Method for preparing 2,2-bis(2-tetrahydrofuranyl)propane by catalytic hydrogenation using a non-noble metal-based catalyst

Abstract

The present invention discloses a preparation method of 2,2-bis(2-tetrahydrofuranyl) propane compound, which is characterized in that 2,2-bis(2-furyl) propane, a hydrogenation catalyst and hydrogen are used as raw materials, and under the action of a non-precious metal Ni-based catalyst, a 2,2-bis(2-tetrahydrofuranyl) propane product is obtained through a hydrogenation reaction at a temperature of 100-200 °C. The hydrogenation process of the present invention avoids the use of organic solvents, improves the operation environment and reduces the production cost. The catalyst is a non-precious metal nickel-based catalyst, which consists of a Ni active metal component, other metal promoter components and a support g-C3N4-montmorillonite. This invention avoids the use of precious metal-based catalysts such as palladium, ruthenium and rhodium. The production process has high selectivity of the target product, few side reactions, high product purity, low catalyst cost, easy separation and reuse, and has great industrial application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of organic chemical industry, and particularly relates to a method for catalytic hydrogenation of 2,2-bis(2-tetrahydrofuryl)propane using a non-precious metal-based catalyst. Background Art

[0002] 2,2-Bis(2-tetrahydrofuryl)propane is an organic compound with important uses and can be used as a structural regulator for producing styrene-based elastomers. 2,2-Bis(2-tetrahydrofuryl)propane (Formula II) can be produced by hydrogenation of 2,2-bis(2-furyl)propane (Formula I). During this hydrogenation reaction process, three isomers are produced in the hydrogenation reaction product 2,2-bis(2-tetrahydrofuryl)propane; among them, the meso isomer has higher value and is more widely used.

[0003]

[0004] Patent application WO2016046575A1 provides a method for enantioselective hydrogenation controlled by chelation using heterogeneous catalysis, and specifically provides a method for hydrogenating 2,2-bis(2-furyl)propane to 2,2-bis(2-tetrahydrofuryl)propane. In this method, the catalyst is preferably palladium on a support, and the support is preferably an alumina or activated carbon support. The catalyst is used in the presence of a lithium salt, preferably a borate. However, the patent method of WO2016046575A1 for producing 2,2-bis(2-tetrahydrofuryl)propane uses a noble metal catalyst, and a relatively high content of meso isomer can only be obtained by mixing a lithium salt (specifically an organic carboxylate, carbonate, hydroxide or borate, etc.) with a palladium-carbon catalyst during the hydrogenation reaction process; and more meso isomers can only be obtained when using a solvent (such as heptane, MTBE, THF, ethanol and isopropanol, etc.); meanwhile, the reusability of the catalyst is not strong and the lifespan of the catalyst is not high.

[0005] Patent CN108997266B discloses a method for hydrogenating 2,2-bis(2-furyl)propane to 2,2-bis(2-tetrahydrofuryl)propane. The method includes using 2,2-bis(2-furyl)propane as a raw material and carrying out a hydrogenation reaction with hydrogen under the condition of using a composite catalyst to obtain the 2,2-bis(2-tetrahydrofuryl)propane. The composite catalyst includes a metal Ru active component, a first promoter of Li, Na and K, a second promoter of Fe, Co and Cu, and supports of carbon, alumina, silica, titanium dioxide, calcium carbonate, lithium aluminate and barium sulfate. The raw material conversion rate is high and the content of meso isomer is high. However, the composite catalyst of this invention still needs to use Ru noble metal, and the first promoters of Li, Na and K have the problem of loss, and the catalyst needs to be supplemented during the cyclic reaction process.

[0006] Therefore, there is a need in the art to provide a new method for hydrogenating 2,2-bis(2-furyl)propane to 2,2-bis(2-tetrahydrofuryl)propane. Summary of the Invention

[0007] The object of the present invention is to provide a method for synthesizing 2,2-bis(2-tetrahydrofuryl)propane with high safety, high conversion rate, few by-products and easy separation of the catalyst. The production process of the present invention has high selectivity of the target product, few side reactions, high product purity, low catalyst cost, easy separation and reuse, and has great industrial application prospects.

