CN117718050A - Modified diatomite supported catalyst and preparation method and application thereof - Google Patents
Modified diatomite supported catalyst and preparation method and application thereof Download PDFInfo
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- CN117718050A CN117718050A CN202311677978.7A CN202311677978A CN117718050A CN 117718050 A CN117718050 A CN 117718050A CN 202311677978 A CN202311677978 A CN 202311677978A CN 117718050 A CN117718050 A CN 117718050A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 85
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000001914 filtration Methods 0.000 claims description 25
- 239000012065 filter cake Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000725 suspension Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000011282 treatment Methods 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000002161 passivation Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004537 pulping Methods 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000013049 sediment Substances 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000003549 soybean oil Substances 0.000 claims description 7
- 235000012424 soybean oil Nutrition 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000003945 anionic surfactant Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052740 iodine Inorganic materials 0.000 abstract description 9
- 239000011630 iodine Substances 0.000 abstract description 9
- 239000008173 hydrogenated soybean oil Substances 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 241000080590 Niso Species 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 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 description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 3
- 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 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 2
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910007573 Zn-Mg Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a supported nickel-based catalyst by modified diatomite. In the catalyst, the mass percent of the carrier is 20-30%, the mass percent of the nickel is 50-75%, and the mass percent of the auxiliary metal is 5-10%; the carrier is modified diatomite, and the auxiliary metal is Mg, mn or Zn. The hydrogenated soybean oil obtained by the method has the lowest iodine value of 63.2, which is obviously lower than that of commercial catalysts and has better reactivity.
Description
Technical Field
The invention belongs to the technical field of catalyst materials, and particularly relates to a modified diatomite supported nickel-based catalyst, and a preparation method and application thereof.
Background
The oil hydrogenation is that under the action of the catalyst, unsaturated C=C double bond and H 2 And (3) carrying out addition reaction to saturate double bonds in the grease. The hydrogenated oil of the oil can effectively improve the melting point, the thermal stability and the oxidation resistance of the oil, improve the color, the smell, the taste and the like of the oil, is an effective means for modifying the oil, and has great economic value and market demand. The conventional domestic grease hydrogenation catalyst is a supported nickel-based catalyst, and is widely applied due to the advantages of high activity, good dispersibility, easy filtration and the like.
Chinese patent application CN109261153A discloses a Ni-Zn-Mg/SiO 2 -TiO 2 Preparation method of supported catalyst, CN109317186A discloses a method for preparing high-dispersion supported nickel-based catalyst by in-situ synthesis, CN103506165A discloses a TiO 2 -Al 2 O 3 The method for preparing the supported nickel-based catalyst by the composite carrier, CN104399467A discloses a method for preparing the grease hydrogenation catalyst by adopting an organic-water system, but the preparation process is complex. The preparation process of the supported nickel-based catalyst in various technical data always has the problems of complex process, higher cost, poor activity and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a modified diatomite supported nickel-based catalyst, and a preparation method and application thereof. The invention provides a supported nickel-based catalyst comprising a support-modified diatomaceous earth, nickel supported on the support, and a co-metal Mg, mn or Zn. The hydrogenated soybean oil obtained by the method has the lowest iodine value of 63.2, which is obviously lower than that of commercial catalysts and has better reactivity.
In order to solve the technical problems, an object of the present invention is to provide a modified diatomaceous earth supported nickel-based catalyst, which comprises a carrier modified diatomaceous earth, and nickel and a co-metal supported on the carrier; wherein, the mass percent of the carrier is 20-30%, the mass percent of the nickel is 50-75%, and the mass percent of the auxiliary metal is 5-10%; the modified diatomite is diatomite obtained by three treatments of water washing, acid washing and roasting of industrial diatomite; the auxiliary metal is Mg, mn or Zn.
Preferably, in the supported nickel-based catalyst, the nickel source is nickel nitrate or nickel sulfate, and the auxiliary metal source is nitrate or sulfate of auxiliary metal.
