CN106431930A - Method for preparing nitrobenzene from benzene - Google Patents
Method for preparing nitrobenzene from benzene Download PDFInfo
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Abstract
Disclosed is a method for preparing nitrobenzene by using nitrogen oxide (NOx) nitrobenzene. The preparing method comprises the steps of transferring a method of 'strong acid' to a method of 'non-acid' to replace 'nitric acid/sulfuric acid' environment, adopting the NOx as a nitrating agent, adopting a sold acid with high stability and high activity as a catalyst, conducting a high atom economy green technology, conducting nitration reaction on benzene and preparing the nitrobenzene in high selectivity. Compared with the prior art, the method can sharply simplify a craft process and equipment and reduce waste production; meanwhile, the method is environmentally friendly, and can reduce production cost and increase resource utilization rate.
Description
Technical field
The present invention relates to a kind of method that high selectivity prepares Nitrobenzol, i.e. a kind of nitrogen oxides (NOx) nitrification benzene high selectivity
Prepare the green method of Nitrobenzol.
Background technology
Nitroaromatic is important organic synthesis intermediate, is the important of production medicine, pesticide, spice and dyestuff etc.
Raw material, and the corresponding nitroaromatic of catalytic hydrogen reduction is the commercial run that synthesis aromatic amine compounds are commonly used, because
The nitration reaction of this aromatic, as a kind of important organic reaction, has obtained extensive research.
Nitrobenzol (NB) is extremely important organic chemical industry's intermediate, can be used for medicine, dyestuff, pesticide, explosive, rubber help
The synthesis of agent etc., mainly for the production of aniline, and then produces various useful organic intermediates, is also used for producing m-nitro sulphur
Multiple medicine such as sour sodium and diphenyl diimide and dyestuff intermediate, are also used as organic solvent.
Traditional Nitrobenzol industrial process is using nitric acid-sulfuric acid mixed acid process, and reaction needs substantial amounts of sulfur acid as catalyst, produces
Raw substantial amounts of spent acid and waste water, etching apparatus, pollutes environment；And nitration reaction selectivity is wayward, easily produce many nitros
Compound and oxygenatedchemicalss.With industrial development with the enhancing of environmental consciousness it is necessary to improve to traditional method.
Wherein design and prepare new catalyst and replace sulphuric acid, thus avoiding the use of nitric-sulfuric acid, reducing the pollution to environment, improving
Resource utilization, reduces energy resource consumption, significant to further investigation green nitration and promotion process of industrialization.
At present, benzene nitration processes include vaporphase nitration and liquid-phase nitration two big class.The nitrating agent big predominantly two that nitration reaction is selected
Kind：Nitric acid and NO2.The main catalyst adopting has traditional solid acid, rare earth metal salt, metal-oxide and ionic liquid
Body etc., is wherein widely paid close attention to the research that novel solid acid replaces sulfuric acid catalysis benzene nitration reaction.
In the liquid-phase nitration of solid acid catalysis, copper nitrate is carried in montmorillonite Gigante et al., with a small amount of fuming nitric aicd
For initiator, Nitrobenzol yield reaches 92%, without oxidized byproduct at room temperature.Smith et al. zeolites as catalysts,
Nitrating agent is made with equimolar nitric acid, acetic anhydride, benzene, alkylbenzene and halobenzene are nitrified in a mild condition, isomer
Yield is 70%～99%, but has acetic acid to produce in nitrifying process.JP48-18239, JP49-18833 in patent disclosed in relatively morning
And JP50-4030, catalyst adopts aroma loaded sulfonic acid because catalysis activity is not high, and easy in inactivation, after by aluminium silicate
(JP50-121234) and the sulphuric acid of inorganic matter carrier load or the infiltrative type catalyst such as phosphoric acid (JP50-126626, JP51-63134,
JP53-12823) replace, but nitrification activity increase rate is less, especially unresolved by-product is many, nitro benzene selective is not high
Problem.
