CN107162884A - The technique that a kind of methanol dehydrogenation produces anhydrous formaldehyde - Google Patents
The technique that a kind of methanol dehydrogenation produces anhydrous formaldehyde Download PDFInfo
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- CN107162884A CN107162884A CN201710549748.0A CN201710549748A CN107162884A CN 107162884 A CN107162884 A CN 107162884A CN 201710549748 A CN201710549748 A CN 201710549748A CN 107162884 A CN107162884 A CN 107162884A
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- copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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Abstract
The invention belongs to chemical technology field, the technique that more particularly to a kind of methanol dehydrogenation produces anhydrous formaldehyde, by soluble copper salt and auxiliary agent homogeneous precipitation in HTS carrier surface, acid modification agent is added after cooling thereto and modified under microwave action, reaction is dried after terminating, air roasting, is produced.Using methanol as raw material, inert gas is reacted as carrier gas in fixed bed reactors, and copper-based catalysts are filled in reaction tube, and reaction tube is sent into reactor and reacted.By in the processing of microwave action acid modification, can effectively strengthen copper-based and HTS synergy, the dispersiveness of catalyst is dramatically increased, the outer Ti content of skeleton of molecular sieve is reduced, and effectively skeleton Ti content increase.
Description
Technical field
The present invention relates to chemical technology field, it particularly relates to the technique that a kind of methanol dehydrogenation produces anhydrous formaldehyde.
Background technology
Formaldehyde is simplest aldehyde in aliphatic series, and chemical property is very active, can synthesize multiple compounds.It is weight
One of basic chemical raw materials wanted, are widely used in the fields such as chemical industry, medicine, dyestuff and agricultural.It is most of be used as Lauxite,
The raw material of phenolic resin and amino resins, secondly for production polyformaldehyde, trimethylolpropane, pentaerythrite, methenamine, pyrrole
The chemical products such as pyridine and isoprene, formaldehyde also act as synthetic perfume, synthesis explosive, synthesis chelating agent, additive synthesis and
Important intermediate of synthesis etc..
Methanol oxidizing process is used industrial production formaldehyde more.By theoretical calculation, its product be formaldehyde and water mixture (mole
Ratio 1:1).Because the vapour pressure of formalin is relatively low and formaldehyde and water formation azeotropic mixture, separation and purification are prepared without water beetle
Aldehyde high energy consumption.But, synthetic resin and the production processes such as methenamine are prepared, it is necessary to which anhydrous formaldehyde, its demand gradually increases.
The formaldehyde and byproduct hydrogen gas that methanol anaerobic dehydrogenation technique is obtained are easily separated, and anhydrous generation, it is to avoid formalin
Lock out operation, and accessory substance be hydrogen, be circularly used for synthesizing methanol；Meanwhile, the reaction is not in methanol oxidation life
The problem of formic acid etching apparatus, so as to be conducive to stabilization and the purification of formalin.In recent years, under research methanol oxygen free condition
Prepare the main exploitation in raw catelyst of emphasis of formaldehyde, including metal and its oxide catalyst, alkali metal salt and molecular sieve
Several classes such as catalyst.Although existing catalyst can catalysis methanol generation formaldehyde, all exist the sintering temperature of catalyst compared with
It is high, the problems such as catalyst strength is relatively low, service life is low, methanol conversion is low, catalytic reaction temperature is higher.
The content of the invention
In view of this, it is existing to solve it is an object of the invention to provide the technique that a kind of methanol dehydrogenation produces anhydrous formaldehyde
The technical problem that catalyst reaction temperatures are higher, methanol conversion is low.
The present invention solves above-mentioned technical problem by the following technical programs：
A kind of methanol dehydrogenation produces the technique of anhydrous formaldehyde, and using methanol as raw material, inert gas is as carrier gas, in fixed bed
Reacted in reactor, copper-based catalysts are filled in reaction tube, reaction tube is sent into reactor, reaction temperature is 200
~300 DEG C；
The copper-based catalysts are made up of soluble copper salt, HTS and auxiliary agent, soluble copper salt, titanium silicon point
The weight ratio of son sieve and auxiliary agent is (8~20)：(80)：(2~6)；
The preparation method of the copper-based catalysts is：By soluble copper salt and auxiliary agent homogeneous precipitation in HTS carrier
Surface, adds acid modification agent and modified under microwave action, microwave power is 300~500w, and temperature control is 61 thereto
~80 DEG C, the reaction time is 60~100min, and 80~100 DEG C of dryings after reaction terminates, 400~600 DEG C of air roastings are produced.
