CN109761860A - A method of reduction nitryl aromatic race substituent prepares amino aromatic series substituent - Google Patents
A method of reduction nitryl aromatic race substituent prepares amino aromatic series substituent Download PDFInfo
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Abstract
The present invention relates to amino aromatic series substituent synthesis technical fields, specifically disclose a kind of method that reduction nitryl aromatic race substituent prepares amino aromatic series substituent.This approach includes the following steps, and water, catalyst are added in first reactor, and the reactor is heated up, and reduction chalybeate is added, adjusts pH, while nitryl aromatic race substituent being added in first reactor, insulation reaction obtains reaction material liquid；The pH of reaction material liquid is adjusted, stabilizer is added in insulation reaction, obtains the first solution containing amino aromatic series substituent and iron black crude product；The pH of the first solution is adjusted, is separated by solid-liquid separation, obtains amino aromatic series substituent.Manufacturing technique method provided by the invention is simple, can be continuously produced, and operational safety and higher selectivity with higher, the reaction time is short, and yield is up to 90% or more, and good product quality, content reaches 98% or more.
Description
Technical field
The present invention relates to amino aromatic series substituent synthesis technical fields more particularly to a kind of reduction nitryl aromatic race to replace
The method that object prepares amino aromatic series substituent.
Background technique
Amino aromatic series substituent is widely used in the fields such as dyestuff, rubber, medicine, pesticide, pigment, auxiliary agent, chemical reagent,
It is important organic synthesis intermediate, is to be catalyzed reduction by nitryl aromatic race substituent and obtained.In the prior art there are many oneself
The method for producing amino aromatic series substituent, can be divided into sodium sulfide reducing, catalytic hydrogenating reduction, electrochemical reduction, iron powder also
The several methods such as original.
Sodium sulfide reducing method is a kind of production technology of comparative maturity, and mitigation is compared in reaction, and selectivity is good, and product easily divides
From, easily realize closed production, the production cycle is shorter, and the corrosivity of equipment is smaller etc..But the method production cost is higher, yield compared with
Iron powder reducing method is low, and the sulfur-containing waste water of generation is more, pollutes the environment, not easy to handle, thus social benefit and economic effect
Benefit is not good enough.
The advantages of hydrogenating reduction is divided into liquid-phase hydrogenatin and restores two methods of gentle phase hydrogenating reduction, hydrogenating reduction is: production
Ability is big, product quality is high, the waste liquid of discharge is few, waste residue is few, has significant superiority for solving problem of environmental pollution.But
There are other easily to restore group such as halogen, carbonyl, nitrile, alkene, alkynes etc., poor selectivity on aromatic ring, catalytic hydrogenation uses hydrogen risk
Greatly, storage, transport difficult, higher cost.
Process of Electrochemical Reduction has many advantages, such as that yield is high, purity is good, easily separated, at low cost compared with chemical reduction method.
But energy consumption is high for the method, at present only in laboratory synthesis and production semi-industrial using more.
Traditional iron powder reducing technique is more classical, has stronger reducing power, is applied basically for all nitro compounds
The reduction of object, but that there is automatization levels is low for the production, and labor intensity of workers is big, generated iron cement containing arylamine and waste water pair
The problems such as environmental pollution is serious.But iron powder reducing method have it is applied widely, for produce the lesser arylamine of tonnage, especially
It is when containing the groups such as other easy reduction groups such as halogen, carbonyl, nitrile, alkene, alkynes in production arylamine molecule, is still a kind of preferable
Method.Therefore, iron powder reducing method is improved to overcome the above problem existing for it that there is important meaning in industrialized production
Adopted and wide application prospect.
Summary of the invention
For the existing above problem, the present invention provides a kind of reduction nitryl aromatic race substituent and prepares the substitution of amino aromatic series
The method of object.
To achieve the above object of the invention, the embodiment of the present invention uses the following technical solution:
A method of reduction nitryl aromatic race substituent prepares amino aromatic series substituent, the method include at least with
Lower step:
Step a, Jiang Shui, catalyst are added in first reactor, and the first reactor is warming up to 60-120 DEG C,
Reduction chalybeate is added, adjusting pH value is 4-9, while nitryl aromatic race substituent being added continuously in first reactor, is carried out
Insulation reaction obtains reaction material liquid；
The pH value of the reaction material liquid is adjusted to 9-13, continues insulation reaction, be added after reaction by step b
Stabilizer stirs evenly, filtering, obtains the first solution containing amino aromatic series substituent and iron black crude product；
Step c, the pH value of first solution is adjusted to 0.5-8, then is separated by solid-liquid separation, obtained amino aromatic series and take
For object.
