CN106431930B - The method for preparing nitrobenzene from benzene - Google Patents
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Abstract
A kind of nitrogen oxides (NOx) nitrify the method that benzene prepares nitrobenzene, i.e. one kind being transferred to " non-acid " method from " strong acid " method, substitute " nitric/sulfuric acid " environment, using NOx as nitrating agent, using novel high-stability, high activity solid acid as catalyst, implement high atom economy green technology, nitration reaction, the highly selective method for preparing nitrobenzene are carried out to benzene.The relatively existing production technology of this method, method of the invention significantly process simplification and equipment, reduction waste can generate, are environmental-friendly, reduce product cost, improve resource utilization.
Description
Technical field
The present invention relates to a kind of highly selective method for preparing nitrobenzene, i.e., a kind of nitrogen oxides (NOx) nitrification benzene Gao Xuan
Selecting property prepares the green method of nitrobenzene.
Background technology
Nitroaromatic is important organic synthesis intermediate, is to produce medicine, pesticide, fragrance and dyestuff etc.
Important source material, and the corresponding nitroaromatic of catalytic hydrogen reduction is the common industry side of synthesis aromatic amine compounds
Method, therefore the nitration reaction of aromatic compound has obtained extensive research as a kind of important organic reaction.
Nitrobenzene (NB) is extremely important organic chemical industry's intermediate, can be used for medicine, dyestuff, pesticide, explosive, rubber and helps
The synthesis of agent etc. mainly for the production of aniline, and then produces various useful organic intermediates, is also used for production m-nitro sulphur
A variety of medicine such as sour sodium and azobenzene and dyestuff intermediate, are also used as organic solvent.
Traditional nitrobenzene industrial process is to use nitric acid-sulfuric acid mixed acid process, and reaction needs a large amount of sulfuric acid to urge
Agent, generates a large amount of spent acid and waste water, and etching apparatus pollutes environment；And nitration reaction is selectively not easy to control, easy tos produce
More nitro compounds and oxygenatedchemicals.With the enhancing of industrial development and environmental consciousness, it is necessary to conventional method
It is improved.It wherein designs and prepares new catalyst and replaces sulfuric acid, to avoid the use of nitric-sulfuric acid, reduce to environment
Pollution improves resource utilization, reduces energy consumption, to further investigation green nitration and process of industrialization is pushed to have important meaning
Justice.
Currently, benzene nitration processes include vaporphase nitration and liquid-phase nitration two major classes.The big master of nitrating agent that nitration reaction is selected
It to be two kinds：Nitric acid and NO2.The catalyst mainly used have traditional solid acid, rare earth metal salt, metal oxide and from
Sub- liquid etc., wherein the research for being catalyzed benzene nitration reaction with novel solid acid substituted sulfuric acid is widely paid close attention to.
In the liquid-phase nitration of solid acid catalysis, copper nitrate is carried in montmorillonite by Gigante et al., with a small amount of hair
Cigarette nitric acid is initiator, and nitrobenzene yield reaches 92% at room temperature, is free of oxidized byproduct.Smith et al. is urged with zeolite
Agent is made nitrating agent with equimolar nitric acid, acetic anhydride, is nitrified in a mild condition to benzene, alkylbenzene and halobenzene, isomery
The yield of body is 70%~99%, but has acetic acid generation in nitrifying process.The JP48-18239 in patent disclosed in relatively morning,
JP49-18833 and JP50-4030, catalyst uses aroma loaded sulfonic acid because catalytic activity is not high, and easy in inactivation, after by silicon
Infiltrative types catalyst (JP50-126626, the JP51- such as the sulfuric acid or phosphoric acid of sour aluminium (JP50-121234) and inorganic matter carrier load
63134, JP53-12823) replace, but nitrification activity increase rate is little, and especially unresolved by-product is more, nitro benzene selective
Not high problem.
In addition, many researchers propose to substitute the nitrification of liquid acid catalysis nitric acid aromatic hydrocarbons with solid acids such as zeolite molecular sieves.
