CN115090308B - Metal-doped sodium super-ionic catalyst and preparation method and application thereof - Google Patents

Metal-doped sodium super-ionic catalyst and preparation method and application thereof Download PDF

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CN115090308B
CN115090308B CN202210765897.1A CN202210765897A CN115090308B CN 115090308 B CN115090308 B CN 115090308B CN 202210765897 A CN202210765897 A CN 202210765897A CN 115090308 B CN115090308 B CN 115090308B
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张俊峰
郑凯文
高启梁
谭猗生
韩怡卓
张清德
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Shanxi Institute of Coal Chemistry of CAS
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    • 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
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
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    • 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
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    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract

The invention discloses a metal doped sodium super-ionic catalyst, a preparation method and application thereof, wherein the catalyst comprises the following components in percentage by mass: 0.06-4%; h 1‑x Ti 2 (PO 4 ) 3‑x (SO 4 ) x :96-99.94%, wherein the doped metal component Me is one or any two of Mn, Y, mo, bi, re, and x=0.7-1. The invention also provides application of the catalyst in direct synthesis of acrylic acid and esters thereof by co-feeding methanol and acetic acid. The catalyst provided by the invention has the advantages of easily available raw materials, low cost and simple synthesis process; when the catalyst is used for synthesizing acrylic acid and esters thereof, the process is simple, the conditions are mild, the product is easy to separate, the acetic acid conversion rate is more than 50%, the selectivity of acrylic acid and acrylic ester can reach more than 60%, and the space-time yield is 30 mu mol.g ‑1 ·min ‑1 The method has wide industrial application prospect.

Description

Metal-doped sodium super-ionic catalyst and preparation method and application thereof
Technical Field
The invention relates to a metal (Mn, Y, mo, bi, re) doped sodium super-ionic catalyst Me/H 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x And a preparation method and application thereof. Belongs to the technical field of catalyst preparation and application.
Background
The direct or indirect mode of converting coal into fuel and chemicals with high added value is an important way for clean utilization of coal, and is also one of important actions for achieving the ambitious goal of double carbon in China. Methanol, a primary product of coal chemical industry, is quite excessive in current productivity, so development and utilization of methanol are always widely paid attention. Among the numerous utilization routes, the preparation of high value-added oxygenates from methanol results in higher utilization of atoms of the route due to the retention of some oxygen. On the other hand, acetic acid is also considerably excessive in productivity as a methanol carbonylation product and a petrochemical by-product, and further development and utilization thereof have been attracting attention.
Acrylic acid is the simplest unsaturated carboxylic acid, is an important high-value organic synthesis raw material, and is widely used in the industries of coating, chemical fiber, adhesive and the like. It is estimated that by 2019 the global acrylic acid and ester demand will reach 1400 ten thousand tons, while our country is the main consumer country of acrylic acid (methyl ester), the demand for acrylic acid will be about half of the total amount, and therefore it is becoming important to develop a multi-way source route for acrylic acid. The industrial production of acrylic acid (methyl ester) mainly adopts five technological processes of cyanoethanol method, acetylene carbonylation method, ketene method, acrylonitrile hydrolysis method and propylene oxidation method. The first few methods have been eliminated due to high toxicity, serious pollution, high energy consumption and investment costs, etc. Currently, the main industrial production process of acrylic acid is a two-step gas phase oxidation process of propylene. The route has higher cost, complex process and larger volatility of petroleum sources of propylene and world petroleum markets. In recent years, scientific researchers have also widely developed research and development work on new technological routes of acrylic acid; acrylic acid synthesis techniques such as a one-step oxidation process of propane, a dehydration process of lactic acid, a condensation process of methanol/formaldehyde and acetic acid, etc. have been developed successively. Acrylic acid is considered as one of the most promising routes [ M.Ai, J.Catal.112 (1988) 194-200 ], M.Ai, J.Catal.124 (1990) 293-296. M.Ai, J.Catal., 124 (1990) 293-296] by aldol condensation of methanol/formaldehyde and acetic acid in combination with the resource endowment of 'more coal and less oil' in China. The most studied routes are currently directed to the synthesis of acrylic acid from formaldehyde and acetic acid using a phosphate catalyst represented by VPO [ M.Ai, et al Bull. Chem. Soc. Jpn., 63 (1990), 199-202 ], a basic catalyst represented by alkali metals such as X.Z. Feng, et al 314 (2014) 132-141, cs, rb [ M.Ai, et al appl. Catalyst A-Gen., 288 (2005) 211-215], and a molecular sieve catalyst represented by ZSM-35 [ Z.L. Ma, et al chem. Commun., 53 (2017) 9071-9074]. Formaldehyde is a highly toxic gas which is very unstable and is generally used in aqueous solutions, but is still easily polymerized for a long time; when formaldehyde is used in the synthesis reaction, a large amount of water is introduced, inhibiting the activity of the catalyst and producing a large amount of wastewater, and the reaction line is blocked due to its polymerization, which limits its large-scale application. The method can save the path of preparing formaldehyde by dehydrogenation of methanol, shorten the process flow, and greatly reduce the process and environmental problems caused by taking formaldehyde as a raw material, so that the path is a technical route with great development potential.