In addition, the solid acid such as many researcher proposition zeolite molecular sieves substitutes the nitrification of liquid acid catalysiss nitric acid aromatic hydrocarbons.Result table
Face zeolite molecular sieve has preferable catalysis activity and selectivity, has the effect of shape selective catalysis, can high selectivity orientation generate
Target product.The zeolite molecular sieve being presently used for benzene with nitric acid vaporphase nitration synthesizing nitryl benzene mainly has：Modenite, modification
Modenite, Y zeolite, modified Y zeolite, ZSM-5 etc..Bertea etc. reported ZSM-5, modenite, Y zeolite and
Modified Y zeolite makees catalyst, can effectively be catalyzed nitric acid and react with benzene vaporphase nitration.But nitrification activity is not high, and the catalyst longevity
Life is very short.US4418230 and US5324872 reports and is mainly modenite using molecular sieve catalyst, and nitration condition is anti-
Answer about 200 DEG C of temperature, benzene and nitric acid mol ratio more than 1.4.Cu Chemical Uetikon company in US5324872 and
The nitrification technology that H- modenite makees catalyst is individually disclosed, in 150～170 DEG C of temperature, benzene is rubbed with nitric acid in US5334781
You compare 1:Under conditions of 0.4, the selectivity of Nitrobenzol up to 92～99%, yield 70～80%, but do not report catalyst stability
Experimental data.
In recent years, heteropolyacid catalyst because of its unique structure and show quasi- liquid phase behavior the features such as, in organic synthesiss
In be widely applied.Chen Jinglin etc. is by H2PW20O40It is supported on SiO2, be catalyzed on wood activated charcoal and alumina support
Agent, carries out vaporphase nitration for nitrating agent to benzene with nitric acid, and result shows, SiO2Carried heteropoly acid has to benzene vaporphase nitration very well
Catalysis activity, Nitrobenzol yield is up to 90.6%.Gong Shuwen et al. adopts silica gel load phosphomolybdic acid ammonium salt (NH4)3PMo12O40)
For catalyst, with 65% nitric acid as nitrating agent, liquid-phase catalysis nitrifies benzene synthesizing nitryl benzene, obtains more satisfactory Nitrobenzol and produces
Thing selectivity and yield.In addition, Sato et al. adopts SO4 2-/TiO2,SO4 2-/ZrO2And SO4 2-/TiO2-ZrO2Deng solid super strong
Acid as catalyst, is nitrating agent with nitric acid, benzene is nitrified, and shows good catalytic performance, and the yield of Nitrobenzol is up to
87.0%.
Nitrating agent used by said method is essentially nitric acid or fuming nitric aicd, and due to being related to water-bearing media, catalyst is unstable, holds
Easy in inactivation.Since nineteen eighty, Suzuki of Kyoto Univ Japan etc. has delivered many with regard to ozone medium on different magazines
In use NO2The paper of nitrated aromatics (Kyodai nitrification process), has carried out substantial amounts of exploratory study, nitrogen oxidation to this
Thing (NOx) have a wide range of applications in many organic reactions, especially NO2Cause extensively as a kind of clean nitrating agent
General concern.The U.S. US4107220 and US5324872 discloses using H type mordenite catalyst NO2Nitrification benzene and benzene
The technology of class aromatic hydrocarbons, in 100～350 DEG C of scopes (preferably 150～250 DEG C), Nitrobenzol yield is less than 80%.US4347389
Make catalyst, benzene and NO with US4415744 (1983) using aluminum-silicon-metal oxide respectively2In 170～225 DEG C of temperature range
And molar ratio range 1：1.5～1：4 carry out nitration reaction, and the yield obtaining Nitrobenzol is 70～90%.Said process is gas
Mutually nitrify, high to equipment requirements, catalyst manufacturing process is loaded down with trivial details, and easy inactivation.
In existing nitrate method, nitric acid dosage very big, catalyst its stability in such a Aquo System is poor, and
And the spent acid waste water of generation is many, and the separating energy consumption of product is high.
Content of the invention
The present invention proposes one kind and transfers to " non-acid " method from " strong acid " method, substitutes " nitric/sulfuric acid " environment, using nitrogen oxides
NOx, as nitrating agent, with novel high-stability, highly active solid acid as catalyst, implements high atom economy green preparation
Technology, carries out liquid phase or gas-liquid nitration reaction, the method that high selectivity prepares Nitrobenzol to benzene.The present invention passes through to change reaction bar
Part (as reactant concentration proportioning, reaction temperature, reaction pressure, response time, catalyst etc.) come to improve benzene conversion ratio and
The selectivity of Nitrobenzol, catalyst can be easily separated, stable, reusable, and in course of reaction, reduzate is NO, can
With recycle and reuse.Relatively existing production technology, the method for the present invention can significantly process simplification and equipment, minimizing
Waste produces, reduces product cost, improves resource utilization.
