CN102463124A - Method for preparing phenol from benzene by one-step method - Google Patents
Method for preparing phenol from benzene by one-step method Download PDFInfo
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- CN102463124A CN102463124A CN2010105430370A CN201010543037A CN102463124A CN 102463124 A CN102463124 A CN 102463124A CN 2010105430370 A CN2010105430370 A CN 2010105430370A CN 201010543037 A CN201010543037 A CN 201010543037A CN 102463124 A CN102463124 A CN 102463124A
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- active carbon
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- activated carbon
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 48
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000003245 coal Substances 0.000 claims abstract description 54
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 41
- 239000012153 distilled water Substances 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 24
- 238000000967 suction filtration Methods 0.000 claims abstract description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 65
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- 229910021655 trace metal ion Inorganic materials 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 5
- 238000002803 maceration Methods 0.000 claims description 4
- 239000003643 water by type Substances 0.000 claims description 3
- 238000010306 acid treatment Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract 1
- 150000002505 iron Chemical class 0.000 abstract 1
- 238000002386 leaching Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 239000008399 tap water Substances 0.000 abstract 1
- 235000020679 tap water Nutrition 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing phenol by a benzene one-step method; the catalyst takes coal-based activated carbon as a carrier and takes iron salt as an active component, and the carrier is treated as follows: adding 100g of coal-based activated carbon washed by water into a flask, adding 250mL of nitric acid solution with the concentration of 2-12 mol/L, and connecting with a condenser pipeRefluxing in 25-90 deg.C water bath for 10 hr, and treating with NaOH or Na2CO3Absorbing tail gas by the solution, fully washing the coal-based activated carbon by tap water until the pH value is unchanged, leaching the coal-based activated carbon by using distilled water for three times, filtering, and drying the coal-based activated carbon in a constant-temperature drying oven at 110 ℃; using Fe with a concentration of 0.04-0.20 mol/L2(SO4)3Soaking 20-50 mL of aqueous solution into the coal-based activated carbon, standing at room temperature for 0.5-24 hours, then performing suction filtration, and drying in a constant-temperature drying oven at 110 ℃; the catalyst has high activity, high selectivity and high stability, reduces the production cost and improves the product quality.
Description
Technical field
The present invention relates to a kind of method for preparing phenol by the benzene one-step method.
Background technology
Phenol is important basic Organic Chemicals, and is of many uses in industry.At present, produce phenol in the industry and mainly adopt the isopropylbenzene process, that is: benzene alkylation obtains isopropylbenzene, cumene oxidation obtains dicumyl peroxide, dicumyl peroxide decomposition generation phenol.This reaction scheme is long, energy consumption of reaction is big, phenol yield is low, have the intermediate product (THE AUTOXIDATION OF CUMENE product) that is prone to blast; And produce accessory substance acetone with the phenol equimolar amounts; And the demand of acetone is much smaller than phenol, so the processing of acetone is a big problem.In addition, need in the three-step reaction to add acid and multiple organic reagent, cause the severe contamination of the wasting of resources, operation inconvenience and environment, do not meet STRATEGIES OF SUSTAINABLE DEVELOPMENT.In recent years; The single step reaction that directly benzene hydroxylation is prepared phenol has attracted various countries researchers' extensive concern; Wherein adopting hydrogen peroxide solution is a kind of clean preparation method that the route of oxidant direct oxidation hydroxylation of benzene synthesizing phenol is considered to be hopeful most to replace cumene method, also is the emphasis of various countries' research always.This technology does not adopt on phenol market at present as yet.Mainly through the effect of certain catalyst, directly with benzene catalytic oxidation synthesizing phenol, its unique side product is a water with hydrogen peroxide, has outstanding advantages such as route is short, Atom economy is high, contamination-free generation for it.If this process application in phenol production, will reduce production costs greatly, improve the product synthetic ratio, fill up a large amount of vacancies of domestic market.The core that realizes this technology is selection of catalysts and preparation.