From the prior literature, few reports on direct synthesis of acrylic acid (methyl ester) from methanol and acetic acid exist, and the catalyst is mainly a VPO catalyst [ M.Ai, et al Bull, chem. Soc. Jpn., 63 (1990), 199-202; X.Z. Feng, et al 314 (2014) 132-141; L.Q.Shen, et al (97) 2019 2699-2707]. Although VPO catalysts show good activity in aldol condensation, such catalysts have poor dehydrogenation activity on methanol, so that intermediate formaldehyde is difficult to generate, and the subsequent aldol condensation process is finally influenced, so that the selectivity of the target product acrylic acid is low, generally not more than 30%, and the space-time yield is low. The technology of using the super ion conductor type catalytic material for synthesizing acrylic acid from methanol and acetic acid is disclosed in Chinese patent CN201811207341.0, wherein the technology mainly uses titanyl sulfate-sulfuric acid hydrate as a titanium source, adopts a two-step synthesis method to prepare the low-load vanadium oxide modified multifunctional catalytic material, and realizes the one-step synthesis of acrylic acid and ester from methanol and acetic acid (methyl ester). The sodium super-ion conductor type material is used as one of important components of the catalyst in the patent, and the catalyst has great potential in the field of catalysis, however, the preparation method of the catalyst has complicated steps, complex preparation process and higher cost in large-scale preparation.
Therefore, if the catalytic efficiency of the catalyst is to be improved, and the direct synthesis of acrylic acid (and ester) from methanol and acetic acid is realized, the designed catalyst needs to simultaneously meet the requirements of methanol dehydrogenation to obtain formaldehyde adsorption species, has aldol condensation activity and can be efficiently cooperated with the active centers, and on the basis of the prior art, a new and simpler synthesis method of the sodium super-ion conductor type catalyst is explored, so that the catalyst is an important means and measure for reducing the cost and promoting the development of technology.
Disclosure of Invention
The invention aims at providing a metal (Mn, Y, mo, bi, re) -doped sodium super-ionic catalyst Me/H 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x The preparation method has the advantages of simple preparation process, low cost, high thermal stability and high activity. The catalyst of the invention is Me/H with a sodium super-ion structure 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x (wherein, me= Mn, Y, mo, bi, re, and the like, and x=0.7-1), the catalyst can be used for directly synthesizing acrylic acid and esters by a one-step method of methanol and acetic acid (methyl ester).
In the invention, the metal (Mn, Y, mo, bi, re) doped sodium super-ionic catalytic material mainly comprises Ti and PO 4 3- Small amount of SO 4 2- The three-dimensional framework solid solution main body structure is formed by connecting vertex angles and the metal doping component. The material has the remarkable characteristics of stable structure and developed pore canal, can simultaneously provide a plurality of active sites for methanol dehydrogenation and aldol condensation, and can efficiently cooperate with each other to play a good catalytic activity under the same operation condition, such as 340-400 ℃, so that the orderly proceeding of the methanol dehydrogenation and aldol condensation reaction can be promoted. The catalyst obtained by the invention can show excellent catalytic effect on direct synthesis of acrylic acid and ester from methanol and acetic acid by combining reaction characteristics and a target product generation path, and the components of the material are common metal salts and oxides, so that the preparation conditions and the method are relatively simple. Further stillIn addition, the method adopts an in-situ doping mode to introduce metal components, so that the catalyst has fewer synthesis steps, is simple and convenient to operate, and can effectively reduce the synthesis cost.
The invention provides a metal (Mn, Y, mo, bi, re) -doped sodium super-ionic catalyst Me/H 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Comprises a doped metal component (Me= Mn, Y, mo, bi, re) and an element component (Ti, P, S, O, H) for forming a main body structure of the sodium super-ion conductor, wherein the mass percentage components are as follows: 0.06-4%; h 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x :96-99.94%, wherein the doping metal component Me may be one or any two of Mn, Y, mo, bi, re, x=0.7-1.
The invention provides a preparation method of a metal (Mn, Y, mo, bi, re) -doped sodium super-ionic catalyst, which comprises the following steps:
titanium sulfate (Ti (SO) 4 ) 2 ) Dissolving a solid sample in deionized water, preparing a solution with the concentration range of 1.4-2.0 mol/L, adding 30wt% hydrogen peroxide as a stabilizer, and polyethylene glycol (PEG, sigma-Aldrich, 15-20 kDa) as a dispersing agent, and uniformly stirring; slowly dripping concentrated phosphoric acid with the concentration of 85%wt, and strongly stirring to obtain solution A; additionally weighing a salt (Me salt) corresponding to the doped metal, and dissolving the salt in distilled water to prepare a solution with the concentration range of 0.01-0.58 mol/L; subsequently, the salt solution doped with the metal is added dropwise to the solution a under stirring; drying the mother solution in a vacuum drying oven at 50-70deg.C for 48-72H, and calcining the dried sample at 550-650deg.C for 8-12H to obtain Me/H doped with Me metal 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x The raw material powder is pressed into tablets, crushed and sieved into particles with 20-40 meshes, and the required catalyst is obtained.
