CN101773842B - Supported catalyst and preparation method thereof - Google Patents
Supported catalyst and preparation method thereof Download PDFInfo
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- CN101773842B CN101773842B CN201010034067A CN201010034067A CN101773842B CN 101773842 B CN101773842 B CN 101773842B CN 201010034067 A CN201010034067 A CN 201010034067A CN 201010034067 A CN201010034067 A CN 201010034067A CN 101773842 B CN101773842 B CN 101773842B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000460 chlorine Substances 0.000 claims abstract description 31
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 transition metal salts Chemical class 0.000 claims abstract description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 11
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 35
- 239000003595 mist Substances 0.000 claims description 20
- 239000012018 catalyst precursor Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 150000001447 alkali salts Chemical class 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 230000001186 cumulative effect Effects 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 150000003891 oxalate salts Chemical class 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 46
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 150000001805 chlorine compounds Chemical class 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000009849 deactivation Effects 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- DNDPLEAVNVOOQZ-UHFFFAOYSA-N 2,3,4,5,6-pentachloropyridine Chemical compound ClC1=NC(Cl)=C(Cl)C(Cl)=C1Cl DNDPLEAVNVOOQZ-UHFFFAOYSA-N 0.000 description 15
- OWWMTVCJAYYHHE-UHFFFAOYSA-N 4-chloropyridine Chemical compound ClC1=C=C=NC=C1 OWWMTVCJAYYHHE-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 150000003222 pyridines Chemical class 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000002779 inactivation Effects 0.000 description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 235000011837 pasties Nutrition 0.000 description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011363 dried mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- BXEMXLDMNMKWPV-UHFFFAOYSA-N pyridine Chemical class C1=CC=NC=C1.C1=CC=NC=C1 BXEMXLDMNMKWPV-UHFFFAOYSA-N 0.000 description 2
- 238000012797 qualification Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a supported catalyst which comprises a carrier and an active component that is supported on the carrier, the carrier is silica, and the active component is at least one of chlorides of transition metals and chlorides of alkaline earth metals. The invention further provides a preparation method of the supported catalyst, which comprises the following steps: (1) water solution of at least one of transition metal salts and alkaline earth metal salts is mixed with silica sol, and then the mixture is dried and roasted, thus preparing a precursor of the catalyst; and (2) the precursor of the catalyst contacts with chlorine, and the contact conditions lead at least part of the transition metals and the alkaline earth metals in the obtained products to exist in the form of chlorides after the contact. The supported catalyst is not easy to be deactivated, the service life is long, the catalyst can be regenerated after deactivation, and the catalytic activity is high, thus improving the efficiency greatly for preparing pyridine polychloride and reducing the production cost.
Description
Technical field
The present invention relates to a kind of loaded catalyst, and this Preparation of catalysts method.
Background technology
4 chloro pyridine is a kind of important organic compound and important synthesis intermediates, can be used for synthetic herbicide, pesticide, bactericide, plant growth regulator and medical pharmacy etc.Penta chloropyridine has higher biologically active; The synthetic intermediate that can be used as agricultural chemicals, medicine and dyestuff; And have characteristics such as wide spectrum, efficient and low toxicity by the synthetic a series of agricultural chemicals of penta chloropyridine, and agricultural development and ecological protection are had great importance, the market potential ten minutes is wide.
The method of existing preparation 4 chloro pyridine or penta chloropyridine mainly contains pyridine liquid phase chlorination and pyridine gas-solid catalysis chloridising etc.Wherein flow process is simple because of having, yield is high has application prospect most for the gas-solid catalysis chloridising.The pyridine gas-solid catalysis chlorination catalyst of having reported is with muriatic loaded catalysts such as activated carbon loaded cobalt as active component, lanthanums; Yet; Carbon distribution in use be prone to take place and causes the inactivation of catalyst in this catalyst, and, can not regenerate behind this catalysqt deactivation.
Summary of the invention
The present invention is in order to overcome the existing easy inactivation that is used to prepare the catalyst of polychlorinated pyridine such as 4 chloro pyridine, penta chloropyridine; And unrenewable shortcoming behind the inactivation provides a kind of new loaded catalyst, and this loaded catalyst is difficult for inactivation; Service life is longer; Can regenerate behind the inactivation, and catalytic activity is very high, thereby has improved the efficient of preparation polychlorinated pyridine greatly and reduced production cost.
