CN116589348A - Preparation method of high-purity nickel acetylacetonate - Google Patents
Preparation method of high-purity nickel acetylacetonate Download PDFInfo
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- CN116589348A CN116589348A CN202310600796.3A CN202310600796A CN116589348A CN 116589348 A CN116589348 A CN 116589348A CN 202310600796 A CN202310600796 A CN 202310600796A CN 116589348 A CN116589348 A CN 116589348A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 title claims abstract 17
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 239000011973 solid acid Substances 0.000 claims abstract description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 40
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 39
- 239000012798 spherical particle Substances 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 10
- 238000000462 isostatic pressing Methods 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 30
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 16
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 46
- 239000000047 product Substances 0.000 description 20
- 239000011259 mixed solution Substances 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/77—Preparation of chelates of aldehydes or ketones
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00033—Continuous processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of high-purity nickel acetylacetonate, which comprises the following steps of S1: ball-milling and mixing nickel oxide powder, solid acid catalyst powder and absolute ethyl alcohol uniformly, performing isostatic pressing operation, and then drying to obtain porous spherical particles of solid acid catalyst composite nickel oxide; s2: adding porous spherical particles of solid acid catalyst composite nickel oxide into one end of a serpentine tube reactor, introducing acetylacetone into the other end of the serpentine tube reactor, and continuously reacting the acetylacetone with the nickel oxide under the action of the solid acid catalyst; s3: after the reaction is finished, the high-purity nickel acetylacetonate product is obtained at the tower bottom after the treatment of the continuous rectifying device. According to the preparation method of the high-purity nickel acetylacetonate, on one hand, the high-purity nickel acetylacetonate product with the purity of more than 99.9% can be prepared, and on the other hand, the continuous production of the high-purity nickel acetylacetonate can be realized, so that the preparation method is simple in process and convenient to operate, and meets the requirements of industrial production.
Description
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a preparation method of high-purity nickel acetylacetonate.
Background
The nickel acetylacetonate product is light green crystalline powder, and has a boiling point of 220-235 ℃ at 14.67kPa, is slightly soluble in water and methanol, and is soluble in solvents such as ether, aromatic hydrocarbon and halogenated hydrocarbon solvents. Is mainly used as a catalyst and is generally used for catalyzing oligomerization, hydrosilation, hydrogenation, reduction, cross coupling, oxidation, conjugate addition, addition to unsaturated bonds, rearrangement and other reactions; can also be used as a resin cross-linking agent, a resin hardening accelerator, a rubber additive and the like; has wide application prospect.
The preparation method of nickel acetylacetonate in the prior art, as disclosed in Chinese patent document CN200510102790.5, discloses a preparation method of nickel acetylacetonate, and specifically discloses a method for preparing nickel acetylacetonate by reacting soluble nickel salt with an alkali solution in a reactor with a jacket and a stirring device to generate nickel hydroxide precipitate, and adding acetylacetone into the reaction mixture; the product yield is more than 95% by precisely controlling the addition amount of the alkali solution and the dosage of the acetylacetone in the crystal transformation process; however, the method is carried out in an intermittent mode, the addition amount of the alkali solution needs to be strictly controlled, and the problems of low production efficiency, low product purity, high control precision requirement and the like exist.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention provides a preparation method of high-purity nickel acetylacetonate, so as to solve the problems of low production efficiency, low product purity and the like of the existing preparation method of nickel acetylacetonate, thereby meeting the requirements of industrial continuous production.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing high-purity nickel acetylacetonate, comprising the following steps:
s1: ball-milling nickel oxide powder, solid acid catalyst powder and absolute ethyl alcohol, uniformly mixing, placing in an isostatic press for isostatic pressing operation, and then drying in a baking oven at 60-80 ℃ to obtain porous spherical particles of solid acid catalyst composite nickel oxide;
s2: adding porous spherical particles of the solid acid catalyst composite nickel oxide obtained in the step S1 into one end of a coiled pipe type reactor, introducing acetylacetone into the other end of the coiled pipe type reactor at a constant speed, and continuously reacting the acetylacetone with the nickel oxide under the action of the solid acid catalyst;
s3: after the reaction is finished, the high-purity nickel acetylacetonate product is obtained at the tower bottom after the treatment of the continuous rectifying device. The reaction product outlet end is arranged at one side close to the feeding end of the porous spherical particles.
