CN109304162B - Method for producing acrylic acid from glycerol - Google Patents
Method for producing acrylic acid from glycerol Download PDFInfo
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- CN109304162B CN109304162B CN201710628240.XA CN201710628240A CN109304162B CN 109304162 B CN109304162 B CN 109304162B CN 201710628240 A CN201710628240 A CN 201710628240A CN 109304162 B CN109304162 B CN 109304162B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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Abstract
The invention relates to a method for producing acrylic acid by glycerol, which mainly solves the problem of low yield of acrylic acid in the process for synthesizing acrylic acid by glycerol in the prior art, and the method for producing acrylic acid by glycerol comprises the steps of contacting a raw material containing glycerol and a raw material containing oxygen with a catalyst, carrying out dehydration reaction on the glycerol to generate acrolein, and further oxidizing the acrolein into acrylic acid; the catalyst comprises a carrier and an active component, wherein the active component comprises at least one of Pt, Re and Rh, so that the technical problem is well solved, and the catalyst can be used in the industrial production of synthesizing acrylic acid from glycerol.
Description
Technical Field
The present invention relates to a process for producing acrylic acid from glycerol.
Background
Acrylic acid (CH)2CH — COOH) is the simplest unsaturated carboxylic acid, which is an important organic synthetic raw material and synthetic resin monomer. Acrylic acid is mainly used for synthesizing high-grade water-absorbent resin, a water treatment agent and the like, a part of acrylic acid is used for esterification to prepare acrylic esters such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and the like, and an acrylic ester polymer is mainly applied to the fields of adhesives, coatings, textiles, plastics, leather, paper making and the like.
Acrylic acid and series products thereof are rapidly developed in recent years, the worldwide production of acrylic acid and esters thereof has reached 770 million t/a in 2015, which is increased by about 27% compared with 607 million t/a at the end of 2013, and the current production devices of acrylic acid are mainly concentrated in the United states, Europe, Japan and China, wherein China is the country where the production capacity of acrylic acid is fastest in recent years, and China exceeds the United states and Europe at the same time in 2012, and has become the world with the largest production capacity of acrylic acid devices. The large-scale equipment for industrially producing acrylic acid all over the world adopts propylene oxidation technology, which has been in the history for decades, and a great deal of technology development makes the production process perfect. However, with the decrease of fossil raw materials and the increase of environmental protection pressure, research on how to use renewable raw materials instead of fossil raw materials for preparing chemicals is increasing, and particularly, the preparation of acrylic acid from glycerol, a natural byproduct obtained from biodiesel products, as a raw material is receiving great attention.
To date, many patents have granted inventions concerning catalysts for a process for producing acrylic acid from acrolein, most of which are catalysts containing molybdenum-vanadium (Mo-V), such as chinese patents CN 1070468C, CN 1031488A, CN 1146438A, CN 100378058C, CN 1031050C, CN 1169619C, CN 1583261a and CN 1146439a, etc., and the catalysts described in these patents are mostly prepared by a process in which a multimetal compound is made into a solution in the presence of a solvent or water, an insoluble oxide is added thereto, evaporated to dryness under heating and stirring, and then calcined, pulverized and molded. However, the element composition described in the currently published patents has a large difference, for example, the main components of the catalyst disclosed in chinese patent CN 1169619C are molybdenum, vanadium and copper, and necessary tellurium is added, so that tellurium is considered to make the active phase molybdenum oxide and copper molybdate of the catalyst more stable, and can delay the deactivation of the catalyst due to Mo loss; the catalyst disclosed in the chinese patent CN 1583261a is a composite compound composed of (i) molybdenum, vanadium, and copper as main active components, (ii) a stabilizing component at least composed of titanium and antimony, and (iii) nickel, iron, silicon, aluminum, alkali metal, and alkaline earth metal; the catalyst disclosed in chinese patent CN 1050779C comprises the elements molybdenum, vanadium, tungsten, copper and nickel in the form of oxides; chinese patent CN 1146439a discloses a catalyst containing molybdenum, vanadium, copper and one or more of the elements tungsten, niobium, tantalum, chromium and cerium, and an oxo metal oxide of HT copper molybdate structure type containing copper, molybdenum and at least one element selected from the elements tungsten, vanadium, niobium and tantalum.