Another object of the present invention provides the method for the said loaded catalyst of preparation.
The invention provides a kind of loaded catalyst, this catalyst comprises carrier and loads on the active component on the said carrier, and said carrier is a silica, and said active component is at least a in the chloride of chloride and alkaline-earth metal of transition metal.
The present invention also provides a kind of preparation method of loaded catalyst, and this method may further comprise the steps:
(1) at least a aqueous solution in transition metal salt and the alkali salt is mixed with Ludox, then the gained mixture is carried out drying and roasting, thereby make catalyst precursor;
(2) said catalyst precursor is contacted with chlorine, the condition of said contact makes in the products therefrom of contact back that the said transition metal of part and alkaline-earth metal exist with its chloride form at least.
In said catalyst provided by the invention, owing to use silica to substitute existing activated carbon as carrier, thus obviously improved the stability of catalytic activity of said catalyst; And this catalyst is difficult for producing carbon distribution, therefore is not easy inactivation adopting pyridine to prepare in the process of polychlorinated pyridine, and service life is longer; In addition, this catalyst can be handled through aerating oxygen at high temperature after inactivation, carries out activation through feeding chlorine then, thereby is able to regeneration, therefore, has improved the utilization rate of catalyst greatly and has reduced the production cost of polychlorinated pyridine.
In addition, the said method preparation technology who prepares catalyst provided by the invention is simple, and process conditions are gentle, thereby is easy to realize the said loaded catalyst of preparation.And; Record according to embodiment can be found out; Adopt the said prepared loaded catalyst of method for preparing catalyst provided by the invention, when being used for the preparation of polychlorinated pyridine such as 4 chloro pyridine, penta chloropyridine, said loaded catalyst has very high catalytic efficiency.
The specific embodiment
Said loaded catalyst provided by the invention comprises carrier and loads on the active component on the said carrier, and said carrier is a silica, and said active component is at least a in the chloride of chloride and alkaline-earth metal of transition metal.
In said catalyst, be benchmark with the gross weight of said catalyst, the content of said active component can be 5-20 weight %, is preferably 7-15 weight %, the content of said carrier can be 80-95 weight %, is preferably 85-93 weight %.Content through making said active component preferably in 7-15 weight %, can guarantee that the catalytic activity of said catalyst is higher on the one hand at 5-20 weight %, thereby guarantees fully to react through the raw material of said catalyst; Can also overcome the higher defective of catalyst cost that causes because of said active component content is excessive on the other hand.Therefore, take all factors into consideration economic factor and catalyst activity, the content of the preferred said activity of such catalysts composition of the present invention is in above-mentioned scope.
In said catalyst; The transition metal that said active component can be used for the method preparing polychlorinated pyridine of various routines or the chloride of alkaline-earth metal; Yet; In order further to improve the catalytic activity of said catalyst, and then improve the catalytic efficiency in the process of preparation polychlorinated pyridine, said active component is preferably at least a in the chloride of cobalt, lanthanum, barium, iron, copper and zinc.
In a kind of preferred implementation of the present invention; Active component in the said catalyst comprises cobalt chloride and lanthanum chloride at least; Under this preferable case; Can significantly improve the catalytic activity of said catalyst, particularly, improve widely at the catalytic efficiency of catalyst described in the process of preparation polychlorinated pyridine.Further under the preferable case, in said catalyst, be benchmark with the gross weight of said catalyst; The content of said cobalt chloride can be 2-9 weight %; 3-8 weight % more preferably, the content of said lanthanum chloride is 2-12 weight %, more preferably 2.5-10 weight %.
In the present invention, the pore volume of said catalyst can be 0.3-0.4 milliliter/gram catalyst, is preferably 0.35-0.4 milliliter/gram catalyst.Said catalyst in above-mentioned pore volume scope has better catalytic activity, and the life-span of longer use.
In said catalyst, the metallic element in the chloride of said transition metal and alkaline-earth metal can be provided by at least a water soluble salt in nitrate, carbonate, oxalates and the chloride of corresponding metal element; Said silica supports is preferably provided by Ludox.
