CN105732349B - A kind of method that methanol dehydrogenation prepares anhydrous formaldehyde - Google Patents
A kind of method that methanol dehydrogenation prepares anhydrous formaldehyde Download PDFInfo
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Abstract
The present invention relates to a kind of method that methanol dehydrogenation prepares anhydrous formaldehyde, this method uses copper-based catalysts, is made up of component copper, co-catalyst and molecular sieve carrier, and wherein molecular sieve carrier passes through hydrothermal dealumination and acid treatment.Detailed process is：It is placed in crystal reaction tube after loading catalyst in fixed bed reactors, prereduction is carried out to catalyst using methanol or hydrogen before reacting.Under normal pressure, for methanol by constant-flux pump sample introduction, methanol charge ratio is 5vol%~80vol%, and methanol feed rate is 0.10~0.30mL/ (gcat.min), inert gas makees carrier gas, is reacted at 400 DEG C~700 DEG C, and it is 30%~90% that chromatogram, which measures methanol conversion, formaldehyde selectivity 25%~78%.The copper-based catalysts of the present invention are hydro-thermal and the molecular sieve supported cupper-based catalyst of acid treatment dealuminzation, the catalyst has coupled carrier molecule and has sieved larger specific surface area and the two big advantage of high activity of copper-based catalysts, with higher catalytic activity and heat endurance, accessory substance is few, and catalyst preparation process is simple.
Description
Technical field
The invention belongs to prepare the field of anhydrous formaldehyde, and in particular 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 resins such as phenolic resin, melamine resin
And a variety of chemical products such as methenamine, BDO, formaldehyde are also synthetic dyestuffs, agricultural chemicals, finely and specialty chemicals
Important source material.
At present, industrial is typically all to prepare formaldehyde using methanol oxidizing process, is contained in the formaldehyde of institute's output substantial amounts of
Water, and the vapour pressure of formalin is relatively low, and formaldehyde and water are readily formed azeotropic mixture, therefore separate and purify formaldehyde very
Difficulty, cause energy consumption big, cost is high.The medicine such as the excellent engineering plastics of synthesis performance and methenamine is to anhydrous formaldehyde in recent years
Demand it is increasing, and at present anhydrous formaldehyde be all by the industrial formol aqueous solution by various methods remove moisture and obtain,
Directly prepare the focus that anhydrous formaldehyde has become research.
The formaldehyde and byproduct hydrogen gas that methanol anaerobic dehydrogenation technique obtains are easily separated, and anhydrous generation, avoid first
The lock out operation of the aldehyde aqueous solution, is effectively saved the expense of investment and its operation of rectifying device, and has obtained high-quality pair
Product-hydrogen；It is molten so as to be advantageous to formaldehyde meanwhile the reaction is not in the problem of methanol oxidation generates formic acid etching apparatus
The stabilization of liquid and purification, and the reusable synthesis in methanol of hydrogen can be obtained.Therefore, by methanol direct dehydrogenation formaldehyde into
For a very promising industrial process.
In recent years, produce the remarkable in economical benefits of anhydrous formaldehyde new technology oneself cause great attention both domestic and external, and open
Substantial amounts of research work is opened up, the emphasis studied at present is concentrated mainly in the exploitation of effective catalyst, including metal and its oxygen
Several classes such as compound catalyst, alkali metal salt and molecular sieve catalyst.CN102274722A discloses new V2O3And support type
V2O3Preparation method, methanol dehydrogenation reaction in show preferably activity.Takagi etc. (Takagi K, Morikawa Y,
Ikawa T.Chemistry Letters, 1985,14 (4)：527-530) to the Cu of different oxidation state in methanol dehydrogenation reaction
Activity studied, as a result find, Cu0PARA FORMALDEHYDE PRILLS(91,95) has very high selectivity.CN101961650A discloses a kind of equal
The method of even co-precipitation prepares new type zirconium-based catalyst and catalysis methanol anaerobic dehydrogenation, and the yield of formaldehyde reaches 60%.Dai Weilin
A series of load silver applied to methanol direct dehydrogenation are disclosed Deng (CN1390639A, CN1537673A, CN1544147A)
The preparation method of catalyst.Patent CN101147872A prepares industrial sodium carbonate catalysis as raw material using industrial sodium bicarbonate and prepares nothing
Water beetle aldehyde, the industrialization that formaldehyde is prepared for methanol dehydrogenation lay the foundation.(Music A, the Batista J, Levec such as Music
J.Applied Catalysis A：General, 1997,165 (1-2)：115-131.) using ZSM-5 molecular sieve catalyst as mother
Body, Na-ZSM-5, Cu-ZSM-5 type molecular sieve catalyst is made using ion-exchange, is achieved in the certain embodiments of methanol
Preferably selectivity.