A large number of studies on the preparation of acrolein by dehydration of glycerol have been reported, for example, in patent CN101070276A, which reported the use of acidic molecular sieves as catalysts200 ℃ at 500 ℃, the pressure of 0.001-3.0MPa and the liquid space velocity of 0.1-100h-1The yield of acrylic acid can reach 70-80%, but the molecular sieve catalyst has the problem of poor high-temperature hydrothermal property: in patents CN102936190A, CN102936189A and CN102942462A, pyridine, imidazole and quaternary ammonium salt ionic liquid are used as catalysts, under the condition that the reaction temperature is 250-350 ℃ and the molar ratio of the ionic liquid to glycerol is 0.1:100-1.5:100, acrolein is prepared by liquid phase dehydration of glycerol, the conversion rate of the glycerol is 100 percent, the yield of the product acrolein is 30.5-68.2 percent, but the ionic liquid catalyst has higher cost and the production efficiency is not as high as that of a fixed bed reactor. Patent CN 105498845A adopts supercritical CO2The CsPW/Zr-MCM-41 catalyst prepared in the environment has the glycerol conversion rate of 65.2-100% and the acrolein selectivity of 56.8-85.4%, but the supercritical condition has high requirements on equipment and large investment.
But the acrylic acid yield of the catalyst in the prior art is low.
Disclosure of Invention
The technical problem to be solved by the invention is that the yield of acrylic acid in the catalyst for preparing acrylic acid by dehydrating and oxidizing glycerol in the prior art is low, and the invention provides a novel method for preparing acrylic acid by dehydrating and oxidizing glycerol, which can efficiently convert non-petroleum-derived glycerol into acrylic acid and has the characteristic of high yield of acrylic acid.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for producing acrylic acid from glycerol comprises contacting a glycerol-containing raw material and an oxygen-containing raw material with a catalyst, performing dehydration reaction on the glycerol to generate acrolein, and further oxidizing the acrolein into acrylic acid; the catalyst comprises a carrier and an active component, wherein the active component comprises at least one selected from Pt, Re and Rh.
In the technical scheme, the reaction temperature is preferably 200-550 ℃, and more preferably 250-350 ℃.
In the technical scheme, the pressure is preferably 0.1-100 bar, and more preferably 0.1-50 bar. In the present invention, unless otherwise specified, the pressures are gauge pressures.
In the above technical scheme, the reactor is not particularly limited, and a tank type, a fixed bed or a fluidized bed reactor may be used, and the fixed bed is preferred in view of production efficiency and catalyst life.
In the above technical scheme, the glycerol-containing raw material may further contain a solvent, the solvent may be water, a hydrocarbon of C6-C20, and the hydrocarbon may be an alkane or an aromatic hydrocarbon.
In the above technical scheme, when the glycerol-containing raw material contains a solvent, the concentration of glycerol is not particularly limited, and those skilled in the art can reasonably select, for example, but not limited to, the concentration of glycerol in the raw material is 10-70% by weight, such as 15%, 20%, 25%, 30%, 35%, 40%, 45%, and the like. More preferably 20 to 50%.
By way of non-limiting example, the oxygen may be pure oxygen, air, oxygen-rich, oxygen-poor, oxygen and N2Mixture, oxygen and inert gas mixture, air and N2Mixtures, mixtures of air and inert gases, and the like.
In the above technical scheme, the space velocity of the raw material is not particularly limited, and may be reasonably selected by those skilled in the art, for example, but not limited to, the gas volume space velocity of the raw material is 50-5000 hours-1More preferably 80 to 1000 hours-1。
The molar ratio of oxygen to glycerol is not particularly limited and can be reasonably determined by one skilled in the art, such as but not limited to 0.5 to 5, such as but not limited to 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.5, 2, 3, etc., but preferably 0.8 to 3.
In the above technical scheme, the content of the active component in the catalyst is preferably more than 0g/L and less than 50g/L, such as but not limited to 0.1g/L, 0.5g/L, 1g/L, 5g/L, 10g/L, 15g/L, 20g/L, 30g/L, 40g/L and the like.