The nitrogen oxides NO that x is more than 1x(x>1) it is the material that a class has strong Nitrification, at a certain temperature, can make
There is nitration reaction in aromatic hydrocarbons, generate corresponding nitration product, and the reduzate NO reacting generation can be with recycle and reuse.
For benzene, have：
The present invention proposes one kind and adopts nitrogen oxides NOxAs nitrating agent, nitration reaction is carried out to benzene, high selectivity prepares nitro
The method of benzene it is characterised in that being not use sulphuric acid and any organic solvent in reaction, by effective setting reactant concentration proportioning,
The conditions such as reaction temperature, response time, reaction pressure, preferred catalyst prepares Nitrobenzol reaching high selectivity, and catalyst
Can be easily separated, stable, reusable, and the reduzate in nitrifying process be NO, can be with recycle and reuse.
The purpose of the present invention is accomplished by：
By benzene and nitrogen oxides NOxDirectly carry out nitration reaction, reactant benzene and nitrogen oxides NOxMol ratio be 1:1～1:20,
Such as 1：1.5～1：10, at 20 DEG C～150 DEG C, the response time is 1h～20h to reaction temperature, and reaction pressure is normal pressure～10
Atmospheric pressure (absolute pressure), thus high selectivity obtains Nitrobenzol；Catalyst can be easily separated, stable, reusable, and nitrifies
During reduzate be NO, can be with recycle and reuse；Its described nitrogen oxides NOxMiddle 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 Nitrobenzol from benzene, and the method comprises the following steps：
(a) nitration reaction：Solid super-strong acid in the carrier load type heteropoly acid (salt) as solid acid catalyst or sulfuric acid
In the presence of, by benzene and NO in closed reactorxOr NOxWith O2Mixture carry out nitre under liquid phase or liquid phase state
Change reaction, obtain (thus high selectivity is obtained) Nitrobenzol, wherein NOxFor meeting 1<x<Any one in 3 nitrogen oxides
Or the mixture of two or more, wherein reactant benzene and NOxMol ratio be 1:1～1:20th, it is preferably 1:1～1:10th, more
It is preferably 1:1～1:5th, more preferably 1:1～1:3；
B () separates：It is isolated by filtration out catalyst and oil phase is purified with (for example passing through distillation), obtain Nitrobenzol.
Preferably, described heteropoly acid is to have one or more of phosphotungstic acid and phosphomolybdic acid of structure with Keggin.
Preferably, described heteropolyacid salt is the mixture of one or more of ammonium phosphotungstate and ammonium phosphomolybdate.
Preferably, the solid super-strong acid of described 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 or
SO4 2-/TiO2One or more of-VPO；Preferably, selected from SO4 2-/VPO、SO4 2-/MoO3-VPO、
SO4 2-/WO3-VPO、SO4 2-/MoO3-VPO、SO4 2-/ZrO2- VPO or SO4 2-/TiO2One or more of-VPO.
Preferably, described catalyst carrier is：Molecular sieve, such as MCM-41, SBA, HZSM-5, modified mordenite,
Y zeolite or modified Y zeolite；Al2O3；Activated carbon；Silica gel；Meerschaum；Or clay class；It is further preferred that catalyst carrier
It 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：By calcination process
The heteropoly acid (salt) crossed is made into aqueous solution, the carrier impregnation that same calcination process is crossed in wherein (such as dip time is 12～15h),
Again through filtering, being dried and after baking, prepared carrier load type heteropoly acid (salt) catalyst.
Preferably, the solid super-strong acid of sulfuric acid is obtained by following method for preparing catalyst：By calcination process mistake
Solid super-strong acid impregnated in concentrated sulphuric acid (such as dip time is 12～15h), then through filtering, being dried and after baking, be obtained
The solid super acid catalyst of sulfuric acid.
Above-described after baking refers to：At a temperature of 200 DEG C～500 DEG C, preferred 300-450 DEG C, calcination activation is processed.
Preferably, the reaction temperature of benzene nitrification is at 20 DEG C～160 DEG C, preferably 40 DEG C～140 DEG C, more preferably 60 DEG C～120 DEG C,
More preferably 70 DEG C～110 DEG C, further preferred 80 DEG C～100 DEG C of scope.
