CN103304366A - Catalytic synthesis process of diphenylmethane - Google Patents
Catalytic synthesis process of diphenylmethane Download PDFInfo
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- CN103304366A CN103304366A CN2013102178536A CN201310217853A CN103304366A CN 103304366 A CN103304366 A CN 103304366A CN 2013102178536 A CN2013102178536 A CN 2013102178536A CN 201310217853 A CN201310217853 A CN 201310217853A CN 103304366 A CN103304366 A CN 103304366A
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Abstract
The invention relates to a catalytic synthesis process of diphenylmethane. The diphenylmethane is prepared through a condensation reaction in the presence of various solid acid catalysts by taking benzene and formaldehyde as raw materials. The weight ratio of the benzene to formaldehyde is 10/1-5/1, the reaction conditions are as follows: the product dimethyl diphenylmethane is obtained by reacting for 3-6 hours at the temperature of 140-180 DEG C. The method for preparing the catalyst comprises the following steps: mixing niobium pentoxide and potassium hydroxide, fully grinding, and roasting in a crucible to obtain a melt; and adding deionized water into the melt for filtering, transferring the filtrate into a beaker, stirring, respectively dripping phosphoric acid and nitric acid, sulfuric acid or glacial acetic acid into the beaker so as to regulate the pH of the system, standing, filtering, performing hot-water washing on the filter cake, drying at the temperature of 100 DEG C for 24 hours, and preparing niobic acid to be used for the catalytic reaction, wherein the niobic acid catalyst prepared by sulfuric acid pickling has the highest catalytic activity. The production process is simple, the catalytic activity is high, the catalyst can be repeatedly utilized, the aftertreatment is convenient, and industrial wastewater is avoided.
Description
Technical field
The present invention relates to a kind of catalysis synthesizing technology and the catalyzer that relates to and method for preparing catalyst that utilizes benzene and formaldehyde cleaning synthesizing diphenyl methane, more particularly, be a kind of benzene and formaldehyde clean synthesizing diphenyl methane under Niobic Acid agent effect synthesis technique.
Background technology
Ditane (Diphenylmethane is called for short DPM) is commonly called as artificial musk's leaf oil, is colourless acicular crystal under the normal temperature, has the fragrance of strong Oleum Pelargonii Graveolentis and sweet orange oil, is the important spices of a class, dyestuff and pharmaceutical intermediate.In pharmacy, Fine Chemical Industry, use as the important intermediate feed of a class: pharmaceutically be widely used in producing diphenhydramine hydrochloride etc.; Be often used as the synergistic agent of agricultural chemical insecticide on the fine chemistry industry or be used as the thermostability that additive changes polyester and burner oil.
Produce a large amount of benzene in the petrochemical process, the ditane that generates high added value through Fu-Ke (Friedel-Crafts) alkylated reaction has become one of important channel of benzene deep processing and utilization.At present, industrial employing benzene and Benzyl Chloride generate ditane through the F-C alkylation under suitable reaction condition and katalysis.This process is mainly used liquid acid and strong solid acid catalyst, as sulfuric acid, hydrofluoric acid, aluminum chloride and zinc chloride etc.The selectivity of ditane is not high on the one hand, has problems such as corrosive equipment, contaminate environment, product aftertreatment technology complexity on the other hand in the use.The researchist has carried out a large amount of research to ditane synthetic catalyst and catalytic process.Patent CN200310109813.6 discloses the method that a kind of environmental friendliness catalyzes and synthesizes ditane, as catalytic carrier load zinc chloride, utilizes benzene and Benzyl Chloride to prepare ditane with the cotton No. 2 clay-SA01 in the Hangzhoupro of modification.The process for catalytic synthesis of the disclosed ditane of patent CN200510010070.6 utilizes benzene and Benzyl Chloride to be raw material, adds ionic-liquid catalyst and obtains ditane.Patent CN200910021708.4 discloses a kind of preparation method of the solid acid catalyst for the preparation of ditane, adopted attapulgite clay as carrier, handle zinc chloride or aluminum chloride on the back loading through sulfuric acid acidation, again this catalyzer is prepared ditane for benzene and Benzyl Chloride.Patent CN201010547100.8 discloses a kind of Catalysts and its preparation method of synthesizing diphenyl methane, and the catalyzer of employing is the metal phosphate catalyst system, through benzene and Benzyl Chloride alkyl generation ditane.