[0008] To achieve the above object, the present invention adopts the following technical solutions:

[0009] A method for preparing a 2,2-bis(2-tetrahydrofuryl)propane compound, using 2,2-bis(2-furyl)propane, a hydrogenation catalyst and hydrogen as raw materials, and under the action of a non-precious metal Ni-based catalyst, hydrogenation reaction is carried out at a temperature of 100-200 °C to obtain a 2,2-bis(2-tetrahydrofuryl)propane product as shown in formula (II):

[0010]

[0011] Among them, the hydrogenation catalyst is made of a Ni active metal component, a metal promoter component, an auxiliary agent and a carrier g-C3N4-montmorillonite.

[0012] Preferably, the preparation method of the catalyst is:

[0013] (1) Mix montmorillonite and deionized water evenly to obtain a mixture, then add a nitrogen-containing compound to the above mixture, stir at 30-100 °C for 1-5 h, then carry out centrifugal separation, and dry and calcine the separated solid to obtain the carrier g-C3N4-montmorillonite;

[0014] (2) Prepare an aqueous solution of the Ni active metal component and the metal promoter component, then add an auxiliary agent, stir and mix evenly, then add the carrier g-C3N4-montmorillonite described in step (1) to the mixture, stir at room temperature for 6-12 hours, then slowly evaporate the water to dryness to obtain a catalyst precursor, and then pyrolyze the catalyst precursor in an inert atmosphere at 400-600 °C for 3-9 h, and finally reduce it in a hydrogen atmosphere at 360-480 °C for 4-12 h to obtain the catalyst.

[0015] Preferably, in step (1), the mass ratio of the montmorillonite to the deionized water is 1:30-60, and the mass ratio of the montmorillonite to the nitrogen-containing compound is 1:0.5-2.

[0016] Preferably, the nitrogen-containing compound is one or more of urea, cyanamide, dicyandiamide, ethylenediamine, and melamine.

[0017] Preferably, in step (2), the Ni active metal component is one or more of nickel chloride, nickel nitrate, and nickel sulfate, the metal promoter component is at least one of Group VIB, Group VIIB, Group IIB, and lanthanide transition metal elements, and the auxiliary agent is selected from at least one of oxalic acid, bipyridine, nitrilotriacetic acid, and dihydroxyethylglycine.

[0018] Preferably, the metal promoter component is selected from at least one of copper nitrate, manganese nitrate, iron nitrate, cobalt nitrate, chromium nitrate, and europium nitrate. The mass ratio of the Ni active metal component to the auxiliary agent is 1.3 - 2.5, the mass ratio of the Ni active metal component to the metal promoter component is 10 - 100, and the mass ratio of the carrier g-C3N4 - montmorillonite to the Ni active metal component is 5 - 50:1.

[0019] Preferably, the hydrogenation reaction conditions for 2,2 - bis(2 - furyl)propane include: temperature of 100 - 200 °C, time of 4 - 20 hours, and reaction pressure of 3 - 12 MPa.

[0020] Preferably, the mass ratio of 2,2 - bis(2 - furyl)propane to the catalyst dosage is 1:0.03 - 0.50.

[0021] Preferably, the hydrogenation reaction conditions include: temperature of 120 - 180 °C, time of 8 - 15 hours, and reaction pressure of 6 - 10 MPa; the mass ratio of 2,2 - bis(2 - furyl)propane to the catalyst dosage is 1:0.5 - 0.20.

[0022] Preferably, the production method further includes: after the reaction, cooling the mixture obtained from the reaction to 5 - 25 °C, and recovering the hydrogenation catalyst by solid - liquid separation of the cooled mixture.

[0023] Preferably, the reaction solution after solid - liquid separation is subjected to vacuum distillation to obtain 2,2 - bis(2 - tetrahydrofuryl)propane product.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] (1) The hydrogenation process of the present invention avoids the use of organic solvents, improves the operating environment, and reduces production costs. The catalyst is a non - noble metal nickel - based catalyst, which is composed of a Ni active metal component, other metal promoter components, and a carrier. This invention avoids the use of noble metal - based catalysts such as palladium, ruthenium, and rhodium. The production process has high selectivity for the target product, few side reactions, high product purity, low catalyst cost, easy separation, and reusability, and has great industrial application prospects.