The acid modification agent is hydrochloric acid and oxalic acid with 10：3~4 volume ratios are mixed.
Described inert gas is more than one or both of nitrogen, argon gas, helium.
The soluble copper salt is more than one or both of copper nitrate, copper chloride, copper acetate or copper sulphate.
The auxiliary agent is the soluble-salt of any one in zinc, bismuth or manganese.
The methanol feed rate is 0.10~0.30ml/ (g cat.min).
It is 10~30mm that copper-based catalysts thickness of bed layer is loaded in the reaction tube.
Methanol dehydrogenation is that methanol is adsorbed in molecular sieve carrier surface and formed first in gas-solid-phase catalytic reaction, course of reaction
Active intermediate complex, and then react, be desorbed generation product, active sites are defective molecular sieves in high-temperature calcination process
Carrier and main active metal.Because acid site has the ability for receiving electronics pair, thus reduce oxygen and hydrogen in methanol hydroxylethyl
Interaction, effectively activated hydroxyl.Main active metal (nickel, copper, silver, gold, platinum, palladium, ruthenium, rhodium), can have in catalyst
C h bond in effect ground activation methanol molecules, effectively catalysis methanol removes hydrogen to the synergy of the two.The addition of co-catalyst
Interacted with main active metal, the electronic state of the main activated centre metal of modulation changes the density of d orbital electron, is more beneficial for
The electronics of c h bond is received, to sum up, the molecular sieve catalyst of Metal Supported is showed in the reaction that methanol dehydrogenation prepares anhydrous formaldehyde
The selectivity of good reactivity and product.
The beneficial effects of the present invention are：By in the processing of microwave action acid modification, can effectively strengthen copper-based and titanium
The synergy of si molecular sieves, dramatically increases the dispersiveness of catalyst, the outer Ti content of skeleton of molecular sieve is reduced, and effectively skeleton
Ti content increase.The specific surface area of catalyst is improved, and reaches 301~351m2/ g, is conducive to improving the conversion ratio and formaldehyde of methanol
Yield.
Embodiment
In order to facilitate the understanding of those skilled in the art, below in conjunction with embodiment, the present invention will be further described.
Embodiment is only to the invention for example, not being the step of not illustrating in limitation of the invention, embodiment
It is prior art, is not described in detail herein.
Embodiment one
A kind of methanol dehydrogenation produces the technique of anhydrous formaldehyde, prepares copper-based catalysts, the copper-based catalysts are by solvable
Property mantoquita, HTS and auxiliary agent are made, and weigh soluble copper salt copper nitrate 8kg, HTS 80kg and auxiliary agent
The nitrate of metallic zinc is zinc nitrate 2kg；By soluble copper salt copper nitrate and auxiliary agent zinc nitrate homogeneous precipitation in HTS
Carrier surface, adds acid modification agent and modified under microwave action, microwave power is 300w, and temperature control is 61 thereto
DEG C, the reaction time is 60min, and 80 DEG C of dryings after reaction terminates, 400 DEG C of air roastings produce copper-based catalysts, after testing, should
The specific surface area of catalyst is 301m2/g。
Using methanol as raw material, inert nitrogen gas is reacted as carrier gas in fixed bed reactors, in reaction tube
It is 10mm to fill filling copper-based catalysts thickness of bed layer in copper-based catalysts, the reaction tube, and reaction tube is sent into reactor,
Methanol feed rate is 0.10ml/ (g cat.min), and reaction temperature is 200 DEG C；Gas-chromatography on-line checking methanol conversion
For 85.7%, formaldehyde yield 54.5%.
The acid modification agent is hydrochloric acid and oxalic acid with 10：3 volume ratios are mixed.