Compared with the existing technology, preparation method provided by the invention has the advantage that
(1) present invention restores nitryl aromatic race substituent using reduction chalybeate in the presence of a catalyst and prepares amino aromatic series
Substituent, by controlling reaction condition such as pH value and reaction temperature, so that reduction reaction selectivity is higher, and in reaction process
Iron black crude solid is only generated, clean and environmental protection, iron oxide black can also continue to enter in reaction process as catalyst, reduce cost, be
Reduction prepares aromatic amine and provides a kind of method for more cleaning economy, solves the arylamine iron cement generated in the prior art and waste water is made
The problem of at pollution.
(2) manufacturing technique method of the present invention is simple, reaction mass successional can carry out from the first reactor input and
Continuous production is realized in output, and operational safety and higher selectivity with higher, the reaction time is short, amino fragrance
Race's substituent yield is up to 90% or more, and good product quality, content reaches 98% or more, coloration power part of the ultra-fine iron oxide black of coproduction
99% or more.
Specifically, it is preferred that in step a, the catalyst is ferroso-ferric oxide, and additional amount is the nitryl aromatic race
Replace the 1-100% of amount of substance.
Preferably, in step a, when nitryl aromatic race substituent and its sodium salt, sylvite or ammonium salt not soluble in water, addition is urged
Also need to add co-catalyst when agent, and the co-catalyst is polyethers, cyclic crown ether class, quaternary ammonium salt or tertiary amine
One of, additive amount is the 1-20% that the nitryl aromatic race replaces amount of substance.
Preferably, in step a, the additional amount of the water is 1-20 times that the nitryl aromatic race replaces amount of substance.
Preferably, in step a, the reduction chalybeate is at least one of 0 valence iron or ferrous iron, and the reduction chalybeate
2-10:1 is calculated as by single nitro with the molar ratio of nitryl aromatic race substituent.
Ferrous iron and 0 valence iron occur electronics with catalyst ferroso-ferric oxide within the scope of certain pH and turn as reducing agent
It moves, nitryl aromatic race substituent can be reduced to amino aromatic series substituent, ferrous iron by the newly-generated ferrous iron of catalyst surface
After electronics transfer under the conditions of certain pH, and iron oxide black is generated, iron oxide black can not only continue as catalyst, moreover it is possible to will be extra
Iron oxide black obtain ultra-fine iron oxide black after post treatment, simultaneous reactions process will not generate salt, safety and environmental protection.
Preferably, in step b, the stabilizer is that dithionite, sulphite, azanol class or salicylic acid are derivative
One of object, and additional amount is that the nitryl aromatic race replaces the 0.5%~20% of amount of substance.
It is added after stabilizer, dithionite, sulphite, azanol class or salicylic acid derivative are as anti-oxidation
Agent, the amino aromatic series substituent that can prevent reaction from obtaining improve the yield of reaction by the dioxygen oxidation in air.
Preferably, in step a, the 0 valence iron is in secondary reduction iron powder, ore iron powder, iron sponge powder or cast iron powder
It is at least one.
Preferably, in step a, the ferrous iron is ferrous sulfate, frerrous chloride, ferrous phosphate, ferrous carbonate or oxalic acid
Ferrous at least one.
Preferably, in step b, the stabilizer is sodium dithionite, sodium sulfite, potassium sulfite, hydroxylamine hydrochloride
Or one of ascorbic acid.
Preferably, in step a, water, catalyst are added in first reactor, and the reactor is warming up to 80-
100 DEG C, reduction chalybeate is added, adjusting pH value is 5-8, while nitryl aromatic race substituent is added continuously to first in 1-4h
In reactor.
Preferably, in step a, the condition of the insulation reaction are as follows: reaction temperature is 60-120 DEG C, reaction time 0.5-
2h。
In step b, the condition of the insulation reaction are as follows: reaction temperature is 60-120 DEG C, reaction time 0-2h.
Preferably, in step b, pH value is adjusted using alkaline matter, and alkaline matter is sodium hydroxide, potassium hydroxide, carbon
One of sour sodium, potassium carbonate, calcium hydroxide, ammonium hydroxide or ammonia.