In the above technical scheme, the carrier preferably comprises alumina, silica, titanium oxide, molecular sieve, rare earth oxide, activated carbon, graphene and Nb2O5、P2O5And clay.
In the above technical solution, the carrier preferably comprises alumina and silicaTitanium oxide, molecular sieve, rare earth oxide, active carbon, graphene and Nb2O5、P2O5And a mixture of at least two of the clays.
In the above technical solution, the carrier more preferably comprises Nb2O5And P2O5A composite oxide of composition, when the composite oxide is represented by the following chemical formula in terms of atomic ratio:
NbPaOx
wherein a is the molar ratio of P to Nb, x is the number of oxygen atoms satisfying the stoichiometric ratio, and a is greater than 0 and less than 15, most preferably greater than 0 and 1.2 or less. By way of non-limiting example, a can be 0.131, 0.231, 0.331, 0.431, 0.531, 0.631, 0.731, 0.831, 0.931, 1.0, 1.0131, 1.131, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and the like.
In the above technical solution, as one of preferable technical solutions, the active component includes both Ru and Pt, and Ru and Pt have an interaction promoting effect in increasing the yield of acrylic acid. The ratio of Ru to Pt is not particularly limited, but is not limited to a weight ratio of Ru to Pt of 0.0131 to 100, more preferably 0.131 to 10, and may be, as non-limiting specific examples, 0.231, 0.331, 0.531, 1, 1.531, 2.031, 2.531, 3, 4, 5, 6, 7, 8, 9, and the like.
In the above technical solution, as a second preferred technical solution, the active component simultaneously includes Ir and Pt, and Ir and Pt have an interaction promoting effect in increasing the yield of acrylic acid. The ratio of Ir and Pt is not particularly limited, but for example, the weight ratio of Ir to Pt is not limited to 0.0131 to 100, more preferably 0.131 to 10, and may be, as non-limiting specific examples, 0.231, 0.331, 0.531, 1, 1.531, 2.031, 2.531, 3, 4, 5, 6, 7, 8, 9, and the like.
The most preferable technical scheme is that the active components simultaneously comprise Pt, Ru and Ir, the Ru and the Ir have synergistic effect on improving the yield of acrylic acid in the presence of Pt, and the three have combined effect on improving the yield of the acrylic acid. The ratio of Ru, Ir and Pt is not particularly limited, such as but not limited to Ru, Ir and Pt being 1 (0.0131-100): 0.0131-100), further 1 (0.131-10): 0.131-10).
The catalyst adopted by the invention can be prepared by adopting a method comprising the following steps:
(1) mixing the compound solution of the active component with a carrier;
(2) and (4) roasting.
In the above technical solution, the temperature for the calcination in the step (2) is preferably 200-. For example, but not limited to, 300 deg.C, 400 deg.C, 500 deg.C, 600 deg.C, 700 deg.C, 800 deg.C, more preferably 400-600 deg.C.
In the above technical scheme, the roasting time in the step (2) is preferably 0.5-100 hours. For example, but not limited to, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 10 hours, 20 hours, 30 hours, and more preferably 3 to 10 hours.
In the above technical scheme, the mixture obtained by mixing in step (1) is preferably dried and then roasted in step (2). The drying temperature is preferably 50 to 200 ℃, for example, but not limited to, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, etc. The drying time is preferably 1 to 100 hours, for example, but not limited to, 5 hours, 6 hours, 8 hours, 9 hours, 10 hours, 12 hours, 24 hours, 36 hours, 72 hours, and the like.
In the above technical solution, the atmosphere for the calcination in the step (2) is preferably an oxidizing atmosphere or an inert atmosphere. The oxidizing atmosphere is preferably an oxygen-containing atmosphere, such as, but not limited to, water vapor, oxygen, air, a mixture of oxygen-containing gas and N2 (and/or inert gas)); the inert atmosphere is selected from at least one of nitrogen and an inert gas such as, but not limited to, at least one selected from He, Ne, and Ar).
In the above embodiment, the oxidizing atmosphere in the step (2) is preferably air for economic reasons.
