CN114315777B - Recycling method of waste containing dehydration byproducts and dioxane byproducts in production process of convallaria majalis - Google Patents
Recycling method of waste containing dehydration byproducts and dioxane byproducts in production process of convallaria majalis Download PDFInfo
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Abstract
The invention provides a resource utilization method of waste materials containing dehydration byproducts and dioxane byproducts in the production process of Convallaria majalis, which takes the waste materials containing the dehydration byproducts and the dioxane byproducts in the production process of Convallaria majalis and water as raw materials, and prepares the Convallaria majalis through hydration reaction under the action of a load type catalyst praseodymium oxide-aluminum oxide load type molybdenum oxide and/or tungsten oxide catalyst. The method can reuse the dehydration byproduct waste in the process of synthesizing the mugwort pyran to synthesize the mugwort pyran which is a valuable product, improves the added value, reduces the production cost and has obvious industrial application value.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a recycling method for waste materials containing dehydration byproducts and dioxane byproducts in the production process of convallaria majalis.
Background
The chemical name of the muguet is 2- (2-methylpropyl) -4-hydroxy-4-methyltetrahydropyran, which is a spice with fresh, soft and natural floral aroma and can be applied to almost all types of perfumes. The convallaria is considered to be the most powerful substitute for other convallaria-type fragrances in the future because of the lack of sensitization, and has great market potential in the future, particularly as a substitute for convaldehyde.
The main synthesis method of the convallaria is an isovaleraldehyde method at present, the isovaleraldehyde and 3-methyl-3-butene-1-ol are used as raw materials, and the method has the advantages of low raw material price, short synthesis steps and low cost.
Patent CN1590384A reports that Japanese Kao corporation uses isovaleraldehyde and 3-methyl-3-butene-1-ol as raw materials, and catalyzed by aqueous solution of methanesulfonic acid at a reaction temperature of 60 DEG CThe reaction time was 6 hours, and the yield was 57.5% based on isopentenol. Patent CN104529969a reports BASF using AmberlystTM 131 as a catalyst, using a continuous process with isovaleraldehyde and 3-methyl-3-buten-1-ol as raw materials, adding 11wt% of water, at 20-25 ℃ for 10h, with a yield of 79%. Patent CN105175372A reports the novel use of solid superacid SO4 2- /ZrO 2 And the like as a catalyst, adopting a continuous method, taking isovaleraldehyde and 3-methyl-3-buten-1-ol as raw materials, wherein the reaction temperature is 110-120 ℃, the reaction time is 2 hours, the yield is 86% calculated by isovaleraldehyde, and the yield is 95% calculated by isopentenol.
It can be seen that in the prior art reported in the above patent, isovaleraldehyde and 3-methyl-3-buten-1-ol are used as raw materials, and an acidic catalyst, particularly a strongly acidic catalyst, is generally used, so that the problem of low selectivity of the reaction is accompanied by the generation of a large amount of waste materials containing dehydration byproducts and dioxane byproducts, and for these waste materials, only BASF patent CN 106164062a currently mentions the reuse of the dehydration byproducts and dioxane byproducts, the method is to convert the dioxane byproducts into the dehydration byproducts by using the acidic catalyst first, and then obtain another perfume, namely the dihydro rose ether through hydrogenation reaction. However, the conventional treatment method adopted by the prior art is still treated as waste liquid after separation for combustion treatment.
In summary, little research is currently being done on the utilization of waste materials containing dehydration byproducts and dioxane byproducts obtained during the synthesis of convalran, and in order to increase the added value of the product, more efficient methods need to be sought to recycle this strand of waste materials.
Disclosure of Invention
The invention provides a resource utilization method of waste containing dehydration byproducts and dioxane byproducts in the production process of the convallaria by taking the waste as a starting material and using a supported catalyst Pr 6 O 11 -Al 2 O 3 -MoO 3 /WO 3 (praseodymium oxide-aluminum oxide-molybdenum oxide/tungsten oxide) and carrying out hydration reaction to obtain the convallaria pyran. The method has simple process and can produce the dehydration byproduct in the process of synthesizing the convallariaThe waste is reused, the high-value muguet pyran product is synthesized with high conversion rate and high selectivity, the added value is improved, the production cost is reduced, and the method has remarkable industrial application value.
