CN105732349A - Method for preparing anhydrous formaldehyde through methanol dehydrogenation - Google Patents
Method for preparing anhydrous formaldehyde through methanol dehydrogenation Download PDFInfo
- Publication number
- CN105732349A CN105732349A CN201410765026.5A CN201410765026A CN105732349A CN 105732349 A CN105732349 A CN 105732349A CN 201410765026 A CN201410765026 A CN 201410765026A CN 105732349 A CN105732349 A CN 105732349A
- Authority
- CN
- China
- Prior art keywords
- copper
- methanol
- molecular sieve
- catalyst
- based catalysts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing anhydrous formaldehyde through methanol dehydrogenation, which employs a copper-based catalyst formed of a component copper, a catalyst promoter, and a molecular sieve carrier, wherein the hydrothermal dealumination and the acid treatment are carried out on the molecular sieve carrier. The method comprises the concrete steps of: filling a quartz reaction tube with the catalyst, and putting the quartz reaction tube in a fixed bed reactor, and pre-reducing the catalyst by using methanol or hydrogen before the reaction is started; under a normal pressure, sampling the methanol through a constant-flux pump, the methanol feed ratio being 5vol%-80vol% and the methanol feed speed being 0.10-0.30 mL/(gcat.*min), taking inert gas as the carrier gas, and carrying out reaction at the temperature between 400 DEG C and 700 DEG C; and measuring the methanol conversion rate between 30% and 90%, and the formaldehyde selectivity between 25% and 78% by a chromatogram. The copper-based catalyst is carried by the dealumination molecular sieve through the hydrothermal treatment and the acid treatment. The catalyst couples the two advantages of large specific surface area of the carrier molecular sieve and high activity of the copper-based catalyst, and has higher catalytic activity and thermal stability. By-products are less, and the catalyst preparation process is simple.
Description
Technical field
The invention belongs to the field preparing anhydrous formaldehyde, be specifically related to a kind of method that methanol dehydrogenation prepares anhydrous formaldehyde.
Background technology
Formaldehyde is a kind of important Organic Chemicals, can be used to produce the thermosetting resin such as phenolic resin, melamine resin and the multiple chemical products such as hexamethylenamine, BDO, and formaldehyde is also the important source material of synthetic dyestuffs, pesticide, fine and specialty chemicals.
At present, the industrial employing methanol oxidizing process that is typically all is to prepare formaldehyde, containing substantial amounts of water in the formaldehyde of institute's output, and the vapour pressure of formalin is relatively low, formaldehyde and water are readily formed azeotropic mixture, therefore separate and purification formaldehyde is very difficult, causing that energy consumption is big, cost is high.The medicine such as engineering plastics and hexamethylenamine that synthesis performance is excellent in recent years is increasing to the demand of anhydrous formaldehyde, and anhydrous formaldehyde is all removed moisture by industrial formol aqueous solution through various methods and obtain at present, directly prepares anhydrous formaldehyde and have become as the focus of research.
Formaldehyde and byproduct hydrogen gas that methanol anaerobic dehydrogenation technique obtains are easily separated, and anhydrous generation, it is to avoid the lock out operation of formalin, are effectively saved the investment of rectifying device and the expense of operation thereof, and obtain the by-product-hydrogen of high-quality；Meanwhile, this reaction does not have methanol oxidation and generates the problem of formic acid etching apparatus, thus being conducive to the stable of formalin and purifying, and is obtained in that hydrogen can be used further to the synthesis of methanol.Therefore, methanol direct dehydrogenation formaldehyde a very promising industrial process is become.