Step 1) the reaction pressure of nitration reaction be 1.12 atmospheric pressure -5MPa, preferably 1.15 atmospheric pressure -4MPa, more preferably
1.2 atmospheric pressure -3MPa, further preferred 1.25 atmospheric pressure -2.5MPa, further preferred 0.5-1.5MPa, 0.8-1.3MPa,
0.9-1.25MPa, 1.09-1.20MPa, such as 1.18, carry out under the pressure of 1.13MPa；For example, reaction pressure is 1.12
Atmospheric pressure～10 atmospheric pressure (absolute pressure or absolute pressure), preferably 1.12 atmospheric pressure～4 atmospheric pressure (absolute pressure).
Nitration reaction is carried out in a batch, semi-continuous or continuous manner.The closed reactor of wherein nitration reaction be by
The autoclave of stainless steel making or tubular reactor.
Catalyst can be easily separated with reusable, nitration reaction produce reduzate be mainly NO, can be with recycle and reuse.
By react in (a) step the gas phase obtaining send in NO oxidation reactor with O2React so as in NO change NOx
To recycle.
Described nitrogen oxides NOxIt is NO2、N2O4、N2O3、N2O5Or their mixture.In addition, NOx and O2
Mixture also is used as nitrating agent.
Specific implementation process of the present invention is：
By benzene, nitrogen oxides NOxAnd catalyst adds an airtight tank reactor to carry out nitration reaction；Reactant nitrogen oxidation
Thing NOxMiddle x is more than 1.0 and is less than 3.0, and preferably x=1.5～2.5 are (as NO2、N2O4、N2O3Or N2O5Deng)；Benzene and nitrogen
Oxide NOxMol ratio is 1：1.5～1：10, particularly preferably 1：1～1：5；Reaction temperature is at 20 DEG C～150 DEG C, excellent
The reaction temperature of choosing is 70 DEG C～100 DEG C；Reaction pressure is normal pressure～10 atmospheric pressure (absolute pressure)；Response time is 1h～20h,
Preferably the response time is 3h～7h；Catalyst is the solid super-strong acid of carried heteropoly acid (salt) or sulfuric acid, preferably phosphorus
Wolframic acid or phosphotungstate are 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, stable, reusable,
And the reduzate in nitrifying process is NO, can be with recycle and reuse, the utilization rate of wherein nitrogen is more than 90%, and can reach
More than 95%；Thus high selectivity obtains Nitrobenzol, the selectivity of Nitrobenzol up to more than 95% or reaches more than 98%.Benzene
High conversion rate is in 50%, or is higher than 55%, or even above 60%, or even above 70%, or even above 85%.If
Improve the temperature of nitration reaction and the time of prolongation nitration reaction slightly, 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 therein one or more.Institute
The heteropolyacid salt stated be ammonium phosphotungstate and ammonium phosphomolybdate therein one or more.
Described catalyst carrier be molecular sieve (as MCM-41, SBA, HZSM-5, modenite, modified mordenite,
Y zeolite, modified Y zeolite etc.), Al2O3Class, activated carbon, silica gel, meerschaum, the carrier such as clay class.Preferably MCM-41,
SBA、HZSM-5.
The solid super-strong acid of described 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.
Therein one or more.
Present invention also offers the preparation method (i.e. method for preparing catalyst) of carrier load type heteropoly acid (salt), the method be by
The heteropoly acid (salt) that calcination process crosses (i.e. pre-treatment) is made into aqueous solution, same calcination process is crossed the carrier impregnation of (i.e. pre-treatment)
In wherein, the time is 12～15h, then is obtained after filtration, drying and after baking.It is miscellaneous many that this infusion process is obtained carrier load type
Sour (salt) catalyst.
Present invention also offers the preparation method (i.e. method for preparing catalyst) of the solid super-strong acid of sulfuric acid, the method is to roast
The solid super-strong acid that burning processed (i.e. pre-treatment) impregnated in concentrated sulphuric acid, the time be 12～15h, then through filter, dry and secondary
It is obtained after roasting.This infusion process is obtained the solid super acid catalyst of sulfuric acid.