[0026] (2) The catalyst of the present invention uses g-C3N4-montmorillonite as a carrier and is made of Ni active metal components, other metal promoter components and auxiliary agents. The prepared catalyst is in the form of Ni / NiC / X / g-C3N4-montmorillonite, where X is a metal promoter element, and part of the nickel element exists in the form of nickel carbide. This catalyst exhibits extremely high catalytic activity in the hydrogenation of 2,2-bis(2-furyl)propane to 2,2-bis(2-tetrahydrofuryl)propane, with a yield of over 97% and a meso isomer content of over 60%. Detailed implementation manners

[0027] In order to make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the following further elaborates on the present invention in combination with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0028] It should be particularly emphasized that, unless otherwise specified, the raw materials or reagents in the present invention are purchased through commercial channels.

[0029] There is no particular limitation on the treatment and purification methods for the mixture after neutralization in the embodiments of the present invention. For example, extraction, distillation, rectification and other methods can be independently used for purification. According to a specific implementation manner of the present invention, the purification is carried out as follows: the separated reaction solution is distilled under reduced pressure to obtain a crude product, and the crude product is rectified to collect the fraction with a gas phase purity ≥ 99%. The embodiments of the present invention use gas chromatography to detect and analyze the purity of 2,2-bis(2-tetrahydrofuryl)propane and the content of its meso isomers.

[0030] Example 1

[0031] A preparation method of a 2,2-bis(2-tetrahydrofuryl)propane compound includes the following steps:

[0032] In a 1L reaction kettle equipped with a mechanical stirrer, a reflux condenser, a temperature controller, add 500.0 g of 2,2-bis(2-furyl)propane and 25.0 g of the catalyst; displace the air in the reaction kettle with nitrogen 5 times and then displace the nitrogen in the reaction kettle with hydrogen 5 times; then fill the reaction kettle with hydrogen to a pressure of 7 Mpa, start stirring, and start the heat preservation reaction when the reaction temperature rises to 150 °C, and keep the temperature for 10 h. The reaction ends. Cool to room temperature, and the reaction mixture is separated from the hydrogenation catalyst by filtration; then the crude product is distilled under reduced pressure and then rectified to collect the fraction with a gas phase purity ≥ 98.5% to obtain the 2,2-bis(2-tetrahydrofuryl)propane product.

[0033] The preparation method of the catalyst includes the following steps

[0034] (1) Mix 50 g of montmorillonite and 2000 g of deionized water evenly to obtain a mixture. Then add 25 g of urea to the above mixture, stir at 60 °C for 3 h, then perform centrifugal separation, dry the separated solid matter, and calcine it at 550 °C for 6 h to obtain the support g-C3N4-montmorillonite;

[0035] (2) Prepare an aqueous solution of 10 g of nickel nitrate and 1 g of copper nitrate, then add 5 g of the auxiliary agent oxalic acid, stir and mix evenly. Then add 200 g of the support g-C3N4-montmorillonite described in step (1) to the mixture, stir at room temperature for 8 hours, then slowly evaporate the water to dryness to obtain a catalyst precursor. Then pyrolyze the catalyst precursor at 550 °C in an inert atmosphere for 8 h, and finally reduce it at 390 °C in a hydrogen atmosphere for 6 h to obtain the Ni / NiC / Cu / g-C3N4-montmorillonite-based catalyst.

[0036] Example 2

[0037] A preparation method of 2,2-bis(2-tetrahydrofuryl)propane compound, comprising the following steps:

[0038] In a 1 L reaction kettle equipped with a mechanical stirrer, a reflux condenser, a temperature controller, add 500.0 g of 2,2-bis(2-furyl)propane and 30.0 g of a catalyst; displace the air in the reaction kettle with nitrogen 5 times and then displace the nitrogen in the reaction kettle with hydrogen 5 times; then fill the reaction kettle with hydrogen to a pressure of 6.5 Mpa, start stirring, and start the heat preservation reaction when the reaction temperature rises to 120 °C, and keep the temperature for 9 h. The reaction ends. Cool to room temperature, and separate the hydrogenation catalyst from the reaction mixture by filtration; then distill the crude product under reduced pressure and perform rectification to collect the fraction with a gas phase purity ≥98.8% to obtain the 2,2-bis(2-tetrahydrofuryl)propane product.

