CN114644585A - Method for preparing indigo white by fluidized bed catalytic hydrogenation - Google Patents
Method for preparing indigo white by fluidized bed catalytic hydrogenation Download PDFInfo
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- CN114644585A CN114644585A CN202011508800.6A CN202011508800A CN114644585A CN 114644585 A CN114644585 A CN 114644585A CN 202011508800 A CN202011508800 A CN 202011508800A CN 114644585 A CN114644585 A CN 114644585A
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- indigo
- catalyst
- fluidized bed
- catalytic hydrogenation
- white
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- CMSRLFLXFXUENW-UHFFFAOYSA-L disodium;2-(3-oxido-1h-indol-2-yl)-1h-indol-3-olate Chemical compound [Na+].[Na+].N1C2=CC=CC=C2C([O-])=C1C1=C([O-])C2=CC=CC=C2N1 CMSRLFLXFXUENW-UHFFFAOYSA-L 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims abstract description 29
- 229940097275 indigo Drugs 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 41
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 17
- 238000005086 pumping Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 10
- 244000060011 Cocos nucifera Species 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- IREVRWRNACELSM-UHFFFAOYSA-J ruthenium(4+);tetrachloride Chemical compound Cl[Ru](Cl)(Cl)Cl IREVRWRNACELSM-UHFFFAOYSA-J 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- VIFKLIUAPGUEBV-UHFFFAOYSA-N 2-(3-hydroxy-1h-indol-2-yl)-1h-indol-3-ol Chemical compound N1C2=CC=CC=C2C(O)=C1C1=C(O)C2=CC=CC=C2N1 VIFKLIUAPGUEBV-UHFFFAOYSA-N 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 238000004043 dyeing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 239000000080 wetting agent Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229930182559 Natural dye Natural products 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FNXLCIKXHOPCKH-UHFFFAOYSA-N bromamine Chemical compound BrN FNXLCIKXHOPCKH-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000989 food dye Substances 0.000 description 1
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000000978 natural dye Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- -1 sulfate ester salt Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
- C07D209/32—Oxygen atoms
- C07D209/36—Oxygen atoms in position 3, e.g. adrenochrome
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing indigo white by catalytic hydrogenation, belonging to the field of fine chemical engineering. And (3) fully contacting the indigo dispersion liquid with a catalyst in a fluidized bed, and carrying out catalytic hydrogenation reaction under the action of hydrogen to obtain the indigo white. The method has the advantages of high efficiency, good product quality, simple catalyst preparation, good catalytic activity, high selectivity, good stability and low comprehensive use cost. Solves the problems of economic benefit and environmental protection of the leucoindigo in the production process, and is suitable for industrial production.
Description
Technical Field
The invention relates to a method for preparing leucoindigo by catalytic hydrogenation, belonging to the field of fine chemical engineering.
Background
Indigo is one of the first natural dyes used by humans, is a deep blue homogeneous powder in appearance, is an important reducing dye, is mainly used for dyeing cotton yarn, cotton cloth, wool or silk, is also used as a food dye and an organic pigment in pure products, or is processed into an organic pigment such as bromoamine blue.
Indigo white, also known as invisible indigo, is an amorphous bluish-green crystal that is readily soluble in water and alkaline solutions and is very easily oxidized to indigo in the air.
At present, domestic indigo is sold mainly as a powdery commodity, and has the defects of coarse particles, wide particle size distribution range, slow and uneven reduction rate, easy uneven dyeing caused by using a dye bath prepared by safe reduction during use, influence on printing and dyeing quality, generation of a large amount of dye-containing wastewater in the printing and dyeing process and high treatment cost. In recent years, indigo white produced by Desida has replaced a part of indigo blue, and the products are steadily increasing. Compared with indigo, the indigo dye is soluble in water, has the advantages of convenient use, high dyeing rate, easy dyeing into deep color, less three wastes and the like, is suitable for large-scale automatic dyeing, and has small color difference.
Regarding the synthesis of leucoindigo, the following synthetic routes are mainly available:
(1) the indigo is reduced and synthesized by sodium hydrosulfite or carbamide dioxide under the alkaline condition by using the highly dispersed indigo dispersion, the reaction speed of reducing the indigo by the sodium hydrosulfite is high under the alkaline condition, but the solution is unstable, the salt content is high, the high-strength indigo is not easy to obtain after drying, in addition, the three wastes are large, and the environmental pollution is serious.
