CN107522181A - The technique that hydroxylamine hydrochloride is prepared using oxime acid hydrolysis method - Google Patents
The technique that hydroxylamine hydrochloride is prepared using oxime acid hydrolysis method Download PDFInfo
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- CN107522181A CN107522181A CN201710166148.6A CN201710166148A CN107522181A CN 107522181 A CN107522181 A CN 107522181A CN 201710166148 A CN201710166148 A CN 201710166148A CN 107522181 A CN107522181 A CN 107522181A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/14—Hydroxylamine; Salts thereof
- C01B21/1409—Preparation
- C01B21/1454—Preparation of hydroxylamine salts by processes not covered by one or more of groups C01B21/1418 - C01B21/1445, e.g. by conversion of one salt into another
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- 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
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
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Abstract
The invention belongs to hydroxylamine hydrochloride preparing technical field, discloses the technique that hydroxylamine hydrochloride is prepared using oxime acid hydrolysis method, and it comprises the following steps：Step a）Raw material cached configuration process, step b）Acidolysis reaction process, step c）Ketoxime rectification working process, step d）Dehydrate process, step e）Ethanol recovery process, step f）Acetaldoxime chemical industry sequence.Present invention process optimizes the process route and technical parameter of methyl ethyl ketoxime acidolysis production hydroxylamine hydrochloride, infiltration vaporization coupling technology is applied, improves product yield and quality, industry technology is promoted and further improves, the development of related industry has been driven, while has realized resource rational utilization.
Description
Technical field
The invention belongs to hydroxylamine hydrochloride preparing technical field, and in particular to the work of hydroxylamine hydrochloride is prepared using oxime acid hydrolysis method
Skill.
Background technology
Hydroxylamine hydrochloride, white needle-like crystals, 152 DEG C of fusing point（Decompose）, proportion 1.67.It is soluble in water, it is dissolved in ethanol, sweet
Oil, insoluble in ether.The easy moisture absorption, is gradually decomposed after making moist, and is corrosive, and is a kind of important organic synthesis intermediate, is used as
Analytical reagent and reducing agent, organic synthesis and the developing and printing of colour motion picture films are also used for, the raw material as medicine and organic synthesis, be used as
Reducing agent and developer etc. and the developing and printing for being used for autochromy and film.Medical industry radonil intermediate and synthesis anticarcinogen
（Hydroxycarbamide）, sulfa drug（Radonil）And agricultural chemicals（Methomyl）Raw material.System dye isatin intermediate.It is additionally operable to aliphatic acid and fertilizer
Soap makees age resistor.
Hydroxylamine salt direct synthesis method mainly includes at present：Electrolytic reduction, catalytic reduction method, calcium oxide method, zinc powder are also
Remote method, acetone oximate method, nitromethane Hydrolyze method, Raschig methods.The industrial process of hydroxylamine salt all Shortcomings at present：
Or cost is higher, or seriously endanger environment.The production method new it is therefore desirable to explore hydroxylamine salt.It is industrial for a long time all with
Hydroxylamine salt produces cyclohexanone oxime, methyl ethyl ketoxime, thus has cyclohexanone oxime, methyl ethyl ketoxime to produce the process of hydroxylamine salt through back reaction and hold
Easily it is considered in the nature of things uneconomic.However as the gradual maturation of the new technologies such as titanium molecular sieve catalysis ketone oxamidinating simultaneously
Move towards the industrialization, production cost is greatly lowered, and methyl ethyl ketoxime can be made without using hydroxylamine salt.Therefore by cyclohexanone oxime, first
The inverse process of the prior synthesizing method of acetophenone oxime-by ketoxime, hydroxylamine salt is produced in acidolysis in acid solution, just possess economical rationality
Property.Ketoxime acidolysis, which prepares hydroxylamine salt, to be turned into presently the most efficiently, succinct approach.
The content of the invention
The defects of in order to overcome prior art, the invention provides the technique for preparing hydroxylamine hydrochloride using oxime acid hydrolysis method.
The present invention is achieved by the following technical solution：
The technique that hydroxylamine hydrochloride is prepared using oxime acid hydrolysis method, it comprises the following steps：
Step a）Raw material cached configuration process, step b）Acidolysis reaction process, step c）Ketoxime rectification working process, step d）Dehydration is dry
Drying process, step e）Ethanol recovery process, step f）Acetaldoxime chemical industry sequence.
