CN1266840A - Process for preparing fluorenone - Google Patents
Process for preparing fluorenone Download PDFInfo
- Publication number
- CN1266840A CN1266840A CN 99112742 CN99112742A CN1266840A CN 1266840 A CN1266840 A CN 1266840A CN 99112742 CN99112742 CN 99112742 CN 99112742 A CN99112742 A CN 99112742A CN 1266840 A CN1266840 A CN 1266840A
- Authority
- CN
- China
- Prior art keywords
- vanadium
- fluorenone
- potassium
- catalyst
- oxalic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000007670 refining Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 45
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 26
- 235000006408 oxalic acid Nutrition 0.000 claims description 18
- 229910052720 vanadium Inorganic materials 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- AMAGVGJJHVRPSI-UHFFFAOYSA-N potassium vanadium Chemical compound [K].[V] AMAGVGJJHVRPSI-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 9
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 9
- 235000011151 potassium sulphates Nutrition 0.000 claims description 9
- 239000012808 vapor phase Substances 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000008262 pumice Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- UKUJCSBWRBWNAV-UHFFFAOYSA-N [Sn].[V] Chemical compound [Sn].[V] UKUJCSBWRBWNAV-UHFFFAOYSA-N 0.000 claims description 7
- 239000012974 tin catalyst Substances 0.000 claims description 7
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 150000008376 fluorenones Chemical class 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000004575 stone Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000003618 dip coating Methods 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
- 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
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- 229910001948 sodium oxide Inorganic materials 0.000 claims 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000005470 impregnation Methods 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 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
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 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
Description
本发明属于精细化工领域，特别涉及用汽相催化氧化方法由芴制备工业芴酮和工业芴酮的精制方法。The invention belongs to the field of fine chemical industry, and in particular relates to the preparation of industrial fluorenone and the refining method of industrial fluorenone from fluorene by vapor-phase catalytic oxidation method.
芴酮是一种重要的化工原料，可以用作为医药、染料和功能性高分子化合物的原料。现有的由芴制备芴酮的方法可分为液相方法和汽相方法两种类型。液相方法有用吡啶做溶剂的(C.A.1958)，有用二甲亚砜做溶剂的(US3875237)。液相法的缺点在于使用有机溶剂和排出液态废料，会造成环境污染，因此，液相法的应用受到限制。汽相方法不排出液相废料，不污染环境，适合于工业应用。已公开的汽相方法有：用五氧化二钒的方法(US-1374695)，用钒酸镁和硫酸钾的方法(Zh Pyirl Khim 35，693-696，用五氧化二钒和氧化锡的方法(化工杂志56(6)413-416)，用五氧化二钒、一氧化硅和硫酸钾的方法(US-2956065)，用钒、钛和碱金属的方法(JP-A-60-233028)。发明专利申请96123084.3公开了一种通过使芴和一种含分子氧的气体的汽相催化氧化生产芴酮的方法。Fluorenone is an important chemical raw material, which can be used as a raw material for medicine, dyes and functional polymer compounds. The existing methods for preparing fluorenones from fluorene can be divided into two types: liquid-phase method and vapor-phase method. The liquid phase method uses pyridine as a solvent (C.A.1958), and uses dimethyl sulfoxide as a solvent (US3875237). The disadvantage of the liquid phase method is that the use of organic solvents and the discharge of liquid waste will cause environmental pollution. Therefore, the application of the liquid phase method is limited. The vapor phase method does not discharge liquid phase waste, does not pollute the environment, and is suitable for industrial applications. Disclosed vapor phase method has: the method (US-1374695) with vanadium pentoxide, the method with magnesium vanadate and potassium sulfate (Zh Pyirl Khim 35,693-696, the method with vanadium pentoxide and tin oxide (Journal of Chemical Industry 56 (6) 413-416), method with vanadium pentoxide, silicon monoxide and potassium sulfate (US-2956065), method with vanadium, titanium and alkali metal (JP-A-60-233028) Invention patent application 96123084.3 discloses a method for producing fluorenone by vapor-phase catalytic oxidation of fluorene and a gas containing molecular oxygen.