In recent years, produce anhydrous formaldehyde remarkable in economical benefits new technology oneself cause great attention both domestic and external, and carried out substantial amounts of research work, the emphasis of research is concentrated mainly in the exploitation of effective catalyst at present, several classes such as including metal and oxide catalyst, alkali metal salt and molecular sieve catalyst.CN102274722A discloses novel V2O3And support type V2O3Preparation method, performance preferably activity in methanol dehydrogenation reacts.The Cu of the different oxidation state activity in methanol dehydrogenation reacts has been studied by Takagi etc. (TakagiK, MorikawaY, IkawaT.ChemistryLetters, 1985,14 (4): 527-530), it was found that Cu0PARA FORMALDEHYDE PRILLS(91,95) has significantly high selectivity.CN101961650A discloses a kind of method of uniform co-precipitation and prepares new type zirconium-based catalyst catalysis methanol anaerobic dehydrogenation, and the yield of formaldehyde reaches 60%.The preparation method that Dai Weilin etc. (CN1390639A, CN1537673A, CN1544147A) disclose the catalyst of a series of load silver being applied to methanol direct dehydrogenation.Patent CN101147872A prepares industrial sodium carbonate catalysis with industrial sodium bicarbonate for raw material and prepares anhydrous formaldehyde, and the industrialization preparing formaldehyde for methanol dehydrogenation lays the foundation.(the MusicA such as Music, BatistaJ, LevecJ.AppliedCatalysisA:General, 1997,165 (1-2): 115-131.) with ZSM-5 molecular sieve catalyst for parent, utilize ion exchange to prepare Na-ZSM-5, Cu-ZSM-5 type molecular sieve catalyst, the certain embodiments of methanol achieves good selectivity.
Based on the above-mentioned catalyst system and catalyzing producing anhydrous formaldehyde developed, this patent combines the advantage of abundant both the molecular sieves in the copper-based catalysts with greater activity and duct and prepares molecular sieve carried copper-based catalysts.But due in molecular sieve rich in aluminum, cause that it is with certain acidity, and then make in the course of reaction of methanol dehydrogenation, acid catalyzed Dehydration of methanol, generate dimethyl ether and water, reduce the selectivity of formaldehyde, and introduce water, run counter to the purpose preparing anhydrous formaldehyde.Therefore, this patent carrier molecule sieve carries out dealumination treatment, has both remained the advantage that high-specific surface area brings and has avoided the side reaction that acid site causes simultaneously so that methanol dehydrogenation is prepared the efficiency of anhydrous formaldehyde and increased substantially.
Summary of the invention
Meaning of the present invention is in that to overcome the shortcoming preparing the used catalyst of anhydrous formaldehyde at present, as: the skewness of copper granule in copper-based catalysts, granule is relatively big, and active surface area is less, and activity is relatively low；Modified molecular sieve catalyst Acidity of Aikalinity difficulty regulation and control, by-product is more；Traditional carbonate or bicarbonate Catalytic active phase are to inertia, and reaction temperature is generally greater than 700 DEG C.Both molecular sieves advantage that this patent combines the copper-based catalysts with greater activity and duct abundant prepares molecular sieve carried copper-based catalysts.This catalyst preparing is simple and stability is high, and reaction condition is comparatively gentle, and conversion ratio is all higher with selectivity.
The specific scheme is that of the anhydrous formaldehyde of present invention design
The preparation of anhydrous formaldehyde adopts copper-based catalysts, it is placed in fixed bed reactors after crystal reaction tube fills copper-based catalysts, before reaction, use methanol or hydrogen that copper-based catalysts is carried out prereduction at a certain temperature, under normal pressure, methanol is by constant-flux pump sample introduction, and noble gas does carrier gas, react at 400 DEG C～700 DEG C, gas chromatogram on-line checking product；
Described copper-based catalysts, in mass, consists of the following composition: the molecular sieve carrier after 1～20 part of copper, the dealuminzation of 100 parts, 0～20 part of promoter；
Described pre-reduction temperature is: 450～750 DEG C, and pre-reduction time is: 0.5～2h.
The preparation of described copper-based catalysts adopts coprecipitation method, and its process is: by the soluble-salt homogeneous precipitation of the soluble-salt of copper and promoter molecular sieve supported surface after dealuminzation, 80～150 DEG C of dry, 400～650 DEG C of air roastings；
Described molecular sieve is the one in ZSM-5, SAPO-11, SAPO-34, NaY, HY or two or more.
Molecular sieve carrier after described dealuminzation, refers to that molecular sieve adopts 100% steam to carry out hydrothermal treatment consists, then then through dilute acid pretreatment, and washing, it is dried overnight at 80～150 DEG C；
Described hydrothermal treatment consists temperature is: 400 DEG C～800 DEG C, pH=4～6 of diluted acid used by acid treatment, and the solid-to-liquid ratio of acid treatment is 1:5～1:10.