Adopting Benzyl Chloride in traditional ditane synthetic route is raw material, and generating has hydrochloric acid by-product; The catalyzer of Cai Yonging often produces the disadvantageous muriate of environment simultaneously, and post-processing step is many.Therefore; adopting benzene and formaldehyde is that (by product of this reaction has only water to the direct condensation reaction generation of raw material ditane; shown in chemical formula one), the solid acid catalyst that employing can reuse is catalyzer, this technology has important meaning to synthetic cost and environment protection aspect.
It is that the direct condensation reaction generation of raw material ditane studies in great detail to benzene and formaldehyde that Hou Zhaoyin etc. have adopted various acid catalysts.Comprising mineral acid as H
2SO
4, HNO
3And H
3PO
4Organic acid: tosic acid (PTS), CF
3COOH and Sc (CF
3SO
3)
3Solid acid: zeolite molecular sieve such as HY, H-ZSM-5 and β-zeolite; Heteropolyacid (phospho-wolframic acid, phospho-molybdic acid, silicotungstic acid), acidic cs salts of heteropolyacid; Organic resin: Aciplex-SiO
2, Nafion-H, Nafion-SiO
2With Amberlyst etc.Aciplex-SiO wherein
2Show better catalytic activity with heteropolyacid.But this type of catalyzer price is high, and production cost is higher.
Summary of the invention
The present invention is directed to Benzyl Chloride reaction generation hydrochloric acid by-product in the existing technology, the high burn into of liquid strong acid catalyst is difficult to be separated and problem such as purifying technique complexity, purpose provide a kind of reaction process simply, environmental protection, the ditane catalysis synthesizing technology of clean and effective and the Catalysts and its preparation method of employing.
Concrete technical scheme of the present invention is as follows:
Concrete catalysis synthesizing technology is as follows:
With benzene and formaldehyde as raw material, its consumption weight ratio is 20/1-2/1, and reaction conditions is: under 100-200 ℃ temperature, the reaction times was at 1-8 hour, intermittent type one step condensation reaction is synthesized under the effect of catalyzer, and catalyzer and reactant consumption weight ratio are 1/50-1/5.
Step of condensation of the present invention is:
(1) benzene and formaldehyde are joined in the reactor, the consumption mole ratio of benzene and formaldehyde is 20/1-2/1;
(2) add catalyzer, the amount ratio 1/50-1/5 of catalyzer and formaldehyde, stirs, under 100-200 ℃ temperature as protective atmosphere with high pure nitrogen, reacts 1-8 hour, and the product that obtains adding oil of mirbane carries out the transformation efficiency analysis as interior mark at GC; The post catalyst reaction centrifugation can be reused after the catalyst recovery;
(3) reaction product is carried out rectifying, unreacted benzene can reclaim the back and reuse;
(4) add solid phase prod after the anhydrous alcohol solution rectifying, rectification under vacuum repeatedly again can obtain the product ditane.
Ditane catalyst for synthesizing that the present invention adopts and preparation method thereof, employing be the Niobic Acid agent of multiple mineral acid acidifying Niobium Pentxoxide preparation.
Ditane synthetic catalyst preparation process of the present invention is:
(1) 200-500 is restrained Niobium Pentxoxide and 300-600 gram potassium hydroxide and mix back fully grinding in agate mortar;
(2) place place it in behind the crucible retort furnace 350-550 ℃ roasting 3-6 hour melt;
(3) add deionized water in the melt and carry out suction filtration, change filtrate over to 5000 ml beakers, stir and in beaker, drip phosphoric acid, nitric acid or sulfuric acid regulation system pH to 0.5-1.5 respectively simultaneously, add Glacial acetic acid and regulate pH to 3.0-6.0, leave standstill suction filtration after 0.5-2 hour, and with 2000 milliliters of hot water washing leaching cake repeatedly;
(4) 100 ℃ were dried by the fire 24 hours, and roasting made niobic acid in 3 hours in 200-500 degree retort furnace, packed in moisture eliminator standby.
