CN101538203B - Method for catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium - Google Patents
Method for catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium Download PDFInfo
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Abstract
The invention discloses a method for catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium, which belongs to the technical field of organic synthesis. In the method, nitric acid with 65 percent of mass fraction concentration is used as a nitrating agent and a reaction is carried out under the conditions of normal pressure and temperature between 60 DEG C and 110 DEG C. The method uses the silicon dioxide loaded with the heteropoly acid ammonium as a catalyst and ensures that a mixed liquor of benzene and the nitric acid is stirred in a kettle type reactor to carry out a benzene nitration reaction, wherein the reaction time is between 1 hour and 7 hours. The method has 100 percent of nitration selectivity, eliminates the unsafe factor that the benzene nitration process generates explosive substances such as multiple nitrobenzene, oxide compounds, and the like and has the characteristics of high yield, reutilization of the catalyst and environmental protection.
Description
Technical field
The present invention relates to a kind of preparation method of mononitro-benzene, specifically, relate to a kind of method of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium, belong to technical field of organic synthesis.
Background technology
Oil of mirbane and other benzene class arene nitro compound are important industrial chemicals; Or important organic solvent; The midbody that can be used as dyestuff, agricultural chemicals and medicine; In particular for producing aniline dyestuff, and two very important midbody mutual-amido two polyanilines developing in recent years and p-aminophenol.
Traditional oil of mirbane industrial process is the nitric acid-sulfuric acid mixed acid process that proposes in 1934, and shortcoming is obvious, the one, need a large amount of sulfuric acid, and produce a large amount of sulfur waste acid and waste water, etching apparatus, contaminate environment; The nitration reaction selectivity is wayward in addition, is prone to produce volatile many nitro-compounds and oxygenatedchemicals.
Along with industrial development; Some new nitration processes have been proposed; Like the adiabatic nitration method of American Cyanamid Company and the joint development of Canadian industrial and the pump circulation nitration processes of Sweden Bofors Nobel Chematur company exploitation; But these methods still use sulfuric acid as catalyzer, not basic etching apparatus, contaminate environment and the nitrated optionally problem of solving.
Be this day disclosure special permission communique (48-18239; 49-18833; 50-4030) propose to be carried on the method that replaces the vitriol oil on the carrier with aromatic sulphonic acid; But this method exists catalyst levels big, and because of byproduct of reaction water is prone to inactivation, and nitrated necessary with concentrated nitric acid more than 90% or nitrosonitric acid.Proposed again afterwards that (JP53-12823) liquid-phase nitration prepares oil of mirbane for JP50-126626, JP51-63134, but nitrification activity is not high, catalyst life short with immersion type catalyzer such as the sulfuric acid of pure aluminium silicate (JP50-121234) and inorganic matter carrier load or phosphoric acid.
Can also adopt the nitric acid or the NO of gasification
2Make nitrating agent.With nitric acid is nitrating agent, and US442006 adopts SiO
2Or Al
2O
3Profit is carried sulfuric acid or phosphoric acid is catalyzer; It is catalyzer that US4418230 adopts mordenite, and the nitration reaction temperature is 200 ℃, and benzene/nitric acid mol ratio is more than 1.4; It is catalyzer that US5324872 and 5334781 adopts H type mordenite and clinoptilolite respectively, and nitrated temperature is 150～170 ℃, benzene/nitric acid mol ratio 2.5, oil of mirbane yield 70～80%.
With NO
2Nitrated for the nitrating agent catalyzed gas, US4347389 uses the P-V-O composite oxide catalysts; US4415744 adopts SO
3Pure aluminium silicate-metal oxide catalyst of handling; EPA0092372 adopts and contains WO at least in addition
3, MoO
3, TiO
2In the acidic mixture formed of one or both MOXs make catalyzer, can reduce and produce nitrated by product; Also have in addition with heteropolyacid, load Phenylsulfonic acid etc. be the vaporphase nitration catalyzer (Journal of OrganicSynthetic Chemical Associate, 1987,45:679); In recent years, the exploitation zeolite [molecular sieve becomes the main direction of benzene and benzene class aromatic nitration technical research, adopts H type mordenite catalyzing N O like US4107220
2Nitrated benzene and benzene class aromatic hydrocarbons, BP2000141 adopts zeolite and crosslinked illiteracy bentonite catalyzer.
