CN107935832A - A kind of method using fabricated by dehydrogenating alcohol for aldehyde or hemiacetal - Google Patents
A kind of method using fabricated by dehydrogenating alcohol for aldehyde or hemiacetal Download PDFInfo
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- CN107935832A CN107935832A CN201711489244.0A CN201711489244A CN107935832A CN 107935832 A CN107935832 A CN 107935832A CN 201711489244 A CN201711489244 A CN 201711489244A CN 107935832 A CN107935832 A CN 107935832A
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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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method using fabricated by dehydrogenating alcohol for aldehyde or hemiacetal, this method improves the efficiency of traditional handicraft dehydrogenation production on the whole, solves the problems, such as the shortcomings that catalyst and process conditions and operational issue generally existing conversion ratio and low selectivity.The preparation method of the hemiacetal of the present invention improves the effective rate of utilization of raw material at the same time, and technique productions cost is also controlled, and reduces pollution.
Description
Technical field
The present invention relates to chemical production technical field, is specially a kind of method using fabricated by dehydrogenating alcohol for aldehyde or hemiacetal.
Background technology
Aldehyde can be produced by the catalytic dehydrogenation of alcohol.In commercial scale, by silver or copper catalyst dehydrogenation with
And oxidative dehydrogenation is carried out in the presence of silver catalyst and oxygen.Dehydrogenation is at a temperature of 270-300 DEG C for example by Zn, Co or Cr
Carried out in the presence of the copper catalyst of activation.Under the ethanol conversion of 30-50%, the acetaldehyde selectivity realized is 90-95%,
The accessory substance of formation is ethyl acetate, crotonaldehyde, higher alcohol and ethene.Oxidative dehydrogenation situation in the presence of air or oxidation
Under, the hydrogen of formation burns at the same time provides required dehydrogenation heat.Industrially, oxidative dehydrogenation is filled out in metal mesh or crystallization
In the presence of the silver catalyst of material form into.But traditional alcohol dehydrogenase technique is due to catalyst problem, process conditions and operation
The shortcomings that problem etc., generally existing conversion ratio and low selectivity.
Second hemiacetal methanol solution is obtained by the hydrate RCH (OH) 2 of aldehyde with molecule alcohol combination RCH (OH) OR '.Half contracts
Aldehyde methanol solution is typically unstable, when solution is distilled, resolves into original aldehyde and alcohol immediately.At present, glycine method is given birth to
Produce glyphosate technique in, first step addition reaction be by unstable hemiacetal methanol solution triethylamine there are under system with it is sweet
Propylhomoserin addition generates intermediate.For these reasons, mostly it is to use paraformaldehyde as raw material in production, under methanol system,
With triethylamine (Et3N) for catalyst, the generation formaldehyde of depolymerization at a certain temperature, formaldehyde generates half unstable contracting with methanol again
Aldehyde methanol solution.Disclose at present by paraformaldehyde in the presence of alcohol organic solvent and catalyst, carry out depolymerization reaction, be made
Formaldehyde.Formaldehyde further reacts the production technology of generation hemiacetal methanol solution with alcohol.Conventional processing methods are in hemiacetal methanol
During solution obtains, technique detour is complicated, and hemiacetal methanol solution need to be by anti-with methanol again after the first aggregated depolymerization again of formaldehyde
It should obtain, add glyphosate production cost, and paraformaldehyde peculiar smell is serious in production, causes serious environmental pollution to ask
Topic.
To sum up state, the solution of these problems is, it is necessary to be improved traditional process.So how to invent one kind
Method and apparatus using fabricated by dehydrogenating alcohol for aldehyde or hemiacetal, this becomes our problems to be solved.
The content of the invention
It is an object of the invention to provide a kind of method and apparatus using fabricated by dehydrogenating alcohol for aldehyde or hemiacetal, to solve to carry on the back
The problem of proposed in scape technology.
