CN117772201A - Preparation method of Ni-based catalyst with small particle size and low reduction temperature - Google Patents
Preparation method of Ni-based catalyst with small particle size and low reduction temperature Download PDFInfo
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- CN117772201A CN117772201A CN202311698276.7A CN202311698276A CN117772201A CN 117772201 A CN117772201 A CN 117772201A CN 202311698276 A CN202311698276 A CN 202311698276A CN 117772201 A CN117772201 A CN 117772201A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 239000002245 particle Substances 0.000 title claims abstract description 23
- 230000009467 reduction Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000003756 stirring Methods 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 30
- 150000002815 nickel Chemical class 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 230000032683 aging Effects 0.000 claims abstract description 19
- 239000012065 filter cake Substances 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- 239000003929 acidic solution Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 125000000123 silicon containing inorganic group Chemical group 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 3
- 239000002244 precipitate Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229940053662 nickel sulfate Drugs 0.000 claims description 2
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 claims description 2
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 2
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical compound [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011268 mixed slurry Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 238000000967 suction filtration Methods 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical group [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a Ni-based catalyst with small particle size and low reduction temperature, which sequentially comprises the following steps: (a) dissolving nickel salt in deionized water to obtain an acidic solution; (b) dissolving a precipitator in deionized water to obtain alkali liquor; (c) Dripping alkali liquor into the acid solution, and stirring to obtain nickel precipitation slurry; (d) stirring and aging the nickel precipitate slurry; (e) Dissolving silicon-containing inorganic salt in deionized water, and stirring until the inorganic salt is dissolved to obtain silicon-containing solution; (f) Dropwise adding the silicon-containing solution into the nickel precipitation slurry mixture, and continuously stirring until the mixture is uniformly mixed; (g) stirring and aging the mixed system; (h) Washing and filtering the mixed system after stirring and ageing by using deionized water to obtain a filter cake; (i) drying the filter cake; (j) And roasting the dried filter cake at high temperature to obtain the Ni-based catalyst. The Ni-based catalyst prepared by the invention has high load, low reduction temperature, small particle size and simple preparation method.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a preparation method of a supported Ni-based catalyst.
Background
The catalysts related to the hydrogenation technology at home and abroad at present can be divided into two main types of noble metal type catalysts and non-noble metal type catalysts. The metal Ni has the advantages of rich resources, low cost and good hydrogenation effect, so that the metal Ni is often used as a main active component of a non-noble metal hydrogenation catalyst and is widely applied to the catalytic hydrogenation industry.
Compared with noble metal catalysts, non-noble metal Ni-based catalysts have lower hydrogenation performance activity, so that a high Ni content is required to be supported on a carrier. However, the high-supported Ni-based catalyst suffers from the problem of the mutual restriction of the dispersity and the reduction degree during the use, mainly because metallic Ni is liable to SiO during the preparation 2 The carrier (an oxide carrier commonly used in industry for preparing supported Ni-based catalysts) forms a layered nickel silicate structure by Ni-O-Si [ T.Mizutani, et al Bulletin of t he Chemical Society of Japan,1990,63 (7): 2094-2098 ]]. Although the formation of the special layered nickel silicate structure is beneficial to improving the dispersity of NiO precursor particles and inhibiting particle aggregation and growth, niO particles are difficult to reduce under the low-temperature condition, so that the reduction degree of the catalyst under the low-temperature condition is reduced, and the prepared supported Ni-based catalyst has to be subjected to reduction pretreatment under the high-temperature condition, so that the production cost of the catalyst and the requirements on equipment and processes are greatly increased. Aiming at the common problem of mutual restriction of dispersity and reduction degree in the preparation process of the supported Ni-based catalyst, the common solutions are as follows: 1) Adding a noble metal auxiliary agent; 2) Synthesizing metal Ni colloid particles by adopting a metal colloid preparation method, and then loading the metal Ni colloid particles on a carrier; 3) SiO is replaced by adopting a carbon material with high specific surface area as a carrier 2 And an oxide support. However, these methods require special equipment (e.g., oxygen-free environment) and are expensive(noble metal is used), and the metal Ni has weak interaction with the carrier (for example, carbon carrier is used).
