CN1112344C - Process for preparing fluorenone - Google Patents
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- CN1112344C CN1112344C CN99112742A CN99112742A CN1112344C CN 1112344 C CN1112344 C CN 1112344C CN 99112742 A CN99112742 A CN 99112742A CN 99112742 A CN99112742 A CN 99112742A CN 1112344 C CN1112344 C CN 1112344C
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- fluorenone
- vanadium
- catalyst
- potassium
- making
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- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000007670 refining Methods 0.000 claims abstract description 9
- 239000012808 vapor phase Substances 0.000 claims abstract description 9
- 229930194542 Keto Natural products 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 19
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 19
- 235000006408 oxalic acid Nutrition 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 16
- 239000011591 potassium Substances 0.000 claims description 16
- 229910052700 potassium Inorganic materials 0.000 claims description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- 150000002220 fluorenes Chemical class 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- 208000006558 Dental Calculus Diseases 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims description 9
- UKUJCSBWRBWNAV-UHFFFAOYSA-N [Sn].[V] Chemical compound [Sn].[V] UKUJCSBWRBWNAV-UHFFFAOYSA-N 0.000 claims description 8
- AMAGVGJJHVRPSI-UHFFFAOYSA-N potassium vanadium Chemical compound [K].[V] AMAGVGJJHVRPSI-UHFFFAOYSA-N 0.000 claims description 8
- 239000004575 stone Substances 0.000 claims description 8
- 239000012974 tin catalyst Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 125000000468 ketone group Chemical group 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- ZBZHVBPVQIHFJN-UHFFFAOYSA-N trimethylalumane Chemical compound C[Al](C)C.C[Al](C)C ZBZHVBPVQIHFJN-UHFFFAOYSA-N 0.000 claims description 2
- 150000008376 fluorenones Chemical class 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 238000003618 dip coating Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- -1 Phthalic anhydride Dibenzofuran Fluorenes Chemical class 0.000 description 1
- YSTWCCHWWMEAKP-UHFFFAOYSA-N [Ti].[V].[Ti] Chemical compound [Ti].[V].[Ti] YSTWCCHWWMEAKP-UHFFFAOYSA-N 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
- C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
- C07C49/643—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system having three rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种芴酮制备方法，包括触媒的制作过程，通过使芴和一种含分子氧的气体在触媒的催化作用下的汽相氧化生产工业芴酮的过程和由工业芴酮精制成精制芴酮的过程。触媒制作过程采用浸涂工艺，包括浸泡、转匀、烘干和焙烧四个阶段，在浸泡过程中进行搅拌，不同触媒选用不同的烘干、焙烧温度。精制过程采用碱金属氢氧化物水溶液除去工业芴酮中的杂质。本发明的触媒具有高效稳定的催化作用，使用寿命长达3～4年，并能制备精制芴酮。A method for preparing fluorenone, including the process of making a catalyst, the process of producing industrial fluorenone by vapor-phase oxidation of fluorene and a gas containing molecular oxygen under the catalytic action of a catalyst, and refining refined fluorenone from industrial fluorenone Keto process. The catalyst production process adopts a dip-coating process, including four stages of soaking, mixing, drying and roasting. Stirring is carried out during the soaking process. Different catalysts use different drying and roasting temperatures. The refining process uses alkali metal hydroxide aqueous solution to remove impurities in industrial fluorenone. The catalyst of the invention has high-efficiency and stable catalytic effect, and the service life is as long as 3 to 4 years, and can prepare refined fluorenone.
Description
The invention belongs to field of fine chemical, particularly prepare the process for purification of Fluorenone and industrial Fluorenone by fluorenes with method for vapor phase catalytic oxidation.