To solve the above problems, the present invention provides following technical solution：
A kind of method using fabricated by dehydrogenating alcohol for aldehyde, this method comprise the following steps：
A, raw materials for production n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, the mixture of alkenols and dehydrogenation are pressed 7:1
Part by weight is added in dehydrogenation reactor；
B, the ZrO2 extrudates impregnated by using 2 solution of Pd (NO3) prepare dehydrogenation, and the dehydrogenation is for inside
Footpath is the work that 3- methanol piperidines (3-MPIP) is dehydrogenated to 3- methanol pyridine (3-PIC) in the tubular reactor of 0.26m-1.3m
Property, 50ml catalyst materials are first taken, and at 80 DEG C when soak time T1 is small for 4-6 in N2 atmosphere for 20% volume hydrogen, so
Afterwards when 200 DEG C soak time T2 is small for 3-4 in pure hydrogen；
C, start metered 3-MPIP, the raw material of 30-120ml/h is passed through in evaporator, and be gasified totally into carrier gas stream, carry
Gas is made of the N2 of 20% volume hydrogen, 0-10% volumes of air and 70-80% volumes, and the total volume flow rate of carrier gas corresponds to
20L/h, the gaseous mixture of raw material are carried out after evaporator by catalyst bed, dehydrogenation under 265 DEG C and atmospheric pressure；
D, after half an hour is reacted, sample is extracted according to 1 time interval when small, and analyzes alcohols and aldehydes content, detects purity,
After purity reaches 98%, with original airspeed, that is, 0.3L/h rerun 1 it is small when, complete dehydrogenation, discharge.
Preferably, the fabricated by dehydrogenating alcohol includes methanol, ethanol, normal propyl alcohol, isopropanol, just for the raw materials for production of the method for aldehyde
Butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, alkenols, alkenols, vinyl alcohol, allyl alcohol, alkynol, propilolic alcohol.
Preferably, this method uses a kind of device using fabricated by dehydrogenating alcohol for aldehyde during preparation, which includes
Dehydrogenation reactor 1, tubular reactor 2, evaporator 3, nitrogen box 4 and air pump 5.
Preferably, the mass fraction of effective catalyst component content of the dehydrogenation is 0.1%~1.2%.
Preferably, in stepb, the internal diameter size of tubular reactor and soak time positive correlation.Effect is prepared in order to improve
Rate, 80 DEG C in 20% volume hydrogen in N2 atmosphere soak time T1（Unit is hour）, activated in pure hydrogen at 200 DEG C
Time T2 unit is hour）With the internal diameter DD of tubular reactor（Unit is m）Meet：
；
In above formula, numerical computations are only carried out, are calculated without unit.
A kind of method using fabricated by dehydrogenating alcohol for hemiacetal, this method comprise the following steps：
A, by raw material, that is, methanol oxidation generation formaldehyde gaseous mixture, absorption equipment is sent into after formaldehyde gaseous mixture is dehydrated, is inhaled with methanol
Hemiacetal methanol solution is obtained after receiving agent contact, counts by volume, includes formaldehyde 40~65%, first in the formaldehyde gaseous mixture
Alcohol 20~30%, water 15~30%；
B, the formaldehyde in step a and the dehydration of methanol gaseous mixture use molecular screen membrane technology, are completed under the pressure of 0.3~0.8MPa
Dehydration；
C, imported after the dehydration of formaldehyde gaseous mixture by first grade absorption tower, methanol absorbing agent is imported by two-level absorption tower, using countercurrently connecing
Tactile absorption pattern, the control of the volume ratio of formaldehyde and methanol is 1 in the first grade absorption tower tail gas：（10~30）；
D, and then in first grade absorption tower nitrogen is passed through, the oxygen in first grade absorption tower is excluded, is heated and controls temperature
Half contracting metaplasia production is carried out under conditions of 400 DEG C~500 DEG C, while nitrogen is continuously passed into one always in process of production
In level absorption tower；
E, it is heating and continuous anti-when persistently completion 2.5 is small to half contracting catalyst of first grade absorption tower inside injection during continuous heating
Should, complete hemiacetal production.
