Preparation method of metavanadate, ammonium metavanadate and metavanadate

Abstract

The invention discloses a preparation method of metavanadate, ammonium metavanadate and metavanadate, and the preparation method of metavanadate comprises the following steps: hydrolyzing waste metavanadate in water in the presence of alkali to obtain a hydrolysate; the waste metavanadate is a part of reaction liquid obtained by removing products and residual raw materials after the metavanadate participates in the catalytic reaction as a catalyst; extracting the hydrolysate by adopting an organic solvent to obtain an extracted water phase; and reacting the extracted water phase with an oxidizing agent to obtain metavanadate. According to the method disclosed by the invention, waste metavanadate is taken as a raw material, so that waste utilization is realized; meanwhile, the method disclosed by the invention is high in reaction efficiency, few in generated by-products and high in yield; used equipment is simple, and the investment cost is low.

Description

Technical Field

[0001] The invention relates to a preparation method of metavanadate, ammonium metavanadate and metavanadate ester. Background Art

[0002] Metavanadate is an important organic catalyst that can be used in homogeneous reactions to catalyze the synthesis of citral, vitamin A, carotenoids, vitamin E, geraniol, nerol and other compounds.

[0003] For example, CN101381283B discloses a method for continuously producing 3-methyl-2-butenol, which is mainly used to produce citral, isophytol (the main intermediate of vitamin E), synthetic vitamin A, and carotenoid intermediates. It is mentioned that 2-methyl-3-butene-2-ol is used as a raw material and vanadium oxo tetraisoprenolate is used as a catalyst to react and generate 3-methyl-2-butenol. US3925185 discloses the preparation of 3-methyl-2-butenol using linalyl vanadate as a catalyst. JP57045121 discloses the preparation of 3-methyl-2-butenol using vanadate silanol ester as a catalyst.

[0004] During the use of metavanadate catalyst, it is easy to be thermally decomposed into low-valent oxides such as vanadium monoxide, vanadium dioxide, vanadium trioxide, and high-valent vanadium pentoxide. As the metavanadate is continuously decomposed, the catalytic efficiency is greatly reduced. The decomposed vanadium pentoxide is oxidizing and acidic. As the metavanadate is continuously decomposed, the accumulated vanadium pentoxide will lead to an increase in side reactions and a greatly reduced yield. Therefore, after a certain period of use, the metavanadate catalyst needs to be reclaimed and prepared into metavanadate for continued use. There are two major categories of waste vanadic acid catalysts reported so far, namely acid immersion method and alkali incineration method. The acid immersion method is to leach vanadium from the waste catalyst with sulfuric acid, hydrochloric acid, etc. This method will produce a large amount of sulfur-containing and halogen-containing acidic wastewater, which is difficult to handle. The alkali incineration method generally involves mixing the spent catalyst with an alkali such as sodium carbonate and burning it in hot air. This method will produce a large amount of sulfur or nitrogen oxide gas when burning the metavanadate catalyst, polluting the air. In addition, there is a risk of explosion of low-boiling components during the incineration process. The incineration process is also accompanied by serious solid agglomeration and problems such as inability to measure the bottom of the incineration. It has high requirements on equipment and high investment costs. Summary of the invention

[0005] The present invention aims to solve the problem that the existing method for recovering vanadium from waste metavanadate residual liquid is prone to produce waste and has a low yield. A method for recovering vanadium from waste metavanadate residual liquid and reusing vanadium is proposed, and further a method for preparing metavanadate, ammonium metavanadate and metavanadate is proposed. The method of the present invention uses green solvent water as a reaction solvent, has a high yield, a simple process and a low investment cost.

[0006] The present invention solves the above technical problems through the following technical solutions:

[0007] The present invention provides a method for preparing metavanadate, which comprises the following steps:

[0008] (1) hydrolyzing the waste metavanadate in water in the presence of a base to obtain a hydrolysis product;

[0009] The waste metavanadate is the part of the reaction liquid obtained after the metavanadate is used as a catalyst to participate in the catalytic reaction, after removing the product and the remaining raw materials;

[0010] (2) extracting the hydrolyzate with an organic solvent to obtain an extracted aqueous phase;

[0011] (3) The aqueous phase after extraction reacts with an oxidant to obtain metavanadate.

[0012] The three steps of the present invention cooperate with each other. Step (2) of organic matter extraction can remove residual organic matter in the hydrolysis product, thereby avoiding the problem that the organic impurities in the hydrolysis product decompose to produce oxygen during the subsequent oxidation, causing the system to be in an oxygen-rich environment, resulting in a sharp increase in the risk of flammability and explosion. In addition, the inventors found during the experiment that when the first step (i.e., step (1)) does not perform the aforementioned hydrolysis step and directly perform the organic solvent extraction and oxidation steps on the waste metavanadate, the yield of the metavanadate finally obtained will decrease.

[0013] In the present invention, the "part of the reaction liquid obtained after the metavanadate is used as a catalyst to participate in the catalytic reaction, after removing the product and the remaining raw materials" generally includes metavanadate, low-valent vanadium oxide, vanadium pentoxide and other impurities generated during the reaction.

[0014] Among them, the product refers to the target product obtained after the metavanadate is used as a catalyst to participate in the catalytic reaction, and the raw material refers to the raw material in the catalytic reaction in which the metavanadate is used as a catalyst. For example, 2-methyl-3-butene-2-ol is catalyzed by dodecanol metavanadate to obtain 3-methyl-2-butene-1-ol, wherein 2-methyl-3-butene-2-ol is the raw material and 3-methyl-2-butene-1-ol is the product.

[0015] The low-valent oxides are conventional in the art, and generally refer to other vanadium oxides except vanadium pentoxide, such as vanadium monoxide, vanadium dioxide, and vanadium trioxide.

[0016] The metavanadate ester is conventional in the art, for example, an ester substance obtained by the reaction of ammonium metavanadate and alcohol.