(2) In DE200914 and DE235047, iron powder and zinc powder are used to reduce indigo into indigo white in alkaline medium, and although the sulfur content in waste water is reduced, the amount of waste slag and waste gas is large, and serious environmental pollution is caused.
(3) Catalytic hydrogenation synthesis of leucoindigo, most typically patent ZL99808570.7 in dessda, discloses a process for the preparation of 25-55% leucoindigo: namely, a mixed alkali solution of sodium hydroxide and potassium hydroxide is adopted to form a salt with hydrogenated and reduced indigo white, and then a stabilizing agent is added to achieve a stable state. The indigo white product synthesized by the process route has high strength and no three wastes, and is an ideal method for preparing the indigo white at present.
CN102516817A discloses a method for preparing indigo white by catalytic hydrogenation, which is different from patent ZL99808570.7 in that the raw material is an oxidized indigo blue suspension without washing and acidification, the alkali is monobasic sodium hydroxide, the indigo blue suspension is subjected to catalytic hydrogenation at a lower reaction temperature, and then the reaction temperature of the system is raised to further perform hydrogenation on the indigo blue. The stabilizing agent selected by the method is a diphosphite antioxidant, aims to prevent the product after hydrogenation from being oxidized and prolong the shelf life, and is different from sodium hydrosulfite used in the prior art.
CN110423492 also discloses a method for preparing indigo white by continuous hydrogenation, which adopts 40% indigo white solution as a substrate (prepared by adopting an intermittent reaction), injects an indigo blue dispersion liquid with certain concentration and a catalyst into a reaction kettle in a continuous feeding mode, pumps out a product after hydrogenation is finished, and keeps the discharge concentration at 39.8-40%. The method only adopts a flow pump on the feeding and discharging modes, and is still a batch reaction in nature.
The synthesis methods are all intermittent reactions, generally have large occupancy rate of equipment, need to regularly load and unload the kettle, have low production capacity, large labor intensity of workers and unstable product quality. And the materials and the catalyst need to be filtered after the reaction, and the nickel catalyst is flammable and unsafe when exposed in the air, so that the filtering process needs to be carried out under the protection of nitrogen, and time and labor are wasted.
GB3281104 reports the synthesis of fixed bed continuous hydrogenation of mixtures of indigo and alkali, but no specific reference is made to the reaction conditions and procedures. In the fixed bed process, if the exothermic effect is obvious, the heat transfer problem exists, the catalyst is usually filled in multiple sections, and meanwhile, the reactant uniformity of all parts of the catalyst is difficult to ensure.
In view of the above, there is a need for a method for preparing indigo white with low production cost, high equipment utilization rate, high product yield and stable product quality. At present, the application of the fluidized bed in catalytic hydrogenation increasingly shows obvious advantages, and in the fluidized bed reaction, fluid is in a complete back-mixing state, so that mass and heat transfer can be more favorably realized.
Disclosure of Invention
Based on the problems in the prior art, the invention provides a method for preparing indigo white by adopting fluidized bed catalytic hydrogenation, so that the production efficiency is greatly improved, the product quality is stable, and the method is more suitable for large-scale industrial production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing indigo white by fluidized bed catalytic hydrogenation is characterized in that indigo blue dispersion liquid is fully contacted with a catalyst in a fluidized bed, and catalytic hydrogenation reaction is carried out under the action of hydrogen to obtain the indigo white.
Further, the indigo white is obtained by utilizing a fluidized bed, adjusting the hydrogen flow rate by using a gas flowmeter, mixing the indigo blue dispersion liquid with a catalyst, pumping the mixture into a reactor by using a high-pressure constant flow pump to perform catalytic hydrogenation reaction, and filtering and separating the mixture after the reaction.
The indigo dispersion liquid is formed by mixing dried industrial indigo filter cakes serving as raw materials with water, adding a dispersing agent under stirring, adding a mixed solution of sodium hydroxide and potassium hydroxide after uniform dispersion, and stirring.
The molar ratio of the sodium hydroxide to the potassium hydroxide is 1: 1-3.
The dispersant is an anionic and/or nonionic surfactant.
The used dispersant is one or a plurality of combinations of commercially available anions (sulfonate, sulfate ester salt and polyacrylamide) and nonionic surfactants (polyether type).