In order to achieve the above object, the present invention is realized by the following technical scheme:
the invention provides a recycling method for waste materials containing dehydration byproducts and dioxane byproducts in the production process of Convallaria majalis, which takes the waste materials containing the dehydration byproducts and the dioxane byproducts in the production process of Convallaria majalis and water as raw materials, and loads molybdenum oxide and/or tungsten oxide catalyst (Pr 6O) on praseodymium oxide-aluminum oxide 11 -Al 2 O 3 -MoO 3 And/or Pr6O 11 -Al 2 O 3 -WO 3 ) Under the action, the convallaria can be prepared through hydration reaction.
In the invention, the production process of the convallaria comprises a dehydration byproduct and a dioxane byproduct waste, wherein the composition comprises at least one of the dehydration byproduct I shown in a formula 1, the dehydration byproduct II shown in a formula 2 and the dehydration byproduct III shown in a formula 3, and optionally a dioxane byproduct IV shown in a formula 4;
preferably, the convallaria pyran production process comprises a dehydration byproduct and a dioxane byproduct waste, and the composition of the convallaria pyran production process comprises a dehydration byproduct I, a dehydration byproduct II, a dehydration byproduct III and a dioxane byproduct IV.
In a specific embodiment, the process for producing the convallaria pyran comprises the steps of, based on 100% of the total mass, dehydrating by-products and dioxane by-product waste:
dehydration by-product I0-50%, preferably 10-30%, more preferably 15-25%;
0-50%, preferably 10-30%, more preferably 15-25% of dehydration by-product II;
from 0 to 50%, preferably from 10 to 30%, more preferably from 15 to 25% of the dehydration by-product III;
0-50%, preferably 10-30%, more preferably 15-25% of dioxane by-product IV;
wherein the contents of the dehydration byproducts I, II and III are different and are 0.
In the invention, the process for producing the mugwort pyran contains dehydration byproducts and dioxane byproducts waste, which are derived from the preparation process of using isovaleraldehyde and 3-methyl-3-butene-1-ol as raw materials and using an acidic catalyst, particularly a strong acid catalyst, and is a byproduct obtained by separating the mugwort pyran from a reaction mixture through rectification, and a small amount of water, acetal and the like can be added in addition to the components. The preparation process of the mugwort pyran is an existing method, the invention has no special requirement, and the technician can adopt any realizable method for preparation, and the details are not repeated here.
In the present invention, the praseodymium oxide-aluminum oxide supported molybdenum oxide and/or tungsten oxide catalyst comprises praseodymium oxide-aluminum oxide (Pr 6 O 11 -Al 2 O 3 ) Composite support, and supported active component molybdenum oxide (MoO) 3 ) And/or tungsten oxide (WO) 3 )；
Preferably, the loading of the active component molybdenum oxide and/or tungsten oxide is 6 to 26.5wt%, preferably 10 to 18wt%, based on 100% of the total mass of the catalyst;
preferably, in the praseodymium oxide-aluminum oxide composite carrier, the mass ratio of praseodymium oxide to aluminum oxide is 1-1.8:1, preferably 1-1.5:1.
preferably, the praseodymium oxide-aluminum oxide supported molybdenum oxide and/or tungsten oxide catalyst is more preferably praseodymium oxide-aluminum oxide supported tungsten oxide.
In the present invention, the praseodymium oxide-aluminum oxide 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-aluminum oxide supported molybdenum oxide and/or tungsten oxide catalyst may be prepared by the following steps:
1) Preparing a composite carrier:
according to the mass ratio of 1:1-1.5, preferably 1:1-1.3, weighing soluble praseodymium salt and soluble aluminum salt, mixing with water to prepare an aqueous solution with the total concentration of 10-40wt%, preferably 20-30wt%, stirring for 10-60min at 20-40 ℃, adding ammonia water with the concentration of 5-25wt%, preferably 10-20wt% to adjust the PH to 9-11, continuously stirring for 10-60min, preferably 20-40min, filtering and washing to neutrality, roasting for 3-12h, preferably 5-9h at 500-900 ℃, preferably 600-800 ℃ to obtain a praseodymium oxide-aluminum oxide composite carrier, and crushing into powder with the granularity of 20-50um for later use;
2) Loading active components:
mixing sodium tungstate and/or ammonium molybdate with water to prepare an aqueous solution with the total concentration of 5-20wt%, preferably 10-15wt%, wherein the total mass of the sodium tungstate and the ammonium molybdate and the composite carrier are 1:2-7, preferably 1:3-5, stirring for 10-60min at 20-40 ℃, preferably 30-35 ℃, preferably 20-40min, drying to constant weight at 90-150 ℃, preferably 110-130 ℃, adding a forming agent and water into the dried substance for forming granulation, drying to constant weight at 90-150 ℃, preferably 110-130 ℃, and roasting for 4-12h, preferably 6-9h at 600-900 ℃, preferably 700-800 ℃ to obtain the praseodymium oxide-aluminum oxide supported molybdenum oxide and/or tungsten oxide catalyst.
