phase solvent and the light-phase solvent is respectively measured, and a cyclic distillation is carried out until the PAH content in the solvent is less than 3%.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention formulates treatment processes respectively according to the PAH content in the feedstock oil, conducts multiple cyclic distillation treatments according to the PAH content, and after the distillation of the feedstock oil meeting the standards, a secondary distillation treatment is carried out according to the PAH content in the light-phase solvent and the heavy-phase solvent, thereby effectively removing the PAH content in the feedstock oil and obtaining a more environmentally friendly high-aromatic hydrocarbon oil. Detailed implementation manners

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0037] Three embodiments provided by the present invention:

[0038] Embodiment 1:

[0039] A preparation method of a new type of heavy-duty environmental protection plasticizer material. The preparation method of the environmental protection plasticizer material is as follows:

[0040] S1: Incoming inspection of raw material oil. The raw material oil is high-aromatic hydrocarbon oil. Before storage, the polycyclic aromatic hydrocarbons in the high-aromatic hydrocarbon oil are measured. High-aromatic hydrocarbon oil with a polycyclic aromatic hydrocarbon content of less than 10% is selected for treatment. The content of high-aromatic hydrocarbon oil in the raw material oil is measured, and the number of distillation times is determined according to the polycyclic aromatic hydrocarbon content. When the polycyclic aromatic hydrocarbon content is less than 10%, one high-temperature distillation is carried out;

[0041] S2: Heating treatment. The inspected and stored high-aromatic hydrocarbon oil is heated at a temperature of 85 - 110 °C to improve the fluidity of the raw material oil and facilitate subsequent filtration;

[0042] S3: Filtering to remove impurities. The raw material oil is filtered to remove particulate impurities. During the filtering process, the raw material oil is kept warm so that the temperature of the raw material oil is maintained at 90 - 95 °C to accelerate the filtering efficiency of the raw material oil;

[0043] For filtering the raw material oil, a silica gel filter paper with a pore size of 0.2 - 0.5 mm is used to separate the particulate impurities in the raw material oil;

[0044] S4: High-temperature distillation. The high-temperature distillation is a single distillation. The distillation is carried out using a distillation column. The distillation column is divided into three distillation stages. The first stage is at the top of the column, with a temperature of 210 - 235 °C; the second stage is in the middle of the column, with a temperature of 185 - 200 °C; the third stage is at the bottom of the column, with a temperature of 160 - 175 °C; the pressure inside the column is controlled at 6 - 10 MPa;

[0045] S5: Formulation blending. The heavy-phase solvent and the light-phase solvent obtained from the high-temperature distillation in S4 are respectively subjected to formulation blending, and the addition ratio of the blending solvent is adjusted according to the polycyclic aromatic hydrocarbon content in the heavy-phase solvent and the light-phase solvent;

[0046] A blending solvent with a total addition ratio of 5 - 7% is added to the heavy-phase solution; a blending solvent with a total weight ratio of 2 - 3% is added to the light-phase solution. The components of the blending solvent are: nitrobenzene 20%, dimethylformamide 30%, sulfolane 35%, furfural 10%, dimethyl sulfoxide 5%;

[0047] S6: Secondary distillation. The reconciled heavy-phase solvent and light-phase solvent are independently subjected to secondary distillation. The temperature for the secondary distillation of the heavy-phase solvent is controlled at 230 - 280 °C at the top of the column, 190 - 220 °C in the middle of the column, and 170 - 185 °C at the bottom of the column, and the pressure is 7.5 MPa.

[0048] The temperature for the secondary distillation of the light-phase solvent is controlled at 240 - 298 °C at the top of the column, 195 - 230 °C in the middle of the column, and 180 - 190 °C at the bottom of the column, and the pressure is 8.0 MPa.

[0049] Measure the content of polycyclic aromatic hydrocarbons in the solvents after the secondary distillation of the heavy-phase solvent and the light-phase solvent respectively, and conduct cyclic distillation until the content of polycyclic aromatic hydrocarbons in the solvent is less than 3%.