The reaction condition is hydrogen flow rate of 2-10 ml/min; the hydrogen pressure is 1.5-3.5 MPa; the reaction temperature is 75-120 ℃; the addition of the dispersant is 0.5 to 3 percent of the raw material by mass; the addition of the catalyst is 0.2-5% by mass of the raw material.
The catalyst is an active component loaded on a carrier, wherein the active component is Pd and Ru, the loading capacity of the active component is 1-10% of the mass fraction of the catalyst, and the mass ratio of the Pd to the Ru is 5-1: 1.
The carrier is treated coconut shell activated carbon.
Further, the method comprises the following steps:
1) weighing palladium chloride and ruthenium chloride according to the proportion, dissolving the palladium chloride and the ruthenium chloride in water, and uniformly mixing for later use;
2) heating and refluxing coconut shell activated carbon with 30% nitric acid (the mass ratio of the activated carbon to the 30% nitric acid is 1:10) for 2 hours, filtering and washing to be neutral, and drying;
3) adding 10 times of water by mass of the treated coconut shell activated carbon obtained in the step 2) into the treated coconut shell activated carbon, mixing uniformly, heating to 30-60 ℃, dropwise adding the palladium chloride-ruthenium chloride mixed solution obtained in the step 1) under stirring for 1-5h, continuously reacting for 1-5h after dropwise adding, adjusting the pH value of the system to 7-8 by using a sodium hydroxide solution, adding hydrazine hydrate, heating to 60-90 ℃, preserving heat for reacting for 1-5h, cooling to room temperature, filtering, washing with water to be neutral, and filtering to obtain the catalyst.
Wherein, the molar ratio of the hydrazine hydrate to the sum of the mole numbers of the palladium chloride and the ruthenium chloride is 1.1-2: 1.
And filtering and separating the catalyst after the reaction to obtain the indigo white, and washing the catalyst with water and alcohol for reuse.
The hydrogenation reduction reaction takes no more hydrogen absorption as a reaction end point (the pointer of a hydrogen pressure gauge begins to descend); and after the reaction is finished, pumping the product into a receiving device, separating the catalyst by a filter screen at the opening of the device to obtain the indigo white, and washing the catalyst with water and alcohol for reuse.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with the traditional batch reaction, the method adopts the fluidized bed to prepare the leucoindigo, thereby avoiding the manual problem and the time-consuming problem caused by opening a kettle for feeding and discharging. And the batch catalytic reaction of the high-pressure autoclave generally has a feeding coefficient not higher than 60% at most, otherwise, the reaction is difficult because of the easy occurrence of material overfill and small hydrogen space.
The fluidized bed reactor has continuous reaction, utilization rate in the reactor can reach nearly 100 percent, reaction time can be obviously saved, production efficiency is high, and product quality is good.
(2) In the fixed bed reactor, the catalyst is fixed on the bed body, and the effect of the catalyst is not greatly different from that of a fluidized bed reactor in solution hydrogenation reaction with better solubility. However, because the indigo dry powder is insoluble in water and the hydrogenation reaction process is an exothermic reaction, if a fixed bed reactor is used, uneven heat transfer is easy to occur, and side reactions are caused. The fluidized bed reaction equipment used by the invention ensures that the fluid is in a complete back-mixing state, so that the temperature and the concentration of the indigo particles in the whole bed are uniform and consistent, and the mass transfer and the heat transfer can be more favorably realized. The reactants and the catalyst can be fully contacted, and products with higher conversion rate and more stable quality can be obtained.
(3) The Pd-Ru/C catalyst used in the invention has high activity and good stability, and the composite catalyst has high selectivity, less side reaction and difficult poisoning, solves the problem that noble metal catalysts such as palladium carbon, Raney nickel and the like are easy to inactivate, can ensure that the catalyst is applied for more than 50 times, and keeps the activity and the selectivity unchanged, thereby not only reducing the cost of the catalyst, but also greatly overcoming the pollution and the energy consumption generated in the regeneration process of the catalyst.
