CN114315777A - Resource utilization method of waste containing dehydration by-product and dioxane by-product in production process of lilac pyrans - Google Patents
Resource utilization method of waste containing dehydration by-product and dioxane by-product in production process of lilac pyrans Download PDFInfo
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Abstract
The invention provides a resource utilization method of waste containing a dehydration byproduct and a dioxane byproduct in the production process of lilan pyran. The method can reuse the dehydration byproduct waste in the synthetic process of the lilan pyran, synthesize a valuable product of the lilan pyran, improve the additional value, reduce the production cost and have obvious industrial application value.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a resource utilization method of waste containing dehydration byproducts and dioxane byproducts in a production process of lilan pyrans.
Background
Convallaria pyran, chemically known as 2- (2-methylpropyl) -4-hydroxy-4-methyltetrahydropyran, is a fragrance having a fresh, soft, natural floral aroma and can be applied in virtually all types of perfumes. Since the lilan pyran has no sensitization, the lilan pyran is considered as the most powerful substitute of other lilan perfumes in the future, particularly as a substitute of lilan aldehyde, and the market potential in the future is huge.
The main synthetic method of the Convallaria pyran at present is an isovaleraldehyde method, isovaleraldehyde and 3-methyl-3-butene-1-ol are used as raw materials in the method, and the method has the advantages of low raw material price, short synthetic steps and low cost.
Patent CN1590384A reports that the yield of prenol is 57.5% by using isovaleraldehyde and 3-methyl-3-buten-1-ol as raw materials, and catalyzing the raw materials with a methanesulfonic acid aqueous solution at a reaction temperature of 60 ℃ for 6 hours. Patent CN104529969A reports that BASF uses amberlystTM 131 as a catalyst, adopts a continuous method, takes isovaleraldehyde and 3-methyl-3-butylene-1-alcohol as raw materials, adds 11 wt% of water, and has the reaction temperature of 20-25 ℃, the reaction time of 10h and the yield of 79%. Patent CN105175372A reports the use of solid superacid SO42-/ZrO2And the like as catalysts, adopting a continuous method, taking isovaleraldehyde and 3-methyl-3-butene-1-ol as raw materials, reacting at the temperature of 110 ℃ and 120 ℃ for 2 hours, calculating the yield by using isovaleraldehyde to be 86 percent, and calculating the yield by using isopentenol to be 95 percent.
It can be seen that in the prior art reported in the above patent, the problem of poor selectivity of the reaction is prevalent when starting from isovaleraldehyde and 3-methyl-3-buten-1-ol using acidic catalysts, in particular strong acidic catalysts, with the concomitant production of large quantities of waste materials containing dehydration by-products and dioxane by-products, for which only BASF patent CN 106164062a currently proposes the reuse of dehydration by-products and dioxane by-products, by first converting the dioxane by-product into a dehydration by-product using an acidic catalyst and then obtaining another fragrance dihydrorose oxide by hydrogenation. However, the conventional treatment method adopted by the prior art still treats the waste liquid as waste liquid after separation.
In summary, the present researches on the utilization of waste materials containing dehydrated byproducts and dioxane byproducts obtained in the process of synthesizing lilac pyrans are very few, and in order to improve the added value of products, a more effective method for recycling the waste materials is required.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the lilac pyranA process for reclaiming the waste containing the dewatering by-product and dioxane by-product in the production process features that the waste is used as initial raw material and the supported catalyst Pr6O11-Al2O3-MoO3/WO3Under the action of (praseodymium oxide-aluminum oxide-molybdenum oxide/tungsten oxide), carrying out hydration reaction to prepare the lilac pyrane. The method has simple process, can reuse the dehydration byproduct waste in the synthetic process of the lilac pyrane, and can synthesize a high-value lilac pyrane product with high conversion rate and high selectivity, thereby improving the additional value, reducing the production cost and having obvious industrial application value.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the invention provides a resource utilization method of waste containing dehydration byproducts and dioxane byproducts in the production process of lilan pyrans, which takes the waste containing the dehydration byproducts and the dioxane byproducts in the production process of the lilan pyrans and water as raw materials, and adopts praseodymium oxide-aluminum oxide loaded molybdenum oxide and/or tungsten oxide catalyst (Pr 6O)11-Al2O3-MoO3And/or Pr6O11-Al2O3-WO3) Under the action of the reaction, the lily of the valley pyran is prepared by hydration reaction.