Fluorenone is a kind of important chemical material, can be used as the raw material of medicine, dyestuff and functional high-polymer compound.The existing method for preparing Fluorenone by fluorenes can be divided into two types of liquid phase process and vapor-phase process.The useful pyridine of liquid phase process is (C.A.1958) of solvent, and useful dromisol is made solvent (US3875237).The shortcoming of liquid phase method is with an organic solvent and discharges liquid waste material that can cause environmental pollution, therefore, the application of liquid phase method is restricted.Vapour phase processes is not discharged the liquid phase waste material, and is free from environmental pollution, is suitable for industrial application.Disclosed vapor-phase process has: with the method (US-1374695) of Vanadium Pentoxide in FLAKES.Method (Zh Pyirl Khim35 with vanadic acid magnesium and vitriolate of tartar, 693-696), method (chemical industry magazine 56 (6) 413～416) with Vanadium Pentoxide in FLAKES and stannic oxide, with the method (US-2956065) of Vanadium Pentoxide in FLAKES, silicon monoxide and vitriolate of tartar, with vanadium, titanium and alkali-metal method (JP-A-60-233028).Application for a patent for invention 96123084.3 discloses the method that a kind of vapor phase catalytic oxidation of the gas by making fluorenes and a kind of molecule-containing keto is produced Fluorenone.
Knownly up to now producing Fluorenone with vapour phase processes by fluorenes, is effectively with the catalyst that contains vanadium, but exists the catalyst life-span short, is not suitable for suitability for industrialized production, and the purity of Fluorenone can only reach the industrial goods grade, and can not reach defective such as highly finished product grade.
The purpose of this invention is to provide a kind of employing and form the vanadium catalyst that contains that dipping process makes by soaking, change processes such as even, oven dry and roasting, the fluorenes of fusing is splashed in the pressurized air stream, flow through reactor that catalyst is housed of airflow is finished oxidizing reaction and is generated industrial Fluorenone, and purifying by alkalimetal oxide solution obtains the preparation method of refining Fluorenone again.
According to process for preparing fluorenone of the present invention, comprise the process of the making processes of catalyst and the gas vapor phase oxidation manufacture Fluorenone under catalysis by making fluorenes and a kind of molecule-containing keto, it is characterized in that:
A) making processes of catalyst adopts dipping process:
1) selects vanadium-containing compound such as ammonium meta-vanadate or sodium metavanadate for use, the atomic ratio of making potassium and vanadium with potassium-containing compound is 0.8～5 vanadium potassium catalyst, it is 0.5～5 vanadium tin catalyst that but person and sn-containing compound are made the atomic ratio of tin and vanadium, perhaps the atomic ratio with titanium-containing compound and potassium-containing compound making titanium and vanadium is 10～30, and the atomic ratio of potassium and vanadium is 0.1～1 vanadium titanium catalyst;
2) medicament with said ratio is dissolved in the oxalic acid aqueous solution that concentration is 0.016g/ml～0.05g/ml, when prescription is selected ammonium meta-vanadate for use, the weight ratio of oxalic acid and ammonium meta-vanadate is 1～2.5, the inert support that accounts for oxalic acid aqueous solution volume 50%～85% is immersed in the dissolving back, enters the immersion process of limit heating, limit stirring then;
3) treat that moisture evaporation is intact after, put into rotary pot 0.5～1 hour, finish to change and spare process;
4) oven dry, roasting 5～20 hours under 70 ℃～650 ℃ temperature then, end of processing.
B) the vapor phase oxidation production of Fluorenone and treating process are:
1) in reactor, puts into one or more catalyst, the raw material melted fluorenes is splashed in the molecule-containing keto air-flow, make the catalyst layer in this airflow passes reactor finish oxidizing reaction, be cooled to purity and be 90%～95% industrial Fluorenone, temperature of reactor is selected 300 ℃～450 ℃ for use, and the phase concentrations of fluorenes is selected 800 g/Nm for use
3～1200g/Nm
3
2) above-mentioned industrial Fluorenone is dissolved in 5%～50% the alkali metal hydroxide aqueous solution, the ratio of industrial Fluorenone and solution is selected 1g for use: 1～5ml, 50 ℃～100 ℃ following constant temperature bakings and constantly stirred 1～5 hour, the cooling back obtains refining Fluorenone.