Preferably, the carrier is diatomite obtained by three treatments, and the specific steps are that the low-cost industrial diatomite is placed in boiling water and stirred for 1-3 hours, and impurities such as sediment are removed by filtration; cooling to 20-50 ℃, and soaking for 6-12 h by using concentrated acid; and (3) filtering and drying, and roasting for 6 hours at 500-800 ℃ in an air atmosphere to obtain the modified diatomite. The concentrated acid is one of hydrochloric acid, sulfuric acid or phosphoric acid; the mass ratio between the concentrated acid and the industrial diatomite is 2-4.
In addition, another object of the present invention is to provide a method for preparing the modified diatomite supported nickel-based catalyst, comprising the steps of: adding nickel salt, auxiliary metal salt and alkaline precipitant into a suspension system containing modified diatomite to obtain a reaction system with pH of 8-12, and placing the reaction system into a microwave reactor for reaction for 1-6 h.
Preferably, the preparation method of the modified diatomite supported nickel-based catalyst specifically comprises the following steps:
step one: weighing a certain amount of modified diatomite, placing the diatomite into a reaction kettle, adding a certain amount of pure water, adding a small amount of surfactant, pulping for 30min under the water bath condition of 20-50 ℃, and stirring to a suspension state;
step two: dissolving soluble nickel salt and auxiliary metal salt in deionized water; the nickel salt is nickel nitrate or nickel sulfate, the auxiliary metal salt is nitrate or sulfate of auxiliary metal, and the auxiliary metal is Mg, mn or Zn;
step three: under the stirring state, the solution in the second step and the alkaline precipitant are added into the suspension in the first step in a dropwise manner, the pH value of a system is controlled to be 8-12 by regulating the dropwise speed of alkali liquor, and the mixture is placed in a microwave reactor for reaction for 1-6 h after being fully and uniformly mixed;
step four: after the reaction is finished, washing and filtering with deionized water to obtain a filter cake, and drying the filter cake at 100 ℃ for 6 hours; grinding the dried filter cake, and then carrying out hydrogen reduction under the high-temperature condition;
step five: and (3) cooling to room temperature, and carrying out surface passivation treatment by using nitrogen doped with a certain amount of air to obtain the modified diatomite supported nickel-based catalyst.
Preferably, the surfactant in the first step is an anionic surfactant, and is selected from one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate, and the dosage of the surfactant is 0.5-1% of the mass of the carrier modified diatomite.
Preferably, in the third step, the alkaline precipitant is Na 2 CO 3 The mass concentration of the alkali liquor is 5-20wt%.
Preferably, in the fourth step, the reduction temperature is 700 ℃, and the reduction time is 3-6 h.
Preferably, the air volume ratio in the fifth step is 5-10%, and the passivation treatment time is 5-10 h.
Furthermore, the invention also provides application of the modified diatomite supported nickel-based catalyst in catalyzing soybean oil hydrogenation reaction.
Compared with the prior art, the invention has the following advantages:
1. the catalyst is prepared by loading active components on the modified diatomite carrier and adopting a deposition precipitation method, and has the advantages of low raw material cost, simple production process and mild reaction conditions. The reaction performance is evaluated by adopting a soybean oil hydrogenation system, and the iodine value of the obtained hydrogenated soybean oil is lower than that of a commercial catalyst, namely the hydrogenated soybean oil shows better reaction performance than the commercial catalyst.
2. The microwave has strong penetrating power, and the microwave reactor is adopted for reaction, so that the reaction time can be effectively shortened, the reaction efficiency is improved, and the energy consumption is reduced.
3. The modified diatomite carrier prepared by the invention has the characteristics of large aperture and large specific surface area, and the catalyst loaded with the active components is fluffy and porous, has uniform particle size distribution, and has good dispersibility and filterability.
4. The catalyst obtained by the invention has certain magnetism, can be used for separating and recovering products and the catalyst, can be reused after being simply treated, and still has equivalent reactivity.