Preferably, the half contracting catalyst is Pt-Al2O3 or Pd-C catalyst systems, and the half contracting catalyst is with Pt-
Al2O3 or Pd-C is first immersed in the solution containing potassium ion or sodium ion by infusion process for carrier, then by 400 DEG C~
500 DEG C of bakings.
Preferably, the raw material can also be ethanol and normal propyl alcohol.
Preferably, this method includes first grade absorption tower using a kind of device using alcohol dehydrogenase production hemiacetal, the device
6th, two-level absorption tower 7, nitrogen injection case 8, high-pressure pump 9.
Compared with prior art, beneficial effects of the present invention are as follows：
It is an advantage of the invention that：
（1）The present invention solves the problems, such as catalyst and technique bar from the efficiency for being integrally improved alcohol dehydrogenase production aldehyde and hemiacetal
The shortcomings that part and operational issue generally existing conversion ratio and low selectivity.
（2）The hemiacetal method of the present invention improves raw material effective rate of utilization at the same time, and technique productions cost is also controlled,
And reduce pollution.
Brief description of the drawings
Fig. 1 is a kind of method flow block diagram using fabricated by dehydrogenating alcohol for aldehyde in the present invention；
Fig. 2 is the apparatus structure schematic diagram being used for using fabricated by dehydrogenating alcohol for the method for aldehyde in the present invention；
Fig. 3 is a kind of method flow block diagram using fabricated by dehydrogenating alcohol for hemiacetal aldehyde in the present invention；
Fig. 4 is the apparatus structure schematic diagram being used for using fabricated by dehydrogenating alcohol for the method for hemiacetal in the present invention.
In figure：1- dehydrogenation reactors, 2- tubular reactors, 3- evaporators, 4- nitrogen box, 5- air pumps, 6- first grade absorption towers,
7- two-level absorption towers, 8- nitrogen injection case, 9- high-pressure pumps.
Embodiment
Below in conjunction with the attached drawing in the embodiment of the present invention, the technical solution in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, instead of all the embodiments.Alcohol in
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without making creative work
Embodiment, belongs to the scope of protection of the invention.
Embodiment 1：
- 4 are please referred to Fig.1, the invention of this reality provides following technical solution：
A kind of method using fabricated by dehydrogenating alcohol for aldehyde, this method comprise the following steps：
A, raw materials for production n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, the mixture of alkenols and dehydrogenation are pressed 7:1
Part by weight is added in dehydrogenation reactor；
B, the ZrO2 extrudates impregnated by using 2 solution of Pd (NO3) prepare dehydrogenation, and the dehydrogenation is for inside
Footpath is the activity that 3- methanol piperidines (3-MPIP) is dehydrogenated to 3- methanol pyridine (3-PIC) in the tubular reactor of 26mm, is first taken
50ml catalyst materials, and 80 DEG C 20% volume hydrogen activated in N2 atmosphere 4 it is small when, then at 200 DEG C in pure hydrogen
It is middle activation 3 it is small when；
C, start metered 3-MPIP, the raw materials for production of 30-120ml/h are passed through in evaporator, and be gasified totally into carrier gas
Stream, carrier gas are made of the N2 of 20% volume hydrogen, 0-10% volumes of air and 70-80% volumes, the total volume flow rate pair of carrier gas
It should be carried out in 20L/h, the gaseous mixture of raw material after evaporator by catalyst bed, dehydrogenation under 265 DEG C and atmospheric pressure；
D, after half an hour is reacted, sample is extracted according to 1 time interval when small, and analyzes alcohols and aldehydes content, detects purity,
After purity reaches 98%, with original airspeed, that is, 0.3L/h rerun 1 it is small when, complete dehydrogenation, discharge.
The fabricated by dehydrogenating alcohol includes methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, different for the raw materials for production of the method for aldehyde
Butanol, sec-butyl alcohol, the tert-butyl alcohol, alkenols, alkenols, vinyl alcohol, allyl alcohol, alkynol, propilolic alcohol.
This method uses a kind of device using fabricated by dehydrogenating alcohol for aldehyde during preparation, which includes dehydrogenation reaction
Device 1, tubular reactor 2, evaporator 3, nitrogen box 4 and air pump 5.The matter of effective catalyst component content of the dehydrogenation
It is 0.1%~1.2% to measure fraction.