When the carrier adopts a structure comprising Nb2O5And P2O5When a composite oxide is formed, it is not limited toBy way of qualitative example, the composite oxide may be prepared by a method comprising the steps of:
(i) mixing a niobium-containing compound with a phosphorus-containing compound;
(ii) and (4) roasting.
In the above technical solution, there may be a crystallization step between the step (ii) and the step (i), and there may also be a drying step after the crystallization and before the step (ii).
In the above technical solution, the mixture obtained in step (i) preferably comprises a crystallization step, and the crystallization step is performed only on the crystallized mixture in step (ii). The crystallization temperature can be selected from 90 to 150 ℃ (such as, but not limited to, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ and the like), and the crystallization time can be selected from 5 to 40 hours (such as, but not limited to, 10 hours, 15 hours, 20 hours, 24 hours, 30 hours, 35 hours and the like).
In the above technical solution, the temperature for the calcination in the step (ii) is preferably 200-.
In the above technical scheme, the roasting time in the step (ii) is preferably 0.5-100 hours. For example, but not limited to, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, 10 hours, 20 hours, 30 hours, and more preferably 3 to 10 hours.
In the above technical solution, the atmosphere for the calcination in the step (ii) is preferably an oxidizing atmosphere or an inert atmosphere. (oxidizing atmospheres are preferably oxygen-containing atmospheres such as, but not limited to, water vapor, oxygen, air, mixtures of oxygen-containing gases with N2 (and/or inert gases)); the inert atmosphere is selected from at least one of nitrogen and an inert gas such as, but not limited to, at least one selected from He, Ne, and Ar).
In the above embodiment, the oxidizing atmosphere in the step (ii) is preferably air for economic reasons.
In the above embodiment, the niobium-containing compound may be, for example, niobium oxalate or niobium tartrate, without limitation.
In the above embodiment, as non-limiting examples of the phosphorus-containing compound, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, and normal or acidic salts of the above acids, such as ammonium salts thereof (for example, but not limited to, ammonium phosphate, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate), and the like can be given.
The key point of the catalyst of the present invention is not in the geometry and size of the carrier, so there is no particular limitation on the shape and size of the carrier, and various shapes and sizes of existing carriers can be used in the present invention and comparable results are obtained. For example, the carrier of the present invention may take the form of a sphere, raschig ring, or cylinder, etc. The spherical diameter can be preferably 3-5 mm; the outer diameter of the raschig ring can be preferably 4-7 mm, the inner diameter is preferably 1.5-3 mm, and the length is preferably 3-5 mm; the cylindrical outer diameter can be preferably 4-7 mm, and the length is preferably 3-5 mm.
The carrier of the present invention is not particularly limited in the manner of shaping, and those commonly used in the art can be selected, such as but not limited to rolling balls, extruding strips, or sheeting; the person skilled in the art can also select the shaping auxiliaries necessary for shaping as appropriate.
The compound of the active ingredient is not particularly limited.
For example, compounds of Ru can be, but are not limited to, ruthenium trichloride, potassium homoruthenate, and the like; the compound of Os may be, but is not limited to, potassium osmate, etc.; the compound of Ir may be, but is not limited to, iridium trichloride, iridium tetrachloride, ammonium chloroiridate, potassium hexachloroiridate, and the like; the compound of Pt may be, but is not limited to, chloroplatinic acid, potassium hexachloroplatinate, potassium chloroplatinite, etc.; the compound of Au may be, but is not limited to, gold tetrachloride, etc.
The solvent used for the compound solution of the active ingredient is not particularly limited, but water is preferred as the solvent in view of safety and economy.
In the examples given below, the evaluation conditions for the investigation of the catalyst were:
a reactor: fixed bed reactor, internal diameter 25.4 mm, reactor length 1500 mm
Catalyst loading: 200ml of
Mass concentration of glycerol aqueous solution: 30 percent of
Reaction temperature: 330 deg.C (when the glycerin water solution has gasified)
Volume space velocity after glycerol gasification: 100 hours-1
Air volume space velocity: 1000 hours1
Reaction time: 2000h
The reaction product was absorbed with 0 diluted acid dissolved in 1L deionized water and the product was analyzed by gas chromatography. And calculating the carbon balance, wherein the carbon balance is effective data when the carbon balance is (95-105)%.
