CN114621124B - Method for synthesizing tert-butyl hydroperoxide from tert-butyl alcohol and hydrogen peroxide - Google Patents
Method for synthesizing tert-butyl hydroperoxide from tert-butyl alcohol and hydrogen peroxide Download PDFInfo
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- CN114621124B CN114621124B CN202210409399.3A CN202210409399A CN114621124B CN 114621124 B CN114621124 B CN 114621124B CN 202210409399 A CN202210409399 A CN 202210409399A CN 114621124 B CN114621124 B CN 114621124B
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- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 60
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 18
- 239000000741 silica gel Substances 0.000 claims description 17
- 229910002027 silica gel Inorganic materials 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000011343 solid material Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 150000001805 chlorine compounds Chemical class 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 229910001510 metal chloride Inorganic materials 0.000 description 10
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- FVBHYZVVSXFCOO-UHFFFAOYSA-N tert-butyl hydrogen sulfate Chemical compound CC(C)(C)OS(O)(=O)=O FVBHYZVVSXFCOO-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BCHLLOWWPPBMNK-UHFFFAOYSA-N 2-hydroperoxy-2-methylpropane;sodium Chemical compound [Na].CC(C)(C)OO BCHLLOWWPPBMNK-UHFFFAOYSA-N 0.000 description 1
- ZTHQBROSBNNGPU-UHFFFAOYSA-N Butyl hydrogen sulfate Chemical group CCCCOS(O)(=O)=O ZTHQBROSBNNGPU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing tert-butyl hydroperoxide from tert-butyl alcohol and hydrogen peroxide, which comprises the following steps: the method comprises the steps of sequentially carrying out first contact on tertiary butanol and hydrogen peroxide and a catalyst A, and then carrying out second contact on the tertiary butanol and the hydrogen peroxide and the catalyst B, wherein the catalyst A comprises a first carrier and a first active component consisting of at least two metal elements in VIII, IIIB and IVB groups loaded on the first carrier; the catalyst B contains a second carrier and a second active component consisting of VIIB metal elements. By adopting the method, the content of the tert-butyl hydroperoxide in the synthesized reaction solution is 9-40%, and the yield of the target product tert-butyl hydroperoxide is 80-96%.
Description
Technical Field
The invention provides a method for synthesizing tert-butyl hydroperoxide by tert-butyl alcohol and hydrogen peroxide.
Background
T-butyl hydroperoxide is commonly used as an initiator for polymer synthesis and has found wide application in organic synthesis. The current industrial production method of tert-butyl hydroperoxide mainly uses a sulfuric acid method, and tert-butyl alcohol and concentrated sulfuric acid are used for reaction to prepare tert-butyl hydrogen sulfate in the first step of the process; secondly, oxidizing with hydrogen peroxide to react with tert-butyl hydrogen sulfate to prepare tert-butyl hydroperoxide; thirdly, removing a water phase product through oil-water layering; fourthly, neutralizing acid in the reactant by using sodium hydroxide, and reacting excessive alkali with tertiary butyl hydroperoxide and alkali to generate sodium salt so as to realize separation of tertiary butyl hydroperoxide and di-tertiary butyl peroxide; and fifthly, acidolysis of tert-butyl hydroperoxide sodium salt by sulfuric acid to generate final product tert-butyl perhydro-hydride. Because a large amount of sulfuric acid is used in the reaction process, equipment corrosion is serious, and 10% -30% of byproduct di-tert-butyl peroxide is inevitably generated in the reaction process, so that the yield of the target product tert-butyl hydroperoxide is low, the separation process is complex, and a large amount of acid-containing wastewater is generated in the separation process.
In the prior art, sulfuric acid is used for synthesis, and equipment corrosion is serious. The byproduct of the technical process is 10 to 30 percent of di-tert-butyl peroxide, and the yield of the target product is low. In order to separate tert-butyl hydroperoxide from di-tert-butyl peroxide, the separation process is complex, acid and alkali are alternately used for reaction in the production process, a large amount of salt-containing and acid-containing wastewater is generated in the production process, and the production process is not environment-friendly.
Disclosure of Invention
The invention aims to provide a method for synthesizing tert-butyl hydroperoxide from tert-butyl alcohol and hydrogen peroxide, which can greatly improve the yield of tert-butyl hydroperoxide.
To achieve the foregoing object, the present invention provides a method for synthesizing tert-butyl hydroperoxide from tert-butanol and hydrogen peroxide, comprising: the method comprises the steps of sequentially carrying out first contact on tertiary butanol and hydrogen peroxide and a catalyst A, and then carrying out second contact on the tertiary butanol and the hydrogen peroxide and the catalyst B, wherein the catalyst A comprises a first carrier and a first active component consisting of at least two metal elements in VIII, IIIB and IVB groups loaded on the first carrier; the catalyst B contains a second carrier and a second active component consisting of VIIB metal elements.
The method can greatly improve the yield of the tert-butyl hydroperoxide, and has the advantages that sulfuric acid is not used for participating in the reaction and separation, and no sulfuric acid wastewater is generated; the method of the invention does not produce byproduct di-tert-butyl peroxide, and can greatly improve the yield of target products.
By adopting the method, the content of the tert-butyl hydroperoxide in the synthesized reaction solution is 9-40%, and the yield of the target product tert-butyl hydroperoxide is 80-96%.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for synthesizing tert-butyl hydroperoxide from tert-butyl alcohol and hydrogen peroxide, which comprises the following steps: the method comprises the steps of sequentially carrying out first contact on tertiary butanol and hydrogen peroxide and a catalyst A, and then carrying out second contact on the tertiary butanol and the hydrogen peroxide and the catalyst B, wherein the catalyst A comprises a first carrier and a first active component consisting of at least two metal elements in VIII, IIIB and IVB groups loaded on the first carrier; the catalyst B contains a second carrier and a second active component consisting of VIIB metal elements.
According to a preferred embodiment of the invention, the first active component contains at least two metallic elements of iron, cobalt, nickel, titanium and molybdenum.
According to a preferred embodiment of the invention, the first active component is preferably a mixture of iron, nickel and molybdenum, more preferably the weight ratio of iron, nickel to molybdenum is 0.1-10:0.1-10:1.
In the present invention, the first support may be various commonly used supports, and according to a preferred embodiment of the present invention, the first support is selected from silica.
According to a preferred embodiment of the invention, the first active component is present in an amount of 3 to 6% by weight, calculated as oxide.
According to a preferred embodiment of the present invention, the preparation method of the catalyst a comprises:
i) Roasting the first carrier source in nitrogen atmosphere and cooling to normal temperature to obtain pretreated carrier powder;
ii) grinding the chlorides of at least two active metals to obtain ground powder;
iii) Dissolving the ground powder in absolute ethyl alcohol to obtain an active component solution;
iii) mixing and contacting the active component solution with carrier powder, and vacuum drying to obtain a solid material;
iiii) calcining the solid material.
According to a preferred embodiment of the invention, the conditions of the calcination in step i) comprise: the temperature is 450-550 ℃ and the time is 2-10 hours.
According to a preferred embodiment of the invention, step ii) the milling is carried out for a period of from 10 to 50 hours.
According to a preferred embodiment of the invention, step iii), the conditions of dissolution comprise: the stirring speed is 500-600 rpm, the temperature is 35-50 ℃, and the weight ratio of the grinding powder to the absolute ethyl alcohol is 1:20-100.
According to a preferred embodiment of the invention, step iii), the temperature of the vacuum drying is 10-50 ℃.
According to a preferred embodiment of the invention, step iiii), the conditions of calcination include a temperature of 900-940 ℃ for a time of 10-100 hours.
According to a preferred embodiment of the invention, the first carrier source is selected from the group consisting of silica gels, preferably silica gels having a specific surface area of 250-350m 2 Per g, pore volume of 0.6-1.0cc/g, pore size of 1-8nm.
According to a preferred embodiment of the present invention, in catalyst B, the second active component contains one or more of iron, manganese and silver.
According to a preferred embodiment of the invention, in catalyst B, the second support is selected from silica.
According to a preferred embodiment of the invention, the second active component is present in catalyst B in an amount of from 5 to 10% by weight, calculated as oxide.
According to a preferred embodiment of the present invention, the preparation method of the catalyst B comprises:
i) Roasting the second carrier source in nitrogen atmosphere and cooling to normal temperature to obtain pretreated carrier powder;
II) grinding the chloride of at least a second active metal to obtain a ground powder;
III) dissolving the ground powder in absolute ethyl alcohol to obtain an active component solution;
IV) mixing and contacting the active component solution with carrier powder, and vacuum drying to obtain a solid material;
v) calcining the solid material.
According to a preferred embodiment of the invention, step I), the conditions of calcination include: the temperature is 450-550 ℃ and the time is 2-10 hours.
According to a preferred embodiment of the invention, step II), the milling time is from 10 to 50 hours.
According to a preferred embodiment of the invention, step III), the conditions of dissolution include: the stirring speed is 500-600 rpm, the temperature is 35-50 ℃, and the weight ratio of the grinding powder to the absolute ethyl alcohol is 1:20-100.
According to a preferred embodiment of the invention, step IV), the temperature of the vacuum drying is 10-50 ℃.
According to a preferred embodiment of the invention, step V), the conditions of calcination include a temperature of 900-940 ℃ for a time of 10-100h.
According to a preferred embodiment of the invention, the first carrier source is selected from the group consisting of silica gels, preferably silica gels having a specific surface area of 250-350m 2 Per g, pore volume of 0.6-1.0cc/g, pore size of 1-8nm.
According to a preferred embodiment of the present invention, the conditions of the first contact include: the temperature is 30-80 ℃, the pressure is 10-200kPag, and the liquid hourly space velocity is 0.5-5h -1 The method comprises the steps of carrying out a first treatment on the surface of the The mole ratio of the tertiary butanol to the hydrogen peroxide is 2-10:1.
according to a preferred embodiment of the present invention, the conditions of the first contact include: the hydrogen peroxide is fed as hydrogen peroxide, and the hydrogen peroxide concentration of the hydrogen peroxide is 20-50 wt%.
According to a preferred embodiment of the present invention, the conditions of the second contact include: the temperature is 30-50 ℃, and the liquid hourly space velocity is 5-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the The pressure is 10-200kPag.
The first and second contacting of the present invention may be carried out in one reactor or in a plurality of reactors, and the reactor types of the present invention include, but are not limited to, fluidized bed, fixed bed, tubular, moving bed reactors, and the like.
According to the present invention, it is preferred that the first contact reactor includes but is not limited to various types of fluidized bed, fixed bed, tubular, moving bed reactors, etc., and the second contact reactor includes but is not limited to one of fluidized bed, fixed bed, etc.
According to the invention, both reactors can be provided with a return line according to the reaction efficiency, and materials are circulated from the outlet of the reactor to the inlet of the reactor so as to fully react by using the materials.
According to the invention, during synthesis, tertiary butanol and hydrogen peroxide are prepared into reaction raw materials in proportion (preferably, the molar ratio of tertiary butanol to hydrogen peroxide is in the range of 2-10:1), and then the raw materials are pumped into the first reactor and the second reactor in sequence through pumps. The reaction temperature is controlled at 30-80 ℃, and the reaction pressure is controlled at 10-200kPag.
The advantages of the present invention are described in detail below by way of examples.
In the present invention, the content of the substances in the reaction solution is obtained by chromatographic analysis, and for this reason, those skilled in the art will recognize that the present invention is not described in detail.
In the present invention, yield is a term of art commonly used, meaning and calculation means thereof are well known to those skilled in the art, and the present invention is not described in detail.
In the invention, the catalyst composition is calculated by feeding.
Example 1
Preparation of a catalyst A:
step i, selecting silica gel meeting technical parameters as a carrier raw material, and selecting a silica gel carrier which meets the following conditions and has a specific surface area of 300m 2 Per g, pore volume 0.8cc/g, pore size 3nm, calcining the selected silica gel in nitrogen atmosphere at 500 deg.C for 4 hours, and cooling to normal temperature in nitrogen atmosphere.
Step ii, weighing ferric chloride and nickel chloride proportionally, and grinding the two chlorides in grinding equipment for 24 hours;
step iii, dissolving the ground metal chloride in absolute ethanol at 45 ℃ at a stirring speed of 550 r/min to obtain an active component solution, wherein the weight ratio of the solid of the metal chloride to the liquid is 1:56;
step iii, adding the silica gel prepared in the step i into the active component solution, keeping stirring for 5 hours, transferring the mixture into a vacuum kettle, and evaporating the liquid phase at the constant temperature of 35 ℃ to obtain a solid phase;
step iIII, the solid phase obtained in the step iIII is transferred into a calciner, and is calcined for 48 hours at 920 ℃ to obtain the catalystThe catalyst A (1 wt% Fe-4 wt% Ni-95 wt% SiO in oxide composition) 2 )。
Preparation of a catalyst B:
step I, selecting silica gel meeting technical parameters as a carrier raw material, and selecting a silica gel carrier which meets the following conditions and has a specific surface area of 300m 2 Per g, pore volume 0.8cc/g, pore size 3nm; roasting the selected silica gel in a nitrogen atmosphere at 450 ℃ for 4 hours, and cooling to normal temperature in the nitrogen atmosphere;
step II, weighing manganese chloride, and putting the manganese chloride into grinding equipment for grinding for 24 hours;
step III, dissolving the ground metal chloride in absolute ethanol at 35 ℃ at a stirring speed of 600 revolutions per minute, wherein the weight ratio of the metal chloride solid to the liquid is 1:40;
step IV, after all the metal chloride is dissolved, adding the silica gel prepared in the step I, and keeping stirring for 5 hours; transferring into a vacuum kettle, and evaporating the liquid phase at a constant temperature of 35 ℃.
Step V, transferring the solid phase obtained in step IV into a calciner, calcining at 940 ℃ for 48 hours to obtain a catalyst B (10 wt% Mn-90 wt% SiO in terms of oxide composition 2 )。
Catalyst A and catalyst B are filled in a fluidized bed reactor, and the molar ratio of tertiary butanol to hydrogen peroxide (hydrogen peroxide is provided, and the hydrogen peroxide concentration is 30 weight percent) is 3:1, pumping raw materials into a first reactor and a second reactor in sequence through a pump;
the operating conditions of the first reactor include: the temperature is 50 ℃, the reaction pressure is 50kPag, and the liquid hourly space velocity is 2h -1 ；
The operating conditions of the second reactor include: the temperature was 45℃and the reaction pressure was 50kPag, the liquid hourly space velocity was 7h -1 ；
Taking liquid after 24 hours, wherein the content of tert-butyl hydroperoxide in the synthesized reaction liquid is 22.5%, and the yield of the target product tert-butyl hydroperoxide is 92%.
Example 2
Preparation of a catalyst A:
step i, selecting parameters conforming to the technologySilica gel is used as carrier material, the silica gel carrier is selected to meet the following conditions, and the specific surface area is 300m 2 Per g, pore volume 0.8cc/g, pore size 3nm, calcining the selected silica gel in nitrogen atmosphere at 550 deg.C for 3 hr, and cooling to normal temperature in nitrogen atmosphere.
Step ii, weighing cobalt chloride and titanium chloride in proportion, and grinding the two chlorides in grinding equipment for 48 hours;
step iii, dissolving the ground metal chloride in absolute ethanol at 50 ℃ at a stirring speed of 500 revolutions per minute to obtain an active component solution, wherein the weight ratio of the solid of the metal chloride to the liquid is 1:35;
step iii, adding the silica gel prepared in the step i into the active component solution, keeping stirring for 5 hours, transferring the mixture into a vacuum kettle, and evaporating the liquid phase at a constant temperature of 40 ℃ to obtain a solid phase;
step iIII, the solid phase obtained in step iii is transferred to a calciner, and calcined at 940 ℃ for 36 hours to obtain catalyst A (0.5 wt% Co-5.5 wt% Ti-94 wt% SiO in terms of oxide composition 2 )。
Preparation of a catalyst B:
step I, selecting silica gel meeting technical parameters as a carrier raw material, and selecting a silica gel carrier which meets the following conditions and has a specific surface area of 300m 2 Per g, pore volume 0.8cc/g, pore size 3nm; roasting the selected silica gel in a nitrogen atmosphere at 400 ℃ for 8 hours, and cooling to normal temperature in the nitrogen atmosphere;
step II, weighing silver chloride, and putting the silver chloride into grinding equipment for grinding for 15 hours;
step III, dissolving the ground metal chloride in absolute ethanol at 50 ℃ at a stirring speed of 500 revolutions per minute, wherein the weight ratio of the metal chloride solid to the liquid is 1:60;
step IV, after all the metal chloride is dissolved, adding the silica gel prepared in the step I, and keeping stirring for 5 hours; transferring into a vacuum kettle, and evaporating the liquid phase at a constant temperature of 50 ℃.
Step V, transferring the solid phase obtained in the step IV into a calciner, and calcining for 60 hours at 900 ℃ to obtainCatalyst B (5 wt% Ag-95 wt% SiO in oxide composition) 2 )。
Catalyst A and catalyst B are filled in a fluidized bed reactor, and the molar ratio of tertiary butanol to hydrogen peroxide (hydrogen peroxide is provided, and the hydrogen peroxide concentration is 30 weight percent) is 3:1, pumping raw materials into a first reactor and a second reactor in sequence through a pump;
the operating conditions of the first reactor include: the temperature is 60 ℃, the reaction pressure is 50kPag, and the liquid hourly space velocity is 1h -1 ；
The operating conditions of the second reactor include: the temperature is 30 ℃, the reaction pressure is 50kPag, and the liquid hourly space velocity is 5h -1 ；
Taking liquid after 24 hours, wherein the content of tert-butyl hydroperoxide in the synthesized reaction liquid is 23.0%, and the yield of the target product tert-butyl hydroperoxide is 94%.
Example 3
The procedure of example 1 was followed, except that in the preparation of catalyst A, the calcination temperature in step iIII was 860℃and the tert-butyl hydroperoxide content in the synthesized reaction solution was 22.2%, and the yield of the objective product tert-butyl hydroperoxide was 91%.
Example 4
The procedure of example 1 was followed, except that during the preparation of catalyst A, the calcination temperature in step iIII was 1000℃and the tert-butyl hydroperoxide content in the synthesized reaction solution was 19.7%, and the yield of the desired product tert-butyl hydroperoxide was 80%.
Example 5
The procedure of example 1 was followed, except that in the preparation of catalyst B, the calcination temperature in step V was 860℃and the tert-butyl hydroperoxide content in the synthesized reaction solution was 22.0%, and the yield of the objective product tert-butyl hydroperoxide was 90.8%.
Example 6
The procedure of example 1 was followed, except that in the preparation of catalyst B, the calcination temperature in step V was 1000℃and the tert-butyl hydroperoxide content in the synthesized reaction solution was 20.1%, and the yield of the objective tert-butyl hydroperoxide was 82%.
Example 7
The procedure of example 1 was followed except that isopropanol was used instead of absolute ethanol in the preparation of catalyst A. In the synthesized reaction solution, the content of tert-butyl hydroperoxide was 20.3%, and the yield of the target product tert-butyl hydroperoxide was 83%.
Example 8
The procedure of example 1 was followed except that in the preparation of catalyst B, tert-butanol was used instead of absolute ethanol. In the synthesized reaction solution, the content of tert-butyl hydroperoxide was 19.1%, and the yield of the target product tert-butyl hydroperoxide was 78%.
Example 9
According to the method of example 1, except that iron chloride, nickel chloride and molybdenum chloride are used as active component sources in the preparation process of the catalyst A, the weight ratio of the three is 1:1:1, and the total active component content is unchanged. In the synthesized reaction solution, the content of tert-butyl hydroperoxide was 23.5%, and the yield of the target product tert-butyl hydroperoxide was 96%.
Example 10
According to the method of example 1, in the preparation process of the catalyst A and the catalyst B, nitrate of an active component is used for replacing chloride, the rest conditions are unchanged, the content of tert-butyl hydroperoxide in the synthesized reaction solution is 21.6%, and the yield of the target product tert-butyl hydroperoxide is 88%.
Comparative example 1
180g of sulfuric acid with the mass fraction of 70% is put into a constant temperature stirring kettle at 35 ℃, and 74g of tertiary butyl alcohol is slowly dripped into the stirring kettle to generate tertiary butyl bisulfate. And (3) under the condition of constant temperature stirring at 40 ℃, the generated tert-butyl hydrogen sulfate is completely dripped into 123g of 30% hydrogen peroxide by mass fraction, and stirring and constant temperature are continuously carried out for 3 hours, so that the tert-butyl hydrogen sulfate is fully reacted. 377g of a reaction solution was obtained, which had a t-butyl hydroperoxide mass concentration of 14.3% and a di-t-butyl peroxide concentration of 1.6%, and the yield of t-butyl hydroperoxide was 60%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (5)
1. A method for synthesizing tert-butyl hydroperoxide from tert-butanol and hydrogen peroxide, comprising: the method comprises the steps of sequentially carrying out first contact on tertiary butanol and hydrogen peroxide and then carrying out second contact on the tertiary butanol and the hydrogen peroxide and the catalyst A, wherein the catalyst A comprises a first carrier and a first active component consisting of at least two metal elements supported on the first carrier, the first active component comprises at least two metal elements of iron, cobalt, nickel, titanium and molybdenum, the first carrier is selected from silicon dioxide, and the content of the first active component in terms of oxide is 3-6 wt%;
the preparation method of the catalyst A comprises the following steps:
i) Roasting the first carrier source in nitrogen atmosphere and cooling to normal temperature to obtain pretreated carrier powder;
ii) grinding the chlorides of at least two active metals to obtain ground powder;
iii) Dissolving the ground powder in absolute ethyl alcohol to obtain an active component solution;
iii) mixing and contacting the active component solution with carrier powder, and vacuum drying to obtain a solid material;
iiii) calcining said solid material;
wherein,
the roasting conditions in step i) include: the temperature is 450-550 ℃ and the time is 2-10 hours;
step ii) grinding for 10-50 hours;
step iii), the conditions of dissolution include: the stirring speed is 500-600 rpm, the temperature is 35-50 ℃, and the weight ratio of the grinding powder to the absolute ethyl alcohol is 1:20-100;
step iii), vacuum drying at 10-50 ℃;
step iiiii), calcining at 900-940 ℃ for 10-100h;
the first carrier source is selected from silica gel with specific surface area of 250-350m 2 Per g, pore volume of 0.6-1.0cc/g, pore canal size of 1-8nm;
the catalyst B contains a second carrier and a second active component; the second active component comprises one or more of iron, manganese and silver, and the second carrier is selected from silicon dioxide; the second active component is present in an amount of 5 to 10% by weight, calculated as oxide;
the preparation method of the catalyst B comprises the following steps:
i) Roasting the second carrier source in nitrogen atmosphere and cooling to normal temperature to obtain pretreated carrier powder;
II) grinding the chloride of the second active metal to obtain ground powder;
III) dissolving the ground powder in absolute ethyl alcohol to obtain an active component solution;
IV) mixing and contacting the active component solution with carrier powder, and vacuum drying to obtain a solid material;
v) calcining the solid material;
step I), the roasting conditions include: the temperature is 450-550 ℃ and the time is 2-10 hours;
step II), grinding for 10-50 hours;
step III), the conditions of dissolution include: the stirring speed is 500-600 rpm, the temperature is 35-50 ℃, and the weight ratio of the grinding powder to the absolute ethyl alcohol is 1:20-100;
step IV), vacuum drying at 10-50 ℃;
step V), calcining at 900-940 ℃ for 10-100h;
the second carrier source is selected from silica gel with specific surface area of 250-350m 2 Per g, pore volume of 0.6-1.0cc/g, pore size of 1-8nm.
2. The process according to claim 1, wherein in catalyst a the first active component is a mixture of iron, nickel and molybdenum in a weight ratio of iron, nickel to molybdenum of 0.1-10:0.1-10:1.
3. The method according to any one of claims 1-2, wherein,
the conditions of the first contact include: the temperature is 30-80 ℃, the pressure is 10-200kPag, and the liquid hourly space velocity is 0.5-5h -1 The method comprises the steps of carrying out a first treatment on the surface of the The mole ratio of the tertiary butanol to the hydrogen peroxide is 2-10:1.
4. the method according to any one of claims 1-2, wherein the hydrogen peroxide is fed as hydrogen peroxide, the hydrogen peroxide concentration of the hydrogen peroxide being 20-50 wt%.
5. The method according to any one of claims 1-2, wherein,
the conditions of the second contact include: the temperature is 30-50 ℃, and the liquid hourly space velocity is 5-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the The pressure is 10-200kPag.
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| CN101314583A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | Method for catalytic oxidation of tert-butanol |
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