The preparation method of a kind of loaded catalyst that the present invention also provides, this method may further comprise the steps:
(1) at least a aqueous solution in transition metal salt and the alkali salt is mixed with Ludox, then the gained mixture is carried out drying and roasting, thereby make catalyst precursor;
(2) said catalyst precursor is contacted with chlorine, the condition of said contact makes in the products therefrom of contact back that the said transition metal of part and alkaline-earth metal exist with its chloride form at least.
In step (1), the concentration of said solution is different and different with the kind of said transition metal salt and alkali salt, and generally, the concentration of said solution can be the 0.01-0.15 grams per milliliter.
In step (1), what said transition metal salt and alkali salt can be in nitrate, carbonate, oxalates and the chlorides is at least a.
In step (1), what the metallic element in said transition metal salt and the alkali salt can be in cobalt, lanthanum, barium, iron, copper and the zinc is at least a.
In a kind of preferred implementation of the present invention, the metallic element in said transition metal salt and the alkali salt comprises cobalt and lanthanum at least.Under this preferable case, can significantly improve the catalytic activity of said catalyst, particularly, improved widely at the catalytic efficiency of catalyst described in the process of preparation polychlorinated pyridine.
In step (1), concentration of silicon dioxide does not have special qualification in the said Ludox, and for the catalyst that guarantees finally to make has advantages of high catalytic activity, concentration of silicon dioxide is preferably 15-30 weight % in the said Ludox.
In step (1); At least a aqueous solution in transition metal salt and the alkali salt and Ludox method of mixing can be comprised: under 15-40 ℃ temperature; Under at the uniform velocity stirring; Making the said solution that makes in said Ludox and the step (1) is 1 with weight ratio: 0.1-1.5 mixes, and keeps and stirred 1-7 hour, thereby makes the mixed solution of abundant dispersion.
In step (1); The method of said drying preferably includes said mixed solution is heated to 80-95 ℃; And under this temperature, make the water evaporates in the said mixture; Water content in mixture is 0.1-15 weight %, is preferably 2-13 weight %, and the mixture that obtains was descended dry 12-72 hour at 105-130 ℃.In the present invention; Be divided into two stages through dry run with said mixed solution; Be lower temperature drying stage (80-95 ℃) and higher temperature drying stage (105-130 ℃); Thereby can improve the specific area of the catalyst that finally makes, and then guarantee that the catalyst that finally makes has advantages of high catalytic activity.
In step (1), the condition of said roasting does not have special qualification, can in the roasting condition of routine, suitably select, and under the preferable case, the condition of said roasting can comprise: temperature is 300-500 ℃, and the time is 5-9 hour.
In step (2), the condition that said catalyst precursor contacts with chlorine can comprise: temperature is 300-400 ℃, is preferably 320-380 ℃, and the time is 2-5 hour, is preferably 2.5-4 hour.
In step (2), said catalyst precursor contacts with chlorine preferably and in the presence of protective gas, carries out, and the volume of chlorine accounts for the 30-90% of cumulative volume of the mist of chlorine and said protective gas.In the present invention, said protective gas is meant the gas that can not react with chlorine and said catalyst precursor, and common said protective gas can be a periodic table of elements group 0 element gas for nitrogen and conventional inert gas.
Below through embodiment the present invention is done further detailed explanation.
Embodiment 1
Present embodiment is used to explain said loaded catalyst provided by the invention and preparation method thereof.
The cobalt nitrate of 104.2 grams and the lanthanum nitrate of 35.7 grams are dissolved in 2000 milliliters the deionized water; After treating fully dissolving; Under room temperature and stirring condition, progressively be added drop-wise in 3.5 kilograms the Ludox of 27 weight %, thereby continue to stir the mixed solution that was fully disperseed in 6 hours after dripping again.Then; Under agitation said mixed liquor is warmed up to 90 ℃; And under this temperature, make the water evaporates in the said mixed solution, and becoming pasty state (water content is 10 weight %) up to mixture, the mixture with this pasty state is placed in the drying box following dry 48 hours at 120 ℃ then.Afterwards, dried mixture is placed in the heating furnace,, thereby obtains catalyst precursor 450 ℃ of following roastings 8 hours.This catalyst precursor is packed in the fixed bed reactors, and the internal diameter of the cylinder of said fixed bed reactors is 32 millimeters, and length is 1200 millimeters.Make said reactor be warming up to 350 ℃ through heating; Begin in said reactor to feed the mist (volume of chlorine account for said mist cumulative volume 60%) of chlorine and nitrogen then; Said mist fed 4 hours with the flow of 1000 ml/min, thereby made loaded catalyst according to the present invention.CoCl in the said catalyst
2Content be about 7.4 weight %, LaCl
3Content be about 2.7 weight %, and the weight of said catalyst is about 1 kilogram; The pore volume that records said catalyst through nitrogen adsorption desorption method is 0.36 a milliliter/gram catalyst.