Prepared Niobic Acid agent can directly apply to benzene and formaldehyde cleaning synthesizing diphenyl methane,
Preferred Niobium Pentxoxide amount is the 300-400 gram among the described solid acid catalyst preparation technology of the present invention; Preferred potassium hydroxide amount is the 400-500 gram; Preferred muffle furnace is 400-500 ℃ of roasting 1-5 hour; Preferably phosphoric acid, nitric acid or sulfuric acid regulation system pH to 0.5-1, Glacial acetic acid is regulated pH to 4.0-5.0; Preferably leave standstill suction filtration after 1-2 hour; Preferably roasting makes niobic acid in 300-400 degree retort furnace;
Described solid acid catalyst of the present invention is Niobium Pentxoxide, the agent of phosphoric acid pickling Niobic Acid, the agent of nitric acid acidwashing Niobic Acid, the agent of sulfuric acid washing Niobic Acid and the agent of acetic acid pickling Niobic Acid.
The Niobic Acid agent that preferred solid acid catalyst of the present invention is sulfuric acid washing.
The raw material of described formaldehyde of the present invention is formalin, trioxane and Paraformaldehyde 96.
The raw material of described formaldehyde of the present invention is preferably trioxane.
The preferable amount mole ratio of described benzene of the present invention and formaldehyde is 10/1-5/1.
The preferable amount of described catalyzer of the present invention and formaldehyde is than 1/20-1/5,
Condensation reaction preferable reaction temperature of the present invention is 140-180 ℃, reaction times 3-6 hour.
Beneficial effect of the present invention is as follows:
Adopt catalyzing and synthesizing of benzene and the direct condensation prepared ditane of formaldehyde, inorganic pickling niobic acid has very high activity and reuses activity as catalyzer, can recycle.This technology is a kind of environmental protection, the green catalysis synthesis technique of ditane efficiently.
The direct condensation of chemical formula one benzene and formaldehyde generates ditane
Embodiment
Embodiment 1
400 gram Niobium Pentxoxides and 560 gram potassium hydroxide are mixed the back in agate mortar, fully grind, place place it in behind the nickel crucible 450 ℃ of roastings of retort furnace 4 hours melt.
Add deionized water in the melt and carry out suction filtration, change filtrate over to 5000 ml beakers, stir and in beaker, drip phosphoric acid, nitric acid or sulfuric acid regulation system pH to 1 respectively simultaneously, add Glacial acetic acid and regulate pH to 5, leave standstill suction filtration after 1 hour, and with 2000 milliliters of hot water washing leaching cake repeatedly, 100 ℃ of bakings made niobic acid in 24 hours, packed in moisture eliminator standby.The niobic acid called after B that obtains according to different mineral acid kinds wherein, C, D, E, and raw material Niobium Pentxoxide called after A.
Table one, Niobium Pentxoxide and different mineral acids prepare niobic acid
Embodiment 2
In 10 liters of three-necked bottles that have reflux condensation mode and a water trap, add 4 liters of benzene and 270 Ke trioxanes, add again and place the standby Niobium Pentxoxide catalyzer of moisture eliminator 100 grams in advance, charge into N
2Protect.Temperature of reaction is 150 ℃, and the reaction times is 5 hours.
With reaction product and catalyzer centrifugation, catalyst recovery can be reused.
Reaction solution carries out rectification under vacuum, unreacted benzene can reclaim the back and reuse; With the solid phase prod after the dissolve with ethanol rectifying, rectification under vacuum twice repeatedly again can obtain solid phase prod 72.73 grams.Identify that through chromatogram, mass spectrum, infrared and nucleus magnetic resonance products obtained therefrom is ditane, according to chromatogram as a result the total recovery of counting yield ditane be 4.81% (be benchmark with the formaldehyde total amount in the raw material).The gained result as shown in Table 2.