Preferably, in step b, the pH value is 10-12.
Preferably, in step c, pH value is adjusted using acidic materials, and acidic materials are hydrochloric acid, sulfuric acid, acetic acid or phosphoric acid
One of.
Preferably, in step c, the pH value is 1-7.
Preferably, the method that the reduction nitryl aromatic race substituent prepares amino aromatic series substituent, further includes coproduction
Ultra-fine iron oxide black technique, the technique specific steps are as follows: iron black crude product, the water for obtaining step b are added in second reactor, are stirred
It mixes and is warming up to 20-100 DEG C, carry out iron black crystal form reforming reaction 0.5-4h, ultra-fine iron oxide black is obtained by filtration.
Preferably, the water of the obtained iron black crude product of step b and its 0.5-10 times of quality is added in second reactor, is stirred
Mix and be warming up to 30-80 DEG C, carry out iron black crystal form reforming reaction 1-2h, filtering, 60-100 DEG C of drying, it is broken obtain ultra-fine iron oxide black,
Wherein crumbling method is at least one of to crush, grind, sieve.It is mentioned here broken to refer to and be generated in drying process
Agglomeration is broken up, rather than bulky grain is broken into smaller particle with special installation.
Preferably, the chemical general formula of nitryl aromatic race substituent is R1-Aryl(R2)-NO2, the amino aromatic series
The chemical general formula of substituent is R1-Aryl(R2)-NH2, in formula, Aryl is aromatic group, R1And R2In at least one be containing not
The group of saturated bond.
Preferably, the Aryl is one of phenyl or naphthyl.
Preferably, the R1And R2It is respectively selected from C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylene, C1-C6Alkynyl, cyanogen
Base, halogen, sulfonic group, formyl, C1-C6Ketone carbonyl or C1-C6One of acyl group.
Detailed description of the invention
It to describe the technical solutions in the embodiments of the present invention more clearly, below will be to needed in the embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for ability
For the those of ordinary skill of domain, without creative efforts, it can also be obtained according to these attached drawings other attached
Figure.
Fig. 1 is the XRD spectrum of ultra-fine iron oxide black prepared by the embodiment of the present invention 1；
Fig. 2 is the IR map of ultra-fine iron oxide black prepared by the embodiment of the present invention 1；
Fig. 3 is the SEM spectrum of ultra-fine iron oxide black prepared by the embodiment of the present invention 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
The embodiment of the present invention provides a kind of method for preparing amino aromatic series substituent co-production of ultrafine iron oxide black, including following step
It is rapid:
Step a, 500mL water, nano ferriferrous oxide 2g and dialkylethers 1.5g are added to open and band
In tetra- mouthfuls of reaction flasks of 1000mL of stirring, and four mouthfuls of reaction flasks are warming up to 60-70 DEG C, reduction chalybeate secondary reduction is added
Iron powder 30g, adjusting pH value are 8-9, this reaction temperature and pH value are maintained, by 4,4 '-dinitrostilbene -2,2 '-disulfonic acid
25g is continuously added in four mouthfuls of reaction flasks in 3-4h, is carried out insulation reaction 0.5h after adding under the conditions of 60-70 DEG C, is obtained
Reaction material liquid；
The pH value of reaction material liquid sodium hydroxide is adjusted to 12-13 by step b, continue under the conditions of 60-70 DEG C into
Sodium sulfite 0.25g is added after reaction, stirs evenly by row insulation reaction 1h, filters, and water washing is obtained containing 4,4 '-two
First solution of amino-stilbene -2,2 '-sodium disulfonate and iron black crude product 39.2g；
Step c, pH value is adjusted to 0.5-1.0 with hydrochloric acid by first solution, filtering, water washing obtain content
For 98.5% 4,4 '-diaminobenzil -2,2 '-disulfonic acid product 27g, yield 99.91%；
Step d, iron black crude product, the 200mL water in step b are added in another open reaction vessel, stirring is warming up to
90-100 DEG C, iron black crystal form reforming reaction 3-4h is carried out, is filtered, is dried, crushes, the iron black 22.8g of ultra-fine grade is obtained after screening,
Coloration power part 99.8%, sieve residue are recovered in step a as reduced iron powder.