Glycerol conversion and product yield are defined as:
by adopting the catalyst of the invention, the yield of the acrylic acid is up to more than 70 percent, and a better technical effect is obtained.
The invention is further illustrated by the following examples:
Detailed Description
Example 1:
400ml of commercially available SiO are taken2Uniformly mixing carrier powder, 20g of graphite and 40g of deionized water, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing the graphite-graphite composite material
Raschig ring carrier particles of (1).
3.5g platinum tetrachloride (PtCl)4) Dissolving in 100g water to obtain a platinum tetrachloride aqueous solution, taking 200ml carrier particles, pouring the platinum tetrachloride aqueous solution into the carrier particles, fully stirring, drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain the catalyst, wherein the catalytic activity is shown in Table 1.
Example 2:
take 400ml ofSelling TiO2Uniformly mixing carrier powder, 20g of graphite and 40g of deionized water, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing the graphite-graphite composite material
Raschig ring carrier particles of (1).
5.2g of ruthenium trichloride hydrate (RuCl)3·3H2O) is dissolved in 100g of water to obtain a ruthenium trichloride aqueous solution, 200ml of carrier particles are taken, the ruthenium trichloride aqueous solution is poured into the carrier particles, the mixture is fully stirred, the mixture is dried at 120 ℃ and roasted at 500 ℃ for 2 hours to obtain the catalyst, and the catalytic activity is shown in table 1.
Example 3:
taking 400ml of commercial niobium pentoxide carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
Raschig ring carrier particles of (1).
3.6g IrCl trichloride hydrate3·3H2O) is dissolved in 100g of water to obtain iridium trichloride aqueous solution, 200ml of carrier particles are taken, the iridium trichloride aqueous solution is poured into the carrier particles, the mixture is fully stirred, the mixture is dried at 120 ℃ and roasted at 500 ℃ for 2 hours to obtain the catalyst, and the catalytic activity is shown in table 1.
Example 4:
taking 400ml of commercial niobium pentoxide carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
Raschig ring carrier particles of (1).
3.5g platinum tetrachloride (PtCl)4) Dissolving in 100g water to obtain a platinum tetrachloride aqueous solution, taking 200ml carrier particles, pouring the platinum tetrachloride aqueous solution into the carrier particles, fully stirring, drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain the catalyst, wherein the catalytic activity is shown in Table 1.
Example 5:
taking 400ml of commercial niobium pentoxide carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
Raschig ring carrier particles of (1).
5.2g of ruthenium trichloride hydrate (RuCl)3·3H2O) is dissolved in 100g of water to obtain a ruthenium trichloride aqueous solution, 200ml of carrier particles are taken, the ruthenium trichloride aqueous solution is poured into the carrier particles, the mixture is fully stirred, the mixture is dried at 120 ℃ and roasted at 500 ℃ for 2 hours to obtain the catalyst, and the catalytic activity is shown in table 1.
Comparative example:
400ml of commercial phosphorus pentoxide carrier powder, 20g of graphite and 40g of deionized water are taken, a violent exothermic reaction occurs in the mixing process, the forming cannot be carried out, and the preparation of the catalyst is stopped.
Example 6:
2mol of niobium oxalate (Nb (HC) are added2O4)5·6H2O) was dissolved in 1L of deionized water, and 2mol of ammonium hydrogen phosphate ((NH)4)2HPO4) Dissolving in 1L deionized water, rapidly mixing the two solutions, crystallizing at 120 deg.C for 24 hr, spray drying to obtain carrier precursor, and calcining at 500 deg.C for 4 hr to obtain NbP1.0OxAnd (3) powder. Taking 400ml of carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
The molded raschig ring carrier particles of (1).
5.2g of ruthenium trichloride hydrate (RuCl)3·3H2O) was dissolved in 100g of water to obtain an aqueous solution of ruthenium trichloride, and 200ml of NbP was taken1.0OxAnd (3) pouring ruthenium trichloride aqueous solution into the carrier particles, fully stirring, drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain the catalyst, wherein the activity of the catalyst is shown in table 1.