In step 1) of the present invention, 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;
in the step 2) of the invention, when a mixture of sodium tungstate and ammonium molybdate is adopted, the mixing mass ratio of the sodium tungstate to the ammonium molybdate is 1:1-1.5, preferably 1:1-1.2.
In step 2) of the present invention, the forming agent is selected from polyacrylamide and/or methylcellulose, preferably methylcellulose;
preferably, the molding agent is added in an amount of 2-10%, preferably 5-8% of the dry matter;
preferably, the water is added in an amount of 20-40%, preferably 25-30% of the dry matter;
preferably, the shaped granulation particles have a particle size of 0.5-6mm, preferably 2-4mm.
In the present invention, the mass ratio of the waste material containing the dehydration byproducts and the dioxane byproducts to water is 1:0.5-30, preferably 1:1-10.
In the present invention, the hydration reaction is preferably carried out in a fixed bed reactor at a pressure of 0.1 to 5MPaG, preferably 1 to 3MPaG; the temperature is 40-90 ℃, preferably 70-85 ℃; the mass airspeed is 0.5-5h -1 Preferably 1-2h -1 。
In the method, after the reaction is finished, the reaction liquid can be separated and purified by a rectifying tower to remove unreacted raw materials and water, then the light components in the system are removed by a light component removal rectifying tower, and finally the convallaria majalis pure product is obtained by a heavy component removal rectifying tower, which is a routine operation in the field, and the method is not particularly limited.
The technical scheme of the invention has the beneficial effects that:
the invention takes the waste material containing the dehydration byproducts obtained in the process of synthesizing the convallaria by taking as the initial raw material, and the convallaria is prepared by hydration and reaction with water under the action of the praseodymium oxide-aluminum oxide supported molybdenum oxide and/or tungsten oxide catalyst, thereby recycling the waste material containing the dehydration byproducts, improving the added value of the raw material and reducing the production cost of the convallaria. The method has the advantages of simple process flow, continuous operation, high conversion rate and high selectivity.
Detailed description of the preferred embodiments
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The main raw material source information adopted in the embodiment of the invention is common commercial raw materials unless otherwise specified:
the process for producing the convallaria comprises the steps of:
the conventional synthesis method of the muguet pyran comprises the following steps: reacting isovaleraldehyde with prenyl alcohol under the catalysis of strong acid, then removing reactants, rectifying, and separating the mugwort pyran at the side line extraction temperature of 78 ℃ under the pressure of 1.1-1.2hPa at the top of the tower and with the number of tower plates of 20, the reflux ratio of 5:1; separating out excessive water and unreacted raw materials, and then, remaining waste;
solid superacid: novel carbon material Changzhou Co Ltd HND-31 particle size: 150-220 mesh.
The main test method adopted by the embodiment of the invention comprises the following steps:
gas chromatography analysis: chromatographic column: agilent Hp-5 column temperature: maintaining at 40deg.C for 5min; heating to 80deg.C, and maintaining for 0min; heating to 300 ℃ at 15 ℃/min, and keeping for 5min; sample injection volume: 0.2ml, classification ratio: 30:1, sample inlet temperature: 280 ℃, detector temperature: 300 ℃.