[0017] In the present invention, the structure of the metavanadate is shown in formula (1):

[0018]

[0019] R is a hydrocarbon group having more than 5 carbon atoms.

[0020] In some embodiments, the hydrocarbon group is any one of decyl, linalyl, dodecyl, isopentenyl and methylbutenyl, preferably dodecyl, isopentenyl or decyl.

[0021] In some embodiments, the metavanadate is dodecanol metavanadate, isopentenol metavanadate or decanol metavanadate.

[0022] In some of the schemes, the alcohol is an alcohol having a carbon number greater than 5, preferably any one of decanol, linalool, dodecanol, isopentenol and methylbutenol, more preferably dodecanol, isopentenol or decanol.

[0023] In some of the schemes, the weight ratio of the alcohol to the ammonium metavanadate is (1-5):1, preferably (1.5-2.5):1, for example, 1.77:1, 1.88:1, 1.89:1, 1.99:1 or 2:1.

[0024] In some embodiments, the reaction temperature is 100-160°C.

[0025] In some embodiments, the reaction time is 20 to 40 minutes, for example, 30 minutes.

[0026] In some embodiments, the metavanadate is dodecanol metavanadate, isopentenol metavanadate or decanol metavanadate.

[0027] In the present invention, the waste metavanadate preferably satisfies at least one of the following conditions: ① the number of consecutive uses of the metavanadate is ≥15 times, ② the impurity content in the reaction liquid obtained by the catalytic reaction is ≥1%, and ③ the time of the catalytic reaction is ≥ twice the time of the first catalytic reaction using the metavanadate.

[0028] In some of the schemes, the catalytic reaction time is preferably the time taken for the reaction to occur until the mass fraction of the remaining raw material in the reaction solution is less than 2%, where % refers to the percentage of the mass of the remaining raw material to the mass of the reaction solution.

[0029] Herein, "impurity content" refers to the content of the product other than the product, remaining raw materials and metavanadate, and the content may be a mass content or a liquid phase normalized content.

[0030] In some of the schemes, the waste metavanadate is dodecanol metavanadate residual liquid, isopentenol metavanadate residual liquid or decanol metavanadate residual liquid.

[0031] In some of the schemes, step (1) includes: mixing the waste metavanadate, water and alkali and reacting them to obtain a hydrolysis product.

[0032] In some of the embodiments, the base is a CO3-containing 2- One or more of alkali metal salts, alkali metal salts containing OH- and alkali metal alkoxides; the CO3-containing 2- The alkali metal salt is preferably sodium carbonate and / or potassium carbonate; the alkali metal salt containing OH- is preferably sodium hydroxide and / or potassium hydroxide; the alkali metal alkoxide is preferably potassium methoxide and / or sodium methoxide.

[0033] In some of the schemes, the weight ratio of the alkali to the spent metavanadate is (0.2-2):1, preferably (0.2-1):1, such as 0.2:1, 0.23:1, 0.29:1 or 0.32:1.

[0034] In some of the schemes, the ratio of the molar amount of the base to the weight of the waste metavanadate is (0.001-0.1) mol:1 g, preferably (0.001-0.01) mol:1 g, for example 0.005 mol:1 g, 0.006 mol:1 g or 0.008 mol:1 g.

[0035] In some of the schemes, the weight ratio of the water to the spent metavanadate is (1-5):1, for example, 2:1.

[0036] In some embodiments, the reaction temperature of the hydrolysis is 90-110° C., preferably 95-105° C. The reaction temperature of the hydrolysis refers to the temperature of the reaction system.

[0037] In some of the schemes, the reaction time of the hydrolysis is 0.5 to 3 hours, preferably 0.5 to 1 hour.

[0038] In some of the schemes, the spent metavanadate is hydrolyzed by reflux.

[0039] In some of the schemes, the hydrolysis reaction is carried out in a sealed environment with a certain pressure, and the pressure is preferably 0.1-1 MPa.

[0040] In some of the schemes, step (2) includes: mixing the hydrolyzate with an organic solvent, extracting the organic components in the hydrolyzate, and obtaining an extracted aqueous phase.

[0041] In some of the schemes, the organic solvent is a water-insoluble organic solvent; the water-insoluble organic solvent is any one of an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, a furan solvent and an ether solvent, the aromatic hydrocarbon solvent is preferably toluene, the halogenated hydrocarbon solvent is most preferably dichloromethane or chlorobenzene, the aliphatic hydrocarbon solvent is preferably n-heptane or n-hexane, the alicyclic hydrocarbon solvent is preferably cyclohexane, the furan solvent is preferably methyltetrahydrofuran, and the ether solvent is preferably methyl tert-butyl ether.

[0042] In some of the schemes, the weight ratio of the organic solvent to the waste metavanadate is (0.05-1):1, preferably (0.05-0.2):1, for example 0.1:1.

[0043] In some of the schemes, the extraction temperature is 25-105°C, preferably 25-40°C, for example 30°C;

[0044] In some of the schemes, the extraction time is 0.5 to 3 hours, preferably 0.5 to 2 hours, such as 1 hour.

[0045] In some of the schemes, a separation step is further included after the extraction reaction is completed, and the separation step is used to separate the organic component; preferably, the separation step specifically includes: allowing the product of the extraction reaction to stand and separate into layers to obtain an aqueous phase and an organic phase, and removing the organic phase to obtain the extracted product.

[0046] In some of the schemes, in step (3), the oxidant is any one of hydrogen peroxide, tert-butyl peroxide, m-chloroperbenzoic acid and peracetic acid, preferably hydrogen peroxide.

[0047] In some of the schemes, in step (3), the weight ratio of the oxidant to the waste metavanadate is (0.05-1):1, preferably (0.1-0.5):1, such as 0.1:1 or 0.14:1.

[0048] In some of the schemes, in step (3), the reaction temperature is 30-60°C.