Example 7:
respectively combine 2 withmol niobium oxalate (Nb (HC)2O4)5·6H2O) was dissolved in 1L of deionized water, and 2mol of ammonium hydrogen phosphate ((NH)4)2HPO4) Dissolving in 1L deionized water, rapidly mixing the two solutions, crystallizing at 120 deg.C for 24 hr, spray drying to obtain carrier precursor, and calcining at 500 deg.C for 4 hr to obtain NbP1.0OxAnd (3) powder. Taking 400ml of carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
The molded raschig ring carrier particles of (1).
3.6g IrCl trichloride hydrate3·3H2O) was dissolved in 100g of water to obtain an iridium trichloride aqueous solution, and 200ml of NbP was taken1.0OxAnd (3) pouring an iridium trichloride aqueous solution into the carrier particles, fully stirring, drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain the catalyst, wherein the activity of the catalyst is shown in table 1.
Example 8:
2mol of niobium oxalate (Nb (HC) are added2O4)5·6H2O) was dissolved in 1L of deionized water, and 2mol of ammonium hydrogen phosphate ((NH)4)2HPO4) Dissolving in 1L deionized water, rapidly mixing the two solutions, crystallizing at 120 deg.C for 24 hr, spray drying to obtain carrier precursor, and calcining at 500 deg.C for 4 hr to obtain NbP1.0OxA carrier powder. Taking 400ml of carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
The molded raschig ring carrier particles of (1).
3.5g platinum tetrachloride (PtCl)4) Dissolving in 100g water to obtain platinum tetrachloride water solution, and collecting 200ml NbP1.0OxCarrier particles, adding aqueous solution of platinum tetrachloride, stirring, baking at 120 deg.C and calcining at 500 deg.C for 2 hr to obtain catalystCatalyst particles, catalytic activity is shown in table 1.
Example 9:
2mol of niobium oxalate (Nb (HC) are added2O4)5·6H2O) was dissolved in 1L of deionized water, and 1.6mol of ammonium hydrogen phosphate ((NH)4)2HPO4) Dissolving in 1L deionized water, rapidly mixing the two solutions, crystallizing at 120 deg.C for 24 hr, spray drying to obtain carrier precursor, and calcining at 500 deg.C for 4 hr to obtain NbP0.8OxA carrier powder. Taking 400ml of carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
The molded raschig ring carrier particles of (1).
5.2g of ruthenium trichloride hydrate (RuCl)3·3H2O) was dissolved in 100g of water to obtain an aqueous solution of ruthenium trichloride, and 200ml of NbP was taken0.8OxAnd (3) pouring ruthenium trichloride aqueous solution into the carrier particles, fully stirring, drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain catalyst particles, wherein the catalytic activity is shown in table 1.
Example 10:
2mol of niobium oxalate (Nb (HC) are added2O4)5·6H2O) was dissolved in 1L of deionized water, and 1mol of ammonium hydrogen phosphate ((NH)4)2HPO4) Dissolving in 1L deionized water, rapidly mixing the two solutions, crystallizing at 120 deg.C for 24 hr, spray drying to obtain carrier precursor, and calcining at 500 deg.C for 4 hr to obtain NbP0.5OxA carrier powder. Taking 400ml of carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
The molded raschig ring carrier particles of (1).
5.2g of ruthenium trichloride hydrate (RuCl)3·3H2O) was dissolved in 100g of water to obtain ruthenium trichlorideAqueous solution, 200ml of NbP0.5OxAnd (3) pouring ruthenium trichloride aqueous solution into the carrier particles, fully stirring, drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain catalyst particles, wherein the catalytic activity is shown in table 1.
Example 11:
2mol of niobium oxalate (Nb (HC) are added2O4)5·6H2O) was dissolved in 1L of deionized water, and 2.4mol of ammonium hydrogen phosphate ((NH)4)2HPO4) Dissolving in 1L deionized water, rapidly mixing the two solutions, crystallizing at 120 deg.C for 24 hr, spray drying to obtain carrier precursor, and calcining at 500 deg.C for 4 hr to obtain NbP1.2OxA carrier powder. Taking 400ml of carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
The molded raschig ring carrier particles of (1).