As a result surface zeolite molecular sieve has preferable catalytic activity and selectivity, has the function of shape selective catalysis, can be highly selective
Orientation generates target product.The zeolite molecular sieve for being presently used for benzene and nitric acid vaporphase nitration synthesizing nitryl benzene mainly has：Mercerising boils
Stone, modified mordenite, Y zeolites, modified Y zeolite, ZSM-5 etc..Bertea etc. reported ZSM-5, modenite, Y zeolites and
Modified Y zeolites as catalysts can effectively be catalyzed nitric acid and be reacted with benzene vaporphase nitration.But nitrification activity is not high, and the catalyst longevity
Life is very short.It is mainly modenite that US4418230 and US5324872, which is reported using molecular sieve catalyst, and nitration condition is anti-
It is about 200 DEG C to answer temperature, benzene and 1.4 or more nitric acid molar ratio.Cu Chemical Uetikon companies in US5324872 and
The nitrification technology that H- modenites make catalyst is individually disclosed in US5334781, in 150~170 DEG C of temperature, benzene rubs with nitric acid
That ratio 1:Under conditions of 0.4, the selectivity of nitrobenzene is up to 92~99%, yield 70~80%, but does not report catalyst stabilization
The experimental data of property.
In recent years, the features such as heteropolyacid catalyst is because of its unique structure and the quasi- liquid phase behavior showed, is having
It is widely applied in machine synthesis.Chen Jinglin etc. is by H2PW20O40It is supported on SiO2, make on wood activated charcoal and alumina support
Catalyst carries out vaporphase nitration using nitric acid as nitrating agent to benzene, the results showed that, SiO2Carried heteropoly acid has benzene vaporphase nitration
Good catalytic activity, nitrobenzene yield is up to 90.6%.Gong Shu texts et al. are using silica gel load phosphomolybdic acid ammonium salt (NH4)3PMo12O40) it is catalyst, using 65% nitric acid as nitrating agent, liquid-phase catalysis nitrifies benzene synthesizing nitryl benzene, obtains more satisfactory
Nitrobenzene product selectivity and yield.In addition, Sato et al. uses SO4 2-/TiO2,SO4 2-/ZrO2And SO4 2-/TiO2-ZrO2Deng
Solid super strong acid as catalyst is nitrating agent with nitric acid, is nitrified to benzene, shows good catalytic performance, nitrobenzene
Yield is up to 87.0%.
Nitrating agent used in the above method is essentially nitric acid or fuming nitric aicd, and due to being related to water-bearing media, catalyst is unstable
It is fixed, it is easy inactivation.Since nineteen eighty, Suzuki of Kyoto Univ Japan etc. has delivered many about ozone on different magazines
NO is used in medium2The paper of nitrated aromatics (Kyodai nitrification processes), has carried out this in a large amount of pilot study, nitrogen
Oxide (NOx) had a wide range of applications in many organic reactions, especially NO2It is caused as a kind of clean nitrating agent
Extensive concern.The U.S. US4107220 and US5324872 are disclosed using H-type mordenite catalyst NO2Nitrify benzene and benzene class
The technology of aromatic hydrocarbons, in 100~350 DEG C of ranges (preferably 150~250 DEG C), nitrobenzene yield is less than 80%.US4347389
Make catalyst, benzene and NO using aluminium-silicon-metal oxide respectively with US4415744 (1983)2In 170~225 DEG C of temperature range
And molar ratio range 1：1.5~1：4 carry out nitration reaction, and the yield for obtaining nitrobenzene is 70~90%.The above process is
Vaporphase nitration, to equipment requirement height, catalyst manufacturing process is cumbersome, and is easy inactivation.
In existing nitrate method, very big, catalyst its stability in such a Aquo System of nitric acid dosage
Difference, and the spent acid waste water generated is more, and also the separating energy consumption of product is high.