Unlike these prior art solutions, the present invention is still a conventional, inexpensive SiO 2 The SiO is realized by adjusting the acid-base environment in the catalyst preparation process on the premise of not using chemical reagents which are toxic and harmful to the environment as carriers 2 On the carrier, the reduction temperature is low<480 ℃ and has small particle size and high load, thereby providing a novel method for breaking through the problem of the mutual restriction of dispersity and reduction degree.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel method for breaking through the commonality problem that the dispersity and the reduction degree are mutually restricted in the preparation of the oxide supported Ni-based catalyst, and the supported Ni-based catalyst has the characteristics of high load, low reduction temperature, small particle size, simple preparation method and the like.
The following describes the technical means adopted to solve the above-mentioned problems.
A method for preparing a Ni-based catalyst with small particle size and low reduction temperature, which comprises the following steps in sequence:
(a) Dissolving nickel salt in deionized water, and regulating the concentration of the nickel salt to ensure that the pH value of the nickel salt is stabilized at 4.8 to obtain an acidic solution; the nickel salt is one of nickel nitrate hexahydrate, anhydrous nickel sulfate, nickel sulfate hexahydrate, nickel sulfate heptahydrate and nickel chloride hexahydrate;
(b) Dissolving a precipitator in deionized water, and stirring until the precipitator is dissolved to obtain alkali liquor; the precipitant is one of ammonium bicarbonate, ammonium carbonate and anhydrous sodium carbonate;
(c) Dropwise adding alkali liquor into the acidic solution obtained in the step (a) at the temperature of 20-35 ℃, controlling the pH value range to 7.5-9.0, and stirring to obtain nickel precipitation slurry;
(d) Placing the nickel precipitate slurry obtained in the step (c) in an environment of 20-50 ℃ for stirring and aging;
(e) Dissolving silicon-containing inorganic salt in deionized water, and stirring until the inorganic salt is dissolved to obtain silicon-containing solution; the silicon-containing inorganic salt is one of sodium silicate nonahydrate, sodium metasilicate and potassium silicate;
(f) Dropwise adding the silicon-containing solution obtained in the step (e) into nickel precipitation slurry, regulating the pH of the reaction system to 8.5-9.0, and continuously stirring until uniform mixing is achieved;
(g) Placing the mixed system obtained in the step (f) in an environment of 20-50 ℃ for stirring and aging;
(h) Washing and filtering the mixed system after stirring and ageing by using deionized water to obtain a filter cake;
(i) Placing the filter cake obtained in the step (h) in an environment of 90-120 ℃ for drying;
(j) Placing the dried filter cake in a high-temperature roasting treatment at 400-800 ℃ for 2-5 h to obtain the Ni-based catalyst, wherein the Ni-based catalyst comprises SiO 2 Carrier and NiO, particle size of NiO is less than 5nm, ni loading = m in catalyst Ni /(m Ni +m SiO2 ) X 100% = 50-80%, where m Ni And m SiO2 The hydrogen reduction temperature of the Ni-based catalyst is not higher than 480 ℃ according to the raw material feeding amount.
Further, the acidic solution in step (a) is specifically configured by the following method: firstly, dissolving nickel salt in deionized water to obtain a low-concentration nickel salt solution with the pH value being more than 4.8, and then adding nickel salt or nickel salt and deionized water for gradual adjustment to enable the pH value to be stable at 4.8, so as to obtain an acidic solution.
Further, the nickel salt described in step (a) is preferably nickel nitrate hexahydrate. In step (a), the nickel salt is nickel nitrate hexahydrate, the nickel nitrate hexahydrate is dissolved in deionized water to prepare a nickel salt solution with the concentration of 0.1mol/L, and the nickel salt solution is added to stabilize the pH value at 4.8, so that an acidic solution is obtained.
Further, in step (b), the precipitant is preferably sodium carbonate.
Further, in the step (b), the concentration of the alkali liquor is 0.1mol/L to 0.5mol/L.
Still further, in the step (b), the precipitant is sodium carbonate, and the concentration of the precipitant is preferably 0.2mol/L.
Further, in step (c), the pH is controlled to 7.5 to 8.5, most preferably 8.0.
Further, in step (d), the aging time is preferably 40 to 90 minutes, most preferably 60 minutes.
Further, in the step (f), the pH of the reaction system is adjusted to 8.8.
Further, in step (g), the aging time is preferably 4 to 7 hours, most preferably 6 hours.
Further, in the step (h), the number of times of washing and filtering with deionized water is preferably 3 to 6.
Further, in the step (i), the drying temperature is 90-120 ℃ and the drying time is 10-15 h; the drying temperature is preferably 110 ℃, and the drying time is preferably 12 hours.