A kind of method using fabricated by dehydrogenating alcohol for hemiacetal, this method comprise the following steps：
A, by raw material, that is, methanol oxidation generation formaldehyde gaseous mixture, absorption equipment is sent into after formaldehyde gaseous mixture is dehydrated, is inhaled with methanol
Hemiacetal methanol solution is obtained after receiving agent contact, counts by volume, includes formaldehyde 40~65%, first in the formaldehyde gaseous mixture
Alcohol 20~30%, water 15~30%；
B, the formaldehyde in step a and the dehydration of methanol gaseous mixture use molecular screen membrane technology, are completed under the pressure of 0.3~0.8MPa
Dehydration；
C, imported after the dehydration of formaldehyde gaseous mixture by first grade absorption tower, methanol absorbing agent is imported by two-level absorption tower, using countercurrently connecing
Tactile absorption pattern, the control of the volume ratio of formaldehyde and methanol is 1 in the first grade absorption tower tail gas：（10~30）；
D, and then in first grade absorption tower nitrogen is passed through, the oxygen in first grade absorption tower is excluded, is heated and controls temperature
Half contracting metaplasia production is carried out under conditions of 400 DEG C~500 DEG C, while nitrogen is continuously passed into one always in process of production
In level absorption tower；
E, it is heating and continuous anti-when persistently completion 2.5 is small to half contracting catalyst of first grade absorption tower inside injection during continuous heating
Should, complete hemiacetal production.
The half contracting catalyst is Pt-Al2O3 or Pd-C catalyst systems, the partly contracting catalyst be with Pt-Al2O3 or
Pd-C is first immersed in the solution containing potassium ion or sodium ion for carrier by infusion process, then by 400 DEG C~500 DEG C bakings
Roasting.The raw material can also be ethanol and normal propyl alcohol.
This method is using a kind of device using alcohol dehydrogenase production hemiacetal, which includes first grade absorption tower 6, two level is inhaled
Receive tower 7, nitrogen injection case 8）, high-pressure pump 9.
Embodiment 2：
- 4 are please referred to Fig.1, the invention of this reality provides following technical solution：
A kind of method using fabricated by dehydrogenating alcohol for aldehyde, this method comprise the following steps：
A, raw materials for production n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, the mixture of alkenols and dehydrogenation are pressed 7:1
Part by weight is added in dehydrogenation reactor；
B, the ZrO2 extrudates impregnated by using 2 solution of Pd (NO3) prepare dehydrogenation, and the dehydrogenation is for inside
Footpath is the activity that 3- methanol piperidines (3-MPIP) is dehydrogenated to 3- methanol pyridine (3-PIC) in the tubular reactor of 1.3m, is first taken
50ml catalyst materials, and 80 DEG C 20% volume hydrogen activated in N2 atmosphere 6 it is small when, then at 200 DEG C in pure hydrogen
It is middle activation 4 it is small when；
C, start metered 3-MPIP, the raw material of 30-120ml/h is passed through in evaporator, and be gasified totally into carrier gas stream, carry
Gas is made of the N2 of 20% volume hydrogen, 0-10% volumes of air and 70-80% volumes, and the total volume flow rate of carrier gas corresponds to
20L/h, the gaseous mixture of raw material are carried out after evaporator by catalyst bed, dehydrogenation under 265 DEG C and atmospheric pressure；
D, after half an hour is reacted, sample is extracted according to 1 time interval when small, and analyzes alcohols and aldehydes content, detects purity,
After purity reaches 98%, with original airspeed, that is, 0.3L/h rerun 1 it is small when, complete dehydrogenation, discharge.
The fabricated by dehydrogenating alcohol includes methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, different for the raw materials for production of the method for aldehyde
Butanol, sec-butyl alcohol, the tert-butyl alcohol, alkenols, alkenols, vinyl alcohol, allyl alcohol, alkynol, propilolic alcohol.