Invention content
The present invention proposes that one kind being transferred to " non-acid " method from " strong acid " method, " nitric/sulfuric acid " environment is substituted, using nitrogen
Oxide NOx as nitrating agent, using novel high-stability, high activity solid acid as catalyst, it is green to implement high atom economy
Color technology of preparing carries out liquid phase or gas-liquid nitration reaction, the highly selective method for preparing nitrobenzene to benzene.The present invention passes through change
Reaction condition (such as reactant concentration proportioning, reaction temperature, reaction pressure, reaction time, catalyst) improves the conversion of benzene
The selectivity of rate and nitrobenzene, catalyst can be easily separated, stablize, is reusable, and reduzate is NO in reaction process, can
With recycling.Relatively existing production technology, method of the invention can significantly process simplification and equipment, reductions
Waste generates, reduces product cost, improves resource utilization.
X is more than 1 nitrogen oxides NOx(x>1) it is a kind of substance with strong nitrification, at a certain temperature, energy
Make aromatic hydrocarbons that nitration reaction occur, generates corresponding nitration product, and reacting the reduzate NO generated can recycle.
For benzene, have：
The present invention proposes a kind of using nitrogen oxides NOxAs nitrating agent, nitration reaction, highly selective preparation are carried out to benzene
The method of nitrobenzene, it is characterised in that it is that sulfuric acid and any organic solvent are not used in reaction, it is dense by the way that reactant is effectively arranged
Spend proportioning, reaction temperature, reaction time, the conditions such as reaction pressure, preferred catalyst prepares nitrobenzene to reach highly selective, and
Catalyst can be easily separated, stablize, is reusable, and the reduzate in nitrifying process is NO, can be recycled.
The purpose of the present invention is to achieve the following：
By benzene and nitrogen oxides NOxDirectly carry out nitration reaction, reactant benzene and nitrogen oxides NOxMolar ratio be 1:1~
1:20, such as 1：1.5~1：10, for reaction temperature at 20 DEG C~150 DEG C, the reaction time is 1h~20h, reaction pressure be normal pressure~
10 atmospheric pressure (absolute pressure) obtain nitrobenzene to highly selective；Catalyst can be easily separated, stablize, is reusable, and nitrify
Reduzate in journey is NO, can be recycled；Nitrogen oxides NO described in itxMiddle x is not less than 1.0.
The method of the present invention is summarized as follows：
The present invention provides a kind of method preparing nitrobenzene from benzene, and this approach includes the following steps：
(a) nitration reaction：As the carrier load type heteropoly acid (salt) of solid acid catalyst or the solid of sulfuric acid
In the presence of super acids, by benzene and NO in closed reactorxOr NOxWith O2Mixture under liquid phase or liquid phase state into
Row nitration reaction obtains and (is made to highly selective) nitrobenzene, wherein NOxTo meet 1<x<It is arbitrary in 3 nitrogen oxides
One or two or more kinds of mixtures, wherein reactant benzene and NOxMolar ratio be 1:1~1:20, it is preferably 1:1~1:
10, it is more preferably 1:1~1:5, it is more preferably 1:1~1:3；
(b) it detaches：Catalyst is isolated by filtration out and oil phase is purified (such as passing through distillation), obtains nitro
Benzene.
It is preferred that the heteropoly acid is one or more of phosphotungstic acid and phosphomolybdic acid with structure with Keggin.
It is preferred that the heteropolyacid salt is one or more mixtures in ammonium phosphotungstate and ammonium phosphomolybdate.
It is preferred that the solid super-strong acid of the sulfuric acid is to be selected from SO4 2-/VPO、SO4 2-/WO3、SO4 2-/MoO3、
SO4 2-/ZrO2、SO4 2-/TiO2、SO4 2-/MoO3-WO3、SO4 2-/MoO3-ZrO2、SO4 2-/MoO3-TiO2、SO4 2-/ZrO2-TiO2、
SO4 2-/MoO3-VPO、SO4 2-/WO3-VPO、SO4 2-/MoO3-VPO、SO4 2-/ZrO2- VPO or SO4 2-/TiO2One kind in-VPO or
It is a variety of；Preferably, it is selected from SO4 2-/VPO、SO4 2-/MoO3-VPO、SO4 2-/WO3-VPO、SO4 2-/MoO3-VPO、SO4 2-/ZrO2-
VPO or SO4 2-/TiO2It is one or more in-VPO.