Further, in the step (j), the high-temperature baking atmosphere is preferably air, the baking temperature is preferably 500 ℃, and the baking treatment time is preferably 3 hours.
The Ni-based catalyst prepared by the invention can be used for hydrogenation reaction of C9 petroleum resin, and the chromaticity of the hydrogenated petroleum resin is reduced, which is more beneficial to the application of petroleum resin.
Compared with the prior art, the invention has the beneficial effects that: the supported Ni-based catalyst prepared by the method has the characteristics of high load, low reduction temperature, small particle size, simple preparation method and the like.
Drawings
Fig. 1 is an XRD spectrum of the Ni-based catalyst prepared from example 1.
FIG. 2 is H of Ni-based catalyst prepared in example 1 2 -TPR profile.
Fig. 3 is an XRD spectrum of the Ni-based catalyst prepared from comparative example 1.
FIG. 4 is H of the Ni-based catalyst prepared in comparative example 1 2 -TPR profile.
Fig. 5 is an XRD spectrum of the Ni-based catalyst prepared from comparative example 2.
FIG. 6 is H of Ni-based catalyst prepared in comparative example 2 2 -TPR profile.
Detailed Description
The technical scheme of the present invention is further described by the following specific examples, but the scope of the present invention is not limited by the following examples.
Example 1
14.54g Ni (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in deionized water to prepare a nickel-containing solution with the concentration of 0.1mol/L, and Ni (NO) is added into the nickel-containing solution 3 ) 2 An aqueous solution to stabilize the pH of the nickel-containing solution at 4.8, wherein Ni (NO 3 ) 2 ·6H 2 The O content is 36.587g; weighing Na 2 CO 3 Dissolving in deionized water, and stirring to prepare alkali liquor with the concentration of 0.2 mol/L; dropwise adding alkali liquor into the nickel-containing solution at 24 ℃ under stirring, and adjusting the pH value to 8.0 to obtain nickel precipitation slurry; then stirring and aging for 60min at 24 ℃; weighing 7.209g K 2 SiO 3 ·nH 2 O is dissolved in deionized water, and stirred to prepare a silicon-containing solution with the concentration of 0.25 mol/L; dropwise adding the silicon-containing solution into the nickel precipitation slurry mixture at 24 ℃ under stirring, and adjusting the pH value of the slurry mixture to 8.8 (about 138mL of silicon-containing solution is consumed) to obtain nickel-silicon slurry mixture; then stirring and aging for 6 hours at 24 ℃; carrying out suction filtration on the nickel-silicon mixed slurry, washing the nickel-silicon mixed slurry with deionized water, and repeating the process for 4 times to obtain a filter cake; drying the washed filter cake in an oven at 110 ℃ for 12 hours; placing the dried filter cake in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min in air atmosphere, and roasting for 3 hours to obtain SiO with 78% load 2 Supported Ni-based catalyst. The XRD spectrum of the catalyst is shown in figure 1. XRD characterization shows that NiO crystal phases mainly exist in the catalyst, and the particle size of NiO in the catalyst is about-3.5 nm through estimation of a Schlemer equation. H of the catalyst 2 The TPR characterization is shown in figure 2. H 2 The TPR characterization shows that the catalyst only has a significant hydrogen consumption peak around 433 ℃. XRD and H as described above 2 TPR characterization shows that NiO with small particle size can be prepared by the method reported by the invention<5 nm), the reduction temperature is low<480 ℃ SiO 2 Supported Ni-based catalyst.
Example 2
The catalyst prepared in the example 1 is adopted to carry out the hydrogenation reaction of the C9 petroleum resin, and the specific method is as follows: 15g of C9 petroleum resin are dissolved in 100g of cyclohexane and 10g of silicon are added after stirring for 1hThe algae soil is stirred for 2 hours continuously, and 15 percent C9 petroleum resin solution is obtained after sedimentation and centrifugation. The chromaticity of the unhydrogenated C9 petroleum resin solution at this time was measured by a petroleum product chromaticity analyzer to be 13. 0.3150g of the supported Ni-based catalyst prepared in example 1 was placed in a fixed bed reactor at 480℃with H 2 Reduction for 2h, followed by use of 1%O at room temperature 2 /N 2 After passivation for 4 hours, the mixture and 70g of 15% C9 petroleum resin solution are placed in a miniature high-temperature high-pressure reaction kettle together. By H 2 Air in the miniature high-temperature high-pressure reaction kettle is replaced, and then H is introduced 2 The hydrogenation reaction of the C9 petroleum resin is carried out under the reaction conditions that the reaction temperature is 230 ℃, the initial pressure is 6MPa, the reaction time is 4 hours and the rotating speed is 500r/min, and the chromaticity of the hydrogenated C9 petroleum resin solution is 0 measured by a petroleum product chromaticity analyzer. The experimental results show that the supported Ni-based catalyst prepared in the example 1 has better hydrogenation reaction performance of the C9 petroleum resin.