In the invention, the production process of the lilian pyran contains dehydration by-products and dioxane by-product waste materials, and the composition of the waste materials comprises at least one of dehydration by-products I shown in formula 1, dehydration by-products II shown in formula 2, dehydration by-products III shown in formula 3 and optional dioxane by-product IV shown in formula 4;
preferably, the lily of the valley pyran production process contains dehydration by-product and dioxane by-product waste, and the composition of the waste simultaneously contains dehydration by-product I, dehydration by-product II, dehydration by-product III and dioxane by-product IV.
In one embodiment, the waste material from the production of lilac pyrans containing dehydration by-products and dioxane by-products comprises, based on 100% of the total mass:
0 to 50%, preferably 10 to 30%, more preferably 15 to 25% of the dehydration by-product I;
0 to 50%, preferably 10 to 30%, more preferably 15 to 25% of the dehydration by-product II;
0 to 50%, preferably 10 to 30%, more preferably 15 to 25% of the dehydration by-product III;
dioxane by-product IV 0 to 50%, preferably 10 to 30%, more preferably 15 to 25%;
wherein the content of the dehydration byproduct I, the dehydration byproduct II and the dehydration byproduct III is not 0 at the same time.
In the present invention, the waste material containing the dehydration by-product and dioxane by-product in the production process of lilac pyrane is derived from a preparation process using isovaleraldehyde and 3-methyl-3-buten-1-ol as raw materials and using an acidic catalyst, particularly a strongly acidic catalyst, and is a by-product obtained by fractionating and separating lilac pyrane from a reaction mixture, and may contain a small amount of water and acetal in addition to the above components. The preparation process of the lily of the valley pyran is the prior method, the invention has no special requirement, and the technicians can adopt any realizable method for preparation, and the details are not repeated here.
In the invention, the praseodymium oxide-alumina supported molybdenum oxide and/or tungsten oxide catalyst comprises praseodymium oxide-alumina (Pr)6O11-Al2O3) Composite carrier and supported active component molybdenum oxide (MoO)3) And/or tungsten oxide (WO)3)；
Preferably, the loading amount of the active component molybdenum oxide and/or tungsten oxide is 6-26.5 wt%, preferably 10-18 wt% based on the total mass of the catalyst being 100%;
preferably, in the praseodymium oxide-alumina composite carrier, the mass ratio of praseodymium oxide to alumina is 1-1.8: 1, preferably 1 to 1.5: 1.
preferably, the praseodymium oxide-alumina supported molybdenum oxide and/or tungsten oxide catalyst, more preferably praseodymium oxide-alumina supported tungsten oxide.
In the present invention, the praseodymium oxide-alumina supported molybdenum oxide and/or tungsten oxide catalyst is a supported catalyst, and the preparation method thereof is known in the art, and in some embodiments, the praseodymium oxide-alumina supported molybdenum oxide and/or tungsten oxide catalyst can be prepared by the following steps:
1) preparing a composite carrier:
according to the mass ratio of 1: weighing soluble praseodymium salt and soluble aluminum salt at a ratio of 1-1.5, preferably 1:1-1.3, mixing the soluble praseodymium salt and the soluble aluminum salt with water to prepare an aqueous solution with a total concentration of 10-40 wt%, preferably 20-30 wt%, then stirring the aqueous solution at a temperature of 20-40 ℃ for 10-60min, adding ammonia water with a concentration of 5-25 wt%, preferably 10-20 wt% to adjust the pH to 9-11, continuing stirring the aqueous solution for 10-60min, preferably 20-40min, filtering and washing the solution to be neutral, then roasting the solution at a temperature of 500-900 ℃, preferably 600-800 ℃ for 3-12h, preferably 5-9h to obtain a praseodymium oxide-aluminum oxide composite carrier, and crushing the praseodymium oxide-aluminum oxide composite carrier into powder with a particle size of 20-50um for later use;
2) loading active components:
mixing sodium tungstate and/or ammonium molybdate with water to prepare aqueous solution with the total concentration of 5-20 wt%, preferably 10-15 wt%, wherein the total mass of the sodium tungstate and the ammonium molybdate and the composite carrier is 1: 2-7, preferably 1: 3-5, stirring at 20-40 ℃, preferably 30-35 ℃ for 10-60min, preferably 20-40min, drying at 90-150 ℃, preferably 110-.