With nitrogen is carrier, with the pyridine vaporization, simultaneously chlorine is preheated to the temperature identical with pyridine, and said pyridine is mixed in premixed device with 1: 10 volume ratio with chlorine; With the adjustment to 330 of the above-mentioned said fixed bed reactors that said catalyst is housed ℃, and make from the mist in the said premixed device with 110h
-1Flow feed in the said fixed bed reactors.Feed in the said fixed bed reactors after 24 hours, 100 hours and 500 hours at said mist respectively; The product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and penta chloropyridine is as shown in table 1 in the conversion ratio of pyridine and the product.
Embodiment 2
Present embodiment is used to explain said loaded catalyst provided by the invention and preparation method thereof.
The cobalt nitrate of 104.2 grams, the lanthanum nitrate of 35.7 grams and the barium chloride of 30 grams are dissolved in 2000 milliliters the deionized water; After treating fully dissolving; Under room temperature and stirring condition, progressively be added drop-wise in 3.5 kilograms the Ludox of 27 weight %, thereby continue to stir the mixed solution that was fully disperseed in 6 hours after dripping again.Then; Under agitation said mixed liquor is warmed up to 95 ℃; And under this temperature, make the water evaporates in the said mixed solution, and becoming pasty state (water content is 5 weight %) up to mixture, the mixture with this pasty state is placed in the drying box following dry 24 hours at 135 ℃ then.Afterwards, dried mixture is placed in the heating furnace,, thereby obtains catalyst precursor 500 ℃ of following roastings 5 hours.This catalyst precursor is packed in the fixed bed reactors, and the internal diameter of the cylinder of said fixed bed reactors is 32 millimeters, and length is 1200 millimeters.Make said reactor be warming up to 400 ℃ through heating; Begin in said reactor to feed the mist (volume of chlorine account for said mist cumulative volume 60%) of chlorine and nitrogen then; Said mist fed 4 hours with the flow of 1000 ml/min, thereby made loaded catalyst according to the present invention.CoCl in the said catalyst
2Content be about 7.4 weight %, LaCl
3Content be about 2.7 weight %, BaCl
2Content be about 0.3 weight %, and the weight of said catalyst is about 1 kilogram; The pore volume that records said catalyst through nitrogen adsorption desorption method is 0.37 a milliliter/gram catalyst.
Method according to embodiment 1 reacts with the preparation polychlorinated pyridine pyridine and chlorine.Feed in the said fixed bed reactors after 24 hours, 100 hours and 500 hours at said mist respectively; The product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and penta chloropyridine is as shown in table 1 in the conversion ratio of pyridine and the product.
Embodiment 3
Present embodiment is used to explain said loaded catalyst provided by the invention and preparation method thereof.
The cobalt nitrate of 35.2 grams, the lanthanum nitrate of 26.5 grams, the barium nitrate of 59 grams and the zinc nitrate of 19 grams are dissolved in 2000 milliliters the deionized water; After treating fully dissolving; Under room temperature and stirring condition, progressively be added drop-wise in 3.5 kilograms the Ludox of 27 weight %, thereby continue to stir the mixed solution that was fully disperseed in 6 hours after dripping again.Then; Under agitation said mixed liquor is warmed up to 80 ℃; And under this temperature, make the water evaporates in the said mixed solution, and becoming pasty state (water content is 13 weight %) up to mixture, the mixture with this pasty state is placed in the drying box following dry 72 hours at 110 ℃ then.Afterwards, dried mixture is placed in the heating furnace,, thereby obtains catalyst precursor 300 ℃ of following roastings 9 hours.This catalyst precursor is packed in the fixed bed reactors, and the internal diameter of the cylinder of said fixed bed reactors is 32 millimeters, and length is 1200 millimeters.Make said reactor be warming up to 300 ℃ through heating; Begin in said reactor to feed the mist (volume of chlorine account for said mist cumulative volume 60%) of chlorine and nitrogen then; Said mist fed 4 hours with the flow of 1000 ml/min, thereby made loaded catalyst according to the present invention.CoCl in the said catalyst
2Content be about 2.5 weight %, LaCl
3Content be about 2.0 weight %, BaCl
2Content be about 5.9 weight %, ZnCl
2Content be about 1.9 weight %, and the weight of said catalyst is about 1 kilogram; The pore volume that records said catalyst through nitrogen adsorption desorption method is 0.39 a milliliter/gram catalyst.