The technical scheme of the invention is further described in detail below with reference to the examples.
Detailed Description
The starting materials involved in the examples of the present invention, unless otherwise specified, may be obtained from commercial sources or synthesized by methods conventional in the art using commercially available starting materials and reagents.
Example 1
The embodiment provides a preparation method of a modified diatomite supported nickel-based catalyst, which comprises the following steps:
step one: stirring 20g of industrial diatomite in boiling water for 3 hours, and filtering to remove impurities such as sediment; cooling to 50 ℃, and soaking for 6 hours by hydrochloric acid; filtering and drying, and roasting for 6 hours in an air atmosphere at 500 ℃ to obtain modified diatomite;
step two: weighing 5g of modified diatomite, placing the modified diatomite into a reaction kettle, adding 300mL of pure water, adding 0.05g of sodium dodecyl benzene sulfonate, pulping for 30min under the water bath condition of 20 ℃, and stirring to a suspension state;
step three: 80.9g of nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O) and 4.5g of magnesium nitrate hexahydrate (Mg (NO) 3 ) 2 ·6H 2 O) dissolving in 100mL of deionized water to obtain an active component solution;
step four: dropwise adding the solution in the third step and 5% NaOH solution into the suspension system in the second step under the stirring state, regulating the dropping speed of alkali liquor to control the pH value of the system to 8-9, fully and uniformly mixing, and then placing the mixture in a microwave reactor for reaction for 6h;
step five: after the reaction is finished, washing and filtering with deionized water to obtain a filter cake, and drying the filter cake at 100 ℃ for 6 hours; grinding the dried filter cake, and then carrying out hydrogen reduction for 6 hours at 700 ℃;
step six: after cooling to room temperature, surface passivation treatment was performed with nitrogen gas containing 5% by volume of air for 10 hours to obtain a supported nickel-based catalyst a.
Example 2
The embodiment provides a preparation method of a modified diatomite supported nickel-based catalyst, which comprises the following steps:
step one: stirring 20g of industrial diatomite in boiling water for 3 hours, and filtering to remove impurities such as sediment; cooling to 50 ℃, and soaking for 6 hours by hydrochloric acid; filtering and drying, and roasting for 6 hours at 800 ℃ in an air atmosphere to obtain modified diatomite;
step two: weighing 5g of modified diatomite, placing the modified diatomite into a reaction kettle, adding 300mL of pure water, adding 0.03g of sodium dodecyl benzene sulfonate, pulping for 30min under the water bath condition of 50 ℃, and stirring to a suspension state;
step three: 80.9g of nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O) and 5.3g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) dissolving in 100mL of deionized water to obtain an active component solution;
step four: dropwise adding the solution in the third step and 10% NaOH solution into the suspension system in the second step under the stirring state, regulating the dropping speed of alkali liquor to control the pH value of the system to 9-10, fully and uniformly mixing, and then placing the mixture in a microwave reactor for reaction for 3h;
step five: after the reaction is finished, washing and filtering with deionized water to obtain a filter cake, and drying the filter cake at 100 ℃ for 6 hours; grinding the dried filter cake, and then carrying out hydrogen reduction for 6 hours at 700 ℃;
step six: after cooling to room temperature, surface passivation treatment was performed with nitrogen containing 5% by volume of air for 10 hours to obtain a supported nickel-based catalyst B.