Specifically, the technique comprises the following steps：
Step a）Raw material caches preparation process：
Hydrochloric acid flows out from storage tank enters preparing tank after pump is pressurized, and a certain proportion of hydrochloric acid is configured to restored acid water, through heat exchange
Enter acidolysis kettle after device heating；Methyl ethyl ketoxime is external from battery limit (BL), into surge tank, enters acidolysis kettle after pump is pressurized, heat exchanger heats；
Step b）Acidolysis reaction process：
By step a）Gained mixed material is started to warm up in acidolysis kettle, and hydroxylamine hydrochloride, MEK, first are generated by stirring reaction
Ethyl ketone is sent to MEK recovery tower after pump is pressurized；Bottom material feeding dehydrates part；
Step c）MEK recovery process：
The overhead condenser of MEK recovery tower goes out battery limit (BL) after material is cooled down, bottom of towe obtains removing the water of MEK, by changing
Go out battery limit (BL) after hot device cooling；
Step d）Dehydrate process：
The reaction product of removing MEK is dehydrated into triple effect evaporator, and when taking off to finite concentration, solution is transferred to
Dehydrating kettle；Under negative pressure, acid gas is steamed from dehydrating kettle, acid gas obtains sour water after condensation, into raw material preparing tank, circulation
Utilize；Nitrogen pressurization is introduced after dehydration, switching heating medium is chilled water, and introduces ethanol to dehydrating kettle, and ethanol is with solid
Into first-stage centrifugal machine；The solid material being centrifuged out enters drier, and the liquid being centrifuged out decrystallizes kettle；Crystallization kettle is under negative pressure
Work, steam the condensed ethanol of being sent into of ethanol, the steam of water and reclaim kettle；Solid material produces hydrochloric acid after drier is dried
Azanol product；
Step e）Ethanol recovery process：
Material in ethanol recovery kettle enters return tank after being cooled to 40 DEG C by tower top cooler, is pumped up back head tank, analyzes
After ethanol content is qualified in kettle liquid, switching heating medium is chilled water, introduces appropriate demineralized water, and kettle liquid is sent into acetaldehyde oximate portion
Point；
Step f）Acetaldoxime chemical industry sequence.
Preferably, the step f）Acetaldoxime chemical industry sequence, comprises the following steps：
Kettle liquid in acetaldehyde oximate kettle is stirred and cooled；40%（v/v）Acetaldehyde is pumped up into acetaldehyde oximate kettle；25%（v/v）Ammonia
Water is pumped up into acetaldehyde oximate kettle；Acetaldehyde oximation reaction is carried out under -0.05MPa, is reacted and is kept liquid pH value about 5- in kettle
6, treat that acetaldehyde is less than 0.1% in acetaldehyde oximate kettle（v/v）When, continuously add ammoniacal liquor and make liquid pH value about 7 in kettle；Switching
Medium is heated, and liquid in acetaldehyde oximate kettle is heated up, carries out distillation operation；Acetaldoxime reclaims with vapor into acetaldoxime
Tower, carry out heat and mass transfer with the liquid from tower top and exchange；Enter second after the condensed device condensation of acetaldoxime come out from tower top
Collected in aldoxime return tank；An acetaldoxime part in acetaldoxime return tank is delivered to tower top by pump and flowed back, another part
Then it is transported to the storage of acetaldoxime tank field；Treat that acetaldehyde oxime content is less than 0.1% in acetaldehyde oximate kettle（v/v）When, stop distillation；Cut
Heating medium is changed, fluid temperature in acetaldehyde oximate kettle kettle is down to 40 DEG C；The solidliquid mixture come out from acetaldehyde oximate kettle enters
Waste water centrifugal filter is filtered, and the waste water filtered out is handled through waste water total pipeline into cesspool, and solid material ammonium chloride is then
Producing region is sent out in entrucking.
The beneficial effect that the present invention obtains mainly includes but is not limited to the following aspects：
1st, the present invention prepares hydroxylamine hydrochloride using methyl ethyl ketoxime, hydrochloric acid as raw material using oxime acidolysis process, and skill is produced with methyl ethyl ketoxime
Art has been jointly formed the process route of oximes-oxime acidolysis, reduces production cost, improves raw material availability, has pollution
The characteristics of small, environmentally friendly and technique is simple.
2nd, present invention process applies infiltration vaporization coupling technology, it is possible to achieve being quickly moved out for byproduct of reaction ketone, beats
Broken acidolysis reaction balance limitation, promotes the generation of target product hydroxylamine hydrochloride, improves reaction conversion ratio.
3rd, present invention process applies membrane separation technique, realizes the farthest cycling and reutilization to MEK, damage
Consume low.MEK is generated after methyl ethyl ketoxime acidolysis, and is used for as raw material in methyl ethyl ketoxime production, recycles, reduces production
Cost.
