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Catalyst for preparing formaldehyde by methanol oxidation

A catalyst, oxidation technology, applied in the direction of physical/chemical process catalyst, metal/metal oxide/metal hydroxide catalyst, carbon-based compound preparation, etc., can solve the problems of high reaction temperature and low yield of target product, etc. To achieve the effect of lowering the reaction temperature, reducing the loss and improving the yield

Active Publication Date: 2014-07-23
TSINGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] However, iron molybdenum oxide catalysts usually have disadvantages such as low yield of target product (formaldehyde) and high reaction temperature.

Method used

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  • Catalyst for preparing formaldehyde by methanol oxidation
  • Catalyst for preparing formaldehyde by methanol oxidation
  • Catalyst for preparing formaldehyde by methanol oxidation

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0020] The preparation method comprises the following steps:

[0021] a) Provide a mixed material containing water-soluble molybdenum salt and soluble vanadium salt

[0022] It should be noted that molybdenum in the catalyst of the present invention can be molybdenum in any oxide form, such as molybdenum oxide or molybdate. More preferred are water soluble molybdenum salts, most preferably the starting material is ammonium molybdate.

[0023] In addition, the vanadium element in the catalyst can be introduced by a similar method, and the preferred starting material is ammonium metavanadate.

[0024] In order to improve the strength of the catalyst, according to some embodiments of the present invention, the step a) includes:

[0025] a-1) preparing the water-soluble molybdenum salt and the soluble vanadium salt into a mixed solution;

[0026] a-2) adding silica sol into the mixed solution to obtain the mixed material.

[0027] Wherein, when the catalyst is used in a fluidi...

Embodiment 1

[0061] 814.6g (NH 4 ) 6 Mo 7 o 24 4H 2 O was added to hot water at 70°C, stirred to dissolve it completely, and 29.8g NH 4 VO 3 , to make material A.

[0062] Add 2500.1g 40% (wt) silica sol to material A to make material B.

[0063] 462.7gNi(NO 3 ) 2 ·6H 2 O was added to hot water at 70°C and stirred to dissolve it completely. After adding 321.4g Fe (NO 3 ) 3 9H 2 O, 169.8gBi (NO 3 ) 3 ·5H 2 O, 124.6gPr(NO 3 ) 3 ·6H 2 After O is stirred and dissolved, material C is made.

[0064] Add material C dropwise to material B under rapid stirring, and after aging for 4 hours at a constant temperature of 80°C, use an atomizing disc with a diameter of 60mm to spray dry it at a speed of 12,000 rpm at 150°C. The catalyst was placed in a rotary roaster, and activated by roasting at 670° C. for 2.5 hours to obtain a finished catalyst.

[0065] The composition of catalyst active components is shown in Table 2, and the evaluation results are shown in Table 3.

Embodiment 2～7

[0067] Except that the starting materials are added according to Table 1, the preparation method is the same as that of Example 1.

[0068] The composition of the catalyst active components is shown in Table 2. The evaluation results are shown in Table 3.

[0069] Table 1 Starting materials and corresponding dosage (unit: g)

[0070]

[0071] Table 2 Catalyst active component composition table

[0072]

[0073] Table 3 Catalyst Activity Evaluation Results

[0074]

[0075] Table 3 is the evaluation result of catalyst activity, as can be seen from the table, the embodiment that the present invention obtains is on methanol conversion rate, formaldehyde selectivity, formaldehyde yield, all compares comparative example (methanol oxidation production formaldehyde iron molybdenum used in industry) Catalyst) test results have been significantly improved, showing better results.

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Abstract

The invention discloses a catalyst for preparing formaldehyde by methanol oxidation. According to the embodiment of the invention, the catalyst takes Mo(a)Ni(b)Fe(c)Bi(d)Pr(e)Co(f)Ce(g)V(h)Cr(i)A(j)O(k) as an active ingredient, wherein A is one or more of lithium, sodium, potassium and rubidium; a, b, c, d, e, f, g, h, i, j and k are atomic number of the elements; a is 10.0-20.0; b is 3.0-7.0; c is 1.0-4.0; d is 0-4.0, e is 0-3.0, f, g, h and i are 0-3.0; j is 0-0.5; k is the number of required oxygen atoms meeting valence of other elements. According to the catalyst disclosed by the invention, the yield of the target product and the stability of the catalyst are improved. On the other hand, the optimal reaction temperature can be lowered by the catalyst disclosed by the invention, and loss of molybdenum in the catalyst and by-products of over oxidation of carbon dioxide and the like are reduced.

Description

technical field [0001] The invention belongs to the field of organic chemical catalysts, in particular to a catalyst for methanol oxidation to formaldehyde. Background technique [0002] Formaldehyde is an important basic organic chemical raw material. It has a huge output and demand in my country at present, and is widely used in chemical industry, medicine, wood processing and petroleum industry and other fields. In the current industrial production of formaldehyde, methanol oxidation is the main method. At present, the most commonly used formaldehyde preparation method is the methanol oxidation method, which can be divided into two categories according to the ratio of methanol to air in the feed - air excess method and methanol excess method. There are many patents on methanol-to-formaldehyde air excess method disclosed at home and abroad, but most of the catalysts are iron molybdenum oxides. Since 1952, iron molybdenum oxide catalysts have been widely developed and uti...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/887C07C47/055C07C45/38
Inventor 韩明汉徐剑韬甄彬王金福
Owner TSINGHUA UNIV
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