CN1173778C - Carried siver catalyst for preparing anhydrous formaldehyde and its preparing process - Google Patents
Carried siver catalyst for preparing anhydrous formaldehyde and its preparing process Download PDFInfo
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- CN1173778C CN1173778C CNB021120560A CN02112056A CN1173778C CN 1173778 C CN1173778 C CN 1173778C CN B021120560 A CNB021120560 A CN B021120560A CN 02112056 A CN02112056 A CN 02112056A CN 1173778 C CN1173778 C CN 1173778C
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- catalyst
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- magnesium
- anhydrous formaldehyde
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention belongs to the technical field of chemical engineering, which is a novel loading type silver catalyst for preparing anhydrous formaldehyde by directly dehydrogenating methanol. The catalyst is prepared by adopting a sol-gel method; after a certain amount of tetraethyl orthosilicate and a water solution containing soluble magnesium salt or an alcoholic solution are mixed, the mixed solution is dropped into an inorganic silver salt water solution; the catalyst is obtained through the steps of gelling, ageing, drying, calcining, etc. The relative weight contents of all components of the silver catalyst comprise (using silicon dioxide as reference 1): 0.1 to 50% of silver and 0.01 to 200% of magnesium. The catalyst is applied to reactions for preparing anhydrous formaldehyde by directly dehydrogenating methanol. The present invention has the advantages of high catalytic activity, long service life, easy preparation and low cost, and is suitable for industrial application.
Description
Technical field
The invention belongs to chemical technology field, is a kind of preparation method that the methyl alcohol direct dehydrogenation is produced the novel supported silver catalyst of anhydrous formaldehyde that is used for.
Background technology
Formaldehyde is the important foundation raw material of chemical industry, is widely used in the intermediate product of chemical products such as producing acetal resin, Lauxite, phenolic resins, pentaerythrite, methenamine and medicine and agricultural chemicals.And in these fields, most of formaldehyde products of using is anhydrous formaldehyde.As producing anhydrous formaldehyde, then need moisture commodity formaldehyde is carried out distillation operation.This not only needs to drop into comparatively considerable equipment, operating cost, but also, cause forming azeotropic system, thereby in actual distillation operation process because formalin relative ideal solution is the minus deviation of certain value, the dehydration separating effect is not good enough, and production cost is high.Utilizing the methyl alcohol direct dehydrogenation to synthesize anhydrous formaldehyde, then is a kind of new process of remarkable in economical benefits.At first, this method does not have water to generate, and can save rectifying device investment and operating cost thereof; But next by-product high-quality hydrogen, and hydrogen is easy to separate from reaction system.It is this that to produce in the anhydrous formaldehyde method crucial technology by the methyl alcohol direct dehydrogenation partly be the catalyst that is adopted, existing patent report is by the molten zinc of zinc, potassium, indium or the aluminium of the catalyst of being made up of copper, silver, silicon (special public clear 41-11853), fusion or the alloy of these metals (special public clear 47-19251), carbon containing or contain the alloy (spy opens clear 48-97808) of zinc and the catalyst (spy opens clear 52-215) be made up of copper, zinc, selenium etc., but these methods have various shortcoming such as catalyst life is short, reactivity is low, do not have industrial application value.In addition, the catalyst that use is made up of copper, zinc, sulphur (spy opens clear 51-1407) and form catalyst by copper, zinc, supply gas state sulfide carries out the method (spy opens clear 51-76209) of methanol dehydrogenation, sneak into sulphur in reaction product or discharge gas, this do not have industrial prospect to the disagreeableness catalyst of environment.A kind of use of catalyst containing sodium makes the formaldehyde yield bring up to 70% (Appl.Catal.2001 (213) 203), but owing to problems such as reaction temperature and catalyst life and regeneration have limited its industrial applications.
Summary of the invention
The objective of the invention is to propose a kind ofly can resist sintering, long service life, novel supported silver catalyst that is used for methyl alcohol direct dehydrogenation system anhydrous formaldehyde of higher formaldehyde productive rate and preparation method thereof is arranged again.This catalyst has advantages of high catalytic activity, prepares easyly, and price is lower, is fit to commercial Application.
The loading type silver catalyst that is used for methyl alcohol direct dehydrogenation system anhydrous formaldehyde that the present invention proposes, combine by silver, silica, magnesia, prepare by sol-gel process, wherein silicon derives from ethyl orthosilicate, the relative weight content of each component is (is benchmark 1 with silica): silver 0.1～50%, magnesium 5～10%.Preferable weight content is: silver-colored 2-30%, magnesium 5-10%; Better weight content is: silver-colored 5-10%, magnesium 5-10%.Here silver exists with the form of argent, and magnesium exists with magnesian form, so claim that the present invention is silver-silica-magnesia catalyst.
The specific surface of above-mentioned loading type silver catalyst is 0.1～5 meter
2/ gram for low specific surface carried silver catalyst, relatively is suitable for the reaction of methyl alcohol direct dehydrogenation system formaldehyde.