In step 1) of the present invention, the soluble aluminum salt is selected from aluminum chloride and/or aluminum sulfate, preferably aluminum sulfate;
the soluble praseodymium salt is selected from praseodymium chloride and/or praseodymium sulfate, preferably praseodymium chloride;
in step 2), when a mixture of sodium tungstate and ammonium molybdate is adopted, the mixing mass ratio of sodium tungstate to ammonium molybdate is 1: 1-1.5, preferably 1: 1-1.2.
In step 2) of the invention, the forming agent is selected from polyacrylamide and/or methylcellulose, preferably methylcellulose;
preferably, the addition amount of the forming agent is 2-10%, preferably 5-8% of the dry substance;
preferably, the water is added in an amount of 20-40%, preferably 25-30%, of the mass of the dry matter;
preferably, the shaped granulated particles have a particle size of 0.5 to 6mm, preferably 2 to 4 mm.
In the present invention, the mass ratio of the waste containing the dehydration by-product and dioxane by-product to water is 1:0.5 to 30, preferably 1:1 to 10.
In the present invention, the hydration reaction, preferably carried out in a fixed bed reactor, is carried out at a pressure of 0.1 to 5MPaG, preferably 1 to 3 MPaG; the temperature is 40-90 ℃, preferably 70-85 ℃; the mass space velocity is 0.5-5h-1Preferably 1-2h-1。
In the method, after the reaction is completed, the reaction solution can be separated and purified by a rectifying tower to remove unreacted raw materials and water, then a light component in the system is removed by a light component removal rectifying tower, and finally a pure Convallaria pyran product is obtained by a heavy component removal rectifying tower.
The technical scheme of the invention has the beneficial effects that:
the waste containing the dehydration byproduct obtained in the synthetic process of the lilan pyran is used as the initial raw material, and the lilan pyran is prepared by hydration and reaction with water under the action of the praseodymium oxide-aluminum oxide loaded molybdenum oxide and/or tungsten oxide catalyst, so that the waste containing the dehydration byproduct is recycled, the additional value of the raw material is improved, and the production cost of the lilan pyran is reduced. The method has the advantages of simple process flow, continuous operation, high conversion rate and high selectivity.
Detailed description of the invention
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The source information of the main raw materials adopted in the embodiment of the invention is common commercial raw materials unless otherwise specified:
the waste material sources of dehydration by-products and dioxane by-products are contained in the production process of the lily of the valley pyran:
the conventional synthetic method of the lilypan comprises the following steps: the isovaleraldehyde and the prenyl alcohol react under the catalysis of strong acid, then reactants are rectified, and the lilac pyran is separated under the tower top pressure of 1.1-1.2hPa, the number of tower plates of 20, the reflux ratio of 5:1 and the lateral line extraction temperature of 78 ℃; separating out the residual water and the residual waste after the unreacted raw materials;
solid super acid: HND-31 granularity of the high star novel carbon material Changzhou Limited company: 150 and 220 meshes.
The embodiment of the invention adopts the following main test methods:
gas chromatographic analysis: a chromatographic column: agilent Hp-5 column temperature: maintaining at 40 deg.C for 5 min; heating to 80 deg.C, and maintaining for 0 min; heating to 300 deg.C at 15 deg.C/min, and maintaining for 5 min; sample introduction volume: 0.2ml, classification ratio: 30:1, injection port temperature: 280 ℃, detector temperature: at 300 ℃.