It is preferred that the catalyst carrier is：Molecular sieve, such as MCM-41, SBA, HZSM-5, modified mordenite, Y boilings
Stone or modified Y zeolite；Al2O3；Activated carbon；Silica gel；Sepiolite；Or clay class；It is further preferred that catalyst carrier is molecular sieve
MCM-41, molecular sieve SBA or molecular sieve HZSM-5.
Preferably, carrier load type heteropoly acid (salt) is obtained by following method for preparing catalyst：It will roasting
Processed heteropoly acid (salt) is made into aqueous solution, by carrier impregnation that same calcination process is crossed in wherein (such as dip time is
12~15h), using filter, drying and after baking, carrier load type heteropoly acid (salt) catalyst is made.
Preferably, the solid super-strong acid of sulfuric acid is obtained by following method for preparing catalyst：It will roasting
Processed solid super-strong acid is impregnated in the concentrated sulfuric acid (such as dip time is 12~15h), using filter, drying and secondary roasting
It burns, the solid super acid catalyst of sulfuric acid is made.
Above-described after baking refers to：At a temperature of 200 DEG C~500 DEG C, preferably 300-450 DEG C at calcination activation
Reason.
It is preferred that the reaction temperature of benzene nitrification is at 20 DEG C~160 DEG C, preferably 40 DEG C~140 DEG C, more preferable 60 DEG C~120
DEG C, more preferable 70 DEG C~110 DEG C, further preferred 80 DEG C~100 DEG C of range.
The reaction pressure of the nitration reaction of step 1) is 1.12 atmospheric pressure -5MPa, preferably 1.15 atmospheric pressure -4MPa, more excellent
Select 1.2 atmospheric pressure -3MPa, further preferred 1.25 atmospheric pressure -2.5MPa, further preferred 0.5-1.5MPa, 0.8-1.3MPa,
It is carried out under 0.9-1.25MPa, 1.09-1.20MPa, such as the pressure of 1.18,1.13MPa；For example, reaction pressure is 1.12 big
The atmospheric pressure (absolute pressure or absolute pressure) of air pressure~10, the atmospheric pressure (absolute pressure) of preferably 1.12 atmospheric pressure~4.
Nitration reaction carries out in a batch, semi-continuous or continuous manner.The wherein closed reaction of nitration reaction
Device is the autoclave or tubular reactor being made of stainless steel.
Catalyst can be easily separated with it is reusable, nitration reaction generate reduzate be mainly NO, can recycle and follow
Ring utilizes.By gas phase obtained by the reaction in (a) step send in NO oxidation reactors with O2It reacts, NO therein is made to turn
Become NOxTo recycle.
The nitrogen oxides NOxIt is NO2、N2O4、N2O3、N2O5Or their mixture.In addition, the mixture of NOx and O2
It also is used as nitrating agent.
Specific implementation process of the present invention is：
By benzene, nitrogen oxides NOxAnd catalyst is added a closed tank reactor and carries out nitration reaction；Reactant nitrogen
Oxide NOxMiddle x is more than 1.0 and is less than 3.0, preferably x=1.5~2.5 (such as NO2、N2O4、N2O3Or N2O5Deng)；Benzene and nitrogen oxides
NOxMolar ratio is 1：1.5~1：10, particularly preferably 1：1~1：5；Reaction temperature is preferred to react at 20 DEG C~150 DEG C
Temperature is 70 DEG C~100 DEG C；Reaction pressure is the atmospheric pressure (absolute pressure) of normal pressure~10；Reaction time is 1h~20h, preferred to react
Time is 3h~7h；Catalyst is carried heteropoly acid (salt) or the solid super-strong acid of sulfuric acid, preferably phosphotungstic acid or phosphorus tungsten
Hydrochlorate is supported on MCM-41 and SO4 2-/VPO、SO4 2-/MoO3-VPO、SO4 2-/WO3-VPO、SO4 2-/MoO3-VPO、SO4 2-/
ZrO2-VPO、SO4 2-/TiO2-VPO；Catalyst can be easily separated, stablize, is reusable, and the reduzate in nitrifying process is
NO can be recycled, and wherein the utilization rate of nitrogen is more than 90%, and can reach 95% or more；It is obtained to highly selective
Nitrobenzene, the selectivity of nitrobenzene is up to 95% or more or reaches 98% or more.The high conversion rate of benzene is in 50%, or is higher than
55%, or even higher than 60%, or even higher than 70%, or even higher than 85%.If improving the temperature and slightly of nitration reaction
Slightly extend the time of nitration reaction, the high conversion rate of benzene is in 98%, or reaches 100%.