[0049] In the present invention, in step (3), the reaction time is preferably such that the content of low-valent vanadium oxide in the oxidation reaction product is ≤ 0.1%. In some schemes, the oxidation time is 0.5 to 1 hour.

[0050] In the present invention, in step (3), the pH value of the reaction solution obtained by the reaction is preferably ≥ 8, for example, pH = 8 to 9. Under this condition, the yield of metavanadate is higher.

[0051] In some of the schemes, when the pH value of the reaction solution obtained by the reaction is less than 8, the step of adjusting the pH value of the reaction solution to ≥ 8 is further included after the reaction is completed.

[0052] In some of the schemes, the step of adjusting the pH value of the reaction solution includes: adding the base to the reaction solution until the pH value of the reaction solution is ≥8.

[0053] In some of the schemes, the preparation method of the metavanadate comprises the following steps:

[0054] (1) mixing the waste metavanadate, water and alkali, and hydrolyzing the waste metavanadate by a reflux method to obtain a hydrolyzate;

[0055] The waste metavanadate is the part of the reaction liquid obtained after the metavanadate is used as a catalyst to participate in the catalytic reaction, after removing the product and the remaining raw materials;

[0056] The metavanadate is dodecanol metavanadate, isopentenol metavanadate or decanol metavanadate;

[0057] The waste metavanadate meets the following conditions: ① the number of times the metavanadate is used continuously is ≥15 times; ② the impurity content of the product obtained by the catalytic reaction is ≥1%; ③ the time of the catalytic reaction is ≥2 times the time of the first catalytic reaction of the metavanadate, and the time of the catalytic reaction is the time taken for the reaction to occur until the mass fraction of the remaining raw material in the reaction solution is less than 2%;

[0058] The waste metavanadate is a residual liquid of dodecanol metavanadate, a residual liquid of isopentenol metavanadate or a residual liquid of decanol metavanadate;

[0059] The alkali is sodium hydroxide or potassium hydroxide;

[0060] The weight ratio of the alkali to the waste metavanadate is (0.2-1):1, such as 0.2:1, 0.23:1, 0.29:1 or 0.32:1;

[0061] The ratio of the molar amount of the base to the weight of the waste metavanadate is (0.001-0.1) mol:1 g, preferably (0.001-0.01) mol:1 g, for example 0.005 mol:1 g, 0.006 mol:1 g or 0.008 mol:1 g;

[0062] The weight ratio of the water to the waste metavanadate is (1-5):1, for example, 2:1;

[0063] The reaction temperature of the hydrolysis is 95-105°C;

[0064] (2) mixing the hydrolyzate with an organic solvent to extract organic components in the hydrolyzate to obtain an extracted aqueous phase;

[0065] The organic solvent is dichloromethane or toluene;

[0066] The weight ratio of the organic solvent to the waste metavanadate is (0.05-0.2):1, for example 0.1:1;

[0067] The extraction temperature is 25-40°C, for example 30°C;

[0068] After the extraction is completed, a separation step is further included, and the separation step specifically includes: allowing the extracted product to stand for stratification to obtain an aqueous phase and an organic phase, and removing the organic phase to obtain the extracted product;

[0069] (3) the aqueous phase after extraction reacts with an oxidant to obtain metavanadate;

[0070] The oxidant is hydrogen peroxide or peracetic acid;

[0071] The weight ratio of the oxidant to the spent metavanadate is (0.1-0.5):1, for example 0.1:1 or 0.14:1.

[0072] The oxidation temperature is 30-60°C;

[0073] The oxidation time is terminated when the content of low-valent vanadium oxide in the oxidation reaction product is ≤ 0.1%.

[0074] The present invention also provides a method for preparing ammonium metavanadate, which comprises the following steps:

[0075] (1) preparing metavanadate by the aforementioned method;

[0076] (2) reacting the metavanadate with an ammonium source to obtain ammonium metavanadate.

[0077] In some of the schemes, the ammonium source is an inorganic ammonium salt or ammonia water; preferably, the inorganic ammonium salt is one or more of ammonium carbonate, ammonium sulfate and ammonium chloride.

[0078] In some embodiments, the temperature of the reaction between the ammonium source and the metavanadate is 30-60°C.

[0079] In some of the schemes, the reaction time of the ammonium source and the metavanadate is 0.5 to 3 hours, preferably 0.5 to 1 hour.

[0080] In some of the schemes, the weight ratio of the ammonium source to the metavanadate is (0.2-5):1, preferably (0.5-3):1, for example 0.59:1, 0.66:1, 0.69:1, 1.65:1, 2.42:1 or 2.44:1.

[0081] In some of the schemes, the molar ratio of the ammonium source to the metavanadate is (1-5):1, preferably (1.5-3):1, for example, 1.51:1, 1.52:1, 1.58:1, 2.24:1 or 2.26:1.

[0082] In some of the schemes, the preparation method of ammonium metavanadate comprises the following steps:

[0083] (1) preparing metavanadate using the aforementioned method for preparing metavanadate, specifically comprising:

[0084] (1.1) mixing the waste metavanadate, water and alkali, and hydrolyzing the waste metavanadate by reflux method to obtain a hydrolysis product;

[0085] The waste metavanadate is the part of the reaction liquid obtained after the metavanadate is used as a catalyst to participate in the catalytic reaction, after removing the product and the remaining raw materials;

[0086] The metavanadate is dodecanol metavanadate, isopentenol metavanadate or decanol metavanadate;

[0087] The waste metavanadate meets the following conditions: ① the number of times the metavanadate is used continuously is ≥15 times; ② the impurity content of the product obtained by the catalytic reaction is ≥1%; ③ the time of the catalytic reaction is ≥2 times the time of the first catalytic reaction of the metavanadate, and the time of the catalytic reaction is preferably the time taken for the reaction to occur until the mass fraction of the remaining raw material in the reaction solution is less than 2%;

[0088] The waste metavanadate is a residual liquid of dodecanol metavanadate, a residual liquid of isopentenol metavanadate or a residual liquid of decanol metavanadate;