Embodiment two
A kind of methanol dehydrogenation produces the technique of anhydrous formaldehyde, prepares copper-based catalysts, the copper-based catalysts are by solvable
Property mantoquita, HTS and auxiliary agent are made, and weigh soluble copper salt copper chloride 20kg, HTS 80kg and auxiliary agent
The nitrate of bismuth metal is bismuth nitrate 6kg；By soluble copper salt copper chloride and auxiliary agent zinc nitrate homogeneous precipitation in HTS
Carrier surface, adds acid modification agent and modified under microwave action, microwave power is 500w, and temperature control is 80 thereto
DEG C, the reaction time is 100min, and 100 DEG C of dryings after reaction terminates, 600 DEG C of air roastings produce copper-based catalysts, after testing,
The specific surface area of the catalyst is 376m2/g。
Using methanol as raw material, inert gas argon gas is reacted as carrier gas in fixed bed reactors, in reaction tube
It is 30mm to fill filling copper-based catalysts thickness of bed layer in copper-based catalysts, the reaction tube, and reaction tube is sent into reactor,
Methanol feed rate is 0.30ml/ (g cat.min), and reaction temperature is 300 DEG C；Gas-chromatography on-line checking methanol conversion
For 87.8%, formaldehyde yield 56.7%.
The acid modification agent is hydrochloric acid and oxalic acid with 10：4 volume ratios are mixed.
Embodiment three
A kind of methanol dehydrogenation produces the technique of anhydrous formaldehyde, prepares copper-based catalysts, the copper-based catalysts are by solvable
Property mantoquita, HTS and auxiliary agent are made, and weigh soluble copper salt copper sulphate 16kg, HTS 80kg and auxiliary agent
The nitrate of manganese metal is manganese nitrate 4kg；By soluble copper salt copper sulphate and auxiliary agent manganese nitrate homogeneous precipitation in HTS
Carrier surface, adds acid modification agent and modified under microwave action, microwave power is 400w, and temperature control is 70 thereto
DEG C, the reaction time is 80min, and 90 DEG C of dryings after reaction terminates, 500 DEG C of air roastings produce copper-based catalysts, after testing, should
The specific surface area of catalyst is 351m2/g。
Using methanol as raw material, inert gas helium is reacted as carrier gas in fixed bed reactors, in reaction tube
It is 20mm to fill filling copper-based catalysts thickness of bed layer in copper-based catalysts, the reaction tube, and reaction tube is sent into reactor,
Methanol feed rate is 0.20ml/ (g cat.min), and reaction temperature is 250 DEG C；Gas-chromatography on-line checking methanol conversion
For 91.1%, formaldehyde yield 59.2%.
The acid modification agent is hydrochloric acid and oxalic acid with 10：3 volume ratios are mixed.
Test example
By investigating the infrared spectrum of titanium-silicon molecular sieve catalyst material, using 960cm-1Locate absworption peak and 550cm-1Place
Absorption peak strength ratio I960/I550To characterize the i.e. effective framework Ti content of relative Ti content in HTS skeleton, it is worth accordingly
Size judges in skeleton relative Ti content, and value shows more greatly higher with respect to Ti content.The HTS of control group is using altogether
Prepared by intermediate processing, i.e., by copper nitrate and the homogeneous precipitation of promoter metal zinc nitrate in HTS carrier surface, 80~100 DEG C
Dry, 400~600 DEG C of air roastings are produced.Test group one to test group three is made using the embodiment of the present invention one to embodiment three
Standby molecular sieve catalyst.Measurement result is shown in Table 1.
Table 1
| Experiment packet | I960/I550 |
| Control group | 0.671 |
| Test group one | 0.723 |
| Test group two | 0.725 |
| Test group three | 0.786 |
By upper table 1 as can be seen that the I of copper-based catalysts prepared by the present invention960/I550Ratio it is (i.e. existing compared with control group
Have copper-based catalysts prepared by method) it is high, show that effective skeleton Ti content of copper-based catalysts prepared by the present invention is higher, catalysis
Efficiency is higher, may advantageously facilitate the conversion of methanol, improves the yield of formaldehyde.
Claims (7)
1. the technique that a kind of methanol dehydrogenation produces anhydrous formaldehyde, it is characterised in that：Using methanol as raw material, inert gas is used as load
Gas, is reacted in fixed bed reactors, and copper-based catalysts are filled in reaction tube, reaction tube is sent into reactor, instead
It is 200~300 DEG C to answer temperature；
The copper-based catalysts are made up of soluble copper salt, HTS and auxiliary agent, soluble copper salt, HTS
And the weight ratio of auxiliary agent is (8~20)：(80)：(2~6)；
The preparation method of the copper-based catalysts is：By soluble copper salt and auxiliary agent homogeneous precipitation in HTS carrier table
Face, adds acid modification agent and modified under microwave action thereto, and microwave power is 300~500w, and temperature control is 61~
80 DEG C, the reaction time is 60~100min, and 80~100 DEG C of dryings after reaction terminates, 400~600 DEG C of air roastings are produced.
