Phenol production method

Abstract

To provide a method for producing phenols that enables sufficient separation between oil and water in an oil-water separation step in the phenol production method.SOLUTION: A method for producing phenols includes: a neutralization step for neutralizing an acid-decomposed cumene hydroperoxide reaction solution with an alkali; an oil-water separation step for separating the neutralized reaction solution into an oil phase liquid and an aqueous phase liquid; and a washing step for mixing the oil phase liquid with washing water to wash it. In the washing step, the mixture of the oil phase liquid and the washing water contains a metal element, excluding alkali metals of Group 1 in the periodic table, of 0.1 mass ppm or more and 25 mass ppm or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a process for producing phenol. [Background technology]

[0002] Phenol is generally produced industrially by the cumene process, which involves oxidizing cumene to produce cumene hydroperoxide (hereinafter referred to as CHP). The process comprises an oxidation step in which a reaction liquid containing CHP is produced, an acid decomposition step in which CHP is acid-decomposed to produce phenol and acetone, a neutralization washing step in which the decomposition product liquid is neutralized and the salt is removed by washing, and a recovery step in which components other than phenol are separated from the washing liquid to recover phenol.

[0003] In the acid decomposition process of the cumene process for producing phenol, an acid such as sulfuric acid is added to efficiently decompose CHP. If any acid remains in the acid decomposition product, it will act as a catalyst for generating heavy products when heated in the subsequent recovery process. Therefore, in the neutralization washing process prior to the recovery process, the acid decomposition product is contacted with wash water containing an alkali such as sodium carbonate, and the acid is extracted and removed into the wash water. At the same time, the neutralization washing process also extracts and removes organic acids that are generated as impurities in the oxidation process for producing CHP.

[0004] The wash water that comes into contact with the acid decomposition product contains the extracted acid and salts, which, when carried into the recovery process, precipitate as sodium salts in the distillation column, causing the column to clog (Patent Document 1). Tower clogging makes the operation of the distillation column unstable, ultimately requiring the plant to be shut down for cleaning, which impedes the plant's continuous operation. Therefore, the wash water after extraction must be separated from the acid decomposition product.

[0005] Furthermore, metal components leach out of metal pipes and equipment in plants due to corrosion, and these leach- ing metal components form salts with organic acids in the acid decomposition products, which precipitate and clog the metal pipes and equipment in plants. For this reason, plants take measures such as changing the materials of metal pipes and equipment to corrosion-resistant materials to prevent the leaching of metal components.

[0006] The separation of the acid decomposition product from the wash water is oil-water separation, and methods for this oil-water separation include static separation, coagulation separation using a filter, and centrifugation.

[0007] The speed of oil-water separation is affected by physical properties such as differences in oil-water density, interfacial tension, and dispersed droplet size, which arise from differences in liquid composition, the presence or absence of surfactants, and mixing and stirring speed, but it has not been fully elucidated how the various impurities and metals generated and mixed in during the various steps of the phenol production process affect oil-water separation. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 7-24211 Summary of the Invention [Problem to be solved by the invention]

[0009] An object of the present invention is to provide a method for producing phenol that can satisfactorily separate oil and water in the oil-water separation step of the phenol production method. [Means for solving the problem]

[0010] The present inventors have found that in the washing step of producing phenol, in which wash water is mixed with the oil phase liquid after oil-water separation for washing, oil-water separability deteriorates when the particle size of the water particles dispersed in the mixture of the oil phase liquid and the wash water is small. Therefore, oil-water separability can be improved by intentionally making a metal element other than an alkali metal belonging to Group 1 of the periodic table present in the mixture at a predetermined concentration.