迄今为止已知用汽相法由芴制取芴酮，用含钒的触媒是有效的，但是存在触媒寿命短，不适合工业化生产；芴酮的纯度只能达到工业品等级，而不能达到精制品等级。So far, it is known that fluorenone is produced from fluorene by vapor phase method, and it is effective to use a catalyst containing vanadium, but the catalyst has a short life and is not suitable for industrial production; the purity of fluorenone can only reach industrial grades, but not fine product grade.
本发明的目的是提供一种采用通过浸泡、转匀、烘干和焙烧等过程组成浸涂工艺制作的含钒触媒，将熔化的芴滴入压缩空气流中，空气流流经装有触媒的反应器完成氧化反应生成工业芴酮，再通过碱金属氢氧化物溶液进行提纯而获得精制芴酮的制备方法。The purpose of the present invention is to provide a vanadium-containing catalyst made by soaking, turning evenly, drying and roasting and other processes to form a dip-coating process. The molten fluorene is dropped into the compressed air flow, and the air flow flows through the catalyst-containing catalyst. The reactor completes the oxidation reaction to generate industrial fluorenone, and then purifies through alkali metal hydroxide solution to obtain the preparation method of refined fluorenone.
按照本发明的芴酮制备方法，包括触媒的制作过程和通过使芴和一种含分子氧的气体在触媒作用下汽相氧化生产工业芴酮的过程，本发明的方法具有下列特点：According to the preparation method of fluorenone of the present invention, it comprises the process of making the catalyst and the process of producing industrial fluorenone by vapor-phase oxidation of fluorene and a gas containing molecular oxygen under the action of the catalyst. The method of the present invention has the following characteristics:
1)选用含钒化合物如偏钒酸铵或偏钒酸钠，和含钾化合物制作钾与钒的原子比为0.8～5的钒钾触媒，或者和含锡化合物制作锡与钒的原子比为0.5～5的钒锡触媒，或者和含钛化合物及含钾化合物制作或钛与钒的原子比为10～30，钾与钒的原子比为0.1～1的钒钛触媒。1) Select a vanadium-containing compound such as ammonium metavanadate or sodium metavanadate, and a potassium-containing compound to make a vanadium-potassium catalyst with an atomic ratio of potassium to vanadium of 0.8 to 5, or a tin-containing compound to make a tin-to-vanadium atomic ratio of A vanadium-tin catalyst of 0.5-5, or a vanadium-titanium catalyst made of a titanium-containing compound and a potassium-containing compound or the atomic ratio of titanium to vanadium is 10-30, and the atomic ratio of potassium to vanadium is 0.1-1.
2)将上述配比的药剂溶解在浓度为0.016～0.05g/ml的草酸水溶液中，配方选用偏钒酸铵时，草酸和偏钒酸铵的重量比为1～2.5，溶解后浸入占草酸水溶液水体积50～85％的惰性载体，然后进入边加热、边搅拌的浸泡过程。2) Dissolve the above-mentioned agent in the oxalic acid aqueous solution with a concentration of 0.016-0.05g/ml. When ammonium metavanadate is selected as the formula, the weight ratio of oxalic acid and ammonium metavanadate is 1-2.5. After dissolving, immerse in oxalic acid The aqueous solution contains an inert carrier with a water volume of 50-85%, and then enters a soaking process while heating and stirring.
3)待水分蒸发完后，放入旋转锅内旋转0.5～1小时，完成转匀过程。3) After the water has evaporated, put it in a rotating pot and rotate for 0.5-1 hour to complete the process of turning evenly.
4)然后在70～650℃温度下烘干、焙烧5～20小时。4) Then drying and roasting at a temperature of 70-650° C. for 5-20 hours.
5)在反应器中放入一种或多种触媒，将熔化的原料芴滴入含分子氧气流中，使该气流流经反应器中的触媒层完成氧化反应，冷却成纯度为90～95％的工业芴酮。反应器温度选用300～450℃，芴的气相浓度选用800～1200g/Nm3。5) Put one or more catalysts into the reactor, drop the melted raw material fluorene into the flow containing molecular oxygen, let the flow flow through the catalyst layer in the reactor to complete the oxidation reaction, and cool to a purity of 90-95 % of industrial fluorenones. The temperature of the reactor is chosen to be 300-450°C, and the gas phase concentration of fluorene is chosen to be 800-1200g/Nm 3 .