4th, the present invention prepares hydroxylamine salt technique using oxime acidolysis, the technique for optimizing methyl ethyl ketoxime acidolysis production hydroxylamine hydrochloride
Route and technical parameter, infiltration vaporization coupling technology is applied, improves product yield and quality, promoted industry technology and enter one
Step improves, and has driven the development of related industry, while realizes resource rational utilization, improves product competitiveness so that enterprise
Strided forward to more harmonization developing direction, there is preferably demonstration meaning and application value.
Brief description of the drawings
Fig. 1 prepares the process chart of hydroxylamine hydrochloride using oxime acid hydrolysis method.
Embodiment
In order that those skilled in the art more fully understand the technical scheme in the application, have below in conjunction with the application
Body embodiment, the present invention is more clearly and completely described, it is clear that described embodiment is only the application one
Divide embodiment, rather than whole embodiments.Based on the embodiment in the application, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, should all belong to the scope of protection of the invention.
Embodiment 1
The technique that hydroxylamine hydrochloride is prepared using oxime acid hydrolysis method, it comprises the following steps：
The technique is using methyl ethyl ketoxime, hydrochloric acid as raw material, using infiltration evaporation-reaction coupling technique, using oxime acidolysis process system
Standby hydroxylamine hydrochloride, mainly includes raw material cached configuration process, acidolysis reaction process, ketoxime rectification working process, dehydrates process, second
Alcohol recovery process, acetaldoxime chemical industry Xu Deng workshop sections.
Step a）Raw material caches preparation process
Hydrochloric acid flows out from storage tank enters preparing tank after pump is pressurized, and a certain proportion of hydrochloric acid is configured to restored acid water；Gone through pump
Enter acidolysis kettle after heat exchanger heating；Methyl ethyl ketoxime is external from battery limit (BL), into surge tank, enters acid after pump supercharging goes heat exchanger to heat
Solve kettle；
Step b）Acidolysis reaction process
By step a）Gained mixed material enters in acidolysis reaction kettle, and acidolysis kettle starts to warm up.Raw material is in reactor by stirring
Reaction generation hydroxylamine hydrochloride, MEK are mixed, MEK is sent to MEK recovery tower after pump is pressurized；Bottom material feeding dehydrates
Part；
Step c）MEK recovery process
The overhead condenser of MEK recovery tower goes out battery limit (BL) after material is cooled down, tower obtains built with 250Y structured packings, bottom of towe
The water of MEK is removed, goes out battery limit (BL) after heat exchanger cools；
Step d）Dehydrate process
The reaction product of removing MEK is dehydrated into triple effect evaporator, and when taking off to finite concentration, solution is transferred to
Dehydrating kettle；Under negative pressure, acid gas is steamed from dehydrating kettle, acid gas obtains sour water after condensation, into raw material preparing tank, circulation
Utilize；
Nitrogen pressurization is introduced after dehydration, switching heating medium is chilled water, and introduces ethanol to dehydrating kettle, ethanol and gone with solid
First-stage centrifugal machine；The solid material being centrifuged out removes drier, and the liquid being centrifuged out decrystallizes kettle；Crystallization kettle works under negative pressure,
Steam the condensed feeding ethanol recovery section of ethanol, the steam of water；Switching heating medium is chilled water, is according to circumstances suitably introduced into
Ethanol, ethanol remove filter centrifugal with bottom solid material, and the solid material being centrifuged out removes drier, and the liquid being centrifuged out is gone
Ethanol recovery section；The solid material sent by centrifuge produces hydroxylamine hydrochloride product after drier is dried；The thing steamed
Expect condensed feeding ethanol recovery section；
Step e）Ethanol recovery process
By dehydrate Lai ethanol enter ethanol recovery kettle, material enters return tank after being cooled to 40 DEG C by tower top cooler,
It is pumped up back head tank, analyzes after ethanol content is qualified in kettle liquid, switching heating medium is chilled water, introduces appropriate demineralized water,
Kettle liquid is sent into acetaldehyde oximate part；
Step f）Acetaldoxime chemical industry sequence
The solution containing hydroxylamine hydrochloride come from ethanol recovery is sent into acetaldehyde oximate kettle, stirs and cools；40% acetaldehyde be pumped up into
Acetaldehyde oximate kettle；25% ammoniacal liquor is pumped up into acetaldehyde oximate kettle.Acetaldehyde oximation reaction is carried out under -0.05MPa, is reacted and is kept
Liquid pH value about 5-6 in kettle, when acetaldehyde is less than 0.1% in acetaldehyde oximate kettle after testing, continuously adds ammoniacal liquor and make liquid in kettle
Body pH value about 7；Switching heating medium, and liquid in acetaldehyde oximate kettle is heated up, carry out distillation operation.Acetaldoxime enters with vapor
Enter acetaldoxime recovery tower, carrying out heat and mass transfer with the liquid from tower top exchanges；The condensed device of acetaldoxime come out from tower top
Enter after condensation in acetaldoxime return tank and collect；An acetaldoxime part in acetaldoxime return tank is delivered to tower top by pump and returned
Stream, another part are then transported to the storage of acetaldoxime tank field.When acetaldehyde oxime content is less than 0.1% in acetaldehyde oximate kettle after testing, stop
Only distill；Switching heating medium, 40 DEG C are down to by fluid temperature in acetaldehyde oximate kettle kettle；The solid-liquid come out from acetaldehyde oximate kettle mixes
Compound is filtered into waste water centrifugal filter, and the waste water filtered out is handled through waste water total pipeline into cesspool, and solid material
Then producing region is sent out in entrucking to ammonium chloride.
