CN110003012A - A kind of preparation method nitrifying organic matter and the nitrification organic matter being prepared - Google Patents
A kind of preparation method nitrifying organic matter and the nitrification organic matter being prepared Download PDFInfo
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- CN110003012A CN110003012A CN201910367591.9A CN201910367591A CN110003012A CN 110003012 A CN110003012 A CN 110003012A CN 201910367591 A CN201910367591 A CN 201910367591A CN 110003012 A CN110003012 A CN 110003012A
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- organic matter
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- paracresol
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
- C07C205/20—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C07C205/21—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings having nitro groups and hydroxy groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C205/22—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to carbon atoms of six-membered aromatic rings having nitro groups and hydroxy groups bound to carbon atoms of the same non-condensed six-membered aromatic ring having one nitro groups bound to the ring
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Abstract
The invention discloses a kind of preparation method for nitrifying organic matter and the nitrification organic matters being prepared, and are related to technical field of organic synthesis.The preparation method of the nitrification organic matter includes: that the organic matter to be nitrified for nitrifying acid solution and molten condition is passed through in micro passage reaction to react；Wherein, it is solid-state under organic matter room temperature to be nitrified, does not solidify and/or be dissolved in nitrification acid solution after nitrifying organic matter and being passed through micro passage reaction.There is good yield and purity without the aftertreatment technology of solvent removal using the nitrification organic matter that the preparation method of above-mentioned nitrification organic matter is prepared.Whole process does not have solvent to participate in reaction, avoids the last handling process of solvent removal；The security performance of entire reaction process is high, and automation control, high production efficiency substantially improves production environment, has biggish industrial application value.
Description
Technical field
The present invention relates to technical field of organic synthesis, and in particular to it is a kind of nitrify organic matter preparation method and be prepared into
The nitrification organic matter arrived.
Background technique
2-nitro-paracresol is a kind of widely used organic synthesis intermediate, can be used for the synthesis of adjacent amino paracresol,
Adjacent amino paracresol is the intermediate for producing fluorescent whitener DT.Therefore, the preparation method of research nitrification organic matter has important
Meaning.It is industrially prepared using the paracresol nitrification process of relatively easy economy, i.e., using benzene as solvent, paracresol is raw material, is used
20% or so dust technology directly nitrifies, and yield is generally less than 80%.Also the document report is with the lesser methylene chloride of toxicity
Solvent replaces steam distillation to purify with vacuum distillation and recrystallization, and highest yield has reached 82.3%.
Traditional technique is produced using interval flask or autoclave, has following defect: (1) paracresol nitration reaction thermal discharge
Greatly, it is easy to " temperature runaway " phenomenon occur；(2) condition controls the oxidized byproduct of bad tarry easily generated, and the solvent used
It needs further to separate, so that isolating and purifying for product becomes difficult, post processing cost is high；(3) batch production stability is poor, shadow
Ring the quality of subsequent chemical products.Equally, there is also the above problems for the synthesis of many compounds similar with 2-nitro-paracresol.
In consideration of it, proposing the application.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods for nitrifying organic matter, it is intended to simplify process route, mention significantly
The yield of the nitrification organic matter such as high 2-nitro-paracresol.
Another object of the present invention is to provide a kind of nitrification organic matters, are prepared by above-mentioned preparation method, product
High income.
The present invention solves its technical problem and adopts the following technical solutions to realize.
The invention proposes a kind of preparation methods for nitrifying organic matter, include the following steps:
The organic matter to be nitrified for nitrifying acid solution and molten condition is passed through in micro passage reaction and is reacted；Wherein, wait nitrify
It is solid-state under organic matter room temperature, nitration acids is not solidified and/or be dissolved in after nitrifying organic matter and being passed through micro passage reaction
In liquid.
The present invention also proposes a kind of nitrification organic matter, is prepared using the preparation method of above-mentioned nitrification organic matter.
The beneficial effect that the embodiment of the present invention provides a kind of preparation method for nitrifying organic matter is: it uses microchannel plate to answer
Device, which carries out successive reaction, can pass through the reaction of short time using the organic matter to be nitrified for nitrifying acid solution and molten condition as raw material
Nitrification organic matter is prepared.Whole process does not have solvent to participate in reaction, avoids the last handling process of solvent removal；It is entire anti-
Answer the security performance of process high, automation control, high production efficiency substantially improves production environment, has biggish industrial application
Value.
The present invention also provides a kind of nitrification organic matters, are prepared by above-mentioned preparation method, and product is gone without solvent
The aftertreatment technology removed has good yield and purity.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the first structure diagram of microchannel reaction unit provided in an embodiment of the present invention；
Fig. 2 is the second structural schematic diagram of microchannel reaction unit provided in an embodiment of the present invention；
Fig. 3 is the third structural schematic diagram of microchannel reaction unit provided in an embodiment of the present invention；
Fig. 4 is the gas chromatogram for the 2-nitro-paracresol that the embodiment of the present invention is prepared；
Fig. 5 is the analysis datagram of gas-chromatography in Fig. 4.