Preferably, the mass ratio of the nickel oxide powder to the solid acid catalyst powder to the absolute ethyl alcohol is 35-40: 3 to 5:5 to 7.
Preferably, the solid acid catalyst powder is prepared from phosphoric acid and phosphorus pentoxide in a ratio of 1: mixing the materials according to the mass ratio, and adding coarse pore silica gel to obtain the product; the phosphoric acid accounts for 5-15% of the solid acid catalyst powder by mass. The solid acid catalyst not only plays a role in catalyzing reaction, but also has a good water absorption effect, thereby promoting the solid acid catalyst to provide protons.
Preferably, the aspect ratio of the coiled pipe type reactor is 25-50: 1.
preferably, the position of the feeding end of the porous spherical particles of the coiled pipe type reactor is higher than that of the feeding end of the acetylacetone, and the coiled pipe type reactor is formed by connecting a plurality of straight pipe sections which are obliquely downward from each other end to end through bent pipe sections. According to the coiled pipe type reactor, the porous spherical particles of the solid acid catalyst composite nickel oxide slowly move downwards by utilizing self gravity, and the full reaction with the upward flowing acetylacetone can be realized without stirring. The S-shaped pipe reactor of the invention is provided with the filter screens at the feeding end of acetylacetone and the outlet end of reaction products so as to prevent solid particles from being carried out along with liquid.
Preferably, the coiled pipe type reactor is provided with a plurality of arc-shaped reaction areas which are arranged continuously on the inner wall of the bottom of the straight pipe section of the reactor, which is contacted with the spherical sponge nickel particles in a moving way. The invention is characterized in that a plurality of arc-shaped reaction areas which are arranged continuously are arranged on the inner wall of the bottom of the straight pipe section of the reactor, so that porous spherical particles have enough residence time and acetylacetone can be fully mixed and reacted in the arc-shaped reaction areas under the action of a solid acid catalyst.
Preferably, the reaction temperature of the coiled pipe type reactor is 90-105 ℃.
Preferably, the residence time of the acetylacetone in the serpentine reactor is 60 to 90min.
Preferably, the operation temperature of the rectifying device is 160-180 ℃, and the operation pressure is normal pressure.
Preferably, the top of the rectifying device is provided with acetylacetone which does not participate in the reaction, and the acetylacetone is recycled to the feed end of the serpentine tube reactor.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the high-purity nickel acetylacetonate, continuous reaction is carried out in the serpentine tube type reactor with unique structural design, so that the contact reaction of the nickel acetylacetonate and the nickel oxide is sufficient, the intermittent reaction is avoided, the frequent material addition is avoided, the process is simple, the operation is convenient, the production efficiency of the nickel acetylacetonate is greatly improved, and the continuous operation requirement of industrial production is met.
According to the preparation method of the high-purity nickel acetylacetonate, the high-purity nickel acetylacetonate is prepared by carrying out the reaction of the acetylacetonate and the metal sponge nickel in the serpentine tube type reactor, and the purity of the product is further improved after rectification treatment, so that the nickel acetylacetonate product with the purity of more than 99.9% is obtained.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
The preparation method of the high-purity nickel acetylacetonate comprises the following steps:
s1: the mass ratio is 35:3:5, after ball milling and mixing evenly, placing the nickel oxide powder, the solid acid catalyst powder and the absolute ethyl alcohol in an isostatic press for isostatic pressing operation, wherein the operation pressure is 50MPa, and then drying in a drying oven at 60 ℃ to obtain porous spherical particles of the solid acid catalyst composite nickel oxide, and the average particle size is 15mm.
S2: the aspect ratio is 25: and 1, adding 10kg of porous spherical particles of the solid acid catalyst composite nickel oxide obtained in the step S1 into one end of the coiled pipe reactor, controlling the reaction temperature of the coiled pipe reactor to 90 ℃, introducing acetylacetone into the other end of the coiled pipe reactor at a constant speed of 1L per hour, and under the action of the solid acid catalyst, allowing the acetylacetone to stay in the coiled pipe reactor for 60min so as to continuously react with the nickel oxide. The feeding end position of the porous spherical particles of the coiled pipe type reactor is higher than the feeding end position of the acetylacetone.