Example 1
Preparation of praseodymium oxide-aluminum oxide supported tungsten oxide catalyst Al 2 O 3 -Pr 6 O 11 -WO 3 ：
1) 100g of praseodymium chloride and 120g of aluminum chloride are prepared into an aqueous solution with the concentration of 25wt percent, the aqueous solution is stirred for 30min at the temperature of 33 ℃, then ammonia water with the concentration of 15wt percent is slowly added into the solution in a dropwise manner to adjust the PH to be 10, the stirring is continued for 30min, after filtering and washing to be neutral, the mixture is roasted for 6h at the temperature of 700 ℃ in the air atmosphere, and Al is obtained 2 O 3 -Pr 6 O 11 And (3) rolling the composite carrier 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 weight percent, and Al is added 2 O 3 -Pr 6 O 11 200g of composite carrier, stirring for 30min at 30 ℃, transferring into a baking oven, drying to constant weight at 120 ℃, weighing 50g of dried product, adding 3g of forming agent methyl cellulose, adding 14g of water for multiple times as a lubricant, stirring uniformly, forming and granulating by a granulator (particle size is 5.2 mm), baking the formed catalyst into constant weight in the baking oven at 130 ℃, transferring to air atmosphere at 750 ℃ and baking for 8h to obtain praseodymium oxide-aluminum oxide supported tungsten oxide catalyst Al 2 O 3 -Pr 6 O 11 -WO 3 The particle size is 5mm.
Active component WO in the catalyst 3 Is 14.9 wt.%;
Al 2 O 3 -Pr 6 O 11 pr in composite carrier 6 O 11 With Al 2 O 3 The mass ratio of (2) is 1.5:1.
example 2
Preparation of praseodymium oxide-aluminum oxide supported molybdenum oxide catalyst Al 2 O 3 -Pr 6 O 11 -MoO 3 ：
1) 100g of praseodymium chloride and 100g of aluminum chloride are prepared into an aqueous solution with the concentration of 10wt percent, the aqueous solution is stirred for 60min at the temperature of 20 ℃, then 5wt percent ammonia water is slowly added into the solution to adjust the PH to be 9, the stirring is continued for 10min, and after filtering and washing to be neutral, the solution is roasted for 12h in an air atmosphere at the temperature of 500 ℃ to obtain Al 2 O 3 -Pr 6 O 11 And (3) rolling the composite carrier into powder with the particle size of 20-50um for later use.
2) 50g of ammonium molybdate was added to prepare an aqueous solution having a concentration of 5wt%, and Al was added 2 O 3 -Pr 6 O 11 350g of composite carrier, stirring for 60min at 20 ℃, transferring into a baking oven, drying to constant weight at 90 ℃, weighing 50g of dried product, adding 4.5g of polyacrylamide as a forming agent, adding 17.5g of water for multiple times as a lubricant, stirring uniformly, forming and granulating by a granulator (particle size of 0.55 mm), putting the formed catalyst into the baking oven at 90 ℃, baking to constant weight, transferring to an air atmosphere at 900 ℃ and baking for 4h to obtain praseodymium oxide-aluminum oxide loaded molybdenum oxide Al 2 O 3 -Pr 6 O 11 -MoO 3 The particle size is 0.5mm.
Active component WO in the catalyst 3 Is 9.5wt%;
Al 2 O 3 -Pr 6 O 11 pr in composite carrier 6 O 11 With Al 2 O 3 The mass ratio of (2) is 1.8:1.
example 3
Preparation of praseodymium oxide-aluminum oxide supported molybdenum oxide and tungsten oxide Al 2 O 3 -Pr 6 O 11 -WO 3 -MoO 2 ：
1) 100g of praseodymium chloride and 150g of aluminum chloride are prepared into an aqueous solution with the concentration of 40wt percent, the aqueous solution is stirred for 10min at the temperature of 40 ℃, then 25wt percent of ammonia water is slowly added into the solution to adjust the PH to be 11, the stirring is continued for 30min, and the aqueous solution is filtered and washedWashing to neutrality, and calcining at 800deg.C in air atmosphere for 3 hr to obtain Al 2 O 3 -Pr 6 O 11 And (3) rolling the composite carrier into powder with the particle size of 20-50um for later use.