Icon: 1- paracresol holder；2- water-bath；3- nitric acid holder；4- metal high voltage constant flow pump；5- microchannel plate
Answer device；6- sampling bottle.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
It is organic to a kind of preparation method for nitrifying organic matter provided in an embodiment of the present invention and the nitrification that is prepared below
Object is specifically described.
A kind of preparation method nitrifying organic matter provided in an embodiment of the present invention comprising acid solution following steps: will be nitrified
It is passed through in micro passage reaction and reacts with the organic matter to be nitrified of molten condition；Preferably, reaction time is in 10s or more,
By taking paracresol reacts as an example, reaction principle is as follows:
It wherein, is solid-state under organic matter room temperature to be nitrified, the organic matter to be nitrified of molten condition is passed through micro passage reaction
Afterwards, organic matter to be nitrified will not be solidified and/or be dissolved in nitrification acid solution.To ensure organic matter to be nitrified in microchannel plate
The state in device is answered, reaction temperature is unsuitable too low, it is preferable that reaction temperature and the difference of the melting temperature of organic matter to be nitrified are
X, X >=-30 DEG C；It is highly preferred that X >=-20 DEG C；It is further preferred that X >=-100 DEG C.
Specifically, solidification does not occur to refer to that the material of most of molten condition will not be undergone phase transition and be changed into solid-state, even if hair
Raw a small amount of solidification can be dissolved in nitrification acid solution or the dissolution that reacts without blocking channel with Flow of Goods and Materials.It is excellent
Choosing, solidification does not occur and refers to that all fused materials will not all solidify.
In some embodiments, organic matter to be nitrified is paranitrochlorobenzene or paracide, and nitrification acid solution is nitric acid and sulphur
The mixed acid of acid；Preferably, the molar ratio of organic matter to be nitrified, nitric acid and sulfuric acid is 1:1-2:1.26-4；Preferably, wait nitrify
The flow of organic matter is 12-25mL/min, and the flow for nitrifying acid solution is 10-40mL/min；Preferably, reaction temperature 60-90
DEG C, reaction time 70-120min.The nitration reaction of paranitrochlorobenzene or paracide is different from paracresol, nitration reaction
Need mixed acid there are the case where reaction.
In a preferred embodiment, organic matter to be nitrified is paracresol, and nitrification acid solution is dust technology, and paracresol can be dilute
Nitration reaction can occur in the presence of nitric acid, reacted without mixed acid.
By taking paracresol reacts as an example, inventor it is creative using nitric acid and the paracresol of molten condition as raw material, use is micro-
Channel reactor is reacted, and avoids the use of solvent, and reaction time is short.It is anti-that whole process does not have solvent to participate in
It answers, avoids the last handling process of solvent removal；" temperature runaway " phenomenon is less likely to occur entire reaction process, and security performance is high, from
Dynamicization control；Reaction time is short and without post-processing link, and high production efficiency has biggish industrial application value.
Fig. 1 is please referred to, micro passage reaction, which is a kind of pipeline reactor continuously flowed, to be manufactured by micro-processing technology
A kind of characteristic size between 10-1000 μm, by device of the Control of chemical reaction in microresponse space.Microreactor
In narrow microchannel shorten mass transfer away from discrete time, while the specific surface area increased also provides for mass transport process
Bigger place realizes it within the scope of millisecond to Microsecond grade radial completely mixed to realize the quick mixing of reaction mass
It closes.The narrow microchannel of microreactor also increases temperature gradient simultaneously, and the specific surface area of increase enhances reactor significantly
Heat-transfer capability.Therefore, the characteristic of micro passage reaction can farthest strengthen chemical reaction process, improve reaction effect
Rate, so that chemical reaction rate is close to its kinetics limit.
Compared with conventional synthesis process, adjacent nitre is continuously prepared using pipeline reactors such as micro passage reactions in the present invention
Base paracresol has the advantage that without using solvent, reduces last handling process；Occupation area of equipment is small, easy to operate, is easy to
Control and amplification；And inventor has found the height of 2-nitro-paracresol product purity made from this method, quality is stablized.
In Fig. 1, by paracresol holder 1, nitric acid holder 3, metal high voltage constant flow pump 4, micro passage reaction 5 and take
Sample bottle 6 forms, and two kinds of raw materials are passed through in micro passage reaction 5 by metal high voltage constant flow pump 4 respectively to react, after then sampling
It is passed through in sampling bottle 6.According to the difference of reaction time, there may be certain difference for sample point, in fact it could happen that such as Fig. 2-3
State.It is equipped with heating mantle (such as water-bath 2) on the material feeding pipe of melting charging, the temperature of heating mantle will not make to melt
The material of charging solidifies, such as subtracts 10 DEG C higher than material fusing point.