Example 1
Preparation of praseodymium oxide-alumina-supported tungsten oxide catalyst Al2O3-Pr6O11-WO3：
1) Preparing aqueous solution with the concentration of 25 wt% by using 100g of praseodymium chloride and 120g of aluminum chloride, stirring the aqueous solution at the temperature of 33 ℃ for 30min, then slowly dropwise adding ammonia water with the concentration of 15 wt% into the solution to adjust the pH value to 10, continuously stirring the solution for 30min, filtering and washing the solution to be neutral, and roasting the solution at the temperature of 700 ℃ for 6h in an air atmosphere to obtain Al2O3-Pr6O11And (3) compounding the carrier, and grinding into powder with the particle size of 20-50um for later use.
2) 50g of sodium tungstate (dihydrate) is prepared into an aqueous solution with the concentration of 13 wt%, and Al is added2O3-Pr6O11200g of composite carrier, stirring for 30min at 30 ℃, transferring to an oven, drying at 120 ℃ to constant weight, weighing 50g of dried material, adding 3g of forming agent methyl cellulose, adding 14g of water as a lubricant for multiple times, stirring uniformly, forming and granulating by a granulator (the particle size is 5.2mm), putting the formed catalyst into an oven at 130 ℃ to dry to constant weight, and transferring to 75 ℃Roasting for 8 hours at 0 ℃ in the air atmosphere to obtain praseodymium oxide-aluminum oxide supported tungsten oxide catalyst Al2O3-Pr6O11-WO3And the particle size is 5 mm.
Active component WO of catalyst3The loading of (b) was 14.9 wt%;
Al2O3-Pr6O11in the composite carrier, Pr6O11With Al2O3The mass ratio of (A) to (B) is 1.5: 1.
example 2
Preparation of praseodymium oxide-alumina-supported molybdenum oxide catalyst Al2O3-Pr6O11-MoO3：
1) Preparing 100g of praseodymium chloride and 100g of aluminum chloride into 10 wt% aqueous solution, stirring at 20 ℃ for 60min, slowly dropwise adding 5 wt% ammonia water into the solution to adjust the pH to 9, continuously stirring for 10min, filtering, washing to be neutral, and roasting at 500 ℃ in the air atmosphere for 12h to obtain Al2O3-Pr6O11And (3) compounding the carrier, and grinding into powder with the particle size of 20-50um for later use.
2) 50g of ammonium molybdate is prepared into aqueous solution with the concentration of 5 wt%, and Al is added2O3-Pr6O11350g of composite carrier, stirring for 60min at 20 ℃, transferring to an oven, drying at 90 ℃ to constant weight, weighing 50g of dried material, adding 4.5g of forming agent polyacrylamide, adding 17.5g of water for multiple times as a lubricant, stirring uniformly, forming and granulating by a granulator (the particle size is 0.55mm), putting the formed catalyst into the 90 ℃ oven to dry to constant weight, transferring to the 900 ℃ air atmosphere, and roasting for 4h to obtain praseodymium oxide-aluminum oxide supported molybdenum oxide Al2O3-Pr6O11-MoO3And the particle size is 0.5 mm.
Active component WO of catalyst3The loading of (B) was 9.5 wt%;
Al2O3-Pr6O11in the composite carrier, Pr6O11With Al2O3The mass ratio of (A) to (B) is 1.8: 1.
example 3
Preparation of praseodymium oxide-aluminum oxide loaded molybdenum oxide and tungsten oxide Al2O3-Pr6O11-WO3-MoO2：
1) Preparing 100g of praseodymium chloride and 150g of aluminum chloride into 40 wt% aqueous solution, stirring the aqueous solution at 40 ℃ for 10min, slowly dropwise adding 25 wt% ammonia water into the aqueous solution to adjust the pH to 11, continuously stirring the aqueous solution for 30min, filtering and washing the solution to be neutral, and roasting the solution at 800 ℃ in the air atmosphere for 3h to obtain Al2O3-Pr6O11And (3) compounding the carrier, and grinding into powder with the particle size of 20-50um for later use.