2. the technique that methanol dehydrogenation as claimed in claim 1 produces anhydrous formaldehyde, it is characterised in that：The acid modification agent is
Hydrochloric acid and oxalic acid are with 10：3~4 volume ratios are mixed.
3. the technique that methanol dehydrogenation as claimed in claim 1 produces anhydrous formaldehyde, it is characterised in that：Described inert gas is
It is more than one or both of nitrogen, argon gas, helium.
4. the technique that methanol dehydrogenation as claimed in claim 1 produces anhydrous formaldehyde, it is characterised in that：The soluble copper salt is
It is more than one or both of copper nitrate, copper chloride, copper acetate or copper sulphate.
5. the technique that methanol dehydrogenation as claimed in claim 1 produces anhydrous formaldehyde, it is characterised in that：The auxiliary agent is zinc, bismuth
Or the soluble-salt of any one in manganese.
6. the technique that methanol dehydrogenation as claimed in claim 1 produces anhydrous formaldehyde, it is characterised in that：The methanol feed rate
For 0.10~0.30ml/ (g cat.min).
7. the technique that methanol dehydrogenation as claimed in claim 1 produces anhydrous formaldehyde, it is characterised in that：Loaded in the reaction tube
Copper-based catalysts thickness of bed layer is 10~30mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710549748.0A CN107162884A (en) | 2017-07-07 | 2017-07-07 | The technique that a kind of methanol dehydrogenation produces anhydrous formaldehyde |
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| CN201710549748.0A CN107162884A (en) | 2017-07-07 | 2017-07-07 | The technique that a kind of methanol dehydrogenation produces anhydrous formaldehyde |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217687A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for preparing anhydrous formaldehyde |
| CN116351463A (en) * | 2021-12-28 | 2023-06-30 | 中国石油天然气股份有限公司 | Catalyst for preparing anhydrous formaldehyde by dehydrogenation of methanol, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508863A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for preparing anhydrous formaldehyde |
| CN104447248A (en) * | 2013-09-12 | 2015-03-25 | 中国科学院大连化学物理研究所 | Preparation method for anhydrous formaldehyde |
| CN105523894A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Cyclohexene oxidation method |
| CN105712857A (en) * | 2014-12-03 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for preparing anhydrous formaldehyde by dehydrogenation of absolute methanol |
| CN105732350A (en) * | 2014-12-12 | 2016-07-06 | 中国科学院大连化学物理研究所 | Method of producing anhydrous formaldehyde through oxygen-free dehydrogenation |
| CN105732349A (en) * | 2014-12-12 | 2016-07-06 | 中国科学院大连化学物理研究所 | Method for preparing anhydrous formaldehyde through methanol dehydrogenation |
-
2017
- 2017-07-07 CN CN201710549748.0A patent/CN107162884A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508863A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for preparing anhydrous formaldehyde |
| CN104447248A (en) * | 2013-09-12 | 2015-03-25 | 中国科学院大连化学物理研究所 | Preparation method for anhydrous formaldehyde |
| CN105523894A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Cyclohexene oxidation method |
| CN105712857A (en) * | 2014-12-03 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for preparing anhydrous formaldehyde by dehydrogenation of absolute methanol |
| CN105732350A (en) * | 2014-12-12 | 2016-07-06 | 中国科学院大连化学物理研究所 | Method of producing anhydrous formaldehyde through oxygen-free dehydrogenation |
| CN105732349A (en) * | 2014-12-12 | 2016-07-06 | 中国科学院大连化学物理研究所 | Method for preparing anhydrous formaldehyde through methanol dehydrogenation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217687A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Method for preparing anhydrous formaldehyde |
| CN116351463A (en) * | 2021-12-28 | 2023-06-30 | 中国石油天然气股份有限公司 | Catalyst for preparing anhydrous formaldehyde by dehydrogenation of methanol, preparation method and application thereof |
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Application publication date: 20170915 |