[0039] The preparation method of the catalyst comprises the following steps:

[0040] (1) Mix 50 g of montmorillonite and 2000 g of deionized water evenly to obtain a mixture. Then add 50 g of monocyanamide to the above mixture, stir at 60 °C for 3 h, then perform centrifugal separation, dry the separated solid matter, and calcine it at 550 °C for 6 h to obtain the support g-C3N4-montmorillonite;

[0041] (2) Add an aqueous solution of 10 g of nickel nitrate and 0.5 g of manganese nitrate, then add 6 g of the auxiliary agent nitrilotriacetic acid, stir and mix evenly. Then add 300 g of the support g-C3N4-montmorillonite described in step (1) to the mixture, stir at room temperature for 8 hours, and then slowly evaporate the water to dryness to obtain a catalyst precursor. Then pyrolyze the catalyst precursor in an inert atmosphere at 550 °C for 8 h, and finally reduce it in a hydrogen atmosphere at 440 °C for 9 h to obtain the Ni / NiC / Mn / g-C3N4-montmorillonite-based catalyst.

[0042] Example 3

[0043] A method for preparing a 2,2-bis(2-tetrahydrofuranyl)propane compound, comprising the following steps:

[0044] In a 1 L reaction kettle equipped with a mechanical stirrer, a reflux condenser, a temperature controller, add 500.0 g of 2,2-bis(2-furanyl)propane and 25.0 g of a catalyst; displace the air in the reaction kettle with nitrogen 5 times and then displace the nitrogen in the reaction kettle with hydrogen 5 times; then fill the reaction kettle with hydrogen to a pressure of 9 Mpa, start stirring, and start the heat preservation reaction when the reaction temperature rises to 170 °C, and keep the temperature for 8 h. The reaction is completed. Cool to room temperature, and separate the hydrogenation catalyst from the reaction mixture by filtration; then distill the crude product under reduced pressure and then carry out rectification to collect the fraction with a gas phase purity ≥ 98.5% to obtain the 2,2-bis(2-tetrahydrofuranyl)propane product.

[0045] The preparation method of the catalyst comprises the following steps

[0046] (1) Mix 50 g of montmorillonite and 2000 g of deionized water evenly to obtain a mixture, then add 75 g of dicyandiamide to the above mixture, stir at 60 °C for 3 h, and then carry out centrifugal separation. Dry the separated solid and calcine it at 550 °C for 6 h to obtain the support g-C3N4-montmorillonite;

[0047] (2) Add an aqueous solution of 10 g of nickel nitrate and 0.4 g of cobalt nitrate, then add 5 g of the auxiliary agent bipyridine, stir and mix evenly. Then add 250 g of the support g-C3N4-montmorillonite described in step (1) to the mixture, stir at room temperature for 8 hours, and then slowly evaporate the water to dryness to obtain a catalyst precursor. Then pyrolyze the catalyst precursor in an inert atmosphere at 550 °C for 8 h, and finally reduce it in a hydrogen atmosphere at 400 °C for 6 h to obtain the Ni / NiC / Co / g-C3N4-montmorillonite-based catalyst.

[0048] Example 4

[0049] A method for preparing a 2,2-bis(2-tetrahydrofuranyl)propane compound, comprising the following steps:

[0050] In a 1-L reaction kettle equipped with a mechanical stirrer, a reflux condenser, and a temperature controller, 500.0 g of 2,2-bis(2-furyl)propane and 40.0 g of a catalyst were added; the air in the reaction kettle was replaced with nitrogen 5 times and then the nitrogen in the reaction kettle was replaced with hydrogen 5 times; then the reaction kettle was filled with hydrogen to a pressure of 10 Mpa, the stirring was started, and when the reaction temperature rose to 130 °C, the heat preservation reaction was started and maintained for 15 h. The reaction was completed. After cooling to room temperature, the hydrogenation catalyst was separated from the reaction mixture by filtration; then the crude product was distilled under reduced pressure and then rectified, and the fraction with a gas phase purity ≥ 98.5% was collected to obtain the 2,2-bis(2-tetrahydrofuryl)propane product.