2) Sodium tungstate (dihydrate) and ammonium molybdate 25g respectively are prepared into an aqueous solution with the total concentration of 20 wt%, and Al is added2O3-Pr6O11100g of carrier, stirring for 10min at 40 ℃, then transferring into an oven, drying at 150 ℃ to constant weight, taking 50g of dried material, adding 1g of forming agent methyl cellulose, adding 10g of water as a lubricant for multiple times, stirring uniformly, forming and granulating by a granulator (the particle size is 6mm), putting the formed catalyst into the oven at 150 ℃ to dry to constant weight, and then transferring to the air atmosphere at 600 ℃ to roast for 12h to obtain praseodymium oxide-aluminum oxide supported molybdenum oxide and tungsten oxide Al2O3-Pr6O11-WO3-MoO3And the particle size is 5.8 mm.
In catalyst WO3The loading amount is 12.9 wt%, MoO3The loading was 13.5 wt%;
Al2O3-Pr6O11in the composite carrier, Pr6O11With Al2O3The mass ratio of (A) to (B) is 1.2: 1.
example 4
Preparing the lilan pyran by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the production process of the lilan pyran:
waste material containing dehydration by-products and dioxane by-products, the composition of which is 100% by mass:
dehydration by-product I26.8%, dehydration by-product II 24.2%, dehydration by-product III 28.6%, dioxane by-product IV 20.1%, balance water and acetal etc.
The catalyst Pr prepared in example 16O11-Al2O3-WO3Loading into fixed bed reactor, introducing the mixture containing dehydration byproduct and dioxane byproduct waste and water at mass ratio of 1:5 into the reactor, and maintaining at mass space velocity of 1.50h-1And carrying out hydration reaction at the temperature of 80 ℃ under the pressure of 2.0MPaG to prepare the lilac pyrane, after the reaction is stable for 3 hours, sampling and analyzing by a gas phase internal standard method, wherein the total yield is 98.01 percent, and the dr value is as follows: 3.0.
wherein the conversion of dehydration by-product I was 99.7%, the conversion of dehydration by-product II was 99.5%, the conversion of dehydration by-product III was 99.8%, and the conversion of dioxane by-product IV was 99.6%.
Example 5
Preparing the lilan pyran by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the production process of the lilan pyran:
waste material containing dehydration by-products and dioxane by-products, the composition of which is 100% by mass: dehydration by-product I1.52%, dehydration by-product II 49.7%, dehydration by-product III 1.89%, dioxane by-product IV 46.5%, balance water and acetal etc.
The catalyst Pr prepared in example 26O11-Al2O3-MoO3Loading into fixed bed reactor, introducing the mixture containing dehydration byproduct and dioxane byproduct waste and water at mass ratio of 1:30 into the reactor, and keeping the mass space velocity at 0.5h-1And carrying out hydration reaction at 40 ℃ under the pressure of 0.1MPaG to prepare the lilac pyrane, after the reaction is stable for 3 hours, sampling and analyzing by a gas phase internal standard method, wherein the total yield is 97.55 percent, and the dr value is as follows: 2.7.
wherein the conversion of dehydration by-product I was 99.6%, the conversion of dehydration by-product II was 99.4%, the conversion of dehydration by-product III was 99.8%, and the conversion of dioxane by-product IV was 99.5%.
Example 6
Preparing the lilan pyran by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the production process of the lilan pyran:
waste material containing dehydration by-products and dioxane by-products, the composition of which is 100% by mass: dehydration by-product I29.6%, dehydration by-product II 47.5%, dehydration by-product III 16.6%, dioxane by-product IV 5.88%, balance water and acetal etc.
The supported catalyst Pr prepared in example 26O11-Al2O3-MoO3Loading into fixed bed reactor, introducing the mixture containing dehydration byproduct and dioxane byproduct waste and water at mass ratio of 1:30 into the reactor, and keeping the mass space velocity at 0.5h-1And carrying out hydration reaction at 40 ℃ under the pressure of 0.1MPaG to prepare the lilac pyrane, after the reaction is stable for 3 hours, sampling and analyzing by a gas phase internal standard method, wherein the total yield is 97.55 percent, and the dr value is as follows: 2.8. wherein the conversion of dehydration by-product I was 99.5%, the conversion of dehydration by-product II was 99.6%, the conversion of dehydration by-product III was 99.8%, and the conversion of dioxane by-product IV was 99.4%.