Example 3
The embodiment provides a preparation method of a modified diatomite supported nickel-based catalyst, which comprises the following steps:
step one: stirring 20g of industrial diatomite in boiling water for 3 hours, and filtering to remove impurities such as sediment; cooling to 20 ℃, and soaking for 12 hours by hydrochloric acid; filtering and drying, and roasting for 6 hours in an air atmosphere at 500 ℃ to obtain modified diatomite;
step two: weighing 5g of modified diatomite, placing the modified diatomite into a reaction kettle, adding 300mL of pure water, adding 0.05g of sodium dodecyl sulfate, pulping for 30min under the water bath condition of 35 ℃, and stirring to a suspension state;
step three: 80.9g of nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O) and 3.8g of manganese nitrate tetrahydrate (Mn (NO) 3 ) 2 ·4H 2 O) dissolving in 100mL of deionized water to obtain an active component solution;
step four: dropwise adding the solution in the third step and 15% NaOH solution into the suspension system in the second step under the stirring state, regulating the dropping speed of alkali liquor to control the pH value of the system to 10-11, fully and uniformly mixing, and then placing the mixture in a microwave reactor for reaction for 1h;
step five: after the reaction is finished, washing and filtering with deionized water to obtain a filter cake, and drying the filter cake at 100 ℃ for 6 hours; grinding the dried filter cake, and then carrying out hydrogen reduction for 3 hours at 700 ℃;
step six: after cooling to room temperature, surface passivation treatment was performed with nitrogen gas containing 10% by volume of air for 5 hours to obtain a supported nickel-based catalyst C.
Example 4
The embodiment provides a preparation method of a modified diatomite supported nickel-based catalyst, which comprises the following steps:
step one: stirring 20g of industrial diatomite in boiling water for 1h, and filtering to remove impurities such as sediment; cooling to 50 ℃, and soaking for 8 hours by hydrochloric acid; filtering and drying, and roasting for 6 hours in an air atmosphere at 500 ℃ to obtain modified diatomite;
step two: weighing 4g of modified diatomite, placing the modified diatomite into a reaction kettle, adding 300mL of pure water, adding 0.04g of sodium dodecyl benzene sulfonate, pulping for 30min under the water bath condition of 50 ℃, and stirring to a suspension state;
step three: 69.4g of nickel sulfate hexahydrate (NiSO) 4 ·6H 2 O) and 7.6g of magnesium sulfate heptahydrate (MgSO) 4 ·7H 2 O) dissolving in 100mL of deionized water to obtain an active component solution;
step four: mixing the solution obtained in the step three with 10% Na under stirring 2 CO 3 Dropwise adding the solution into the suspension system in the second step, regulating the dropping speed of the alkali liquor to control the pH value of the system to 9-10, fully and uniformly mixing, and then placing the mixture into a microwave reactor for reaction for 6h;
step five: after the reaction is finished, washing and filtering with deionized water to obtain a filter cake, and drying the filter cake at 100 ℃ for 6 hours; grinding the dried filter cake, and then carrying out hydrogen reduction for 3 hours at 700 ℃;
step six: after cooling to room temperature, surface passivation treatment was performed with nitrogen gas containing 5% by volume of air for 10 hours to obtain a supported nickel-based catalyst D.
Example 5
The embodiment provides a preparation method of a modified diatomite supported nickel-based catalyst, which comprises the following steps:
step one: stirring 20g of industrial diatomite in boiling water for 1h, and filtering to remove impurities such as sediment; cooling to 20 ℃, and soaking for 8 hours by using hydrochloric acid; filtering and drying, and roasting for 6 hours at 800 ℃ in an air atmosphere to obtain modified diatomite;
step two: weighing 4g of modified diatomite, placing the modified diatomite into a reaction kettle, adding 300mL of pure water, adding 0.04g of sodium dodecyl benzene sulfonate, pulping for 30min under the water bath condition of 20 ℃, and stirring to a suspension state;
step three: 69.4g of nickel sulfate hexahydrate (NiSO) 4 ·6H 2 O) and 6.6g of zinc sulfate heptahydrate (ZnSO) 4 ·7H 2 O) dissolving in 100mL of deionized water to obtain an active component solution;
step four: mixing the solution obtained in the step three with 15% Na under stirring 2 CO 3 Adding the solution into the suspension system II in the step II in a dropwise manner, regulating and controlling the pH value of the alkaline solution dropwise to 10-11, and fully and uniformly mixingThen placing the mixture in a microwave reactor for reaction for 3 hours;
step five: after the reaction is finished, washing and filtering with deionized water to obtain a filter cake, and drying the filter cake at 100 ℃ for 6 hours; grinding the dried filter cake, and then carrying out hydrogen reduction for 6 hours at 700 ℃;
step six: after cooling to room temperature, surface passivation treatment was performed with nitrogen containing 5% by volume of air for 6 hours to obtain a supported nickel-based catalyst E.