[0050] S7: Outgoing inspection.

[0051] Example 2:

[0052] The preparation method of the environmentally friendly plasticizer material is as follows:

[0053] S1: Incoming inspection of raw material oil. The raw material oil is high-aromatic oil. Before storage, the polycyclic aromatic hydrocarbons in the high-aromatic oil are measured. When the content of polycyclic aromatic hydrocarbons is greater than 10% and less than 20%, secondary distillation is carried out.

[0054] S2: Heating treatment. The incoming high-aromatic oil after inspection is heated at a temperature of 85 - 110 °C to improve the fluidity of the raw material oil and facilitate subsequent filtration.

[0055] S3: Filtering to remove slag. The raw material oil is filtered to remove particulate impurities in the raw material oil. During the filtering process, the raw material oil is kept warm so that the temperature of the raw material oil is maintained at 90 - 95 °C to accelerate the filtering efficiency of the raw material oil.

[0056] For the filtration of the raw material oil, a silica gel filter paper with a pore size of 0.2 - 0.5 mm is used to separate the particulate impurities in the raw material oil.

[0057] S4: High-temperature distillation. High-temperature distillation is the first distillation. The distillation is carried out using a distillation column. The distillation column is divided into three distillation stages. The first stage is at the top of the column, with a temperature of 210 - 235 °C; the second stage is in the middle of the column, with a temperature of 185 - 200 °C; the third stage is at the bottom of the column, with a temperature of 160 - 175 °C; the pressure inside the column is controlled at 6 - 10 MPa. For the raw material oil with a polycyclic aromatic hydrocarbon content greater than 10% in the raw material oil, the content of polycyclic aromatic hydrocarbons in the light-phase solvent obtained by distillation is measured until the content of polycyclic aromatic hydrocarbons is less than 5%.

[0058] S5: Formulation blending. The heavy-phase solvent and the light-phase solvent obtained from the high-temperature distillation in S4 are respectively subjected to formulation blending, and the addition ratio of the blending solvent is adjusted according to the content ratio of polycyclic aromatic hydrocarbons in the heavy-phase solvent and the light-phase solvent.

[0059] Add a blending solvent with a total addition ratio of 5-7% to the heavy-phase solution; add a blending solvent with a total weight ratio of 2-3% to the light-phase solution. The components of the blending solvent are: 20% nitrobenzene, 30% dimethylformamide, 35% sulfolane, 10% furfural, and 5% dimethyl sulfoxide.

[0060] S6: Secondary distillation. The blended heavy-phase solvent and light-phase solvent are independently subjected to secondary distillation. The secondary distillation temperature of the heavy-phase solvent is controlled at 230-280 °C at the top of the column, 190-220 °C in the middle of the column, and 170-185 °C at the bottom of the column, and the pressure is 7.5 MPa.

[0061] The secondary distillation temperature of the light-phase solvent is controlled at 240-298 °C at the top of the column, 195-230 °C in the middle of the column, and 180-190 °C at the bottom of the column, and the pressure is 8.0 MPa.

[0062] Measure the content of polycyclic aromatic hydrocarbons in the solvents obtained from the secondary distillation of the heavy-phase solvent and the light-phase solvent respectively, and perform cyclic distillation until the content of polycyclic aromatic hydrocarbons in the solvent is less than 3%.

[0063] S7: Outgoing inspection.

[0064] Example 3:

[0065] The preparation method of the environmentally friendly plasticizer material is as follows:

[0066] S1: Incoming inspection of raw material oil. The raw material oil is high-aromatic hydrocarbon oil. Before storage, the polycyclic aromatic hydrocarbons in the high-aromatic hydrocarbon oil are measured. Select raw material oil with a polycyclic aromatic hydrocarbon content greater than 20%, and perform cyclic distillation according to the excess ratio. After cyclic distillation, measure the polycyclic aromatic hydrocarbon content again.