With respect to vaporphase nitration, the liquid-phase nitration patent is less, and major cause is not find the effective catalyst that is fit to the liquid-phase nitration reaction.CN101033192A uses one or both metal oxide modified MFI topological framework molecular sieve of Mg, Ca, Sr, Sb, Bi, Mo to be catalyzer; 65% nitric acid is nitrating agent; In tank reactor, 90～110 ℃ of normal pressures, nitric acid/benzene volume ratio 2/1～6/1 is carried out nitration reaction; Or process cylinder or the leafy careless type catalyzer that forms with extruding after pseudo-boehmite mixes by above-mentioned modified molecular screen, and in fixed-bed reactor, 50～80 ℃ of normal pressures, nitric acid/benzene mole is than 2/1～6/1 mixed solution charging air speed, 0.5～4h
-1, carry out liquid-solid nitration reaction.This method one substituted benzene selectivity is 100%, has stopped the unsafe factor in the benzene nitrifying process, and the nitrated transformation efficiency of benzene is more than 70%; But that this method catalyst preparation process comprises is molecular sieve modified, drying and roasting etc., comparatively loaded down with trivial details, and does not provide catalyzer to reuse data.
Summary of the invention
The method that the objective of the invention is to overcome above-mentioned deficiency and a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium is provided; This method mononitration selectivity 100%; Eliminate the benzene nitration processes and generate many oil of mirbane and oxygenatedchemicals etc. and cause the unsafe factor of quick-fried thing, and have that high yield, catalyzer can reuse, the characteristics of environmental protection.
The present invention's technical scheme of taking of dealing with problems is: a kind of method of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium; It is a nitrating agent with massfraction concentration 65% nitric acid; In normal pressure, temperature is to react under 60～110 ℃ of conditions; It is characterized in that it makes catalyzer with loading silicon dioxide with heteropoly acid ammonium, make benzene and nitric acid mixed solution carry out the benzene nitration reaction under in tank reactor, stirring, the reaction times is 1～7h.
The method of described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium, wherein said heteropoly acid ammonium are to belong to the ammonium salt that contains the oxygen polyacid that atom and phosphorus atom mol ratio form at 12: 1 by any one and a kind of phosphoric acid solubility ammonium salt down payment in ammonium molybdate, ammonium tungstate, the ammonium meta-vanadate.
The method of described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium, wherein said titanium pigment acid ammonium salt are primary ammonium phosphate or Secondary ammonium phosphate or ammonium phosphate.
The method of described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium; Wherein said heteropoly acid ammonium is to belong to the ammonium salt that contains the oxygen polyacid that atom and phosphorus atom mol ratio form at 12: 1 by any two kinds in ammonium molybdate, ammonium tungstate, the ammonium meta-vanadate with a kind of phosphoric acid solubility ammonium salt down payment; The mol ratio of two kinds of atoms metals is 1: 11～11: 1, preferred 5: 7～7: 5.
The method of described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium, the charge capacity of wherein said loading silicon dioxide with heteropoly acid ammonium catalyzer counts 1～40%, preferred 5～20% with MOX and silicon-dioxide quality ratio.
The method of described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium, wherein said catalyst levels are that every 10ml benzene adds 0.2～2.0g loading silicon dioxide with heteropoly acid ammonium catalyzer.
The method of described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium, wherein said benzene and nitric acid volume ratio are 1: 1～1: 6, preferred 1: 3～1: 4.
The method of described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium, wherein said stirring is the preferred 2～7h of time of reaction down, most preferably 5h.
The method of described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium; Used loading silicon dioxide with heteropoly acid ammonium Preparation of catalysts method is: tetraethyl silicate is tetraethyl silicate by volume: ethanol: water=1: 1～6: 1～6 wiring solution-formings; At 60～90 ℃ of heating down, heating 10～60min; With in ammonium molybdate, ammonium tungstate, the ammonium meta-vanadate one or both and a kind of phosphoric acid solubility ammonium salt down payment belongs to atom and the phosphorus atom mol ratio is dissolved in deionized water at 12: 1, adding nitric acid, to regulate PH be 1～5,60～90 ℃ of heating down; Heating 1～6h, the alcohol solution adding with pre-heated tetraethyl silicate continues 60～90 ℃ of heating; Occur until gel; Behind ageing 10～36h, dry under 80～130 ℃, can use after the drying.Described titanium pigment acid ammonium salt is primary ammonium phosphate, Secondary ammonium phosphate, ammonium phosphate.