People (U.S.Pat.No.6355847B1) such as Tsuruya S used V/Al in 2002
2O
3Or Zn-V/Al
2O
3Or Cu/HZSM-5 is catalyst, and molecular oxygen is an oxidant, and ascorbic acid is a reducing agent, and acetic acid is solvent, obtains 8% maximum phenol yield.Document (Catal.Commun.2007,8,693; Appl.Clay.Sci.2006,33,1; J.Mol.Catal.A:Chem.2002,184,215; ) to contain the vanadium molecular sieve be catalyst to the working load type, is oxidant with the hydrogen peroxide, acetic acid or acetonitrile are solvent, obtaining phenol yield is 0.33%～20%, selectivity 40%～93%.Yet in acetonitrile solvent, react phenol selectivity higher (87%), but product yield lower (2.5%); In acetic acid, react the easy solution-off of active component.Document Catal.Today 2000,61,137 reports mix vanadium and make the V-Si molecular sieve catalyst in the skeleton, can avoid the active component solution-off, but phenol yield lower (0.33～1.2%).Because it is loaded down with trivial details that these catalyst are made, the Preparation of Catalyst cost is higher, and the reaction time is longer, does not therefore all realize commercialization.People such as Zhang Jin (Chinese invention patent ZL2003101041091) employing active carbon is a catalyst, and hydrogen peroxide is an oxidant, and glacial acetic acid is a solvent, obtain phenol yield and be up to 13%, but reaction temperature higher relatively (60 ℃).
Active carbon is except that molecular sieve and aluminium oxide, and the 3rd has the excellent carrier of high-ratio surface, and in addition, the characteristics that active carbon also has are: 1) inexpensive, be easy to get; 2) each metal ion species such as iron, copper there is very strong absorption affinity, has been used for adsorbing and removing or has reclaimed each metal ion species such as iron, copper; 3) activated carbon surface has various groups, and is verified: these groups play important even conclusive effect in the various functions of active carbon; 4) active carbon is oleophylic in essence, to organic compound, particularly arene is had very strong absorption.After in active carbon, introducing metal active constituent, metal component will interact with the activated carbon surface oxy radical, influences catalyst activity jointly.
Summary of the invention
The purpose of this invention is to provide a kind of by the synthetic method for preparing phenol of benzene one-step method; Synthesizing uses catalyst to be carrier with coal mass active carbon; With the molysite is active component; Carrier carries out oxidation processes with nitric acid to its surface before using, and adopts infusion process to introduce active component, and catalyst has high activity, high selectivity and high stability through relatively mild processing.
Of the present inventionly a kind ofly prepare the method for phenol, with 20mL acetonitrile, 1mL benzene, 7mLH by the benzene one-step method
2O
2(mass percent is 30%) and 0.5g catalyst join in the two neck bottles, in 30 ℃ of waters bath with thermostatic control, react 8h;
Described catalyst is by following method preparation:
(1) grinds active carbon
Get the 100g coal mass active carbon, grind, screening; Get 40-80 purpose particle, fully wash, remove inorganic impurities such as activated carbon surface dust with running water; With distilled water washing 3 times, remove the trace metal ion that is adsorbed onto activated carbon surface, more then in 110 ℃ of oven dry of thermostatic drying chamber.
(2) nitric acid oxidation modified activated carbon
The active carbon that 100g was washed adds the 500mL flask, and adding 250mL concentration again is 2～12mol/L salpeter solution, connects condenser pipe, in 25～90 ℃ of water-bath reflow treatment 10 hours, with NaOH or Na
2CO
3Solution absorption tail gas, constant with the abundant detergent active charcoal of running water then to pH, use distilled water drip washing again three times, suction filtration is in 110 ℃ of oven dry of thermostatic drying chamber.
(3) load iron
Accurately take by weighing 0.7997g～3.9978g Fe
2(SO
4)
3Be dissolved in the 50mL distilled water, be mixed with the Fe that concentration is 0.04～0.20mol/L
2(SO
4)
3The aqueous solution is got 15g active carbon after treatment, measures 20～50mL Fe
2(SO
4)
3Aqueous solution Immesion active carbon, room temperature was placed 0.5～24 hour; Suction filtration then is in 110 ℃ of oven dry of thermostatic drying chamber.The optimum preparating condition of above-mentioned catalyst is: the concentration of nitric acid is 12mol/L, and the nitric acid treatment temperature is 90 ℃, Fe
2(SO
4)
3The concentration of maceration extract is 0.175mol/L, and the maceration extract volume is 25mL, and dip time is 0.5 hour.
