Method for producing treated oil and adsorbent

Abstract

The present invention provides a novel method for producing treated oil, which contributes to reducing carbon dioxide emissions, by adsorbing acidic impurities from impurity-containing oil to produce treated oil, and a novel adsorbent that adsorbs acidic impurities from impurity-containing oil. [Solution] The method for producing treated oil according to the present invention includes a step of adsorbing acidic components contained in the oil to be treated using an adsorbent, and is characterized in that the adsorbent contains synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials. The adsorbent according to the present invention is used for adsorbing and removing acidic components contained in the oil to be treated, and is synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials, and is in powder or granular form, and contains 50% by weight or more of synthetic calcium carbonate synthesized from carbon dioxide or a gas containing carbon dioxide and cement-containing waste.

Description

[Technical Field]

[0001] The present invention relates to a method for producing treated oil, including the production of lubricating oil and lubricating base oil, which includes a step of removing impurities from impurity-containing oil, and an adsorbent for adsorbing and removing impurities from impurity-containing oil. [Background technology]

[0002] Naphthenic acid contained in naphthenic crude oil is an impurity in lubricating oils, so the manufacturing process for lubricating oils and lubricating base oils incorporates a hydrorefining process and a deacidification distillation process using alkalis such as sodium hydroxide to remove naphthenic acid (see, for example, Patent Document 1).

[0003] Regarding the production of lubricating base oil, there is a production method in which, in order to obtain lubricating base oil with excellent oxidation stability and heat resistance, a heavy oil fraction obtained by distilling crude oil is refined with a solvent, and the resulting raffinate is subjected to an adsorption treatment using a silicate-based adsorbent (a silica-magnesia adsorbent) (see, for example, Patent Document 2).

[0004] The method for producing lubricating base oil described in Patent Document 2 uses a silica-magnesia adsorbent for refining, but regardless of the production of lubricating base oil, there are many cases in which adsorbents such as activated clay are used to remove impurities from oils containing impurities. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 11-241074 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-189563 Summary of the Invention [Problem to be solved by the invention]

[0006] In response to the recent rise in environmental awareness, efforts are being made to reduce carbon dioxide emissions in the manufacturing process of lubricating oils and lubricating base oils, as well as in the process of removing impurities from impurity-containing oils to produce treated oils.In order to popularize manufacturing processes that reduce carbon dioxide emissions, it is also important that these processes are economically efficient.

[0007] An object of the present invention is to provide a novel method for producing treated oil by adsorbing acidic impurities from impurity-containing oil to produce treated oil, which contributes to reducing carbon dioxide emissions, and a novel adsorbent that adsorbs acidic impurities from impurity-containing oil. [Means for solving the problem]

[0008] The present invention relates to a method for producing treated oil, which includes a step of adsorbing acidic components contained in the oil to be treated using an adsorbent, characterized in that the adsorbent contains synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials.

[0009] The method for producing treated oil according to the present invention is characterized in that the acidic component is mainly composed of naphthenic acid and / or carboxylic acid.

[0010] The method for producing a processed oil according to the present invention is characterized in that the processed oil is crude oil, and the processed oil is a lubricating oil, a lubricating base oil, or a lubricating base oil intermediate, or the processed oil is a raffinate, extract, or lubricating base oil intermediate obtained by refining a fraction obtained by distilling crude oil with a solvent, and the processed oil is a lubricating oil or a lubricating base oil, or the processed oil is a lubricating base oil and the processed oil is a lubricating oil.

[0011] The method for producing treated oil according to the present invention is characterized in that the oil to be treated is used lubricating oil, and the treated oil is recycled lubricating oil.

[0012] The present invention relates to an adsorbent used for adsorbing and removing acidic components contained in oil to be treated, which is synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials, and is characterized in that the adsorbent is in powder or granular form and contains 50% by weight or more of synthetic calcium carbonate synthesized from carbon dioxide or a gas containing carbon dioxide and cement-containing waste. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a novel method for producing treated oil by adsorbing acidic impurities from impurity-containing oil, which contributes to reducing carbon dioxide emissions, and a novel adsorbent that adsorbs acidic impurities from impurity-containing oil. [Brief explanation of the drawings]

[0014] [Figure 1] 10 shows experimental results of Example 2 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] The method for producing treated oil of the present invention includes a step of adsorbing acidic components contained in the oil to be treated using an adsorbent, and is characterized in that the adsorbent contains synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials.