Based on the catalyst system and catalyzing of the above-mentioned production anhydrous formaldehyde developed, this patent is combined with the copper-based of greater activity
Molecular sieve carried copper-based catalysts are prepared in the advantage both molecular sieve that catalyst and duct are enriched.But due to dividing
Aluminium is rich in son sieve, causes it to carry certain acidity, and then so that occur in the course of reaction of methanol dehydrogenation acid catalyzed
Dehydration of methanol, dimethyl ether and water are generated, reduces the selectivity of formaldehyde, and introduce water, run counter to and prepare anhydrous formaldehyde
Purpose.Therefore, this patent carrier molecule sieve carries out dealumination treatment, had both remained the advantage that high-specific surface area is brought while had avoided
Side reaction caused by acid site so that the efficiency that methanol dehydrogenation prepares anhydrous formaldehyde increases substantially.
The content of the invention
Meaning of the present invention is to overcome prepares the shortcomings that anhydrous formaldehyde uses catalyst at present, such as：Cupper-based catalyst
The skewness of copper particle in agent, particle is larger, and active surface area is smaller, and activity is relatively low；Modified molecular sieve catalyst acid
Alkaline difficult regulation and control, accessory substance are more；Traditional carbonate or bicarbonate catalytic activity relative inertness, reaction temperature is typically high
In 700 DEG C.This patent combines both abundant molecular sieves of copper-based catalysts with greater activity and duct advantage and prepared
Obtain molecular sieve carried copper-based catalysts.The catalyst preparation is simple and stability is high, and reaction condition is more gentle, conversion ratio
It is higher with selectivity.
The concrete scheme for the anhydrous formaldehyde that the present invention designs is：
The preparation of anhydrous formaldehyde uses copper-based catalysts, is placed on admittedly after copper-based catalysts are filled in crystal reaction tube
In fixed bed reactor, before reaction, copper-based catalysts are carried out with prereduction using methanol or hydrogen at a certain temperature, under normal pressure,
Methanol makees carrier gas by constant-flux pump sample introduction, inert gas, is reacted at 400 DEG C~700 DEG C, gas-chromatography on-line checking product；
The copper-based catalysts, in mass, consist of the following composition：Molecule after 1~20 part of copper, 100 parts of dealuminzation
Sieve carrier, 0~20 part of co-catalyst；
The pre-reduction temperature is：450~750 DEG C, pre-reduction time is：0.5~2h.
The preparation of the copper-based catalysts uses coprecipitation method, and its process is：By the soluble-salt and co-catalyst of copper
Molecular sieve carrier surface of the soluble-salt homogeneous precipitation after dealuminzation, 80~150 DEG C of dryings, 400~650 DEG C of air roastings；
Described molecular sieve is ZSM-5, SAPO-11, SAPO-34, one kind in NaY, HY or two or more.
Molecular sieve carrier after the dealuminzation, refer to that molecular sieve carries out hydro-thermal process using 100% steam, then again through dilute
Acid treatment, wash, be dried overnight at 80~150 DEG C；
The hydro-thermal process temperature is：400 DEG C~800 DEG C, pH=4~6 of diluted acid used in acid treatment, the solid-liquid of acid treatment
Than for 1：5~1：10.
The diluted acid is the conventional acid solution that acid treatment is carried out to molecular sieve, is preferably (NH4)2SiF6, citric acid, oxalic acid,
H2SiF6, hydrochloric acid, it is more than one or both of sulfuric acid.
The co-catalyst is more than one or both of zinc, chromium or potassium.
The soluble-salt of the copper is preferably more than one or both of copper nitrate, copper chloride, copper acetate or copper sulphate,
The soluble-salt of the co-catalyst is preferably more than one or both of nitrate, chloride or sulfate.
The filling copper-based catalysts thickness of bed layer is 5mm~60mm, methanol charge ratio 5vol%~80vol% (volumes
Meter), methanol feed rate is 0.10~0.30ml/ (gcat.Min), reaction temperature is 400 DEG C~700 DEG C.