Described diluted acid i.e. the conventional acid solution that molecular sieve carries out acid treatment, it is preferred to (NH4)2SiF6, citric acid, oxalic acid, H2SiF6, hydrochloric acid, one or more in sulphuric acid.
Described promoter is one or more in zinc, chromium or potassium.
The soluble-salt of described copper is preferably one or more in copper nitrate, copper chloride, Schweinfurt green or copper sulfate, and the soluble-salt of described promoter is preferably one or more in nitrate, chloride or sulfate.
Described filling copper-based catalysts thickness of bed layer is 5mm～60mm, and methanol feeding is than 5vol%～80vol% (stereometer), and methanol feed rate is 0.10～0.30ml/ (gcat.Min), reaction temperature is 400 DEG C～700 DEG C.
Described noble gas is one or more in nitrogen, argon, helium, and flow velocity is 50mL/min～210mL/min.
Owing to molecular sieve has the duct of prosperity, abundant specific surface area, it is widely used today as catalyst or the carrier of catalytic reaction process.But due in molecular sieve rich in aluminum, cause that molecular sieve has certain acidity, and then make in the course of reaction of methanol dehydrogenation, acid catalyzed Dehydration of methanol, generate dimethyl ether and water, reduce the selectivity of formaldehyde, and introduce water, have impact on the purity of anhydrous formaldehyde.Therefore, for preparing highly purified anhydrous formaldehyde it is first necessary to effectively shield the acid site of molecular sieve.Dealumination process is a kind of effective means of the Molecular regulator sieve Acidity of Aikalinity that catalytic field adopts, generally can adopt the methods such as high-temperature roasting, hydrothermal treatment consists and chemical dealuminization that structure and the Acidity of molecular sieve are modified, to change the acid distribution of catalyst, improve the stability of catalyst.Wherein, hydrothermal dealumination process easily realizes and does not introduce any heteroion.Studies have shown that water-heat process is only stripped of framework aluminum, make non-framework aluminum, therefore, follow-up needs continues pickling, dissolves elimination non-framework aluminum, thus reaching effectively to remove the purpose in all acid sites.Molecular sieve is carried out the carrier after hydrothermal dealumination as copper-based catalysts by this patent, is applied to methanol dehydrogenation and prepares anhydrous formaldehyde.
Compare with existing catalyst system and catalyzing, have the advantage that
1) owing to molecular sieve has the duct of prosperity, bigger specific surface area, the surface that in copper-based catalysts, the copper even particulate dispersion of precipitation enriches in molecular sieve, therefore, the granule of formation is less, and active surface area is big, and activity significantly improves.
2) hydrothermal dealumination maintains outside the good structure of molecular sieve, significantly reduces the acidity of molecular sieve catalyst, and then inhibits the dehydration that in methanol dehydrogenation process, acid catalysis causes, decreases the generation of by-product, improves selectivity and the purity of formaldehyde；
3) catalyst preparation process is simple, and catalyst stability is good, has expanded methanol anaerobic dehydrogenation and has prepared the catalyst system and catalyzing of formaldehyde.
Detailed description of the invention
In order to the present invention is further elaborated, several be embodied as case is given below, but the invention is not restricted to these embodiments.
Embodiment 1
Weigh 5gZSM-5 and be placed in quartz boat, pass into 100% steam, be warming up to 800 DEG C with 6.5 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 50mLpH=4.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 90 DEG C.Weigh the ZSM-5 molecular sieve after 1.9g nitrate trihydrate copper, 2.3g zinc nitrate hexahydrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=8, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 80 DEG C of baking ovens and dry overnight.In air, roasting 4h at 550 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.600 DEG C, Reduction of methanol activation copper-based catalysts 1h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 40vol%, by constant-flux pump sample introduction, reacts at 550 DEG C, and methanol feed rate is 0.11mL/ (gcat. min), and gas chromatogram on-line checking methanol conversion is 50%, and formaldehyde selectivity is 30%.