[0016] In the method for producing treated oil of the present invention, the treated oil is an oil containing acidic components. Examples of the treated oil include crude oils such as naphthenic-based crude oil and paraffin-based crude oil, which contain naphthenic acid, an acidic component, and lubricating oil base oil intermediates and lubricating oil base oils, such as raffinates and extracts obtained from naphthenic-based crude oil and paraffin-based crude oil through distillation, solvent refining, etc. Raffinates are components that are not solvent-extracted in solvent refining, while extracts are components that are solvent-extracted in solvent refining. Other examples of oils containing acidic components include used lubricating oils. Used lubricating oils also contain acidic components.

[0017] However, in the method for producing treated oil of the present invention, the treated oil is not limited to the above-mentioned crude oil, lubricating oil base oil intermediate, lubricating oil base oil, used lubricating oil, etc., but can be widely applied to oils containing acidic components.

[0018] The acidic components contained in the treated oil are not particularly limited. In the method for producing treated oil of the present invention, the adsorption treatment of acidic components using an adsorbent is evaluated using the acid value. The acid value is defined in JIS K2501:2003 Petroleum products and lubricants - Neutralization number test method as "the number of milligrams (mg) of potassium hydroxide required to neutralize the acidic components contained in 1 g of sample."

[0019] According to JIS K2501:2003 Petroleum products and lubricants - Neutralization number test method, acidic components are defined as "organic acids, inorganic acids, esters, phenolic compounds, lactone acids, resins, heavy metal salts, salts of ammonia and other salts of weakly basic components, salts of polybasic acids, and additives such as antioxidants and detergents."

[0020] As described above, there are various acidic components that are evaluated by acid value. In the method for producing treated oil of the present invention, when the treated oil is the above-mentioned crude oil, lubricant base oil intermediate, lubricant base oil, or used lubricant oil, the acidic components contained in the treated oil are acidic components whose main components are naphthenic acid and / or carboxylic acid, or acidic components containing additives, depending on the properties or origin of the treated oil.

[0021] In the method for producing treated oil of the present invention, the adsorbent for adsorbing acidic components contained in the oil to be treated is a powdered or granular adsorbent containing synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials. As described in the examples below, this adsorbent has excellent adsorption performance for acidic components contained in the oil to be treated and can be used for various oils. Hereinafter, an adsorbent containing synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials may be referred to as a synthetic calcium carbonate adsorbent.

[0022] A synthetic calcium carbonate adsorbent is typically obtained by diluting concrete sludge, such as ready-mixed concrete or concrete sludge washed from a concrete mixer truck, with water, removing the solids by solid-liquid separation, blowing exhaust gas containing carbon dioxide into the dilution, immobilizing the carbon dioxide as calcium carbonate, and then separating the solids from the liquid. The recovered solids are dried and then crushed to a predetermined particle size.

[0023] The manufacturing method for the synthetic calcium carbonate adsorbent is essentially the same as the method of reacting carbon dioxide with cement-containing waste to immobilize the carbon dioxide (https: / / www.ncic.co.jp>uploads>2021 / 03.pdf, JP 2024-130324 A). According to JP 2024-130324 A, the raw material for the cement-containing waste can include concrete sludge, residual concrete, returned concrete, coal ash, carbide slag, and other materials.

[0024] The carbon dioxide used in the production of the synthetic calcium carbonate adsorbent is generally exhaust gas containing carbon dioxide, such as combustion exhaust gas or boiler exhaust gas, but carbon dioxide separated and recovered from exhaust gas containing carbon dioxide may also be used.

[0025] In the method for producing treated oil of the present invention, the particle size of the powdered or granular synthetic calcium carbonate adsorbent used is preferably small from the viewpoint of contact efficiency between the treated oil and the synthetic calcium carbonate adsorbent. On the other hand, a granular form is preferred from the viewpoint of solid-liquid separation between the treated oil and the synthetic calcium carbonate adsorbent after adsorption treatment. The powdered or granular form may be appropriately selected depending on the properties of the treated oil, such as viscosity, and the operating conditions, such as the operating temperature.

[0026] From the viewpoint of application to existing manufacturing processes that include a step of adsorbing impurities in the oil to be treated, it is preferable that the powdered synthetic calcium carbonate adsorbent has an average particle size of 5 μm to 20 μm, and that the granular synthetic calcium carbonate adsorbent has an average particle size of 100 μm to 300 μm, as measured by laser diffraction. This average particle size is similar to that of activated clay and silica-magnesia adsorbents used to remove impurities from oil, making it easy to apply to existing manufacturing processes that include a step of adsorbing impurities in the oil to be treated.