According to process for preparing fluorenone of the present invention, when making vanadium potassium catalyst, potassium-containing compound is selected vitriolate of tartar for use; When making vanadium tin catalyst, sn-containing compound is selected tin protochloride for use; When making the vanadium titanium catalyst, vanadium titanium titanium-containing compound is selected metatitanic acid or metatitanic acid or titanium dioxide for use, and potassium-containing compound is selected vitriolate of tartar for use.
According to process for preparing fluorenone of the present invention, described inert support is selected float stone or inert substances such as silicon carbide or aluminium carbide or silicon-dioxide for use, and shape can be saddle type, cylindricality, post particle shape etc., and particle diameter can be selected 3mm～15mm for use, preferred 3mm～10mm.
Catalyst according to making catalyst method made of the present invention, because through soaking, catalytic substance is penetrated in all slits of carrier, and after the drying, roasting, closely combine with carrier, simultaneously owing to handle through changeing even, the catalytic substance ground carrier surface that distributes equably, densely, the katalysis and the work-ing life of having improved catalyst significantly.Evidence, according to the catalyst of method made of the present invention, can reach 3～4 years work-ing life, improves more than 2 times than prior art, is suitable for industrial application.
According to process for preparing fluorenone of the present invention, but not only high productivity to obtain purity be 90%～95% industrial Fluorenone but also can to produce purity be 97%～98% refining Fluorenone.Treating process is mainly removed phthalic anhydride in the industrial Fluorenone with alkali hydroxide soln.
The invention will be further described below in conjunction with embodiment.
Embodiment 1: the making processes of vanadium potassium catalyst
In 600ml water, add 10g～30g oxalic acid and make the oxalic acid aqueous solution that concentration is 0.016g/ml～0.05g/ml, in this solution, add 11.7g ammonium meta-vanadate and 13.9g～87.0g vitriolate of tartar, make atomic ratio=0.8～5 of potassium and vanadium, the 300ml float stone is immersed in the dissolving back, after immersion, commentaries on classics are spared, under 70 ℃ and 120 ℃ of temperature, carry out secondary drying each 3～5 hours, promptly make vanadium potassium catalyst.
Embodiment 2: the making processes of vanadium tin catalyst
In 600ml water, add 10～30g oxalic acid and make the oxalic acid aqueous solution that concentration is 0.016g/ml～0.05g/ml, in this solution, add ammonium vanadate 11.7g and 94.5～545g tin protochloride, make atomic ratio=0.5～5 of tin and vanadium, the 300ml float stone is immersed in the dissolving back, after immersion, commentaries on classics are spared, 100 ℃～110 ℃ roasting temperature oven dry, then respectively 240 ℃～260 ℃ and 400 ℃～450 ℃ roasting temperatures 2～4 hours, 635 ℃～645 ℃ roasting temperatures 6～10 hours, make vanadium tin catalyst at last.
Embodiment 3: the making processes of vanadium titanium catalyst
In 600ml water, add 10g～30g oxalic acid and make the oxalic acid aqueous solution that concentration is 0.016g/ml～0.05g/ml, in this solution, add the vanadium titanium atom than the ammonium meta-vanadate 11.7g and the metatitanic acid 82g～246g that are 10～30, add vitriolate of tartar 17.4g～174g, make the atomic ratio of potassium and vanadium reach 0.1～1, mixing dissolves the back and immerses the 500ml float stone, after immersion, commentaries on classics are spared, under 100 ℃～110 ℃ temperature, dry, again respectively 240 ℃～260 ℃ and 400 ℃～450 ℃ roasting temperatures 2～4 hours, at last 520 ℃～540 ℃ roasting temperatures 6～10 hours.
Embodiment 4: make with extra care producing of Fluorenone
Get industrial Fluorenone 20g and put into 20ml～100ml aqueous sodium hydroxide solution of 5%～50%, constant temperature is 1～5 hour under 50 ℃～100 ℃ temperature, and constantly stirs, and cooling drying is finished refining Fluorenone process then.