Embodiment 2
Weigh 5gNaY and be placed in quartz boat, pass into 100% steam, be warming up to 600 DEG C with 5 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 40mLpH=4.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 80 DEG C.Weigh the NaY type molecular sieve after 0.8g nine water chromic nitrate, 1.9g nitrate trihydrate copper, 2.3g zinc nitrate hexahydrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=8, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 150 DEG C of baking ovens and dry overnight.In air, roasting 4h at 650 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.600 DEG C, Reduction of methanol activation copper-based catalysts 1h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 40vol%, by constant-flux pump sample introduction, reacts at 550 DEG C, and methanol feed rate is 0.11mL/ (gcat. min), and gas chromatogram on-line checking methanol conversion is 63%, and formaldehyde selectivity is 57%.
Embodiment 3
Weigh 5gHY and be placed in quartz boat, pass into 100% steam, be warming up to 700 DEG C with 5 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 50mLpH=5.0, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 80 DEG C.Weigh the HY molecular sieve after 1.9g nitrate trihydrate copper, 2.3g zinc nitrate hexahydrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the solution of potassium carbonate of preparation 1mol/L regulates above-mentioned system pH=8, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 120 DEG C of baking ovens and dry overnight.In air, roasting 4h at 550 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.350 DEG C, Reduction of methanol activation copper-based catalysts 0.5h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 40vol%, by constant-flux pump sample introduction, reacts at 550 DEG C, and methanol feed rate is 0.11mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 55%, and formaldehyde selectivity is 47%.
Embodiment 4
Weigh 5gSAPO-11 and be placed in quartz boat, pass into 100% steam, be warming up to 600 DEG C with 2 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 40mLpH=4.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 90 DEG C.Weigh the SAPO-11 molecular sieve after 1.9g nitrate trihydrate copper, 1.6g nine water chromic nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 100 DEG C of baking ovens and dry overnight.In air, roasting 4h at 400 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 650 DEG C, methanol prereduction activation copper-based catalysts 2h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 11vol%, by constant-flux pump sample introduction, reacts at 600 DEG C, and methanol feed rate is 0.04mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 69%, and formaldehyde selectivity is 78%.
Embodiment 5
Weigh 5gSAPO-11 and be placed in quartz boat, pass into 100% steam, be warming up to 600 DEG C with 2 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 50mLpH=6.0, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 90 DEG C.Weigh the SAPO-11 molecular sieve after 2.3g zinc nitrate hexahydrate, 1.9g nitrate trihydrate copper and 1.6g nine water chromic nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 130 DEG C of baking ovens and dry overnight.In air, roasting 4h at 450 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 450 DEG C, hydrogen prereduction activation copper-based catalysts 1h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 5vol%, by constant-flux pump sample introduction, reacts at 500 DEG C, and methanol feed rate is 0.02mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 65%, and formaldehyde selectivity is 75%.
Embodiment 6
Weigh 5gSAPO-11 and be placed in quartz boat, pass into 100% steam, be warming up to 750 DEG C with 5 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 40mLpH=4.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 90 DEG C.Weigh the SAPO-11 molecular sieve after 2.3g zinc nitrate hexahydrate, 1.9g nitrate trihydrate copper and 1.6g nine water chromic nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 100 DEG C of baking ovens and dry overnight.In air, roasting 4h at 600 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 650 DEG C, methanol prereduction activation copper-based catalysts 2h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 5vol%, by constant-flux pump sample introduction, reacts at 600 DEG C, and methanol feed rate is 0.02mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 90%, and formaldehyde selectivity is 78%.
Embodiment 7
Weigh 5gSAPO-34 and be placed in quartz boat, pass into 100% steam, be warming up to 600 DEG C with 6 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 40mLpH=4.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 90 DEG C.Weigh the SAPO-34 molecular sieve after 2.3g zinc nitrate hexahydrate, 1.9g nitrate trihydrate copper and 0.8g nine water chromic nitrate, 0.52g potassium nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 100 DEG C of baking ovens and dry overnight.In air, roasting 4h at 550 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 600 DEG C, methanol prereduction activation copper-based catalysts 1h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 5vol%, by constant-flux pump sample introduction, reacts at 650 DEG C, and methanol feed rate is 0.02mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 79%, and formaldehyde selectivity is 50%.