[0027] Representative physical property values ​​of a synthetic calcium carbonate adsorbent are shown below. A synthetic calcium carbonate adsorbent having the physical property values ​​shown here has excellent adsorption performance for acidic components contained in the oil to be treated, as will be described in the Examples below. However, the physical property values ​​of the synthetic calcium carbonate adsorbent are not limited to these. CaCO3 content: 50% by weight or more Specific surface area: 47~60m 2 / g (Nitrogen adsorption-BET multi-point method) Average pore diameter: 7.5 to 12 nm (calculated value)

[0028] As the synthetic calcium carbonate adsorbent, commercially available synthetic calcium carbonate synthesized by reacting carbon dioxide-containing gas with concrete sludge can also be used. For example, Calcarbo (registered trademark) from Idemitsu Kosan Co., Ltd. is a powdered product containing synthetic calcium carbonate synthesized by reacting carbon dioxide-containing gas with concrete sludge, which contains 50% calcium carbonate (by weight) and has a carbon dioxide fixation amount of 0.07 g / g.

[0029] Synthetic calcium carbonate or powder containing synthetic calcium carbonate, including Calcarbo (registered trademark), which is synthesized using carbon dioxide-containing gas and concrete sludge as raw materials, has been used as a concrete admixture (filler), a raw material for mortar, concrete products, asphalt mixture filler, chemical product filler, and a purifying agent for water purification, but it has not been known to be used as an adsorbent that adsorbs acidic components from acidic component-containing oils.

[0030] The method for producing treated oil of the present invention can be said to provide a new use for synthetic calcium carbonate or powder containing synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials.

[0031] The method for adsorbing acidic components contained in the oil to be treated using a synthetic calcium carbonate adsorbent is not particularly limited, and any known method can be used. Specifically, the synthetic calcium carbonate adsorbent is added to the oil to be treated, and the mixture is stirred and mixed while heating as necessary, to allow the acidic components to be adsorbed by the synthetic calcium carbonate adsorbent.

[0032] The operating conditions for the adsorption treatment may be determined appropriately depending on the properties of the oil to be treated, such as the viscosity of the oil, the content of acidic components, etc. Judging from the examples described below, if the amount of synthetic calcium carbonate adsorbent added to the oil to be treated is 1 to 5 wt %, the heating temperature is 25 to 60°C, and the stirring intensity is medium, the acidic components contained in the oil to be treated can be adsorbed in about 1 to 3 hours, and the acid value can be reduced by up to about 0.5 mgKOH / g.

[0033] After the acidic components contained in the oil to be treated have been adsorbed using the synthetic calcium carbonate adsorbent, the synthetic calcium carbonate adsorbent can be separated by a known solid-liquid separation method such as centrifugation or filtration.

[0034] In the method for producing treated oil of the present invention, the treated oil is treated oil in which acidic components have been adsorbed by an adsorbent, and the treated oil may also be treated oil in which the acidic components have been adsorbed by an adsorbent and further post-treated.

[0035] Examples of treated oils include lubricating oils obtained by treating crude oils such as naphthene-based crude oils and paraffin-based crude oils, lubricating oil base oils or lubricating oil base oil intermediates, or raffinates, extracts or lubricating oil base oil intermediates obtained by refining fractions obtained by distilling crude oils with solvents, lubricating oil base oils, or lubricating oils obtained by treating lubricating oil base oils, and even recycled lubricating oils obtained by treating used lubricating oils. However, the treated oils are not limited to the above lubricating oils, and may be oils other than lubricating oils.

[0036] As described above, the method for producing treated oil of the present invention is characterized in that the adsorbent contains synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials. Synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials contributes to reducing greenhouse gas and industrial waste emissions by fixing carbon dioxide, and the method for producing treated oil of the present invention using an adsorbent containing this synthetic calcium carbonate can be said to be a method for producing treated oil that contributes to reducing carbon dioxide.

[0037] Furthermore, adsorbents containing synthetic calcium carbonate, which are synthesized using carbon dioxide or gas containing carbon dioxide and cement-containing waste as raw materials, are extremely inexpensive compared to activated clay and silica-magnesia adsorbents used to remove impurities from the oil being treated, and the method for producing treated oil of the present invention using such adsorbents is also highly economical.

[0038] Furthermore, the method for producing treated oil of the present invention uses an adsorbent containing synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials when adsorbing acidic components from oil containing acidic components, and therefore can be easily applied to existing production processes that include a step of adsorbing impurities in the treated oil using activated clay or a silica-magnesia adsorbent.