In conclusion, the method has the advantages of high efficiency, good product quality, simple catalyst preparation, good catalytic activity, high selectivity, good stability and low comprehensive use cost. Solves the problems of economic benefit and environmental protection of the leucoindigo in the production process, and is suitable for industrial production.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
4.6g of palladium chloride (261mmol) are dissolved in 40ml of concentrated hydrochloric acid and diluted with 200ml of water; ruthenium chloride 3.8g (183mmol) was dissolved in 200ml of water, and the two solutions were mixed for use. 159.6g of coconut shell activated carbon treated by 2.4L of water and nitric acid is added into a 5L four-mouth bottle, the prepared palladium chloride-ruthenium chloride mixed solution is dripped into the bottle under stirring at 50 ℃, the dripping time is controlled to be about 2 hours, and the stirring is continued for 1 hour after the dripping is finished, so that the coconut shell activated carbon is completely permeated into the activated carbon. Adjusting pH value to 7-8 with 15% sodium hydroxide solution, adding 40ml 85% hydrazine hydrate, heating to 90 deg.C, holding for 2h, cooling to 25 deg.C, filtering, washing with water to neutrality, and vacuum filtering until no water drops. The resulting catalyst was 5% Pd-Ru/C (mass ratio Pd: Ru ═ 3: 2).
The desired content of catalyst can be obtained by adjusting the amounts of Pd and Ru in the same manner (for example, 1 to 10 wt% Pd-Ru/C, mass ratio Pd: Ru ═ 5-1: 1).
Example 2
687ml of water is added into 262g of indigo powder, predispersion is carried out by a dispersion machine, 2g of dispersing agent 5040,1g of wetting agent CF-10, 40g of sodium hydroxide and 56g of potassium hydroxide are sequentially added in the stirring process, and the dispersion is continued until uniform dispersion liquid is formed.
Indigo is immiscible with water to form a dispersion which enables it to pump reactants into the fluidized bed reactor via a high pressure constant flow pump.
Weighing 8g of self-made Pd-Ru/C catalyst (with the moisture content of 55 percent and the mass ratio of Pd: Ru being 2:3), adding the catalyst into indigo dispersion, adjusting various parameters of the fluidized bed reactor, pumping the dispersion into reaction equipment by using a high-pressure constant-flow pump at the temperature of 100 ℃ and the pressure of 1.5MPa until the reaction does not absorb hydrogen any more, cooling, pumping the product into bearing equipment, arranging a filter screen at the position of an equipment port, separating the catalyst to obtain indigo white, and washing the catalyst with water and then washing with alcohol for reuse.
The yield of the indigo white obtained by the method is 98.93%, and the purity is 99.45%.
Example 3
687ml of water is added into 262g of indigo powder, predispersion is carried out by a dispersion machine, 1g of dispersing agent MF, 2g of wetting agent X-405, 32g of sodium hydroxide and 61.6g of potassium hydroxide are sequentially added in the stirring process, and the dispersion is continued until uniform dispersion liquid is formed.
Weighing 10g of self-made Pd-Ru/C catalyst (containing 55% of moisture and the mass ratio of Pd: Ru being 1:1), adding the self-made Pd-Ru/C catalyst into indigo dispersion, adjusting various parameters of a fluidized bed reactor, pumping the dispersion into reaction equipment by using a high-pressure constant flow pump at the temperature of 90 ℃ and the pressure of 2.5MPa until hydrogen is not absorbed any more in the reaction, cooling, pumping a product into supporting equipment, arranging a filter screen at the position of an equipment port, separating out the catalyst to obtain indigo white, and washing the catalyst with water and alcohol for reuse.
The yield of the indigo white obtained by the method is 98.59%, and the purity is 99.51%.
Example 4
262g of indigo powder is added into 600ml of the indigo white dispersion in example 2, predispersion is carried out by a dispersion machine (industrially, under the protection of nitrogen, the predispersion is carried out in a reaction kettle, and the oxidation of indigo white is prevented), 2g of a dispersing agent 5040,1g of a wetting agent CF-10, 40g of sodium hydroxide and 56g of potassium hydroxide are sequentially added in the stirring process, and the dispersion is continued until a uniform dispersion is formed.
Weighing 8g of self-made Pd-Ru/C catalyst (containing 55% of moisture and the mass ratio of Pd: Ru being 4:1), adding the self-made Pd-Ru/C catalyst into indigo dispersion, adjusting various parameters of a fluidized bed reactor, pumping the dispersion into reaction equipment by using a high-pressure constant flow pump at the temperature of 100 ℃ and the pressure of 1.5MPa until hydrogen is not absorbed any more in the reaction, cooling, pumping a product into supporting equipment, arranging a filter screen at the position of an equipment port, separating out the catalyst to obtain indigo white, and washing the catalyst with water and alcohol for reuse.