2) 25g of sodium tungstate (dihydrate) and ammonium molybdate are respectively prepared into an aqueous solution with the total concentration of 20 weight percent, and Al is added 2 O 3 -Pr 6 O 11 100g of carrier, stirring for 10min at 40 ℃, transferring into a baking oven, drying at 150 ℃ to constant weight, taking 50g of dried product, adding 1g of methyl cellulose as a forming agent, adding 10g of water for multiple times as a lubricant, stirring uniformly, forming and granulating by a granulator (particle size is 6 mm), putting the formed catalyst into the baking oven at 150 ℃ to constant weight, transferring to the air atmosphere at 600 ℃ and roasting for 12h to obtain praseodymium oxide-aluminum oxide loaded molybdenum oxide and tungsten oxide Al 2 O 3 -Pr 6 O 11 -WO 3 -MoO 3 The particle size is 5.8mm.
WO in the catalyst 3 The loading is 12.9wt percent, moO 3 The loading was 13.5wt%;
Al 2 O 3 -Pr 6 O 11 pr in composite carrier 6 O 11 With Al 2 O 3 The mass ratio of (2) is 1.2:1.
example 4
Preparing the muguet by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the muguet production process:
waste material containing dehydration byproducts and dioxane byproducts, the composition of which comprises, based on 100% of the total mass:
26.8% of dehydration byproduct I, 24.2% of dehydration byproduct II, 28.6% of dehydration byproduct III, 20.1% of dioxane byproduct IV, and the balance of water, acetal and the like.
Catalyst Pr prepared in example 1 6 O 11 -Al 2 O 3 -WO 3 Filling the mixture into a fixed bed reactor, introducing the mixture containing the dehydration byproducts, the dioxane byproducts, the waste and the water in a mass ratio of 1:5 into the reactor, and carrying out mass space velocity for 1.50h -1 Hydration reaction at 80 deg.C and 2.0MPaG pressure to prepare the convallaria pyranAfter 3h of reaction had stabilized, samples were taken and analyzed by gas phase internal standard method with a total yield of 98.01%, dr value: 3.0.
wherein the conversion of the dehydration by-product I is 99.7%, the conversion of the dehydration by-product II is 99.5%, the conversion of the dehydration by-product III is 99.8%, and the conversion of the dioxane by-product IV is 99.6%.
Example 5
Preparing the muguet by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the muguet production process:
waste material containing dehydration byproducts and dioxane byproducts, the composition of which comprises, based on 100% of the total mass: dehydration by-product I1.52%, dehydration by-product II 49.7%, dehydration by-product III 1.89%, dioxane by-product IV 46.5%, and the balance water and acetal, etc.
Catalyst Pr prepared in example 2 6 O 11 -Al 2 O 3 -MoO 3 Filling the mixture into a fixed bed reactor, introducing the mixture containing the dehydration byproducts, the dioxane byproducts, the waste materials and the water in a mass ratio of 1:30 into the reactor, and carrying out mass space velocity for 0.5h -1 Hydration reaction is carried out at 40 ℃ under the pressure of 0.1MPaG to prepare the convallaria, after the reaction is stable for 3 hours, sampling is carried out by a gas phase internal standard method, the total yield is 97.55%, and the dr value is: 2.7.
wherein the conversion of the dehydration by-product I is 99.6%, the conversion of the dehydration by-product II is 99.4%, the conversion of the dehydration by-product III is 99.8%, and the conversion of the dioxane by-product IV is 99.5%.
Example 6
Preparing the muguet by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the muguet production process:
waste material containing dehydration byproducts and dioxane byproducts, the composition of which comprises, based on 100% of the total mass: dehydration by-product I29.6%, dehydration by-product II 47.5%, dehydration by-product III16.6%, dioxane by-product IV 5.88%, and the balance water and acetal, etc.
Supported catalyst Pr prepared in example 2 6 O 11 -Al 2 O 3 -MoO 3 Filling the mixture into a fixed bed reactor, introducing the mixture containing the dehydration byproducts, the dioxane byproducts, the waste materials and the water in a mass ratio of 1:30 into the reactor, and carrying out mass space velocity for 0.5h -1 Hydration reaction is carried out at 40 ℃ under the pressure of 0.1MPaG to prepare the convallaria, after the reaction is stable for 3 hours, sampling is carried out by a gas phase internal standard method, the total yield is 97.55%, and the dr value is: 2.8. wherein the conversion of the dehydration by-product I is 99.5%, the conversion of the dehydration by-product II is 99.6%, the conversion of the dehydration by-product III is 99.8%, and the conversion of the dioxane by-product IV is 99.4%.