[0051] The preparation method of the catalyst includes the following steps

[0052] (1) 50 g of montmorillonite and 2000 g of deionized water were mixed evenly to obtain a mixture, then 30 g of urea was added to the above mixture, and the mixture was stirred at 60 °C for 3 h, and then centrifuged. The separated solid was dried and calcined at 550 °C for 6 h to obtain the support g-C3N4-montmorillonite.

[0053] (2) An aqueous solution of 10 g of nickel nitrate and 0.6 g of iron nitrate was prepared, then 7 g of the auxiliary agent oxalic acid was added and stirred and mixed evenly. Then 400 g of the support g-C3N4-montmorillonite described in step (1) was added to the mixture, and the mixture was stirred at room temperature for 8 h. Then the water was slowly evaporated to dryness to obtain a catalyst precursor. Then the catalyst precursor was pyrolyzed at 600 °C in an inert atmosphere for 8 h, and finally reduced at 450 °C in a hydrogen atmosphere for 6 h to obtain the Ni / NiC / Fe / g-C3N4-montmorillonite-based catalyst.

[0054] Example 5

[0055] A preparation method of a 2,2-bis(2-tetrahydrofuryl)propane compound includes the following steps:

[0056] In a 1-L reaction kettle equipped with a mechanical stirrer, a reflux condenser, and a temperature controller, 500.0 g of 2,2-bis(2-furyl)propane and 25.0 g of a catalyst were added; the air in the reaction kettle was replaced with nitrogen 5 times and then the nitrogen in the reaction kettle was replaced with hydrogen 5 times; then the reaction kettle was filled with hydrogen to a pressure of 7 Mpa, the stirring was started, and when the reaction temperature rose to 150 °C, the heat preservation reaction was started and maintained for 10 h. The reaction was completed. After cooling to room temperature, the hydrogenation catalyst was separated from the reaction mixture by filtration; then the crude product was distilled under reduced pressure and then rectified, and the fraction with a gas phase purity ≥ 98.5% was collected to obtain the 2,2-bis(2-tetrahydrofuryl)propane product.

[0057] The preparation method of the catalyst includes the following steps

[0058] (1) Mix 50 g of montmorillonite and 2000 g of deionized water evenly to obtain a mixture. Then add 35 g of ethylenediamine to the above mixture and stir at 60 °C for 3 h. After that, perform centrifugal separation, and dry the separated solid matter and calcine it at 550 °C for 6 h to obtain the support g-C3N4-montmorillonite;

[0059] (2) Add an aqueous solution of 10 g of nickel nitrate and 0.25 g of europium nitrate, then add 4 g of the auxiliary agent dihydroxyethylglycine, stir and mix evenly. Then add 300 g of the support g-C3N4-montmorillonite described in step (1) to the mixture, stir at room temperature for 8 h, and then slowly evaporate the water to dryness to obtain a catalyst precursor. Then pyrolyze the catalyst precursor in an inert atmosphere at 500 °C for 8 h, and finally reduce it at 450 °C in a hydrogen atmosphere for 8 h to obtain the Ni / NiC / Eu / g-C3N4-montmorillonite-based catalyst.

[0060] Comparative Example 1

[0061] A preparation method of a 2,2-bis(2-tetrahydrofuryl)propane compound, comprising the following steps:

[0062] In a 1 L reaction kettle equipped with a mechanical stirrer, a reflux condenser, a temperature controller, add 500.0 g of 2,2-bis(2-furyl)propane and 25.0 g of a catalyst; displace the air in the reaction kettle with nitrogen 5 times and then displace the nitrogen in the reaction kettle with hydrogen 5 times; then fill the reaction kettle with hydrogen to a pressure of 7 Mpa, start stirring, and start the heat preservation reaction when the reaction temperature rises to 150 °C, and keep the temperature for 10 h. The reaction ends. Cool to room temperature, and separate the hydrogenation catalyst from the reaction mixture by filtration; then distill the crude product under reduced pressure and perform rectification to collect the fraction with a gas phase purity ≥98.5% to obtain the 2,2-bis(2-tetrahydrofuryl)propane product.