The present invention provides a kind of method for preparing catalyst by benzene one-step method synthesizing phenol, makes catalyst under relatively mild reaction condition, have high activity, high selectivity and high stability, improves working condition, reduces production costs, and improves the quality of products.
(1) catalyst preparation process is simple, and is inexpensive, cost is low;
(2) catalyst efficiency is high, and product phenol yield and selectivity are high;
(3) catalyst performance stabilised, the life-span is long, can be recycled serviceability temperature low (30 ℃).
Therefore, the present invention has considerable prospects for commercial application.
The specific embodiment
Embodiment 1
Get the 100g coal mass active carbon, grind, the 40-80 order is got in screening.Running water fully washs, and removes inorganic impurities such as activated carbon surface dust.With distilled water washing 3 times, remove the trace metal ion that is adsorbed onto the coal mass active carbon surface again.Put into baking oven, 110 ℃ of oven dry.Add coal mass active carbon that 100g washed in the 500mL flask, add the HNO of 250mL 10mol/L
3Solution connects condenser pipe, in 90 ℃ of water-bath reflux, with NaOH solution absorption tail gas, handles 10 hours.Constant with the abundant washing acid active carbon processed of running water to pH, use distilled water drip washing again three times.The vavuum pump suction filtration is put into baking oven, 110 ℃ of oven dry.Take by weighing 3.5090g Fe
2(SO
4)
3In 50mL distilled water, prepare the Fe of 0.175mol/L
2(SO
4)
3Solution, to wherein adding the coal mass active carbon that 15g handled, normal temperature leaves standstill, dipping 0.5h, the vavuum pump suction filtration is put into baking oven, 110 ℃ of oven dry.
Embodiment 2
Get the 100g coal mass active carbon, grind, the 40-80 order is got in screening.Running water fully washs, and removes inorganic impurities such as activated carbon surface dust.With distilled water washing 3 times, remove the trace metal ion that is adsorbed onto the coal mass active carbon surface again.Put into baking oven, 110 ℃ of oven dry.Add coal mass active carbon that 100g washed in the 500mL flask, add the HNO of 250mL 12mol/L
3Solution connects condenser pipe, in 90 ℃ of water-bath reflux, with NaOH solution absorption tail gas, handles 10 hours.The coal mass active carbon of handling with the abundant washing acid of running water is constant to pH, uses distilled water drip washing again three times.The vavuum pump suction filtration is put into baking oven, 110 ℃ of oven dry.Take by weighing 3.5090g Fe
2(SO
4)
3In 50mL distilled water, prepare the Fe of 0.175mol/L
2(SO
4)
3Solution, to wherein adding the coal mass active carbon that 15g handled, normal temperature leaves standstill, dipping 0.5h, the vavuum pump suction filtration is put into baking oven, 110 ℃ of oven dry.
Embodiment 3
Get the 100g coal mass active carbon, grind, the 40-80 order is got in screening.Running water fully washs, and removes inorganic impurities such as activated carbon surface dust.With distilled water washing 3 times, remove the trace metal ion that is adsorbed onto the coal mass active carbon surface again.Put into baking oven, 110 ℃ of oven dry.Add coal mass active carbon that 100g washed in the 500mL flask, add the HNO of 250mL 2mol/L
3Solution connects condenser pipe, in 90 ℃ of water-bath reflux, with NaOH solution absorption tail gas, handles 10 hours.The coal mass active carbon of handling with the abundant washing acid of running water is constant to pH, uses distilled water drip washing again three times.The vavuum pump suction filtration is put into baking oven, 110 ℃ of oven dry.Take by weighing 3.5090g Fe
2(SO
4)
3In 50mL distilled water, prepare the Fe of 0.175mol/L
2(SO
4)
3Solution, to wherein adding the coal mass active carbon that 15g handled, normal temperature leaves standstill, dipping 0.5h, the vavuum pump suction filtration is put into baking oven, 110 ℃ of oven dry.