Heteropoly acid of the present invention be have the phosphotungstic acid of Keggin (gram more) structure and phosphomolybdic acid it is one such or
It is several.The heteropolyacid salt is that ammonium phosphotungstate and ammonium phosphomolybdate are one such or several.
The catalyst carrier be molecular sieve (such as MCM-41, SBA, HZSM-5, modenite, modified mordenite,
Y zeolites, modified Y zeolite etc.), Al2O3Class, activated carbon, silica gel, sepiolite, the carriers such as clay class.Preferably MCM-41, SBA,
HZSM-5。
The solid super-strong acid of the sulfuric acid is selected from SO4 2-/VPO、SO4 2-/WO3、SO4 2-/MoO3、SO4 2-/ZrO2、
SO4 2-/TiO2、SO4 2-/MoO3-WO3、SO4 2-/MoO3-ZrO2、SO4 2-/MoO3-TiO2、SO4 2-/ZrO2-TiO2、SO4 2-/MoO3-
VPO、SO4 2-/WO3-VPO、SO4 2-/MoO3-VPO、SO4 2-/ZrO2-VPO、SO4 2-/TiO2- VPO etc. is one such or several.
The present invention also provides the preparation method of carrier load type heteropoly acid (salt) (i.e. method for preparing catalyst), this method
It is that calcination process is crossed to the heteropoly acid (salt) of (i.e. pre-treatment) to be made into aqueous solution, same calcination process is crossed to the load of (i.e. pre-treatment)
Body is impregnated in wherein, and the time is 12~15h, is made using after filter, drying and after baking.The infusion process is made carrier loaded
Type heteropoly acid (salt) catalyst.
The present invention also provides the preparation method of the solid super-strong acid of sulfuric acid (i.e. method for preparing catalyst), this method
It is that calcination process is crossed to the solid super-strong acid of (i.e. pre-treatment) to be impregnated in the concentrated sulfuric acid, the time is 12~15h, using filter, dry
It is made after dry and after baking.The solid super acid catalyst of sulfuric acid is made in the infusion process.
In front in the method for preparing catalyst, the pre-treatment of the solid super-strong acid of heteropoly acid (salt) or sulfuric acid
Calcination temperature is 200~500 DEG C, and preferably 300~400 DEG C, the time is 4~10h, preferably 6~8h.
In front in the method for preparing catalyst, the drying refers to gained catalyst in normal pressure and 100~150 DEG C
Lower drying 1~4h, preferably 2~3h.
In front in the method for preparing catalyst, the after baking temperature of gained catalyst is 200~500 DEG C, excellent
300~400 DEG C are selected, the time is 1~5h, preferably 2~3h.
It is cooling in tank reactor after nitration reaction according to benzene nitration method provided by the invention, it is separated by filtration
Catalyst, and gas chromatographic analysis is carried out to product, the selectivity of the conversion ratio and product of benzene is calculated with internal standard method.
In the nitration method of the application, the reactor used in benzene nitration reaction is usually closed reactor, excellent
Choosing is non-tubular reactor, more preferably pressure autoclave type reactor or autoclave.It is preferred that above-described reactor is one
A closed reactor (non-ducted reactor) such as pressure autoclave type reactor or autoclave or two or three or four
Or five or six or seven or eight or more concatenated closed reactors such as pressure autoclave type reactor or reaction under high pressures
Kettle.Or in addition, the reactor used in step (a) is closed reactor, such as tubular reactor.Above-described reaction
What device was preferably made of stainless steel.Reactor described here is preferably tubular reactor or tower reactor, can also be
Single kettle type reactor or multi-continuous stirred tank reactor etc..