S3: after the reaction is finished, the qualified mixed solution of acetylacetone and nickel acetylacetonate appears at the outlet end of the reaction product of the coiled pipe type reactor, the mixed solution is treated by a continuous rectifying device, the operating temperature is 165 ℃, the operating pressure is normal pressure, the acetylacetone which does not participate in the reaction is obtained at the top of the rectifying device, the acetylacetone is circulated to the feeding end of the coiled pipe type reactor, and the high-purity nickel acetylacetonate product is obtained after the tower kettle is circularly operated by a reboiler and then passes through impurity removing equipment.
The solid acid catalyst powder is prepared from phosphoric acid and phosphorus pentoxide according to the following weight ratio of 1: mixing the materials according to the mass ratio, and adding coarse pore silica gel to obtain the product; the phosphoric acid accounts for 10% of the solid acid catalyst powder by mass.
The feeding end position of the porous spherical particles of the coiled pipe type reactor is higher than the feeding end position of the acetylacetone, and the coiled pipe type reactor is formed by connecting a plurality of straight pipe sections which are obliquely downward from head to tail through bent pipe sections; the coiled pipe type reactor is characterized in that a plurality of arc-shaped reaction areas which are continuously arranged are arranged on the inner wall of the bottom of the straight pipe section of the reactor, which is in moving contact with spherical sponge nickel particles.
Through testing, the yield of the nickel acetylacetonate is 95.8 percent (relative to nickel), and the purity of the prepared high-purity nickel acetylacetonate is more than 99.9 percent, thereby meeting the quality requirement.
Example 2
The preparation method of the high-purity nickel acetylacetonate comprises the following steps:
s1: the mass ratio is 37:4:6, after the nickel oxide powder, the solid acid catalyst powder and the absolute ethyl alcohol are ball-milled and mixed uniformly, placing the mixture in an isostatic press for isostatic pressing operation, wherein the operation pressure is 45MPa, and then drying the mixture in a drying oven at 70 ℃ to obtain porous spherical particles of the solid acid catalyst composite nickel oxide, and the average particle size is 16mm.
S2: the aspect ratio is 30: and 1, adding 9kg of porous spherical particles of the solid acid catalyst composite nickel oxide obtained in the step S1 into one end of a coiled pipe reactor, controlling the reaction temperature of the coiled pipe reactor to be 95 ℃, introducing acetylacetone into the other end of the coiled pipe reactor at a constant speed of 1L per hour, and under the action of the solid acid catalyst, allowing the acetylacetone to stay in the coiled pipe reactor for 65min so as to continuously react with the nickel oxide.
S3: after the reaction is finished, the qualified mixed solution of acetylacetone and nickel acetylacetonate appears at the outlet end of the reaction product of the coiled pipe type reactor, the mixed solution is treated by a continuous rectifying device, the operating temperature is 160 ℃, the operating pressure is normal pressure, the acetylacetone which does not participate in the reaction is obtained at the top of the rectifying device, the acetylacetone is circulated to the feeding end of the coiled pipe type reactor, and the high-purity nickel acetylacetonate product is obtained after the tower kettle is circularly operated by a reboiler and then passes through impurity removing equipment.
The solid acid catalyst powder is prepared from phosphoric acid and phosphorus pentoxide according to the following weight ratio of 1: mixing the materials according to the mass ratio, and adding coarse pore silica gel to obtain the product; the phosphoric acid accounts for 5% of the solid acid catalyst powder by mass.
The feeding end position of the porous spherical particles of the coiled pipe type reactor is higher than the feeding end position of the acetylacetone, and the coiled pipe type reactor is formed by connecting a plurality of straight pipe sections which are obliquely downward from head to tail through bent pipe sections; the coiled pipe type reactor is characterized in that a plurality of arc-shaped reaction areas which are continuously arranged are arranged on the inner wall of the bottom of the straight pipe section of the reactor, which is in moving contact with spherical sponge nickel particles.
Through testing, the yield of the nickel acetylacetonate is 95.3 percent (relative to nickel), and the purity of the prepared high-purity nickel acetylacetonate is more than 99.9 percent, thereby meeting the quality requirement.
Example 3
The preparation method of the high-purity nickel acetylacetonate comprises the following steps:
s1: the mass ratio is 40:5:7, after the nickel oxide powder, the solid acid catalyst powder and the absolute ethyl alcohol are ball-milled and mixed uniformly, placing the mixture in an isostatic press for isostatic pressing operation, wherein the operation pressure is 60MPa, and then drying the mixture in an oven at 80 ℃ to obtain porous spherical particles of the solid acid catalyst composite nickel oxide, and the average particle size is 14mm.