5.2g of ruthenium trichloride hydrate (RuCl)3·3H2O) was dissolved in 100g of water to obtain an aqueous solution of ruthenium trichloride, 200ml of NbP was taken1.2OxAnd (3) pouring ruthenium trichloride aqueous solution into the carrier particles, fully stirring, drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain catalyst particles, wherein the catalytic activity is shown in table 1.
Example 12:
2mol of niobium oxalate (Nb (HC) are added2O4)5·6H2O) was dissolved in 1L of deionized water, and 2mol of ammonium hydrogen phosphate ((NH)4)2HPO4) Dissolving in 1L deionized water, rapidly mixing the two solutions, crystallizing at 120 deg.C for 24 hr, spray drying to obtain carrier precursor, and calcining at 500 deg.C for 4 hr to obtain NbP1.0OxA carrier powder. Taking 400ml of carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
The molded raschig ring carrier particles of (1).
2.6g of ruthenium trichloride hydrate (RuCl)3·3H2O) and 1.8g of iridium trichloride hydrate (IrCl)3·3H2O) is dissolved in 100g of water to obtain a ruthenium trichloride-iridium trichloride aqueous solution, 200ml of NbP is taken1.0OxAnd (3) carrier particles, pouring the aqueous solution into the carrier particles, fully stirring, drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain catalyst particles, wherein the catalytic activity is shown in table 1.
Example 13:
2mol of niobium oxalate (Nb (HC) are added2O4)5·6H2O) was dissolved in 1L of deionized water, and 2mol of ammonium hydrogen phosphate ((NH)4)2HPO4) Dissolving in 1L deionized water, rapidly mixing the two solutions, crystallizing at 120 deg.C for 24 hr, spray drying to obtain carrier precursor, and calcining at 500 deg.C for 4 hr to obtain NbP1.0OxA carrier powder. Taking 400ml of carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
The molded raschig ring carrier particles of (1).
2.6g of ruthenium trichloride hydrate (RuCl)3·3H2O) and 1.75g of platinum tetrachloride (PtCl)4) Dissolving in 100g of water to obtain ruthenium trichloride-platinum tetrachloride (PtCl)4) Aqueous solution, 200ml of NbP1.0OxAnd (3) carrier particles, pouring the aqueous solution into the carrier particles, fully stirring, drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain catalyst particles, wherein the catalytic activity is shown in table 1.
Example 14:
2mol of niobium oxalate (Nb (HC) are added2O4)5·6H2O) was dissolved in 1L of deionized water, and 2mol of ammonium hydrogen phosphate ((NH)4)2HPO4) Dissolving in 1L deionized water, rapidly mixing the two solutions, crystallizing at 120 deg.C for 24 hr, spray drying to obtain carrier precursor, and calcining at 500 deg.C for 4 hr to obtain NbP1.0OxA carrier powder. Taking 400ml of carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
The molded raschig ring carrier particles of (1).
1.8g IrCl trichloride hydrate3·3H2O) and 1.75g of platinum tetrachloride (PtCl)4) Dissolving in 100g of water to obtain iridium trichloride-platinum tetrachloride (PtCl)4) Aqueous solution, 200ml of NbP1.0OxAnd (3) carrier particles, pouring the aqueous solution into the carrier particles, fully stirring, drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain catalyst particles, wherein the catalytic activity is shown in table 1.
Example 15:
2mol of niobium oxalate (Nb (HC) are added2O4)5·6H2O) was dissolved in 1L of deionized water, and 2mol of ammonium hydrogen phosphate ((NH)4)2HPO4) Dissolving in 1L deionized water, rapidly mixing the two solutions, crystallizing at 120 deg.C for 24 hr, spray drying to obtain carrier precursor, and calcining at 500 deg.C for 4 hr to obtain NbP1.0OxA carrier powder. Taking 400ml of carrier powder, 20g of graphite and 40g of deionized water, uniformly mixing, tabletting and forming, drying at 120 ℃, roasting at 500 ℃ for 2 hours, and preparing
The molded raschig ring carrier particles of (1).