[0011] That is, the gist of the present invention relates to a method for producing phenol, which comprises a neutralization step of neutralizing an acid decomposition reaction solution of cumene hydroperoxide with an alkali, an oil-aqueous separation step of separating the neutralized reaction solution into an oil phase liquid and an aqueous phase liquid, and a washing step of mixing wash water with the oil phase liquid for washing, wherein the mixture of the oil phase liquid and the wash water in the washing step contains metal elements belonging to Group 1 of the periodic table, excluding alkali metals, in an amount of 0.1 ppm by mass or more and 25 ppm by mass or less. [Effects of the Invention]

[0012] According to the present invention, there is provided a method for producing phenol, which can perform good oil-water separation in the oil-water separation step in the production of phenol. As a result, it is possible to prevent salts, organic acids, etc. contained in the neutralization wash water from being carried over to the oil-water separator and further to downstream purification equipment such as a distillation column, thereby preventing the pipes from clogging, and it is possible to operate the oil-water separator and downstream purification equipment stably for a long period of time. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic diagram of an oil-water separation experimental device. DETAILED DESCRIPTION OF THE INVENTION

[0014] The present invention will be described in detail below, but the present invention is not limited to the following description and can be practiced with any modifications within the scope of the gist of the present invention.

[0015] Unless otherwise specified, the numerical ranges expressed using "to" in this specification are "to " means a range including the numbers written before and after as the lower and upper limits, and "A to B" means a range including the numbers written before and after as the lower and upper limits, It means greater than or equal to A and less than or equal to B. In this specification, "ppm by mass" refers to "ppm" calculated using mass as the unit, and 1 ppm by mass = 1 × 10 -4 The percentages represent mass %.

[0016] [Phenol manufacturing method] The present invention relates to a process for producing phenol based on the cumene process. The method for producing phenol of the present invention is a method for producing phenol comprising a neutralization step, an oil-water separation step, and a washing step, which will be described later.

[0017] In the method for producing phenol of the present invention, the neutralization step, the oil-water separation step, and the washing step can be repeated in this order any number of times. Furthermore, the method for producing phenol of the present invention may have a recovery step described below after the washing step.

[0018] Furthermore, the phenol production method of the present invention may include, before the neutralization step, a cumene oxidation step described below and a CHP acid decomposition step described below. Furthermore, the phenol production method of the present invention can include a CHP concentration step described below between the oxidation step and the acid decomposition step.

[0019] As a general embodiment of the method for producing phenol, a known method such as the conditions described in JP-A-2017-178826 can be used.

[0020] Each of the above steps will be explained in order below.

[0021] [Cumene oxidation process] The phenol production method of the present invention may include a step of oxidizing cumene to produce CHP before the neutralization step described below. The cumene used in the oxidation of cumene is preferably one that has been purified to 99.5% by weight or more by distillation after reacting benzene with propylene. This may be mixed with cumene recovered from the CHP concentration step described below, or cumene obtained by hydrogenating α-methylstyrene separated in a distillation column from a mixture of phenol, acetone, etc. after phenol synthesis.

[0022] The oxidation reaction of cumene is carried out by blowing a mixed gas containing oxygen and an inert gas at 40°C to 130°C under normal or increased pressure. Examples of the mixed gas include air and air with an increased or decreased oxygen concentration, with air with an increased oxygen concentration being preferred. The oxidation reactor may be one in which the reaction is carried out in a single stage or in multiple stages of two or more stages. In the latter case, an additional mixed gas containing oxygen and an inert gas is usually supplied at each stage. When α-methylstyrene is one of the desired products, conditions suitable for the plant can be selected so that the desired amount of dimethylbenzyl alcohol is produced during the oxidation reaction. The above-mentioned oxidation reaction of cumene yields a cumene solution containing 10 to 40 wt % of CHP.

[0023] [CHP concentration process] The phenol production method of the present invention may include a CHP concentration step in which the cumene solution containing CHP obtained in the oxidation step is concentrated after the above-mentioned cumene oxidation step and before the neutralization step described below, or before the CHP acid decomposition step described below which is carried out before the neutralization step described below. The cumene solution obtained in the above-described cumene oxidation step is concentrated to a CHP concentration of preferably 65% ​​by weight or more, more preferably 80% by weight or more, and more preferably 80% by weight to 90% by weight. Because CHP undergoes a violent cleavage reaction at high temperatures or in the presence of a catalyst, a concentration of 90% by weight or less is preferable from a safety standpoint. The method for concentrating the cumene solution is not particularly limited, but it is preferably concentrated under reduced pressure. This vacuum concentration also allows for the degassing of air introduced during the oxidation reaction. The concentrated CHP solution is diluted with acetone and then subjected to the subsequent acid decomposition step.