In foregoing method for preparing catalyst, the pre-treatment roasting of the solid super-strong acid of heteropoly acid (salt) or sulfuric acid
Temperature is 200～500 DEG C, preferably 300～400 DEG C, and the time is 4～10h, preferably 6～8h.
In foregoing method for preparing catalyst, described drying refers to that gained catalyst is dried at normal pressure and 100～150 DEG C
1～4h, preferably 2～3h.
In foregoing method for preparing catalyst, the after baking temperature of gained catalyst is 200～500 DEG C, preferably
300～400 DEG C, the time is 1～5h, preferably 2～3h.
The benzene nitration method being provided according to the present invention, after in tank reactor, nitration reaction terminates, cooling, filtration separation is catalyzed
Agent, and gas chromatographic analysiss are carried out to product, calculate the conversion ratio of benzene and the selectivity of product with internal standard method.
In the nitration method of the application, the reactor used in benzene nitration reaction is usually closed reactor, preferably right and wrong
Tubular reactor, more preferably pressure autoclave type reactor or autoclave.Preferably, above-described reactor be one airtight
Formula reactor (non-ducted reactor) as pressure autoclave type reactor or autoclave, or two or three or four or five or
Six or seven or eight or closed reactor such as pressure autoclave type reactor or the autoclave of more series connection.Or in addition,
Reactor used in step (a) is closed reactor, such as tubular reactor.Above-described reactor is preferably by not
Rust steel making.Reactor described here be preferably tubular reactor or tower reactor or single kettle type reactor or
Multi-continuous stirred tank reactor etc..
Preferably, mixed using mixing apparatus (as stirring paddle or stirring rod) in above-described nitrator, for example right
For non-ducted reactor using dynamic mixing device such as stirring paddle or stirring rod or for tubular reactor using static mixed
Conjunction equipment or static mixer.
When reactor used in nitration reaction is a reactor, the method for the present invention can be carried out in a batch mode.When
Reactor used in nitration reaction is two or three or four or five or six or seven or eight or more series connection are anti-
Answer device (as pressure tank reactor or autoclave), or during tubular reactor, the method for the present invention can be with semicontinuous side
Formula or continuation mode are carried out.
Preferably, in the benzene nitration method of the present invention, " under liquid phase or liquid phase state, carrying out nitration reaction " refer to by
Liquid NOxMix with benzene (for example by liquid NOxIt is dissolved in benzene), enter at elevated temperatures and in stirring or under being sufficiently mixed
Row nitration reaction.
" under liquid phase state " described herein refers to existing liquid reaction mixture in reactor, simultaneously in reaction mixing
Exist on the top of thing or liquid level gas phase (containing or mainly contain NO gas produced by reaction).
Preferably, in above-described nitration reaction step, by liquid NOxLess than 20 DEG C, preferably shorter than 15 DEG C of (examples
As less than 5 DEG C) at a temperature of be dissolved in benzene formation reactant mixture.Preferably, the reactant mixture being formed is in airtight reaction
Reacted at the temperature (reaction temperature as described above) raising in device.
In the method for application, by NO before reactions or when reaction startsx(for example lower temperature as less than 20 DEG C, preferably low
In 15 DEG C or less than 5 DEG C) under) it is dissolved in formation liquid reaction mixture in benzene, then in closed reactors in the temperature raising
Degree is lower to be continued to be reacted in the form of liquid mixture, especially during the course of the reaction or be sufficiently mixed while reaction or
Stirring.Pressure in this application or pressure refer to absolute pressure (unit：Atmospheric pressure or MPa).
By react in (a) step the gas phase obtaining send in NO oxidation reactor with O2React so as in NO change
NOxTo recycle.
Advantages of the present invention：
1st, in the application, NOx consumption is little, and NOx can recycle, and produced reduzate NO, by joining
Oxygen can generate NOx again and recycle.
2nd, do not produce spent acid in the application, and product can be easily separated, catalyst also can be easily separated and reuses, and catalyst
Such a anhydrous system show stable, the spent acid waste water of generation is few.
Specific embodiment
Following examples are intended to the present invention is described, rather than limitation of the present invention.
Embodiment 1：Weigh 2.5g benzene and 7.37gNO2(mol ratio is 1:5) it is placed in the sealable tank reactor of 100ml (i.e.