The mass ratio of the raw materials is Ti (SO) 4 ) 2 ：30wt%H 2 O 2 ：PEG：Me salt：85wt%H 3 PO 4 =（14-18.88）：（15.28-18）：（5.04-6）：（0.018-1.369）：9.76；
Wherein the salt corresponding to the doped metal is manganese sulfate MnSO 4 ·H 2 O, yttrium nitrate Y (NO) 3 ) 3 ·6H 2 O, ammonium molybdate (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, bismuth nitrate Bi (NO) 3 ) 3 ·5H 2 O, ammonium rhenate NH 4 ReO 4 One or two of them. I.e., doping the metal component, one or a combination of any two of these metal salts may be selected for catalyst preparation.
The invention provides the metal (Mn, Y, mo, bi, re) -doped sodium super-ionic catalyst Me/H 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x The application of the method in direct synthesis of acrylic acid and esters thereof from methanol and acetic acid.
The application of the catalyst comprises the following steps: the catalyst is applied to the reaction of directly synthesizing acrylic acid and esters thereof from methanol and acetic acid, and the catalytic reaction is carried out in a fixed bed reactor; the reactor was placed vertically and a fixed amount of 20-40 mesh particle size catalyst was placed in the middle of the reactor. The catalyst is heated to the reaction temperature under the mixed atmosphere of oxygen and nitrogen; when the catalytic reaction is carried out, the molar ratio of raw material methanol to acetic acid is controlled to be 1-4:1, the space velocity of reaction liquid is controlled to be 1-2 mL/(g.h), the reaction temperature is controlled to be 340-400 ℃, the reaction pressure is normal pressure, and in the reaction process, oxygen-nitrogen mixed gas with the oxygen volume fraction of 20-100% is used as oxidizing atmosphere and carrier gas, and the gas flow rate is controlled to be 5-15 mL/min per gram of catalyst.
The invention has the beneficial effects that:
(1) In the catalytic system of the invention, the metal (Mn, Y, mo, bi, re) doped with H is used 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x The components are all easy to obtain and the raw material cost is lowThe synthesis process is simple, and mass production can be realized on a large scale;
(2) Under the catalysis of the catalyst, when the direct synthesis of acrylic acid and esters from methanol and acetic acid is performed, the acetic acid conversion rate is more than 50%, the selectivity of acrylic acid and acrylic ester can reach more than 60%, and the space-time yield is 30 mu mol.g -1 ·min -1 The above realizes the one-step high-efficiency conversion of methanol and acetic acid into acrylic acid (ester); the raw material methanol involved in the process is the most basic product of coal chemical industry, and acetic acid can be obtained through paths of coal chemical industry, petrochemical industry, biomass and the like, so that the cost is low.
(3) The reaction operation for catalyzing and synthesizing the acrylic acid and the acrylic ester is simple, the requirements on equipment are low, the reaction condition is relatively mild, the product is easy to separate, the industrialized application prospect is wide, and the method is a novel potential technological route for downstream development of methanol and acrylic acid (acrylic ester) production.
Drawings
Fig. 1 is an XRD spectrum of the catalyst prepared in example 1.
Fig. 2 is an SEM image of the catalyst prepared in example 2.
Fig. 3 is a TEM image of the catalyst prepared in example 3.
Fig. 4 is a TEM image of the catalyst prepared in example 5.
Fig. 5 is an XRD spectrum of the catalyst prepared in example 6.
Fig. 6 is an XRD spectrum of the catalyst prepared in example 7.
Fig. 7 is an XRD spectrum of the catalyst prepared in example 8.
Fig. 8 is an SEM image of the catalyst prepared in example 9.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1
1. Mn/H doped with metal Mn 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Preparation of the Material
Weigh 14gTi (SO) 4 ) 2 The solid sample was dissolved in 40g deionized water,sequentially adding 15.28g 30wt% hydrogen peroxide and 5.04g polyethylene glycol (PEG, sigma-Aldrich, 15-20 kDa), and stirring uniformly; slowly dripping concentrated phosphoric acid with the concentration of 9.76 and g being 85%, and strongly stirring to obtain a solution A; another weight of 0.0181g of MnSO 4 ·H 2 O is prepared into 0.0115mol/L solution; subsequently, under stirring, mnSO is added 4 Dropwise adding the solution into the solution A; drying the mother solution in a vacuum drying oven at 50deg.C for 72. 72H, and calcining the dried sample at 600deg.C for 10H to obtain Mn/H doped with 0.06wt% metal Mn 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Raw material powder. The X-ray electron diffraction pattern of the prepared catalyst was as follows:
FIG. 1 shows an XRD spectrum of the catalyst prepared in this example, showing that the catalyst prepared in one pot method can show NASICON material and TiP 2 O 7 The common characteristic diffraction peak indicates that the synthesized catalyst consists of mixed crystals.