S2: the aspect ratio is 35: and (2) adding 11kg of porous spherical particles of the solid acid catalyst composite nickel oxide obtained in the step (S1) into one end of the coiled pipe reactor, controlling the reaction temperature of the coiled pipe reactor to 105 ℃, introducing acetylacetone into the other end of the coiled pipe reactor at a constant speed of 1L per hour, and under the action of the solid acid catalyst, allowing the acetylacetone to stay in the coiled pipe reactor for 70min so as to continuously react with the nickel oxide.
S3: after the reaction is finished, the qualified mixed solution of acetylacetone and nickel acetylacetonate appears at the outlet end of the reaction product of the coiled pipe type reactor, the mixed solution is treated by a continuous rectifying device, the operating temperature is 180 ℃, the operating pressure is normal pressure, the acetylacetone which does not participate in the reaction is obtained at the top of the rectifying device, the acetylacetone is circulated to the feeding end of the coiled pipe type reactor, and the high-purity nickel acetylacetonate product is obtained after the tower kettle is circularly operated by a reboiler and then passes through impurity removing equipment.
The solid acid catalyst powder is prepared from phosphoric acid and phosphorus pentoxide according to the following weight ratio of 1: mixing the materials according to the mass ratio, and adding coarse pore silica gel to obtain the product; the phosphoric acid accounts for 15% of the solid acid catalyst powder by mass.
The feeding end position of the porous spherical particles of the coiled pipe type reactor is higher than the feeding end position of the acetylacetone, and the coiled pipe type reactor is formed by connecting a plurality of straight pipe sections which are obliquely downward from head to tail through bent pipe sections; the coiled pipe type reactor is characterized in that a plurality of arc-shaped reaction areas which are continuously arranged are arranged on the inner wall of the bottom of the straight pipe section of the reactor, which is in moving contact with spherical sponge nickel particles.
Through testing, the yield of the nickel acetylacetonate is 96.2 percent (relative to nickel), and the purity of the prepared high-purity nickel acetylacetonate is more than 99.9 percent, thereby meeting the quality requirement.
Example 4
The preparation method of the high-purity nickel acetylacetonate comprises the following steps:
s1: the mass ratio is 36:5:5, after ball milling and mixing evenly, placing the nickel oxide powder, the solid acid catalyst powder and the absolute ethyl alcohol in an isostatic press for isostatic pressing operation, wherein the operation pressure is 50MPa, and then drying in a drying oven at 60 ℃ to obtain porous spherical particles of the solid acid catalyst composite nickel oxide, and the average particle size is 15mm.
S2: the aspect ratio is 40: and 1, adding 10kg of porous spherical particles of the solid acid catalyst composite nickel oxide obtained in the step S1 into one end of a coiled pipe reactor, controlling the reaction temperature of the coiled pipe reactor to be 95 ℃, introducing acetylacetone into the other end of the coiled pipe reactor at a constant speed of 1.2L per hour, and under the action of the solid acid catalyst, allowing the acetylacetone to stay in the coiled pipe reactor for 70min so as to continuously react with the nickel oxide.
S3: after the reaction is finished, the qualified mixed solution of acetylacetone and nickel acetylacetonate appears at the outlet end of the reaction product of the coiled pipe type reactor, the mixed solution is treated by a continuous rectifying device, the operating temperature is 170 ℃, the operating pressure is normal pressure, the acetylacetone which does not participate in the reaction is obtained at the top of the rectifying device, the acetylacetone is circulated to the feeding end of the coiled pipe type reactor, and the high-purity nickel acetylacetonate product is obtained after the tower kettle is circularly operated by a reboiler and then passes through impurity removing equipment.
The solid acid catalyst powder is prepared from phosphoric acid and phosphorus pentoxide according to the following weight ratio of 1: mixing the materials according to the mass ratio, and adding coarse pore silica gel to obtain the product; the phosphoric acid accounts for 12% of the solid acid catalyst powder by mass.