[0063] The preparation method of the catalyst comprises the following steps

[0064] Add an aqueous solution of 10 g of nickel nitrate and 1 g of copper nitrate, then add 5 g of the auxiliary agent oxalic acid, stir and mix evenly. Then add 200 g of the support montmorillonite to the mixture, stir at room temperature for 8 h, and then slowly evaporate the water to dryness to obtain a catalyst precursor. Then pyrolyze the catalyst precursor in an inert atmosphere at 550 °C for 8 h, and finally reduce it at 390 °C in a hydrogen atmosphere for 6 h to obtain the Ni / NiC / Cu / montmorillonite-based catalyst.

[0065] Measure the products described in Examples 1-5 and Comparative Example 1, and the specific results are as follows:

[0066]

[0067] The above description illustrates a preferred embodiment of the present invention and should not be construed as limiting the scope of the claims of the present invention. Without departing from the principle and spirit of the present invention, any modification, equivalent replacement, and improvement should be considered within the scope of the claims of the present invention.

Claims

1. A method for preparing a 2,2-bis(2-tetrahydrofuranyl)propane compound, characterized in that, Using 2,2-bis(2-furyl)propane, a hydrogenation catalyst, and hydrogen as raw materials, under the action of a non-precious metal Ni-based catalyst, a 2,2-bis(2-tetrahydrofuryl)propane product shown in formula (II) is prepared by a hydrogenation reaction at a temperature of 100-200 °C: Among them, the hydrogenation catalyst is made of Ni active metal component, metal promoter component, auxiliary agent and carrier g-C3N4-montmorillonite; The preparation method of the catalyst is as follows: (1) Mix montmorillonite and deionized water evenly to obtain a mixture, then add a nitrogen-containing compound to the above mixture, stir at 30-100 °C for 1-5 h, then centrifuge and separate, and dry and calcine the separated solid to obtain the support g-C3N4-montmorillonite; (2) Prepare an aqueous solution of the Ni active metal component and the metal promoter component, then add an auxiliary agent, stir and mix evenly, then add the support g-C3N4-montmorillonite described in step (1) to the mixture, stir at room temperature for 6-12 hours, then slowly evaporate the water to dryness to obtain a catalyst precursor, and then pyrolyze the catalyst precursor in an inert atmosphere at 400-600 °C for 3-9 h, and finally reduce it in a hydrogen atmosphere at 360-480 °C for 4-12 h to obtain the Ni / NiC / X / g-C3N4-montmorillonite-based catalyst, where X is a metal promoter element; In step (1), the mass ratio of montmorillonite to deionized water is 1:30-60, and the mass ratio of montmorillonite to the nitrogen-containing compound is 1:0.5-2. The nitrogen-containing compound is one or more of urea, monocyanamide, dicyandiamide, ethylenediamine, and melamine; In step (2), the Ni active metal component is one or more of nickel chloride, nickel nitrate, and nickel sulfate, and the auxiliary agent is selected from at least one of oxalic acid, bipyridine, nitrilotriacetic acid, and dihydroxyethylglycine; The metal promoter component is selected from at least one of copper nitrate, manganese nitrate, iron nitrate, cobalt nitrate, chromium nitrate, and europium nitrate. The mass ratio of the Ni active metal component to the auxiliary agent is 1.3:2.5, the mass ratio of the Ni active metal component to the metal promoter component is 10:100, and the mass ratio of the support g-C3N4-montmorillonite to the Ni active metal component is 5-50:

1.

2. The method according to claim 1, wherein The hydrogenation reaction conditions of 2,2-bis(2-furyl)propane include: the temperature is 100-200 °C, the time is 4-20 hours, and the reaction pressure is 3-12 MPa.

3. The method according to claim 1, characterized in that, The mass ratio of the amount of 2,2-bis(2-furyl)propane to the catalyst is 1:0.03-0.

50.

4. The method according to claim 2, wherein The hydrogenation reaction conditions include: the temperature is 120-180 °C, the time is 8-15 hours, and the reaction pressure is 6-10 MPa; the mass ratio of the amount of 2,2-bis(2-furyl)propane to the catalyst is 1:0.5-0.

20.

5. The method according to claim 1, characterized in that, The method further includes: after the reaction, cooling the reaction mixture to 5-25 °C, and recovering the hydrogenation catalyst by solid-liquid separation of the cooled mixture.

6. The method according to claim 5, wherein The reaction solution after solid-liquid separation is subjected to vacuum distillation to obtain a 2,2-bis(2-tetrahydrofuryl)propane product.

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