2. Catalyst Performance test
2g of the catalyst is placed in the middle part of a reactor, the upper part of the reactor is filled with a magnetic ring, the temperature is raised to 360 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 21%, the mixed raw materials of methanol and acetic acid with the mol ratio of 1:1 are injected into a reaction system at the feeding speed of 2 mL/h, and the reaction pressure is controlled at 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2 h, after waiting 1h, the product was collected and analyzed. The conversion of acetic acid was 52.2%, the selectivity of acrylic acid and methyl acrylate in the main product was 64.3%, and the space-time yield was 34.15. Mu. Mol. G -1 ·min -1 Methyl acetate selectivity was 20.9%, dimethyl ether selectivity was 2.3%, acetaldehyde selectivity was 1.1%, propionaldehyde selectivity was 0.6%, acrolein selectivity was 2.4%, propionic acid selectivity was 1.34%, and gas phase product selectivity was 6.56%.
Example 2
1. Mn/H doped with Mn+Bi metal 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Preparation of the Material
Weigh 18.88g of Ti (SO 4 ) 2 Dissolving a solid sample in 40g of deionized water, sequentially adding 16g of 30wt% hydrogen peroxide and 6g of polyethylene glycol (PEG, sigma-Aldrich, 15-20 kDa), and uniformly stirring; slowly dripping 9.76g of concentrated phosphoric acid with the concentration of 85 percent, and strongly stirring to obtain solution A; another weight of 0.68g MnSO 4 ·H 2 O、0.50gBi(NO 3 ) 3 ·5H 2 Dissolving O solid in water to prepare a solution with Mn+Bi ion solubility of 0.5751 mol/L; subsequently, the mn+bi-containing solution was added dropwise to the solution a under stirring; drying the mother solution in a vacuum drying oven at 60deg.C for 72H, and calcining the dried sample at 580 deg.C for 8H to obtain a product containing 1.58wt% Mn+1.5% wtBI/H 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Raw material powder. TEM (FIG. 2) preparing the sample shows that there are a large number of pore structures on its surface.
Fig. 2 shows an SEM image of the catalyst prepared in this example. The figure shows that the bimetallic doped synthetic catalyst consists of irregular massive particles, but the surface of the catalyst is distributed with rich pore channel structures.
2. Catalyst Performance test
2g of the catalyst is placed in the middle part of a reactor, the upper part of the reactor is filled with a magnetic ring, the temperature is raised to 380 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 21%, the mixed raw materials of methanol and acetic acid with the mol ratio of 1.5:1 are injected into a reaction system at the feeding speed of 3 mL/h, and the reaction pressure is controlled at 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2 h, after waiting 1h, the product was collected and analyzed. The conversion of acetic acid was 60.2%, the selectivity of acrylic acid and methyl acrylate in the main product was 69.8%, and the space-time yield was 37.02. Mu. Mol. G -1 ·min -1 Methyl acetate selectivity was 14.6%, dimethyl ether selectivity was 2.9%, acetaldehyde selectivity was 0.93%, propionaldehyde selectivity was 0.66%, acrolein selectivity was 3.74%, propionic acid selectivity was 0.98%, and gas phase product selectivity was 5.98%.
The evaluation data show that the catalyst synthesized by the in-situ method can be used for efficiently converting methanol and acetic acid into the target product acrylic acid (ester) in one step.
Example 3
1. Y/H doped with metal Y 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Preparation of the Material
Weigh 16g Ti (SO) 4 ) 2 Dissolving a solid sample in 40g of deionized water, sequentially adding 15.28g of 30wt% hydrogen peroxide and 5.04g of polyethylene glycol (PEG, sigma-Aldrich, 15-20 kDa), and uniformly stirring; slowly dripping 9.76g of concentrated phosphoric acid with the concentration of 85 percent, and strongly stirring to obtain solution A; additional weight 2.0218g Y (NO) 3 ) 3 ·6H 2 O is prepared into 0.4428mol/L solution; subsequently, Y (NO 3 ) 3 Dropwise adding the solution into the solution A; drying the mother solution in a 70 ℃ vacuum drying oven for 72H after the dripping is completed, roasting the dried sample at 650 ℃ for 12H, and finally obtaining the doped Y/H containing 3.94wt% of metal Y 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Raw material powder.
Fig. 3 shows a TEM image of the catalyst prepared in this example. The figure shows that the catalyst prepared by the one-pot method has a rough surface, but has a pore structure in the bulk phase.
2. Catalyst Performance test
The catalyst 2g is placed in the middle of a reactor, the upper part of the reactor is filled with a magnetic ring, the temperature is raised to 360 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 21 percent, the mixed raw materials of methanol and acetic acid with the mol ratio of 1:1 are injected into a reaction system at the feeding speed of 3 mL/h, and the reaction pressure is controlled at 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2 h, after waiting 1h, the product was collected and analyzed. The conversion of acetic acid was 54.3%, the selectivity to acrylic acid and methyl acrylate in the main product was 60.7%, the space-time yield was 2.59 g-1 min-1, the selectivity to methyl acetate was 24.74%, the selectivity to dimethyl ether was 2.31%, the selectivity to acetaldehyde was 2.05%, the selectivity to propionaldehyde was 1.88%, the selectivity to acrolein was 2.46%, the selectivity to propionic acid was 0.45%, and the selectivity to gas phase product was 4.78%.
Example 4
1. Mn/H doped with metal Mn 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Preparation of the Material
Weigh 18g of Ti (SO) 4 ) 2 Dissolving a solid sample in 40g of deionized water, sequentially adding 18g of 30wt% hydrogen peroxide and 5.04g of polyethylene glycol (PEG, sigma-Aldrich, 15-20 kDa), and uniformly stirring; slowly dripping 9.76g of concentrated phosphoric acid with the concentration of 85 percent, and strongly stirring to obtain solution A; 0.7660g of MnSO is additionally weighed 4 ·H 2 O is prepared into 0.3451mol/L solution; subsequently, under stirring, mnSO is added 4 Dropwise adding the solution into the solution A; drying the mother solution in a vacuum drying oven at 50deg.C for 72. 72H, and calcining the dried sample at 600deg.C for 10H to obtain Mn/H doped with 1.89wt% metal Mn 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Raw material powder.
2. Catalyst Performance test
The catalyst 2g is placed in the middle of a reactor, the upper part of the reactor is filled with a magnetic ring, the temperature is raised to 390 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 21 percent, the mixed raw materials of methanol and acetic acid with the mol ratio of 2:1 are injected into a reaction system at the feeding speed of 4 mL/h, and the reaction pressure is controlled at 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2 h, after waiting 1h, the product was collected and analyzed. The conversion of acetic acid was 65.7%, the selectivity to acrylic acid and methyl acrylate in the main product was 63.4%, the space-time yield was 33.98. Mu. Mol. G-1. Min-1, the selectivity to methyl acetate was 18.9%, the selectivity to dimethyl ether was 2.06%, the selectivity to acetaldehyde was 1.76%, the selectivity to propionaldehyde was 1.48%, the selectivity to acrolein was 2.97%, the selectivity to propionic acid was 0.77%, and the selectivity to gas phase product was 8.04%.
Example 5
1. Mo/H doped with metallic Mo 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Preparation of the Material
Weigh 14gTi (SO) 4 ) 2 Dissolving a solid sample in 40g of deionized water, sequentially adding 17g of 30wt% hydrogen peroxide and 5.5g of polyethylene glycol (PEG, sigma-Aldrich, 15-20 kDa), and uniformly stirring; slowly dripping 9.76g of concentrated phosphoric acid with the concentration of 85 percent, and strongly stirring to obtain solution A; another 0.2289g (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O is prepared into 0.0198mol/L solution; subsequently, under stirring conditions, (NH) 4 ) 6 Mo 7 O 24 Dropwise adding the solution into the solution A; drying the mother solution in a 60 ℃ vacuum drying oven for 72H after the dripping is completed, roasting the dried sample at 580 ℃ for 10H, and finally obtaining the Mo/H doped with 1.33wt% of metallic Mo 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Raw material powder. The transmission electron microscope test of the raw powder is shown in fig. 4. It can be seen that the catalyst has a developed mesoporous channel structure.
Fig. 4 shows a TEM image of the catalyst prepared in this example, which shows that the synthetic catalyst has a certain pore structure and the pore diameter is concentrated in the range of 10-20 nm.
2. Catalyst Performance test
The catalyst 2g is placed in the middle of a reactor, the upper part of the reactor is filled with a magnetic ring, the temperature is raised to 360 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 21%, the mixed raw materials of methanol and acetic acid with the mol ratio of 1:1 are injected into a reaction system at the feeding speed of 3 mL/h, and the reaction pressure is controlled at 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2 h, after waiting 1h, the product was collected and analyzed. The conversion of acetic acid was 59.9%, the selectivity to acrylic acid and methyl acrylate in the main product was 58.4%, the space-time yield was 31.98. Mu. Mol. G-1. Min-1, the selectivity to methyl acetate was 19.3%, the selectivity to dimethyl ether was 2.95%, the selectivity to acetaldehyde was 1.81%, the selectivity to propionaldehyde was 1.69%, the selectivity to acrolein was 4.14%, the selectivity to propionic acid was 1.61%, and the selectivity to gas phase product was 10.62%.
Example 6
1. Bi/H doped with metallic Bi 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Preparation of the Material
Weigh 18.88g of Ti (SO 4 ) 2 Dissolving a solid sample in 40g of deionized water, sequentially adding 15.28g of 30wt% hydrogen peroxide and 5.04g of polyethylene glycol (PEG, sigma-Aldrich, 15-20 kDa), and uniformly stirring; slowly dripping 9.76g of concentrated phosphoric acid with the concentration of 85 percent, and strongly stirring to obtain solution A; 0.5863g Bi (NO) 3 ) 3 ·5H 2 O is prepared into 0.0858mol/L solution; subsequently, bi (NO 3 ) 3 Dropwise adding the solution into the solution A; drying the mother solution in a vacuum drying oven at 50deg.C for 72. 72H, and calcining the dried sample at 600deg.C for 10H to obtain Bi/H doped with 1.79wt% of metal Bi 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Raw material powder.
Fig. 5 shows an XRD spectrum of the catalyst prepared in this example, which shows that the catalyst prepared in this example has good crystallinity, and no diffraction peaks of other phases are found, indicating that the catalyst used in the present invention can be successfully synthesized using titanium sulfate.
2. Catalyst Performance test
The catalyst 2g is placed in the middle of a reactor, the upper part of the reactor is filled with a magnetic ring, the temperature is raised to 360 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 21 percent, the mixed raw materials of methanol and acetic acid with the mol ratio of 1:1 are injected into a reaction system at the feeding speed of 2 mL/h, and the reaction pressure is controlled at 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2 h, after waiting 1h, the product was collected and analyzed. The conversion of acetic acid was 74.6%, the selectivity to acrylic acid and methyl acrylate in the main product was 78.9%, the space-time yield was 52.97 g-1 min-1, the selectivity to methyl acetate was 6.02%, the selectivity to dimethyl ether was 2.44%, the selectivity to acetaldehyde was 2.16%, the selectivity to propionaldehyde was 1.93%, the selectivity to acrolein was 2.59%, the selectivity to propionic acid was 0.74%, and the selectivity to gas phase product was 4.67%.
Example 7
1. Mn/H doped with metal Mn 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Preparation of the Material
Weigh 16g Ti (SO) 4 ) 2 Dissolving a solid sample in 40g of deionized water, sequentially adding 15.28g of 30wt% hydrogen peroxide and 6g of polyethylene glycol (PEG, sigma-Aldrich, 15-20 kDa), and uniformly stirring; slowly dripping 9.76g of concentrated phosphoric acid with the concentration of 85 percent, and strongly stirring to obtain solution A; 0.2317g of MnSO is additionally weighed 4 ·H 2 O is prepared into 0.1150mol/L solution; subsequently, under stirring, mnSO is added 4 Dropwise adding the solution into the solution A; drying the mother solution in a vacuum drying oven at 50deg.C for 72. 72H, and calcining the dried sample at 600deg.C for 10H to obtain Mn/H doped with 0.63wt% metal Mn 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Raw material powder.
FIG. 6 shows the XRD patterns of the catalyst prepared in this example, showing that the synthesized catalyst generally exhibits a NASICON material crystalline phase, but the material is still doped with a small amount of TiP 2 O 7 A crystalline phase.
2. Catalyst Performance test
The catalyst 2g is placed in the middle of a reactor, the upper part of the reactor is filled with a magnetic ring, the temperature is raised to 380 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 21%, the mixed raw materials of methanol and acetic acid with the mol ratio of 1.5:1 are injected into a reaction system at the feeding speed of 3 mL/h, and the reaction pressure is controlled at 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2 h, after waiting 1h, the product was collected and analyzed. The conversion of acetic acid was 61.9%, the selectivity to acrylic acid and methyl acrylate in the main product was 66.5%, the space-time yield was 35.82 g-1 min-1, the selectivity to methyl acetate was 18.47%, the selectivity to dimethyl ether was 1.79%, the selectivity to acetaldehyde was 1.85%, the selectivity to propionaldehyde was 1.47%, the selectivity to acrolein was 2.68%, the selectivity to propionic acid was 0.82%, and the selectivity to gas phase product was 7.76%.
Example 8
1. Re/H doped with metal Re 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Preparation of the Material
Weigh 18g of Ti (SO) 4 ) 2 Dissolving a solid sample in 40g of deionized water, sequentially adding 15.28g of 30wt% hydrogen peroxide and 5.04g of polyethylene glycol (PEG, sigma-Aldrich, 15-20 kDa), and uniformly stirring; slowly dripping 9.76g of concentrated phosphoric acid with the concentration of 85 percent, and strongly stirring to obtain solution A; another weight of 0.0145 and 0.0145gNH 4 ReO 4 A solution configured to be 0.0041 mol/L; subsequently, NH is added under stirring 4 ReO 4 Dropwise adding the solution into the solution A; drying the mother solution in a vacuum drying oven at 50deg.C for 72. 72H, and calcining the dried sample at 550deg.C for 12H to obtain Re/H doped with 0.08wt% of metal Re 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Raw material powder. XRD testing was performed on the obtained samples, as shown in fig. 7. It can be seen that the introduction of the Re component causes a certain change in the crystalline phase of the sample, but the structural characteristics of the NASICON material are generally maintained.
2. Catalyst Performance test
The catalyst 2g is placed in the middle of a reactor, the upper part of the reactor is filled with a magnetic ring, the temperature is raised to 370 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 50%, the mixed raw materials of methanol and acetic acid with the mol ratio of 1:1 are injected into a reaction system at the feeding speed of 2 mL/h, and the reaction pressure is controlled at 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2 h, after waiting 1h, the product was collected and analyzed. The conversion of acetic acid was 75.6%, the selectivity to acrylic acid and methyl acrylate in the main product was 84.2%, the space-time yield was 58.63 g-1 min-1, the selectivity to methyl acetate was 4.82%, the selectivity to dimethyl ether was 2.07%, the selectivity to acetaldehyde was 1.39%, the selectivity to propionaldehyde was 1.02%, the selectivity to acrolein was 1.16%, the selectivity to propionic acid was 0.87%, and the selectivity to gas phase product was 4.11%.
From the performance evaluation of the catalyst, the catalyst obtained by adopting Re modified NASICON material can be used for efficiently and directly converting methanol acetic acid into acrylic acid and ester, and the related reaction index is at the leading level at home and abroad.
Example 9
1. Bi/H doped with metallic Bi 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Preparation of the Material
Weigh 16g Ti (SO) 4 ) 2 Dissolving a solid sample in 40g of deionized water, sequentially adding 15.28g of 30wt% hydrogen peroxide and 5.04g of polyethylene glycol (PEG, sigma-Aldrich, 15-20 kDa), and uniformly stirring; slowly dripping 9.76g of concentrated phosphoric acid with the concentration of 85 percent, and strongly stirring to obtain solution A; another 0.0620g Bi (NO) 3 ) 3 ·5H 2 O is prepared into 0.0107mol/L solution; subsequently, bi (NO 3 ) 3 Dropwise adding the solution into the solution A; drying the mother solution in a vacuum drying oven at 60deg.C for 72H, and calcining the dried sample at 600deg.C for 8H to obtain Bi/H doped with 0.22wt% metal Bi 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Raw material powder.
Fig. 8 shows SEM pictures of the catalyst prepared in this example, and it can be seen from the figure that the synthesized catalyst after Bi doping has a smaller particle size and a rich intragranular cross-cell channels.
2. Catalyst Performance test
The catalyst 2g is placed in the middle of a reactor, the upper part of the reactor is filled with a magnetic ring, the temperature is raised to 350 ℃ in a pure oxygen flow of 20 ml/min, the mixed raw materials of methanol and acetic acid with the molar ratio of 4:1 are injected into a reaction system at the feeding speed of 8 mL/h, and the reaction pressure is controlled at 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2 h, after waiting 1h, the product was collected and analyzed. The conversion of acetic acid was 72.3%, the selectivity to acrylic acid and methyl acrylate in the main product was 76.9%, the space-time yield was 50.22 g-1 min-1, the selectivity to methyl acetate was 8.01%, the selectivity to dimethyl ether was 3.08%, the selectivity to acetaldehyde was 2.12%, the selectivity to propionaldehyde was 1.87%, the selectivity to acrolein was 0.98%, the selectivity to propionic acid was 1.28%, and the selectivity to gas phase product was 5.26%.
Example 10
1. Re/H doped with metal Re 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Preparation of the Material
Weigh 14gTi (SO) 4 ) 2 Dissolving a solid sample in 40g of deionized water, sequentially adding 16g of 30wt% hydrogen peroxide and 5.04g of polyethylene glycol (PEG, sigma-Aldrich, 15-20 kDa), and uniformly stirring; slowly dripping 9.76g of concentrated phosphoric acid with the concentration of 85 percent, and strongly stirring to obtain solution A; 0.3696g NH 4 ReO 4 A solution of 0.1651 mol/L; subsequently, NH is added under stirring 4 ReO 4 Dropwise adding the solution into the solution A; drying the mother solution in a vacuum drying oven at 50deg.C for 72H, and calcining the dried sample at 650deg.C for 10H to obtain Re/H doped with 3.07wt% metal Re 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x Raw material powder.
2. Catalyst Performance test
The catalyst 2g is placed in the middle of a reactor, the upper part of the reactor is filled with a magnetic ring, the temperature is raised to 400 ℃ in an oxygen-nitrogen mixed gas flow with the oxygen volume fraction of 30 percent, the mixed raw materials of methanol and acetic acid with the mol ratio of 1:1 are injected into a reaction system at the feeding speed of 3 mL/h, and the reaction pressure is controlled at 0.1 MPa. The raw materials pass through a magnetic ring preheating zone to catalyze the bed reaction, the products are guided into a cold trap absorption device to carry out gas-liquid separation, and liquid-phase products are collected. Reaction 2 h, after waiting 1h, the product was collected and analyzed. The conversion of acetic acid was 77.2%, the selectivity to acrylic acid and methyl acrylate in the main product was 81.1%, the space-time yield was 54.94 g-1 min-1, the selectivity to methyl acetate was 6.06%, the selectivity to dimethyl ether was 1.71%, the selectivity to acetaldehyde was 1.23%, the selectivity to propionaldehyde was 0.97%, the selectivity to acrolein was 0.84%, the selectivity to propionic acid was 0.67%, and the selectivity to gas phase product was 6.92%.