[0024] [CHP acid decomposition process] The phenol production method of the present invention can include, after the above-mentioned cumene oxidation step or the CHP concentration step and before the neutralization step described below, a CHP acid decomposition step in which the CHP-containing cumene solution obtained in the oxidation step or the concentration step is decomposed in the presence of an acid catalyst to produce a solution containing phenol and acetone. Specifically, in the cumene solution containing CHP obtained in the concentration step, a cleavage reaction of CHP is caused in the presence of an acid catalyst to obtain a mixture containing phenol, acetone, α-methylstyrene resulting from the aforementioned dimethylbenzyl alcohol, and other by-products. The acid catalyst includes sulfuric acid.

[0025] The acid decomposition reaction of CHP is usually carried out under conditions of a reaction temperature of 60° C. to 90° C. The acid decomposition reaction of CHP is an exothermic reaction, and heat is removed. Almost all of the CHP is cleaved to produce phenol and acetone, and by-products include phenol dimers, heavy ends (HE) such as cumylphenol, and acid decomposition products consisting of a mixture of organic acids. That is, the acid decomposition reaction liquid obtained by decomposing CHP using an acid catalyst is a solution containing phenol and acetone, and the solution also contains α-methylstyrene and other by-products, as well as acid decomposition products including HE, organic acids, etc.

[0026] [Neutralization process] The method for producing phenol of the present invention includes a neutralization step of neutralizing the acid decomposition reaction solution of CHP with an alkali. One embodiment of the neutralization step in the present invention includes a step of neutralizing with an alkali the acid decomposition reaction solution obtained by decomposing CHP in the presence of an acid catalyst in the above-mentioned CHP acid decomposition step, and washing the solution (hereinafter simply referred to as "neutralizing with an alkali"). The neutralization wash water used in neutralizing with an alkali may be an aqueous alkali solution. In the neutralization step, a solution containing phenol and acetone is contacted multiple times with neutralization wash water such as an alkaline aqueous solution. This neutralizes the acid catalyst, such as sulfuric acid, used in the acid decomposition of CHP to obtain a neutralization salt. The neutralization salt, along with organic acids and other by-products from the cumene oxidation step and the CHP acid decomposition step, are then transferred to the neutralization wash water and extracted. The contact between the solution containing phenol and acetone and the neutralization wash water is preferably carried out countercurrently and in multiple stages. These treatments in the neutralization step can be carried out using a known mixing device, such as a line mixer.

[0027] The neutralizing agent used in the neutralization with an alkaline aqueous solution may be an aqueous solution of ammonia, an aqueous solution of a basic compound containing an alkali metal or alkaline earth metal, or an anion exchange resin. Among these, an aqueous solution of a sodium-containing basic compound such as sodium phenolate, sodium hydroxide, or sodium carbonate is preferably used. The sodium-containing basic compound in this aqueous solution is preferably added in an amount such that the pH of the aqueous phase after neutralization is about 6.

[0028] [Oil / water separation process] The method for producing phenol of the present invention includes an oil-aqueous separation step of separating the reaction liquid neutralized in the neutralization step into an oil phase liquid and an aqueous phase liquid. The mixture of the acid decomposition product after neutralization and washing and the neutralization washing water obtained in the neutralization step is separated into an aqueous phase and an oil phase liquid (organic phase) using an oil-water separator, and the oil phase liquid is obtained by removing the aqueous phase. Note that when neutralization is performed using an alkali metal-containing basic compound, some of the phenol becomes a salt with the alkali metal (sodium phenate, etc.) and migrates to the aqueous phase, resulting in a decrease in phenol yield. Therefore, it is preferable to add a salt such as sodium sulfate to the aqueous phase to prevent the phenol in the oil phase liquid from migrating to the aqueous phase. Furthermore, these treatments in the oil-water separation step can be carried out using a known oil-water separation device such as a static separation tank.

[0029] [Cleaning process] The washing step in the present invention includes a washing step in which the oil phase liquid obtained in the oil-aqueous separation step is mixed with wash water for washing. The acid decomposition step of CHP is preferably carried out using sulfuric acid as described above, and the sulfuric acid used is converted to Glauber's salt (sodium sulfate decahydrate) in the neutralization step. The oil phase liquid separated in the oil-water separation step contains neutralized salts such as Glauber's salt, so the oil phase liquid is further washed to remove them.