Described inert gas is the one or more in nitrogen, argon gas, helium, and flow velocity is 50mL/min~210mL/
min。
Because molecular sieve has flourishing duct, abundant specific surface area, catalytic reaction process is widely used today as
Catalyst or carrier.But due to being rich in aluminium in molecular sieve, cause molecular sieve that there is certain acidity, and then cause in methanol
Acid catalyzed Dehydration of methanol occurs in the course of reaction of dehydrogenation, generates dimethyl ether and water, reduces the selectivity of formaldehyde, and
Water is introduced, have impact on the purity of anhydrous formaldehyde.Therefore, must effectively be shielded first for the anhydrous formaldehyde of high-purity is prepared
The acid site of molecular sieve.Dealumination process is a kind of effective means for the regulation molecular sieve acid-base property that catalytic field uses, and typically may be used
To be modified using the methods of high-temperature roasting, hydro-thermal process and chemical dealuminization the structure and Acidity of molecular sieve, to change
The acid distribution of catalyst, improve the stability of catalyst.Wherein, hydrothermal dealumination process easily realize and do not introduce it is any it is miscellaneous from
Son.Studies have shown that water-heat process is only stripped of framework aluminum, non-framework aluminum is made, it is therefore, follow-up to need to continue acid
Wash, dissolving removing non-framework aluminum, so as to reach the purpose for effectively removing all acid sites.This patent takes off molecular sieve progress hydro-thermal
Carrier after aluminium as copper-based catalysts, anhydrous formaldehyde is prepared applied to methanol dehydrogenation.
Compare, have the advantage that with existing catalyst system and catalyzing：
1) because molecular sieve has a flourishing duct, larger specific surface area, the copper particle precipitated in copper-based catalysts is equal
Even to be scattered in the abundant surface of molecular sieve, therefore, the particle of formation is smaller, and active surface area is big, and activity significantly improves.
2) hydrothermal dealumination is maintained outside the preferable structure of molecular sieve, is significantly reduced the acidity of molecular sieve catalyst, is entered
And dehydration caused by acid catalysis during methanol dehydrogenation is inhibited, reduce the generation of accessory substance, improve the choosing of formaldehyde
Selecting property and purity；
3) catalyst preparation process is simple, and catalyst stability is good, has expanded the catalysis that methanol anaerobic dehydrogenation prepares formaldehyde
System.
Embodiment
In order to which the present invention will be described in further detail, several specific implementation cases are given below, but the present invention is unlimited
In these embodiments.
Embodiment 1
Weigh 5g ZSM-5 to be placed in quartz boat, be passed through 100% vapor, be warming up to 800 DEG C with 6.5 DEG C/min, keep
Cool down after 2h, add above-mentioned sample in 50mL pH=4.5 dilute acid soln after taking-up, filter, wash after 90 DEG C of stirring 1h
Wash, the molecular sieve carrier after drying dealuminzation.After weighing 1.9g nitrate trihydrates copper, 2.3g zinc nitrate hexahydrates and above-mentioned dealuminzation
ZSM-5 molecular sieve is added into 250mL water, and 30min is stirred at 80 DEG C, and the sodium carbonate liquor for preparing 1mol/L adjusts above-mentioned system
PH=8, continue to stir 30min, filter while hot, the hot wash that 80 DEG C of 1L to neutrality, be placed in 80 DEG C of baking ovens and dried
Night.4h is calcined at 550 DEG C in air, produces copper-based catalysts.The 2g catalyst tablet formings are weighed, sieve takes 14~25 mesh, will
It is filled into quartz tube reactor.600 DEG C, Reduction of methanol activation copper-based catalysts 1h.At ambient pressure, nitrogen gas carry
Gas, 40vol% methanol are reacted at 550 DEG C by constant-flux pump sample introduction, and methanol feed rate is 0.11mL/ (gcat.min),
Gas-chromatography on-line checking methanol conversion is 50%, and formaldehyde is selectively 30%.
Embodiment 2
Weigh 5g NaY to be placed in quartz boat, be passed through 100% vapor, 600 DEG C are warming up to 5 DEG C/min, after keeping 2h
Cooling, above-mentioned sample is added in 40mL pH=4.5 dilute acid soln after taking-up, filter, wash, dry after 80 DEG C of stirring 1h
The dry molecular sieve carrier produced after dealuminzation.Weigh the water chromic nitrates of 0.8g nine, 1.9g nitrate trihydrates copper, 2.3g zinc nitrate hexahydrates and on
State the NaY type molecular sieves after dealuminzation to add into 250mL water, 30min is stirred at 80 DEG C, the sodium carbonate liquor for preparing 1mol/L is adjusted
Above-mentioned system pH=8 is saved, continues to stir 30min, filters while hot, the hot wash that 80 DEG C of 1L to neutrality, be placed on 150 DEG C
Dried overnight in baking oven.4h is calcined at 650 DEG C in air, produces copper-based catalysts.The 2g catalyst tablet formings are weighed, sieve takes
14~25 mesh, are filled with into quartz tube reactor.600 DEG C, Reduction of methanol activation copper-based catalysts 1h.At ambient pressure, nitrogen
Gas gas makees carrier gas, and 40vol% methanol is reacted, methanol feed rate 0.11mL/ by constant-flux pump sample introduction at 550 DEG C
(gcat.min), gas-chromatography on-line checking methanol conversion is 63%, and formaldehyde is selectively 57%.