3. Catalyst stability test
The catalyst continuously and stably runs for 150 h under the experimental conditions, still keeps the initial activity, and the selectivity and space-time yield of the acrylic acid and the methyl acrylate are gradually reduced after 150 h and reach 39.1 percent, 28.48 g-1 min after 200 h -1 The catalyst shows excellent activity and stability in direct synthesis of acrylic acid from methanol and acetic acid, and has great application potential.

Claims (6)

1. A metal doped sodium super ionic catalyst characterized by: comprises Mn, Y, mo, bi, re metal modified components and Ti, P, S, O, H element components forming a main body structure of the sodium super-ion conductor, wherein the mass percentage components of the metal modified components are Me:0.06-4%; h 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x :96-99.94%, wherein the doped metal component Me is one or any two of Mn, Y, mo, bi, re, and x=0.7-1.
2. A method for preparing the metal-doped sodium super ionic catalyst of claim 1, comprising the steps of:
weighing titanium sulfate Ti (SO) 4 ) 2 Dissolving a solid sample in deionized water to prepare a solution with the concentration range of 1.4-2.0 mol/L, adding 30wt% hydrogen peroxide as a stabilizer and polyethylene glycol PEG as a dispersing agent, and uniformly stirring; slowly dripping concentrated phosphoric acid with the concentration of 85%wt, and strongly stirring to obtain solution A; in addition, the salt Mesalt corresponding to the doped metal is weighed and dissolved in distilled water to prepare a solution with the concentration range of 0.01-0.58 mol/L; subsequently, the salt solution doped with the metal is added dropwise to the solution a under stirring; drying the mother solution in a vacuum drying oven at 50-70deg.C for 48-72H, and calcining the dried sample at 550-650deg.C for 8-12H to obtain Me/H doped with Me metal 1-x Ti 2 (PO 4 ) 3-x (SO 4 ) x The raw material powder is pressed into tablets, crushed and sieved into particles with 20-40 meshes, and the required catalyst is obtained.
3. The method for preparing the metal-doped sodium super ionic catalyst according to claim 2, wherein: the mass ratio of each raw material is Ti (SO) 4 ) 2 ：30wt%H 2 O 2 ：PEG：Me salt：85wt%H 3 PO 4 =（14-18.88）：（15.28-18）：（5.04-6）：（0.018-1.369）：9.76；
Wherein, the salt Mesalt corresponding to the doped metal is manganese sulfate MnSO 4 ·H 2 O, yttrium nitrate Y (NO) 3 ) 3 ·6H 2 O, ammonium molybdate (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, bismuth nitrate Bi (NO) 3 ) 3 ·5H 2 O, ammonium rhenate NH 4 ReO 4 One or two of them.
4. Use of the catalyst of claim 1 in direct synthesis of acrylic acid and esters thereof from methanol and acetic acid.
5. The use according to claim 4, characterized by the steps of:
the catalyst is applied to the reaction of directly synthesizing acrylic acid and esters thereof from methanol and acetic acid, the catalytic reaction is carried out in a fixed bed reactor, and the catalyst with 20-40 mesh particle size is arranged in the middle of the reactor; the catalyst is heated to the reaction temperature under the mixed atmosphere of oxygen and nitrogen; when the catalytic reaction is carried out, the molar ratio of raw material methanol to acetic acid is controlled to be 1-4:1, the space velocity of reaction liquid is controlled to be 1-2 mL/(g.h), the reaction temperature is controlled to be 340-400 ℃, the reaction pressure is normal pressure, in the reaction process, the mixed gas of oxygen and nitrogen with the volume fraction of 20-100% is used as oxidizing atmosphere and carrier gas, and the gas flow rate is controlled to be 5-15 mL/min per gram of catalyst.
6. The use according to claim 4, characterized in that: conversion of acetic acidThe conversion rate is more than 50%, the selectivity performance of acrylic acid and acrylic ester is more than 60%, and the space-time yield is 30 mu mol g -1 ·min -1 The above.
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CN112279233A (en) * 2020-10-21 2021-01-29 宁波大学 Cl-Doped epsilon-LiVOPO4Lithium fast ion conductor and liquid phase preparation method thereof

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CN109244444A (en) * 2018-08-29 2019-01-18 湘潭大学 A kind of lithium-rich manganese-based layered oxide positive electrode and preparation method thereof of niobium doping
CN109364967A (en) * 2018-10-17 2019-02-22 中国科学院山西煤炭化学研究所 A kind of multi-functional catalysis material of superionic conductors type and preparation method and application
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