Embodiment 4
The Preparation of catalysts method is basically with embodiment 2, and difference is the Fe for preparing
2(SO
4)
3Solution concentration is different.Take by weighing 3.9988g Fe
2(SO
4)
3In 50mL distilled water, prepare 0.14mol/L Fe
2(SO
4)
3Solution.
Embodiment 5
The Preparation of catalysts method is basically with embodiment 2, and difference is the Fe for preparing
2(SO
4)
3Solution concentration is different.Take by weighing 3.9988g Fe
2(SO
4)
3In 50mL distilled water, prepare 0.20mol/L Fe
2(SO
4)
3Solution.
Embodiment 6
Basically with embodiment 2, difference is Fe to the Preparation of catalysts method
2(SO
4)
3The asynchronism(-nization) of solution impregnation active carbon.Dip time is 24h in this example.
Embodiment 7
Basically with embodiment 2, difference is Fe to the Preparation of catalysts method
2(SO
4)
3The asynchronism(-nization) of solution impregnation active carbon.Dip time is 10h in this example.
Embodiment 8
Get the 100g coal mass active carbon, grind, the 40-80 order is got in screening.Running water fully washs, and removes inorganic impurities such as coal mass active carbon surface dirt.With distilled water washing 3 times, remove the trace metal ion that is adsorbed onto the coal mass active carbon surface again.Put into baking oven, 110 ℃ of oven dry.Add 100g and washed 40-80 order coal mass active carbon in the 500mL flask, add the HNO of 250mL12mol/L
3Solution connects condenser pipe, in 90 ℃ of water bath with thermostatic control reflux, uses Na
2CO
3Solution absorption tail gas was handled 10 hours.Running water fully washs to pH constant, uses distilled water drip washing again three times.Suction filtration is put into baking oven, 110 ℃ of oven dry.Take by weighing 3.5090g Fe
2(SO
4)
3In 50mL distilled water, prepare the Fe of 0.175mol/L
2(SO
4)
3Solution.Measure 25mL Fe
2(SO
4)
3Solution is in beaker, and to wherein adding the coal mass active carbon that 15g handled, normal temperature leaves standstill, dipping 0.5h, and the vavuum pump suction filtration is put into baking oven, 110 ℃ of oven dry.
Embodiment 9
Get the 100g coal mass active carbon, grind, the 40-80 order is got in screening.Running water fully washs, and removes inorganic impurities such as coal mass active carbon surface dirt.With distilled water washing 3 times, remove the trace metal ion that is adsorbed onto the coal mass active carbon surface again.Put into baking oven, 110 ℃ of oven dry.Add 100g and washed 40-80 order coal mass active carbon in the 500mL flask, add the HNO of 250mL12mol/L
3Solution connects condenser pipe, in 90 ℃ of water bath with thermostatic control reflux, uses Na
2O
3Solution absorption tail gas was handled 10 hours.Running water fully washs to pH constant, uses distilled water drip washing again three times.Suction filtration is put into baking oven, 110 ℃ of oven dry.Take by weighing 3.5090g Fe
2(SO
4)
3In 50mL distilled water, prepare the Fe of 0.175mol/L
2(SO
4)
3Solution.Measure 20mL Fe
2(SO
4)
3Solution is in beaker, and to wherein adding the coal mass active carbon that 15g handled, normal temperature leaves standstill, dipping 0.5h, and the vavuum pump suction filtration is put into baking oven, 110 ℃ of oven dry.
Embodiment 10
Get the 100g coal mass active carbon, grind, the 40-80 order is got in screening.Running water fully washs, and removes inorganic impurities such as coal mass active carbon surface dirt.With distilled water washing 3 times, remove the trace metal ion that is adsorbed onto the coal mass active carbon surface again.Put into baking oven, 110 ℃ of oven dry.Add 100g and washed 40-80 order active carbon in the 500mL flask, add the HNO of 250mL 10mol/L
3Solution connects condenser pipe, in 25 ℃ of water bath with thermostatic control reflux, uses Na
2CO
3Solution absorption tail gas was handled 10 hours.Running water fully washs to pH constant, uses distilled water drip washing again three times.Suction filtration is put into baking oven, 110 ℃ of oven dry.Take by weighing 3.5090g Fe
2(SO
4)
3In 50mL distilled water, prepare the Fe of 0.175mol/L
2(SO
4)
3Solution.Measure 25mL Fe
2(SO
4)
3Solution is in beaker, and to wherein adding the coal mass active carbon that 15g handled, normal temperature leaves standstill, dipping 0.5h, and the vavuum pump suction filtration is put into baking oven, 110 ℃ of oven dry.