Specifically, paracresol (industrial raw material) needs are heated to molten condition before being passed through reactor, are such as heated to
40℃.Nitric acid is the dust technology (industrial raw material) of volume fraction 20-40%；Preferably 25-35%；More preferably 28-32%,
Dust technology can use volume fraction to be diluted to obtain for 65% commercially available nitric acid, and the concentration of dust technology is controlled in above range
Inside it is advisable, reaction process is easy to control within this range, it is not easy to " temperature runaway " phenomenon occur.
In order to improve the yield of product, the used in amounts of two kinds of raw materials will be controlled in a certain range, paracresol and nitric acid
Molar ratio is 1:1.1-1.2.It using the slightly excessive mode of nitric acid, reacts paracresol more fully, guarantees 2-nitro-paracresol
Yield.
The micro passage reaction used in the embodiment of the present invention can be commercially available conventional micro passage reaction, preferably originally
The reactor of the bold and generous Chemical Engineering Technology Co., Ltd independent research in company Shandong, production, specific Patent No. 201610932350.0,
201610965286.6.The channel depth of micro passage reaction is 0.3-1.0mm, and total liquid inventory is that 10-100mL (can be according to reality
Border needs to be adjusted, such as 60.0mL, 40.0mL, 20.0mL)；The form in channel is umbrella shape, and micro passage reaction uses
Two-sided heat exchange structure.The processing of micro passage reaction mainly using the micro-processing technologies such as etching, wire cutting, laser boring method come
It realizes.
In some embodiments by the way of once feeding, the flow velocity of paracresol is 10-40mL/min, the flow velocity of nitric acid
For for 20-90mL/min；Preferably, the flow velocity of paracresol is 25-30mL/min, and the flow velocity of nitric acid is 30-45mL/min.It is right
The flow control of cresols and nitric acid within the above range, can adapt to the structure of micro passage reaction, make to react when shorter
Interior fully reacting improves production efficiency.
In a further embodiment by the way of feeding at least twice, nitric acid is by the way of sectional feeding, it is preferable that
Nitric acid by the way of feeding in two times；It is highly preferred that second of the nitric acid feed time fed is the 1/ of overall reaction duration
, it is further preferred that the feed time of second of charging is the 1/50-2/3 of overall reaction duration.Nitric acid it is secondary into
The phase is advisable the control of material time in the reaction, does the supplement of nitric acid amount in mid-term.Inventors have found that using the side of nitric acid sectional feeding
Formula can further increase the yield of reaction, and nitric acid can rise in rebellion if being added at one time answers leading portion to react excessively violent, thermal discharge
Greatly, cause temperature to increase, increase the generation of side reaction, selectivity reduces；Reaction temperature can be effectively controlled using nitric acid secondary feeds
Degree, avoids local temperature excessively high, reduces the generation of side reaction, improves selectivity.
In some embodiments by the way of feeding three times, it is preferred that secondary charging opportunity, selection stop in reaction
Stay the 1/200-3/6 of time t；The charging opportunity of third time selects in reaction time 3/6-5/6.
Optionally, it is preferable that when feeding number is n times, and when 2n≤200, select 200, the m times feed time is total
React (2m-1)/200- (2m+1)/200 of duration t；Preferably, when feeding number is n times, and when 2n > 200, the m times into
Expect that the time is (2m-1)/2n- (2m+1)/2n of overall reaction duration t.
You need to add is that by the way of sectional feeding, the overall structure figure of reaction is as shown in figure 3, compare and Fig. 1-2
Which increase one group of metal high voltage constant flow pumps for conveying nitric acid.
Further, general secondary feeds are faster than primary charging, and when such as feeding for the first time, the flow velocity of paracresol is
30-45mL/min, the flow velocity of nitric acid are 20-30mL/min；When second of charging, the flow velocity of nitric acid is 50-65mL/min；It is preferred that
Ground, when feeding for the first time, the flow velocity of paracresol is 35-40mL/min, and the flow velocity of nitric acid is 23-28mL/min；Second of charging
When, the flow velocity of nitric acid is 55-60mL/min.Second of flow velocity fed of nitric acid is faster advisable, when suitable reaction stops
Interior abundant reaction, second feeds that nitric acid flow velocity is excessively slow or the too fast raising for being unfavorable for yield, controls in 55-60mL/min
It is advisable.