[0030] The oil phase liquid may be washed using a mixer such as a line mixer and an oil-water separator such as a static separator tank, similar to the apparatus used for neutralization, or may be washed using an extraction separator such as a coalescer. The aqueous phase obtained after washing with the oil phase liquid may be used as wash water in the neutralization washing step described above. This allows the recovery of phenol that has migrated to the aqueous phase.

[0031] The washing water used for washing the oil phase liquid is not particularly limited, but ion-exchanged water or distilled water can be used. The step of washing the oil phase liquid is carried out for the purpose of removing salts from the oil phase liquid, and the washing water used in the step of washing the oil phase liquid needs to have a lower content of salts such as sodium sulfate than the washing water used in the neutralization step.

[0032] In the phenol production method of the present invention, the lower limit of the content of metal elements, excluding alkali metals belonging to Group 1 of the periodic table (hereinafter simply referred to as "alkali metals belonging to Group 1"), contained in the mixed liquid at the inlet of the oil phase liquid washing step, consisting of the oil phase liquid discharged from the outlet of the neutralization step and the wash water used to wash the oil phase liquid, is 0.1 mass ppm or more, preferably 0.2 mass ppm or more, and more preferably 0.5 mass ppm or more, relative to the total mass of the mixed liquid, from the viewpoint of improving oil-water separability after washing the oil phase liquid in the oil phase liquid washing step. On the other hand, the upper limit of the content of metal elements, excluding alkali metals belonging to Group 1, in the mixed liquid is 25 mass ppm or less, more preferably 3 mass ppm or less, and more preferably 2 mass ppm or less, relative to the total mass of the mixed liquid, from the viewpoint of preventing clogging due to precipitation of metal salts in the oil phase liquid washing step and subsequent steps.

[0033] The upper and lower limits can be combined in any desired manner. For example, the content of metal elements excluding alkali metals belonging to Group 1 in the mixed solution is 0.1 mass ppm to 25 mass ppm, preferably 0.2 mass ppm to 3 mass ppm, and more preferably 0.5 mass ppm to 2 mass ppm, relative to the total mass of the mixed solution.

[0034] The reason for excluding the content of alkali metals belonging to Group 1 from the content of metal elements is that when alkali metals belonging to Group 1, such as sodium, are present, oil-water separability deteriorates, and therefore the content of metal elements excluding alkali metals belonging to Group 1 is important for improving oil-water separability.

[0035] A method for controlling the content of metal elements excluding alkali metals belonging to Group 1 includes a method in which washing water containing metal elements excluding alkali metals belonging to Group 1 is prepared in advance, and in the washing step, the washing water is mixed with the oil phase liquid so that the content of the metal elements in the mixture of the oil phase liquid and the washing water is within the range of 0.1 ppm by mass or more and 25 ppm by mass or less.

[0036] Alternatively, methods for controlling the content of metal elements excluding alkali metals belonging to Group 1 include known methods such as adding eluted metal by placing a sacrificial metal material in an intermediate tank or the like installed between processes.

[0037] The alkali metals belonging to Group 1 are not particularly limited, but examples include lithium, sodium, potassium, rubidium, etc. Among these, sodium and potassium are preferred.

[0038] Metal elements other than alkali metals belonging to Group 1 are not particularly limited, but include typical metals belonging to Periods 4 and 5 of the periodic table. From the viewpoint of ease of handling, iron, copper, and zinc can be mentioned. Among them, iron is preferred.

[0039] If an alkali metal belonging to Group 1, such as sodium, and an organic acid coexist in the oil phase liquid washing step, the oil-water separability after oil phase liquid washing deteriorates. Therefore, in the present invention, it is preferable to set the concentration of at least one of an alkali metal belonging to Group 1, such as sodium, and an organic acid in a mixed liquid at the inlet of the oil phase liquid washing step, which is made of the oil phase liquid discharged from the outlet of the neutralization step and the washing water used to wash the oil phase liquid, to a predetermined value or less.

[0040] The concentration of the alkali metal belonging to Group 1, such as sodium, in the mixed solution is preferably 250 ppm by mass or less, more preferably 100 ppm by mass or less, relative to the total mass of the mixed solution.