The method of described a kind of loading silicon dioxide with heteropoly acid ammonium catalyst synthesizing nitrobenzene; Used loading silicon dioxide with heteropoly acid ammonium Preparation of catalysts method is preferred: with tetraethyl silicate is tetraethyl silicate by volume: ethanol: water=1: 1～3: 1～3 wiring solution-formings; At 70～85 ℃ of heating down, heating 20～40min; With in ammonium molybdate, ammonium tungstate, the ammonium meta-vanadate one or both and a kind of phosphoric acid solubility ammonium salt down payment belongs to atom and the phosphorus atom mol ratio is dissolved in deionized water at 12: 1, adding nitric acid, to regulate PH be 1～3,70～85 ℃ of heating down; Heating 2～5h with the alcohol solution adding of pre-heated tetraethyl silicate, continues 70～85 ℃ of heating down; Occur until gel; Behind ageing 12～24h, dry under 90～110 ℃, can use after the drying.
The invention has the beneficial effects as follows: the nitrated transformation efficiency of benzene is high, and the mononitro-benzene selectivity is good; Catalyzer is stable especially, prepares easyly, can reuse; Because catalyzer is solid, to react and be solid-liquid reaction, the reaction back is prone to handle, and the easily separated recovery of catalyzer, and reaction system sulfur acid have not solved the problems such as etching apparatus and environmental protection of mixed acid process.
Embodiment
According to method provided by the invention, after nitration reaction finishes in tank reactor, cooling; Filtering separation catalyzer and reaction mixture, catalyzer are reused and are no less than the reaction mixture sat layering 5 times; Separate organic phase, and use deionized water wash, gas chromatographic analysis is carried out in sampling.Analytical data calculates nitrated transformation efficiency and selectivity by following formula:
The nitrated transformation efficiency of benzene=(benzene residual content/benzene add-on in the 1-reaction product) * 100%
One nitrated selectivity of benzene=(in the reaction product in mononitro-benzene amount/reaction product various benzene nitration product total amounts) * 100%
Through following examples the present invention is further described below.
Embodiment 1
With the 100ml tetraethyl silicate is tetraethyl silicate by volume: ethanol: water=1: 2: 2 wiring solution-forming, at 70～80 ℃ of heating 40min; 3.3g ammonium molybdate and 0.18g primary ammonium phosphate are dissolved in deionized water, and adding nitric acid accent PH is 1, at 70～80 ℃ of heating 5h; The alcohol solution of pre-heated tetraethyl silicate is added; Continuation occurs until gel, behind the ageing 12h 70～80 ℃ of heating; In 110 ℃ of dryings, getting charge capacity (in MOX and silicon-dioxide quality ratio) is No. 1,10% silicon dioxide carried ammonium phosphomolybdate catalyst sample.
Embodiment 2
With the 100ml tetraethyl silicate is tetraethyl silicate by volume: ethanol: water=1: 2: 2 wiring solution-forming, at 70～80 ℃ of heating 40min; 3.1g ammonium tungstate and 0.11g primary ammonium phosphate are dissolved in deionized water, and adding nitric acid accent PH is 1, at 70～80 ℃ of heating 5h; The alcohol solution of pre-heated tetraethyl silicate is added; Continuation occurs until gel, behind the ageing 20h 70～80 ℃ of heating; In 110 ℃ of dryings, getting charge capacity is No. 2,10% silicon dioxide carried ammonium phosphowolframate catalyst sample.
Embodiment 3
With the 100ml tetraethyl silicate is tetraethyl silicate by volume: ethanol: water=1: 2: 2 wiring solution-forming, at 70～80 ℃ of heating 40min; 1.75g ammonium meta-vanadate and 1.7g primary ammonium phosphate are dissolved in deionized water, and adding nitric acid accent PH is 1, at 70～80 ℃ of heating 5h; The alcohol solution of above-mentioned tetraethyl silicate is added; Continuation occurs until gel, behind the ageing 30h 70～80 ℃ of heating; In 110 ℃ of dryings, getting charge capacity is No. 3,10% silicon dioxide carried phosphorus ammonium vanadate catalyst sample.
Embodiment 4
Change into 1.65g ammonium molybdate and 0.09g primary ammonium phosphate are dissolved in the deionized water except that 3.3g ammonium molybdate and 0.18g primary ammonium phosphate being dissolved in deionized water, all the other are operated with embodiment 1, charge capacity be No. 4,5% silicon dioxide carried ammonium phosphomolybdate catalyst sample.