The feeding end position of the porous spherical particles of the coiled pipe type reactor is higher than the feeding end position of the acetylacetone, and the coiled pipe type reactor is formed by connecting a plurality of straight pipe sections which are obliquely downward from head to tail through bent pipe sections; the coiled pipe type reactor is characterized in that a plurality of arc-shaped reaction areas which are continuously arranged are arranged on the inner wall of the bottom of the straight pipe section of the reactor, which is in moving contact with spherical sponge nickel particles.
Through testing, the yield of the nickel acetylacetonate is 95.5 percent (relative to nickel), and the purity of the prepared high-purity nickel acetylacetonate is more than 99.9 percent, thereby meeting the quality requirement.
Example 5
The preparation method of the high-purity nickel acetylacetonate comprises the following steps:
s1: the mass ratio is 38:4:5, after ball milling and mixing evenly, placing the nickel oxide powder, the solid acid catalyst powder and the absolute ethyl alcohol in an isostatic press for isostatic pressing operation, wherein the operation pressure is 50MPa, and then drying in a drying oven at 70 ℃ to obtain porous spherical particles of the solid acid catalyst composite nickel oxide, and the average particle size is 15mm.
S2: the aspect ratio is 45: and 1, adding 10kg of porous spherical particles of the solid acid catalyst composite nickel oxide obtained in the step S1 into one end of a coiled pipe reactor, controlling the reaction temperature of the coiled pipe reactor to 90 ℃, introducing acetylacetone into the other end of the coiled pipe reactor at a constant speed of 1.5L per hour, and under the action of the solid acid catalyst, allowing the acetylacetone to stay in the coiled pipe reactor for 80min so as to continuously react with the nickel oxide.
S3: after the reaction is finished, the qualified mixed solution of acetylacetone and nickel acetylacetonate appears at the outlet end of the reaction product of the coiled pipe type reactor, the mixed solution is treated by a continuous rectifying device, the operating temperature is 160 ℃, the operating pressure is normal pressure, the acetylacetone which does not participate in the reaction is obtained at the top of the rectifying device, the acetylacetone is circulated to the feeding end of the coiled pipe type reactor, and the high-purity nickel acetylacetonate product is obtained after the tower kettle is circularly operated by a reboiler and then passes through impurity removing equipment.
The solid acid catalyst powder is prepared from phosphoric acid and phosphorus pentoxide according to the following weight ratio of 1: mixing the materials according to the mass ratio, and adding coarse pore silica gel to obtain the product; the phosphoric acid accounts for 7% of the solid acid catalyst powder by mass.
The feeding end position of the porous spherical particles of the coiled pipe type reactor is higher than the feeding end position of the acetylacetone, and the coiled pipe type reactor is formed by connecting a plurality of straight pipe sections which are obliquely downward from head to tail through bent pipe sections; the coiled pipe type reactor is characterized in that a plurality of arc-shaped reaction areas which are continuously arranged are arranged on the inner wall of the bottom of the straight pipe section of the reactor, which is in moving contact with spherical sponge nickel particles.
Through testing, the yield of the nickel acetylacetonate is 96.1 percent (relative to nickel), and the purity of the prepared high-purity nickel acetylacetonate is more than 99.9 percent, thereby meeting the quality requirement.
Example 6
The preparation method of the high-purity nickel acetylacetonate comprises the following steps:
s1: the mass ratio is 40:3:7, after ball milling and mixing evenly, placing the nickel oxide powder, the solid acid catalyst powder and the absolute ethyl alcohol in an isostatic press for isostatic pressing operation, wherein the operation pressure is 50MPa, and then drying in a drying oven at 60 ℃ to obtain porous spherical particles of the solid acid catalyst composite nickel oxide, and the average particle size is 15mm.
S2: the aspect ratio is 50: and 1, adding 10kg of porous spherical particles of the solid acid catalyst composite nickel oxide obtained in the step S1 into one end of a coiled pipe reactor, controlling the reaction temperature of the coiled pipe reactor to be 95 ℃, introducing acetylacetone into the other end of the coiled pipe reactor at a constant speed of 1.5L per hour, and under the action of the solid acid catalyst, allowing the acetylacetone to stay in the coiled pipe reactor for 90min so as to continuously react with the nickel oxide.