Embodiment 2
The embodiment of the present invention provides a kind of method for preparing amino aromatic series substituent co-production of ultrafine iron oxide black, including following step
It is rapid:
Step a, 400mL water and ferroso-ferric oxide 20g are added in opening and tetra- mouthfuls of reaction flasks of 1000mL with stirring,
And four mouthfuls of reaction flasks are warming up to 80-90 DEG C, reduction chalybeate ore iron powder 20g is added, adjusting pH value is 5-6, maintains this
Reaction temperature and pH value, by 4,4 '-dinitrostilbene -2,2 '-dioctyl phthalate 30g are continuously added to four mouthfuls of reaction flasks in 2-3h
In, insulation reaction 1h is carried out after adding under the conditions of 80-90 DEG C, obtains reaction material liquid；
The pH value of reaction material liquid potassium hydroxide is adjusted to 12-12.5, continued under the conditions of 80-90 DEG C by step b
Insulation reaction 1h is carried out, potassium sulfite 4g is added after reaction, stirs evenly, is filtered, water washing is obtained containing 4,4 '-two
First solution of amino-stilbene -2,2 '-potassium diformate and iron black crude product 45.8g；
Step c, pH value is adjusted to 1-1.5 with sulfuric acid by first solution, filtering, water washing, obtaining content is
The 4 of 98.1%, 4 '-diaminobenzil -2,2 '-diformazan acid product 29.8g, yield 98.7%；
Step d, iron black crude product, the 100mL water in step b are added in another open reaction vessel, stirring is warming up to
80-90 DEG C, iron black crystal form reforming reaction 2-3h is carried out, is filtered, is dried, crushes, the iron black 40.5g of ultra-fine grade is obtained after screening,
Coloration power part 105.5%, sieve residue are recovered in step a as reduced iron powder.
Embodiment 3
The embodiment of the present invention provides a kind of method for preparing amino aromatic series substituent co-production of ultrafine iron oxide black, including following step
It is rapid:
Step a, 350mL water, ferroso-ferric oxide 10g and dialkylethers 6g are added to opening and with stirring
In tetra- mouthfuls of reaction flasks of 1000mL, and four mouthfuls of reaction flasks are warming up to 90-100 DEG C, reduction chalybeate iron sponge powder 30g are added,
Adjusting pH value is 6-7, maintains this reaction temperature and pH value, and 5- nitro -2- propyl-benzoyl nitrile 40g is continuous in 2.5-3h
It is added in four mouthfuls of reaction flasks, carries out insulation reaction 2h after adding under the conditions of 90-100 DEG C, obtain reaction material liquid；
The pH value of reaction material liquid sodium carbonate is adjusted to 9-10, ascorbic acid 8g is added, stirs evenly by step b,
Filtering, water washing are obtained containing the first solution of 5- amino -2- propyl-benzoyl nitrile and iron black crude product 48.1g；
Step c, pH value is adjusted to 6-7 with sulfuric acid by first solution, filtering, water washing, obtaining content is
98.3% 5- amino -2- propyl-benzoyl nitrile product 32.12g, yield 91.53%；
Step d, iron black crude product, the 100mL water in step b are added in another open reaction vessel, stirring is warming up to
70-80 DEG C, iron black crystal form reforming reaction 2.5-3h is carried out, is filtered, is dried, crushes, the iron oxide black of ultra-fine grade is obtained after screening
38.6g, coloration power part 99.5%, sieve residue are recovered in step a as reduced iron powder.
Embodiment 4
The embodiment of the present invention provides a kind of method for preparing amino aromatic series substituent co-production of ultrafine iron oxide black, including following step
It is rapid:
Step a, 50mL water, ferroso-ferric oxide 0.5g and TEBA 4g are added to opening and tetra- mouthfuls of 250mL with stirring is anti-
It answers in bottle, and four mouthfuls of reaction flasks is warming up to 70-80 DEG C, reduction chalybeate cast iron powder 16g is added, adjusting pH value is 7-7.5,
This reaction temperature and pH value are maintained, 3- (2- isobutyl group oxygroup -4- nitro) phenylpropen 20g is continuously added to four in 2-2.5h
In mouth reaction flask, insulation reaction 1.5h is carried out after adding under the conditions of 70-80 DEG C, obtains reaction material liquid；
The pH value of reaction material liquid potassium carbonate is adjusted to 10-10.5, sodium dithionite 1g is added, stirs by step b
It mixes uniformly, filtering, water washing, obtains the first solution containing 3- (2- isobutyl group oxygroup -4- amino) phenylpropen and iron oxide black is thick
Product 18.63g；
Step c, pH value is adjusted to 7-7.5 with acetic acid by first solution, liquid separation is washed organic phase, contained
3- (2- isobutyl group oxygroup -4- amino) phenylpropen product 16.32g that amount is 98.4%, yield 92.04%；
Step d, iron black crude product, the 150mL water in step b are added in another open reaction vessel, stirring is warming up to
60-70 DEG C, iron black crystal form reforming reaction 3.5-4h is carried out, is filtered, is dried, crushes, the iron oxide black of ultra-fine grade is obtained after screening
13.5g, coloration power part 101.3%, sieve residue are recovered in step a as reduced iron powder.