Embodiment 8
Weigh 5gNaY and be placed in quartz boat, pass into 100% steam, be warming up to 450 DEG C with 2 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 50mLpH=5.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 100 DEG C.Weigh the NaY molecular sieve after 2.3g zinc nitrate hexahydrate, 1.9g nitrate trihydrate copper and 0.8g nine water chromic nitrate, 0.52g potassium nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 100 DEG C of baking ovens and dry overnight.In air, roasting 4h at 550 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 400 DEG C, hydrogen prereduction activation copper-based catalysts 1h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 5vol%, by constant-flux pump sample introduction, reacts at 550 DEG C, and methanol feed rate is 0.02mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 72%, and formaldehyde selectivity is 63%.
Embodiment 9
Weigh 5gHY and be placed in quartz boat, pass into 100% steam, be warming up to 600 DEG C with 5 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 40mLpH=4.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 90 DEG C.Weigh the HY molecular sieve after 2.3g zinc nitrate hexahydrate, 1.9g nitrate trihydrate copper and 0.8g nine water chromic nitrate, 0.52g potassium nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 100 DEG C of baking ovens and dry overnight.In air, roasting 4h at 550 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 550 DEG C, methanol prereduction activation copper-based catalysts 1h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 60vol%, by constant-flux pump sample introduction, reacts at 500 DEG C, and methanol feed rate is 0.58mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 38%, and formaldehyde selectivity is 36%.
Embodiment 10
Weigh 5gNaY and be placed in quartz boat, pass into 100% steam, be warming up to 400 with 1 DEG C/min℃, keep cooling after 2h, after taking-up, above-mentioned sample added in the dilute acid soln of 40mLpH=4.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 90 DEG C.Weigh the NaY molecular sieve after 2.3g zinc nitrate hexahydrate, 1.9g nitrate trihydrate copper and 0.8g nine water chromic nitrate, 0.52g potassium nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 100 DEG C of baking ovens and dry overnight.In air, roasting 4h at 550 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 500 DEG C, methanol prereduction activation copper-based catalysts 1h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 60vol%, by constant-flux pump sample introduction, reacts at 500 DEG C, and methanol feed rate is 0.47mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 46%, and formaldehyde selectivity is 32%.
Embodiment 11
Weigh 5gNaY and be placed in quartz boat, pass into 100% steam, be warming up to 600 DEG C with 2 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 40mLpH=4.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 90 DEG C.Weigh the NaY molecular sieve after 2.3g zinc nitrate hexahydrate, 1.9g nitrate trihydrate copper and 0.8g nine water chromic nitrate, 0.52g potassium nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 100 DEG C of baking ovens and dry overnight.In air, roasting 4h at 550 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 600 DEG C, methanol prereduction activation copper-based catalysts 1h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 80vol%, by constant-flux pump sample introduction, reacts at 500 DEG C, and methanol feed rate is 0.29mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 47%, and formaldehyde selectivity is 53%.
Embodiment 12
Weigh 5gSAPO-11 and be placed in quartz boat, pass into 100% steam, be warming up to 550 DEG C with 2 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 50mLpH=6.0, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 80 DEG C.Weigh the SAPO-11 molecular sieve after 2.3g zinc nitrate hexahydrate, 1.9g nitrate trihydrate copper and 1.6g nine water chromic nitrate, 1.04g potassium nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 100 DEG C of baking ovens and dry overnight.In air, roasting 4h at 550 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 600 DEG C, methanol prereduction activation copper-based catalysts 1h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 30vol%, by constant-flux pump sample introduction, reacts at 550 DEG C, and methanol feed rate is 0.11mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 77%, and formaldehyde selectivity is 62%.
Embodiment 13
Weigh 5gZSM-5 and be placed in quartz boat, pass into 100% steam, be warming up to 600 DEG C with 2 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 40mLpH=4.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 90 DEG C.Weigh the ZSM-5 molecular sieve after 2.3g zinc nitrate hexahydrate, 1.6g nine water chromic nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 100 DEG C of baking ovens and dry overnight.In air, roasting 4h at 550 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 700 DEG C, methanol prereduction activation copper-based catalysts 1h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 80vol%, by constant-flux pump sample introduction, reacts at 650 DEG C, and methanol feed rate is 0.28mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 62%, and formaldehyde selectivity is 57%.