[0067] S2: Heating treatment. The high-aromatic hydrocarbon oil inspected and stored is subjected to heating treatment at a heating temperature of 85-110 °C to improve the fluidity of the raw material oil and facilitate subsequent filtration.

[0068] S3: Filtration to remove slag. The raw material oil is filtered to remove particulate impurities in the raw material oil. During the filtration process, the raw material oil is kept warm so that the temperature of the raw material oil remains at 90-95 °C to accelerate the filtration efficiency of the raw material oil.

[0069] For the filtration of the raw material oil, silica gel filter paper with a pore size of 0.2-0.5 mm is used to separate the particulate impurities in the raw material oil.

[0070] S4: High-temperature distillation. High-temperature distillation is a primary distillation process that uses a distillation column. The distillation column is divided into three distillation stages. The first stage is at the top of the column, with a temperature of 210 - 235 °C; the second stage is in the middle of the column, with a temperature of 185 - 200 °C; the third stage is at the bottom of the column, with a temperature of 160 - 175 °C. The pressure inside the column is controlled at 6 - 10 MPa. For the feedstock oil with a polycyclic aromatic hydrocarbon (PAH) content greater than 10% in the feedstock oil, the PAH content in the light-phase solvent obtained by distillation is measured until the PAH content is less than 5%.

[0071] S5: Formulation blending. The heavy-phase solvent and the light-phase solvent obtained from the high-temperature distillation in S4 are respectively subjected to formulation blending, and the addition ratio of the blending solvent is adjusted according to the PAH content ratio in the heavy-phase solvent and the light-phase solvent.

[0072] The total amount of the blending solvent added to the heavy-phase solution is 5 - 7% by weight; the total amount of the blending solvent added to the light-phase solution is 2 - 3% by weight. The components of the blending solvent are: nitrobenzene 20%, dimethylformamide 30%, sulfolane 35%, furfural 10%, dimethyl sulfoxide 5%.

[0073] S6: Secondary distillation. The blended heavy-phase solvent and light-phase solvent are independently subjected to secondary distillation. The secondary distillation temperature of the heavy-phase solvent is controlled at 230 - 280 °C at the top of the column, 190 - 220 °C in the middle of the column, and 170 - 185 °C at the bottom of the column, with a pressure of 7.5 MPa.

[0074] The secondary distillation temperature of the light-phase solvent is controlled at 240 - 298 °C at the top of the column, 195 - 230 °C in the middle of the column, and 180 - 190 °C at the bottom of the column, with a pressure of 8.0 MPa.

[0075] The PAH content in the solvents obtained from the secondary distillation of the heavy-phase solvent and the light-phase solvent is respectively measured, and the cyclic distillation is carried out until the PAH content in the solvent is less than 3%.

[0076] S7: Product inspection.

[0077] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

Claims

1. A preparation method of a heavy-duty environmentally friendly plasticizer material, characterized in that: The preparation method of the environmentally friendly plasticizer material is as follows: S1: Incoming inspection of raw material oil; S2: Heat treatment; S3: Filtering to remove slag; S4: High-temperature distillation; S5: Formulation blending: The components of the blending solvent are: nitrobenzene 20%, dimethylformamide 30%, sulfolane 35%, furfural 10%, dimethyl sulfoxide 5%; For the heavy-phase solution and the light-phase solution obtained from the high-temperature distillation in S4, formulation blending is carried out respectively, and the addition ratio of the blending solvent is adjusted according to the polycyclic aromatic hydrocarbon content in the heavy-phase solution and the light-phase solution; The total addition ratio of the blending solvent in the heavy-phase solution is 5-7%, and the total weight ratio of the blending solvent added to the light-phase solution is 2-3%; S6: Secondary distillation: The light-phase solution and the heavy-phase solution after blending in S5 are independently subjected to secondary distillation; S7: Outgoing inspection.