The yield of the indigo white obtained by the method is 98.53%, and the purity is 99.42%.
Example 5
262g of indigo powder is added into 600ml of the indigo dispersion in example 2, predispersed by a disperser (which is carried out in a reaction kettle under the protection of nitrogen industrially to prevent the oxidation of indigo), 3g of dispersant 5027, 48g of sodium hydroxide and 44.8g of potassium hydroxide are added in turn during stirring, and the dispersion is continued until a uniform dispersion is obtained.
Weighing 15g of self-made Pd-Ru/C catalyst (containing 55% of moisture and the mass ratio of Pd: Ru being 2:1), adding the self-made Pd-Ru/C catalyst into indigo dispersion, adjusting various parameters of a fluidized bed reactor, pumping the dispersion into a reaction device by using a high-pressure constant flow pump at the temperature of 80 ℃ and the pressure of 1MPa until hydrogen is not absorbed any more in the reaction, cooling, pumping a product into a supporting device, separating the catalyst by using a filter screen at the position of a device port to obtain indigo white, and washing the catalyst with water and then washing with alcohol for reuse.
The yield of the indigo white obtained by the method is 98.66%, and the purity is 99.65%.
High-concentration indigo white products can be obtained by examples 4 and 5.
Example 6
Adding 687ml of water into 262g of indigo powder, pre-dispersing by a dispersion machine, sequentially adding 2g of dispersing agent NNO, 2g of wetting agent CF-10, 40g of sodium hydroxide and 56g of potassium hydroxide in the stirring process, and continuously dispersing until uniform dispersion liquid is formed.
Adding the Pd-Ru/C catalyst recovered in the example 1 into indigo dispersion, adjusting various parameters of a fluidized bed reactor, pumping the dispersion into a reaction device by using a high-pressure constant flow pump at the temperature of 90 ℃ and the pressure of 2.0MPa until hydrogen is not absorbed any more in the reaction, cooling, pumping a product into a receiving device, separating the catalyst by using a filter screen at the position of a device opening to obtain indigo white, washing the catalyst by using water, and washing the catalyst by using alcohol.
The indigo white obtained by the above method has yield of 98.53% and purity of 99.46%.
Example 7
262g of indigo powder is added into 600ml of the indigo white dispersion in example 2, predispersion is carried out by a dispersion machine (industrially, under the protection of nitrogen, the predispersion is carried out in a reaction kettle to prevent the indigo white from being oxidized), 2g of dispersing agent MF, 2g of wetting agent X-405, 40g of sodium hydroxide and 56g of potassium hydroxide are sequentially added in the stirring process, and the dispersion is continued until the uniform dispersion is formed.
Adding the Pd-Ru/C catalyst recovered in the example 6 into indigo dispersion, adjusting various parameters of a fluidized bed reactor, pumping the dispersion into a reaction device by using a high-pressure constant flow pump at the temperature of 110 ℃ and the pressure of 2.5MPa until hydrogen is not absorbed any more in the reaction, cooling, pumping a product into a receiving device, separating the catalyst by using a filter screen at the position of a device port to obtain indigo white, washing the catalyst by using water, and washing the catalyst by using alcohol.
The yield of the indigo white obtained by the method is 98.41%, and the purity is 99.31%.
Examples 8 to 17
Examples 6-50 are run using catalyst, and to compensate for operating losses, 5% of new catalyst was added to each 5 batches of the run, and part of the test results are shown in table 1.
| Experiment number | Catalyst addition/g | Yield/% | Purity/%) |
| 6 | 0 | 98.53 | 99.46 |
| 7 | 0 | 98.41 | 99.31 |
| 8 | 0 | 98.35 | 99.24 |
| 9 | 0 | 98.23 | 99.19 |
| 10 | 0.4 | 98.67 | 99.58 |
| 11 | 0 | 98.54 | 99.45 |
| 12 | 0 | 98.42 | 99.37 |
| 13 | 0 | 98.33 | 99.28 |
| 14 | 0 | 98.25 | 99.16 |
| 15 | 0.4 | 98.66 | 99.52 |
| …… | |||
| 41 | 0 | 98.53 | 99.42 |
| 42 | 0 | 98.44 | 99.38 |
| 43 | 0 | 98.36 | 99.26 |
| 44 | 0 | 98.26 | 99.16 |
| 45 | 0.4 | 98.65 | 99.55 |
| 46 | 0 | 98.57 | 99.45 |
| 47 | 0 | 98.46 | 99.33 |
| 48 | 0 | 98.33 | 99.21 |
| 49 | 0 | 98.21 | 99.12 |
| 50 | 0.4 | 98.69 | 99.52 |
As can be seen from the above table, the catalyst can meet the requirement of applying more than 50 times in combination with the fluidized bed process, and the comprehensive use cost is low.