Embodiment 14
Weigh 5gNaY and be placed in quartz boat, pass into 100% steam, be warming up to 650 DEG C with 2 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 40mLpH=4.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 90 DEG C.Weigh the NaY molecular sieve after 2.3g zinc nitrate hexahydrate, 1.9g nitrate trihydrate copper and 0.8g nine water chromic nitrate, 0.52g potassium nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 100 DEG C of baking ovens and dry overnight.In air, roasting 4h at 550 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 350 DEG C, hydrogen prereduction activation copper-based catalysts 2h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 80vol%, by constant-flux pump sample introduction, reacts under 400C, and methanol feed rate is 0.29mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 42%, and formaldehyde selectivity is 54%.
Embodiment 15
Weigh 5gNaY and be placed in quartz boat, pass into 100% steam, be warming up to 600 DEG C with 2 DEG C/min, cool down after keeping 2h, after taking-up, above-mentioned sample is added in the dilute acid soln of 40mLpH=4.5, stir after 1h the molecular sieve carrier after sucking filtration, washing, drying dealuminzation in 90 DEG C.Weigh the NaY molecular sieve after 2.3g zinc nitrate hexahydrate, 1.9g nitrate trihydrate copper and 0.8g nine water chromic nitrate, 0.52g potassium nitrate and above-mentioned dealuminzation to add to 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor of preparation 1mol/L regulates above-mentioned system pH=6, continue stirring 30min, filtered while hot, the hot wash of 1L80 DEG C, to neutral, be placed in 100 DEG C of baking ovens and dry overnight.In air, roasting 4h at 550 DEG C, obtains copper-based catalysts.Weighing this catalyst tablet forming of 2g, sieve takes 14～25 orders, is filled with to quartz tube reactor.At 600 DEG C, methanol prereduction activation copper-based catalysts 1h.At ambient pressure, nitrogen gas does carrier gas, and the methanol of 22vol%, by constant-flux pump sample introduction, reacts at 550 DEG C, and methanol feed rate is 0.08mL/ (gcat.Min), gas chromatogram on-line checking methanol conversion is 71%, and formaldehyde selectivity is 42%.
Claims (7)
1. the method that a methanol dehydrogenation prepares anhydrous formaldehyde, it is characterised in that:
The preparation of anhydrous formaldehyde adopts copper-based catalysts, it is placed in fixed bed reactors after crystal reaction tube fills copper-based catalysts, before reaction, use methanol or hydrogen that copper-based catalysts is carried out prereduction at a certain temperature, under normal pressure, methanol is by constant-flux pump sample introduction, and noble gas does carrier gas, react at 400 DEG C～700 DEG C, gas chromatogram on-line checking product；
Described copper-based catalysts, in mass, consists of the following composition: the molecular sieve carrier after 1～20 part of copper, the dealuminzation of 100 parts, 0～20 part of promoter；
Described pre-reduction temperature is: 450～750 DEG C, and pre-reduction time is: 0.5～2h.
2. in accordance with the method for claim 1, it is characterised in that:
The preparation of described copper-based catalysts adopts coprecipitation method, and its process is: by the soluble-salt homogeneous precipitation of the soluble-salt of copper and promoter molecular sieve supported surface after dealuminzation, 80～150 DEG C of dry, 400～650 DEG C of air roastings；
Described molecular sieve is the one in ZSM-5, SAPO-11, SAPO-34, NaY, HY or two or more.
3. the method described in claim 1 or 2, it is characterised in that:
Molecular sieve carrier after described dealuminzation, refers to that molecular sieve adopts 100% steam to carry out hydrothermal treatment consists, then then through dilute acid pretreatment, and washing, it is dried overnight at 80～150 DEG C；
Described hydrothermal treatment consists temperature is: 400 DEG C～800 DEG C, pH=4～6 of diluted acid used by acid treatment, and the solid-to-liquid ratio of acid treatment is 1:5～1:10.
4. the method described in claim 1,2 or 3, it is characterised in that:
Described promoter is one or more in zinc, chromium or potassium.