[0089] The alkali is sodium hydroxide or potassium hydroxide;

[0090] The weight ratio of the alkali to the waste metavanadate is (0.2-1):1, such as 0.2:1, 0.23:1, 0.29:1 or 0.32:1;

[0091] The ratio of the molar amount of the base to the weight of the waste metavanadate is (0.001-0.1) mol:1 g, preferably (0.001-0.01) mol:1 g, for example 0.005 mol:1 g, 0.006 mol:1 g or 0.008 mol:1 g;

[0092] The weight ratio of the water to the waste metavanadate is (1-5):1, for example, 2:1;

[0093] The reaction temperature of the hydrolysis is 95-105°C;

[0094] (1.2) mixing the hydrolyzate with an organic solvent to extract organic components in the hydrolyzate to obtain an extracted aqueous phase;

[0095] The organic solvent is dichloromethane or toluene;

[0096] The weight ratio of the organic solvent to the waste metavanadate is (0.05-0.2):1, for example 0.1:1;

[0097] The extraction temperature is 25-40°C, for example 30°C;

[0098] After the extraction is completed, a separation step is further included, and the separation step specifically includes: allowing the extracted product to stand for stratification to obtain an aqueous phase and an organic phase, and removing the organic phase to obtain the extracted product;

[0099] (1.3) the aqueous phase after extraction reacts with an oxidant to obtain metavanadate;

[0100] The oxidant is hydrogen peroxide or peracetic acid;

[0101] The weight ratio of the oxidant to the spent metavanadate is (0.1-0.5):1, for example 0.1:1 or 0.14:1.

[0102] The oxidation temperature is 30-60°C;

[0103] The oxidation time is when the content of low-valent vanadium oxide in the oxidation reaction product is ≤ 0.1% as the end point;

[0104] (2) reacting the metavanadate with an ammonium source to obtain ammonium metavanadate;

[0105] The ammonium source is ammonium sulfate or ammonium chloride;

[0106] The reaction temperature of the ammonium source and the metavanadate is 30 to 60° C.

[0107] The weight ratio of the ammonium source to the waste metavanadate is (0.5-3):1, such as 0.59:1, 0.66:1, 0.69:1, 1.65:1, 2.42:1 or 2.44:1;

[0108] The molar ratio of the ammonium source to the metavanadate is (1.5-3):1, for example, 1.51:1, 1.52:1, 1.58:1, 2.24:1 or 2.26:1.

[0109] The present invention also provides a method for preparing a metavanadate, which comprises the following steps:

[0110] (1) preparing ammonium metavanadate by the aforementioned method;

[0111] (2) reacting the ammonium metavanadate with alcohol to obtain metavanadate ester.

[0112] In some of the schemes, the alcohol is an alcohol having a carbon number greater than 5; preferably, the alcohol is any one of decanol, linalool, dodecanol, isopentenol and methylbutenol, and more preferably, the alcohol is dodecanol or isopentenol.

[0113] In some of the schemes, the weight ratio of the alcohol to the ammonium metavanadate is (1-5):1, preferably (1.5-2.5):1, for example, 1.77:1, 1.88:1, 1.89:1, 1.99:1 or 2:1.

[0114] In some embodiments, the reaction temperature is 100-160°C.

[0115] In some embodiments, the reaction time is 20 to 40 minutes, for example, 30 minutes.

[0116] In some of the schemes, the preparation method of the metavanadate comprises the following steps:

[0117] (1) preparing ammonium metavanadate using the aforementioned preparation method of ammonium metavanadate, specifically comprising:

[0118] (1.1) mixing the waste metavanadate, water and alkali, and hydrolyzing the waste metavanadate by reflux method to obtain a hydrolysis product;

[0119] The waste metavanadate is the part of the reaction liquid obtained after the metavanadate is used as a catalyst to participate in the catalytic reaction, after removing the product and the remaining raw materials;

[0120] The metavanadate is dodecanol metavanadate, isopentenol metavanadate or decanol metavanadate;

[0121] The waste metavanadate meets the following conditions: ① the number of times the metavanadate is used continuously is ≥15 times; ② the impurity content of the product obtained by the catalytic reaction is ≥1%; ③ the time of the catalytic reaction is ≥2 times the time of the first catalytic reaction of the metavanadate, and the time of the catalytic reaction is preferably the time taken for the reaction to occur until the mass fraction of the remaining raw material in the reaction solution is less than 2%;

[0122] The waste metavanadate is a residual liquid of dodecanol metavanadate, a residual liquid of isopentenol metavanadate or a residual liquid of decanol metavanadate;

[0123] The alkali is sodium hydroxide or potassium hydroxide;

[0124] The weight ratio of the alkali to the waste metavanadate is (0.2-1):1, such as 0.2:1, 0.23:1, 0.29:1 or 0.32:1;

[0125] The ratio of the molar amount of the base to the weight of the waste metavanadate is (0.001-0.1) mol:1 g, preferably (0.001-0.01) mol:1 g, for example 0.005 mol:1 g, 0.006 mol:1 g or 0.008 mol:1 g;

[0126] The weight ratio of the water to the waste metavanadate is (1-5):1, for example, 2:1;

[0127] The reaction temperature of the hydrolysis is 95-105°C;

[0128] (1.2) mixing the hydrolyzate with an organic solvent to extract organic components in the hydrolyzate to obtain an extracted aqueous phase;

[0129] The organic solvent is dichloromethane or toluene;

[0130] The weight ratio of the organic solvent to the waste metavanadate is (0.05-0.2):1, for example 0.1:1;

[0131] The extraction temperature is 25-40°C, for example 30°C;

[0132] After the extraction is completed, a separation step is further included, and the separation step specifically includes: allowing the extracted product to stand for stratification to obtain an aqueous phase and an organic phase, and removing the organic phase to obtain the extracted product;

[0133] (1.3) the aqueous phase after extraction reacts with an oxidant to obtain metavanadate;

[0134] The oxidant is hydrogen peroxide or peracetic acid;

[0135] The weight ratio of the oxidant to the spent metavanadate is (0.1-0.5):1, for example 0.1:1 or 0.14:1.