Embodiment 11
Get the 100g coal mass active carbon, grind, the 40-80 order is got in screening.Running water fully washs, and removes inorganic impurities such as coal mass active carbon surface dirt.With distilled water washing 3 times, remove the trace metal ion that is adsorbed onto the coal mass active carbon surface again.Put into baking oven, 110 ℃ of oven dry.Add 100g and washed 40-80 order coal mass active carbon in the 500mL flask, add the HNO of 250mL 10mol/L
3Solution connects condenser pipe, in 60 ℃ of water bath with thermostatic control reflux, uses Na
2CO
3Solution absorption tail gas was handled 10 hours.Running water fully washs to pH constant, uses distilled water drip washing again three times.Suction filtration is put into baking oven, 110 ℃ of oven dry.Take by weighing 3.5090g Fe
2(SO
4)
3In 50mL distilled water, prepare the Fe of 0.175mol/L
2(SO
4)
3Solution.Measure 25mL Fe
2(SO
4)
3Solution is in beaker, and to wherein adding the coal mass active carbon that 15g handled, normal temperature leaves standstill, dipping 0.5h, and the vavuum pump suction filtration is put into baking oven, 110 ℃ of oven dry.
Embodiment 12
Get the 100g coal mass active carbon, grind, the 40-80 order is got in screening.Running water fully washs, and removes inorganic impurities such as coal mass active carbon surface dirt.With distilled water washing 3 times, remove the trace metal ion that is adsorbed onto the coal mass active carbon surface again.Put into baking oven, 110 ℃ of oven dry.Add 100g and washed 40-80 order coal mass active carbon in the 500mL flask, add the HNO of 250mL 10mol/L
3Solution connects condenser pipe, in 60 ℃ of water bath with thermostatic control reflux, uses Na
2CO
3Solution absorption tail gas was handled 10 hours.Running water fully washs to pH constant, uses distilled water drip washing again three times.Suction filtration is put into baking oven, 110 ℃ of oven dry.Take by weighing 0.7997g Fe
2(SO
4)
3In 50mL distilled water, prepare the Fe of 0.04mol/L
2(SO
4)
3Solution.Measure 25mL Fe
2(SO
4)
3Solution is in beaker, and to wherein adding the coal mass active carbon that 15g handled, normal temperature leaves standstill, dipping 0.5h, and the vavuum pump suction filtration is put into baking oven, 110 ℃ of oven dry.
Embodiment 13
Get in above preparation catalyst 0.5g and the 50mL two neck bottles, add the 20mL acetonitrile, 1mL benzene, 7mLH
2O
2(mass percent is 30%), in 30 ℃ of waters bath with thermostatic control, reaction 8h, result such as following table:
| Catalyst | Phenol yield % | Phenol selectivity % |
| Embodiment 1 | 22.5 | 85.6 |
| Embodiment 2 | 19.0 | 85.4 |
| Embodiment 3 | 18.2 | 88.1 |
| Embodiment 4 | 16.0 | 88.4 |
| Embodiment 5 | 16.9 | 90.4 |
| Embodiment 6 | 16.0 | 88.7 |
| Embodiment 7 | 17.7 | 91.0 |
| Embodiment 8 | 17.8 | 91.6 |
| Embodiment 9 | 19.0 | 86.8 |
| Embodiment 10 | 18.4 | 86.7 |
| Embodiment 11 | 22.0 | 83.8 |
| Embodiment 12 | 15.2 | 85.6 |
Claims (2)
1. one kind prepares the method for phenol by the benzene one-step method, is 30% H with 20mL acetonitrile, 1mL benzene, 7mL mass percent
2O
2Join in the two neck bottles with the 0.5g catalyst, in 30 ℃ of waters bath with thermostatic control, react 8h; It is characterized in that: described catalyst is to be carrier with the coal mass active carbon, is active component with the molysite, and catalyst is prepared by following method:
(1) grinds active carbon
Get coal mass active carbon, grind, screening; Get 40-80 purpose particle, fully wash, remove activated carbon surface dust, inorganic impurity with running water; With distilled water washing 3 times, remove the trace metal ion that is adsorbed onto the coal mass active carbon surface, more then in 110 ℃ of oven dry of thermostatic drying chamber;