Example 7
Preparing the muguet by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the muguet production process:
waste material containing dehydration byproducts and dioxane byproducts, the composition of which comprises, based on 100% of the total mass: dehydration by-product I38.2%, dehydration by-product II 10.3%, dehydration by-product III 48.7%, dioxane by-product IV 2.7%, and the balance water and acetal, etc.
Supported catalyst Pr prepared in example 3 6 O 11 -Al 2 O 3 -WO 3 -MoO 3 Filling the mixture into a fixed bed reactor, introducing the mixture containing the dehydration byproducts, the dioxane byproducts, the waste and the water in a mass ratio of 1:1 into the reactor, and taking a mass space velocity of 1.0h -1 Hydration reaction is carried out at 70 ℃ under the pressure of 0.8MPaG to prepare the convallaria, after the reaction is stable for 3 hours, sampling is carried out by a gas phase internal standard method, the total yield is 97.45%, and the dr value is: 2.9.
wherein the conversion of the dehydration by-product I is 99.4%, the conversion of the dehydration by-product II is 99.6%, the conversion of the dehydration by-product III is 99.6%, and the conversion of the dioxane by-product IV is 99.7%.
Example 8
Preparing the muguet by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the muguet production process:
waste material containing dehydration byproducts and dioxane byproducts, the composition of which comprises, based on 100% of the total mass: 49.8% of dehydration byproduct I, 15.8% of dehydration byproduct II, 16.6% of dehydration byproduct III, 17.2% of dioxane byproduct IV, and the balance of water, acetal and the like.
Supported catalyst Pr6O prepared in example 1 11 -Al 2 O 3 -WO 3 Filling the mixture into a fixed bed reactor, introducing the mixture containing the dehydration byproducts, the dioxane byproducts, the waste and the water in a mass ratio of 1:0.8 into the reactor, and controlling the mass space velocity to be 2.0h -1 Hydration reaction is carried out at the temperature of 85 ℃ and the pressure of 6.0MPaG to prepare the mugwort pyran, after the reaction is stable for 3 hours, sampling is carried out by a gas phase internal standard method, the total yield is 98.0 percent, and the dr value is: 3.0.
wherein the conversion of the dehydration by-product I is 99.4%, the conversion of the dehydration by-product II is 99.6%, the conversion of the dehydration by-product III is 99.3%, and the conversion of the dioxane by-product IV is 99.3%.
Example 9
Preparing the muguet by utilizing waste materials containing dehydration byproducts and dioxane byproducts in the muguet production process:
waste material containing dehydration byproducts and dioxane byproducts, the composition of which comprises, based on 100% of the total mass: dehydration by-product I2.55%, dehydration by-product II45.6%, dehydration by-product III 35.8%, dioxane by-product IV 15.6%, and the balance water and acetal, etc.
Supported catalyst Pr6O prepared in example 1 11 -Al 2 O 3 -WO 3 Filling the mixture into a fixed bed reactor, introducing the mixture containing the dehydration byproducts, the dioxane byproducts, the waste and the water in a mass ratio of 1:0.5 into the reactor, and controlling the mass space velocity to be 4.0h -1 Hydration reaction is carried out at the temperature of 88 ℃ and the pressure of 5.0MPaG to prepare the mugwort pyran, after the reaction is stable for 3 hours, sampling is carried out by a gas phase internal standard method, the total yield is 97.9%, and the dr value is: 3.1.
wherein the conversion of the dehydration by-product I is 99.1%, the conversion of the dehydration by-product II is 99.7%, the conversion of the dehydration by-product III is 99.6%, and the conversion of the dioxane by-product IV is 99.4%.
Comparative example 1
The process of example 4 differs only in that: the catalyst was replaced with solid superacid HND-31, and the total yield was 42.6% with dr value as analyzed by gas phase internal standard method: 1.4.
wherein the conversion of the dehydration by-product I is 70.5%, the conversion of the dehydration by-product II is 71.3%, the conversion of the dehydration by-product III is 74.4%, and the conversion of the dioxane by-product IV is 71.8%.