Embodiment 5
The embodiment of the present invention provides a kind of method for preparing amino aromatic series substituent co-production of ultrafine iron oxide black, including following step
It is rapid:
Step a, 50mL water, ferroso-ferric oxide 8g and cyclodextrin 1g are added to opening and tetra- mouthfuls of 100mL with stirring is anti-
It answers in bottle, and four mouthfuls of reaction flasks is warming up to 80-90 DEG C, reduction chalybeate ferrous sulfate 90g is added, adjusting pH value is 4-5,
This reaction temperature and pH value are maintained, 5- (2- nitro -4- (3- acetone dichloride base)) phenyl pentyne 10g is continuously added in 1-2h
In four mouthfuls of reaction flasks, insulation reaction 0.5-1h is carried out after adding under the conditions of 85-90 DEG C, obtains reaction material liquid；
The pH value of reaction material liquid ammonium hydroxide is adjusted to 10.5-11 by step b, and hydroxylamine hydrochloride 0.5g is added, and stirring is equal
Even, filtering, water washing, obtains the first solution containing 5- (2- amino -4- (3- acetone dichloride base)) phenyl pentyne and iron oxide black is thick
Product 33.73g；
Step c, pH value is adjusted to 6.5-7 with sulfuric acid by first solution, liquid separation is washed organic phase, contained
5- (2- amino -4- (3- acetone dichloride base)) phenyl pentyne product 8.19g that amount is 98.7%, yield 90.57%；
Step d, iron black crude product, the 75mL water in step b are added in another open reaction vessel, stirring is warming up to
50-60 DEG C, iron black crystal form reforming reaction 1-2h is carried out, is filtered, is dried, crushes, the iron black 32.84g of ultra-fine grade is obtained after screening,
Coloration power part 99.2%.
Embodiment 6
The embodiment of the present invention provides a kind of method for preparing amino aromatic series substituent co-production of ultrafine iron oxide black, including following step
It is rapid:
Step a, 500mL water, ferroso-ferric oxide 50g and tetrabutylammonium bromide 0.5g are added to opening and with stirring
In tetra- mouthfuls of reaction flasks of 1000mL, and four mouthfuls of reaction flasks are warming up to 75-80 DEG C, reduction chalybeate frerrous chloride 415g are added,
Adjusting pH value is 5-5.5, maintains this reaction temperature and pH value, by 4,4 '-dinitrostilbene -2,2 '-disulfonic acid 50g are in 2-
It is continuously added in 3h in four mouthfuls of reaction flasks, carries out insulation reaction 1h after adding under the conditions of 75-80 DEG C, obtain reaction material liquid；
The pH value of reaction material liquid calcium hydroxide is adjusted to 11-11.5, continued under the conditions of 75-80 DEG C by step b
Insulation reaction 0.5h is carried out, sodium dithionite 4g is added after reaction, stirs evenly, is filtered, water washing, is obtained containing 4,
The first solution of 4 '-dinitrostilbenes -2,2 '-disulfonic acid calcium and iron black crude product 215.39g；
Step c, pH value is adjusted to 1.5-2 with hydrochloric acid by first solution, filtered, water washing, obtaining content is
The 4 of 99.06%, 4 '-dinitrostilbene -2,2 '-disulfonic acid product 53.75g, yield 99.75%；
Step d, iron black crude product, the 200mL water in step b are added in another open reaction vessel, stirring is warming up to
40-50 DEG C, iron black crystal form reforming reaction 3-4h is carried out, is filtered, is dried, crushes, the iron oxide black of ultra-fine grade is obtained after screening
211.03g, coloration power part 108.9%.