5. in accordance with the method for claim 2, it is characterized in that: the soluble-salt of described copper is preferably one or more in copper nitrate, copper chloride, Schweinfurt green or copper sulfate, and the soluble-salt of described promoter is preferably one or more in nitrate, chloride or sulfate.
6. in accordance with the method for claim 1, it is characterised in that:
Described filling copper-based catalysts thickness of bed layer is 5mm～60mm, and methanol feeding is than 5vol%～80vol% (stereometer), and methanol feed rate is 0.10～0.30ml/ (gcat.Min), reaction temperature is 400 DEG C～700 DEG C.
7. in accordance with the method for claim 1, it is characterised in that:
Described noble gas is one or more in nitrogen, argon, helium, and flow velocity is 50mL/min～210mL/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410765026.5A CN105732349B (en) | 2014-12-12 | 2014-12-12 | A kind of method that methanol dehydrogenation prepares anhydrous formaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410765026.5A CN105732349B (en) | 2014-12-12 | 2014-12-12 | A kind of method that methanol dehydrogenation prepares anhydrous formaldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105732349A true CN105732349A (en) | 2016-07-06 |
| CN105732349B CN105732349B (en) | 2018-01-23 |
Family
ID=56240609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410765026.5A Active CN105732349B (en) | 2014-12-12 | 2014-12-12 | A kind of method that methanol dehydrogenation prepares anhydrous formaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105732349B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107162884A (en) * | 2017-07-07 | 2017-09-15 | 册亨荣畅化工科技发展有限公司 | The technique that a kind of methanol dehydrogenation produces anhydrous formaldehyde |
| CN107899572A (en) * | 2017-10-24 | 2018-04-13 | 安徽省福泰精细化工有限责任公司 | A kind of preparation method for the catalyst for electrolytic silver for being used to produce formaldehyde |
| CN107971003A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | It is a kind of to contain phosphorous and assistant for calalytic cracking of Beta molecular sieves of carried metal and preparation method thereof |
| CN107971002A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | It is a kind of containing rich in mesoporous assistant for calalytic cracking of Beta molecular sieves and preparation method thereof |
| CN107970998A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof |
| CN107971000A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking containing phosphorous Beta molecular sieves and preparation method thereof |
| CN107970997A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof |
| CN108620093A (en) * | 2018-05-15 | 2018-10-09 | 常州博能新能源有限公司 | A kind of hydrogen production from methanol-steam reforming copper-based catalysts activation method |
| CN113070096A (en) * | 2021-03-22 | 2021-07-06 | 西安交通大学 | Biomass oxidative cracking catalyst based on modified H-Beta molecular sieve, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4014939A (en) * | 1974-06-07 | 1977-03-29 | Mitsubishi Gas Chemical Company, Inc. | Process for producing formaldehyde |
-
2014
- 2014-12-12 CN CN201410765026.5A patent/CN105732349B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4014939A (en) * | 1974-06-07 | 1977-03-29 | Mitsubishi Gas Chemical Company, Inc. | Process for producing formaldehyde |
Non-Patent Citations (3)
| Title |
|---|
| ANDREJA MUSIC，ET AL.: "Gas-phase catalytic dehydrogenation of methanol to formaldehyde over ZnO/SiO2 based catalysts, zeolites, and phosphates", 《APPLIED CATALYSIS A: GENERAL》 * |
| 谢茂松等: "静态水热脱铝处理对HZSM-5分子筛的结构、酸性和催化性能的影响", 《石油化工》 * |
| 邝生鲁等: "甲醇催化脱氢合成无水甲醛", 《现代化工》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970997A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof |
| CN107971000B (en) * | 2016-10-21 | 2019-12-27 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent containing phosphorus-containing Beta molecular sieve and preparation method thereof |
| CN107971003A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | It is a kind of to contain phosphorous and assistant for calalytic cracking of Beta molecular sieves of carried metal and preparation method thereof |
| CN107971002A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | It is a kind of containing rich in mesoporous assistant for calalytic cracking of Beta molecular sieves and preparation method thereof |