Industrial Fluorenone and refining Fluorenone are carried out stratographic analysis, draw the result shown in the following table:
| Phthalic anhydride | Dibenzofuran | Fluorenes | Fluorenone | Unknown material | |
| The industry Fluorenone | 3.99 | 0.20 | 1.2 | 94.02 | 0.59 |
| Refining Fluorenone | - | 0.20 | 1.20 | 98.01 | 0.59 |
According to process for preparing fluorenone of the present invention, but the raw material fluorenes can be the fluorenes of appointing kind, and the purity of raw material is not had very strict restriction yet, generally greater than 60%, is preferably greater than 80%, the gas preferred compressed air of molecule-containing keto.
Go out the catalyst that can use other type according to process for preparing fluorenone of the present invention, three kinds of cited catalyst are preferred catalyst.These catalyst can use separately, also can be used, and use proportions for preferred vanadium potassium catalyst and vanadium titanium catalyst (or vanadium tin catalyst).
Claims (9)
1, a kind of preparation method of Fluorenone comprises it is characterized in that the process of the making processes of catalyst and the gas vapor phase oxidation manufacture Fluorenone under catalysis by making fluorenes and a kind of molecule-containing keto:
A) making processes of catalyst adopts dipping process:
1) selects vanadium-containing compound such as ammonium meta-vanadate or sodium metavanadate for use, the atomic ratio of making potassium and vanadium with potassium-containing compound is 0.8～5 vanadium potassium catalyst, perhaps the atomic ratio with sn-containing compound making tin and vanadium is 0.5～5 vanadium tin catalyst, perhaps the atomic ratio with titanium-containing compound and potassium-containing compound making titanium and vanadium is 10～30, the atomic ratio of potassium and vanadium is 0.1～1 vanadium titanium catalyst
2) medicament with said ratio is dissolved in the oxalic acid aqueous solution that concentration is 0.016g/ml～0.05g/ml, when prescription is selected ammonium meta-vanadate for use, the weight ratio of oxalic acid and ammonium meta-vanadate is 1～2.5, the inert support that accounts for oxalic acid aqueous solution volume 50%～85% is immersed in the dissolving back, enter the immersion process of limit heating, limit stirring then
3) treat that moisture evaporation is intact after, put into the rotary pot internal rotation 0.5～1 hour, finish the even process of changeing,
4) oven dry, roasting 5～20 hours under 70 ℃～650 ℃ temperature then, end of processing,
B) the vapor phase oxidation production of Fluorenone and treating process are:
1) in reactor, put into one or more catalyst, the raw material melted fluorenes splashed in the molecule-containing keto air-flow, make the catalyst layer in this airflow passes reactor finish oxidizing reaction, be cooled to purity and be 90%～95% industrial Fluorenone,
2) above-mentioned industrial Fluorenone is dissolved in 5%～50% the alkali metal hydroxide aqueous solution, the ratio of industrial Fluorenone and solution is selected 1g for use: 1～5ml, 50 ℃～100 ℃ following constant temperature bakings and constantly stirred 1～5 hour, the cooling back obtains refining Fluorenone.
2, the preparation method of Fluorenone according to claim 1 is characterized in that the potassium-containing compound of described making vanadium potassium catalyst is selected vitriolate of tartar for use.
3, the preparation method of Fluorenone according to claim 1 is characterized in that the sn-containing compound of described making vanadium tin catalyst is selected tin protochloride for use.
4, the preparation method of Fluorenone according to claim 1 is characterized in that the titanium-containing compound of described making vanadium titanium catalyst is selected metatitanic acid or metatitanic acid or titanium dioxide for use, and potassium-containing compound is selected vitriolate of tartar for use.
5, the preparation method of Fluorenone according to claim 1 is characterized in that described inert support selects float stone or silicon carbide or aluminium carbide or silicon-dioxide.