It is preferred that mixed using mixing apparatus (such as agitating paddle or stirring rod) in above-described nitrator,
Such as using dynamic mixing device such as agitating paddle or stirring rod for non-ducted reactor or for tubular reactor
Use static mixing device or static mixer.
When reactor used in nitration reaction is a reactor, method of the invention can with intermittent mode into
Row.Reactor used in nitration reaction is two or three or four or five or six or seven or eight or more
When a tandem reactor (such as pressure tank reactor or autoclave) or tubular reactor, method of the invention can
It is carried out with semi continuous mode or continuation mode.
Preferably, in the benzene nitration method of the present invention, " carrying out nitration reaction under liquid phase or liquid phase state " is
Refer to liquid NOxMixed with benzene (such as by liquid NOxIt is dissolved in benzene), at elevated temperatures and is stirring or be sufficiently mixed
Lower carry out nitration reaction.
Described herein refers to the existing liquid reaction mixture in reactor " under liquid phase state ", while anti-
Answer on the top or liquid level of mixture that there are gas phases (containing or mainly contain NO gases caused by reaction).
Preferably, in above-described nitration reaction step, by liquid NOxLess than 20 DEG C, preferably shorter than 15 DEG C
It is dissolved in benzene at a temperature of (such as less than 5 DEG C) and forms reaction mixture.It is preferred that being formed by reaction mixture closed
It is reacted at raised temperature (reaction temperature as described above) in reactor.
In the method for application, by NO when before reactions or reaction startsx(such as lower temperature as less than 20 DEG C,
Preferably shorter than 15 DEG C or be less than 5 DEG C) under) be dissolved in benzene and form liquid reaction mixture, then exist in closed reactors
Continue to be reacted in the form of liquid mixture at raised temperature, especially carry out during the reaction or while reaction
It is sufficiently mixed or stirs.Pressure or pressure in this application refers to absolute pressure (unit：Atmospheric pressure or MPa).
By gas phase obtained by the reaction in (a) step send in NO oxidation reactors with O2It reacts, makes NO therein
Change NOxTo recycle.
Advantages of the present invention：
1, NOx dosages are seldom in the application, and NOx can be recycled, generated reduzate NO, by matching oxygen
NOx recyclings can be generated again.
2, spent acid is not generated in the application, and product can be easily separated, catalyst also can be easily separated and reuse, and urge
Agent shows stabilization in such a anhydrous system, and the spent acid waste water of generation is few.
Specific implementation mode
Following embodiment is intended to illustrate invention, rather than limiting the invention.
Embodiment 1：Weigh 2.5g benzene and 7.37gNO2(molar ratio 1:5) it is placed in the sealable still reaction of 100ml
In device (autoclave of i.e. stainless steel making), reaction pressure is 0.15 megapascal, cooling after reacting 6h at 90 DEG C, reaction
Product carries out gas-chromatography internal standard analysis, and the conversion ratio for obtaining benzene is 37.1%, and nitro benzene selective is 90.4%.
Embodiment 2：Reaction step with embodiment 1, the difference is that, 0.2g HPW/MCM-41 are added in a kettle
Catalyst (is prepared, the load capacity of phosphotungstic acid HPW is 30%, and calcination for activation temperature is 400 DEG C, and soak time is using infusion process
3h), the conversion ratio for obtaining benzene is 58.7%, and the selectivity of mononitro-benzene is 98.2%.
Embodiment 3：Reaction step with embodiment 1, the difference is that, nitrating agent N2O3, the conversion ratio for obtaining benzene is
27.5%, the selectivity of nitrobenzene is 89.2%.
Embodiment 4：：Reaction step with embodiment 1, the difference is that, nitrating agent N2O5, the conversion ratio for obtaining benzene is
31.58%, the selectivity of nitrobenzene is 87.59%.