Embodiment 3
Weigh 5g HY to be placed in quartz boat, be passed through 100% vapor, 700 DEG C are warming up to 5 DEG C/min, keep cold after 2h
But, above-mentioned sample is added in 50mL pH=5.0 dilute acid soln after taking-up, filters, washs after 80 DEG C of stirring 1h, drying
Produce the molecular sieve carrier after dealuminzation.Weigh the HY molecules after 1.9g nitrate trihydrates copper, 2.3g zinc nitrate hexahydrates and above-mentioned dealuminzation
Sieve is added into 250mL water, and 30min is stirred at 80 DEG C, and the solution of potassium carbonate for preparing 1mol/L adjusts above-mentioned system pH=8, after
Continuous stirring 30min, filters, the hot wash that 80 DEG C of 1L to neutrality, is placed in 120 DEG C of baking ovens and dries overnight while hot.Air
In be calcined 4h at 550 DEG C, produce copper-based catalysts.Weigh the 2g catalyst tablet formings, sieve takes 14~25 mesh, be filled with to
In quartz tube reactor.350 DEG C, Reduction of methanol activation copper-based catalysts 0.5h.At ambient pressure, nitrogen gas make carrier gas,
40vol% methanol is reacted, methanol feed rate is 0.11mL/ (g by constant-flux pump sample introduction at 550 DEG Ccat.Min), gas phase
Chromatogram on-line checking methanol conversion is 55%, and formaldehyde is selectively 47%.
Embodiment 4
Weigh 5g SAPO-11 to be placed in quartz boat, be passed through 100% vapor, be warming up to 600 DEG C with 2 DEG C/min, keep
Cool down after 2h, add above-mentioned sample in 40mL pH=4.5 dilute acid soln after taking-up, filter, wash after 90 DEG C of stirring 1h
Wash, the molecular sieve carrier after drying dealuminzation.After weighing 1.9g nitrate trihydrates copper, the water chromic nitrates of 1.6g nine and above-mentioned dealuminzation
SAPO-11 molecular sieves are added into 250mL water, and 30min is stirred at 80 DEG C, and the sodium carbonate liquor for preparing 1mol/L adjusts above-mentioned body
It is pH=6, continues to stir 30min, filter while hot, the hot wash that 80 DEG C of 1L to neutrality, be placed in 100 DEG C of baking ovens and dry
It is dry to stay overnight.4h is calcined at 400 DEG C in air, produces copper-based catalysts.The 2g catalyst tablet formings are weighed, sieve takes 14~25
Mesh, it is filled with into quartz tube reactor.At 650 DEG C, methanol prereduction activation copper-based catalysts 2h.At ambient pressure, nitrogen
Gas makees carrier gas, and 11vol% methanol is reacted, methanol feed rate 0.04mL/ by constant-flux pump sample introduction at 600 DEG C
(gcat.Min), gas-chromatography on-line checking methanol conversion is 69%, and formaldehyde is selectively 78%.
Embodiment 5
Weigh 5g SAPO-11 to be placed in quartz boat, be passed through 100% vapor, be warming up to 600 DEG C with 2 DEG C/min, keep
Cool down after 2h, add above-mentioned sample in 50mL pH=6.0 dilute acid soln after taking-up, filter, wash after 90 DEG C of stirring 1h
Wash, the molecular sieve carrier after drying dealuminzation.Weigh 2.3g zinc nitrate hexahydrates, 1.9g nitrate trihydrates copper and the water nitre of 1.6g nine
SAPO-11 molecular sieves after sour chromium and above-mentioned dealuminzation are added into 250mL water, and 30min is stirred at 80 DEG C, prepare 1mol/L carbon
Acid sodium solution adjusts above-mentioned system pH=6, continues to stir 30min, filters while hot, the hot wash that 80 DEG C of 1L to neutrality, by it
It is placed in 130 DEG C of baking ovens and dries overnight.4h is calcined at 450 DEG C in air, produces copper-based catalysts.Weigh the 2g catalyst tablettings
Shaping, sieve take 14~25 mesh, are filled with into quartz tube reactor.At 450 DEG C, hydrogen prereduction activation copper-based catalysts
1h.At ambient pressure, nitrogen gas make carrier gas, and 5vol% methanol is reacted, methanol charging speed by constant-flux pump sample introduction at 500 DEG C
Spend for 0.02mL/ (gcat.Min), gas-chromatography on-line checking methanol conversion is 65%, and formaldehyde is selectively 75%.