S3: after the reaction is finished, the qualified mixed solution of acetylacetone and nickel acetylacetonate appears at the outlet end of the reaction product of the coiled pipe type reactor, the mixed solution is treated by a continuous rectifying device, the operating temperature is 170 ℃, the operating pressure is normal pressure, the acetylacetone which does not participate in the reaction is obtained at the top of the rectifying device, the acetylacetone is circulated to the feeding end of the coiled pipe type reactor, and the high-purity nickel acetylacetonate product is obtained after the tower kettle is circularly operated by a reboiler and then passes through impurity removing equipment.
The solid acid catalyst powder is prepared from phosphoric acid and phosphorus pentoxide according to the following weight ratio of 1: mixing the materials according to the mass ratio, and adding coarse pore silica gel to obtain the product; the phosphoric acid accounts for 12% of the solid acid catalyst powder by mass.
The feeding end position of the porous spherical particles of the coiled pipe type reactor is higher than the feeding end position of the acetylacetone, and the coiled pipe type reactor is formed by connecting a plurality of straight pipe sections which are obliquely downward from head to tail through bent pipe sections; the coiled pipe type reactor is characterized in that a plurality of arc-shaped reaction areas which are continuously arranged are arranged on the inner wall of the bottom of the straight pipe section of the reactor, which is in moving contact with spherical sponge nickel particles.
Through testing, the yield of the nickel acetylacetonate is 95.4 percent (relative to nickel), and the purity of the prepared high-purity nickel acetylacetonate is more than 99.9 percent, thereby meeting the quality requirement.
It follows that the present patent offers considerable advantages over the techniques currently in use. The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims.
Claims (10)
1. A preparation method of high-purity nickel acetylacetonate, which is characterized by comprising the following steps:
s1: ball-milling nickel oxide powder, solid acid catalyst powder and absolute ethyl alcohol, uniformly mixing, placing in an isostatic press for isostatic pressing operation, and then drying in a baking oven at 60-80 ℃ to obtain porous spherical particles of solid acid catalyst composite nickel oxide;
s2: adding porous spherical particles of the solid acid catalyst composite nickel oxide obtained in the step S1 into one end of a coiled pipe type reactor, introducing acetylacetone into the other end of the coiled pipe type reactor at a constant speed, and continuously reacting the acetylacetone with the nickel oxide under the action of the solid acid catalyst;
s3: after the reaction is finished, the high-purity nickel acetylacetonate product is obtained at the tower bottom after the treatment of the continuous rectifying device.
2. The method for preparing high purity nickel acetylacetonate according to claim 1, wherein the mass ratio of the nickel oxide powder, the solid acid catalyst powder and the absolute ethyl alcohol is 35-40: 3 to 5:5 to 7.
3. The method for preparing high purity nickel acetylacetonate according to claim 1 wherein the solid acid catalyst powder is prepared from phosphoric acid and phosphorus pentoxide in a ratio of 1: mixing the materials according to the mass ratio, and adding coarse pore silica gel to obtain the product; the phosphoric acid accounts for 5-15% of the solid acid catalyst powder by mass.
4. The method for preparing high purity nickel acetylacetonate according to claim 1, wherein the aspect ratio of the serpentine tube reactor is 25-50: 1.
5. the method for preparing high-purity nickel acetylacetonate according to claim 1, wherein the porous spherical particles of the serpentine tube reactor are positioned at a position higher than the feeding end of the acetylacetonate, and the serpentine tube reactor is formed by connecting a plurality of straight tube sections which are obliquely downward from end to end through bent tube sections.
6. The method for preparing high-purity nickel acetylacetonate according to claim 1, wherein the serpentine tube type reactor is provided with a plurality of arc-shaped reaction areas which are arranged continuously on the inner wall of the bottom of the straight tube section of the reactor where spherical sponge nickel particles are in motion contact.
7. The method for preparing high purity nickel acetylacetonate according to claim 1, wherein the reaction temperature of the serpentine tube reactor is 105-120 ℃.
8. The method for producing high purity nickel acetylacetonate according to claim 1, wherein the residence time of the acetylacetonate in the serpentine reactor is 60 to 90 minutes.
9. The method for producing high purity nickel acetylacetonate according to claim 1, wherein the rectification apparatus is operated at a temperature of 160 to 180℃and a pressure of normal pressure.
10. The method for preparing high-purity nickel acetylacetonate according to claim 1, wherein the top of the rectifying device is provided with acetylacetone which does not participate in the reaction, and the acetylacetone is recycled to the feeding end of the serpentine tube reactor.
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