Example 7
Preparing the lilan pyran by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the production process of the lilan pyran:
waste material containing dehydration by-products and dioxane by-products, the composition of which is 100% by mass: dehydration by-product I38.2%, dehydration by-product II 10.3%, dehydration by-product III 48.7%, dioxane by-product IV 2.7%, balance water and acetal etc.
The supported catalyst Pr prepared in example 36O11-Al2O3-WO3-MoO3Loading into fixed bed reactor, introducing the mixture containing dehydration byproduct and dioxane byproduct waste and water at mass ratio of 1:1 into the reactor, and maintaining at mass space velocity of 1.0h-1And the pressure is 0.8MPaG, the hydration reaction is carried out at 70 ℃ to prepare the lilac pyrane, after the reaction is stabilized for 3 hours, a sample is taken and analyzed by a gas phase internal standard method, the total yield is 97.45 percent, and the dr value: 2.9.
wherein the conversion of dehydration by-product I was 99.4%, the conversion of dehydration by-product II was 99.6%, the conversion of dehydration by-product III was 99.6%, and the conversion of dioxane by-product IV was 99.7%.
Example 8
Preparing the lilan pyran by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the production process of the lilan pyran:
waste material containing dehydration by-products and dioxane by-products, the composition of which is 100% by mass: dehydration by-product I49.8%, dehydration by-product II 15.8%, dehydration by-product III 16.6%, dioxane by-product IV 17.2%, balance water and acetal etc.
The supported catalyst Pr6O prepared in example 111-Al2O3-WO3Loading into fixed bed reactor, introducing the mixture containing dehydration byproduct and dioxane byproduct waste and water at mass ratio of 1:0.8, and keeping the mass space velocity at 2.0h-1And carrying out hydration reaction at 85 ℃ under the pressure of 6.0MPaG to prepare the lilac pyrane, after the reaction is stable for 3 hours, sampling and analyzing by a gas phase internal standard method, wherein the total yield is 98.0 percent, and the dr value is as follows: 3.0.
wherein the conversion of dehydration by-product I was 99.4%, the conversion of dehydration by-product II was 99.6%, the conversion of dehydration by-product III was 99.3%, and the conversion of dioxane by-product IV was 99.3%.
Example 9
Preparing the lilan pyran by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the production process of the lilan pyran:
waste material containing dehydration by-products and dioxane by-products, the composition of which is 100% by mass: dehydration by-product I2.55%, dehydration by-product II 45.6%, dehydration by-product III 35.8%, dioxane by-product IV 15.6%, balance water and acetal etc.
The supported catalyst Pr6O prepared in example 111-Al2O3-WO3Loading into fixed bed reactor, introducing the mixture containing dehydration byproduct and dioxane byproduct waste and water at mass ratio of 1:0.5, and keeping the mass space velocity at 4.0h-1The pressure is 5.0MPaG, and the hydration reaction is carried out at 88 ℃ to prepare the bellAnd (3) taking a sample to analyze by a gas phase internal standard method after the reaction is stable for 3 hours, wherein the total yield is 97.9 percent, and the dr value: 3.1.
wherein the conversion of dehydration by-product I was 99.1%, the conversion of dehydration by-product II was 99.7%, the conversion of dehydration by-product III was 99.6%, and the conversion of dioxane by-product IV was 99.4%.
Comparative example 1
The method of example 4 is referred to, except that: the catalyst was replaced with solid super acid HND-31, and the sample was analyzed by gas phase internal standard method with a total yield of 42.6% and dr value: 1.4.
wherein the conversion of dehydration by-product I was 70.5%, the conversion of dehydration by-product II was 71.3%, the conversion of dehydration by-product III was 74.4%, and the conversion of dioxane by-product IV was 71.8%.
Comparative example 2
The catalyst was prepared as in example 1, except that in step 1) no aluminium chloride was added, and the other conditions were unchanged, to give the catalyst Pr6O11-WO3。
The method of example 4 is referred to, except that: the catalyst adopts Pr6O11-WO3The sample was analyzed by gas phase internal standard method, the total yield was 70.7%, dr value: 2.0.
wherein the conversion of dehydration by-product I was 86.2%, the conversion of dehydration by-product II was 79.7%, the conversion of dehydration by-product III was 84.5%, and the conversion of dioxane by-product IV was 79.8%.
Comparative example 3
The catalyst was prepared as in example 1, except that no praseodymium chloride was added in step 1) and the other conditions were unchanged to obtain catalyst Al2O3-WO3。
The method of example 4 is referred to, except that: the catalyst adopts Al2O3-WO3Sampling and analyzing by a gas phase internal standard method, wherein the total yield is 76.5 percent, and the dr value is as follows: 2.2.
wherein the conversion of dehydration by-product I was 85.3%, the conversion of dehydration by-product II was 82.6%, the conversion of dehydration by-product III was 84.3%, and the conversion of dioxane by-product IV was 86.6%.
Comparative example 4
The catalyst was prepared as in example 1, except that sodium tungstate in step 2) was replaced by chromium chloride of equal mass, and the other conditions were unchanged to obtain catalyst Al2O3-Pr6O11-CrO3。
The method of example 4 is referred to, except that: the catalyst adopts Al2O3-Pr6O11-CrO3Sampling was analyzed by gas phase internal standard method with an overall yield of 84.5%, dr value: 2.3.
wherein the conversion of dehydration by-product I was 87.5%, the conversion of dehydration by-product II was 87.4%, the conversion of dehydration by-product III was 86.8%, and the conversion of dioxane by-product IV was 87.8%.
Comparative example 5
The catalyst was prepared as in example 1, except that in step 2) sodium tungstate was replaced by equal mass niobium pentachloride, and other conditions were unchanged to obtain catalyst Al2O3-Pr6O11-Nb2O5。
The method of example 4 is referred to, except that: the catalyst adopts Al2O3-Pr6O11-Nb2O5Sampling and analyzing by a gas phase internal standard method, wherein the total yield is 71.6 percent, and the dr value is as follows: 1.9.
wherein the conversion of dehydration by-product I was 88.6%, the conversion of dehydration by-product II was 87.9%, the conversion of dehydration by-product III was 88.3%, and the conversion of dioxane by-product IV was 88.8%.
Comparative example 5
The catalyst was prepared as in example 1, except that in step 2) the composite support was replaced with an equal mass of ZrO, and other conditions were unchanged to obtain a catalyst ZrO-WO3。
The method of example 4 is referred to, except that: the catalyst adopts ZrO-WO3Sampling by gas phase internal standard method analysis, totalYield 67.5%, dr value: 2.0.
wherein the conversion of dehydration by-product I was 70.6%, the conversion of dehydration by-product II was 73.5%, the conversion of dehydration by-product III was 72.4%, and the conversion of dioxane by-product IV was 75.8%.
Claims (10)
1. A resource utilization method of waste materials containing dehydration byproducts and dioxane byproducts in the production process of lilan pyrans is characterized in that the waste materials containing the dehydration byproducts, the dioxane byproducts and water in the production process of the lilan pyrans are used as raw materials, and the lilan pyrans are prepared through hydration reaction under the action of praseodymium oxide-aluminum oxide loaded molybdenum oxide and/or tungsten oxide catalysts.
2. The method according to claim 1, wherein the lily of the valley pyran production process contains dehydration by-products and dioxane by-product waste materials, the composition comprising at least one of dehydration by-product I of formula 1, dehydration by-product II of formula 2, dehydration by-product III of formula 3, and optionally dioxane by-product IV of formula 4;
preferably, the lily of the valley pyran production process contains dehydration by-product and dioxane by-product waste, and the composition of the waste simultaneously contains dehydration by-product I, dehydration by-product II, dehydration by-product III and dioxane by-product IV.
3. The process according to claim 1 or 2, wherein the waste material from the production of lilac pyrans containing dehydration by-products and dioxane by-products consists of, based on 100% of the total mass:
0 to 50%, preferably 10 to 30%, more preferably 15 to 25% of the dehydration by-product I;
0 to 50%, preferably 10 to 30%, more preferably 15 to 25% of the dehydration by-product II;
0 to 50%, preferably 10 to 30%, more preferably 15 to 25% of the dehydration by-product III;
dioxane by-product IV 0 to 80%, preferably 10 to 30%, more preferably 15 to 25%;
wherein the content of the dehydration byproduct I, the dehydration byproduct II and the dehydration byproduct III is not 0 at the same time.