Embodiment 6
Weigh 5g SAPO-11 to be placed in quartz boat, be passed through 100% vapor, be warming up to 750 DEG C with 5 DEG C/min, keep
Cool down after 2h, add above-mentioned sample in 40mL pH=4.5 dilute acid soln after taking-up, filter, wash after 90 DEG C of stirring 1h
Wash, the molecular sieve carrier after drying dealuminzation.Weigh 2.3g zinc nitrate hexahydrates, 1.9g nitrate trihydrates copper and the water nitre of 1.6g nine
SAPO-11 molecular sieves after sour chromium and above-mentioned dealuminzation are added into 250mL water, and 30min is stirred at 80 DEG C, prepare 1mol/L carbon
Acid sodium solution adjusts above-mentioned system pH=6, continues to stir 30min, filters while hot, the hot wash that 80 DEG C of 1L to neutrality, by it
It is placed in 100 DEG C of baking ovens and dries overnight.4h is calcined at 600 DEG C in air, produces copper-based catalysts.Weigh the 2g catalyst tablettings
Shaping, sieve take 14~25 mesh, are filled with into quartz tube reactor.At 650 DEG C, methanol prereduction activation copper-based catalysts
2h.At ambient pressure, nitrogen gas make carrier gas, and 5vol% methanol is reacted, methanol charging speed by constant-flux pump sample introduction at 600 DEG C
Spend for 0.02mL/ (gcat.Min), gas-chromatography on-line checking methanol conversion is 90%, and formaldehyde is selectively 78%.
Embodiment 7
Weigh 5g SAPO-34 to be placed in quartz boat, be passed through 100% vapor, be warming up to 600 DEG C with 6 DEG C/min, keep
Cool down after 2h, add above-mentioned sample in 40mL pH=4.5 dilute acid soln after taking-up, filter, wash after 90 DEG C of stirring 1h
Wash, the molecular sieve carrier after drying dealuminzation.Weigh 2.3g zinc nitrate hexahydrates, 1.9g nitrate trihydrates copper and the water nitre of 0.8g nine
SAPO-34 molecular sieves after sour chromium, 0.52g potassium nitrate and above-mentioned dealuminzation are added into 250mL water, are stirred 30min at 80 DEG C, are matched somebody with somebody
1mol/L processed sodium carbonate liquor adjusts above-mentioned system pH=6, continues to stir 30min, filters while hot, the hot water wash that 80 DEG C of 1L
Wash to neutrality, be placed in 100 DEG C of baking ovens and dry overnight.4h is calcined at 550 DEG C in air, produces copper-based catalysts.Weigh
The 2g catalyst tablet formings, sieve take 14~25 mesh, are filled with into quartz tube reactor.At 600 DEG C, methanol prereduction is lived
Change copper-based catalysts 1h.At ambient pressure, nitrogen gas make carrier gas, and 5vol% methanol is anti-at 650 DEG C by constant-flux pump sample introduction
Should, methanol feed rate is 0.02mL/ (gcat.Min), gas-chromatography on-line checking methanol conversion is 79%, formaldehyde selection
Property is 50%.
Embodiment 8
Weigh 5g NaY to be placed in quartz boat, be passed through 100% vapor, 450 DEG C are warming up to 2 DEG C/min, after keeping 2h
Cooling, above-mentioned sample is added in 50mL pH=5.5 dilute acid soln after taking-up, filter, wash, dry after 100 DEG C of stirring 1h
The dry molecular sieve carrier produced after dealuminzation.Weigh 2.3g zinc nitrate hexahydrates, 1.9g nitrate trihydrates copper and the water chromic nitrates of 0.8g nine,
NaY molecular sieve after 0.52g potassium nitrate and above-mentioned dealuminzation is added into 250mL water, and 30min is stirred at 80 DEG C, prepares 1mol/L
Sodium carbonate liquor adjust above-mentioned system pH=6, continue to stir 30min, filter while hot, the hot wash that 80 DEG C of 1L to neutrality,
It is placed in 100 DEG C of baking ovens and dries overnight.4h is calcined at 550 DEG C in air, produces copper-based catalysts.Weigh the 2g catalyst
Compression molding, sieve take 14~25 mesh, are filled with into quartz tube reactor.At 400 DEG C, hydrogen prereduction activation cupper-based catalyst
Agent 1h.At ambient pressure, nitrogen gas make carrier gas, and 5vol% methanol is reacted, methanol charging by constant-flux pump sample introduction at 550 DEG C
Speed is 0.02mL/ (gcat.Min), gas-chromatography on-line checking methanol conversion is 72%, and formaldehyde is selectively 63%.