Embodiment 5
Change into 6.6g ammonium molybdate and 0.36g primary ammonium phosphate are dissolved in the deionized water except that 3.3g ammonium molybdate and 0.18g primary ammonium phosphate being dissolved in deionized water, all the other are operated with embodiment 1, charge capacity be No. 5,20% silicon dioxide carried ammonium phosphomolybdate catalyst sample.
Embodiment 6
Change into 3.3g ammonium molybdate and 0.2g Secondary ammonium phosphate are dissolved in the deionized water except that 3.3g ammonium molybdate and 0.18g primary ammonium phosphate being dissolved in deionized water, all the other are operated with embodiment 1, charge capacity be No. 6,10% silicon dioxide carried ammonium phosphomolybdate catalyst sample.
Embodiment 7
Change into 6.6g ammonium molybdate and 0.16g ammonium phosphate are dissolved in the deionized water except that 3.3g ammonium molybdate and 0.18g primary ammonium phosphate being dissolved in deionized water, all the other are operated with embodiment 1, charge capacity be No. 7,10% silicon dioxide carried ammonium phosphomolybdate catalyst sample.
Embodiment 8
Transfer PH 1 to change into and add nitric acid to transfer PH be 4 except that adding nitric acid, all the other operates with embodiment 1, must charge capacity be No. 8,10% silicon dioxide carried ammonium phosphomolybdate catalyst sample.
Embodiment 9
Change into 1.65g ammonium molybdate and 1.55g ammonium tungstate and 0.145g primary ammonium phosphate are dissolved in the deionized water except that 3.3g ammonium molybdate and 0.18g primary ammonium phosphate being dissolved in deionized water; All the other operations are with embodiment 1, and getting charge capacity is No. 9,10% silicon dioxide carried P-Mo-Wo acid ammonium catalyst sample.
Embodiment 10
Except that with the 100ml tetraethyl silicate by volume for tetraethyl silicate: ethanol: water=1: 2: 2 wiring solution-forming changes into the 100ml tetraethyl silicate is tetraethyl silicate by volume: ethanol: water=1: 1: 3 wiring solution-forming; All the other operations are with embodiment 1, and getting charge capacity is No. 10,10% silicon dioxide carried ammonium phosphomolybdate catalyst sample.
Embodiment 11
Except that changing into 80～90 ℃ of heating 3h at 70～80 ℃ of heating 5h, all the other operates with embodiment 1, must charge capacity are No. 11,10% silicon dioxide carried ammonium phosphomolybdate catalyst sample.
Embodiment 12
Change into 1.65g ammonium molybdate and 0.88g ammonium meta-vanadate and 0.94g primary ammonium phosphate are dissolved in the deionized water except that 3.3g ammonium molybdate and 0.18g primary ammonium phosphate being dissolved in deionized water; All the other operations are with embodiment 1, and getting charge capacity is No. 12,10% silicon dioxide carried molybdovanaphosphoric acid ammonium catalyst sample.
Embodiment 13
Change into 2.2g ammonium molybdate and 1g ammonium tungstate and 0.16g primary ammonium phosphate are dissolved in the deionized water except that 3.3g ammonium molybdate and 0.18g primary ammonium phosphate being dissolved in deionized water; All the other operations are with embodiment 1, and getting charge capacity is No. 13,10% silicon dioxide carried molybdovanaphosphoric acid ammonium catalyst sample.
Embodiment 14
Add No. 1, the heteropoly acid ammonium catalyst sample of 10g embodiment 1 preparation to the 500ml round-bottomed flask, add 50ml benzene and 150ml65% nitric acid, normal pressure; Controlled temperature is 70～80 ℃, carries out the benzene nitration reaction under in tank reactor, stirring, and the reaction times is 5h; After being cooled to room temperature, filtering separation catalyzer, reaction mixture sat layering; Separate organic phase, and use deionized water wash, the dry product sample that gets.
The contrast experiment 1
In 11 500ml round-bottomed flasks, add the heteropoly acid ammonium catalyst sample respectively No. 1, No. 2, No. 3, No. 4, No. 5, No. 6, No. 7, No. 8, No. 9, No. 10, No. 11 each 10g, ensuing operation such as embodiment 14, final product sampling carrying out gas chromatographic analysis.Experimental result is listed in table 1.