6)将上述工业芴酮溶入5～50％的碱金属氢氧化物水溶液中，工业芴酮和溶液的比例选用1∶1～5g/ml，在50～100℃下恒温烘烤并不断搅拌1～5小时，冷却后获得精制芴酮。6) Dissolve the above-mentioned industrial fluorenone into 5-50% aqueous alkali metal hydroxide solution, the ratio of industrial fluorenone to the solution is 1:1-5g/ml, bake at a constant temperature of 50-100°C and keep stirring After cooling for 1-5 hours, refined fluorenone is obtained.
按照本发明，在制作钒钾触媒时，含钾化合物选用硫酸钾；制作钒锡触媒时，含锡化合物选用氯化亚锡；制作钒钛触媒时，含钛化合物选用偏钛酸或钛酸或二氧化钛。According to the present invention, when making the vanadium-potassium catalyst, the potassium-containing compound selects potassium sulfate for use; when making the vanadium-tin catalyst, the tin-containing compound selects tin protochloride for use; Titanium dioxide.
按照本发明的芴酮制备方法，所述的惰性载体选用浮石或碳化硅或氧化铝或二氧化硅等惰性物质，形状可为鞍形、柱形、柱粒形等，粒径可选用3～15mm，优选3～10mm。According to the preparation method of fluorenone of the present invention, the inert carrier is selected from inert materials such as pumice or silicon carbide or alumina or silicon dioxide, and the shape can be saddle-shaped, columnar, columnar, etc., and the particle size can be selected from 3 to 15mm, preferably 3-10mm.
按照本发明的制作触媒方法所制作的触媒，由于经过浸泡，触媒物质渗透到载体的所有缝隙中，并经烘干、焙烧后，和载体紧密地结合在一起，同时由于经过转匀处理，触媒物质均匀地、密实地分布在载体表面，显著地提高了触媒的催化作用和使用寿命。试验证明，按照本发明的方法所制作的触媒，使用寿命可达3～4年，比现有技术提高2倍以上，适合于工业应用。According to the catalyst made by the method for making catalyst of the present invention, due to soaking, the catalyst substance penetrates into all the gaps of the carrier, and after drying and roasting, it is closely combined with the carrier, and simultaneously due to the uniform treatment, the catalyst The substances are evenly and densely distributed on the surface of the carrier, which significantly improves the catalytic effect and service life of the catalyst. The test proves that the service life of the catalyst produced by the method of the invention can reach 3-4 years, which is more than 2 times higher than that of the prior art, and is suitable for industrial application.
按照本发明的芴酮制备方法，既可高产率地获得纯度为90～95％的工业芴酮，又可制取纯度为97～98％的精制芴酮。精制过程主要是用碱金属氢氧化物溶液除去工业芴酮中的苯酐。According to the preparation method of the fluorenone of the present invention, the industrial fluorenone with a purity of 90-95% can be obtained with a high yield, and the refined fluorenone with a purity of 97-98% can also be prepared. The refining process is mainly to remove phthalic anhydride in industrial fluorenone with alkali metal hydroxide solution.
下面结合实施例对本发明作进一步说明。The present invention will be further described below in conjunction with embodiment.
实施例1：钒钾触媒的制作过程Embodiment 1: the manufacture process of vanadium potassium catalyst
在600ml水中加入10～30g草酸制成浓度为0.016～0.05g/ml的草酸水溶液，于此溶液中加入11.7g偏钒酸铵和13.9～87.0g硫酸钾，使钾和钒的原子比＝0.8～5，溶解后浸入300ml浮石，经浸泡、转匀后，在70℃和120℃温度下进行二次烘干3～5小时，即制成钒钾触媒。Add 10-30g of oxalic acid to 600ml of water to make an aqueous oxalic acid solution with a concentration of 0.016-0.05g/ml, add 11.7g of ammonium metavanadate and 13.9-87.0g of potassium sulfate to this solution, so that the atomic ratio of potassium and vanadium = 0.8 ~5. After dissolving, immerse in 300ml of pumice stone, after soaking and turning evenly, carry out secondary drying at 70°C and 120°C for 3-5 hours to make a vanadium-potassium catalyst.