Embodiment 9
Weigh 5g HY to be placed in quartz boat, be passed through 100% vapor, 600 DEG C are warming up to 5 DEG C/min, keep cold after 2h
But, above-mentioned sample is added in 40mL pH=4.5 dilute acid soln after taking-up, filters, washs after 90 DEG C of stirring 1h, drying
Produce the molecular sieve carrier after dealuminzation.Weigh 2.3g zinc nitrate hexahydrates, 1.9g nitrate trihydrates copper and the water chromic nitrates of 0.8g nine,
HY molecular sieves after 0.52g potassium nitrate and above-mentioned dealuminzation are added into 250mL water, are stirred 30min at 80 DEG C, are prepared 1mol/L's
Sodium carbonate liquor adjusts above-mentioned system pH=6, continues to stir 30min, filters while hot, the hot wash that 80 DEG C of 1L to neutrality, will
It is placed in 100 DEG C of baking ovens and dried overnight.4h is calcined at 550 DEG C in air, produces copper-based catalysts.Weigh the 2g catalyst pressures
Sheetmolding, sieve take 14~25 mesh, are filled with into quartz tube reactor.At 550 DEG C, methanol prereduction activation copper-based catalysts
1h.At ambient pressure, nitrogen gas make carrier gas, and 60vol% methanol is reacted, methanol charging speed by constant-flux pump sample introduction at 500 DEG C
Spend for 0.58mL/ (gcat.Min), gas-chromatography on-line checking methanol conversion is 38%, and formaldehyde is selectively 36%.
Embodiment 10
Weigh 5g NaY to be placed in quartz boat, be passed through 100% vapor, 400 are warming up to 1 DEG C/min℃, keep 2h after it is cold
But, above-mentioned sample is added in 40mL pH=4.5 dilute acid soln after taking-up, filters, washs after 90 DEG C of stirring 1h, drying
Produce the molecular sieve carrier after dealuminzation.Weigh 2.3g zinc nitrate hexahydrates, 1.9g nitrate trihydrates copper and the water chromic nitrates of 0.8g nine,
NaY molecular sieve after 0.52g potassium nitrate and above-mentioned dealuminzation is added into 250mL water, and 30min is stirred at 80 DEG C, prepares 1mol/L
Sodium carbonate liquor adjust above-mentioned system pH=6, continue to stir 30min, filter while hot, the hot wash that 80 DEG C of 1L to neutrality,
It is placed in 100 DEG C of baking ovens and dries overnight.4h is calcined at 550 DEG C in air, produces copper-based catalysts.Weigh the 2g catalyst
Compression molding, sieve take 14~25 mesh, are filled with into quartz tube reactor.At 500 DEG C, methanol prereduction activation cupper-based catalyst
Agent 1h.At ambient pressure, nitrogen gas make carrier gas, and 60vol% methanol is reacted, methanol charging by constant-flux pump sample introduction at 500 DEG C
Speed is 0.47mL/ (gcat.Min), gas-chromatography on-line checking methanol conversion is 46%, and formaldehyde is selectively 32%.
Embodiment 11
Weigh 5g NaY to be placed in quartz boat, be passed through 100% vapor, 600 DEG C are warming up to 2 DEG C/min, after keeping 2h
Cooling, above-mentioned sample is added in 40mL pH=4.5 dilute acid soln after taking-up, filter, wash, dry after 90 DEG C of stirring 1h
The dry molecular sieve carrier produced after dealuminzation.Weigh 2.3g zinc nitrate hexahydrates, 1.9g nitrate trihydrates copper and the water chromic nitrates of 0.8g nine,
NaY molecular sieve after 0.52g potassium nitrate and above-mentioned dealuminzation is added into 250mL water, and 30min is stirred at 80 DEG C, prepares 1mol/L
Sodium carbonate liquor adjust above-mentioned system pH=6, continue to stir 30min, filter while hot, the hot wash that 80 DEG C of 1L to neutrality,
It is placed in 100 DEG C of baking ovens and dries overnight.4h is calcined at 550 DEG C in air, produces copper-based catalysts.Weigh the 2g catalyst
Compression molding, sieve take 14~25 mesh, are filled with into quartz tube reactor.At 600 DEG C, methanol prereduction activation cupper-based catalyst
Agent 1h.At ambient pressure, nitrogen gas make carrier gas, and 80vol% methanol is reacted, methanol charging by constant-flux pump sample introduction at 500 DEG C
Speed is 0.29mL/ (gcat.Min), gas-chromatography on-line checking methanol conversion is 47%, and formaldehyde is selectively 53%.