[0041] Methods for reducing the concentration of alkali metals belonging to Group 1, such as sodium, include lowering the pH by adding acid (preferably sulfuric acid) to the wash water in the neutralization wash process, and increasing the washing efficiency by using multiple stages of oil-water separation equipment.

[0042] The concentration of the organic acid in the mixed solution is preferably 520 ppm by mass or less, more preferably 100 ppm by mass or less, based on the total mass of the mixed solution. The organic acid referred to here includes acids such as formic acid, acetic acid, and oxalic acid, which are by-produced in the cumene oxidation reaction. From the viewpoint of reducing the concentration of sodium sulfate contained in the washing water, the sulfuric acid concentration in the mixed solution is preferably 50 ppm by mass or less, and more preferably 20 ppm by mass or less, relative to the total mass of the mixed solution.

[0043] Methods for reducing the organic acid concentration include increasing the pH by adding alkalis to the wash water in the neutralization step, increasing the washing efficiency by using multi-stage wash oil-water separation equipment, etc. The alkalis to be added can be the same as those used in the alkaline wash water in the neutralization step described above.

[0044] [Recovery process] The method for producing phenol of the present invention may include, after the above-mentioned washing step, a recovery step of distilling the oil phase liquid after washing to recover phenol. In the recovery process, the mixture containing phenol, acetone, α-methylstyrene, and heavy ends (HE) on the oil phase liquid side is separated into each component by distillation.

[0045] Regarding distillation, known methods can be used, such as the conditions described in JP-A-2015-178476 and JP-A-2015-182986.

[0046] The number of distillations and the number of distillations to extract each component can be determined arbitrarily. Typically, the first distillation targets light components, particularly acetone, and removes water and unreacted cumene. The second distillation removes phenol and α-methylstyrene. The remaining product is called heavy ends (HE), and the distillate is then subjected to a third distillation to separate phenol and α-methylstyrene. Alternatively, the first distillation targets acetone and α-methylstyrene, and removes water and unreacted cumene. The second distillation separates phenol and HE. Separating the acetone and α-methylstyrene from the first distillation is also possible. In either case, more distillations than the number of target products are required, and the number of distillations is increased to further improve purity. Extractive distillation, in which an appropriate solvent is added to the distillate as needed, can also be performed.

[0047] After distillation, phenol of the desired purity is obtained as the product. [Example]

[0048] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In these examples, experiments simulating the oil-water separation process in the phenol production process were carried out to confirm the effects of the method of the present invention.

[0049] The acetone, cumene, α-methylstyrene, phenol, formic acid, and sodium hydroxide used in the examples and comparative examples were special grade reagents manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Furthermore, as a metal element excluding alkali metals belonging to Group 1, Polytetsu (product name, manufactured by Nittetsu Mining Co., Ltd., main component: aqueous solution of polyferric sulfate) (hereinafter referred to as "Polytetsu reagent") was used.

[0050] [Oil-water separation experiment] The oil-water separation experimental apparatus shown in Figure 1 was used in the examples and comparative examples. This oil-water separation experimental apparatus is composed of a raw material tank 2 with an internal volume of 1.8 L and equipped with an agitator 1, a liquid transfer pump 4, and a coalescer tank 6 with an internal volume of 0.7 L. The coalescer tank 6 has a carbon fiber filter element 5 with a capacity of 100 mL and a filtration accuracy of 15 μm.

[0051] The oil-water separation experiment was carried out according to the following procedure. 1 kg of the raw material liquid was charged into raw material tank 2, and then mixed and stirred with a stirrer 1 until the liquid became uniform, and the liquid temperature was raised to 40°C with heater 3. Thereafter, the liquid was fed at a flow rate of 150 mL / min with liquid feed pump 4 and passed through filter element 5 to separate the oil and water. The separated aqueous phase was allowed to settle in coalescer tank 6, and the separated oil phase liquid was obtained from outlet nozzle 7.

[0052] The water concentration in the separated oil phase was determined by the Karl Fischer reagent volumetric titration method using a moisture meter (product name: CA-200 model, manufactured by Nitto Seiko Analytech Co., Ltd.).TM 3 mg of titrant SS-Z (manufactured by Mitsubishi Chemical Corporation) and Aquamicron (registered trademark) dehydrated solvent KTX (for ketones, non-pyridine / chloroform) (manufactured by Mitsubishi Chemical Corporation) were used.