Comparative example 1
14.54g Ni (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in deionized water to prepare nickel-containing solution with the concentration of 0.1mol/L, and the pH value is changed at about 5.4; weighing Na 2 CO 3 Dissolving in deionized water, and stirring to prepare alkali liquor with the concentration of 0.2 mol/L; dropwise adding alkali liquor into the nickel-containing solution at 24 ℃ under stirring, and adjusting the pH value to 8.0 to obtain nickel precipitation slurry; then, stirring and aging for 60min at 24 ℃; 13.864g of Na is weighed 2 SiO 3 ·9H 2 O is dissolved in deionized water, and stirred to prepare a silicon-containing solution with the concentration of 0.25 mol/L; dropwise adding the silicon-containing solution into the nickel precipitation slurry mixture at 24 ℃ under stirring to obtain nickel-silicon slurry mixture, wherein the pH value is 11; then stirring and aging for 6 hours at 24 ℃; carrying out suction filtration on the nickel-silicon mixed slurry, washing with deionized water, and repeating for 5 times to obtain a filter cake; drying the washed filter cake in an oven at 110 ℃ for 12 hours; placing the dried filter cake in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min in air atmosphere, and roasting for 3 hours to obtain SiO with 50% load 2 The XRD spectrum of the supported Ni-based catalyst is shown in figure 3. XRD characterization illustrates the main components in the catalystNiO crystal phase exists, and the particle size of NiO in the catalyst is estimated to be about 2.6nm through a Schler equation. FIG. 4 is H of the catalyst 2 TPR spectrum, showing that the hydrogen consumption peak of the catalyst appears at about 630 ℃. The characterization results of FIGS. 3 and 4 illustrate SiO as prepared using the method reported in comparative example 1 2 The particle size of NiO of the supported Ni-based catalyst was similar to that of the catalyst prepared by the method reported in example 1, but the reduction temperature was higher than 600 ℃.
Comparative example 2
14.54g Ni (NO) was weighed out 3 ) 2 ·6H 2 Dissolving O in deionized water to prepare nickel-containing solution with concentration of 0.1mol/L, and adding 0.05mol/L HNO 3 The pH value of the solution is regulated to 4.8; weighing Na 2 CO 3 Dissolving in deionized water, and stirring to prepare alkali liquor with the concentration of 0.2 mol/L; dropwise adding alkali liquor into the nickel-containing solution at the temperature of 24 ℃ below zero under the stirring condition, and regulating the pH value to 8.0 to obtain nickel precipitation mixed slurry; then stirring and aging for 60min at the temperature of 24 ℃; weighing 7.714g K 2 SiO 3 ·nH 2 O is dissolved in deionized water, and stirred to prepare a silicon-containing solution with the concentration of 0.25 mol/L; dropwise adding the silicon-containing solution into the nickel precipitation slurry mixture at the temperature of 24 ℃ below zero under the stirring condition to obtain nickel-silicon slurry mixture; with 0.05mol/L HNO 3 The pH value of the nickel-silicon mixed slurry is regulated to 8.8 by the solution; then stirring and aging for 6 hours at the temperature of 24 ℃; carrying out suction filtration on the nickel-silicon mixed slurry, washing with deionized water, and repeating for 5 times to obtain a filter cake; drying the washed filter cake in an oven at 110 ℃ for 12 hours; placing the dried filter cake in a muffle furnace, heating to 500 ℃ at a heating rate of 5 ℃/min in air atmosphere, and roasting for 3 hours to obtain SiO with 50% load 2 Supported Ni-based catalyst. The XRD spectrum of the catalyst is shown in figure 5. XRD characterization shows that NiO crystal phases mainly exist in the catalyst, and the particle size of NiO in the catalyst is about-2.1 nm through estimation of a Schlemer equation. FIG. 6 is H of the catalyst 2 TPR spectrum, showing that the hydrogen consumption peak of the catalyst appears at about 610 ℃. The characterization results of FIGS. 5 and 6 illustrate SiO as prepared using the method reported in comparative example 2 2 Supported Ni-based catalyst having NiO particle size and method reported in example 1The catalyst prepared had similar particle size but had a reduction temperature of greater than 600 ℃.