(2) nitric acid oxidation modification coal mass active carbon
The coal mass active carbon that 100g was washed adds flask, and adding 250mL concentration again is 2～12mol/L salpeter solution, connects condenser pipe, in 25～90 ℃ of water-bath reflow treatment 10 hours, with NaOH or Na
2CO
3Solution absorption tail gas, it is constant to pH fully to wash coal mass active carbon with running water then, uses distilled water drip washing again three times, and suction filtration is in 110 ℃ of oven dry of thermostatic drying chamber;
(3) load iron
Accurately take by weighing 0.7997g～3.9978g Fe
2(SO
4)
3Be dissolved in the 50mL distilled water, be mixed with the Fe that concentration is 0.04～0.20mol/L
2(SO
4)
3The aqueous solution; Get 15g coal mass active carbon after treatment, measure 20～50mL Fe
2(SO
4)
3Aqueous solution dipping coal mass active carbon, room temperature was placed 0.5～24 hour, and suction filtration then is in 110 ℃ of oven dry of thermostatic drying chamber.
2. prepare the method for phenol according to claim is described by the benzene one-step method, it is characterized in that: above-mentioned Preparation of catalysts condition is: the concentration of nitric acid is 12mol/L, and the nitric acid treatment temperature is 90 ℃, Fe
2(SO
4)
3The concentration of maceration extract is 0.175mol/L, and the maceration extract volume is 25mL, and dip time is 0.5 little.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103349984A (en) * | 2013-07-23 | 2013-10-16 | 昆明贵研催化剂有限责任公司 | Preparation method of coal columnar palladium-carbon catalyst used for hydrogenation of masson pine |
| CN109134203A (en) * | 2018-09-18 | 2019-01-04 | 四川大学 | A method of 2,5- chlorophenesic acid is prepared by activated carbon containing iron catalysis 1,4- dichloro benzene hydroxylation |
| CN115739155A (en) * | 2022-11-17 | 2023-03-07 | 中国科学院山西煤炭化学研究所 | Heteroatom modified metal catalyst and preparation method and application thereof |
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| JP2001316303A (en) * | 2000-03-01 | 2001-11-13 | San Kaihatsu Kk | Method for recovery of styrene monomer from polystyrene resin by catalytic method |
| US20020058586A1 (en) * | 2000-09-27 | 2002-05-16 | Kyung-Il Choi | Method for preparing a catalyst for selective catalytic reduction of nitrogen oxides |
| CN101612594A (en) * | 2008-06-27 | 2009-12-30 | 北京化工大学 | A kind of method of preparing supported iron-based composite catalyst by dipping method |
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| US20020058586A1 (en) * | 2000-09-27 | 2002-05-16 | Kyung-Il Choi | Method for preparing a catalyst for selective catalytic reduction of nitrogen oxides |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103349984A (en) * | 2013-07-23 | 2013-10-16 | 昆明贵研催化剂有限责任公司 | Preparation method of coal columnar palladium-carbon catalyst used for hydrogenation of masson pine |
| CN103349984B (en) * | 2013-07-23 | 2014-12-17 | 昆明贵研催化剂有限责任公司 | Preparation method of coal columnar palladium-carbon catalyst used for hydrogenation of masson pine |
| CN109134203A (en) * | 2018-09-18 | 2019-01-04 | 四川大学 | A method of 2,5- chlorophenesic acid is prepared by activated carbon containing iron catalysis 1,4- dichloro benzene hydroxylation |
| CN115739155A (en) * | 2022-11-17 | 2023-03-07 | 中国科学院山西煤炭化学研究所 | Heteroatom modified metal catalyst and preparation method and application thereof |
| CN115739155B (en) * | 2022-11-17 | 2024-03-22 | 中国科学院山西煤炭化学研究所 | Heteroatom modified metal catalyst and preparation method and application thereof |
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