[0136] The oxidation temperature is 30-60°C;

[0137] The oxidation time is when the content of low-valent vanadium oxide in the oxidation reaction product is ≤ 0.1% as the end point;

[0138] (2) reacting the metavanadate with an ammonium source to obtain ammonium metavanadate;

[0139] The ammonium source is ammonium sulfate or ammonium chloride;

[0140] The reaction temperature of the ammonium source and the metavanadate is 30 to 60° C.

[0141] The weight ratio of the ammonium source to the waste metavanadate is (0.5-3):1, such as 0.59:1, 0.66:1, 0.69:1, 1.65:1, 2.42:1 or 2.44:1;

[0142] The molar ratio of the ammonium source to the metavanadate is (1.5-3):1, for example, 1.51:1, 1.52:1, 1.58:1, 2.24:1 or 2.26:1;

[0143] (3) reacting the ammonium metavanadate with an alcohol to obtain a metavanadate ester;

[0144] The alcohol is dodecanol, isopentenol or decanol;

[0145] The weight ratio of the alcohol to the ammonium metavanadate is (1.5-2.5):1, such as 1.77:1, 1.88:1, 1.89:1, 1.99:1 or 2:1;

[0146] The reaction temperature is 100-160°C.

[0147] The positive and progressive effects of the present invention are:

[0148] The method of the invention uses waste metavanadate as raw material, thus realizing waste utilization; meanwhile, the method of the invention has high reaction efficiency, generates less by-products and has high yield; the equipment used is simple and the investment cost is low. DETAILED DESCRIPTION

[0149] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0150] The residual liquid in the following embodiments refers to the reaction in which each metavanadate catalyst participates in the catalytic reaction of 2-methyl-3-butene-2-ol to obtain 3-methyl-2-butene-1-ol. After each reaction, the raw material 2-methyl-3-butene-2-ol and the target product 3-methyl-2-butene-1-ol are evaporated, and the remaining part is the catalyst residual liquid. The catalyst residual liquid is used 15 times. After the 15th reaction, the liquid phase normalized content of impurities in the product is 1.1-1.2%. The time of the 15th catalytic reaction is 2-2.2 times the time of the first catalytic reaction. The catalytic reaction time is the time used for the reaction until the mass fraction of the remaining raw material in the reaction liquid is less than 2%. After the 15th reaction, the raw material and the target product are evaporated, and the remaining part is the residual liquid in the following embodiments.

[0151] In the following examples, the yield of each metavanadate = the mass of the metavanadate actually obtained / the theoretical amount of the metavanadate.

[0152] In the following examples, the initial addition amount of dodecanol metavanadate is 468.4 g. After 15 applications, Get 500g The residual liquid of diol metavanadate; the initial addition amount of isopentenol metavanadate is 306.5g, After 15 applications, 500 g of isopentenol metavanadate residual liquid was obtained; the initial addition amount of decyl alcohol metavanadate was 468.3 g, and after 15 applications, 500 g of decyl alcohol metavanadate residual liquid was obtained.

[0153] The metavanadate structure in the following examples is:

[0154]

[0155] Example 1

[0156] Add 468.4 g of dodecanol metavanadate, 500 g of dodecanol metavanadate residual liquid obtained after 15 times of application, 1000 mL of water, and 100 g of sodium hydroxide to a 3000 mL reaction bottle, heat to 95-105 ° C and reflux for 30 minutes, cool to 30 ° C, add 50 g of dichloromethane, extract at an internal temperature of 30 ° C for 1 hour, stand and separate, remove the lower organic phase, add 50 g of hydrogen peroxide at an internal temperature of 30-60 ° C and react for 0.5 hours to obtain an oxidation reaction liquid;

[0157] The amount of sodium metavanadate in the oxidation reaction liquid was determined to be 210.8 g by titration, and the total amount of low-valent vanadium oxides in the oxidation reaction liquid was determined to be ≤0.1% by ion chromatography.

[0158] 140.1 g of ammonium chloride was added to the oxidation reaction solution at an internal temperature of 30-60°C and the reaction was carried out for 0.5 hours. The water-insoluble ammonium metavanadate solid generated by the reaction was rapidly precipitated and 202.3 g of ammonium metavanadate solid was obtained by filtration.

[0159] Solid ammonium metavanadate was dissolved in 380 g of dodecanol at 100-160° C. and reacted for 30 minutes. The dodecanol was evaporated to obtain 463.7 g of the product.

[0160] The product has a normalized content of dodecanol metavanadate of ≥98% through liquid phase detection, and the yield of dodecanol metavanadate reaches 99%.

[0161] Example 2

[0162] Add 468.4 g of dodecanol metavanadate, 500 g of dodecanol metavanadate residual liquid obtained after 15 times of application, 1000 mL of water, and 147.0 g of potassium hydroxide to a 3000 mL reaction bottle, heat to 95-105 ° C and reflux for 30 minutes, cool to 30 ° C, add 50 g of dichloromethane, extract at an internal temperature of 30 ° C for 1 hour, stand and separate, remove the lower organic phase, add 50 g of hydrogen peroxide at an internal temperature of 30-60 ° C and react for 0.5 hours to obtain an oxidation reaction liquid;

[0163] The potassium metavanadate in the oxidation reaction liquid was measured by titration method and the content was 238.8 g. The total amount of low-valent vanadium oxide in the oxidation reaction liquid was measured by ion chromatography and was ≤0.1%.

[0164] 140.1 g of ammonium chloride was added to the clear solution at an internal temperature of 30-60° C. and the reaction was carried out for 0.5 hours. The water-insoluble ammonium metavanadate solid generated by the reaction was rapidly precipitated and 202.4 g of ammonium metavanadate solid was obtained by filtration.