[0039] Furthermore, the method for producing treated oil of the present invention and the powdered or granular adsorbent containing synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials, which contains 50% by weight or more of synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials, can adsorb and remove acidic components without adversely affecting the properties of the treated oil, as will be shown in the examples described later, and therefore can be widely applied to methods for producing treated oil which include a step of adsorbing acidic components contained in the oil to be treated using an adsorbent. [Example]

[0040] Example 1 Naphthene-based crude oil was fractionated into each fraction using a vacuum distillation unit, and the fractionated lubricating oil was subjected to solvent extraction using furfural as a solvent to obtain a raffinate, which was used as the treated oil.

[0041] The adsorbent used was Calcarbo (registered trademark) from Idemitsu Kosan Co., Ltd. Calcarbo (registered trademark) is made from concrete sludge and carbon dioxide in boiler exhaust gas. The calcium in the concrete sludge is reacted with the carbon dioxide to synthesize calcium carbonate, which is then dehydrated, dried, and crushed to obtain a powder containing more than 50% by weight of calcium carbonate.

[0042] The physical properties of Carbohydrate are as follows: Average particle size (D50): 7.5 μm (laser diffraction method) Specific surface area: 60m 2 / g (Nitrogen adsorption-BET multi-point method) Total pore volume: 0.18 cm 3 / g (Nitrogen adsorption - one-point method (up to relative pressure 0.98)) Average pore diameter: 12 nm (calculated value) (average pore diameter = 4 × total pore volume / specific surface area × 10 3 ) Pore ​​volume: 0.13 cm 3 / g (nitrogen adsorption - BJH method)

[0043] The oil to be treated and the adsorbent were mixed in a weight ratio of 95:5, placed in a beaker, heated to 60°C with a heater, and stirred and mixed with a stirrer for 1 hour to carry out the adsorption treatment. After that, the mixture was left to stand for 5 minutes to separate, and then naturally filtered using filter paper to obtain the treated oil.

[0044] The acid value of the treated oil was measured using an automatic titrator (Kyoto Electronics MCU-710M / S) in accordance with the acid value measurement method in JIS K2501:2003 Petroleum products and lubricants - Neutralization number test method. The physical properties of the treated oil were also measured. The measurement methods for the physical properties are listed in Table 1.

[0045] Comparative Examples 1 to 7 The adsorbents used were porous and environmentally friendly. Specifically, fossil coral (Coral International Co., Ltd.), ore (Nihonkai Mining Co., Ltd.), scallop shells (Aomori Ecocycle Industry Cooperative), used ground coffee powder (Allied Coffee Roasters Co., Ltd.), cashew nut powder, synthetic calcium carbonate (Shiraishi Kogyo Co., Ltd.: Brilliant-1500), and calcium carbonate (Hayashi Pure Chemical Industries Co., Ltd.: calcium carbonate (for research and experiment use), concentration ≥ 98.0%) were used as adsorbents. Adsorption treatment was performed in the same manner as in Example 1, and the acid value and physical properties were measured. The results of Example 1 and Comparative Examples 1 to 7 are shown in Table 1.

[0046] As shown in Table 1, in Example 1, in which adsorption treatment was carried out using Carcarbo (registered trademark) as the adsorbent, the acid value decreased from 0.08 mg KOH / g to 0.01 mg KOH / g. Furthermore, as shown in Table 1, physical properties such as kinematic viscosity, total sulfur content, and ring analysis value remained unchanged before and after the adsorption treatment. Furthermore, filtration of the adsorbent using filter paper after the adsorption treatment was satisfactory with no clogging.

[0047] On the other hand, when fossil coral (Comparative Example 1), ore (Comparative Example 2), or scallop shells (Comparative Example 3) were used as adsorbents, the acid value hardly decreased. When synthetic calcium carbonate (Comparative Example 6) or calcium carbonate (Comparative Example 7) was used as adsorbents, the acid value decreased to 0.04 mg KOH / g, but this is still higher than that of Carcarbo (registered trademark) in Example 1. Furthermore, when used ground coffee powder (Comparative Example 4) or cashew nut powder (Comparative Example 5) were used as adsorbents, the acid value increased compared to the treated oil.

[0048] [Table 1]

[0049] Example 2 The vacuum distillation residue obtained by vacuum distillation of naphthenic crude oil was mixed with low-viscosity oil V1, and this was solvent refined using furfural as a solvent to obtain raffinate. Furthermore, the low-viscosity oil V1 contained in the raffinate was removed by distillation to obtain oil V1R, which was used as the treated oil. Oil V1R was a lubricating base oil and had an acid value of 0.06 mg KOH / g.