Embodiment 3
According to the same reaction conditions (150 ℃, 5 hours) of embodiment 2, raw material is formed (4 liters of, trioxanes of benzene, 270 grams) and separating step, and catalyzer is selected B successively for use, C, D, E, the yield of the product ditane that obtains as shown in Table 2:
The yield of benzene and the direct synthesizing diphenyl methane of first under table two, the different pickling Niobic Acid agent effect
Embodiment 4
According to the same reaction conditions (150 ℃, 5 hours) of embodiment 2, raw material is formed (4 liters of, trioxanes of benzene, 270 grams) and separating step, catalyzer is selected the D catalyzer of roasting under the differing temps for use, investigated 200 successively, 300, the yield of ditane under the catalyst action of 400 and 500 degree roastings, gained the results are shown in Table three:
The yield of ditane under table three, the differing temps roasting D catalyst action
Embodiment 5
According to the same reaction conditions (5 hours) of embodiment 2, raw material is formed (4 liters of, trioxanes of benzene, 270 grams) and separating step, has investigated successively and has adopted the D catalyzer (100 ℃ of different temperature of reaction, 120 ℃, 140 ℃, 160 ℃ and 180 ℃) yield of ditane down, gained the results are shown in Table four:
The yield of benzene and the direct synthesizing diphenyl methane of formaldehyde under table four, the differential responses temperature
Embodiment 6
According to the same reaction conditions (150 ℃) of embodiment 2, raw material is formed (4 liters of, trioxanes of benzene, 270 grams) and separating step, investigated the yield of (3 hours, 4 hours, 5 hours, 6 hours and 7 hours) employing D catalyst synthesizing diphenyl methane under the different reaction times successively, gained the results are shown in Table five:
The yield of table five, different generated time benzene and the direct synthesizing diphenyl methane of formaldehyde
Embodiment 7
According to the same reaction conditions (150 ℃, 5 hours) of embodiment 2, raw material is formed (4 liters of, trioxanes of benzene, 270 grams) and separating step, the yield of ditane when investigating the D catalyzer and reusing for 5 times.Gained the results are shown in Table six:
Table six, D catalyzer are reused active
Comparative Examples 1
According to embodiment 2 similar reaction conditionss (150 ℃, 5 hours), change raw material and consist of 4 liters of benzene, utilize formalin solution (1 liter of 27% solution) or Paraformaldehyde 96 (polymerization degree is 1000) 270 grams, adopt identical separating step, the yield of ditane when investigating the use of D catalyzer.Gained the results are shown in Table seven:
The activity of table seven, different formaldehyde raw material synthesizing diphenyl methanes
Claims (9)
1. simple, the environmental protection of a reaction process, the ditane catalysis synthesizing technology of clean and effective and the Catalysts and its preparation method of employing, it is characterized in that adopting benzene and formaldehyde condensation to prepare ditane, wherein catalyzer is the Niobic Acid agent that different mineral acid pickling prepare.
Benzene and formaldehyde cleaning synthesizing diphenyl methane, concrete catalysis synthesizing technology is as follows:
As raw material, its consumption weight ratio is 20/1-2/1 with benzene and formaldehyde, and reaction conditions is: under 100-200 ℃ temperature, the reaction times is at 1-8 hour, amount ratio 1/50-1/5 under the effect of catalyzer, and intermittent type one step condensation reaction is synthetic.
Step of condensation of the present invention is:
(1) benzene and formaldehyde are joined in the reactor, the consumption mole ratio of benzene and formaldehyde is 20/1-2/1;
(2) add catalyzer, the amount ratio 1/50-1/5 of catalyzer and formaldehyde, stirs, under 100-200 ℃ temperature as protective atmosphere with high pure nitrogen, reacts 1-8 hour, and the product that obtains adding oil of mirbane carries out the transformation efficiency analysis as interior mark at GC; The post catalyst reaction centrifugation can be reused after the catalyst recovery;
(3) reaction product is carried out rectifying, unreacted benzene can reclaim the back and reuse;
(4) add solid phase prod after the anhydrous alcohol solution rectifying, rectification under vacuum repeatedly again can obtain the product ditane.