Method according to embodiment 1 reacts with the preparation polychlorinated pyridine pyridine and chlorine.Feed in the said fixed bed reactors after 24 hours, 100 hours and 500 hours at said mist respectively; The product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and penta chloropyridine is as shown in table 1 in the conversion ratio of pyridine and the product.
Embodiment 4
Present embodiment is used to explain said loaded catalyst provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares said catalyst and pyridine and chlorine is reacted; Different is; In the process of the said catalyst of preparation, replace the cobalt nitrate of 104.2 grams with the ferric oxalate of 145.7 grams, thereby contain the FeCl of the 7.4 weight % that have an appointment in the catalyst that makes
3LaCl with about 2.7 weight %
3In addition; Feed in the said fixed bed reactors after 24 hours, 100 hours and 500 hours at said mist respectively; The product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and penta chloropyridine is as shown in table 1 in the conversion ratio of pyridine and the product.
Embodiment 5
Present embodiment is used to explain said loaded catalyst provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares said catalyst and pyridine and chlorine is reacted; Different is that in the process of the said catalyst of preparation, the consumption of cobalt nitrate is 21.1 grams; The consumption of lanthanum nitrate is 35.7 grams, thereby contains the CoCl of the 1.5 weight % that have an appointment in the catalyst that makes
2LaCl with about 2.7 weight %
3In addition; Feed in the said fixed bed reactors after 24 hours, 100 hours and 500 hours at said mist respectively; The product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and penta chloropyridine is as shown in table 1 in the conversion ratio of pyridine and the product.
Embodiment 6
Present embodiment is used to explain said loaded catalyst provided by the invention and preparation method thereof.
Method according to embodiment 1 prepares said catalyst and pyridine and chlorine is reacted; Different is; Through sintering temperature being controlled to be 380 ℃, roasting time is controlled to be 4.5 hours, is 0.45 milliliter/gram catalyst thereby make the pore volume of the catalyst that finally makes.In addition; Feed in the said fixed bed reactors after 24 hours, 100 hours and 500 hours at said mist respectively; The product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and penta chloropyridine is as shown in table 1 in the conversion ratio of pyridine and the product.
Embodiment 7
Present embodiment is used to explain said loaded catalyst provided by the invention and preparation method thereof.
Method according to embodiment 3 prepares said catalyst and pyridine and chlorine is reacted; Different is in the process of the said catalyst of preparation, not use zinc nitrate; And the consumption of cobalt nitrate is 35.2 grams; The consumption of lanthanum nitrate is 21.2 grams, and the consumption of barium nitrate is 74.0 grams, thereby contains the CoCl of the 2.5 weight % that have an appointment in the catalyst that makes
2, about 1.6 weight % LaCl
3BaCl with about 5.9 weight %
2In addition; Feed in the said fixed bed reactors after 24 hours, 100 hours and 500 hours at said mist respectively; The product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and penta chloropyridine is as shown in table 1 in the conversion ratio of pyridine and the product.
Comparative Examples 1
Preparation contains 74 gram CoCl
2With 27 gram LaCl
3Mixed solution; Be that 0.7 millimeter activated carbon is added in the said mixed solution under agitation then with the average particulate diameter of 899 grams; After activated carbon all is added in the said mixed solution, continue again to stir 4 hours, then 85 ℃ dry 24 hours down, thereby obtain 1 kilogram catalyst.
This catalyst is filled in the fixed bed reactors, and the internal diameter of the cylinder of said fixed bed reactors is 32 millimeters, and length is 1200 millimeters.
Then, the method according to embodiment 1 reacts pyridine and chlorine.Feed in the said fixed bed reactors after 24 hours, 100 hours and 500 hours at said mist respectively; The product analysis that makes after adopting high performance liquid chromatography to reaction learns that the content of 4 chloro pyridine and penta chloropyridine is as shown in table 1 in the conversion ratio of pyridine and the product.