Embodiment 2
The present invention has investigated ketoxime species, feed way, material proportion, material concentration, reaction temperature, reaction time at ambient pressure
The influence of hydroxylamine hydrochloride is prepared to ketoxime acidolysis etc. factor.
1st, oxime acidolysis prepares hydroxylamine hydrochloride reflex action experimentation data analysis
1. the selection of ketoxime
The hydrochloric acid that mass concentration is 15% is prepared, weighs a certain amount of methyl ethyl ketoxime and cyclohexanone oxime respectively with hydrochloric acid in normal pressure 80
Disposable charging reaction 1 hour on DEG C.H+All it is 1.5 with ketoxime mol ratio.React post analysis and calculate ketoxime conversion ratio and hydrochloric acid
The selectivity of azanol, it is as a result as shown in table 1 below.
The different ketoxime of table 1 and hydrochloric acid reaction result
| Sequence number | Reaction mass | Methyl ethyl ketoxime conversion ratio % | Ketone selectivity % | Hydroxylamine hydrochloride selectivity % |
| 1 | Methyl ethyl ketoxime+hydrochloric acid | 15.16 | 78.48 | 98.22 |
| 2 | Cyclohexanone oxime+hydrochloric acid | 13.15 | 72.96 | 91.79 |
As a result show：Methyl ethyl ketoxime is easier to convert in hydrochloric acid than cyclohexanone oxime under the same terms.Using cyclohexanone oxime as raw material
Reaction hydroxylamine hydrochloride selectivity compared with methyl ethyl ketoxime reaction it is less than normal；The selectivity of another acid hydrolysate cyclohexanone is also correspondingly
Less than the selectivity of butanone, this is probably that cyclohexanone oxime is easier that the flat of non-acidolysis occurs in acidic aqueous solution than methyl ethyl ketoxime
Rearrangement reaction production caprolactam easily occurs in acid condition for row side reaction, i.e. cyclohexanone oxime.Contrast two reaction products
Selectivity be believed that methyl ethyl ketoxime is more suitable for making reaction raw materials and hydrochloric acid reaction than cyclohexanone oxime.
2. the selection of feed way
It is 15%, H in 80 DEG C of normal pressure, hydrochloric acid mass concentration+Methyl ethyl ketoxime is carried out under conditions of being 1.5 with methyl ethyl ketoxime mol ratio
With the reaction of hydrochloric acid, the reaction time is all 1 hour.Influence of the feed way to reaction result is investigated, two groups of experiments are respectively one
Secondary property charging reaction and be continuously added drop-wise to methyl ethyl ketoxime in hydrochloric acid reacts.React post analysis and calculate ketoxime conversion ratio and hydrochloric acid hydroxyl
The selectivity of amine, it is as a result as shown in table 2 below.
The reaction result of 2 different feed way of table
| Sequence number | Feed way | Methyl ethyl ketoxime conversion ratio % | The selective % of butanone | Hydroxylamine hydrochloride yield % |
| 1 | Disposable charging | 15.16 | 78.48 | 98.22 |
| 2 | Methyl ethyl ketoxime is added dropwise | 13.01 | 73.84 | 98.51 |
As a result show：The methyl ethyl ketoxime conversion ratio of 2# reactions reacts less than 1#, because it is of equal value that methyl ethyl ketoxime is added dropwise into charging
In the concentration for reducing methyl ethyl ketoxime, the concentration of butanone also can be reduced correspondingly caused by acidolysis, and 2# reactions are than the fourth of 1# reactions
Ketone is selectively slightly lower, and this is probably because the order of reaction of methyl ethyl ketoxime is more than the company of butanone in the rate equation of acidolysis main reaction
The order of reaction of butanone in the rate equation of string side reaction.The hydroxylamine hydrochloride that charging and disposable charging reaction is added dropwise is selective all
More than 98% and there is no significant difference, illustrate that hydroxylamine hydrochloride is relatively stable in the reaction, its selectivity is hardly by methyl ethyl ketoxime
The influence of change in concentration.The conversion ratio of two experiments of contrast can illustrate：Disposable feed molar ratio is added dropwise charging and is more beneficial for first and second
Acidolysis reaction of the ketoxime in hydrochloric acid.
