CN109304165B - Catalyst for synthesizing acrylic acid from glycerol - Google Patents

Catalyst for synthesizing acrylic acid from glycerol Download PDF

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CN109304165B
CN109304165B CN201710628264.5A CN201710628264A CN109304165B CN 109304165 B CN109304165 B CN 109304165B CN 201710628264 A CN201710628264 A CN 201710628264A CN 109304165 B CN109304165 B CN 109304165B
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catalyst
carrier
acrylic acid
glycerol
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CN109304165A (en
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徐文杰
杨斌
王伟华
赵相武
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • 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
    • B01J23/54—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
    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
    • 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
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a catalyst for synthesizing acrylic acid by glycerol, a preparation method of the catalyst and application of the catalyst in the aspect of synthesizing acrylic acid by glycerol, which mainly solve the problem of low yield of the catalyst in the prior art.

Description

Catalyst for synthesizing acrylic acid from glycerol
Technical Field
The invention relates to a catalyst for synthesizing acrylic acid by glycerol, application thereof in the aspect of preparing acrylic acid by glycerol and a preparation method of the catalyst.
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 researches on acrolein preparation by glycerol dehydration have been reported, for example, patent CN101070276A reports that an acidic molecular sieve is used as a catalyst, 200--1The yield of acrylic acid can reach 70-80%, but the molecular sieve catalyst has the problem of poor high-temperature hydrothermal property: patent 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 glycerol liquid phase dehydration, 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, the production efficiency is not as high as that of a fixed bed reactor, and the like. 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
One of the technical problems to be solved by the invention is the problem that the acrylic acid yield of the catalyst for preparing acrylic acid by dehydrating and oxidizing glycerol in the prior art is low, and the catalyst for synthesizing acrylic acid from glycerol is provided, can efficiently convert non-petroleum-source glycerol into acrylic acid, and has the characteristic of high acrylic acid yield.
The second technical problem to be solved by the present invention is to provide a method for preparing the catalyst.
The invention aims to solve the technical problem and provides application of the catalyst in the production of acrylic acid by dehydration and oxidation of glycerol.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows:
the catalyst for synthesizing acrylic acid from glycerol comprises a carrier and an active component, wherein the active component comprises at least one of Ru, Os and Ag.
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 solution, the carrier preferably comprises alumina, silica, titania, molecular sieve, rare earth oxygenCompound, activated carbon, graphene, Nb2O5、P2O5And clay.
In the above technical scheme, the carrier preferably comprises alumina, silica, titanium oxide, molecular sieve, rare earth oxide, activated 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 1.211 or less. By way of non-limiting example, a can be 0.1, 0.2, 0.3, 0.411, 0.511, 0.611, 0.711, 0.811, 0.911, 1.0, 1.011, 1.11, 2.11, 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 Ir, and Ru and Ir have an interaction promoting effect in increasing the yield of acrylic acid. The ratio of Ru and Ir is not particularly limited, and for example, but not limited to, the weight ratio of Ru to Ir is 0.011 to 100, more preferably 0.11 to 10, and may be, as non-limiting specific examples, 0.2, 0.3, 0.411, 0.511, 1, 1.511, 2.11, 2.5, 3, 4, 5, 6, 7, 8, 9, and the like.
In the above technical solution, as a second preferred technical solution, 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, and for example, but not limited to, the weight ratio of Ru to Pt is 0.011 to 100, more preferably 0.11 to 10, and may be, as non-limiting specific examples, 0.2, 0.3, 0.411, 0.511, 1, 1.511, 2.11, 2.5, 3, 4, 5, 6, 7, 8, 9, and the like.
The most preferable technical scheme is that the active components simultaneously comprise Ru, Ir and Pt, the Ir and the Pt have a synergistic effect on the aspect of improving the yield of acrylic acid in the presence of Ru, and the three have a combined effect on the aspect of 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 (0.011-100): 0.011-100), further 1 (0.11-10): 0.11-10).
To solve the second technical problem, the technical solution of the present invention is as follows:
the method for preparing the catalyst according to any one of the above technical problems, comprising:
(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 P2O5In the case of a composite oxide of composition, by way of non-limiting 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. (the oxidizing atmosphere is preferably an oxygen-containing atmosphere, such as, but not limited to, water vapor, oxygen, air, oxygen-containing gas and N2(and/or inert gas)); selection under inert atmosphereAt 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 order to solve the third technical problem, the technical scheme of the invention is as follows:
use of a catalyst according to any of the preceding claims for the production of acrylic acid by the dehydration oxidation of glycerol.
The specific application method can be as follows:
the method for synthesizing acrylic acid by glycerol comprises the step of carrying out dehydration oxidation reaction on glycerol and oxygen in the presence of the catalyst in one of the technical schemes to obtain acrylic acid.
Key to the present invention is the catalyst, and in the case of the catalyst disclosed herein, the skilled person can rationally select the oxidant and the process conditions without inventive step, such as but not limited to:
the glycerol is preferably used in the form of a solution diluted with a solvent to give a glycerol solution.
The solvent can be selected from water and hydrocarbon of C6-C20, the hydrocarbon can be alkane or arene, but water is preferred from the viewpoint of economy and safety.
The concentration of the glycerol solution is not particularly limited, and may be appropriately selected by those skilled in the art, for example, but not limited to, the concentration of glycerol is 10 to 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.
The space velocity of the raw material is not particularly limited, and can be reasonably selected by those skilled in the art, such as but not limited to, the gas volume space velocity of the glycerol solution 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.
The reaction temperature is preferably 200 to 550 ℃, and more preferably 250 to 350 ℃.
The pressure of the reaction is preferably 0.1 to 100bar, more preferably 0.1 to 30 bar. In the present invention, unless otherwise specified, the pressures are gauge pressures.
The reactor is not particularly limited, and a tank type, a fixed bed or a fluidized bed reactor may be employed, and a fixed bed catalyst is preferred in view of production efficiency and catalyst life.
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:
Figure BDA0001363291440000071
Figure BDA0001363291440000072
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
Figure BDA0001363291440000073
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:
400ml of commercially available TiO was 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
Figure BDA0001363291440000081
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
Figure BDA0001363291440000082
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, and the carrier particles are fully stirredDrying at 120 ℃ and roasting at 500 ℃ for 2 hours to obtain the catalyst, wherein 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
Figure BDA0001363291440000083
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
Figure BDA0001363291440000084
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, and spray dryingDrying to obtain carrier precursor, and roasting 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
Figure BDA0001363291440000091
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:
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
Figure BDA0001363291440000092
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) dissolved in 1L of deionized water, 2mol of diammonium hydrogen phosphate((NH4)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
Figure BDA0001363291440000101
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 NbP1.0OxAnd (3) carrier particles, wherein a platinum tetrachloride aqueous solution is poured into the carrier particles, the carrier particles are fully stirred, dried at 120 ℃ and roasted at 500 ℃ for 2 hours to obtain catalyst particles, and the 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
Figure BDA0001363291440000102
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
Figure BDA0001363291440000103
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 taken0.5OxAnd (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
Figure BDA0001363291440000111
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 taken1.2OxCarrier particles, an aqueous solution of ruthenium trichloride is poured into the carrier particles, and the carrier particles are filled with the aqueous solutionStirring, drying at 120 deg.C, and calcining at 500 deg.C for 2 hr to obtain catalyst particles with catalytic activity 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
Figure BDA0001363291440000112
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
Figure BDA0001363291440000121
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
Figure BDA0001363291440000122
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. 400ml of the carrier powder was taken out,20g of graphite and 40g of deionized water are evenly mixed, then the mixture is flaked and formed, dried at 120 ℃ and roasted at 500 ℃ for 2 hours to prepare the graphite-based composite material
Figure BDA0001363291440000123
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
Figure BDA0001363291440000141
Note: in comparative example P2O5The molding was not successful and thus no further data were available.

Claims (7)

1. The catalyst for synthesizing acrylic acid from glycerol comprises a carrier and an active component, wherein the active component comprises Ru;
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 catalyst of claim 1, wherein the content of the active component in the catalyst is more than 0g/L and less than 50 g/L.
3. A process for preparing a catalyst as claimed in any one of claims 1 to 2, comprising:
(1) mixing the compound solution of the active component with a carrier;
(2) roasting;
the preparation method of the carrier comprises the following steps:
(i) mixing a niobium-containing compound with a phosphorus-containing compound;
(ii) and (4) roasting.
4. The preparation method as claimed in claim 3, wherein the calcination temperature is 200-1000 ℃.
5. The method according to claim 3, wherein the calcination is carried out for a time of 0.5 to 100 hours.
6. The method according to claim 3, wherein the mixture obtained by mixing in the step (1) is dried and then calcined in the step (2).
7. The method according to claim 6, wherein the drying temperature is 50 to 200 ℃.
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