[0053] [Example 1] Ion-exchanged water, acetone, cumene, α-methylstyrene, phenol, formic acid, sulfuric acid, sodium hydroxide, and polytetrafluoroethylene reagent were mixed to obtain the mixture shown in Table 1. The amount of the polytetrafluoroethylene reagent added was such that the iron content in the final mixture was 1.0 ppm by mass. The resulting mixture was subjected to oil-water separation using the oil-water separation experimental apparatus shown in Figure 1, and the water concentration in the resulting oil phase liquid (hereinafter referred to as "oil phase water concentration") was measured. The results are shown in Table 1.

[0054] [Examples 2 to 4] The polytetrafluoroethylene reagent was added so that the iron content in the mixed solution was 0.5 ppm by mass, 0.2 ppm by mass, and 0.1 ppm by mass, respectively, to obtain the mixed solutions shown in Table 1. The experiment was carried out in the same manner as in Example 1, and the water concentration in the oil phase was measured. The results are shown in Table 1.

[0055] [Comparative Example 1] The mixed solution shown in Table 1 was obtained without using the Polytetsu reagent. The experiment was carried out in the same manner as in Example 1, and the water concentration in the oil phase was measured. The results are shown in Table 1.

[0056] [Table 1]

[0057] [Consideration] In Examples 1 to 4, the water concentration in the oil phase after the oil-water separation experiment was low. On the other hand, in Comparative Example 1, the mixed liquid did not contain any metal elements other than alkali metals belonging to Group 1, and therefore the water concentration in the oil phase after the oil-water separation experiment was high.

[0058] From the above results, it is expected that in the production of phenol having a neutralization step, an oil-water separation step, and an oil phase liquid washing step as defined in claim 1, good oil-water separability can be achieved by intentionally adding a metal element, excluding alkali metals belonging to Group 1, to the mixture of oil phase liquid and wash water at the inlet of the washing step. Phenol is consumed in large quantities as a raw material for, for example, epoxy resins, polycarbonate resins, phenolic resins, and polyester resins, and is therefore produced in large quantities on an industrial scale of, for example, 100,000 tons per year or more. Therefore, in the production of phenol, improving oil-water separability even slightly, for example, reducing the water concentration in the oil phase brought into the distillation column by even 1%, is industrially important from the viewpoint of reducing production costs by reducing the energy required for heating in the distillation column and suppressing the precipitation of salts dissolved in the free water in the oil phase. [Explanation of symbols]

[0059] 1 Raw material mixer 2 Raw material tank 3 Raw material tank heater 4. Liquid transfer pump 5 filter elements 6 Coalescer tank 7 Oil phase outlet nozzle 8. Aqueous phase outlet nozzle

Claims

1. a neutralization step of neutralizing the acid decomposition reaction solution of cumene hydroperoxide with an alkali; an oil-water separation step of separating the neutralized reaction liquid into an oil phase liquid and an aqueous phase liquid; a washing step of mixing wash water with the oil phase liquid for washing; In a method for producing phenol, a mixed solution of the oil phase liquid and the wash water in the washing step containing metal elements, excluding alkali metals belonging to Group 1 of the periodic table, and metal elements belonging to Periods 4 and 5 of the periodic table, in an amount of 0.1 ppm by mass or more and 25 ppm by mass or less.

2. 2. The method for producing phenol according to claim 1, wherein in the washing step, the wash water containing the metal element is mixed with the oil phase liquid so that the content of the metal element in a mixed liquid of the oil phase liquid and the wash water is within a range of 0.1 ppm by mass to 25 ppm by mass.

3. A method for producing phenol as described in claim 1 or 2, wherein the metal element is any one of iron, copper and zinc.

4. The method for producing phenol according to claim 3, wherein the metal element is iron.

5. The method for producing phenol according to any one of claims 1 to 4, further comprising an oxidation step of oxidizing cumene to produce cumene hydroperoxide, prior to the neutralization step.

6. The method for producing phenol according to any one of claims 1 to 5, further comprising, after the washing step, a recovery step of distilling the oil phase liquid after washing to recover phenol.

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