Table 1
| Catalyst sample number | The nitrated transformation efficiency of benzene (%) | Mononitro-benzene selectivity (%) |
| 1 | 92 | 100 |
| 2 | 88 | 100 |
| 3 | 83 | 100 |
| 4 | 69 | 100 |
| 5 | 81 | 100 |
| 6 | 85 | 100 |
| 7 | 78 | 100 |
| 8 | 89 | 100 |
| 9 | 90 | 100 |
| 10 | 79 | 100 |
| 11 | 80 | 100 |
The result can find out from table 1, and loading silicon dioxide with heteropoly acid ammonium catalyzer provided by the invention has higher catalytic activity and single substitution product selectivity to the benzene nitration reaction.
The contrast experiment 2
In each 500ml round-bottomed flask, add 1,5,10 and No. 1,20g catalyst sample respectively, add 50ml benzene and 150ml65% nitric acid, other is operated with embodiment 14.Analyze experimental result and list in table 2.
Table 2
| Catalyst levels (g) | The nitrated transformation efficiency of benzene (%) | Mononitro-benzene selectivity (%) | |
| Comparative example 1 | 1 | 56 | 100 |
| Comparative example 2 | 5 | 79 | 100 |
| Comparative example 3 | 10 | 92 | 100 |
| Comparative example 4 | 20 | 86 | 100 |
The result can find out from table 2, when catalyst levels is low, also can realize the present invention.
The contrast experiment 3
In four 500ml round-bottomed flasks, add the 10g catalyst sample respectively No. 2,50ml benzene, each adds 65% nitric acid 50ml; 100ml, 150ml, 200ml makes benzene in each reaction system/nitric acid volume ratio be respectively 1/1; 1/2,1/3,1/4, other is identical with embodiment 14.Analyze experimental result and list in table 3.
Table 3
| Benzene/nitric acid volume ratio | The nitrated transformation efficiency of benzene (%) | Mononitro-benzene selectivity (%) | |
| Comparative example 5 | 1/1 | 65 | 100 |
| Comparative example 6 | 1/2 | 79 | 100 |
| Comparative example 7 | 1/3 | 88 | 100 |
| Comparative example 8 | 1/4 | 90 | 100 |
The result can find out from table 3, when benzene and nitric acid volume ratio less than 1/3, also can reach the preferable nitrated transformation efficiency of benzene.
The contrast experiment 4
In each 500ml round-bottomed flask, add the 10g catalyst sample respectively No. 9,50ml benzene and 150ml65% nitric acid are regulated and control 70～80 ℃, stir nitration reaction 1h respectively, 3h, 5h and 7h, other is identical with embodiment 14.Analyze experimental result and list in table 4.
Table 4
| Reaction times (h) | The nitrated transformation efficiency of benzene (%) | Mononitro-benzene selectivity (%) | |
| Comparative example 9 | 1 | 52 | 100 |
| Comparative example 10 | 3 | 75 | 100 |
| Comparative example 11 | 5 | 90 | 100 |
| Comparative example 12 | 7 | 93 | 100 |
The result can find out from table 4, when the reaction times is 5h, reaches the best nitrated transformation efficiency of benzene.
The contrast experiment 5
To press embodiment 14 for No. 1 by embodiment 14 catalyst system therefor samples and use four times continuously, and measure transformation efficiency and selectivity at every turn respectively, the result sees table 5.
Table 5:
| The catalyzer access times | The nitrated transformation efficiency of benzene (%) | Selectivity (%) |
| For the first time | 92 | 100 |
| For the second time | 87 | 100 |
| For the third time | 78 | 100 |
| The 4th time | 72 | 100 |
The result can find out from table 5, be repeatedly used catalyzer after, still have the nitrated transformation efficiency of higher benzene.
Claims (7)
1. the method for a catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium; It is a nitrating agent with massfraction concentration 65% nitric acid; In normal pressure, temperature is to react under 60～110 ℃ of conditions; It is characterized in that it makes catalyzer with loading silicon dioxide with heteropoly acid ammonium, make benzene and nitric acid mixed solution carry out the benzene nitration reaction under in tank reactor, stirring, the reaction times is 1～7h; Described heteropoly acid ammonium is to belong to the ammonium salt that contains the oxygen polyacid that atom and phosphorus atom mol ratio form at 12: 1 by any one and a kind of phosphoric acid solubility ammonium salt down payment in ammonium molybdate, ammonium tungstate, the ammonium meta-vanadate; Or described heteropoly acid ammonium is to belong to the ammonium salt that contains the oxygen polyacid that atom and phosphorus atom mol ratio form at 12: 1 by any two kinds in ammonium molybdate, ammonium tungstate, the ammonium meta-vanadate with a kind of phosphoric acid solubility ammonium salt down payment, and the mol ratio of two kinds of atoms metals is 1: 11～11: 1.