Embodiment 5：Reaction step with embodiment 1, the difference is that, benzene and NO2Molar ratio is 1:3, obtain benzene conversion
Rate is 15.5%, and nitro benzene selective is 90.2%.
Embodiment 6：Reaction step with embodiment 1, the difference is that, reaction temperature be 120 DEG C, obtain the conversion ratio of benzene
It is 46.4%, the selectivity of nitrobenzene is 67.0%.
Embodiment 7：Reaction step with embodiment 1, the difference is that, in a kettle be added phosphomolybdic acid (HPMo) be catalyzed
Agent, the conversion ratio for obtaining benzene are 43.5%, and the selectivity of nitrobenzene is 93.2%.
Embodiment 8：Reaction step with embodiment 1, the difference is that, in a kettle be added ammonium phosphotungstate (AMPW) urge
Agent, the conversion ratio for obtaining benzene are 41.6%, and the selectivity of nitrobenzene is 93.6%.
Embodiment 9：Reaction step with embodiment 1, the difference is that, SO is added in a kettle4 2-/ vpo catalyst,
The conversion ratio for obtaining benzene is 60.2%, and the selectivity of nitrobenzene is 95.8%.
Embodiment 10：Reaction step with embodiment 1, the difference is that, reaction time 8h obtains the conversion ratio of benzene
It is 37.3%, the selectivity of mononitro-benzene is 89.9%.
Embodiment 11：Reaction step with embodiment 2, the difference is that, reaction time 8h, the conversion ratio for obtaining benzene is
73.4%, the selectivity of nitrobenzene is 98.8%.
Embodiment 12：Reaction step with embodiment 1, the difference is that, 0.2g SO are added in a kettle4 2-/WO3It urges
Agent, the conversion ratio for obtaining benzene are 58.0%, and the selectivity of nitrobenzene is 98.9%.
Embodiment 13：Reaction step with embodiment 1, the difference is that, 0.2g SO are added in a kettle4 2-/MoO3-
WO3, the conversion ratio for obtaining benzene is 55.6%, and the selectivity of nitrobenzene is 97.3%.
Embodiment 14：Reaction step with embodiment 1, the difference is that, 0.2g SO are added in a kettle4 2-/WO3-
VPO, the conversion ratio for obtaining benzene are 68.3%, and the selectivity of nitrobenzene is 96.4%.
Embodiment 15：Reaction step with embodiment 1, the difference is that, reaction pressure be 0.3 megapascal, obtain benzene turn
Rate is 43.8%, and the selectivity of nitrobenzene is 97.9%.
Embodiment 16：Reaction step with embodiment 2, the difference is that, the roasting in the activation of the after baking of catalyst
Temperature is 300 DEG C, and the conversion ratio for obtaining benzene is 53.2%, and the selectivity of nitrobenzene is 97.6%.
Embodiment 17：Reaction step with embodiment 2, the difference is that, the time of the after baking of catalyst activation is
1h, the conversion ratio for obtaining benzene are 30.9%, and the selectivity of nitrobenzene is 96.5%.
Embodiment 18：Reaction step with embodiment 2, the difference is that, 0.2g activation process is added in a kettle
Vanadium phosphorus oxygen compound Cu-VPO (wherein the calcination for activation temperature of compound is 400 DEG C, soak time 3h), obtains the conversion of benzene
Rate is 42.4%, and the selectivity of mononitro-benzene is 92.2%.
Embodiment 19：Reaction step with embodiment 2, the difference is that, 0.2g activation process is added in a kettle
Vanadium phosphorus oxygen compound Co-AlVPO (wherein the calcination for activation temperature of compound is 400 DEG C, soak time 3h), obtains turning for benzene
Rate is 43.5%, and the selectivity of mononitro-benzene is 93.4%.