[0165] Solid ammonium metavanadate was dissolved in 358 g of dodecanol at 100-160°C and reacted for 30 minutes. The dodecanol was evaporated to obtain 463.8 g of product.

[0166] The product has a liquid phase normalized content of dodecanol metavanadate of ≥98% through liquid phase detection, and the yield of dodecanol metavanadate reaches 99%.

[0167] Example 3

[0168] Add 468.4 g of dodecanol metavanadate, 500 g of dodecanol metavanadate residue obtained after 15 times of application, 1000 mL of water, and 100 g of sodium hydroxide to a 3000 mL reaction bottle, heat to 95-105 ° C and reflux for 30 minutes, cool to 30 ° C, add 50 g of toluene, extract at an internal temperature of 30 ° C for 1 hour, stand and separate, remove the upper organic phase, add 70 g of peracetic acid at an internal temperature of 30-60 ° C and react for 0.5 hours;

[0169] The amount of sodium metavanadate in the oxidation reaction liquid was determined to be 202.2 g by titration, and the total amount of low-valent vanadium oxides in the oxidation reaction liquid was determined to be ≤0.1% by ion chromatography.

[0170] 140.0 g of ammonium chloride was added to the clear solution at an internal temperature of 30-60° C. and the reaction was carried out for 0.5 hours. The water-insoluble ammonium metavanadate solid generated by the reaction was rapidly precipitated and filtered to obtain 194.1 g of ammonium metavanadate solid.

[0171] Solid ammonium metavanadate was dissolved in 388.1 g of dodecanol at 100-160°C and reacted for 30 minutes. The dodecanol was evaporated to obtain 444.9 g of the product.

[0172] The product was found to be pure dodecanol metavanadate by liquid phase detection, and the yield of dodecanol metavanadate reached 95.0%.

[0173] Example 4

[0174] Add 468.4 g of dodecanol metavanadate, 500 g of dodecanol metavanadate residue obtained after 15 times of application, 1000 mL of water, and 100 g of sodium hydroxide to a 3000 mL reaction bottle, heat to 95-105 ° C and reflux for 30 minutes, cool to 30 ° C, add 50 g of toluene, extract at an internal temperature of 30 ° C for 1 hour, stand and separate, remove the upper organic phase, add 50 g of hydrogen peroxide at an internal temperature of 30-60 ° C and react for 0.5 hours;

[0175] The amount of sodium metavanadate in the oxidation reaction liquid was determined to be 209.5 g by titration, and the total amount of low-valent vanadium oxides in the oxidation reaction liquid was determined to be ≤0.1% by ion chromatography.

[0176] 346.1 g of ammonium sulfate was added to the clear solution at an internal temperature of 30-60°C and reacted for 0.5 hours. The water-insoluble ammonium metavanadate solid generated by the reaction was rapidly precipitated and filtered to obtain 201.1 g of ammonium metavanadate solid.

[0177] The ammonium metavanadate solid was dissolved in 400 g of dodecanol at 100-160° C. and reacted for 30 minutes. The dodecanol was evaporated to obtain 460.9 g of the product.

[0178] The product is pure dodecanol metavanadate through liquid phase detection, and the yield of dodecanol metavanadate reaches 98.4%.

[0179] Example 5

[0180] Add 306.5 g of isopentanol metavanadate obtained by applying 500 g of isopentanol metavanadate residue after 15 times of application, 1000 mL of water, and 161.2 g of sodium hydroxide to a 3000 mL reaction bottle, heat to 95-105° C. and reflux for 30 minutes, cool to 30° C., add 50 g of toluene, extract at an internal temperature of 30° C. for 1 hour, stand and separate, remove the upper organic phase, add 50 g of hydrogen peroxide at an internal temperature of 30-60° C. and react for 0.5 hour;

[0181] The amount of sodium metavanadate in the oxidation reaction liquid was determined to be 220.1 g by titration, and the total amount of low-valent vanadium oxides in the oxidation reaction liquid was determined to be ≤0.1% by ion chromatography.

[0182] After the reaction was completed, 532.4 g of ammonium sulfate was added at an internal temperature of 30-60° C. and the reaction was carried out for 0.5 hours. The water-insoluble ammonium metavanadate solid generated by the reaction was rapidly precipitated and 211.3 g of ammonium metavanadate solid was obtained by filtration.

[0183] Solid ammonium metavanadate was dissolved in 400 g of isopentenol at 100-160°C and reacted for 30 minutes. The isopentenol was evaporated to obtain 303.4 g of product.

[0184] The product is pure isopentenol metavanadate through liquid phase detection, and the yield of isopentenol metavanadate reaches 99%.

[0185] Example 6

[0186] Add 468.3 g of decyl metavanadate, 500 g of decyl metavanadate residue obtained after 15 times of application, 1000 mL of water, and 116.2 g of sodium hydroxide to a 3000 mL reaction bottle, heat to 95-105 ° C and reflux for 30 minutes, cool to 30 ° C, add 50 g of toluene, extract at an internal temperature of 30 ° C for 1 hour, stand and separate, remove the upper organic phase, add 50 g of hydrogen peroxide at an internal temperature of 30-60 ° C and react for 0.5 hours;

[0187] The amount of sodium metavanadate in the oxidation reaction liquid was determined to be 235.4 g by titration, and the total amount of low-valent vanadium oxides in the oxidation reaction liquid was determined to be ≤0.1% by ion chromatography.

[0188] After the reaction was completed, 575.3 g of ammonium sulfate was added at an internal temperature of 30-60° C. and the reaction was carried out for 0.5 hours. The water-insoluble ammonium metavanadate solid generated by the reaction was rapidly precipitated and 226.0 g of ammonium metavanadate solid was obtained by filtration.