1.2g IrCl trichloride hydrate3·3H2O), 1.2g of platinum tetrachloride (PtCl)4) And 1.7g of ruthenium trichloride hydrate (RuCl)3·3H2O) is dissolved in 100g of water to obtain an iridium trichloride-platinum tetrachloride-ruthenium trichloride aqueous solution, 200ml of NbP is taken1.0OxAnd (3) carrier particles, pouring the aqueous solution into the carrier particles, fully stirring, drying at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain catalyst particles, wherein the catalytic activity is shown in table 1.
Table 1: catalyst Components and evaluation results
Note: in comparative example P2O5The molding was not successful and thus no further data were available.
Claims (8)
1. A method for producing acrylic acid from glycerol comprises contacting a glycerol-containing raw material and an oxygen-containing raw material with a catalyst, performing dehydration reaction on the glycerol to generate acrolein, and further oxidizing the acrolein into acrylic acid; the catalyst comprises a carrier and an active component, wherein the active component comprises Pt;
the carrier comprises Nb2O5And P2O5A composite oxide of the composition; the composite oxide is represented by the following chemical formula in terms of atomic ratio:
NbPaOx
wherein a is the molar ratio of P to Nb, x is the number of oxygen atoms satisfying the stoichiometric ratio, and a is 0.5 to 1.2.
2. The method according to claim 1, wherein the reaction temperature is 200 to 550 ℃.
3. The process as claimed in claim 1, wherein the reaction pressure is from 0.1 to 100 bar.
4. The method as set forth in claim 1, characterized in that the glycerol-containing raw material contains a solvent.
5. The method according to claim 4, wherein the concentration of glycerin in the glycerin-containing raw material is 10 to 70% by weight.
6. The method as set forth in claim 4, wherein the solvent is at least one of water or a C6-C20 hydrocarbon.
7. The method of claim 6, wherein the hydrocarbon is an alkane or an aromatic hydrocarbon.
8. The method as set forth in claim 1, wherein the gas volume space velocity of the raw material is 100 to 5000 hours-1。
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Citations (7)
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| CN101248033A (en) * | 2005-04-25 | 2008-08-20 | 阿肯马法国公司 | Method for producing acrylic acid from glycerol |
| CN101563311A (en) * | 2006-12-19 | 2009-10-21 | 阿肯马法国公司 | Method for preparing acrylic acid from glycerol |
| CN101796012A (en) * | 2007-09-06 | 2010-08-04 | 阿肯马法国公司 | The method that is used for the reactive evaporation of glycerine |
| CN101801902A (en) * | 2007-09-20 | 2010-08-11 | 阿肯马法国公司 | Process for manufacturing acrolein from glycerol |
| CN102482189A (en) * | 2009-07-22 | 2012-05-30 | 阿肯马法国公司 | Method for producing bioresourced acrylic acid from glycerol |
| CN102482187A (en) * | 2009-07-22 | 2012-05-30 | 阿肯马法国公司 | Method for producing bioresourced acrylic acid from glycerol |
| CN103328428A (en) * | 2011-01-28 | 2013-09-25 | 阿肯马法国公司 | Improved process for manufacturing acrolein/acrylic acid |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248033A (en) * | 2005-04-25 | 2008-08-20 | 阿肯马法国公司 | Method for producing acrylic acid from glycerol |
| CN101563311A (en) * | 2006-12-19 | 2009-10-21 | 阿肯马法国公司 | Method for preparing acrylic acid from glycerol |
| CN101796012A (en) * | 2007-09-06 | 2010-08-04 | 阿肯马法国公司 | The method that is used for the reactive evaporation of glycerine |
| CN101801902A (en) * | 2007-09-20 | 2010-08-11 | 阿肯马法国公司 | Process for manufacturing acrolein from glycerol |
| CN102482189A (en) * | 2009-07-22 | 2012-05-30 | 阿肯马法国公司 | Method for producing bioresourced acrylic acid from glycerol |
| CN102482187A (en) * | 2009-07-22 | 2012-05-30 | 阿肯马法国公司 | Method for producing bioresourced acrylic acid from glycerol |
| CN103328428A (en) * | 2011-01-28 | 2013-09-25 | 阿肯马法国公司 | Improved process for manufacturing acrolein/acrylic acid |
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