2. The preparation method of a heavy-duty environmental protection plasticizer material according to claim 1, characterized in that: Based on S1 in the preparation method of the environmentally friendly plasticizer material: The raw material oil is high-aromatic hydrocarbon oil. Before storage, the polycyclic aromatic hydrocarbons in the high-aromatic hydrocarbon oil are measured, and high-aromatic hydrocarbon oil with a polycyclic aromatic hydrocarbon content of less than 10% is selected for treatment.

3. The preparation method of a heavy-duty environmental protection plasticizer material according to claim 1, characterized in that: Based on S1 in the preparation method of the environmentally friendly plasticizer material: Measure the content of high-aromatic hydrocarbon oil in the raw material oil, and determine the number of distillation times according to the polycyclic aromatic hydrocarbon content. When the polycyclic aromatic hydrocarbon content is less than 10%, one-time high-temperature distillation is carried out; When the polycyclic aromatic hydrocarbon content is greater than 10% and less than 20%, secondary distillation is carried out; When the polycyclic aromatic hydrocarbon content is greater than 20%, cyclic distillation is carried out according to the excess ratio, and the polycyclic aromatic hydrocarbon content is measured again after cyclic distillation.

4. The preparation method of a heavy-duty environmental protection plasticizer material according to claim 1, characterized in that: Based on S2 in the preparation method of the environmentally friendly plasticizer material: The high-aromatic hydrocarbon oil inspected and stored is subjected to heat treatment, and the heating temperature is 85-110°C, which is used to improve the fluidity of the raw material oil and facilitate subsequent filtration treatment.

5. The preparation method of a heavy-duty environmental protection plasticizer material according to claim 1, characterized in that: Based on S3 in the preparation method of the environmentally friendly plasticizer material: The raw material oil is filtered to remove particulate impurities in the raw material oil. During the filtration process, the raw material oil is kept warm so that the temperature of the raw material oil remains at 90-95°C, which is used to accelerate the filtration efficiency of the raw material oil; For the filtration of the raw material oil, silica gel filter paper with a pore size of 0.2-0.5 mm is used to separate the particulate impurities in the raw material oil.

6. The preparation method of a heavy-duty environmental protection plasticizer material according to claim 1, characterized in that: Based on S4 in the preparation method of the environmentally friendly plasticizer material: The high-temperature distillation is a one-time distillation. The distillation is carried out using a distillation column. The distillation column is divided into three distillation stages. The first stage is the top of the column, with a temperature of 210-235°C; the second stage is the middle of the column, with a temperature of 185-200°C; the third stage is the bottom of the column, with a temperature of 160-175°C; The pressure in the column is controlled at 6-10 MPa.

7. The preparation method of a heavy-duty environmental protection plasticizer material according to claim 1, characterized in that: Based on S4 in the preparation method of the environmentally friendly plasticizer material: For the raw material oil with a polycyclic aromatic hydrocarbon content greater than 10% in the raw material oil, the polycyclic aromatic hydrocarbon content in the light-phase solution obtained by distillation is measured. If the polycyclic aromatic hydrocarbon content is greater than 5%, it is subjected to secondary distillation with the heavy-phase solution.

8. The preparation method of a heavy-duty environmentally friendly plasticizer material according to claim 1, characterized in that: Based on S6 in the preparation method of the environmentally friendly plasticizer material: The light and heavy solutions separately blended in S5 are independently subjected to secondary distillation. The secondary distillation temperature of the heavy-phase solution is controlled at 230-280°C at the top of the column, 190-220°C in the middle of the column, and 170-185°C at the bottom of the column, and the pressure is 7.5 MPa; The secondary distillation temperature of the light-phase solution is controlled at 240 - 298 °C at the top of the column, 195 - 230 °C in the middle of the column, and 180 - 190 °C at the bottom of the column, and the pressure is 8.0 MPa; The polycyclic aromatic hydrocarbon content in the solutions of the secondary distillation of the heavy-phase solution and the light-phase solution is measured respectively, and cyclic distillation is carried out until the polycyclic aromatic hydrocarbon content in the solution is less than 3%.