Example 6
The embodiment provides a preparation method of a modified diatomite supported nickel-based catalyst, which comprises the following steps:
step one: stirring 20g of industrial diatomite in boiling water for 1h, and filtering to remove impurities such as sediment; cooling to 20 ℃, and soaking for 10 hours by hydrochloric acid; filtering and drying, and roasting for 6 hours in an air atmosphere at 500 ℃ to obtain modified diatomite;
step two: weighing 4g of modified diatomite, placing the modified diatomite into a reaction kettle, adding 300mL of pure water, adding 0.03g of sodium dodecyl sulfate, pulping for 30min under the water bath condition of 35 ℃, and stirring to a suspension state;
step three: 69.4g of nickel sulfate hexahydrate (NiSO) 4 ·6H 2 O) and 5.2g of manganese sulfate monohydrate (MnSO) 4 ·H 2 O) dissolving in 100mL of deionized water to obtain an active component solution;
step four: mixing the solution obtained in the step three with 20% Na under stirring 2 CO 3 Dropwise adding the solution into the suspension system in the second step, regulating the dropping speed of the alkali liquor to control the pH value of the system to 11-12, fully and uniformly mixing, and then placing the mixture into a microwave reactor for reaction for 1h;
step five: after the reaction is finished, washing and filtering with deionized water to obtain a filter cake, and drying the filter cake at 100 ℃ for 6 hours; grinding the dried filter cake, and then carrying out hydrogen reduction for 6 hours at 700 ℃;
step six: after cooling to room temperature, surface passivation treatment was performed with nitrogen gas containing 10% by volume of air for 8 hours to obtain a supported nickel-based catalyst F.
Evaluation of Performance
The following is a method for determining the oil hydrogenation activity of one of the essential features of the catalyst to be used in the present invention, the raw material used is soybean oil having an initial iodine value (abbreviated as IV) of 135 mg/g, and the oil is hydrogenated to reach an iodine value of less than 70, which is satisfactory.
In a 1L autoclave having a magnetic stirrer and a stirring speed of 800rpm, 500g of soybean oil was evaluated for hydrogenation performance at 200℃under a hydrogen pressure of 0.8MPa with a catalyst charge amount of 0.05% by mass of the raw material, and an iodine value IV obtained by hydrogenating the soybean oil after sufficient reaction was used as an evaluation criterion.
The reaction results are shown in the following table:
| catalyst examples | Reaction time (min) | IV(mg/g) |
| Example 1 catalyst A | 150 | 63.2 |
| EXAMPLE 2 catalyst B | 150 | 64.0 |
| EXAMPLE 3 catalyst C | 170 | 66.4 |
| EXAMPLE 4 catalyst D | 150 | 64.2 |
| EXAMPLE 5 catalyst E | 150 | 63.5 |
| EXAMPLE 6 catalyst F | 170 | 65.9 |
| Commercial catalyst | 150 | 67.0 |
Note that: the commercial catalyst was PRICAT 9920 catalyst from Zhuang Xinmo Feng
As can be seen from the results, the catalysts (A-F) of the present invention were all more effective in the hydrogenation of soybean oil, the iodine value of hydrogenated soybean oil was as low as 63.2, and the activities exhibited were all higher than those of commercial catalysts. The iodine value below 67.0 was also achieved with example (C, F) with a slight extension of the reaction time, whereas lower iodine values could not be achieved with commercial catalysts.