Claims (10)
1. A preparation method of a Ni-based catalyst with small particle size and low reduction temperature is characterized by comprising the following steps: the preparation method sequentially comprises the following steps:
(a) Dissolving nickel salt in deionized water, and regulating the concentration of the nickel salt to ensure that the pH value of the nickel salt is stabilized at 4.8 to obtain an acidic solution; the nickel salt is one of nickel nitrate hexahydrate, anhydrous nickel sulfate, nickel sulfate hexahydrate, nickel sulfate heptahydrate and nickel chloride hexahydrate;
(b) Dissolving a precipitator in deionized water, and stirring until the precipitator is dissolved to obtain alkali liquor; the precipitant is one of ammonium bicarbonate, ammonium carbonate and anhydrous sodium carbonate;
(c) Dropwise adding alkali liquor into the acidic solution obtained in the step (a) at the temperature of 20-35 ℃, controlling the pH value range to 7.5-9.0, and stirring to obtain nickel precipitation slurry;
(d) Placing the nickel precipitate slurry obtained in the step (c) in an environment of 20-50 ℃ for stirring and aging;
(e) Dissolving silicon-containing inorganic salt in deionized water, and stirring until the inorganic salt is dissolved to obtain silicon-containing solution; the silicon-containing inorganic salt is one of sodium silicate nonahydrate, sodium metasilicate and potassium silicate;
(f) Dropwise adding the silicon-containing solution obtained in the step (e) into nickel precipitation slurry, regulating the pH of the reaction system to 8.5-9.0, and continuously stirring until uniform mixing is achieved;
(g) Placing the mixed system obtained in the step (f) in an environment of 20-50 ℃ for stirring and aging;
(h) Washing and filtering the mixed system after stirring and ageing by using deionized water to obtain a filter cake;
(i) Placing the filter cake obtained in the step (h) in an environment of 90-120 ℃ for drying;
(j) Placing the dried filter cake in a high-temperature roasting treatment at 400-800 ℃ for 2-5 h to obtain the Ni-based catalyst, wherein the Ni-based catalyst comprises SiO 2 Carrier and NiO, particle size of NiO is less than 5nm, ni loading = m in catalyst Ni /(m Ni +m SiO2 ) X 100% = 50-80%, where m Ni And m SiO2 The hydrogen reduction temperature of the Ni-based catalyst is not higher than 480 ℃ according to the raw material feeding amount.
2. The method of manufacturing according to claim 1, wherein: the acidic solution in step (a) is specifically configured by the following method: firstly, dissolving nickel salt in deionized water to obtain a low-concentration nickel salt solution with the pH value being more than 4.8, and then adding nickel salt or nickel salt and deionized water for gradual adjustment to enable the pH value to be stable at 4.8, so as to obtain an acidic solution.
3. The method of manufacturing as claimed in claim 2, wherein: in the step (a), the nickel salt is nickel nitrate hexahydrate, nickel nitrate is taken and dissolved in deionized water to prepare nickel salt solution with the concentration of 0.1mol/L, and the nickel salt solution is added to stabilize the pH value at 4.8, so that an acidic solution is obtained.
4. The method of manufacturing according to claim 1, wherein: in the step (b), the concentration of the alkali liquor is 0.1mol/L to 0.5mol/L, preferably the precipitant is sodium carbonate, and the concentration of the precipitant is 0.2mol/L.
5. The method of manufacturing according to claim 1, wherein: in step (c), the pH is controlled to 7.5 to 8.5, preferably 8.0.
6. The method of manufacturing according to claim 1, wherein: in the step (d), the aging time is 40-90 min.
7. The method of manufacturing according to claim 1, wherein: in step (f), the pH of the reaction system is adjusted to 8.8.
8. The method of manufacturing according to claim 1, wherein: in the step (g), the aging time is 4-7 h.
9. The method of manufacturing according to claim 1, wherein: in the step (i), the drying temperature is 90-120 ℃ and the drying time is 10-15 h.
10. The method of manufacturing according to claim 1, wherein: in the step (j), the high-temperature roasting atmosphere is air, the roasting temperature is 500 ℃, and the roasting treatment time is 3 hours.
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