Embodiment 7
The embodiment of the present invention provides a kind of method for preparing amino aromatic series substituent co-production of ultrafine iron oxide black, including following step
It is rapid:
Step a, 100mL water, ferroso-ferric oxide 5g and tetrabutylammonium bromide 2g be added to opening and with the 500mL of stirring
In four mouthfuls of reaction flasks, and four mouthfuls of reaction flasks are warming up to 110-120 DEG C, be added reduction chalybeate frerrous chloride 27.5g and
15.5g reduced iron powder, adjusting pH value are 7.5-8, this reaction temperature and pH value are maintained, by 4- p-nitrotoluene-o-sulfonic acid 4- 30g in 1-
It is continuously added in 1.5h in four mouthfuls of reaction flasks, carries out insulation reaction 0.5h after adding under the conditions of 110-120 DEG C, reacted
Feed liquid；
The pH value of reaction material liquid ammonia is adjusted to 11.2-11.5 by step b, continue under the conditions of 85-90 DEG C into
Row insulation reaction 1.5h, the company of addition hydroxylamine hydrochloride 7g, stirs evenly after reaction, filters, and water washing is obtained containing 4- nitro
The first solution of Toluene-2,4-diisocyanate-ichthyodin and iron black crude product 32.87g；
Step c, pH value is adjusted to 2-3 with hydrochloric acid by first solution, filtered, water washing, obtaining content is
99.13% 4- amino toluene -2- sulfonic acid product 25.76g, yield 98.75%；
Step d, iron black crude product, the 200mL water in step b are added in another open reaction vessel, stirring is warming up to
30-40 DEG C, iron black crystal form reforming reaction 3-4h is carried out, is filtered, is dried, crushes, the iron black 31.53g of ultra-fine grade is obtained after screening,
Coloration power part 102.6%.
Embodiment 8
The embodiment of the present invention provides a kind of method for preparing amino aromatic series substituent co-production of ultrafine iron oxide black, including following step
It is rapid:
Step a, 250mL water, ferroso-ferric oxide 3g and tetrabutylammonium chloride 3g be added to opening and with the 500mL of stirring
In four mouthfuls of reaction flasks, and four mouthfuls of reaction flasks are warming up to 100-110 DEG C, ferrous sulfate 19g and 19.5g ore iron is added
Powder, adjusting pH value are 7-8, maintain this reaction temperature and pH value, and the bromo- 4- nitronaphthalene 30g of 1- methyl -2- is continuous in 2-2.5h
It is added in four mouthfuls of reaction flasks, carries out insulation reaction 1.5h after adding under the conditions of 100-110 DEG C, obtain reaction material liquid；
The pH value of reaction material liquid ammonia is adjusted to 11.5-12.0, continued under the conditions of 95-100 DEG C by step b
Insulation reaction 0.5h is carried out, the company of addition hydroxylamine hydrochloride 5g, stirs evenly after reaction, filters, and water washing is obtained containing 1- first
First solution of the bromo- 4- amino naphthalenes of base -2- and iron black crude product 35.42g；
Step c, pH value is adjusted to 5-6 with hydrochloric acid by first solution, filtered, liquid separation, water washing obtains content
For the 98.53% bromo- 4- amino naphthalenes product 24.14g of 1- methyl -2-, yield 91.73%；
Step d, iron black crude product, the 100mL water in step b are added in another open reaction vessel, stirring is warming up to
20-30 DEG C, iron black crystal form reforming reaction 3-4h is carried out, is filtered, is dried, crushes, the iron black 34.41g of ultra-fine grade is obtained after screening,
Coloration power part 105.7%.
The characteristic for the ultra-fine iron oxide black that embodiment provides in order to better illustrate the present invention below obtains embodiment 1 super
The iron black of thin grade carries out performance detection, including X-ray diffraction, infrared spectroscopy and scanning electron microscope analysis, analyzes result such as Fig. 1-3 institute
Show.