The autoclave of stainless steel making) in, reaction pressure is 0.15 MPa, after reaction 6h at 90 DEG C, cooling, and reaction is produced
Thing carries out gas chromatogram internal standard analysis, and the conversion ratio obtaining benzene is 37.1%, and nitro benzene selective is 90.4%.
Embodiment 2：With embodiment 1, difference is reactions steps, adds 0.2g HPW/MCM-41 to urge in a kettle.
(using infusion process preparation, the load capacity of phosphotungstic acid HPW is 30% to agent, and calcination for activation temperature is 400 DEG C, soak time
For 3h), the conversion ratio obtaining benzene is 58.7%, and the selectivity of mononitro-benzene is 98.2%.
Embodiment 3：With embodiment 1, difference is reactions steps, and nitrating agent is N2O3, the conversion ratio obtaining benzene is 27.5%,
The selectivity of Nitrobenzol is 89.2%.
Embodiment 4：：With embodiment 1, difference is reactions steps, and nitrating agent is N2O5, the conversion ratio obtaining benzene is
31.58%, the selectivity of Nitrobenzol is 87.59%.
Embodiment 5：With embodiment 1, difference is reactions steps, benzene and NO2Mol ratio is 1:3, obtain benzene conversion ratio
For 15.5%, nitro benzene selective is 90.2%.
Embodiment 6：With embodiment 1, difference is reactions steps, and reaction temperature is 120 DEG C, and the conversion ratio obtaining benzene is
46.4%, the selectivity of Nitrobenzol is 67.0%.
Embodiment 7：With embodiment 1, difference is reactions steps, adds phosphomolybdic acid (HPMo) catalysis in a kettle.
Agent, the conversion ratio obtaining benzene is 43.5%, and the selectivity of Nitrobenzol is 93.2%.
Embodiment 8：With embodiment 1, difference is reactions steps, adds ammonium phosphotungstate (AMPW) to urge in a kettle.
Agent, the conversion ratio obtaining benzene is 41.6%, and the selectivity of Nitrobenzol is 93.6%.
Embodiment 9：With embodiment 1, difference is reactions steps, adds SO in a kettle.4 2-/ vpo catalyst, obtains
Conversion ratio to benzene is 60.2%, and the selectivity of Nitrobenzol is 95.8%.
Embodiment 10：With embodiment 1, difference is reactions steps, and the response time is 8h, and it obtains the conversion ratio of benzene and is
37.3%, the selectivity of mononitro-benzene is 89.9%.
Embodiment 11：With embodiment 2, difference is reactions steps, and the response time is 8h, and the conversion ratio obtaining benzene is 73.4%,
The selectivity of Nitrobenzol is 98.8%.
Embodiment 12：With embodiment 1, difference is reactions steps, adds 0.2g SO in a kettle.4 2-/WO3Catalysis
Agent, the conversion ratio obtaining benzene is 58.0%, and the selectivity of Nitrobenzol is 98.9%.
Embodiment 13：With embodiment 1, difference is reactions steps, adds 0.2g SO in a kettle.4 2-/MoO3-WO3,
The conversion ratio obtaining benzene is 55.6%, and the selectivity of Nitrobenzol is 97.3%.
Embodiment 14：With embodiment 1, difference is reactions steps, adds 0.2g SO in a kettle.4 2-/WO3- VPO,
The conversion ratio obtaining benzene is 68.3%, and the selectivity of Nitrobenzol is 96.4%.
Embodiment 15：With embodiment 1, difference is reactions steps, and reaction pressure is 0.3 MPa, obtains the conversion of benzene
Rate is 43.8%, and the selectivity of Nitrobenzol is 97.9%.
Embodiment 16：With embodiment 2, difference is reactions steps, the sintering temperature in the after baking activation of catalyst
For 300 DEG C, the conversion ratio obtaining benzene is 53.2%, and the selectivity of Nitrobenzol is 97.6%.
Embodiment 17：With embodiment 2, difference is reactions steps, and the time of the after baking activation of catalyst is 1h,
The conversion ratio obtaining benzene is 30.9%, and the selectivity of Nitrobenzol is 96.5%.
Embodiment 18：With embodiment 2, difference is reactions steps, adds the vanadium phosphorus of 0.2g activation processing in a kettle.
Oxygen complex Cu-VPO (the calcination for activation temperature of wherein complex is 400 DEG C, and soak time is 3h), obtains the conversion ratio of benzene
For 42.4%, the selectivity of mononitro-benzene is 92.2%.