2. as follows according to the described prepared mineral acid acidifying Niobic Acid agent preparation process of claim 1:
(1) 200-500 is restrained Niobium Pentxoxide and 300-600 gram potassium hydroxide and mix back fully grinding in agate mortar;
(2) place place it in behind the crucible retort furnace 350-550 ℃ roasting 3-6 hour melt;
(3) add deionized water in the melt and carry out suction filtration, change filtrate over to 5000 ml beakers, stir and in beaker, drip phosphoric acid, nitric acid or sulfuric acid regulation system pH to 0.5-1.5 respectively simultaneously, add Glacial acetic acid and regulate pH to 3.0-6.0, leave standstill suction filtration after 0.5-2 hour, and with 2000 milliliters of hot water washing leaching cake repeatedly;
(4) 100 ℃ were dried by the fire 24 hours, and roasting made niobic acid in 3 hours in 200-500 degree retort furnace, packed in moisture eliminator standby.
3. the raw material according to the described formaldehyde of the present invention of claim 1 is formalin, trioxane and Paraformaldehyde 96.
4. the raw material according to the described formaldehyde of the present invention of claim 3 is preferably trioxane.
5. the preferable amount mole ratio according to the described benzene of the present invention of claim 1 and formaldehyde is 10/1-5/1.
6. the preferable amount according to the described catalyzer of the present invention of claim 1 and formaldehyde compares 1/20-1/5.
7. be 140-180 ℃ according to the described condensation reaction preferable reaction temperature of the present invention of claim 1, reaction times 3-6 hour.
8. be Niobium Pentxoxide, the agent of phosphoric acid pickling Niobic Acid, the agent of nitric acid acidwashing Niobic Acid, the agent of sulfuric acid washing Niobic Acid and the agent of acetic acid pickling Niobic Acid according to the described solid acid catalyst of the present invention of claim 2.The Niobic Acid agent that preferred solid acid catalyst of the present invention is sulfuric acid washing.
9. be the 300-400 gram according to preferred Niobium Pentxoxide amount among the described solid acid catalyst preparation technology of the present invention of claim 2; Preferred potassium hydroxide amount is the 400-500 gram; Preferred muffle furnace is 400-500 ℃ of roasting 4-5 hour; Preferably phosphoric acid, nitric acid or sulfuric acid regulation system pH to 0.5-1, Glacial acetic acid is regulated pH to 4.0-5.0; Preferably leave standstill suction filtration after 1-2 hour; Preferably roasting makes niobic acid in 300-400 degree retort furnace.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253413A (en) * | 2020-02-27 | 2020-06-09 | 北京石油化工学院 | Preparation method of isosorbide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0135145A2 (en) * | 1983-08-17 | 1985-03-27 | CBMM Internacional Ltda. | Solid acid catalysts and process of producing the same |
| US4652544A (en) * | 1984-08-21 | 1987-03-24 | Cbmm Internacional Ltda. | Solid acid catalyst of acid-treated hydrated niobium oxide and method for its preparation |
| CN1676498A (en) * | 2005-01-14 | 2005-10-05 | 浙江大学 | Dimethyl diphenyl methane catalytic synthesizing process |
-
2013
- 2013-05-31 CN CN2013102178536A patent/CN103304366A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0135145A2 (en) * | 1983-08-17 | 1985-03-27 | CBMM Internacional Ltda. | Solid acid catalysts and process of producing the same |
| US4652544A (en) * | 1984-08-21 | 1987-03-24 | Cbmm Internacional Ltda. | Solid acid catalyst of acid-treated hydrated niobium oxide and method for its preparation |
| CN1676498A (en) * | 2005-01-14 | 2005-10-05 | 浙江大学 | Dimethyl diphenyl methane catalytic synthesizing process |
Non-Patent Citations (4)
| Title |
|---|
| HOU ZHAOYIN，等: "Catalytic synthesis of diphenylmethane from benzene and formalin with water-tolerant solid acids", 《APPLIED CATALYSIS A：GENERAL》 * |
| 田都浩三，等: "《新固体酸和碱及其催化作用》", 30 November 1992, 化学工业出版社 * |
| 程月红，等: "铌酸的合成与表征", 《工业催化》 * |
| 陈君琴，等: "酸处理对铌酸催化剂性能的影响", 《工业催化》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111253413A (en) * | 2020-02-27 | 2020-06-09 | 北京石油化工学院 | Preparation method of isosorbide |
| CN111253413B (en) * | 2020-02-27 | 2021-07-13 | 北京石油化工学院 | Preparation method of isosorbide |
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Application publication date: 20130918 |