[0050] Adsorption treatment using an adsorbent (Carcarbo (registered trademark)) was carried out in the same manner as in Example 1, and the resulting treated oil was analyzed. The amount of adsorbent added to the treated oil was 0.5 wt% and 1.0 wt%.

[0051] The results are shown in Table 2 and Figure 1. As shown in Table 2 and Figure 1, when 0.5 wt% of adsorbent was added to the treated oil, the acid value dropped to 0.02 mg KOH / g, and when 1.0 wt% of adsorbent was added, the acid value dropped to 0.01 mg KOH / g. As shown in Table 2, when 1.0 wt% of adsorbent was added, the acid value of the treated oil was lower than that of the current product (lubricating oil). In addition to the acid value, the other properties of the treated oil were also equivalent to those of the current product. The current product (current product) reduces the acid value by adding caustic soda to oil V1R to create sodium naphthenate water and then discharging the water.

[0052] [Table 2]

[0053] Example 3 The low-viscosity oil V1 was mixed with the vacuum distillation residue obtained by vacuum distillation of naphthenic crude oil, and the mixture was solvent refined using furfural to obtain extract V1E, which was used as the treated oil. The acid value of the treated oil was 6.16 mg KOH / g.

[0054] Adsorption treatment using an adsorbent (Carcarbo (registered trademark)) was carried out in the same manner as in Example 1, and the resulting treated oil was analyzed. When the amount of adsorbent added to the treated oil was 5 wt%, the acid value of the treated oil decreased to 6.00 mg KOH / g.

[0055] Example 4 Naphthene-based crude oil was used as the treated oil and subjected to adsorption treatment using an adsorbent (Carcarbo (registered trademark)) in the same manner as in Example 1, and the resulting treated oil was analyzed. The properties of the naphthene-based crude oil were a density of 0.9372 g / cm 3 The acid value was 1.66 mg KOH / g. The amount of adsorbent added to the treated oil was 5 wt% and 10 wt%.

[0056] The results are shown in Table 3. The acid value of the treated oil decreased to 1.13 mg KOH / g when the amount of adsorbent added was 5 wt%, and to 1.04 mg KOH / g when the amount of adsorbent added was 10 wt%. There were no changes in the density, kinematic viscosity, total sulfur content, etc. before and after the adsorption treatment.

[0057] [Table 3]

[0058] Example 5 Used lubricating oil (waste lubricating oil) was used as the oil to be treated, and adsorption treatment was carried out using an adsorbent (Carcarb (registered trademark)) in the same manner as in Example 1, and the resulting treated oil was analyzed. The properties of the treated oil were as follows: density: 0.864 g / cm 3 The acid value was 1.29 mg KOH / g. The amount of adsorbent added to the treated oil was 5 wt% and 10 wt%.

[0059] The results are shown in Table 4. The acid value of the treated oil decreased to 0.93 mg KOH / g when the amount of adsorbent added was 5 wt%, and to 0.81 mg KOH / g when the amount of adsorbent added was 10 wt%. There were no changes in the density, kinematic viscosity, total sulfur content, etc. before and after the adsorption treatment.

[0060] [Table 4]

Claims

1. A method for producing treated oil, comprising a step of adsorbing acidic components contained in treated oil using an adsorbent, A method for producing treated oil, characterized in that the adsorbent contains synthetic calcium carbonate synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials.

2. 2. The method for producing treated oil according to claim 1, wherein the acidic component is mainly composed of naphthenic acid and / or carboxylic acid.

3. The oil to be treated is crude oil, and the treated oil is a lubricant, a lubricant base oil, or a lubricant base oil intermediate; Alternatively, the treated oil is a raffinate, extract or lubricating oil base oil intermediate obtained by refining a fraction obtained by distilling crude oil with a solvent, and the treated oil is a lubricating oil or a lubricating oil base oil, 3. The method for producing a treated oil according to claim 1, wherein the oil to be treated is a lubricating base oil, and the treated oil is a lubricating oil.

4. 3. The method for producing treated oil according to claim 1, wherein the oil to be treated is used lubricating oil, and the treated oil is recycled lubricating oil.

5. This adsorbent is used to adsorb and remove acidic components contained in the oil to be treated, and is synthesized using carbon dioxide or a gas containing carbon dioxide and cement-containing waste as raw materials.

1. An adsorbent in powder or granular form, characterized in that it contains 50% by weight or more of synthetic calcium carbonate synthesized from carbon dioxide or a gas containing carbon dioxide and cement-containing waste.

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