Embodiment 19：With embodiment 2, difference is reactions steps, adds the vanadium phosphorus of 0.2g activation processing in a kettle.
Oxygen complex Co-AlVPO (the calcination for activation temperature of wherein complex is 400 DEG C, and soak time is 3h), obtains the conversion of benzene
Rate is 43.5%, and the selectivity of mononitro-benzene is 93.4%.
Claims (10)
1. the method preparing Nitrobenzol from benzene, the method comprises the following steps：
(a) nitration reaction：Solid in the carrier load type heteropoly acid as solid acid catalyst or heteropolyacid salt or sulfuric acid
In the presence of super acids, by benzene and NO in closed reactorxOr NOxWith O2Mixture under liquid phase or liquid phase state
Carry out nitration reaction, obtain Nitrobenzol, wherein NOxFor meeting 1<x<In 3 nitrogen oxides any one or two or more
Mixture, wherein reactant benzene and NOxMol ratio be 1:1～1:20th, it is preferably 1:1～1:10th, more preferably 1:1～1:5、
More preferably 1:1～1:3；
B () separates：It is isolated by filtration out catalyst and oil phase is purified, obtain Nitrobenzol.
2. method according to claim 1, wherein said heteropoly acid is phosphotungstic acid and the phosphomolybdic acid with structure with Keggin
One or more of.
3. method according to claim 1 and 2, wherein said heteropolyacid salt is in ammonium phosphotungstate and ammonium phosphomolybdate
Plant or multiple mixture.
4. the method according to any one of claim 1-3, the solid super-strong acid of wherein said sulfuric acid is to be selected from
In 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 or more of-VPO；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-/TiO2One or more of-VPO.
5. the method according to any one of claim 1-4 is it is characterised in that described catalyst carrier is：Molecular sieve
Class, such as MCM-41, SBA, HZSM-5, modified mordenite, Y zeolite or modified Y zeolite；Al2O3；Activated carbon；
Silica gel；Meerschaum；Or clay class；Preferably, catalyst carrier is molecular sieve MCM-41, molecular sieve SBA or molecular sieve
HZSM-5.
6. the method according to any one of claim 1-5, wherein carrier load type heteropoly acid or heteropolyacid salt are to pass through
Following method for preparing catalyst is obtained：The heteropoly acid that cross calcination process or heteropolyacid salt are made into aqueous solution, by same roasting
The carrier impregnation processing in wherein (such as dip time be 12～15h), then through filtering, being dried and after baking, prepared carrier
Carried heteropoly acid or heteropolyacid salt catalyst；Or
The solid super-strong acid of wherein sulfuric acid is obtained by following method for preparing catalyst：The solid that calcination process is crossed
Super acids impregnated in (such as dip time is 12～15h) in concentrated sulphuric acid, then through filtering, being dried and after baking, prepared sulphuric acid promotees
The solid super acid catalyst entering.
7. method according to claim 6, wherein after baking refers to：At 200 DEG C～500 DEG C, preferred 300-450 DEG C
At a temperature of calcination activation process.
8. the method according to any one of claim 1-7 it is characterised in that：Reaction temperature is at 20 DEG C～160 DEG C,
Preferably 40 DEG C～140 DEG C, more preferably 60 DEG C～120 DEG C, more preferably 70 DEG C～110 DEG C, further preferred 80 DEG C～100 DEG C.
9. the method according to any one of claim 1-8 it is characterised in that：Step 1) nitration reaction pressure be
1.12 atmospheric pressure -5MPa, preferably 1.15 atmospheric pressure -4MPa, more preferably 1.2 atmospheric pressure -3MPa, further preferred 1.25 air
Pressure -2.5MPa, further preferred 0.5-1.5MPa, 0.8-1.3MPa, 0.9-1.25MPa, 1.09-1.20MPa, such as 1.18,
Carry out under the pressure of 1.13MPa；For example, reaction pressure is 1.12 atmospheric pressure～10 atmospheric pressure (absolute pressure), preferably 1.12
Atmospheric pressure～4 atmospheric pressure (absolute pressure).
10. the method according to any one in claim 1-9, wherein the method are to enter in a batch, semi-continuous or continuous manner
Row；And/or
Wherein closed reactor is by the autoclave of stainless steel making or tubular reactor.
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