实施例2：钒锡触媒的制作过程Embodiment 2: the manufacture process of vanadium-tin catalyst
在600ml水中加入10～30g草酸制成浓度为0.016～0.05g/ml的草酸水溶液，于此溶液中加入11.7g偏钒酸铵和94.5～545g氯化亚锡，使锡和钒的原子比＝0.5～5，溶解后浸入300ml浮石，经浸泡、转匀后，在100～ll0℃温度下烘干然后分别在240～260℃和400～450℃温度下焙烧2～4小时，最后在635～645℃温度下焙烧6～10小时，制成钒锡触媒。Add 10～30g oxalic acid in 600ml water and make concentration be the oxalic acid aqueous solution of 0.016～0.05g/ml, add 11.7g ammonium metavanadate and 94.5～545g stannous chloride in this solution, make the atomic ratio of tin and vanadium= 0.5～5, after dissolving, immerse in 300ml pumice stone, after soaking and turning evenly, dry at 100～110℃, then roast at 240～260℃ and 400～450℃ respectively for 2～4 hours, finally at 635～ Roast at 645°C for 6-10 hours to make a vanadium-tin catalyst.
实施例3：钒钛触媒的制作过程Embodiment 3: the manufacture process of vanadium-titanium catalyst
在600ml水中加入10～30g草酸制成浓度为0.016～0.05g/ml的草酸水溶液，于此溶液中加入钛钒原子比为10～30的偏钒酸铵11.7g，偏钛酸82～246g，加入硫酸钾17.4～174g，使钾和钒原子比达到0.1～1，混匀溶化后浸入500ml浮石，经浸泡、转匀后，在100～110℃温度下烘干，再在240～260℃和400～450℃温度下焙烧2～4小时，最后在520～540℃温度下焙烧6～10小时。Add 10-30g of oxalic acid to 600ml of water to make an aqueous oxalic acid solution with a concentration of 0.016-0.05g/ml, add 11.7g of ammonium metavanadate with a titanium-vanadium atomic ratio of 10-30, and 82-246g of metatitanic acid to the solution. Add 17.4-174g of potassium sulfate to make the atomic ratio of potassium and vanadium reach 0.1-1, mix and dissolve, then immerse in 500ml of pumice stone, after soaking and turning evenly, dry at 100-110°C, then dry at 240-260°C and Calcining at 400-450°C for 2-4 hours, and finally at 520-540°C for 6-10 hours.
实施例4：精制芴酮的制取Embodiment 4: the preparation of refined fluorenone
取工业芴酮20g放入5～50％的20～l00ml氢氧化钠水溶液中，在50～100℃温度下恒温1～5小时，并不断搅拌，然后冷却干燥，完成精制芴酮过程。对工业芴酮和精制芴酮进行色谱分析，得出下表所示的结果：
按照本发明的芴酮制备方法，原料芴可以是任何种类的芴，对原料的纯度也没有很严格的限制，一般大于60％，优选大于80％，含分子氧的气体优选压缩空气。According to the preparation method of fluorenone of the present invention, the raw material fluorene can be any kind of fluorene, and the purity of the raw material is not strictly limited, generally greater than 60%, preferably greater than 80%, and the gas containing molecular oxygen is preferably compressed air.
按照本发明，也可以使用其它类型的触媒，所列举的三种触媒为优选触媒。这些触媒可以单独使用，也可以配合使用，优选钒钾触媒和钒钛触媒(或钒锡触媒)按比例配合使用。Other types of catalysts may also be used in accordance with the present invention, and the three listed are preferred catalysts. These catalysts can be used alone or in combination, preferably vanadium-potassium catalyst and vanadium-titanium catalyst (or vanadium-tin catalyst) are used in proportion.