This method uses a kind of device using fabricated by dehydrogenating alcohol for aldehyde during preparation, which includes dehydrogenation reaction
Device 1, tubular reactor 2, evaporator 3, nitrogen box 4 and air pump 5.The matter of effective catalyst component content of the dehydrogenation
It is 0.1%~1.2% to measure fraction.
A kind of method using fabricated by dehydrogenating alcohol for hemiacetal, this method comprise the following steps：
A, by raw material, that is, methanol oxidation generation formaldehyde gaseous mixture, absorption equipment is sent into after formaldehyde gaseous mixture is dehydrated, is inhaled with methanol
Hemiacetal methanol solution is obtained after receiving agent contact, counts by volume, includes formaldehyde 40~65%, first in the formaldehyde gaseous mixture
Alcohol 20~30%, water 15~30%；
B, the formaldehyde in step a and the dehydration of methanol gaseous mixture use molecular screen membrane technology, are completed under the pressure of 0.3~0.8MPa
Dehydration；
C, imported after the dehydration of formaldehyde gaseous mixture by first grade absorption tower, methanol absorbing agent is imported by two-level absorption tower, using countercurrently connecing
Tactile absorption pattern, the control of the volume ratio of formaldehyde and methanol is 1 in the first grade absorption tower tail gas：（10~30）；
D, and then in first grade absorption tower nitrogen is passed through, the oxygen in first grade absorption tower is excluded, is heated and controls temperature
Half contracting metaplasia production is carried out under conditions of 400 DEG C~500 DEG C, while nitrogen is continuously passed into one always in process of production
In level absorption tower；
E, it is heating and continuous anti-when persistently completion 2.5 is small to half contracting catalyst of first grade absorption tower inside injection during continuous heating
Should, complete hemiacetal production.
The half contracting catalyst is Pt-Al2O3 or Pd-C catalyst systems, the partly contracting catalyst be with Pt-Al2O3 or
Pd-C is first immersed in the solution containing potassium ion or sodium ion for carrier by infusion process, then by 400 DEG C~500 DEG C bakings
Roasting.The raw material can also be ethanol and normal propyl alcohol.
This method is using a kind of device using alcohol dehydrogenase production hemiacetal, which includes first grade absorption tower 6, two level is inhaled
Receive tower 7, nitrogen injection case 8）, high-pressure pump 9.
Embodiment 3：
- 4 are please referred to Fig.1, the invention of this reality provides following technical solution：
A kind of method using fabricated by dehydrogenating alcohol for aldehyde, this method comprise the following steps：
A, raw materials for production n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, the mixture of alkenols and dehydrogenation are pressed 7:1
Part by weight is added in dehydrogenation reactor；
B, the ZrO2 extrudates impregnated by using 2 solution of Pd (NO3) prepare dehydrogenation, and the dehydrogenation is for inside
Footpath is DD（Unit is m）Tubular reactor in 3- methanol piperidines (3-MPIP) is dehydrogenated to the work of 3- methanol pyridine (3-PIC)
Property, first takes 50ml catalyst materials, and 80 DEG C 20% volume hydrogen activated in N2 atmosphere T1 it is small when, then at 200 DEG C
When activation T2 is small in pure hydrogen；The internal diameter size of tubular reactor and soak time positive correlation；In order to improve preparation efficiency,
80 DEG C in 20% volume hydrogen in N2 atmosphere soak time T1（Unit is hour）, in 200 DEG C of soak times in pure hydrogen
T2 units are hour）With the internal diameter DD of tubular reactor（Unit is m）Meet：；
C, start metered 3-MPIP, the raw material of 30-120ml/h is passed through in evaporator, and be gasified totally into carrier gas stream, carry
Gas is made of the N2 of 20% volume hydrogen, 0-10% volumes of air and 70-80% volumes, and the total volume flow rate of carrier gas corresponds to
20L/h, the gaseous mixture of raw material are carried out after evaporator by catalyst bed, dehydrogenation under 265 DEG C and atmospheric pressure；
D, after half an hour is reacted, sample is extracted according to 1 time interval when small, and analyzes alcohols and aldehydes content, detects purity,
After purity reaches 98%, with original airspeed, that is, 0.3L/h rerun 1 it is small when, complete dehydrogenation, discharge.