Further, reaction time 10-60s；Preferably 15-40s；More preferably 19-21s.Using the present invention
Embodiment provide synthesis technology can fully reacting in a short period of time, the reaction time adjacent nitro of about 10s or more
Paracresol can reach very high yield, exist to further increase the yield reaction time control of 2-nitro-paracresol
20s or so is advisable.
Further, reaction temperature is 20-40 DEG C；Preferably 25-35 DEG C；More preferably 29-31 DEG C.Reaction temperature is unsuitable
Too high or too low, reaction temperature is crossed low reaction and is carried out not exclusively, the low yield of 2-nitro-paracresol；Reaction temperature is excessively high to be made instead
It should be not easily controlled, be easy to happen " temperature runaway " phenomenon.
The embodiment of the invention also provides a kind of 2-nitro-paracresols, prepare using the preparation method of above-mentioned nitrification organic matter
And it obtains.In a preferred embodiment, the conversion ratio of 2-nitro-paracresol is 98% or more, and the purity of 2-nitro-paracresol is greater than
98%.The 2-nitro-paracresol that above-mentioned preparation method is prepared has with short production cycle, high income, product purity height etc. excellent
Point has the good market competitiveness.
Feature and performance of the invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of preparation methods for nitrifying organic matter (2-nitro-paracresol), include the following steps:
Two metal high voltage constant flow pumps are connect with first two feed inlet of micro passage reaction, and are rushed with aqueous solvent
It washes.Sampling bottle is cleaned up, dry after be connected to the 6th discharge port of micro passage reaction after.Micro passage reaction solvent
After rinsing well, full of 30% nitric acid solution.
Micro passage reaction temperature is set as 20 DEG C, and paracresol is placed in water-bath or insulating box and is heated in molten
Paracresol and nitric acid mol ratio is arranged as 1:1.3 in state, and the flow of paracresol and 30% nitric acid solution is respectively 18.5mL/min
And 41.5mL/min, into mixing in micro passage reaction, the residence time is 60s (effective liquid holdup is 60.0mL).It reacted
Temperature control collects reaction solution at 20 DEG C or so in journey, carries out the measurement of 2-nitro-paracresol content.
Embodiment 2
The present embodiment provides a kind of preparation methods for nitrifying organic matter (2-nitro-paracresol), include the following steps:
Two metal high voltage constant flow pumps are connect with first two feed inlet of micro passage reaction, and are rushed with aqueous solvent
It washes.Sampling bottle is cleaned up, dry after be connected to the 6th discharge port of micro passage reaction after.Micro passage reaction solvent
After rinsing well, full of 30% nitric acid solution.
Micro passage reaction temperature is set as 30 DEG C, and paracresol is placed in water-bath or insulating box and is heated to 40 DEG C in molten
Melt state, setting paracresol and nitric acid mol ratio are 1:1.3, and paracresol and the flow of 30% nitric acid solution are respectively
18.5mL/min and 41.5mL/min, into mixing in micro passage reaction, the residence time is that (effective liquid holdup is 60s
60.0mL).Temperature control collects reaction solution at 30 DEG C or so in reaction process, carries out the measurement of 2-nitro-paracresol content.
Embodiment 3
The present embodiment provides a kind of preparation methods for nitrifying organic matter (2-nitro-paracresol), include the following steps:
Two metal high voltage constant flow pumps are connect with first two feed inlet of micro passage reaction, and are rushed with aqueous solvent
It washes.Sampling bottle is cleaned up, dry after be connected to the 6th discharge port of micro passage reaction after.Micro passage reaction solvent
After rinsing well, full of 30% nitric acid solution.
Micro passage reaction temperature is set as 40 DEG C, and paracresol is placed in water-bath or insulating box and is heated to 40 DEG C in molten
Melt state, setting paracresol and nitric acid mol ratio are 1:1.3, and paracresol and the flow of 30% nitric acid solution are respectively
18.5mL/min and 41.5mL/min, into mixing in micro passage reaction, the residence time is that (effective liquid holdup is 60s
60.0mL).Temperature control collects reaction solution at 40 DEG C or so in reaction process, carries out the measurement of 2-nitro-paracresol content.
Embodiment 4
The present embodiment provides a kind of preparation methods for nitrifying organic matter (2-nitro-paracresol), include the following steps:
Two metal high voltage constant flow pumps are connect with first two feed inlet of micro passage reaction, and are rushed with aqueous solvent
It washes.Sampling bottle is cleaned up, dry after be connected to the 6th discharge port of micro passage reaction after.Micro passage reaction solvent
After rinsing well, full of 30% nitric acid solution.
Micro passage reaction temperature is set as 30 DEG C, and paracresol is placed in water-bath or insulating box and is heated to 40 DEG C in molten
Melt state, paracresol and nitric acid mol ratio is set for 1:1.1, the flow of paracresol and 35% nitric acid solution is respectively 20mL/
Min and 40mL/min, into mixing in micro passage reaction, the residence time is 60s (effective liquid holdup is 60.0mL).It reacted
Temperature control collects reaction solution at 30 DEG C or so in journey, carries out the measurement of 2-nitro-paracresol content.