3. the influence of material proportion
Prepare mass concentration（W/W）For 15% hydrochloric acid, according to H+Be respectively 1.2 with methyl ethyl ketoxime mol ratio, 1.4,1.5,1.6,
2.0, disposable charging reaction 1 hour on 80 DEG C of normal pressure.React the selection that post analysis calculate ketoxime conversion ratio and hydroxylamine hydrochloride
Property, it is as a result as shown in table 3 below.
The different sour oximes of table 3 than reaction result
As a result show：With H+With the increase of methyl ethyl ketoxime mol ratio, the conversion ratio of methyl ethyl ketoxime gradually increases, but increased width
Degree gradually slows down；The selectivity of hydroxylamine hydrochloride remains basically stable；The selectivity of butanone is gradually reduced and fall gradually increases.This
It is because the H of increase reaction+With the proportioning of methyl ethyl ketoxime, the substantially H in reaction solution is increased+First is reduced while concentration
The concentration of acetophenone oxime.The relatively result of each experiment of this group, while in order to reach higher methyl ethyl ketoxime conversion ratio, have enough
The selectivity of butanone and hydroxylamine hydrochloride, by H+It is more suitable to be set to 1.5 with methyl ethyl ketoxime mol ratio.
4. the influence of material concentration
Fixed H+It is 1.5 with methyl ethyl ketoxime mol ratio, prepares HCL mass concentrations（w/w）Respectively 10%, 12.5%, 15%, 20%,
25% hydrochloric acid solution, 80 DEG C of normal pressure upper disposable charging reaction 1 hour.React post analysis and calculate ketoxime conversion ratio and hydrochloric acid hydroxyl
The selectivity of amine, it is as a result as shown in table 4 below.
The reaction result of 4 different concentration of hydrochloric acid of table
| Sequence number | The mass concentration of hydrochloric acid（%） | Methyl ethyl ketoxime conversion ratio % | Butanone selectivity % | Hydroxylamine hydrochloride yield % |
| 1 | 10 | 13.07 | 83.05 | 95.2 |
| 2 | 12.5 | 14.14 | 79.89 | 96.66 |
| 3 | 15 | 15.16 | 78.48 | 98.22 |
| 4 | 20 | 16.39 | 71.98 | 98.68 |
| 5 | 25 | 17.17 | 64.6 | 98.35 |
As a result show：When concentration of hydrochloric acid increase, because the real reaction concentration of discharge reduction methyl ethyl ketoxime in reaction solution also accordingly increases
Greatly.Material concentration increases the speed reacted at then identical temperature and increased, and raw material methyl ethyl ketoxime turns within the identical reaction time
Rate increases therewith.However, with reaction hydrochloric acid and methyl ethyl ketoxime concentration while increase, the selectivity of butanone is obvious on the contrary
Decline, it is seen that the increase of concentration of hydrochloric acid is to the facilitation highly significant of butanone consecutive side reaction when being reacted at 72 DEG C, more than first
Acetophenone oxime increases the facilitation to acidolysis main reaction with concentration of hydrochloric acid.The selectivity of hydroxylamine hydrochloride is with the increase of concentration of hydrochloric acid
It is increased slightly, therefore stability of the hydroxylamine hydrochloride in hydrochloric acid solution may have certain relation with acid concentration, larger is sour dense
Degree can suppress the decomposition of hydroxylamine hydrochloride.It can also be seen that methyl ethyl ketoxime conversion ratio is with the increase of material concentration from upper table
Its amplification tapers into.This be probably because acidolysis main reaction equilibrium conversion it is inherently smaller, when reaction rate increase,
Main reaction also highlights sooner close to or up balance, back reaction to the depression effect of positive reaction quickly.Relatively each reality of this group
Result is tested, in order to ensure that butanone and hydroxylamine salt all have a higher selectivity, the hydrochloric acid of 15% concentration is advantageous in reaction.