Material phase analysis is carried out with iron oxide black of the X-ray diffractometer to the ultra-fine grade of gained, diffracting spectrum such as Fig. 1, Fig. 1 show this hair
The sample of bright preparation is the ferroferric oxide powder of pure phase.Spectrum analysis is carried out with infrared spectrometer, spectrum such as Fig. 2,
589cm-1Place is the Absorption Characteristics peak of Fe-O, illustrates to generate Fe3O4.With scanning electron microscope to the ultra-fine grade of preparation it is iron black into
Row scanning, electromicroscopic photograph is as shown in figure 3, show spherical in shape, the partial size 100-600nm in iron oxide black of the ultra-fine grade of preparation.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of method that reduction nitryl aromatic race substituent prepares amino aromatic series substituent, it is characterised in that: the method
It at least includes the following steps:
Step a, Jiang Shui, catalyst are added in first reactor, and the first reactor is warming up to 60-120 DEG C, are added
Chalybeate is restored, adjusting pH value is 4-9, while nitryl aromatic race substituent being added in first reactor, insulation reaction is carried out,
Obtain reaction material liquid；
The pH value of the reaction material liquid is adjusted to 9-13, continues insulation reaction by step b, is added stablizes after reaction
Agent stirs evenly, filtering, obtains the first solution containing amino aromatic series substituent and iron black crude product；
Step c, the pH value of first solution is adjusted to 0.5-8, then is separated by solid-liquid separation, obtain the substitution of amino aromatic series
Object.
2. the method that reduction nitryl aromatic race substituent prepares amino aromatic series substituent as described in claim 1, feature
Be: in step a, the catalyst is ferroso-ferric oxide, and additional amount is the 1- that the nitryl aromatic race replaces amount of substance
100%；And/or
In step a, when catalyst is added when nitryl aromatic race substituent and its sodium salt, sylvite or ammonium salt not soluble in water
Also need to add co-catalyst, and the co-catalyst is one of polyethers, cyclic crown ether class, quaternary ammonium salt or tertiary amine,
Additive amount is the 1-20% that the nitryl aromatic race replaces amount of substance；And/or
In step a, the additional amount of the water is 1-20 times that the nitryl aromatic race replaces amount of substance.
3. the method that reduction nitryl aromatic race substituent prepares amino aromatic series substituent as described in claim 1, feature
Be: in step a, the reduction chalybeate is at least one of 0 valence iron or ferrous iron, and the reduction chalybeate and the nitro
The molar ratio of aromatic series substituent is calculated as 2-10:1 by single nitro；And/or
In step b, the stabilizer is one of dithionite, sulphite, azanol class or salicylic acid derivative,
And additional amount is that the nitryl aromatic race replaces the 0.5%~20% of amount of substance.
4. the method that reduction nitryl aromatic race substituent prepares amino aromatic series substituent as claimed in claim 3, feature
Be: in step a, the 0 valence iron is at least one of secondary reduction iron powder, ore iron powder, iron sponge powder or cast iron powder；
And/or
In step a, the ferrous iron is at least the one of ferrous sulfate, frerrous chloride, ferrous phosphate, ferrous carbonate or ferrous oxalate
Kind；And/or
In step b, the stabilizer is in sodium dithionite, sodium sulfite, potassium sulfite, hydroxylamine hydrochloride or ascorbic acid
One kind.
5. the method that reduction nitryl aromatic race substituent prepares amino aromatic series substituent as described in claim 1, feature
It is: in step a, water, catalyst is added in first reactor, and the reactor is warming up to 80-100 DEG C, is added
Chalybeate is restored, adjusting pH value is 5-8, while nitryl aromatic race substituent is being added continuously to first reactor in 1-4h
In；And/or
In step a, the condition of the insulation reaction are as follows: reaction temperature is 60-120 DEG C, reaction time 0.5-2h；And/or
In step b, the condition of the insulation reaction are as follows: reaction temperature is 60-120 DEG C, reaction time 0-2h.
6. the method that reduction nitryl aromatic race substituent prepares amino aromatic series substituent as described in claim 1, feature
It is:
In step b, using alkaline matter adjust pH value, and alkaline matter be sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
One of calcium hydroxide, ammonium hydroxide or ammonia；And/or
In step b, the pH value is 10-12；And/or
In step c, pH value is adjusted using acidic materials, and acidic materials are one of hydrochloric acid, sulfuric acid, acetic acid or phosphoric acid；With/
Or
In step c, the pH value is 1-7.
7. the method that reduction nitryl aromatic race substituent prepares amino aromatic series substituent as described in claim 1, feature
It is: further includes co-production of ultrafine iron oxide black technique, the technique specific steps are as follows: iron black crude product, the water for obtaining step b are added to
In second reactor, stirring is warming up to 20-100 DEG C, carries out iron black crystal form reforming reaction 0.5-4h, ultra-fine iron oxide black is obtained by filtration.