Embodiment 5
The present embodiment provides a kind of preparation methods for nitrifying organic matter (2-nitro-paracresol), include the following steps:
Two metal high voltage constant flow pumps are connect with first two feed inlet of micro passage reaction, and are rushed with aqueous solvent
It washes.Sampling bottle is cleaned up, dry after be connected to the 6th discharge port of micro passage reaction after.Micro passage reaction solvent
After rinsing well, full of 30% nitric acid solution.
Micro passage reaction temperature is set as 30 DEG C, and paracresol is placed in water-bath or insulating box and is heated to 40 DEG C in molten
Melt state, setting paracresol and nitric acid mol ratio are 1:1.5, and paracresol and the flow of 28% nitric acid solution are respectively
16.7mL/min and 43.4mL/min, into mixing in micro passage reaction, the residence time is that (effective liquid holdup is 60s
60.0mL).Temperature control collects reaction solution at 30 DEG C or so in reaction process, carries out the measurement of 2-nitro-paracresol content.
Embodiment 6
The present embodiment provides a kind of preparation methods for nitrifying organic matter (2-nitro-paracresol), include the following steps:
Two metal high voltage constant flow pumps are connect with first two feed inlet of micro passage reaction, and are rushed with aqueous solvent
It washes.Sampling bottle is cleaned up, dry after be connected to the 6th discharge port of micro passage reaction after.Micro passage reaction solvent
After rinsing well, full of 30% nitric acid solution.
Micro passage reaction temperature is set as 30 DEG C, and paracresol is placed in water-bath or insulating box and is heated to 40 DEG C in molten
Melt state, setting paracresol and nitric acid mol ratio are 1:1.5, and paracresol and the flow of 20% nitric acid solution are respectively
15.0mL/min and 45.0mL/min, into mixing in micro passage reaction, the residence time is that (effective liquid holdup is 60s
60.0mL).Temperature control collects reaction solution at 30 DEG C or so in reaction process, carries out the measurement of 2-nitro-paracresol content.
Embodiment 7
The present embodiment provides a kind of preparation methods for nitrifying organic matter (2-nitro-paracresol), include the following steps:
Two metal high voltage constant flow pumps are connect with first two feed inlet of micro passage reaction, and are rushed with aqueous solvent
It washes.Sampling bottle is cleaned up, dry after be connected to the 6th discharge port of micro passage reaction after.Micro passage reaction solvent
After rinsing well, full of 30% nitric acid solution.
Micro passage reaction temperature is set as 30 DEG C, and paracresol is placed in water-bath or insulating box and is heated to 40 DEG C in molten
Melt state, setting paracresol and nitric acid mol ratio are 1:1.5, and paracresol and the flow of 40% nitric acid solution are respectively
21.5mL/min and 38.5mL/min, into mixing in micro passage reaction, the residence time is that (effective liquid holdup is 60s
60.0mL).Temperature control collects reaction solution at 30 DEG C or so in reaction process, carries out the measurement of 2-nitro-paracresol content.
Embodiment 8
The present embodiment provides a kind of preparation methods for nitrifying organic matter (2-nitro-paracresol), include the following steps:
Two metal high voltage constant flow pumps are connect with first two feed inlet of micro passage reaction, and are rushed with aqueous solvent
It washes.Sampling bottle is cleaned up, dry after be connected to after the 4th discharge port of micro passage reaction (see Fig. 1).Microchannel plate is answered
After device solvent washing is clean, full of 30% nitric acid solution.
Micro passage reaction temperature is set as 30 DEG C, and paracresol is placed in water-bath or insulating box and is heated to 40 DEG C in molten
Melt state, setting paracresol and nitric acid mol ratio are 1:1.3, and paracresol and the flow of 32% nitric acid solution are respectively
18.5mL/min and 41.5mL/min, into mixing in micro passage reaction, the residence time is that (effective liquid holdup is 40s
40.0mL).Temperature control collects reaction solution at 30 DEG C or so in reaction process, carries out the measurement of 2-nitro-paracresol content.
Embodiment 9
The present embodiment provides a kind of preparation methods for nitrifying organic matter, include the following steps:
Two metal high voltage constant flow pumps will be connect with first two feed inlet of micro passage reaction, and be rushed with aqueous solvent
It washes.Sampling bottle is cleaned up, dry after be connected to after second discharge port of micro passage reaction (such as Fig. 2).Microchannel plate is answered
After device solvent washing is clean, full of 30% nitric acid solution.