5. the influence of reaction temperature
Prepare the hydrochloric acid that mass concentration is 15%, the H fixed in hydrochloric acid+It is 1.5 with methyl ethyl ketoxime mol ratio, respectively in normal pressure 70
DEG C, 80 DEG C, 90 DEG C, 100 DEG C of upper disposable charging reactions 1 hour.React post analysis and calculate ketoxime conversion ratio and hydroxylamine hydrochloride
Selectivity, it is as a result as shown in table 5 below.
Reaction result under the different temperatures of table 5
| Sequence number | Reaction temperature | Methyl ethyl ketoxime conversion ratio | Butanone selectivity | Hydroxylamine hydrochloride yield |
| 1 | 70 | 14.06 | 81.12 | 98.6 |
| 2 | 80 | 15.16 | 78.48 | 98.22 |
| 3 | 90 | 17.33 | 74.45 | 96.43 |
| 4 | 100 | 21.47 | 38.37 | 92.75 |
As a result show：With the rise of reaction temperature, the conversion ratio of methyl ethyl ketoxime significantly improves；Under the selectivity of butanone is gradual
Drop, in 92 DEG C of normal pressure（Boiling）Shi Fanying, which declines, to be especially apparent；Under the selectivity of hydroxylamine hydrochloride rises also with temperature
Drop.The reason for methyl ethyl ketoxime conversion ratio is raised and significantly increased with temperature is, for such a endothermic reaction of acidolysis reaction, temperature
Degree rise can not only kinetically accelerate the progress of reaction, and can thermodynamically promote the movement of chemical reaction equilibrium,
Increase the degree that positive reaction can be carried out.
With the rising of reaction temperature, butanone, hydroxylamine hydrochloride are selectively gradually reduced.Because heating accelerates pair instead
The speed answered, and in the temperature range of experiment（62~92℃）Speed constant pair of the speed constant of interior side reaction than main reaction
Temperature is more sensitive, i.e., parallel side reaction or butanone, hydroxylamine hydrochloride series connection side reaction activation energy it is bigger than main reaction activation energy.
Relatively this group of experimental result thinks：It is more suitable that acidolysis reaction of the methyl ethyl ketoxime in hydrochloric acid is carried out at 82 DEG C.
6. the influence in reaction time
The hydrochloric acid that mass concentration is 15% is prepared, weighing a certain amount of methyl ethyl ketoxime makes H+It is 1.5 with methyl ethyl ketoxime mol ratio,
The upper disposable charging reaction of 82 DEG C of normal pressure, the respectively sampling point when reaction is carried out 0.5 hour, 1 hour, 2 hours, 3 hours
Analysis.The selectivity that post analysis calculate ketoxime conversion ratio and hydroxylamine hydrochloride is reacted, it is as a result as shown in table 6 below.
The reaction result of the differential responses time of table 6
| Sequence number | Reaction time | Methyl ethyl ketoxime conversion ratio | Butanone selects habit | Hydroxylamine hydrochloride yield |
| 1 | 0.5 | 14.40 | 84.25 | 97.17 |
| 2 | 1 | 17.33 | 74.45 | 96.43 |
| 3 | 2 | 18.62 | 64.59 | 96.42 |
| 4 | 3 | 19.78 | 55.09 | 96.25 |
As a result show：After a rapid increase process of the conversion ratio of methyl ethyl ketoxime by reacting previous hour, the speed of rising
Rate substantially slows down；The selectivity of butanone declines always, and its corresponding yield has one from small to large, close to after a limiting value
Substantially constant process；The selectivity of hydroxylamine salt then maintains certain level all the time, with reaction be declined slightly.This
Illustrate it is high in reaction starting stage material concentration, can rapid acidolysis into butanone and hydroxylamine hydrochloride.As production concentration is gradually increased,
The side reaction of butanone and hydroxylamine salt also progressively strengthens, and main reaction is selectively declined.When reaction proceed to 1 it is small when or so connect
Balance that is near or reaching acidolysis reaction, back reaction are readily apparent that to the inhibitory action of positive reaction.Acidolysis reaction continues
It is considered that mainly driven by the series connection side reaction of butanone：The amount for the butanone that methyl ethyl ketoxime acidolysis obtains is roughly equivalent to fourth
The amount of ketonic decomposition, while the hydroxylamine salt in solution is built up, methyl ethyl ketoxime and butanone are constantly being consumed.Due to reaction
Purpose is not only to increase the conversion ratio of methyl ethyl ketoxime and hydroxylamine salt selectivity, also to take into account the selectivity of butanone, therefore it is small to react 1
When it is more suitable.
2nd, acidolysis reaction process optimization experimentation data analysis, is shown in Table 7.