Similar or higher reactivity was found in the case of other raw materials such as castor oil, palm oil, coconut oil, etc.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent structural changes of the above embodiment according to the technical matter of the present invention still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The modified diatomite supported nickel-based catalyst is characterized by comprising carrier modified diatomite, and nickel and auxiliary metal supported on the carrier; wherein, the mass percent of the carrier is 20-30%, the mass percent of the nickel is 50-75%, and the mass percent of the auxiliary metal is 5-10%; the modified diatomite is diatomite obtained by three treatments of water washing, acid washing and roasting of industrial diatomite; the auxiliary metal is Mg, mn or Zn.
2. The modified diatomaceous earth supported nickel-based catalyst of claim 1, wherein the supported nickel-based catalyst comprises nickel nitrate or nickel sulfate as the source of nickel and nitrate or sulfate as the source of co-metal as the co-metal.
3. The modified diatomite supported nickel-based catalyst according to claim 1, wherein the carrier is diatomite obtained by three treatments, and the specific steps are that industrial diatomite is placed in boiling water and stirred for 1-3 hours, and impurities such as sediment are removed by filtration; cooling to 20-50 ℃, and soaking for 6-12 h by using concentrated acid; filtering and drying, and roasting for 6 hours at 500-800 ℃ in an air atmosphere to obtain modified diatomite; the concentrated acid is one of hydrochloric acid, sulfuric acid or phosphoric acid; the mass ratio between the concentrated acid and the industrial diatomite is 2-4.
4. A method for preparing the modified diatomaceous earth supported nickel-based catalyst according to any one of claims 1 to 3, comprising the steps of: adding nickel salt, auxiliary metal salt and alkaline precipitant into a suspension system containing modified diatomite to obtain a reaction system with pH of 8-12, and placing the reaction system into a microwave reactor for reaction for 1-6 h.
5. The preparation method according to claim 4, comprising the following steps:
step one: weighing a certain amount of modified diatomite, placing the diatomite into a reaction kettle, adding a certain amount of pure water, adding a small amount of surfactant, pulping for 30min under the water bath condition of 20-50 ℃, and stirring to a suspension state;
step two: dissolving soluble nickel salt and auxiliary metal salt in deionized water; the nickel salt is nickel nitrate or nickel sulfate, the auxiliary metal salt is nitrate or sulfate of auxiliary metal, and the auxiliary metal is Mg, mn or Zn;
step three: under the stirring state, the solution in the second step and the alkaline precipitant are added into the suspension in the first step in a dropwise manner, the pH value of a system is controlled to be 8-12 by regulating the dropwise speed of alkali liquor, and the mixture is placed in a microwave reactor for reaction for 1-6 h after being fully and uniformly mixed;
step four: after the reaction is finished, washing and filtering with deionized water to obtain a filter cake, and drying the filter cake at 100 ℃ for 6 hours; grinding the dried filter cake, and then carrying out hydrogen reduction under the high-temperature condition;
step five: and (3) cooling to room temperature, and carrying out surface passivation treatment by using nitrogen doped with a certain amount of air to obtain the modified diatomite supported nickel-based catalyst.
6. The preparation method according to claim 5, wherein the surfactant in the first step is an anionic surfactant selected from sodium dodecyl benzene sulfonate and sodium dodecyl sulfate, and the amount of the surfactant is 0.5-1% of the mass of the carrier modified diatomite.
7. The method according to claim 5, wherein in the third step, the alkaline precipitant is Na 2 CO 3 The mass concentration of the alkali liquor is 5-20wt%.
8. The method according to claim 5, wherein the reduction temperature in the fourth step is preferably 700℃and the reduction time is 3 to 6 hours.
9. The method according to claim 5, wherein the air volume ratio in the fifth step is 5-10%, and the passivation treatment time is 5-10 h.
10. Use of a modified diatomaceous earth supported nickel-based catalyst according to any one of claims 1-3 for catalyzing a soybean oil hydrogenation reaction.
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