Micro passage reaction temperature is set as 30 DEG C, and paracresol is placed in water-bath or insulating box and is heated to 40 DEG C in molten
Melt state, setting paracresol and nitric acid mol ratio are 1:1.3, and paracresol and the flow of 30% nitric acid solution are respectively
18.5mL/min and 41.5mL/min, into mixing in micro passage reaction, the residence time is that (effective liquid holdup is 20s
20.0mL).Temperature control collects reaction solution at 30 DEG C or so in reaction process, carries out the measurement of 2-nitro-paracresol content.
Embodiment 10
The present embodiment provides a kind of preparation methods for nitrifying organic matter, include the following steps:
Two metal high voltage constant flow pumps are connect with first two feed inlet of micro passage reaction, in addition a metal height
Pressure constant flow pump connects (such as Fig. 3) at second feed inlet, and is rinsed with aqueous solvent.Sampling bottle is cleaned up, dry after connect
After being connected to second discharge port of micro passage reaction.After micro passage reaction solvent washing is clean, the nitric acid full of 30% is molten
Liquid.
Micro passage reaction temperature is set as 30 DEG C, and paracresol is placed in water-bath or insulating box and is heated to 40 DEG C in molten
Melt state, setting paracresol and nitric acid mol ratio are 1:1.3, and paracresol and the flow of two strand of 30% nitric acid solution are respectively
37mL/min and 24.9mL/min, 58.1mL/min, into being mixed in micro passage reaction, residence time 20s.Second strand of nitre
Acid is added when reacting one third, and temperature control collects reaction solution at 30 DEG C or so in reaction process, carries out adjacent nitro to first
The measurement of phenol content.
Embodiment 11
The present embodiment provides a kind of preparation methods for nitrifying organic matter, and specific steps are roughly the same with embodiment 8, difference
It is in reaction time 10s.
Embodiment 12
The present embodiment provides a kind of preparation methods for nitrifying organic matter, and specific steps are roughly the same with embodiment 8, difference
It is in reaction time 20s.
Embodiment 13
The present embodiment provides a kind of preparation methods for nitrifying organic matter, and specific steps are roughly the same with embodiment 10, different
Place is: paracresol and the flow of two strand of 30% nitric acid solution are respectively 30mL/min, 20mL/min, 50mL/min.
Embodiment 14
The present embodiment provides a kind of preparation methods for nitrifying organic matter, and specific steps are roughly the same with embodiment 10, different
Place is: paracresol and the flow of two strand of 30% nitric acid solution are respectively 45mL/min, 30mL/min, 65mL/min.
Embodiment 15
The present embodiment provides a kind of preparation methods for nitrifying organic matter, and specific steps are roughly the same with embodiment 10, different
Place is: paracresol and the flow of two strand of 30% nitric acid solution are respectively 35mL/min, 23mL/min, 55mL/min.
Embodiment 16
The present embodiment provides a kind of preparation methods for nitrifying organic matter, and specific steps are roughly the same with embodiment 10, different
Place is: paracresol and the flow of two strand of 30% nitric acid solution are respectively 40mL/min, 28mL/min, 60mL/min.
Embodiment 17
The present embodiment provides a kind of preparation methods of 2,4-dinitrochlorobenzene, include the following steps:
One heat pump and a metal high voltage constant flow pump are connect with first two feed inlet of micro passage reaction, are used in combination
Solvent washing.Sampling bottle is cleaned up, dry after be connected to the tenth discharge port of micro passage reaction after.By 65% nitric acid and
98% sulfuric acid is mixed according to molar ratio 1:1.2, prepares nitration mixture.Micro passage reaction solvent washing is clean.
Micro passage reaction temperature is set as 90 DEG C, and paranitrochlorobenzene is placed in oil bath pan and is heated to 100 DEG C in molten
State, the molar ratio that paranitrochlorobenzene and nitric acid-sulfuric acid is arranged is that the flow of 1:1.05:1.26. paranitrochlorobenzene and nitration mixture is
22.6mL/min, 27.4mL/min, into being mixed in micro passage reaction, residence time 2min.Temperature control in reaction process
System collects reaction solution at 90 DEG C or so, carries out gas chromatographic detection.
Embodiment 18
The present embodiment provides the preparation methods of one kind 2,5- dichloronitrobenzene, include the following steps:
Two tetrafluoro high pressure constant flow pumps are connect with first two feed inlet of micro passage reaction, and use solvent washing.
Sampling bottle is cleaned up, dry after be connected to second discharge port of micro passage reaction after.By 65% nitric acid and 98% sulfuric acid
It is mixed according to molar ratio 1:2, prepares nitration mixture.Micro passage reaction solvent washing is clean.