8. the method that reduction nitryl aromatic race substituent prepares amino aromatic series substituent as claimed in claim 7, feature
It is: the water of the obtained iron black crude product of step b and its 0.5-10 times of quality is added in second reactor, stirring is warming up to
30-80 DEG C, carry out iron black crystal form reforming reaction 1-2h, filtering, 60-100 DEG C of drying, it is broken obtain ultra-fine iron oxide black, wherein being crushed
Mode is at least one of to crush, grind, sieve.
9. as the described in any item reduction nitryl aromatic race substituents of claim 1-8 prepare the side of amino aromatic series substituent
Method, it is characterised in that: the chemical general formula of nitryl aromatic race substituent is R1-Aryl(R2)-NO2, the amino aromatic series takes
Chemical general formula for object is R1-Aryl(R2)-NH2, in formula, Aryl is aromatic group, R1And R2In at least one be containing insatiable hunger
With the group of key.
10. the method that reduction nitryl aromatic race substituent prepares amino aromatic series substituent as claimed in claim 9, feature
Be: the Aryl is one of phenyl or naphthyl；And/or
The R1And R2It is respectively selected from C1-C6Alkyl, C1-C6Alkoxy, C1-C6Alkylene, C1-C6Alkynyl, cyano, halogen, sulfonic acid
Base, formyl, C1-C6Ketone carbonyl or C1-C6One of acyl group.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021129268A1 (en) * | 2019-12-25 | 2021-07-01 | 河北彩客化学股份有限公司 | Method for preparing iron oxide red pigment and simultaneously producing aromatic amine |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4358431A (en) * | 1980-07-29 | 1982-11-09 | Bayer Aktiengesellschaft | Production of magnetic iron oxides |
| CN1060284A (en) * | 1988-08-08 | 1992-04-15 | 哈尔滨师范大学 | The preparation method of 4-amino-3-methylphenol |
| CN1458134A (en) * | 2003-06-03 | 2003-11-26 | 枝江开元化工有限责任公司 | Iron powder reducing method for simultaneously producing organic product and ferric oxide black |
| CN103193690A (en) * | 2013-04-11 | 2013-07-10 | 河北华戈染料化学股份有限公司 | Method for preparing 4, 4'-diamido stilbene-2, 2'-disulfonic acid |
| CN105085332A (en) * | 2015-08-03 | 2015-11-25 | 彩客化学（东光）有限公司 | Method for selectively reducing and preparing arylamine through aromatic nitro compounds when ferric oxide/Fe(II) coexists |
| CN106831460A (en) * | 2017-02-24 | 2017-06-13 | 青铜峡市嘉华化工有限公司 | The preparation method of the aminobenzoic acid of 3 methyl 4 |
-
2019
- 2019-02-28 CN CN201910151132.7A patent/CN109761860A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4358431A (en) * | 1980-07-29 | 1982-11-09 | Bayer Aktiengesellschaft | Production of magnetic iron oxides |
| CN1060284A (en) * | 1988-08-08 | 1992-04-15 | 哈尔滨师范大学 | The preparation method of 4-amino-3-methylphenol |
| CN1458134A (en) * | 2003-06-03 | 2003-11-26 | 枝江开元化工有限责任公司 | Iron powder reducing method for simultaneously producing organic product and ferric oxide black |
| CN103193690A (en) * | 2013-04-11 | 2013-07-10 | 河北华戈染料化学股份有限公司 | Method for preparing 4, 4'-diamido stilbene-2, 2'-disulfonic acid |
| CN105085332A (en) * | 2015-08-03 | 2015-11-25 | 彩客化学（东光）有限公司 | Method for selectively reducing and preparing arylamine through aromatic nitro compounds when ferric oxide/Fe(II) coexists |
| CN106831460A (en) * | 2017-02-24 | 2017-06-13 | 青铜峡市嘉华化工有限公司 | The preparation method of the aminobenzoic acid of 3 methyl 4 |
Non-Patent Citations (1)
| Title |
|---|
| JORG KLAUSEN ET AL: "Reduction of Substituted Nitrobenzenes by Fe(II) in Aaueous Mineral Susiensions", 《ENVIRON. SCI. TECHNOL.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021129268A1 (en) * | 2019-12-25 | 2021-07-01 | 河北彩客化学股份有限公司 | Method for preparing iron oxide red pigment and simultaneously producing aromatic amine |
| US11512006B2 (en) | 2019-12-25 | 2022-11-29 | Hebei Caike Chemical Co., Ltd. | Method for simultaneously preparing iron oxide red pigment and aromatic amine |
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