The fabricated by dehydrogenating alcohol includes methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, different for the raw materials for production of the method for aldehyde
Butanol, sec-butyl alcohol, the tert-butyl alcohol, alkenols, alkenols, vinyl alcohol, allyl alcohol, alkynol, propilolic alcohol.
This method uses a kind of device using fabricated by dehydrogenating alcohol for aldehyde during preparation, which includes dehydrogenation reaction
Device 1, tubular reactor 2, evaporator 3, nitrogen box 4 and air pump 5.The matter of effective catalyst component content of the dehydrogenation
It is 0.1%~1.2% to measure fraction.
A kind of method using fabricated by dehydrogenating alcohol for hemiacetal, this method comprise the following steps：
A, by raw material, that is, methanol oxidation generation formaldehyde gaseous mixture, absorption equipment is sent into after formaldehyde gaseous mixture is dehydrated, is inhaled with methanol
Hemiacetal methanol solution is obtained after receiving agent contact, counts by volume, includes formaldehyde 40~65%, first in the formaldehyde gaseous mixture
Alcohol 20~30%, water 15~30%；
B, the formaldehyde in step a and the dehydration of methanol gaseous mixture use molecular screen membrane technology, are completed under the pressure of 0.3~0.8MPa
Dehydration；
C, imported after the dehydration of formaldehyde gaseous mixture by first grade absorption tower, methanol absorbing agent is imported by two-level absorption tower, using countercurrently connecing
Tactile absorption pattern, the control of the volume ratio of formaldehyde and methanol is 1 in the first grade absorption tower tail gas：（10~30）；
D, and then in first grade absorption tower nitrogen is passed through, the oxygen in first grade absorption tower is excluded, is heated and controls temperature
Half contracting metaplasia production is carried out under conditions of 400 DEG C~500 DEG C, while nitrogen is continuously passed into one always in process of production
In level absorption tower；
E, it is heating and continuous anti-when persistently completion 2.5 is small to half contracting catalyst of first grade absorption tower inside injection during continuous heating
Should, complete hemiacetal production.
The half contracting catalyst is Pt-Al2O3 or Pd-C catalyst systems, the partly contracting catalyst be with Pt-Al2O3 or
Pd-C is first immersed in the solution containing potassium ion or sodium ion for carrier by infusion process, then by 400 DEG C~500 DEG C bakings
Roasting.The raw material can also be ethanol and normal propyl alcohol.
This method is using a kind of device using alcohol dehydrogenase production hemiacetal, which includes first grade absorption tower 6, two level is inhaled
Receive tower 7, nitrogen injection case 8）, high-pressure pump 9.
In summary, the present invention from be integrally improved traditional handicraft dehydrogenation production efficiency, solve the problems, such as catalyst and
The shortcomings that process conditions and operational issue generally existing conversion ratio and low selectivity, while the hemiacetal method of the present invention improves original
Material effective rate of utilization, technique productions cost are also controlled, and reduce pollution, possess larger technological break-through.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To modify to the technical solution described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent replacement, improvement and so on, should be included in the present invention's
Within protection domain.
Claims (8)
1. a kind of method using fabricated by dehydrogenating alcohol for aldehyde, this method comprises the following steps：
A, raw materials for production n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, the mixture of alkenols and dehydrogenation are pressed 7:1
Part by weight is added in dehydrogenation reactor；
B, the ZrO2 extrudates impregnated by using 2 solution of Pd (NO3) prepare dehydrogenation, and the dehydrogenation is for inside
Footpath is the activity that 3- methanol piperidines (3-MPIP) is dehydrogenated to 3- methanol pyridine (3-PIC) in the tubular reactor of 26mm, is first taken
50ml catalyst materials, and 80 DEG C 20% volume hydrogen activated in N2 atmosphere 4 it is small when, then at 200 DEG C in pure hydrogen
It is middle activation 3 it is small when；
C, start metered 3-MPIP, the raw material of 30-120ml/h is passed through in evaporator, and be gasified totally into carrier gas stream, carry
Gas is made of the N2 of 20% volume hydrogen, 0-10% volumes of air and 70-80% volumes, and the total volume flow rate of carrier gas corresponds to
20L/h, the gaseous mixture of raw material are carried out after evaporator by catalyst bed, dehydrogenation under 265 DEG C and atmospheric pressure；
D, after half an hour is reacted, sample is extracted according to 1 time interval when small, and analyzes alcohols and aldehydes content, detects purity,
After purity reaches 98%, with original airspeed, that is, 0.3L/h rerun 1 it is small when, complete dehydrogenation, discharge.