[0189] Solid ammonium metavanadate was dissolved in 400 g of decanol at 100-160°C and reacted for 30 minutes. The decanol was evaporated to obtain 463.6 g of product.

[0190] The product is pure decyl alcohol metavanadate through liquid phase detection, and the yield of decyl alcohol metavanadate reaches 99%.

Claims

1. A method for preparing metavanadate, characterized in that: It includes the following steps: (1) hydrolyzing the waste metavanadate in water in the presence of a base to obtain a hydrolysis product; The waste metavanadate is the part of the reaction liquid obtained after the metavanadate is used as a catalyst to participate in the catalytic reaction, after removing the product and the remaining raw materials; (2) extracting the hydrolyzate with an organic solvent to obtain an extracted aqueous phase; (3) The aqueous phase after extraction reacts with an oxidant to obtain metavanadate.

2. The method for preparing metavanadate according to claim 1, characterized in that: The waste metavanadate meets at least one of the following conditions: ① the number of times the metavanadate is used continuously is ≥15 times; ② the impurity content in the reaction liquid obtained by the catalytic reaction is ≥1%; ③ the time of the catalytic reaction is ≥2 times the time of the first catalytic reaction using the metavanadate, and the time of the catalytic reaction is preferably the time used for the reaction until the mass fraction of the remaining raw material in the reaction liquid is less than 2%, and % refers to the percentage of the mass of the remaining raw material to the mass of the reaction liquid; And / or, the waste metavanadate is a residual liquid of dodecanol metavanadate, a residual liquid of isopentenol metavanadate or a residual liquid of decanol metavanadate; And / or, the structure of the metavanadate is shown in formula (1): R is a hydrocarbon group having a carbon number greater than 5, and the hydrocarbon group is preferably any one of decyl, linalyl, dodecyl, isopentenyl and methylbutenyl, and more preferably dodecyl, isopentenyl or decyl; more preferably, the metavanadate is dodecanol metavanadate, isopentenol metavanadate or decanol metavanadate.

3. The method for preparing metavanadate according to claim 1, characterized in that: Step (1) comprises: mixing the waste metavanadate, water and alkali and reacting them to obtain a hydrolysis product; Preferably, the preparation method of the metavanadate satisfies one or more of the following conditions: ① The alkali is a CO3-containing 2- One or more of alkali metal salts, alkali metal salts containing OH- and alkali metal alkoxides; the CO3-containing 2- The alkali metal salt is preferably sodium carbonate and / or potassium carbonate; the alkali metal salt containing OH- is preferably sodium hydroxide and / or potassium hydroxide; the alkali metal alkoxide is preferably potassium methoxide and / or sodium methoxide; ② The weight ratio of the alkali to the waste metavanadate is (0.2-2):1, preferably (0.2-1):1, such as 0.2:1, 0.23:1, 0.29:1 or 0.32:1; ③ The ratio of the molar amount of the base to the weight of the waste metavanadate is (0.001-0.1) mol:1 g, preferably (0.001-0.01) mol:1 g, for example 0.005 mol:1 g, 0.006 mol:1 g or 0.008 mol:1 g; ④ The weight ratio of the water to the waste metavanadate is (1-5):1, for example 2:1; ⑤ The reaction temperature of the hydrolysis is 90-110°C, preferably 95-105°C; ⑥ The reaction time of the hydrolysis is 0.5 to 3 hours, preferably 0.5 to 1 hour.

4. The method for preparing metavanadate according to claim 1, characterized in that: Step (2) comprises: mixing the hydrolyzate with the organic solvent, extracting the organic components in the hydrolyzate to obtain an extracted aqueous phase; Preferably, step (2) satisfies one or more of the following conditions: ① The organic solvent is a water-insoluble organic solvent; the water-insoluble organic solvent is any one of an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, a furan solvent and an ether solvent, the aromatic hydrocarbon solvent is preferably toluene, the halogenated hydrocarbon solvent is very preferably dichloromethane or chlorobenzene, the aliphatic hydrocarbon solvent is preferably n-heptane or n-hexane, the alicyclic hydrocarbon solvent is preferably cyclohexane, the furan solvent is preferably methyltetrahydrofuran, and the ether solvent is preferably methyl tert-butyl ether; ② The weight ratio of the organic solvent to the waste metavanadate is (0.05-1):1, preferably (0.05-0.2):1, for example 0.1:1; ③ The extraction temperature is 25-105°C, preferably 25-40°C, for example 30°C; ④ The extraction time is 0.5 to 3 hours, preferably 0.5 to 2 hours, for example 1 hour; ⑤ After the extraction is completed, a separation step is also included, and the separation step is used to separate the organic component; preferably, the separation step specifically includes: allowing the extracted product to stand and separate into layers to obtain an aqueous phase and an organic phase, and removing the organic phase to obtain the extracted product.

5. The method for preparing metavanadate according to claim 1, characterized in that: Step (3) satisfies one or more of the following conditions: ① The oxidant is any one of hydrogen peroxide, tert-butyl peroxide, m-chloroperbenzoic acid and peracetic acid, preferably hydrogen peroxide; ② The weight ratio of the oxidant to the waste metavanadate is (0.05-1):1, preferably (0.1-0.5):1, for example 0.1:1 or 0.14:1; ③ The reaction temperature is 30-60°C; ④ The reaction time is such that the content of low-valent vanadium oxide in the reaction solution obtained by the reaction is ≤ 0.1% as the end point, for example, the oxidation time is 0.5 to 1 h; ⑤ The pH value of the reaction liquid obtained by the reaction is ≥8; preferably, when the pH value of the reaction liquid obtained by the reaction is <8, the reaction further comprises the step of adjusting the pH value of the reaction liquid to ≥8 after completion; more preferably, the step of adjusting the pH value of the reaction liquid to ≥8 comprises: adding the alkali to the reaction liquid until the pH value of the reaction liquid is ≥8.