Claims (9)
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 true CN1266840A (en) | 2000-09-20 |
| CN1112344C CN1112344C (en) | 2003-06-25 |
Family
ID=5276012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99112742A Expired - Fee Related CN1112344C (en) | 1999-03-15 | 1999-03-15 | Process for preparing fluorenone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1112344C (en) |
Cited By (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 |
| CN102381953A (en) * | 2011-09-07 | 2012-03-21 | 山西大学 | Method for extracting and purifying fluorenone from industrial wastes generated in production of benzoic acid |
| CN109092337A (en) * | 2018-09-09 | 2018-12-28 | 辽宁科技学院 | A kind of catalyst for producing Fluorenone for fluorenes gaseous oxidation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69609804T2 (en) * | 1995-12-11 | 2001-01-11 | Nippon Shokubai Co. Ltd., Osaka | Process for the production of fluorenone |
-
1999
- 1999-03-15 CN CN99112742A patent/CN1112344C/en not_active Expired - Fee Related
Cited By (6)
| 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 |
| CN102381953A (en) * | 2011-09-07 | 2012-03-21 | 山西大学 | Method for extracting and purifying fluorenone from industrial wastes generated in production of benzoic acid |
| 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 |
| CN109092337A (en) * | 2018-09-09 | 2018-12-28 | 辽宁科技学院 | A kind of catalyst for producing Fluorenone for fluorenes gaseous oxidation |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1112344C (en) | 2003-06-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4025891B2 (en) | Method for producing shell catalyst for catalytic gas phase oxidation of aromatic hydrocarbons | |
| US1914557A (en) | Catalyst and process of preparing the same | |
| KR100407528B1 (en) | Process for producing an oxide catalyst for oxidation or ammoxidation | |
| CN1162329C (en) | Multimetal oxides containing silver and vanadium and uses thereof | |
| JPS63253080A (en) | Method for producing phthalic anhydride | |
| NL7908630A (en) | PROCESS FOR THE PREPARATION OF PHTALIC ACID ANHYDRIDE AND CATALYST FOR A SIMILAR PROCESS | |
| CN1829678B (en) | Multimetal oxides containing silver, vanadium and promoter metals and uses thereof | |
| US6632772B2 (en) | Method of coating a catalyst to a support for use in acrolein oxidation | |
| CN1938086B (en) | Catalyst having a silver-vanadium oxide phase and a promoter phase | |
| JP2005527346A (en) | Catalyst-precursor for maleic anhydride production and process for producing the same | |
| EP0004591B1 (en) | Shell catalyst, process for its preparation and its use for the preparation of anthraquinones | |
| CN1266840A (en) | Process for preparing fluorenone | |
| FR2781801A1 (en) | PROCESS FOR THE PREPARATION OF PYROMELLIC DIANHYDRIDE | |
| US4002653A (en) | Manufacture of anthraquinone | |
| US2464825A (en) | Catalysts for oxidizing furfural and preparation thereof | |
| JPS5857374A (en) | Preparation of phthalic anhydride | |
| US2157965A (en) | Process for producing phthalic anhydride | |
| JPS594445A (en) | Catalyst composition for producing unsaturated carboxylic acid and use | |
| CN115038523B (en) | Composition for catalyst production, method for producing composition for catalyst production, and method for producing oxide catalyst | |
| JPH04182450A (en) | Production of methacrylic acid | |
| CN119613241B (en) | A method for preparing 2-methyl-1,4-naphthoquinone by photocatalysis | |
| US1892766A (en) | Catalytic removal of hydrogen or oxygen containing groups from organic compounds | |
| JP2005349393A (en) | Catalyst for vapor-phase oxidation for production of phthalic anhydride from orthoxylene and/or naphthalene, its preparation method, and vapor-phase oxidation method using the catalyst | |
| CN101784341B (en) | Method of preparing catalyst for production of acrylic acid using reactive ball milling | |
| US1844390A (en) | Catalytic oxidation of acenaphthylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ANGANG NEW STEEL ROLLING CO., LTD. Free format text: FORMER OWNER: ANSHAN IRON +. STEEL GROUP CORP. Effective date: 20070316 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C56 | Change in the name or address of the patentee |
Owner name: ANGANG STOCK CO., LTD. Free format text: FORMER NAME OR ADDRESS: ANGANG NEW STEEL ROLLING CO., LTD. |
|
| CP03 | Change of name, title or address |
Address after: 114009, No. 63, Wuyi Road, MTR Eastern District, Liaoning, Anshan Patentee after: ANGANG STEEL COMPANY LIMITED Address before: 114009, No. 63, Wuyi Road, MTR Eastern District, Liaoning, Anshan Patentee before: Angang New Steel Co.,Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20070316 Address after: 114009, No. 63, Wuyi Road, MTR Eastern District, Liaoning, Anshan Patentee after: Angang New Steel Co.,Ltd. Address before: 114001 No. 31 Shengli Road, Tiedong District, Liaoning, Anshan Patentee before: Anshan Iron and Steel Group Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030625 Termination date: 20150315 |
|
| EXPY | Termination of patent right or utility model |