The reaction experiment result of table 7
| Sequence number | Reaction condition | Methyl ethyl ketoxime conversion ratio % | Hydroxylamine hydrochloride yield % |
| 1 | Normal pressure | 16.73 | 91.43 |
| 2 | It is evaporated under reduced pressure | 67.24 | 92.71 |
| 3 | Pervaporation Technology | 97.07 | 95.36 |
As a result show：The method for removing product butanone is evaporated under reduced pressure while reaction, can greatly promote the acid of methyl ethyl ketoxime
Solution reaction balance moves to positive direction, promotes raw material conversion, conversion ratio is than reacting much bigger under normal pressure.But still there is material damage
Serious problems are lost, because negative pressure not only takes the butanone of azeotropic gasification and water out of caused by reaction intermediate pump, can also be incited somebody to action
Methyl ethyl ketoxime is taken out of.Butanone and methyl ethyl ketoxime in the gas steamed do not have total condensation collection, and a part has been lost to vacuum
In pump and environment, it is difficult to all reclaimed, must be improved.
Pervaporation Technology is applied while reaction, up to more than 97%, product yield reaches methyl ethyl ketoxime conversion ratio
More than 95%；Oxime acidolysis reaction speed removes the speed of ketone much larger than infiltration evaporation, and infiltration evaporation mass transport process turns into coupling process
Rate-determining steps；Coupling process later stage, the extremely low ketone concentration in reaction solution limit the further up speed of conversion ratio；It is few
The transmission of quantitative response thing oxime limits the further raising of conversion ratio.When using high concentration reaction solution, azanol crystal can be
Directly separated out in reaction system.
Conclusion：Oxime acidolysis prepares the research of hydroxylamine hydrochloride reflex action.It is disposable to add using methyl ethyl ketoxime and hydrochloric acid reaction
Material, hydrochloric acid are 1.5 with methyl ethyl ketoxime mol ratio, and hydrochloric acid mass concentration is 15%, and 82 DEG C of reaction temperature is 1 hour reaction time, right
The conversion ratio 16.73% for the methyl ethyl ketoxime answered, hydroxylamine hydrochloride conversion ratio 91.43%.
Acidolysis reaction Study of optimization.By contrast and experiment, Pervaporation Technology is relatively evaporated under reduced pressure, can
More effectively reaction product ketone is constantly removed, does not reach equilibrium concentration all the time, so that raw material constantly converts, is improved former
Expect conversion ratio, suppress the generation of side reaction, promote being continuously generated for target product.And almost do not had using Pervaporation Technology
Loss of material, and it is evaporated under reduced pressure that by negative pressure to be influenceed loss of material serious.Compare two methods, Pervaporation Technology is with more excellent
Gesture.
3. indicators of overall performance and the comparison of domestic and international similar advanced technology, are shown in Table 8.
The different hydroxylamine hydrochloride production and technical indication contrasts of table 8
| Sequence number | Process names | Methyl ethyl ketoxime conversion ratio | Hydroxylamine hydrochloride selectivity | Hydroxylamine hydrochloride yield |
| 1 | New technology | 97.07 | 99.72 | 95.36 |
| 2 | Traditional handicraft | 76.51 | 98.68 | 88.07 |
Above in association with specific embodiment, invention has been described, it will be appreciated by those skilled in the art that these are retouched
It is all exemplary to state, and is not limiting the scope of the invention.Those skilled in the art can be according to the essence of the present invention
God and principle make various variants and modifications to the present invention, and these variants and modifications are also within the scope of the invention.
Claims (3)
1. preparing the technique of hydroxylamine hydrochloride using oxime acid hydrolysis method, it comprises the following steps：
Step a）Raw material cached configuration process, step b）Acidolysis reaction process, step c）Ketoxime rectification working process, step d）Dehydration is dry
Drying process, step e）Ethanol recovery process, step f）Acetaldoxime chemical industry sequence.