Micro passage reaction temperature is set as 60 DEG C, and paracide is placed in oil bath pan and is heated to 65 DEG C or so in molten
Paracide and nitric acid-sulfuric acid mol ratio is arranged as 1:2:4 in state, and the flow of paracide and mixed acid solution is respectively
14.8mL/min and 19.2mL/min, into being mixed in micro passage reaction, residence time 70s.Temperature control in reaction process
System collects reaction solution at 60 DEG C or so, carries out gas chromatographic detection.
Comparative example 1
This comparative example provides a kind of preparation method for nitrifying organic matter, and with embodiment 8 the step of is roughly the same, difference
Place essentially consists in: raw material uses paracresol solution and nitric acid, the specific steps are as follows:
Two metal high voltage constant flow pumps are connect with first two feed inlet of micro passage reaction, in addition a metal height
Pressure constant flow pump connects at second feed inlet, and is rinsed with aqueous solvent.Sampling bottle is cleaned up, dry after be connected to it is micro- logical
(see Fig. 3) after the 4th discharge port of road reactor.After micro passage reaction solvent washing is clean, the nitric acid full of 30% is molten
Liquid.
Micro passage reaction temperature is set as 30 DEG C, is 2.0mol/L to first by the concentration that paracresol is dissolved in toluene formation
Phenol solution is fitted into container bottle, and wherein paracresol and nitric acid mol ratio are 1:1.3, the flow difference of paracresol solution and nitric acid
For 50.3mL/min and 9.7mL/min, residence time 60s, temperature control collects reaction at 30 DEG C or so in reaction process
Liquid carries out the measurement of 2-nitro-paracresol content.
Comparative example 2
This comparative example provides a kind of preparation method for nitrifying organic matter, uses existing intermittent reaction flask as anti-
Answer device, the specific steps are as follows: build pilot plant test device: four-hole boiling flask connection constant pressure forces down liquid funnel, thermometer, ball-type condensation
Pipe, by flask as in thermostat water bath.It measures 15.0mL20% nitric acid solution to be added in flask, the original of melting is slowly added dropwise
Expect paracresol, controls temperature at 10 DEG C hereinafter, being added dropwise, sampling carries out gas chromatographic detection；Temperature is risen into 20 DEG C of stirrings
After 2h, sampling carries out gas chromatographic detection.
Comparative example 3
This comparative example provides a kind of preparation method for nitrifying organic matter, and with embodiment 8 the step of is roughly the same, difference
Place essentially consists in: temperature control is at 15 DEG C or so in reaction process.
Comparative example 4
This comparative example provides a kind of preparation method for nitrifying organic matter, and with embodiment 8 the step of is roughly the same, difference
Place essentially consists in: temperature control is at 50 DEG C or so in reaction process.
Test example 1
The gas chromatogram of product is obtained in testing example 8, as a result sees Fig. 4-Fig. 5.
From Fig. 4-5 it is found that the characteristic peak of product is the corresponding peak retention time 8.599min, the product being prepared is neighbour
Nitro-p-cresol, purity 98.13.
Test example 2
Testing example 1-18 and the conversion ratio and selectivity for comparing 1-4, test result are shown in Table 1, test method equipment:
Instrument: Agilent gas-chromatography；Column type number: HP-5 is detected,；Detector: FID；Column temperature: 280 DEG C.
1 conversion ratio of table, selectivity test result
Wherein, 1. it is the data for dripping detection that the data in comparative example 2 are respectively as follows: for two；2. being after extending 2h
The data of detection.
As can be seen from Table 1, the preparation method of 2-nitro-paracresol provided in an embodiment of the present invention passes through the anti-of short time
It answers, the 2-nitro-paracresol being prepared has very high yield and purity, and since solvent-free participation is reacted, after being not necessarily to
The step of reason, is suitable for promoting and applying.
Comparative example 9 and embodiment 10 by the way of nitric acid sectional feeding it is found that can further increase product
Selectivity.
Comparative example 10 and comparative example 1-2 it is found that preparation method provided in an embodiment of the present invention relative in comparative example 2
Prior art can be obviously improved the conversion ratio of raw material；Compared to comparative example 1 it is found that in the case where no solvent participates in,
There is no decline for the yield of product.
Comparative example 10 and comparative example 3-4 are it is found that reaction temperature control is in range provided in an embodiment of the present invention
Preferably, temperature is excessively high or temperature is too low will affect feed stock conversion.
In conclusion a kind of preparation method for nitrifying organic matter provided by the invention, is connected using micro passage reaction
Continuous reaction, using nitric acid and the paracresol of molten condition as raw material, is prepared adjacent nitro pair by the reaction of short time 10s or more
Cresols.Whole process does not have solvent to participate in reaction, avoids the last handling process of solvent removal.