2. according to the method for the described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium of claim 1, it is characterized in that described titanium pigment acid ammonium salt is primary ammonium phosphate or Secondary ammonium phosphate or ammonium phosphate.
3. according to the method for the described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium of claim 1; It is characterized in that; When described heteropoly acid ammonium be by in ammonium molybdate, ammonium tungstate, the ammonium meta-vanadate any two kinds with a kind of phosphoric acid solubility ammonium salt down payment belong to that atom and phosphorus atom mol ratio form at 12: 1 contain the ammonium salt of oxygen polyacid the time, the mol ratio of two kinds of atoms metals is 5: 7～7: 5.
4. according to the method for the described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium of claim 1, it is characterized in that the charge capacity of described loading silicon dioxide with heteropoly acid ammonium catalyzer counts 1～40% with MOX and silicon-dioxide quality ratio.
5. according to the method for the described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium of claim 1, it is characterized in that described catalyst levels is that every 10ml benzene adds 0.2～2.0g loading silicon dioxide with heteropoly acid ammonium catalyzer.
6. according to the method for the described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium of claim 1, it is characterized in that described benzene and nitric acid volume ratio are 1: 1～6: 1.
7. according to the method for the described a kind of catalyzing and synthesizing nitrobenzene by loading silicon dioxide with heteropoly acid ammonium of claim 1, it is characterized in that the time of reaction is 2～7h down in described stirring.
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| CN103483204B (en) * | 2011-03-21 | 2014-12-10 | 南通大学 | Preparation method of ethyl 5-nitro salicylate |
| CN102627564A (en) * | 2012-03-25 | 2012-08-08 | 聊城大学 | Green method for nitrifying benzene with nitric acid to prepare nitrobenzen |
| CN104588060B (en) * | 2013-11-03 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of preparing dimethyl ether by dewatering methanol catalyst and preparation method thereof |
| CN105642352B (en) * | 2014-12-02 | 2017-12-08 | 中国石油化工股份有限公司 | The preparation method of heteropoly acid ammonium salt catalyst |
| CN110560084A (en) * | 2018-06-06 | 2019-12-13 | 中国石油化工股份有限公司 | Preparation method and application of nitration catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4772757A (en) * | 1984-03-16 | 1988-09-20 | Bayer Aktiengesellschaft | Process for the production of nitrobenzene |
| US20040024267A1 (en) * | 2002-07-31 | 2004-02-05 | Council Of Scientific And Industrial Research | Process for vapor phase nitration of benzene using nitric acid over molybdenum silica catalyst |
| CN101033192A (en) * | 2006-03-06 | 2007-09-12 | 北京夏一催化技术有限公司 | Method of preparing nitrobenzene from benzene by nitric acid nitrating |
-
2009
- 2009-04-08 CN CN2009100204347A patent/CN101538203B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4772757A (en) * | 1984-03-16 | 1988-09-20 | Bayer Aktiengesellschaft | Process for the production of nitrobenzene |
| US20040024267A1 (en) * | 2002-07-31 | 2004-02-05 | Council Of Scientific And Industrial Research | Process for vapor phase nitration of benzene using nitric acid over molybdenum silica catalyst |
| CN101033192A (en) * | 2006-03-06 | 2007-09-12 | 北京夏一催化技术有限公司 | Method of preparing nitrobenzene from benzene by nitric acid nitrating |
Non-Patent Citations (4)
| Title |
|---|
| 方东等.芳香族化合物绿色硝化反应研究进展.《含能材料》.2008,第16卷(第1期),103-113. * |
| 金明善等.负载型杂多酸催化剂用于硝基苯的催化合成.《分子催化》.2007,第21卷 * |
| 韩岩淘等.负载型杂多酸催化苯硝化反应研究.《精细石油化工》.2005,(第5期),1-4. * |
| 龚树文等.活性炭负载磷钼钨杂多酸催化苯的硝化反应研究.《工业催化》.2008,第16卷229-231. * |
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