Table 1
Can find out by table 1; Adopt service life of the prepared loaded catalyst of preparation method of loaded catalyst provided by the invention longer; Have very high catalytic activity, and can generate 4 chloro pyridine and/or penta chloropyridine with higher selectivity catalysis pyridine and chlorine reaction.In addition; In said loaded catalyst, contain cobalt chloride and lanthanum chloride at least; And the content of cobalt chloride is 2-9 weight %; When the content of lanthanum chloride is 2-12 weight %, makes that the content of 4 chloro pyridine in the product that pyridine and chlorine reaction generate and/or penta chloropyridine is higher relatively, thereby show better catalytic activity.
Claims (7)
1. a loaded catalyst is characterized in that, this catalyst comprises carrier and load on the active component on the said carrier, and said carrier is a silica, and said active component is at least a in the chloride of chloride and alkaline-earth metal of transition metal; At least comprise cobalt chloride and lanthanum chloride in the said active component; And in said catalyst, be benchmark with the gross weight of said catalyst, the content of said cobalt chloride is 2-9 weight %; The content of said lanthanum chloride is 2-12 weight %, and the pore volume of said catalyst is 0.3-0.4 milliliter/gram catalyst.
2. catalyst according to claim 1 wherein, in said catalyst, is a benchmark with the gross weight of said catalyst, and the content of said active component is 5-20 weight %, and the content of said carrier is 80-95 weight %.
3. the preparation method of the described loaded catalyst of claim 1 is characterized in that, this method may further comprise the steps:
(1) at least a aqueous solution in transition metal salt and the alkali salt is mixed with Ludox, then the gained mixture is carried out drying and roasting, thereby make catalyst precursor;
Metallic element in said transition metal salt and the alkali salt comprises cobalt and lanthanum at least;
(2) said catalyst precursor is contacted with chlorine, the condition of said contact makes in the products therefrom of contact back that the said transition metal of part and alkaline-earth metal exist with its chloride form at least;
In step (1), the condition of said roasting comprises: temperature is 300-500 ℃, and the time is 5-9 hour;
And the consumption of cobalt and lanthanum makes in the catalyst that obtains, and is benchmark with the gross weight of said catalyst, and the content of said cobalt chloride is 2-9 weight %, and the content of said lanthanum chloride is 2-12 weight %;
And the pore volume of said catalyst is 0.3-0.4 milliliter/gram catalyst.
4. method according to claim 3; Wherein, In step (1), the method for said drying comprises said mixed solution is heated to 80-95 ℃, and under this temperature, makes the water evaporates in the said mixture; Water content in mixture is 0.1-15 weight %, and the mixture that obtains was descended dry 12-72 hour at 105-130 ℃.
5. method according to claim 3, wherein, in step (1), said transition metal salt and alkali salt are at least a in nitrate, carbonate, oxalates and the chloride.
6. method according to claim 3, wherein, in step (2), the condition that said catalyst precursor contacts with chlorine comprises: temperature is 300-400 ℃, the time is 2-5 hour.
7. according to claim 3 or 6 described methods, wherein, in step (2), said catalyst precursor contacts in the presence of protective gas with chlorine and carries out, and the volume of chlorine accounts for the 30-90% of cumulative volume of the mist of chlorine and said protective gas.
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| CN113244934B (en) * | 2021-05-25 | 2022-11-08 | 上海华谊（集团）公司 | Catalyst for producing 2,3,6-trichloropyridine and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1657164A (en) * | 2004-12-22 | 2005-08-24 | 东南大学 | Catalyst for preparing penta chloropyridine and its preparation method |
| CN1772380A (en) * | 2005-10-31 | 2006-05-17 | 东南大学 | Catalyst for gas-solid phase synthesis of 2-chloro-5-trichloro methyl pyridine and its prepn |
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| CN1657164A (en) * | 2004-12-22 | 2005-08-24 | 东南大学 | Catalyst for preparing penta chloropyridine and its preparation method |
| CN1772380A (en) * | 2005-10-31 | 2006-05-17 | 东南大学 | Catalyst for gas-solid phase synthesis of 2-chloro-5-trichloro methyl pyridine and its prepn |
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