The invention allows for the preparation method of above-mentioned carried silver catalyst, its concrete steps are: according to above-mentioned usage ratio, with ethyl orthosilicate (TEOS) with join in water-soluble inorganic silver salt (for example silver nitrate, silver acetate, actol etc.) aqueous solution after the aqueous solution that contains the magnesium soluble-salt or alcoholic solution mix, adopt sol-gel process (SOL-GEL method), pass through into glue aging technique, boil off solvent wherein then, roasting again, granulation promptly gets this catalyst.
Among the above-mentioned preparation method, ethyl orthosilicate can once add, and also can drip by certain speed.Inorganic silver salt is silver nitrate, actol, silver acetate preferably; The concentration of its aqueous solution is between 0.001mol/L～1.000mol/L, and magnesium adopts water-soluble inorganic salt solution form to add, nitrate preferably, and its component content is generally 0.01～200% of silica, and reasonable is 5～10% (weight ratios).The above-mentioned solution that mixes is stirred (electromagnetic agitation or mechanical agitation), become the glue temperature to be generally 50～200 ℃, becoming the glue temperature preferably is 60～150 ℃.After treating that colloid solidification is gel, remove low boiling point solvent.The removal method can be placement, infrared lamp oven dry, low-temperature vacuum drying or muffle furnace roasting etc. in the air, and reasonable is to adopt low-temp vacuum method for drying.Dried catalyst is roasting under given atmosphere again.The atmosphere of roasting is generally air, oxygen, nitrogen, argon gas or hydrogen, is preferably nitrogen or argon gas.Sintering temperature is generally 500～1500 ℃, and reasonable temperature is 700～1000 ℃.Catalyst after the roasting can be worn into the particle of all size on demand, and reasonable granularity is 20～80 orders.
Can test with the following method activity of such catalysts provided by the invention:
The present invention adopts the fixed bed flow method to investigate catalyst activity.By Bubbling method methanol steam (vapourizing temperature is 30～60 ℃) is sent into reactor and contact 450～750 ℃ of reaction temperatures, H in reacted methanol content, content of formaldehyde and the tail gas with catalyst
2, CO and CO
2Content measure by gas chromatography respectively.
Reactor is that an internal diameter is 4.5 millimeters a quartz ampoule, and the novel load silver catalyst that makes places the reaction tube constant temperature zone, and catalytic bed temperature is measured with nickel chromium-nickel silicon thermocouple, and the point for measuring temperature of thermocouple places catalytic bed bottom centre place.
The temperature of the outer electric furnace of conditioned reaction device makes the reaction temperature of catalytic bed be stabilized in required numerical value.Among the present invention, reaction condition should be controlled at appropriate value.The reaction bed temperature is between 450～750 ℃.The catalyst bed layer height is between 5～50mm.The reacting gas air speed is controlled at 1 * 10
4～30 * 10
4Hr
-1Between (under the standard state).
Catalyst provided by the invention has following advantage:
1, the catalytic activity height of catalyst, the silver that the present invention makes-silica-magnesia catalyst in the reaction of methyl alcohol direct dehydrogenation system anhydrous formaldehyde, can obtain surpassing 75% formaldehyde yield, and it is nearly 80% that the selectivity of formaldehyde also reaches, and has industrial value.
2, the anti-sintering of this catalyst series can prolong life of catalyst greatly.
3, this catalyst is insensitive to response parameter, broad between the operating space, and elasticity is big, is convenient to production control, is suitable for industrial application.
4, this Preparation of Catalyst is simple, and consumption silver amount is low, is convenient to large-scale industrial production.
The specific embodiment
The invention is further illustrated by the following examples.
Embodiment 1: take by weighing the 0.75g silver nitrate and be dissolved in 100mL water, add 5.56g Mg (NO
3)
26H
2O, treat that dissolving is placed in the 250mL three-necked bottle, dropwise add the 33mL ethyl orthosilicate, simultaneously violent electromagnetic agitation is kept 70 ℃ of oil bath temperatures, and adding 50mL gelatinizing agent～isopropyl alcohol, load onto reflux condensing tube, stir colloidal sol curing after three hours, stop to stir, be warming up to 100 ℃, evaporating solvent 12 hours.Be transferred to a crucible,, be transferred to 700 ℃ of roastings of muffle furnace 6 hours then, be crushed to 40～60 orders, can get the Ag-SiO of silver content 5% with infrared lamp baking 24 hours
2-MgO catalyst is designated as the 1# catalyst.
Embodiment 2: take by weighing the 1.5g silver nitrate and be dissolved in 100mL water, add 5.56g Mg (NO
3)
26H
2O, treat the dissolving be placed on-the 250mL three-necked bottle in, disposable adding 33mL ethyl orthosilicate, simultaneously violent electromagnetic agitation is kept 75 ℃ of oil bath temperatures, and adding 50mL gelatinizing agent～ethanol, load onto reflux condensing tube, stir colloidal sol curing after six hours, stop to stir, be warming up to 90 ℃, evaporating solvent 24 hours.Be transferred to a crucible,, be transferred to 650 ℃ of roastings of muffle furnace 10 hours then, be crushed to 40～60 orders, can get the Ag-SiO of silver content 10% with infrared lamp baking 24 hours
2-MgO catalyst is designated as the 2# catalyst.