Claims (7)
1. the method for preparing nitrobenzene from benzene, this approach includes the following steps：
(a) nitration reaction：In the presence of the solid super-strong acid as the sulfuric acid of solid acid catalyst, in closed reactor
In by benzene and NOxOr NOxWith O2Mixture carry out nitration reaction under liquid phase or liquid phase state, obtain nitrobenzene, wherein
NOxTo meet 1<x<The mixture of any one or more in 3 nitrogen oxides, wherein reactant benzene and NOxMolar ratio be
1:1~1:20, wherein the solid super-strong acid of the sulfuric acid is selected from SO4 2-/VPO、SO4 2-/MoO3-VPO、SO4 2-/WO3-
VPO、SO4 2-/ZrO2- VPO or SO4 2-/TiO2It is one or more in-VPO；
(b) it detaches：Catalyst is isolated by filtration out and oil phase is purified, obtains nitrobenzene.
2. according to the method described in claim 1, wherein, reactant benzene and NOxMolar ratio be 1:1~1:3.
3. according to the method described in claim 1, the solid super-strong acid of wherein sulfuric acid is by following catalyst preparation side
What method was obtained：The solid super-strong acid that calcination process is crossed is impregnated in the concentrated sulfuric acid, using filter, drying and after baking, system
Obtain the solid super acid catalyst of sulfuric acid.
4. according to the method described in claim 3, wherein after baking refers to：Calcination activation at a temperature of 200 DEG C~500 DEG C
Processing.
5. according to the method described in any one of claim 1-3, it is characterised in that：Reaction temperature is at 20 DEG C~160 DEG C.
6. according to the method described in any one of claim 1-3, it is characterised in that：The nitration reaction pressure of step (a) is
It is carried out under the pressure of 1.12 atmospheric pressure -5MPa.
7. according to the method for any one of claim 1-3, wherein this method be in a batch, semi-continuous or continuous manner into
Capable；And/or
Wherein closed reactor is the autoclave or tubular reactor being made of stainless steel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510474520.0A CN106431930B (en) | 2015-08-05 | 2015-08-05 | The method for preparing nitrobenzene from benzene |
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| CN108745390B (en) * | 2018-06-05 | 2020-10-27 | 嘉禾县佳禾米业股份有限公司 | Visible light photocatalyst and preparation and application thereof |
| CN109232257B (en) * | 2018-09-04 | 2021-03-09 | 浙江工业大学 | Method and device for preparing methyl nitrobenzene in pipeline mode |
| CN109369453B (en) * | 2018-09-04 | 2021-06-25 | 浙江工业大学 | Method and device for preparing 2-chloro-5-nitrobenzonitrile through pipelining |
| CN109647291B (en) * | 2018-12-10 | 2021-08-24 | 浙江工业大学 | Tubular reactor with nano tin oxide-aluminum oxide solid acid coating as well as preparation method and application of tubular reactor |
| CN109675508B (en) * | 2018-12-11 | 2021-05-07 | 浙江工业大学 | Preparation method and application of perfluorosulfonic acid resin/solid acid microfibrillated microchannel reactor |
| CN112010757A (en) * | 2020-08-07 | 2020-12-01 | 临沂大学 | Method for preparing nitrobenzene by catalyzing polyoxometallate |
| CN111974416A (en) * | 2020-09-25 | 2020-11-24 | 浙江皇马科技股份有限公司 | Supported solid super acidic catalyst, preparation method and application thereof, and preparation method of ethoxylated trimethylolpropane |
| CN114349643A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Method for preparing nitro compound by solid acid nitration of aromatic compound |
| CN113233984B (en) * | 2020-11-03 | 2023-04-21 | 江苏方圆芳纶研究院有限公司 | Method for preparing nitrobenzene by recycling nitrified waste acid |
| CN115466183B (en) * | 2022-09-22 | 2024-04-26 | 湖南工程学院 | Co-production method of aromatic hydrocarbon nitration and oxidation products |
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| CN101531596A (en) * | 2008-10-21 | 2009-09-16 | 浙江工业大学 | Preparation method for dinitrotoluene |
| CN102513161B (en) * | 2011-11-25 | 2013-10-23 | 湘潭大学 | Naphthalene nitration catalyst as well as preparation method and application thereof |
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| US6291726B1 (en) * | 1998-02-18 | 2001-09-18 | Inha University Foundation | Process for nitration of aromatic compounds using a non-acid type nitration process |
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