2. technique according to claim 1, it is characterised in that the technique comprises the following steps：
Step a）Raw material caches preparation process：
Hydrochloric acid flows out from storage tank enters preparing tank after pump is pressurized, and acidolysis kettle is entered after heat exchanger heats；Methyl ethyl ketoxime enters buffering
Tank, enter acidolysis kettle after pump is pressurized, heat exchanger heats；
Step b）Acidolysis reaction process：
By step a）Gained mixed material is started to warm up in acidolysis kettle, and hydroxylamine hydrochloride, MEK, first are generated by stirring reaction
Ethyl ketone is sent to MEK recovery tower after pump is pressurized；
Step c）MEK recovery process：
The overhead condenser of MEK recovery tower goes out battery limit (BL) after material is cooled down, bottom of towe obtains removing the water of MEK, by changing
Go out battery limit (BL) after hot device cooling；
Step d）Dehydrate process：
The reaction product of removing MEK is dehydrated into triple effect evaporator, and when taking off to finite concentration, solution is transferred to
Dehydrating kettle；Under negative pressure, acid gas is steamed from dehydrating kettle, acid gas obtains sour water after condensation, into hydrochloric acid preparing tank, circulation
Utilize；Nitrogen pressurization is introduced after dehydration, switching heating medium is chilled water, and introduces ethanol to dehydrating kettle, and ethanol is with solid
Into first-stage centrifugal machine；The solid material being centrifuged out enters drier, after drier is dried, produces hydroxylamine hydrochloride product；
The liquid being centrifuged out decrystallizes kettle, and crystallization kettle works under negative pressure, steams that ethanol, the steam of water are condensed to be sent into ethanol recovery
Kettle；
Step e）Ethanol recovery process：
Material in ethanol recovery kettle enters return tank after being cooled to 40 DEG C by tower top cooler, is pumped up back head tank, analyzes
After ethanol content is qualified in kettle liquid, switching heating medium is chilled water, introduces appropriate demineralized water, and kettle liquid is sent into acetaldehyde oximate portion
Point；
Step f）Acetaldoxime chemical industry sequence.
3. technique according to claim 1 or 2, it is characterised in that the step f）Acetaldoxime chemical industry sequence, including following step
Suddenly：
Kettle liquid in acetaldehyde oximate kettle is stirred and cooled；40%（v/v）Acetaldehyde is pumped up into acetaldehyde oximate kettle；25%（v/v）Ammonia
Water is pumped up into acetaldehyde oximate kettle；Acetaldehyde oximation reaction is carried out under -0.05MPa, is reacted and is kept liquid pH value about 5- in kettle
6, treat that acetaldehyde is less than 0.1% in acetaldehyde oximate kettle（v/v）When, continuously add ammoniacal liquor and make liquid pH value about 7 in kettle；Switching
Medium is heated, and liquid in acetaldehyde oximate kettle is heated up, carries out distillation operation；Acetaldoxime reclaims with vapor into acetaldoxime
Tower, carry out heat and mass transfer with the liquid from tower top and exchange；Enter second after the condensed device condensation of acetaldoxime come out from tower top
Collected in aldoxime return tank；An acetaldoxime part in acetaldoxime return tank is delivered to tower top by pump and flowed back, another part
Then it is transported to the storage of acetaldoxime tank field；Treat that acetaldehyde oxime content is less than 0.1% in acetaldehyde oximate kettle（v/v）When, stop distillation；Cut
Heating medium is changed, fluid temperature in acetaldehyde oximate kettle kettle is down to 40 DEG C；The solidliquid mixture come out from acetaldehyde oximate kettle enters
Waste water centrifugal filter filters, and the waste water filtered out then fills through waste water total pipeline into cesspool processing, solid material ammonium chloride
Car sends out producing region.
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| CN110482505A (en) * | 2019-09-12 | 2019-11-22 | 东华理工大学 | A method of azanol is prepared using nitrogen |
| CN110845323A (en) * | 2019-11-15 | 2020-02-28 | 山东省化工研究院 | Preparation method of hydroxylamine formate |
| CN111333043A (en) * | 2020-03-06 | 2020-06-26 | 山东省化工研究院 | Process for preparing hydroxylamine salt by continuous hydrolysis of oxime |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108584893A (en) * | 2018-06-15 | 2018-09-28 | 中触媒新材料股份有限公司 | A kind of hydroxylamine hydrochloride synthetic method |
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| CN110482505B (en) * | 2019-09-12 | 2022-08-26 | 东华理工大学 | Method for preparing hydroxylamine by using nitrogen |
| CN110845323A (en) * | 2019-11-15 | 2020-02-28 | 山东省化工研究院 | Preparation method of hydroxylamine formate |
| CN110845323B (en) * | 2019-11-15 | 2022-04-26 | 山东省化工研究院 | Preparation method of hydroxylamine formate |
| CN111333043A (en) * | 2020-03-06 | 2020-06-26 | 山东省化工研究院 | Process for preparing hydroxylamine salt by continuous hydrolysis of oxime |
| CN111333043B (en) * | 2020-03-06 | 2023-05-09 | 山东省化工研究院 | Process for preparing hydroxylamine salt by oxime continuous hydrolysis |
| CN112409208A (en) * | 2020-11-30 | 2021-02-26 | 中触媒新材料股份有限公司 | Method for preparing acetaldoxime by adopting continuous method |
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