6, the preparation method of Fluorenone according to claim 1 and 2, it is characterized in that described vanadium potassium catalyst making processes makes the oxalic acid aqueous solution that concentration is 0.016g/ml～0.05g/ml for add 10g～30g oxalic acid in 600ml water, go into 11.7g ammonium meta-vanadate and 13.9g～87.0g vitriolate of tartar in this solution, make atomic ratio=0.8～5 of potassium and vanadium, the 300ml float stone is immersed in the dissolving back, through soak, change even after, under 70 ℃ and 120 ℃ of temperature, carried out secondary drying respectively 3～5 hours.
7, preparation method according to claim 1 or 3 described Fluorenones, it is characterized in that described vanadium tin catalyst making processes makes the oxalic acid aqueous solution that concentration is 0.016g/ml～0.05g/ml for add 10g～30g oxalic acid in 600ml water, go into 11.7g ammonium meta-vanadate and 94.5～545g tin protochloride in this solution, make atomic ratio=0.5～5 of tin and vanadium, the 300ml float stone is immersed in the dissolving back, through soaking, after commentaries on classics is even, 100 ℃～110 ℃ roasting temperature oven dry, then respectively 240 ℃～260 ℃ and 400 ℃～450 ℃ roasting temperatures 2～4 hours, at last 635 ℃～645 ℃ roasting temperatures 6～10 hours.
8, preparation method according to claim 1 or 4 described Fluorenones, it is characterized in that described vanadium titanium catalyst making processes makes the oxalic acid aqueous solution that concentration is 0.016g/ml～0.05g/ml for add 10g～30g oxalic acid in 600ml water, in this solution, add the titanium vanadium atom than the ammonium meta-vanadate 11.7g and the metatitanic acid 82～246g that are 10～30, add vitriolate of tartar 17.4～174g, make the atomic ratio of potassium and vanadium reach 0.1～1, mixing dissolves the back and immerses the 500ml float stone, through soaking, after commentaries on classics is even, under 100 ℃～110 ℃ temperature, dry, again respectively 240 ℃～260 ℃ and 400 ℃～450 ℃ roasting temperatures 2～4 hours, at last 520 ℃～540 ℃ roasting temperatures 6～10 hours.
9, the preparation method of Fluorenone according to claim 1, it is characterized in that described industrial Fluorenone 20g puts into 20ml～100ml aqueous sodium hydroxide solution of 5%～50%, constant temperature is 1～5 hour under 50 ℃～100 ℃ temperature, and constantly stirs, cooling drying is finished treating process then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112742A CN1112344C (en) | 1999-03-15 | 1999-03-15 | Process for preparing fluorenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112742A CN1112344C (en) | 1999-03-15 | 1999-03-15 | Process for preparing fluorenone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1266840A CN1266840A (en) | 2000-09-20 |
| CN1112344C true CN1112344C (en) | 2003-06-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99112742A Expired - Fee Related CN1112344C (en) | 1999-03-15 | 1999-03-15 | Process for preparing fluorenone |
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| CN (1) | CN1112344C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100343217C (en) * | 2004-09-28 | 2007-10-17 | 上海焦化有限公司 | Method for oxidizing fluorene to 9-fluorenone |
| CN101385970B (en) * | 2008-10-29 | 2011-09-21 | 黑龙江省科学院石油化学研究院 | Catalyst for producing 9-fluorenone, preparation method thereof, and production method of 9-fluorenone |
| CN102381953B (en) * | 2011-09-07 | 2013-07-10 | 山西大学 | Method for extracting and purifying fluorenone from industrial wastes generated in production of benzoic acid |
| CN109092337B (en) * | 2018-09-09 | 2021-02-23 | 辽宁科技学院 | A kind of catalyst for preparing fluorenone by gas-phase oxidation of fluorene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0779264A1 (en) * | 1995-12-11 | 1997-06-18 | Nippon Shokubai Co., Ltd. | Method for production of fluorenone |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0779264A1 (en) * | 1995-12-11 | 1997-06-18 | Nippon Shokubai Co., Ltd. | Method for production of fluorenone |
| CN1156715A (en) * | 1995-12-11 | 1997-08-13 | 株式会社日本触媒 | Method for production of fluorenone |
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| CN1266840A (en) | 2000-09-20 |
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