A kind of 2. method using fabricated by dehydrogenating alcohol for aldehyde according to claim 1, it is characterised in that：The fabricated by dehydrogenating alcohol is standby
The raw materials for production of the method for aldehyde include methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol, the tert-butyl alcohol, chain
Enol, alkenols, vinyl alcohol, allyl alcohol, alkynol, propilolic alcohol.
A kind of 3. method using fabricated by dehydrogenating alcohol for aldehyde according to any one of claim 1 or 2, it is characterised in that：Should
Method uses a kind of device using fabricated by dehydrogenating alcohol for aldehyde during preparation, which includes dehydrogenation reactor（1）, tubular type
Reactor（2）, evaporator（3）, nitrogen box（4）And air pump（5）.
4. the method according to any one of claim 1-3 using fabricated by dehydrogenating alcohol for aldehyde, it is characterised in that：Described is de-
The mass fraction of effective catalyst component content of hydrogen catalyst is 0.1%~1.2%.
A kind of 5. method using fabricated by dehydrogenating alcohol for hemiacetal, it is characterised in that：This method comprises the following steps：
A, by raw material, that is, methanol oxidation generation formaldehyde gaseous mixture, absorption equipment is sent into after formaldehyde gaseous mixture is dehydrated, is inhaled with methanol
Hemiacetal methanol solution is obtained after receiving agent contact, counts by volume, includes formaldehyde 40~65%, first in the formaldehyde gaseous mixture
Alcohol 20~30%, water 15~30%；
B, the formaldehyde in step a and the dehydration of methanol gaseous mixture use molecular screen membrane technology, are completed under the pressure of 0.3~0.8MPa
Dehydration；
C, imported after the dehydration of formaldehyde gaseous mixture by first grade absorption tower, methanol absorbing agent is imported by two-level absorption tower, using countercurrently connecing
Tactile absorption pattern, the control of the volume ratio of formaldehyde and methanol is 1 in the first grade absorption tower tail gas：（10~30）；
D, and then in first grade absorption tower nitrogen is passed through, the oxygen in first grade absorption tower is excluded, is heated and controls temperature
Half contracting metaplasia production is carried out under conditions of 400 DEG C~500 DEG C, while nitrogen is continuously passed into one always in process of production
In level absorption tower；
E, it is heating and continuous anti-when persistently completion 2.5 is small to half contracting catalyst of first grade absorption tower inside injection during continuous heating
Should, complete hemiacetal production.
A kind of 6. method using fabricated by dehydrogenating alcohol for hemiacetal according to claim 5, it is characterised in that：Half contracting is urged
Agent is Pt-Al2O3 or Pd-C catalyst systems, and the half contracting catalyst is to pass through dipping by carrier of Pt-Al2O3 or Pd-C
Method is first immersed in the solution containing potassium ion or sodium ion, then by 400 DEG C~500 DEG C bakings.
7. according to a kind of method using fabricated by dehydrogenating alcohol for hemiacetal of 5 or 6 any one of them of claim, it is characterised in that：
The raw material can also be ethanol and normal propyl alcohol.
A kind of 8. method using fabricated by dehydrogenating alcohol for hemiacetal according to any one of claim 5-7, it is characterised in that：
This method includes first grade absorption tower using a kind of device using alcohol dehydrogenase production hemiacetal, the device（6）, two-level absorption tower
（7）, nitrogen injection case（8）, high-pressure pump（9）.
Priority Applications (1)
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