Embodiment 12
Weigh 5g SAPO-11 to be placed in quartz boat, be passed through 100% vapor, be warming up to 550 DEG C with 2 DEG C/min, keep
Cool down after 2h, add above-mentioned sample in 50mL pH=6.0 dilute acid soln after taking-up, filter, wash after 80 DEG C of stirring 1h
Wash, the molecular sieve carrier after drying dealuminzation.Weigh 2.3g zinc nitrate hexahydrates, 1.9g nitrate trihydrates copper and the water nitre of 1.6g nine
SAPO-11 molecular sieves after sour chromium, 1.04g potassium nitrate and above-mentioned dealuminzation are added into 250mL water, are stirred 30min at 80 DEG C, are matched somebody with somebody
1mol/L processed sodium carbonate liquor adjusts above-mentioned system pH=6, continues to stir 30min, filters while hot, the hot water wash that 80 DEG C of 1L
Wash to neutrality, be placed in 100 DEG C of baking ovens and dry overnight.4h is calcined at 550 DEG C in air, produces copper-based catalysts.Weigh
The 2g catalyst tablet formings, sieve take 14~25 mesh, are filled with into quartz tube reactor.At 600 DEG C, methanol prereduction is lived
Change copper-based catalysts 1h.At ambient pressure, nitrogen gas make carrier gas, and 30vol% methanol is anti-at 550 DEG C by constant-flux pump sample introduction
Should, methanol feed rate is 0.11mL/ (gcat.Min), gas-chromatography on-line checking methanol conversion is 77%, formaldehyde selection
Property is 62%.
Embodiment 13
Weigh 5g ZSM-5 to be placed in quartz boat, be passed through 100% vapor, be warming up to 600 DEG C with 2 DEG C/min, keep 2h
After cool down, above-mentioned sample is added in 40mL pH=4.5 dilute acid soln after taking-up, stirred in 90 DEG C after 1h filter, washing,
Molecular sieve carrier after drying dealuminzation.After weighing 2.3g zinc nitrate hexahydrates, the water chromic nitrates of 1.6g nine and above-mentioned dealuminzation
ZSM-5 molecular sieve is added into 250mL water, and 30min is stirred at 80 DEG C, and the sodium carbonate liquor for preparing 1mol/L adjusts above-mentioned system
PH=6, continue to stir 30min, filter while hot, the hot wash that 80 DEG C of 1L to neutrality, be placed in 100 DEG C of baking ovens and dry
Overnight.4h is calcined at 550 DEG C in air, produces copper-based catalysts.The 2g catalyst tablet formings are weighed, sieve takes 14~25 mesh,
It is filled with into quartz tube reactor.At 700 DEG C, methanol prereduction activation copper-based catalysts 1h.At ambient pressure, nitrogen gas
Make carrier gas, 80vol% methanol is reacted, methanol feed rate is 0.28mL/ (g by constant-flux pump sample introduction at 650 DEG Ccat.·
Min), gas-chromatography on-line checking methanol conversion is 62%, and formaldehyde is selectively 57%.
Embodiment 14
Weigh 5g NaY to be placed in quartz boat, be passed through 100% vapor, 650 DEG C are warming up to 2 DEG C/min, after keeping 2h
Cooling, above-mentioned sample is added in 40mL pH=4.5 dilute acid soln after taking-up, filter, wash, dry after 90 DEG C of stirring 1h
The dry molecular sieve carrier produced after dealuminzation.Weigh 2.3g zinc nitrate hexahydrates, 1.9g nitrate trihydrates copper and the water chromic nitrates of 0.8g nine,
NaY molecular sieve after 0.52g potassium nitrate and above-mentioned dealuminzation is added into 250mL water, and 30min is stirred at 80 DEG C, prepares 1mol/L
Sodium carbonate liquor adjust above-mentioned system pH=6, continue to stir 30min, filter while hot, the hot wash that 80 DEG C of 1L to neutrality,
It is placed in 100 DEG C of baking ovens and dries overnight.4h is calcined at 550 DEG C in air, produces copper-based catalysts.Weigh the 2g catalyst
Compression molding, sieve take 14~25 mesh, are filled with into quartz tube reactor.At 350 DEG C, hydrogen prereduction activation cupper-based catalyst
Agent 2h.At ambient pressure, nitrogen gas make carrier gas, and 80vol% methanol is reacted, methanol charging by constant-flux pump sample introduction under 400C
Speed is 0.29mL/ (gcat.Min), gas-chromatography on-line checking methanol conversion is 42%, and formaldehyde is selectively 54%.