Comparative example 2
A catalyst was prepared according to the procedure of example 1 except that in step 1), no aluminum chloride was added, and the other conditions were unchanged, to obtain a catalyst Pr6O 11 -WO 3 。
The process of example 4 differs only in that: pr6O is adopted as a catalyst 11 -WO 3 Samples were analyzed by gas phase internal standard method with a total yield of 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
A catalyst was prepared according to the procedure of example 1 except that praseodymium chloride was not added in step 1), and other conditions were unchanged, to prepare catalyst Al 2 O 3 -WO 3 。
The process of example 4 differs only in that: the catalyst adopts Al 2 O 3 -WO 3 Samples were analyzed by gas phase internal standard method with a total yield of 76.5%, dr value: 2.2.
wherein the conversion of the dehydration by-product I is 85.3%, the conversion of the dehydration by-product II is 82.6%, the conversion of the dehydration by-product III is 84.3%, and the conversion of the dioxane by-product IV is 86.6%.
Comparative example 4
A catalyst was prepared as in example 1, except that sodium tungstate was replaced with equal mass of chromium chloride in step 2), with the other conditions unchanged, to obtain catalyst Al 2 O 3 -Pr 6 O 11 -CrO 3 。
The process of example 4 differs only in that: the catalyst adopts Al 2 O 3 -Pr 6 O 11 -CrO 3 The samples were 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
A catalyst was prepared as in example 1, except that sodium tungstate was replaced with equal mass of niobium pentachloride in step 2), with the other conditions unchanged, to obtain catalyst Al 2 O 3 -Pr 6 O 11 -Nb 2 O 5 。
The process of example 4 differs only in that: the catalyst adopts Al 2 O 3 -Pr 6 O 11 -Nb 2 O 5 Samples were analyzed by gas phase internal standard method for a total yield of 71.6%, dr value: 1.9.
wherein the conversion of the dehydration by-product I is 88.6%, the conversion of the dehydration by-product II is 87.9%, the conversion of the dehydration by-product III is 88.3%, and the conversion of the dioxane by-product IV is 88.8%.
Comparative example 5
A catalyst was prepared in the same manner as in example 1 except that the composite support in step 2) was replaced with an equal mass of ZrO, and the other conditions were unchanged, to prepare a catalyst ZrO-WO 3 。
The process of example 4 differs only in that: the catalyst adopts ZrO-WO 3 Samples were analyzed by gas phase internal standard method with a total yield of 67.5%, dr value: 2.0.
wherein the conversion of the dehydration by-product I is 70.6%, the conversion of the dehydration by-product II is 73.5%, the conversion of the dehydration by-product III is 72.4%, and the conversion of the dioxane by-product IV is 75.8%.
Claims (24)
1. A recycling method for waste materials containing dehydration byproducts and dioxane byproducts in the production process of the convallaria by taking the waste materials containing the dehydration byproducts and the dioxane byproducts and water in the production process of the convallaria as raw materials is characterized in that the convallaria by being prepared by hydration reaction under the action of a praseodymium oxide-aluminum oxide supported molybdenum oxide and/or tungsten oxide catalyst;
the production process of the convallaria comprises a dehydration byproduct and a dioxane byproduct waste, wherein the composition comprises at least one of a dehydration byproduct I shown in a formula (1), a dehydration byproduct II shown in a formula (2), a dehydration byproduct III shown in a formula (3) and a dioxane byproduct IV shown in a formula (4);
2. the method of claim 1, wherein the process for producing the convalran comprises a dehydration byproduct and a dioxane byproduct waste material, the composition of which comprises a dehydration byproduct I, a dehydration byproduct II, a dehydration byproduct III, and a dioxane byproduct IV.
3. The method according to claim 1, wherein the process for producing the convalran comprises the steps of, based on 100% of the total mass, dehydrating by-products and dioxane by-product waste:
10-30% of dehydration byproduct I;
10-30% of dehydration byproduct II;
10-30% of dehydration byproduct III;
10-30% of dioxane by-product IV.
4. A process according to claim 3, wherein the process for producing the convallaria comprises a waste of dehydrated byproducts and dioxane byproducts, the composition comprising, based on 100% of the total mass:
15-25% of dehydration byproduct I;
15-25% of dehydration byproduct II;
15-25% of dehydration byproduct III;
15-25% of dioxane by-product IV.
5. The method according to claim 1, wherein the praseodymium oxide-aluminum oxide supported molybdenum oxide and/or tungsten oxide catalyst comprises a praseodymium oxide-aluminum oxide composite carrier and a supported active component molybdenum oxide and/or tungsten oxide;
the loading of the active component molybdenum oxide and/or tungsten oxide is 6-26.5wt% based on 100% of the total mass of the catalyst.
6. The method according to claim 5, wherein the loading of the active component molybdenum oxide and/or tungsten oxide is 10-18wt%, based on 100% of the total mass of the catalyst.
7. The method according to claim 5, wherein the mass ratio of praseodymium oxide to aluminum oxide in the praseodymium oxide-aluminum oxide composite carrier is 1 to 1.8:1.
8. the method according to claim 7, wherein the mass ratio of praseodymium oxide to aluminum oxide in the praseodymium oxide-aluminum oxide composite carrier is 1 to 1.5:1.
9. the method of claim 1, wherein the praseodymium-alumina supported molybdenum oxide and/or tungsten oxide catalyst is praseodymium-alumina supported tungsten oxide.
10. The method according to claim 1, wherein the praseodymium oxide-aluminum oxide supported molybdenum oxide and/or tungsten oxide catalyst is prepared by the steps of:
1) Preparing a composite carrier:
according to the mass ratio of 1:1-1.5, weighing soluble praseodymium salt and soluble aluminum salt, mixing with water to prepare an aqueous solution with the total concentration of 10-40wt%, stirring for 10-60min at 20-40 ℃, adding ammonia water with the concentration of 5-25wt% to adjust the PH to 9-11, continuously stirring for 10-60min, filtering, washing to be neutral, roasting for 3-12h at 500-900 ℃ to obtain a praseodymium oxide-aluminum oxide composite carrier, and crushing into powder with the granularity of 20-50 mu m for later use;
2) Loading active components:
mixing sodium tungstate and/or ammonium molybdate with water to prepare an aqueous solution with the total concentration of 5-20wt%, wherein the total mass of the sodium tungstate and the ammonium molybdate and the composite carrier are 1: adding praseodymium oxide-aluminum oxide composite carrier in a mass ratio of 2-7, stirring for 10-60min at 20-40 ℃, drying at 90-150 ℃ to constant weight, adding forming agent and water into the dried product for forming granulation, drying at 90-150 ℃ to constant weight, and roasting at 600-900 ℃ for 4-12h to obtain the praseodymium oxide-aluminum oxide supported molybdenum oxide and/or tungsten oxide catalyst.
11. The method according to claim 10, wherein in the preparation method of the praseodymium-alumina supported molybdenum oxide and/or tungsten oxide catalyst, in step 1), the soluble aluminum salt is selected from aluminum chloride and/or aluminum sulfate;
the soluble praseodymium salt is selected from praseodymium chloride and/or praseodymium sulfate.
12. The method according to claim 10, 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 sodium tungstate to ammonium molybdate is 1:1 to 1.5;
the forming agent is selected from polyacrylamide and/or methylcellulose.
13. The method according to claim 12, wherein the mixing mass ratio of sodium tungstate to ammonium molybdate is 1:1-1.2.
14. The method according to claim 10, wherein in step 2), the molding agent is added in an amount of 2 to 10% of the dry mass.
15. The method of claim 14, wherein the shaping agent is added in an amount of 5-8% of the dry mass.
16. The method according to claim 10, wherein in step 2), the water is added in an amount of 20-40% of the dry mass.
17. The method of claim 16, wherein the water is added in an amount of 25-30% of the dry mass.
18. The method according to claim 10, wherein in step 2), the shaped granulation particles have a particle size of 0.5-6mm.
19. The method of claim 18, wherein the shaped granulation particles have a particle size of 2-4mm.
20. The method of claim 1, wherein the mass ratio of waste containing dehydration byproducts and dioxane byproducts to water is 1:0.5-30.
21. The method of any one of claims 1-8, wherein the mass ratio of waste containing dehydration byproducts and dioxane byproducts to water is 1:1-10.
22. The process according to claim 1, wherein the hydration reaction is carried out at a pressure of 0.1 to 5MPaG, a temperature of 40 to 90 ℃ and a mass space velocity of 0.5 to 5 hours -1 。
23. The method of claim 22, wherein the hydration reaction is carried out at a pressure of 1-3MPaG, a temperature of 70-85 ℃ and a mass space velocity of 1-2h -1 。
24. The method of claim 1, wherein the hydration reaction is carried out in a fixed bed reactor.
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