Table 2 shows the influence of each reaction equipment and catalyst type on the yield of leucoindigo under the same feeding amount, and it can be seen that the catalytic hydrogenation of fluidized bed equipment to prepare leucoindigo can achieve ideal effects in both product quality and yield.
Claims (10)
1. A method for preparing indigo white by fluidized bed catalytic hydrogenation is characterized in that: and (3) fully contacting the indigo dispersion liquid with a catalyst in a fluidized bed, and carrying out catalytic hydrogenation reaction under the action of hydrogen to obtain the indigo white.
2. The process for preparing indigo white by fluidized bed catalytic hydrogenation according to claim 1, characterized in that: and (2) regulating the hydrogen flow rate by using a fluidized bed and a gas flow meter, mixing the indigo dispersion liquid with a catalyst, pumping the mixture into a reactor by using a high-pressure constant flow pump for catalytic hydrogenation reaction, and filtering and separating the mixture after the reaction to obtain the indigo white.
3. The process for preparing indigo white by fluidized bed catalytic hydrogenation according to claim 1, characterized in that: the indigo dispersion liquid is formed by mixing dried industrial indigo filter cakes serving as raw materials with water, adding a dispersing agent under stirring, adding a mixed solution of sodium hydroxide and potassium hydroxide after uniform dispersion, and stirring.
4. The process for preparing indigo white by fluidized bed catalytic hydrogenation according to claim 3, characterized in that: the molar ratio of the sodium hydroxide to the potassium hydroxide is 1: 1-3.
5. The process for preparing indigo white by fluidized bed catalytic hydrogenation according to claim 3, characterized in that: the dispersant is an anionic and/or nonionic surfactant.
6. A process for the preparation of indigo white by fluidized bed catalytic hydrogenation according to any of claims 1 to 3, characterized in that: the reaction condition is hydrogen flow rate of 2-10 ml/min; the hydrogen pressure is 1.5-3.5 MPa; the reaction temperature is 75-120 ℃; the addition amount of the dispersant is 0.5 to 3 percent of the raw material by mass; the addition of the catalyst is 0.2-5% of the raw material by mass.
7. The process for the preparation of indigo white by fluidized-bed catalytic hydrogenation according to claim 1 or 2, characterized in that: the catalyst is an active component loaded on a carrier, wherein the active component is Pd and Ru, the loading capacity of the active component is 1-10% of the mass fraction of the catalyst, and the mass ratio of the Pd to the Ru is 5-1: 1.
8. The process for preparing indigo white by fluidized bed catalytic hydrogenation according to claim 7, characterized in that: the carrier is treated coconut shell activated carbon.
9. The process for preparing indigo white by fluidized bed catalytic hydrogenation according to claim 7, characterized in that:
1) weighing palladium chloride and ruthenium chloride according to the proportion, dissolving the palladium chloride and the ruthenium chloride in water, and uniformly mixing for later use;
2) heating and refluxing coconut shell activated carbon with 30% nitric acid (the mass ratio of the activated carbon to the 30% nitric acid is 1:10) for 2 hours, filtering and washing to be neutral, and drying;
3) adding 10 times of water by mass of the treated coconut shell activated carbon obtained in the step 2) into the treated coconut shell activated carbon, mixing uniformly, heating to 30-60 ℃, dropwise adding the palladium chloride-ruthenium chloride mixed solution obtained in the step 1) under stirring for 1-5h, continuously reacting for 1-5h after dropwise adding, adjusting the pH value of the system to 7-8 by using a sodium hydroxide solution, adding hydrazine hydrate, heating to 60-90 ℃, keeping the temperature for reacting for 1-5h, cooling to room temperature, filtering, washing to be neutral, and filtering to obtain the catalyst.
10. The process for preparing indigo white by fluidized bed catalytic hydrogenation according to claim 1, characterized in that: and filtering and separating the catalyst after the reaction to obtain the indigo white, and washing the catalyst with water and alcohol for reuse.
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