A kind of 2-nitro-paracresol provided by the invention, is prepared by above-mentioned preparation method, and product is gone without solvent
The aftertreatment technology removed has good yield and purity.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of preparation method for nitrifying organic matter, which comprises the steps of:
The organic matter to be nitrified for nitrifying acid solution and molten condition is passed through in micro passage reaction and is reacted；
It wherein, is solid-state under the organic matter room temperature to be nitrified, it is described after nitrifying organic matter and being passed through the micro passage reaction
It does not solidify and/or is dissolved in the nitrification acid solution；
Preferably, reaction time is in 10s or more；
Preferably, any one of the organic matter to be nitrified in paracresol, paranitrochlorobenzene and paracide；More preferably
For paracresol；
Preferably, the difference of the melting temperature of reaction temperature and the organic matter to be nitrified is X, X >=-30 DEG C；It is highly preferred that X
≥-20℃；It is further preferred that X >=-100 DEG C.
2. the preparation method of nitrification organic matter according to claim 1, which is characterized in that the organic matter to be nitrified is pair
Nitro-chlorobenzene or paracide, the nitrification acid solution are the mixed acid of nitric acid and sulfuric acid；
Preferably, the molar ratio of the organic matter to be nitrified, the nitric acid and the sulfuric acid is 1:1-2:1.26-4；
Preferably, the flow of the organic matter to be nitrified is 12-25mL/min, and the flow of the nitrification acid solution is 10-40mL/
min；
Preferably, reaction temperature is 60-90 DEG C, reaction time 70-120min.
3. the preparation method of nitrification organic matter according to claim 1, which is characterized in that the organic matter to be nitrified is pair
Cresols, the nitrification acid solution are dust technology；
Preferably, the dust technology is the dust technology of volume fraction 20-40%；Preferably 25-35%；More preferably 28-32%；
Preferably, the molar ratio of the paracresol and the nitric acid is 1:1.1-1.2.
4. the preparation method of nitrification organic matter according to claim 3, which is characterized in that reaction time 10-
60s；Preferably 15-40s；More preferably 19-21s.
5. the preparation method of nitrification organic matter according to claim 3, which is characterized in that reaction temperature is 20-40 DEG C；It is excellent
It is selected as 25-35 DEG C；More preferably 29-31 DEG C.
6. the preparation method of nitrification organic matter according to claim 3, which is characterized in that by the paracresol with 10-
The flow velocity of 40mL/min is passed through the micro passage reaction, the nitric acid is passed through with the flow velocity of 20-90mL/min described micro- logical
Road reactor, the hybrid reaction in the micro passage reaction；
Preferably, the flow velocity of the paracresol is 25-30mL/min, and the flow velocity of the nitric acid is 30-45mL/min.
7. nitrifying the preparation method of organic matter according to any one of claim 3-6, which is characterized in that the nitric acid is adopted
With the mode fed at least twice,
Preferably, the nitric acid by the way of feeding twice；It is highly preferred that second of the nitric acid feed time fed
For the 1/200-2/3 of overall reaction duration；It is further preferred that the feed time of second of charging is the 1/50- of overall reaction duration
2/3；
Preferably, when feeding number is n times, and when 2n≤200, the m time feed time for overall reaction duration t (2m-1)/
200-(2m+1)/200；
Preferably, when feeding number is n times, and when 2n > 200, the m time feed time for overall reaction duration t (2m-1)/
2n-(2m+1)/2n。
8. the preparation method of nitrification organic matter according to claim 7, which is characterized in that described right when feeding for the first time
The flow velocity of cresols is 30-45mL/min, and the flow velocity of the nitric acid is 20-30mL/min；When second of charging, the stream of the nitric acid
Speed is 50-65mL/min；
Preferably, when feeding for the first time, the flow velocity of the paracresol is 35-40mL/min, and the flow velocity of the nitric acid is 23-
28mL/min；When second of charging, the flow velocity of the nitric acid is 55-60mL/min.
9. the preparation method of nitrification organic matter according to claim 1, which is characterized in that the micro passage reaction leads to
Road depth is 0.3-1.0mm, total liquid inventory 10-100mL；
Preferably, the form in the channel is umbrella shape, and the micro passage reaction uses two-sided heat exchange structure.
10. a kind of nitrification organic matter, which is characterized in that the system of application nitrification organic matter of any of claims 1-9
Preparation Method is prepared；
Preferably, the nitrification organic matter is 2-nitro-paracresol, 2,4-dinitrochlorobenzene or 2,5- dichloronitrobenzene；
Preferably, the conversion ratio of the nitrification organic matter is 98% or more；
Preferably, the purity of the nitrification organic matter is greater than 98%.
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| CN112661649A (en) * | 2020-12-25 | 2021-04-16 | 宁波龙欣精细化工有限公司 | 2, 6-dinitro-4-tert-amylphenol and preparation method thereof |
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