Embodiment 15
Weigh 5g NaY to be placed in quartz boat, be passed through 100% vapor, 600 DEG C are warming up to 2 DEG C/min, after keeping 2h
Cooling, above-mentioned sample is added in 40mL pH=4.5 dilute acid soln after taking-up, filter, wash, dry after 90 DEG C of stirring 1h
The dry molecular sieve carrier produced after dealuminzation.Weigh 2.3g zinc nitrate hexahydrates, 1.9g nitrate trihydrates copper and the water chromic nitrates of 0.8g nine,
NaY molecular sieve after 0.52g potassium nitrate and above-mentioned dealuminzation is added into 250mL water, and 30min is stirred at 80 DEG C, prepares 1mol/L
Sodium carbonate liquor adjust above-mentioned system pH=6, continue to stir 30min, filter while hot, the hot wash that 80 DEG C of 1L to neutrality,
It is placed in 100 DEG C of baking ovens and dries overnight.4h is calcined at 550 DEG C in air, produces copper-based catalysts.Weigh the 2g catalyst
Compression molding, sieve take 14~25 mesh, are filled with into quartz tube reactor.At 600 DEG C, methanol prereduction activation cupper-based catalyst
Agent 1h.At ambient pressure, nitrogen gas make carrier gas, and 22vol% methanol is reacted, methanol charging by constant-flux pump sample introduction at 550 DEG C
Speed is 0.08mL/ (gcat.Min), gas-chromatography on-line checking methanol conversion is 71%, and formaldehyde is selectively 42%.
Claims (7)
1. a kind of method that methanol dehydrogenation prepares anhydrous formaldehyde, it is characterised in that：
The preparation of anhydrous formaldehyde uses copper-based catalysts, and fixed bed is placed on after filling copper-based catalysts in crystal reaction tube
In reactor, before reaction, copper-based catalysts are carried out with prereduction using methanol or hydrogen at a certain temperature, under normal pressure, methanol
By constant-flux pump sample introduction, inert gas makees carrier gas, is reacted at 400 DEG C~700 DEG C, gas-chromatography on-line checking product；
The copper-based catalysts, in mass, consist of the following composition：It is molecular sieve supported after 1~20 part of copper, 100 parts of dealuminzation
Body, 0~20 part of co-catalyst；
The pre-reduction temperature is：450~750 DEG C, pre-reduction time is：0.5~2h.
2. in accordance with the method for claim 1, it is characterised in that：
The preparation of the copper-based catalysts uses coprecipitation method, and its process is：By the soluble-salt of copper and co-catalyst can
Molecular sieve carrier surface of the soluble homogeneous precipitation after dealuminzation, 80~150 DEG C of dryings, 400~650 DEG C of air roastings；
Described molecular sieve is ZSM-5, SAPO-11, SAPO-34, one kind in NaY, HY or two or more.
3. according to the method described in claim 1 or 2, it is characterised in that：
Molecular sieve carrier after the dealuminzation, refer to molecular sieve using 100% steam carry out hydro-thermal process, then again through diluted acid at
Reason, wash, be dried overnight at 80~150 DEG C；
The hydro-thermal process temperature is：400 DEG C~800 DEG C, pH=4~6 of diluted acid used in acid treatment, the solid-to-liquid ratio of acid treatment is
1：5~1：10.
4. in accordance with the method for claim 1, it is characterised in that：
The co-catalyst is more than one or both of zinc, chromium or potassium.
5. in accordance with the method for claim 2, it is characterised in that：
The soluble-salt of the copper is preferably more than one or both of copper nitrate, copper chloride, copper acetate or copper sulphate, described
The soluble-salt of co-catalyst is preferably more than one or both of nitrate, chloride or sulfate.
6. in accordance with the method for claim 1, it is characterised in that：
The filling copper-based catalysts thickness of bed layer is 5mm~60mm, methanol charge ratio 5vol%~80vol% (stereometer),
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 inert gas is that more than one or both of nitrogen, argon gas, helium flow velocity is 50mL/min~210mL/
min。
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| 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 |
| CN107971002B (en) * | 2016-10-21 | 2019-12-27 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent containing Beta molecular sieve rich in mesopores 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 |
| 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 |
| CN107971003B (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 and metal-loaded Beta molecular sieve 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 |
| 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 |
| 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 |
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