Embodiment 3: take by weighing the 2.25g silver nitrate and be dissolved in 100mL water, add 5.56g Mg (NO
3)
26H
2The O dissolving, using 50mL ethanol instead is gelatinizing agent, and addend drips 1mol/L HNO
3Assist into glue, surplus with example 2, can get the Ag-SiO of silver content 15%
2-MgO catalyst is designated as the 3# catalyst.
Embodiment 4: take by weighing the 3.0g silver nitrate and be dissolved in 100mL water, add 2.28 Mg (NO
3)
26H
2After the O dissolving, using the 50mL diglycol instead is gelatinizing agent, surplus with example 1, can get silver content and be 20% Ag-SiO
2-MgO catalyst is designated as the 4# catalyst.
Embodiment 5: take by weighing the 3.75g silver nitrate and be dissolved in 100mL water, add 5.56g Mg (NO
3)
26H
2O dissolving, adopting the 50mL tert-butyl alcohol is gelatinizing agent, surplus with example 3, can get silver content and be 25% Ag-SiO
2-MgO catalyst is counted the 5# catalyst.
Embodiment 6: take by weighing the 4.5g silver nitrate and be dissolved in 100mL water, add 5.56g Mg (NO
3)
26H
2O dissolving, adopting 50mL ethanol is gelatinizing agent, surplus with example 3, can get silver content and be 30% Ag-SiO
2-MgO catalyst is counted the 6# catalyst.
6 catalyst of embodiment 1～embodiment 6 are carried out active testing, and condition that is adopted and best yield are listed in respectively
Table 1.
Table 1. silver-silica-magnesia catalyst optimum reaction condition and active result
| Catalyst | Temperature (℃) | Methanol conversion (mol%) | Formaldehyde yield (mol%) | CO+CO 2Productive rate (mol%) |
| 1# | 645 | 79.9 | 58.7 | 21.2 |
| 2# | 630 | 94.4 | 62.9 | 31.5 |
| 3# | 655 | 94.6 | 63.8 | 30.8 |
| 4# | 635 | 96.6 | 75.1 | 21.5 |
| 5# | 620 | 94.0 | 70.9 | 23.1 |
| 6# | 620 | 90.7 | 64.8 | 25.9 |
Claims (6)
1, a kind of loading type silver catalyst that is used for methyl alcohol direct dehydrogenation system anhydrous formaldehyde, combine by silver, silica, magnesia, what it is characterized in that each component is that the weight content of radix 1 is with respect to silica: silver 0.1～50%, magnesium 5～10%, silver exists with the form of argent, and magnesium exists with magnesian form.
2, a kind of preparation method of loading type silver catalyst according to claim 1, it is characterized in that: according to usage ratio, with ethyl orthosilicate with after the aqueous solution that contains the magnesium soluble-salt or alcoholic solution mix, join in the inorganic silver saline solution,, pass through into glue, aging technique by sol-gel process, boil off solvent wherein then, roasting again, granulation promptly gets this catalyst.
3, Preparation of catalysts method according to claim 2 is characterized in that inorganic silver salt is a kind of of silver nitrate, actol or silver acetate, the concentration of the aqueous solution at 0.001mol/l between the 1.000mol/l; Magnesium adopts water-soluble inorganic salt solution form to add, and content is the percentage by weight of the 5-10% of silica; Becoming the glue temperature is 50～200 ℃, and sintering temperature is 500～1500 ℃.
4, Preparation of catalysts method according to claim 3, it is characterized in that into the glue temperature is 60～150 ℃.
5, Preparation of catalysts method according to claim 3 is characterized in that sintering temperature is 700～1000 ℃.
6, Preparation of catalysts method according to claim 2 is characterized in that calcination atmosphere is air, oxygen, nitrogen, hydrogen or radon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021120560A CN1173778C (en) | 2002-06-13 | 2002-06-13 | Carried siver catalyst for preparing anhydrous formaldehyde and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021120560A CN1173778C (en) | 2002-06-13 | 2002-06-13 | Carried siver catalyst for preparing anhydrous formaldehyde and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1390639A CN1390639A (en) | 2003-01-15 |
| CN1173778C true CN1173778C (en) | 2004-11-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021120560A Expired - Fee Related CN1173778C (en) | 2002-06-13 | 2002-06-13 | Carried siver catalyst for preparing anhydrous formaldehyde and its preparing process |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348570C (en) * | 2004-10-26 | 2007-11-14 | 中国科学院长春应用化学研究所 | Method for catalytic oxidation preparation of methyl formate from methanol |
| CN101961650B (en) * | 2010-09-10 | 2012-08-29 | 常州大学 | Zirconium base catalyst, preparation method and application in preparation of anhydrous formaldehyde |
| CN107827720B (en) * | 2017-10-24 | 2021-02-26 | 安徽省福泰精细化工有限责任公司 | Production method for improving concentration of formaldehyde |
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2002
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