CN1100667A - Catalyst for prepn. of formaldehyde by oxidation of methanol - Google Patents
Catalyst for prepn. of formaldehyde by oxidation of methanol Download PDFInfo
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- CN1100667A CN1100667A CN 93117583 CN93117583A CN1100667A CN 1100667 A CN1100667 A CN 1100667A CN 93117583 CN93117583 CN 93117583 CN 93117583 A CN93117583 A CN 93117583A CN 1100667 A CN1100667 A CN 1100667A
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Abstract
The catalyst is prepared from active molybdenum component and structural assistant metal oxide by coprecipitation method, it can be two components, three components or four components, when using coprecipitation method, the precipitate is no longer washed by nitrified solution, thus simplifying the process and reducing the pollution and corrosion, the catalyst produced is highly stable, active and selective.
Description
The invention belongs to the organic catalyst compound field.
Formaldehyde is the important Organic Ingredients that is used to produce phenolic resins, Lauxite, melamine resin, vinylon fiber, black tropine, pentaerythrite, 1,4-butanediol etc.Industrial formaldehyde is mainly made by the methyl alcohol direct oxidation, and mostly that was adopted in its synthesis technique is silver-colored series catalysts in the past, is now replaced by metal oxide catalyst gradually.
Technology with the preparation of metal oxides catalyst has obtained open in following several pieces of patents.At European patent Eup0423692A
1In the narration be with molybdenum oxide and metal (chromium, vanadium, aluminium, iron, tungsten, magnesium) oxide is stated from as the activity of such catalysts component on a kind of inert fiber carrier made from thermal resistance material silica, the preparation of this carrier is by traditional wave inception machine the silica fibre sheet to be rolled out corrugated, form crosslinked ripple stone column structure with stone column shape structural body again, carrier is an adhesive with silica or antimony oxide, see this Preparation of catalysts process thus owing to will make this inert carrier earlier, and become complicated and not easy to operate, moreover resulting formaldehyde yield is the highest in methanol oxidation just has only 95.6% for the catalyst that obtains according to this method.At american documentation literature USP4,420, the preparation of molybdenum-iron oxide catalyst has been described in 421, it adopts sodium molybdate (the dead catalyst effect by sodium hydrate aqueous solution and trioxygen-containing molybdenum makes) as the molybdenum source, soluble ferric iron salt is joined in the sodium molybdate solution control PH to form through co-precipitation between 5.0-5.5, this catalyst is in methanol oxidation system formaldehyde, its conversion ratio has only 93%-95%(mol), formaldehyde yield 92%(mol), selectivity 97%(mol), tracing it to its cause is, when do the molybdenum source with sodium molybdate, the catalyst that obtain not contain sodium is very difficult.After catalyst contains insoluble sodium salt, thereby cause the reaction of quickening the methyl alcohol burning, form CO
2And H
2O is so that reduce the yield of formaldehyde.The preparation method of a kind of chromium that is used for methanol oxidation system formaldehyde equally, iron, molybdenum catalyst has been proposed in the patent documentation SU1109192 of the former Soviet Union, this method and content described in the invention are the most close, its preparation process is to add ammonium hydroxide in ammonium heptamolybdate, in the solution of gained, add Cr(Cr+Fe then)=chromic nitrate of 0.5-0.9 and the mixture of iron nitrate aqueous solution, till the solution pH value reaches 3.6-4.4 co-precipitation end.Then sediment is separated mother liquor, use the water through the nitric acid acidifying to be washed, this has brought inevitable etching problem to equipment.What this method of complying with made is stability, activity and the not high enough catalyst of selectivity.In addition, the content of chromium is greater than 50% in this catalyst component, and the cost that this has improved catalyst is unsuitable for industrial production.
In view of the problem that above-mentioned prior art exists, it is higher to the objective of the invention is to develop a kind of stability, activity and selectivity, and chromium content is less than 50% low-cost catalyst, to be used for the technology of methanol oxidation system formaldehyde.This catalyst is mixed mutually with structural promoter M by the active constituent molybdenum and forms, and M selects in the oxide of iron, chromium, cobalt or their mixture.Promptly the catalyst of being invented can be two component molybdenums, iron; Also can be three component molybdenums, iron, cobalt or molybdenum, iron, chromium; Can also be four component molybdenums, iron, cobalt, chromium.Catalyst Mo/M is the 1.5-5(atomic ratio).
The present invention seeks to by can being iron, cobalt, chromium or their mixture with M() nitrate aqueous solution join in the ammonium heptamolybdate aqueous solution and obtain sediment, and realize control PH＜3.5.The detailed preparation process of catalyst is as described below:
Catalyst of the present invention adopts the coprecipitation preparation, at first in the ammonium heptamolybdate aqueous solution, add 20%-25% ammonium hydroxide, the PH that makes solution is 6.3-9, purpose is intended to change ammonium heptamolybdate into positive ammonium molybdate, because charging rate is to generating the big or small extremely important of catalyst crystal grain, precipitation reaction was generally finished in 1-60 minute, under strong agitation, can be iron, cobalt, chromium or their mixture with M(then) nitrate aqueous solution join in the ammonium molybdate solution.When the PH of suspension reached 1.0-3.5, the method with adding rare ammonium hydroxide remained unchanged PH, till precipitation reaction finishes.This PH scope can guarantee active constituent (iron, chromium, molybdenum, cobalt etc.), and co-precipitation is come out from solution to greatest extent, and makes and have high stability, active and catalyst optionally.Stirred for several hour still after precipitation reaction finishes.Promptly remove mother liquor with filtration method, precipitation is carried out drying with distilled water washing between 80 ℃-200 ℃, and rear catalyst is through pulverizing, sieve into the 10-20 order, and calcines under 370 ℃-450 ℃, obtains the catalyst finished product.Adopt different proportionings (atomic ratio) in the different component catalysts.Two component catalysts: Mo: Fe=1: (0.2-0.67); Three component catalysts: Mo: Fe: Co=1: (0.2-0.67): (0.002-0.33) or Mo: Fe: Cr=1: (0.2-0.67): (0.002-0.33); Four component catalysts: Mo: Fe: Co: Cr=1: (0.2-0.67): (0.002-0.33): (0.002-0.33).
In sum, Preparation of catalysts of the present invention is finished by operations such as co-precipitation, filtration, washing, drying, calcinings.The evaluation test of this catalyst is that the catalyst with certain volume places fixed bed reactors, feeds methyl alcohol and air Mixture and produces formaldehyde.Usually methanol content is the 2.5%-6%(mole), be preferably the 6%(mole), air mass flow be 60 liters/time, in air speed 10
4-2 * 10
4Hr
-1, be preferably 1.5 * 10
4Hr
-1, 300 ℃-380 ℃ of reaction temperatures, preferably 340 ℃-380 ℃ the time, formaldehyde yield 95.6%-98.8%, formaldehyde conversion ratio are 99%-100%, the formaldehyde selectivity is 98.8%-99.9%.
Hence one can see that, adopts the molybdenum-iron catalyst of coprecipitation preparation of the present invention to have following characteristics:
1, catalyst activity height of the present invention, selectivity is good, can see no matter being two component molybdenums, iron catalyst, three component molybdenums, iron, Co catalysts or molybdenum, iron, chrome catalysts by table 1, still four component molybdenums, iron, chromium, Co catalysts all obtain satisfied result in evaluation test.
2, because the catalyst composition can be two components, three components or four components, this has brought greater flexibility to Preparation of catalysts.
3, when catalyst adds the chromium component, chromium content can be less than 50%, and do not influence activity of such catalysts and selectivity.Simultaneously, because this invention catalyst chromium content is far below 50%, the cost of catalyst has obtained tangible reduction.
4, adopt coprecipitation to prepare catalyst, when precipitation reaction takes place until end, the pH value of its suspension all maintains in the scope of 1.0-3.5, this can guarantee that active constituent (iron, chromium, molybdenum, cobalt) is precipitated out to greatest extent from solution, thereby helps to improve activity of such catalysts and selectivity.
5, in preparation catalyst process, sediment no longer adopts the solution washing through the nitric acid acidifying, and uses the deionized water washing instead, and this makes more convenient to operate, has also avoided because the corrosion that the introducing of nitric acid brings to equipment.
Embodiment 1
Under strong agitation, to 560 milliliter 15%, PH is that to add concentration in 7.2 the ammonium heptamolybdate aqueous solution be 8% iron nitrate solution, when the PH of suspension reaches 1.4, begin to add concentration and be 10% ammonium hydroxide solution,diluted, its PH is remained unchanged, and till precipitation reaction finished, precipitation reaction was finished in 21 minutes.This moment, suspension should continue to stir 2 hours, will precipitate with mother liquor after filtering and separate, and then used the distilled water washing precipitation, and is dry down at 80-200 ℃.Calcined 5 hours down at 400 ℃.Catalyst is made up of Mo, Fe two components, and the Mo/Fe atomic ratio is 2.34 in the catalyst.When reaction temperature is 340 ℃, air speed is 1.5 * 10
4Hr
-1With methanol concentration be the 6%(mole) time, methanol conversion is the 100%(mole), the formaldehyde yield is the 98%(mole).
Embodiment 2
With example 1, to PH be 7.5, concentration is to add 10% nitrate aqueous solution in 15% the ammonium molybdate solution, wherein contain ferric nitrate 105 grams, cobalt nitrate 4.5 grams, the pH value when precipitation stops is 2.3, precipitation reaction was carried out 12 minutes, calcined 4 hours down at 450 ℃, it is Mo, Fe, Co three components, wherein Mo/(Fe+Co that catalyst is formed) atomic ratio is 2.5, is 0.04 Co/(Fe+Co).In reaction temperature is under 320 ℃, and methanol conversion is the 98.9%(mole), selectivity is the 98.2%(mole), the formaldehyde yield is the 97.1mol%(mole).
Embodiment 3
With example 1, to PH be 6.8, concentration is to add 10% nitrate aqueous solution in 20% the ammonium molybdate solution, wherein contain 82 gram ferric nitrates and 27.2 gram chromic nitrates, precipitation reaction carries out at the end that PH is 1.8, will precipitate lasting 15 minutes, calcining heat is 430 ℃, it is Mo, Fe, Cr three components, wherein Mo/(Fe+Cr that catalyst is formed)=2.52, Cr/(Fe+Cr)=0.25, evaluation result is a methanol conversion 100%(mole), formaldehyde yield 98.8%(mole).
Embodiment 4
With example 1, to PH be 6.6, concentration is to add 10% nitrate aqueous solution in 15% the ammonium molybdate solution, wherein contains ferric nitrate 100 grams, chromic nitrate 9.5 grams and cobalt nitrate 6 restrain.Precipitation reaction at the end pH value is 2.5, precipitation continues 32 minutes, it is four components that catalyst is formed, Mo/(Fe+Cr+Co wherein) atomic ratio is 2.38, Cr/(Fe+Cr+Co) be 0.08 and Co/(Fe+Cr+Co)=0.05, catalyst is under 340 ℃, and evaluation result is that methanol conversion is the 100%(mole), formaldehyde yield 98.8%(mole).
Comparative example:
This test is to be undertaken by the method for patent SU1109192.
113.6 gram ammonium heptamolybdates are dissolved in 420 ml waters, so that the concentration of solution is 20.5%, the hydro-oxidation aqueous ammonium makes its PH=6.8, mixing strongly down, the aqueous solution (solution concentration is 10%) that will contain 81 gram ferric nitrates and 27.2 gram chromic nitrates joins in the ammonium molybdate solution.When the suspension pH value reaches 4, begin to add 10% ammonium hydroxide, its pH value is remained unchanged, till precipitation reaction finished, precipitation continued 17 minutes.After this, suspension continues to stir 2 hours, will precipitate with mother liquor and separate, and adopts the acidifying water washing of PH=4.Calcined 4 hours down at 420 ℃ dry back.Catalyst is made up of Mo, Fe, Cr three components, wherein Mo/(Fe+Cr) atomic ratio is 2.5, Cr/(Fe+Cr)=0.25.When reaction temperature was 340 ℃, methanol conversion was the 100%(mole), the formaldehyde yield is the 92.6%(mole).
Above different embodiment and comparative example is enumerated Preparation of catalysts technology and evaluation result is listed in the table below.
Claims (6)
1, a kind of carbon monoxide-olefin polymeric by methanol oxidation system formaldehyde, it is to adopt molybdenum as Main Ingredients and Appearance, and adds the catalyst that other metal oxide is made structural promoter, it is characterized in that: this catalyst can be molybdenum, iron two components; Can be molybdenum, iron, chromium or molybdenum, iron, cobalt three components; Can also be molybdenum, iron, chromium, cobalt four components.
2, according to claim 1, when catalyst is two component molybdenums, iron, its Mo: Fe=1: (0.2-0.67); When in the catalyst when three component molybdenums, iron, cobalt or molybdenum, iron, chromium, its Mo: Fe: Co=1: (0.2-0.67): (0.002-0.33) or Mo: Fe: Cr=1: (0.2-0.67): (0.002-0.33); Mo: Fe: Co: Cr=1: (0.2-0.67): (0.002-0.33): (0.002-0.33) when catalyst is four component molybdenums, iron, cobalt, chromium.
3, a kind of catalyst by methanol oxidation system formaldehyde, it adopts coprecipitation to make, it is characterized in that: solution adopts the mode that feeds the variable concentrations Ammonia to keep different PH scopes before and after the precipitation, to guarantee that catalyst activity component is precipitated out to greatest extent from solution.
4, as described in the claim 3, be that to add concentration in the 15%-20% Ammoniun Heptamolybdate Solution be 20-25% ammonium hydroxide in the concentration of preparation in advance, so that solution PH is 6.3-9, thereby guarantee that ammonium heptamolybdate changes positive ammonium molybdate into.
5, as described in the claim 3, in in ammonium molybdate solution, adding the containing metal nitrate aqueous solution of selecting as required under the strong agitation, obtain suspension, and with the mode that adds ammonium hydroxide solution,diluted, keep solution PH 1.0-3.5, till the solution precipitation reaction finishes, be precipitated out to greatest extent to guarantee the active constituent that is added, thereby make high activity and high selecting catalyst.
6, as described in the claim 3, precipitation reaction need be controlled in 1-60 minute and finish, so that the catalyst that makes has suitable crystal grain and structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93117583A CN1044339C (en) | 1993-09-24 | 1993-09-24 | Catalyst for prepn. of formaldehyde by oxidation of methanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93117583A CN1044339C (en) | 1993-09-24 | 1993-09-24 | Catalyst for prepn. of formaldehyde by oxidation of methanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1100667A true CN1100667A (en) | 1995-03-29 |
| CN1044339C CN1044339C (en) | 1999-07-28 |
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ID=4992095
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93117583A Expired - Fee Related CN1044339C (en) | 1993-09-24 | 1993-09-24 | Catalyst for prepn. of formaldehyde by oxidation of methanol |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103244C (en) * | 1999-08-09 | 2003-03-19 | 中国石油化工集团公司 | Novel load silver catalyst and preparation process thereof |
| CN100413584C (en) * | 2003-12-09 | 2008-08-27 | 南化集团研究院 | Fe-Mo catalyst for preparing formaldehyde through methanol oxidation and preparation process thereof |
| CN102274722A (en) * | 2011-06-17 | 2011-12-14 | 中国科学院福建物质结构研究所 | V2O3 for preparing anhydrous formaldehyde by directly dehydrogenizing methanol as well as supported V2O3 catalyst and preparation method thereof |
| CN1792443B (en) * | 2004-12-22 | 2012-05-02 | 舒德化学催化剂意大利有限责任公司 | Catalysts for oxidation of methanol to formaldehyde |
| CN106693981A (en) * | 2016-12-22 | 2017-05-24 | 中国科学院山西煤炭化学研究所 | Iron-molybdenum catalyst for formaldehyde synthesis through methanol oxidation as well as preparation method and application |
| CN108816241A (en) * | 2018-06-04 | 2018-11-16 | 常州新日催化剂有限公司 | The preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst |
| CN113368863A (en) * | 2021-07-01 | 2021-09-10 | 大连瑞克科技股份有限公司 | Preparation method of eggshell type iron-molybdenum catalyst containing silicon dioxide |
| CN114345362A (en) * | 2020-10-12 | 2022-04-15 | 中石化南京化工研究院有限公司 | Iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation and preparation method thereof |
| WO2022142709A1 (en) | 2020-12-29 | 2022-07-07 | 上海华谊新材料有限公司 | Supported composite oxide catalyst and preparation and use thereof |
| WO2022142708A1 (en) | 2020-12-29 | 2022-07-07 | 上海华谊新材料有限公司 | Composite oxide catalyst, preparation method therefor, and use thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1134538B (en) * | 1980-12-02 | 1986-08-13 | Euteco Impianti Spa | PROCEDURE FOR THE PREPARATION OF CATALYSTS SUITABLE FOR THE PRODUCTION OF FORMALDEHYDE FROM METHANOL |
| SU1109192A1 (en) * | 1982-04-14 | 1984-08-23 | Предприятие П/Я А-1788 | Process for preparing chromium ferrous molybdenum catalyst for oxidizing methanol |
| IT1214489B (en) * | 1985-04-24 | 1990-01-18 | Ausind Spa | HIGH YIELD AND HIGH MECHANICAL RESISTANCE CATALYSTS, PARTICULARLY SUITABLE FOR METHANOL OXIDATION TO FORMALDEHYDE. |
| CZ286616B6 (en) * | 1989-10-16 | 2000-05-17 | Haldor Topsoe A/S | Catalyst for preparing aldehydes |
-
1993
- 1993-09-24 CN CN93117583A patent/CN1044339C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1103244C (en) * | 1999-08-09 | 2003-03-19 | 中国石油化工集团公司 | Novel load silver catalyst and preparation process thereof |
| CN100413584C (en) * | 2003-12-09 | 2008-08-27 | 南化集团研究院 | Fe-Mo catalyst for preparing formaldehyde through methanol oxidation and preparation process thereof |
| CN1792443B (en) * | 2004-12-22 | 2012-05-02 | 舒德化学催化剂意大利有限责任公司 | Catalysts for oxidation of methanol to formaldehyde |
| CN102274722A (en) * | 2011-06-17 | 2011-12-14 | 中国科学院福建物质结构研究所 | V2O3 for preparing anhydrous formaldehyde by directly dehydrogenizing methanol as well as supported V2O3 catalyst and preparation method thereof |
| CN106693981A (en) * | 2016-12-22 | 2017-05-24 | 中国科学院山西煤炭化学研究所 | Iron-molybdenum catalyst for formaldehyde synthesis through methanol oxidation as well as preparation method and application |
| CN106693981B (en) * | 2016-12-22 | 2020-05-01 | 中国科学院山西煤炭化学研究所 | Iron-molybdenum catalyst for synthesizing formaldehyde by oxidizing methanol, preparation method and application thereof |
| CN108816241A (en) * | 2018-06-04 | 2018-11-16 | 常州新日催化剂有限公司 | The preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst |
| CN114345362A (en) * | 2020-10-12 | 2022-04-15 | 中石化南京化工研究院有限公司 | Iron-molybdenum-based catalyst for preparing formaldehyde by methanol oxidation and preparation method thereof |
| WO2022142709A1 (en) | 2020-12-29 | 2022-07-07 | 上海华谊新材料有限公司 | Supported composite oxide catalyst and preparation and use thereof |
| WO2022142708A1 (en) | 2020-12-29 | 2022-07-07 | 上海华谊新材料有限公司 | Composite oxide catalyst, preparation method therefor, and use thereof |
| CN113368863A (en) * | 2021-07-01 | 2021-09-10 | 大连瑞克科技股份有限公司 | Preparation method of eggshell type iron-molybdenum catalyst containing silicon dioxide |
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| Publication number | Publication date |
|---|---|
| CN1044339C (en) | 1999-07-28 |
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