4. The method according to any one of claims 1 to 3, wherein the praseodymium oxide-alumina supported molybdenum oxide and/or tungsten oxide catalyst comprises a praseodymium oxide-alumina composite carrier, and supported active components molybdenum oxide and/or tungsten oxide;
preferably, the loading amount of the active component molybdenum oxide and/or tungsten oxide is 6-26.5 wt%, preferably 10-18 wt% based on the total mass of the catalyst being 100%;
preferably, in the praseodymium oxide-alumina composite carrier, the mass ratio of praseodymium oxide to alumina is 1-1.8: 1, preferably 1 to 1.5: 1.
5. the method of any one of claims 1 to 4, wherein the praseodymium oxide-alumina supported molybdenum oxide and/or tungsten oxide catalyst is praseodymium oxide-alumina supported tungsten oxide.
6. The method according to any one of claims 1 to 5, wherein the praseodymium oxide-alumina supported molybdenum oxide and/or tungsten oxide catalyst is prepared by the following steps:
1) preparing a composite carrier:
according to the mass ratio of 1: weighing soluble praseodymium salt and soluble aluminum salt at a ratio of 1-1.5, preferably 1:1-1.3, mixing with water to prepare an aqueous solution with a total concentration of 10-40 wt%, preferably 20-30 wt%, then stirring at 20-40 ℃ for 10-60min, adding ammonia water with a concentration of 5-25 wt%, preferably 10-20 wt% to adjust the pH to 9-11, continuing stirring for 10-60min, preferably 20-40min, filtering, washing to neutrality, then roasting at 500-;
2) loading active components:
mixing sodium tungstate and/or ammonium molybdate with water to prepare aqueous solution with the total concentration of 5-20 wt%, preferably 10-15 wt%, wherein the total mass of the sodium tungstate and the ammonium molybdate and the composite carrier is 1: 2-7, preferably 1: 3-5, stirring at 20-40 ℃, preferably 30-35 ℃ for 10-60min, preferably 20-40min, drying at 90-150 ℃, preferably 110-.
7. The process according to any one of claims 1 to 6, wherein the praseodymium oxide-alumina supported molybdenum oxide and/or tungsten oxide catalyst is prepared by a process wherein in step 1) the soluble aluminium salt is selected from aluminium chloride and/or aluminium sulphate, preferably aluminium sulphate;
the soluble praseodymium salt is selected from praseodymium chloride and/or praseodymium sulfate, preferably praseodymium chloride.
8. The method according to any one of claims 1 to 7, wherein in the preparation method of the praseodymium oxide-aluminum oxide supported molybdenum oxide and/or tungsten oxide catalyst, in the step 2), when a mixture of sodium tungstate and ammonium molybdate is used, the mixing mass ratio of the sodium tungstate to the ammonium molybdate is 1: 1-1.5, preferably 1: 1-1.2;
the forming agent is selected from polyacrylamide and/or methylcellulose, preferably methylcellulose;
preferably, the addition amount of the forming agent is 2-10%, preferably 5-8% of the mass of the dry substance;
preferably, the water is added in an amount of 20-40%, preferably 25-30%, of the mass of the dry matter;
preferably, the shaped granulated particles have a particle size of 0.5 to 6mm, preferably 2 to 4 mm.
9. The process according to any one of claims 1 to 8, characterized in that the mass ratio of the waste material containing dehydration by-products and dioxane by-products to water is from 1:0.5 to 30, preferably from 1:1 to 10.
10. The process according to any one of claims 1 to 9, characterized in that the hydration reaction, preferably carried out in a fixed bed reactor, is carried out at a pressure of 0.1 to 5MPaG, preferably 1 to 3 MPaG; the temperature is 40-90 ℃, preferably 70-85 ℃; the mass space velocity is 0.5-5h-1Preferably 1-2h-1。
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