6. The method for preparing metavanadate according to claim 1, characterized in that: The preparation method of the metavanadate comprises the following steps: (1) mixing the waste metavanadate, water and alkali, and hydrolyzing the waste metavanadate by a reflux method to obtain a hydrolyzate; The waste metavanadate is the part of the reaction liquid obtained after the metavanadate is used as a catalyst to participate in the catalytic reaction, after removing the product and the remaining raw materials; The metavanadate is dodecanol metavanadate, isopentenol metavanadate or decanol metavanadate; The waste metavanadate meets the following conditions: ① the number of times the metavanadate is used continuously is ≥15 times; ② the impurity content of the product obtained by the catalytic reaction is ≥1%; ③ the time of the catalytic reaction is ≥2 times the time of the first catalytic reaction using the metavanadate, and the time of the catalytic reaction is the time taken for the reaction to occur until the mass fraction of the remaining raw material in the reaction solution is less than 2%; The waste metavanadate is a residual liquid of dodecanol metavanadate, a residual liquid of isopentenol metavanadate or a residual liquid of decanol metavanadate; The alkali is sodium hydroxide or potassium hydroxide; The weight ratio of the alkali to the waste metavanadate is (0.2-1):1, such as 0.2:1, 0.23:1, 0.29:1 or 0.32:1; The ratio of the molar amount of the base to the weight of the waste metavanadate is (0.001-0.01) mol:1 g, for example, 0.005 mol:1 g, 0.006 mol:1 g or 0.008 mol:1 g; The weight ratio of the water to the waste metavanadate is (1-5):1, for example, 2:1; The reaction temperature of the hydrolysis is 95-105°C; (2) mixing the hydrolyzate with an organic solvent to extract organic components in the hydrolyzate to obtain an extracted aqueous phase; The organic solvent is dichloromethane or toluene; The weight ratio of the organic solvent to the waste metavanadate is (0.05-0.2):1, for example 0.1:1; The extraction temperature is 25-40°C, for example 30°C; After the extraction is completed, a separation step is further included, and the separation step specifically includes: allowing the extracted product to stand for stratification to obtain an aqueous phase and an organic phase, and removing the organic phase to obtain the extracted product; (3) adding an oxidant to the extracted product to react to obtain metavanadate; The oxidant is hydrogen peroxide or peracetic acid; The weight ratio of the oxidant to the waste metavanadate is (0.1-0.5):1, for example 0.1:1 or 0.14:1; The reaction temperature is 30-60°C; The reaction time is terminated when the content of low-valent vanadium oxide in the reaction solution obtained by the reaction is ≤0.1%.

7. A method for preparing ammonium metavanadate, characterized in that: It includes the following steps: (1) preparing metavanadate using the method for preparing metavanadate according to any one of claims 1 to 6; (2) reacting the metavanadate with an ammonium source to obtain ammonium metavanadate; Preferably, the preparation method of ammonium metavanadate satisfies one or more of the following conditions: ① The ammonium source is an inorganic ammonium salt or ammonia water. Preferably, the inorganic ammonium salt is one or more of ammonium carbonate, ammonium sulfate and ammonium chloride; ② The reaction temperature of the ammonium source and the metavanadate is 30-60° C.; ③ The reaction time of the ammonium source and the metavanadate is 0.5 to 3 hours, preferably 0.5 to 1 hour; ④ The weight ratio of the ammonium source to the metavanadate is (0.2-5):1, preferably (0.5-3):1, for example, 0.59:1, 0.66:1, 0.69:1, 1.65:1, 2.42:1 or 2.44:1; ⑤ The molar ratio of the ammonium source to the metavanadate is (1-5):1, preferably (1.5-3):1, for example 1.51:1, 1.52:1, 1.58:1, 2.24:1 or 2.26:

1.

8. The method for preparing ammonium metavanadate according to claim 7, characterized in that: The preparation method of the ammonium metavanadate comprises the following steps: (1) preparing metavanadate by the method for preparing metavanadate according to claim 6; (2) reacting the metavanadate with an ammonium source to obtain ammonium metavanadate; The ammonium source is ammonium sulfate or ammonium chloride; The reaction temperature of the ammonium source and the metavanadate is 30 to 60° C. The weight ratio of the ammonium source to the metavanadate is (0.5-3):1, such as 0.59:1, 0.66:1, 0.69:1, 1.65:1, 2.42:1 or 2.44:1; The molar ratio of the ammonium source to the metavanadate is (1.5-3):1, for example, 1.51:1, 1.52:1, 1.58:1, 2.24:1 or 2.26:

1.

9. A method for preparing a metavanadate, characterized in that: It includes the following steps: (1) preparing ammonium metavanadate by the method for preparing ammonium metavanadate according to claim 7 or 8; (2) reacting the ammonium metavanadate with an alcohol to obtain a metavanadate ester; Preferably, the preparation method of the metavanadate satisfies one or more of the following conditions: ① The alcohol is an alcohol having a carbon number greater than 5, preferably any one of decanol, linalool, dodecanol, isopentenol and methylbutenol, preferably dodecanol, isopentenol or decanol; ② The weight ratio of the alcohol to the ammonium metavanadate is (1-5):1, preferably (1.5-2.5):1, such as 1.77:1, 1.88:1, 1.89:1, 1.99:1 or 2:1; ③ The reaction temperature is 100-160°C; ④ The reaction time is 20 to 40 minutes, for example 30 minutes.

10. The method for preparing a metavanadate according to claim 9, characterized in that: The preparation method of the metavanadate comprises the following steps: (1) preparing ammonium metavanadate by the preparation method of ammonium metavanadate according to claim 8; (2) reacting the ammonium metavanadate with an alcohol to obtain a metavanadate ester; The alcohol is dodecanol, isopentenol or decanol; The weight ratio of the alcohol to the ammonium metavanadate is (1.5-2.5):1, such as 1.77:1, 1.88:1, 1.89:1, 1.99:1 or 2:1; The reaction temperature is 100-160°C.

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