| CN107970998A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking of propylene enhancing and preparation method thereof |
| CN107971000A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking containing phosphorous Beta molecular sieves and preparation method thereof |
| CN107970998B (en) * | 2016-10-21 | 2019-12-27 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent for increasing propylene yield and preparation method thereof |
| CN107970997B (en) * | 2016-10-21 | 2020-03-24 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent for increasing propylene yield and preparation method thereof |
| CN107162884A (en) * | 2017-07-07 | 2017-09-15 | 册亨荣畅化工科技发展有限公司 | The technique that a kind of methanol dehydrogenation produces anhydrous formaldehyde |
| CN107899572A (en) * | 2017-10-24 | 2018-04-13 | 安徽省福泰精细化工有限责任公司 | A kind of preparation method for the catalyst for electrolytic silver for being used to produce formaldehyde |
| CN107899572B (en) * | 2017-10-24 | 2020-10-16 | 安徽省福泰精细化工有限责任公司 | Preparation method of electrolytic silver catalyst for producing formaldehyde |
| CN108620093A (en) * | 2018-05-15 | 2018-10-09 | 常州博能新能源有限公司 | A kind of hydrogen production from methanol-steam reforming copper-based catalysts activation method |
| CN113070096A (en) * | 2021-03-22 | 2021-07-06 | 西安交通大学 | Biomass oxidative cracking catalyst based on modified H-Beta molecular sieve, and preparation method and application thereof |
| CN113070096B (en) * | 2021-03-22 | 2022-07-12 | 西安交通大学 | Biomass oxidative cracking catalyst based on modified H-Beta molecular sieve, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105732349B (en) | 2018-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105732349A (en) | Method for preparing anhydrous formaldehyde through methanol dehydrogenation | |
| CN105732350B (en) | A kind of method that anaerobic dehydrogenation prepares anhydrous formaldehyde | |
| US10898888B2 (en) | Preparation and application of magnetic metallic oxide cross-linked acidic polyionic liquid | |
| CN101830821B (en) | Chemical synthesis method of N-alcoxyloxalyl alanine ester | |
| CN103785470A (en) | Preparation method of catalyst for synthesis of acrylic acid | |
| CN102786499B (en) | Method for preparing cyclohexene oxide | |
| CN109794285B (en) | Catalyst for preparing glycolic acid by carbonylation of formaldehyde and preparation method and application thereof | |
| CN104193606A (en) | Technique for preparing acetone from synthetic gas | |
| CN113603574B (en) | Method for catalyzing catalytic oxidation reaction of cyclopentene by using short-site silicotungstic heteropolyacid salt catalyst | |
| CN106608865B (en) | Power-economizing method for ethylene carbonate Lipase absobed | |
| CN102274722A (en) | V2O3 for preparing anhydrous formaldehyde by directly dehydrogenizing methanol as well as supported V2O3 catalyst and preparation method thereof | |
| CN101993350B (en) | Production method of glycol | |
| CN102381922B (en) | Method for compounding ethylene by ethanol | |
| CN105384616A (en) | Synthetic method for methoxyacetone | |
| CN101993349B (en) | Method for producing glycol by using oxalic ester | |
| CN106631731B (en) | Method for preparing benzaldehyde by catalytic oxidation of benzyl alcohol with binuclear morpholine phosphotungstate | |
| CN105037073B (en) | A kind of synthetic method of biaryl compounds | |
| CN109305912B (en) | Method for preparing 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate by condensing isobutyraldehyde | |
| CN103626810A (en) | Method for catalyzing glucose by using magnetic solid acid to produce methyl glucoside | |
| CN114436808B (en) | CO based on cyclic conversion of imidazolecarboxylate and imidazolecarbonate 2 Method for preparing formic acid by hydrogenation | |
| CN104610014A (en) | Method for preparing m-dichlorobenzene by catalyzing isomerization of p-dichlorobenzene by using nano ZSM-12 molecular sieve | |
| CN100391955C (en) | Synthetic method for strotium renelate intermediate | |
| CN102786500B (en) | Preparation method of cyclohexene oxide | |
| CN103709010A (en) | Method for synthesizing cyclohexanol by reacting cyclohexene, carboxylic acid and water | |
| CN114029072A (en) | Solid super acidic catalyst and method for preparing isooctyl p-methoxycinnamate by using same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |