CN114377687B - Iron-based butene oxidative dehydrogenation catalyst and preparation method thereof - Google Patents
Iron-based butene oxidative dehydrogenation catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 125
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 44
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 title claims abstract description 29
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 48
- 239000011701 zinc Substances 0.000 claims abstract description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 31
- 239000011029 spinel Substances 0.000 claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 239000011777 magnesium Substances 0.000 claims description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 28
- 229910052749 magnesium Inorganic materials 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 28
- 230000032683 aging Effects 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 20
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 238000003980 solgel method Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 229910016287 MxOy Inorganic materials 0.000 claims 1
- 238000000975 co-precipitation Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 52
- 239000008367 deionised water Substances 0.000 description 42
- 229910021641 deionized water Inorganic materials 0.000 description 42
- 238000003756 stirring Methods 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 229910002804 graphite Inorganic materials 0.000 description 11
- 239000010439 graphite Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical class O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—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
- B01J23/005—Spinels
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
An iron-based butene oxidative dehydrogenation catalyst and a preparation method thereof are provided. The catalyst is prepared from spinel type ferrite and alpha-Fe 2 O 3 The main active components comprise the following components in percentage by weight: fe (Fe) 2 O 3 70％～90％，MgO 5％～20％、ZnO 1.5％～10％、M x O y_ 0.5 to 5 percent, wherein M is one or more than one of V, mn, al, ca. The catalyst is prepared by preparing spinel type ferrite containing iron, acid and zinc, then performing coprecipitation reaction on the spinel type ferrite, ferric salt and M salt, and performing conventional post-treatment to obtain the finished catalyst. The catalyst has the advantages of safe production process, environmental protection and good stability; the active phase is distributed uniformly, and the catalyst has good activity.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to an iron-based butene oxidative dehydrogenation catalyst and a preparation method thereof.
Background
The oxidative dehydrogenation of butene to butadiene is an important source of butadiene, which has been paid attention to by many domestic units in the last 60 th century, and a kiloton-scale industrial device for the oxidative dehydrogenation of n-butene to butadiene was built in 1969 in China, and then a large-scale oxidative dehydrogenation device for n-butene was built in 1971.
Butene oxidative dehydrogenation catalysts have undergone ternary molybdenum-based catalysts, six-membered molybdenum-based catalysts, iron-based catalysts under the common efforts of related units in China.
At present, most of domestic butene oxidative dehydrogenation catalysts are iron catalysts, ammonia water is generally adopted as a precipitator, coprecipitation reaction is carried out with iron, magnesium and zinc, and after precipitation, aging, drying, activation and molding are carried out to prepare butadiene catalysts, for example:
patent application CN107308942A discloses a catalyst for preparing butadiene by oxidative dehydrogenation of butene and a preparation method thereof, wherein ferric nitrate, zinc nitrate and magnesium nitrate are prepared into a solution according to a certain molar ratio, ammonia water is added for coprecipitation, and then steps of aging, drying, calcining, crushing and the like are carried out to obtain the modified zinc ferrite catalyst.
Patent application CN105618064a discloses a preparation method of butene oxidative dehydrogenation catalyst, which comprises the first step of adding ammonia water into aqueous solution containing iron, zinc and calcium elements in a positive titration manner to control the system pH to 7.0-8.0; stopping adding ammonia water dropwise and continuously introducing CO 2 Maintaining the pH of the system unchanged for 0.5-2 hours, adding sesbania powder, and aging, washing, drying and roasting the obtained precipitate to obtain the butene oxidative dehydrogenation catalyst.
The catalyst prepared by the method has a large amount of free zinc, magnesium and other ions in the mother solution after precipitation reaction, can not be discharged, ammonia water is used in the washing process, and the environment is seriously polluted, on the other hand, the loss of zinc and magnesium can cause the change of the active phase of the catalyst, and the reaction conditions are required to be strictly controlled, so that the stability and the repeatability of the catalyst production are poor.
Thus, a new butene oxidative dehydrogenation catalyst and a preparation method thereof are needed to solve the above technical problems.
Disclosure of Invention
In order to solve the problems existing in the existing butene oxidative dehydrogenation catalysts in the production and industrial application processes, the invention is mainly improved in terms of catalyst formula composition, preparation method, preparation process conditions and the like.
The invention aims to provide an iron-based butene oxidative dehydrogenation catalyst and a preparation method thereof. The catalyst has the advantages of safe production process, environmental protection, good stability, uniform active phase distribution and good catalyst activity.
The invention provides a preparation method of an iron-based butene oxidative dehydrogenation catalyst, which is prepared from spinel type ferrite and alpha-Fe 2 O 3 As a main active component, the catalyst comprises the following components in percentage by weight: fe (Fe) 2 O 3 70% -90% (the Fe) 2 O 3 Content of Fe contained in ferrite 2 O 3 And alpha-Fe 2 O 3 Both) MgO 5-20%, znO 1.5-10%, M x O y 0.5 to 5 percent, wherein M is one or more than one of V, mn, al, ca, and x and y respectively represent M x O y Wherein O is-2 valence, and the valence of M is +2y/x valence; the preparation method is characterized by comprising the following steps of:
(1) Preparing spinel type ferrite containing iron, magnesium and zinc;
(2) And (3) carrying out precipitation reaction on ferric salt, salt containing M and spinel type ferric salt obtained in the step (1) and a precipitant, and carrying out post-treatment on a product obtained by the precipitation reaction to obtain a finished catalyst.
The preparation method of the catalyst comprises the following steps:
(A1) Preparing spinel type iron salt containing iron, magnesium and zinc by using a compound containing iron, magnesium and zinc;
(A2) Crushing the obtained spinel type ferrite to a certain mesh number, and adding water to uniformly mix to obtain first slurry;
(A3) Preparing a second solution comprising an iron salt and a salt comprising M;
(A4) Preparing a precipitant solution;
(A5) The second solution and the precipitant solution flow into the first slurry to carry out precipitation reaction;
(A6) And after the precipitation is finished, carrying out post-treatment on a product obtained by the precipitation reaction to obtain a finished catalyst.
Wherein in the step (1) or (A1), the spinel-type ferrite is prepared by a precipitation method, a mechanical mixing method, or a sol-gel method.
Wherein said step (1) or (A1) comprises the following step (B1): uniformly mixing iron, magnesium and zinc-containing compounds, adding organic acid, performing sol-gel reaction at a certain temperature, and roasting the product obtained by the sol-gel reaction to obtain spinel type ferrite
Wherein in the step (A1) or (B1), the compound containing iron, magnesium and zinc comprises one or more of sulfate, nitrate and oxide of iron, magnesium and zinc.
Wherein in the step (B1), the organic acid is selected from one or more of acetic acid, formic acid, oxalic acid and citric acid.
Wherein in the step (B1), the temperature of the sol-gel reaction is 50-120 ℃.
Wherein in the step (B1), the roasting temperature is 600-900 ℃ and the roasting time is 5-10h.
Wherein, in the step (A2), the spinel-type ferrite is crushed to 80-400 meshes.
Wherein in the step (2) or (A3), the ferric salt is one or more of sulfate, nitrate and chloride of iron.
Wherein in the step (2) or (A3), the salt containing M is one or more of sulfate, nitrate and chloride containing M.
Wherein in the step (2) or (A4), the precipitant is one or more of sodium hydroxide, sodium carbonate, ammonia water and sodium bicarbonate.
Wherein in the step (2) or (A5), the temperature of the precipitation reaction is 5-40 ℃ and the time is 0.5-9h.
Wherein in the step (2) or (A5), the pH of the precipitation reaction is controlled to be 8.0-10.0.
Wherein in the step (2) or (A6), the post-treatment comprises aging, washing, activating and forming.
Wherein the aging temperature is 5-40deg.C, and the aging time is 0.5-15h.
Wherein the liquid used for washing is one or more of deionized water, ammonia water, sodium carbonate solution and sodium bicarbonate solution.
Wherein the activation temperature is 600-900 ℃ and the activation time is 5-35h.
Wherein the shaping comprises: crushing the activated catalyst to 8-200 meshes, adding deionized water accounting for 2-8% of the mass percent of the catalyst, adding graphite accounting for 0.1-3% of the mass percent of the catalyst, uniformly mixing, and forming.
The invention also provides an iron-based butene oxidative dehydrogenation catalyst, which is prepared by the preparation method of the iron-based butene oxidative dehydrogenation catalyst.
The invention also provides a method for preparing butadiene by oxidative dehydrogenation of butene, which adopts the iron-based butene oxidative dehydrogenation catalyst.
The invention has the following beneficial technical effects:
the preparation method of the catalyst provided by the invention is characterized in that spinel type ferrate containing iron, magnesium and zinc is prepared firstly, and then the ferrite, ferric salt and M salt are subjected to coprecipitation reaction, and the preparation method has the advantages that:
(1) Iron, magnesium and zinc are firstly prepared to form a spinel type ferrite structure, the problem of zinc and magnesium ion loss caused by coprecipitation of Cheng Zhongtie, magnesium and zinc salts and ammonia water produced by a catalyst can be effectively avoided, and the zinc and magnesium contents in a solution of the catalyst are lower than 1.0mg/L in the production and washing processes, so that the production process is safe and environment-friendly;
(2) The spinel type ferrite structure is prepared by firstly preparing iron, magnesium and zinc, so that the problems that zinc and magnesium are lost differently due to fluctuation of reaction pH value in the coprecipitation process of iron, magnesium and zinc salt and ammonia water, the content of catalyst components is changed, and the repeatability of catalyst production and the stability of performance are affected can be effectively avoided;
(3) Through preparing spinel type ferrate first, then coprecipitating ferrite, ferric salt and M salt, the ferrite, ferric oxide and M oxide can be dispersed more uniformly through precipitation reaction, and the activity of the catalyst is improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
An amount of deionized water and 51.9g of Fe were added 2 O 3 Adding into a three-neck flask, adding a certain amount of acetic acid, stirring, adjusting a water bath to maintain the temperature of the reaction solution at 60 ℃, and stirring for 30min. 12g MgO,2g ZnO and a certain amount of deionized water are added into a three-neck flask, the reaction temperature is adjusted to 105 ℃, stirring is continued for 10 hours, the mixture is poured into the beaker to be dried at 120 ℃, and then the mixture is roasted for 8 hours at 800 ℃ in a muffle furnace, so that spinel type ferrite is obtained. Crushing ferrite to 80-180 meshes, and adding deionized water to uniformly mix for later use. 112.2g FeCl was weighed out 3 ·6H 2 O，2.5gMn(NO 3 ) 2 Adding deionized water to prepare Fe 3+ The concentration is 1.0mol.L -1 Preparing sodium bicarbonate solution with the mass fraction of 15%, flowing the solution A and the sodium bicarbonate solution into a beaker filled with spinel type ferrite slurry, maintaining the reaction temperature at 25 ℃, reacting for 1h, precipitating to pH value of 9.0, aging the reaction solution at 25 ℃ for 5h after the precipitation is finished, filtering after the aging is finished, washing with deionized water, drying at 90 ℃ after the washing is finished, heating a muffle furnace to 700 ℃ for activating for 30h to obtain a semi-finished catalyst, crushing to 8-180 meshes, adding 0.5g of graphite and 5g of deionized water, uniformly mixing, and tabletting to obtain the finished catalyst I.
Through analysis, in the preparation process of the catalyst I, zinc ions and magnesium ions do not exist in the mother solution after the precipitation is finished.
Example 2
An amount of deionized water and 51.9g of Fe were added 2 O 3 Adding a certain amount of formic acid into a three-neck flask, stirring, adjusting a water bath to maintain the temperature of the reaction solution at 60 ℃, and stirring for 30min. Adding 12g MgO,2g ZnO and a certain amount of deionized water into a three-neck flask, regulating the reaction temperature to 105 ℃, continuously stirring for 10h, pouring into the beaker, drying at 120 ℃, and roasting for 8h at 850 ℃ in a muffle furnace to obtain the spinel-type ferrite. Crushing ferrite to 300-400 meshes, and adding deionized water to uniformly mix for later use. 167.5g of Fe (NO) was weighed again 3 ) 3 ·6H 2 O、1.73gVCl 3 Adding deionized water to prepare Fe 3+ The concentration is 1.0mol.L -1 In addition, preparing an ammonia water solution with the mass fraction of 15%, flowing the solution A and the ammonia water solution into a beaker filled with spinel type ferrite slurry, maintaining the reaction temperature at 35 ℃ for 1h, precipitating the pH value at 9.5, aging the reaction solution at 25 ℃ for 5h after the precipitation is finished, filtering after the aging is finished, washing with ammonia water, drying at 90 ℃ after the washing is finished, heating a muffle furnace to 800 ℃ for activating for 30h to obtain a semi-finished catalyst, crushing to 10-200 meshes, adding 0.5g of graphite and 7g of deionized water, uniformly mixing, and tabletting to obtain the finished catalyst II.
Example 3
An amount of deionized water and 262.6g of Fe (NO 3 ) 3 ·9H 2 O is added into a three-neck flask, a certain amount of oxalic acid is added, stirring is carried out, a water bath is regulated to maintain the temperature of the reaction liquid at 60 ℃, and stirring is carried out for 30min. Adding 12g of MgO,2g of ZnO and a certain amount of deionized water into a three-neck flask, regulating the reaction temperature to 105 ℃, continuously stirring for 10 hours, pouring into the beaker, drying at 120 ℃, and roasting at 800 ℃ for 8 hours in a muffle furnace to obtain spinel type ferrite. Crushing ferrite to 180-300 meshes, and adding deionized water to uniformly mix for later use. 112.2g of FeCl are weighed again 3 ·6H 2 O、4.2gAl(NO 3 ) 3 Adding deionized water to prepare Fe 3+ The concentration is 1.0mol.L -1 In addition, preparing a sodium carbonate solution with the mass fraction of 15%, flowing the solution A and the sodium carbonate solution into a beaker filled with spinel type ferrite slurry, maintaining the reaction temperature at 25 ℃ for 1h, precipitating the pH value at 10.0, aging the reaction solution at 25 ℃ for 5h after the precipitation is finished, filtering the reaction solution after the aging is finished, washing the reaction solution with deionized water, drying the reaction solution at 90 ℃ after the washing is finished, heating a muffle furnace to 800 ℃ for activating the reaction solution for 30h to obtain a semi-finished catalyst, crushing the semi-finished catalyst to 8-80 meshes, adding 0.5g of graphite and 8g of deionized water, uniformly mixing, and tabletting to obtain the finished catalyst III.
Example 4
An amount of deionized water and 262.6g of Fe (NO 3 ) 3 ·9H 2 O、76.9gMg(NO 3 ) 2 ·6H 2 O、7.3g Zn(NO 3 ) 2 ·6H 2 Adding O into a three-neck flask, adding a certain amount of citric acid, stirring, adjusting the reaction temperature to 105 ℃ by adjusting a water bath, continuously stirring for 10 hours, pouring into the beaker, drying at 120 ℃, and roasting at 800 ℃ for 8 hours in a muffle furnace to obtain spinel type ferrite. Crushing ferrite to 80-300 meshes, and adding deionized water to uniformly mix for later use. 167.5g of Fe (NO) was weighed again 3 ) 3 ·6H 2 O、2.5gMn(NO 3 ) 2 Adding deionized water to prepare Fe 3+ The concentration is 1.0mol.L -1 Preparing sodium bicarbonate solution with the mass fraction of 15%, flowing the solution A and the sodium bicarbonate solution into a beaker filled with spinel type ferrite slurry, maintaining the reaction temperature at 25 ℃ for 1h, precipitating the pH value at 9.5, aging the reaction solution at 25 ℃ for 5h after the precipitation is finished, filtering the reaction solution after the aging is finished, washing the reaction solution with deionized water, drying the reaction solution at 90 ℃ after the washing is finished, heating a muffle furnace to 700 ℃ for activating the reaction solution for 30h to obtain a semi-finished catalyst, crushing the semi-finished catalyst to 8-180 meshes, adding 0.5g of graphite and 8g of deionized water, uniformly mixing, and tabletting to obtain the finished catalyst IV.
Example 5
An amount of deionized water and 51.9g of Fe were added 2 O 3 Adding 12g of MgO and 2g of ZnO into a three-neck flask, adding a certain amount of acetic acid, stirring, adjusting the water bath to adjust the reaction temperature to 110 ℃, continuously stirring for 10 hours, pouring into the beaker, drying at 120 ℃, and roasting for 8 hours at 750 ℃ in a muffle furnace to obtain spinel-type ferrite. Crushing ferrite to 80-300 meshes, and adding deionized water to uniformly mix for later use. 165.8g of Fe are weighed out again 2 (SO 4 ) 3 、2.5gMn(NO 3 ) 2 Adding deionized water to prepare Fe 3+ The concentration is 1.0mol.L -1 In addition, preparing sodium bicarbonate solution with the mass fraction of 15%, flowing the solution A and the sodium bicarbonate solution into a beaker filled with spinel-type ferrite slurry, maintaining the reaction temperature at 35 ℃ for 1h, precipitating the pH value at 8.5, aging the reaction solution at 35 ℃ for 5h after the precipitation is finished, filtering after the aging is finished, and washing with deionized waterAnd after washing, drying at 90 ℃, heating to 800 ℃ in a muffle furnace, activating for 30 hours to obtain a semi-finished catalyst, crushing to 8-200 meshes, adding 0.2g of graphite and 5g of deionized water, uniformly mixing, and tabletting to obtain the finished catalyst V.
Example 6
An amount of deionized water and 51.9g of Fe were added 2 O 3 Adding into a three-neck flask, adding a certain amount of acetic acid, stirring, adjusting a water bath to maintain the temperature of the reaction solution at 60 ℃, and stirring for 30min. Adding 12g of MgO,2g of ZnO and a certain amount of deionized water into a three-neck flask, regulating the reaction temperature to 110 ℃, continuously stirring for 10 hours, pouring into the beaker, drying at 120 ℃, and roasting at 800 ℃ for 8 hours in a muffle furnace to obtain spinel-type ferrite. Crushing ferrite to 80-400 meshes, and adding deionized water to uniformly mix for later use. Weighing FeCl 3 ·6H 2 O 112.2g，2.5gMn(NO 3 ) 2 Adding deionized water to prepare Fe 3+ The concentration is 1.0mol.L -1 In addition, preparing a sodium hydroxide solution with the mass fraction of 15%, flowing the solution A and the sodium hydroxide solution into a beaker filled with spinel type ferrite slurry, maintaining the reaction temperature at 25 ℃, reacting for 1h, precipitating to pH value of 9.9, aging the reaction solution at 25 ℃ for 5h after the precipitation is finished, filtering after the aging is finished, washing with deionized water, drying at 90 ℃ after the washing is finished, heating a muffle furnace to 800 ℃ for activating for 30h to obtain a semi-finished catalyst, crushing to 8-200 meshes, adding 0.3g of graphite and 7g of deionized water, uniformly mixing, and tabletting to obtain the finished catalyst VI.
Comparative example 1
A certain amount of deionized water and 85g of Fe 2 O 3 Adding into a three-neck flask, adding a certain amount of acetic acid, stirring, adjusting a water bath to maintain the temperature of the reaction solution at 60 ℃, and stirring for 30min. MgO12g, znO 2g, V 2 O 5 Adding 1g and a certain amount of deionized water into a three-neck flask, regulating the reaction temperature to 105 ℃, continuously stirring for 10 hours, pouring into the beaker, placing into a baking oven for baking at 120 ℃, heating a muffle furnace to 800 ℃ for baking for 8 hours to obtain a semi-finished catalyst, crushing to 8-200 meshes, adding 0.3g of graphite and 7g of deionized water, uniformly mixing, and tabletting to form the finished catalystVII。
Comparative example 2
Weighing Fe (NO) 3 ) 3 ·9H 2 O 430g，Mg(NO 3 ) 2 ·6H 2 O 76.9g，Zn(NO 3 ) 2 ·6H 2 O7.4g，2.5gMn(NO 3 ) 2 Adding deionized water to prepare Fe 3+ The concentration is 1.0mol.L -1 Slowly dripping citric acid solution into the solution A, regulating the reaction temperature to 105 ℃, continuously stirring for 10 hours, pouring into a beaker, placing into a baking oven for baking at 120 ℃, heating a muffle furnace to 800 ℃ for roasting for 8 hours to obtain a semi-finished catalyst, crushing to 8-200 meshes, adding 0.3g of graphite and 7g of deionized water, uniformly mixing, and tabletting to obtain the finished catalyst VIII.
Comparative example 3
Weighing Fe (NO) 3 ) 3 ·9H 2 O 430g，Mg(NO 3 ) 2 ·6H 2 O 80.97g，Zn(NO 3 ) 2 ·6H 2 O 74.37g，2.5gMn(NO 3 ) 2 Adding deionized water into the solution to prepare 1.12LFe 3+ The concentration is 1.0mol.L -1 In addition, preparing an ammonia water solution with the mass fraction of 15%, adding the solution A and the ammonia water solution into a beaker for co-current coprecipitation, maintaining the reaction temperature at 25 ℃, reacting for 1h, precipitating to obtain a pH value of 9.8, aging the reaction solution at 25 ℃ for 5h after the precipitation is finished, filtering after the aging is finished, washing with ammonia water, drying in a baking oven at 90 ℃, heating a muffle furnace to 700 ℃ for activating for 30h to obtain a semi-finished catalyst, crushing to 8-200 meshes, adding 0.3g of graphite and 7g of deionized water, uniformly mixing, and tabletting to obtain the finished catalyst IX.
Through analysis, during the preparation of the catalyst IX, the mother liquor after the end of precipitation contained 9.6g/L of zinc ions and 296mg/L of magnesium ions.
Comparative example 4
Weigh 85g Fe 2 O 3 Mechanically mixing MgO12g,ZnO 2g,MnO 1g, heating to 700 deg.C, activating for 30 hr to obtain semi-finished catalyst, crushing to 8-200 mesh, adding 0.3g graphite and 7g deionized water, mixing, tabletting, and shapingFinished catalyst X.
Comparative example 5
The activity comparison and evaluation are carried out by selecting a catalyst XI for preparing butadiene by oxidative dehydrogenation of butene, which is currently used in domestic industry, as a reference catalyst.
Crushing the catalysts of the examples and the comparative examples to 10-20 meshes, taking 3ml of the catalyst, filling the catalyst into a fixed bed reactor with an inner diameter of 12mm, and performing activity evaluation, wherein the activity evaluation conditions are as follows: butene space velocity 400h -1 The catalyst activity at 350 ℃, 400 ℃, 450 ℃, 500 ℃ and 550 ℃ was evaluated by the water-to-olefin molar ratio 17 and the oxygen-to-olefin molar ratio 0.55, and the catalyst activity evaluation results are shown in tables 1 to 3.
TABLE 1 catalyst conversion (%)
| Reaction temperature | 350℃ | 400℃ | 450℃ | 500℃ | 550℃ |
| Catalyst I | 65.98 | 64.95 | 61.53 | 54.29 | 39.83 |
| Catalyst II | 64.98 | 64.32 | 60.85 | 54.33 | 39.65 |
| Catalyst III | 65.03 | 64.57 | 60.01 | 54.12 | 39.7 |
| Catalyst IV | 65.14 | 64.58 | 60.75 | 54.31 | 39.56 |
| Catalyst V | 65.05 | 64.78 | 60.96 | 54.29 | 39.66 |
| Catalyst VI | 64.89 | 64.56 | 61.13 | 54.43 | 39.72 |
| Catalyst VII | 62.73 | 60.8 | 56.43 | 46.54 | 32.35 |
| Catalyst VIII | 62.83 | 60.95 | 56.83 | 46.85 | 32.76 |
| Catalyst IX | 64.85 | 63.24 | 59.75 | 52.98 | 38.21 |
| Catalyst X | 60.85 | 56.89 | 38.45 | 31.5 | 25.93 |
| Catalyst XI | 65.04 | 64.05 | 59.76 | 53.48 | 38.75 |
TABLE 2 catalyst yield (%)
TABLE 3 catalyst Selectivity (%)
| Reaction temperature | 350℃ | 400℃ | 450℃ | 500℃ | 550℃ |
| Catalyst I | 98.58 | 97.80 | 96.49 | 95.05 | 91.66 |
| Catalyst II | 98.09 | 97.57 | 95.99 | 94.86 | 90.92 |
| Catalyst III | 98.45 | 97.40 | 96.38 | 95.01 | 90.78 |
| Catalyst IV | 98.80 | 97.57 | 95.54 | 94.00 | 91.25 |
| Catalyst V | 98.16 | 97.45 | 95.88 | 93.66 | 90.97 |
| Catalyst VI | 98.30 | 97.24 | 95.55 | 94.01 | 90.91 |
| Catalyst VII | 95.71 | 95.15 | 93.83 | 88.89 | 83.40 |
| Catalyst VIII | 95.26 | 94.59 | 93.52 | 89.16 | 82.97 |
| Catalyst IX | 98.43 | 97.38 | 95.03 | 92.58 | 89.82 |
| Catalyst X | 93.28 | 88.98 | 87.00 | 84.29 | 72.89 |
| Catalyst XI | 98.17 | 96.92 | 95.13 | 93.03 | 90.27 |
The catalyst of the embodiment is prepared by adopting the method of the invention, a spinel type ferrite structure is formed firstly, and then the spinel type ferrite, ferric salt and M salt are subjected to precipitation reaction, so that the ferrite, ferric oxide and M oxide can be dispersed more uniformly, and the performance of the prepared catalyst is superior to that of the comparative example.
The catalysts VII and VIII of comparative examples 1 and 2 were prepared by sol-gel method using oxides or nitrates of iron, zinc, M, and magnesium, and could not form a large amount of ferrite spinel structure, but formed a part of iron, magnesium, zinc, M metal oxide phase and a part of ferrite spinel mixed phase, so the catalyst performance was inferior to that of the example catalyst.
The catalyst IX of comparative example 3 adopts ammonia water as a precipitator to carry out coprecipitation reaction with nitrate of iron, magnesium and zinc, ammonia water is adopted in the washing process, a large amount of zinc and magnesium ions exist in the catalyst mother liquor, zinc ions also exist in the washing liquor, and the ammonia water and the zinc and magnesium-containing wastewater generated in the production process seriously pollute the environment.
The catalyst X in comparative example 4 is prepared by directly adopting a mechanical mixing method, the dispersion degree of the active phase of the catalyst is poor, and the prepared catalyst has poor performance.
In comparative example 5, ammonia water is adopted as a precipitant to carry out coprecipitation reaction with iron, magnesium and zinc, so that a large amount of zinc and magnesium ions exist in the mother liquor, and the pH values of different batches are changed in the production process, so that the loss of zinc and magnesium is different, and the content of catalyst components is different.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. Preparation method of iron-based butene oxidative dehydrogenation catalyst, wherein the catalyst is prepared from spinel type ferrite and alpha-Fe 2 O 3 As a main active component, the catalyst comprises the following components in percentage by weight: fe (Fe) 2 O 3 70%～90%，MgO 5%～20%、ZnO 1.5%～10%、M x O y 0.5% -5%, wherein M is one or more of V, mn, al, ca, x and y respectively represent the valence of O in MxOy to be-2, and the valence of M is +2y/x, and the preparation method is characterized by comprising the following steps:
(1) Preparing spinel type ferrite containing iron, magnesium and zinc;
(2) Carrying out precipitation reaction on ferric salt, salt containing M and spinel type ferric salt obtained in the step (1) and a precipitator, and carrying out post-treatment on a product obtained by the precipitation reaction to obtain a finished catalyst;
wherein in the step (1), the spinel-type ferrite is prepared by a precipitation method, a mechanical mixing method, or a sol-gel method.
2. The method for preparing an iron-based butene oxidative dehydrogenation catalyst according to claim 1, wherein the preparation method comprises the following steps:
(A1) Preparing spinel type iron salt containing iron, magnesium and zinc by using a compound containing iron, magnesium and zinc;
(A2) Crushing the obtained spinel type ferrite to a certain mesh number, and adding water to uniformly mix to obtain first slurry;
(A3) Preparing a second solution comprising an iron salt and a salt comprising M;
(A4) Preparing a precipitant solution;
(A5) The second solution and the precipitant solution flow into the first slurry to carry out precipitation reaction;
(A6) And after the precipitation is finished, carrying out post-treatment on a product obtained by the precipitation reaction to obtain a finished catalyst.
3. The method for preparing an iron-based butene oxidative dehydrogenation catalyst according to claim 1 or 2, wherein in the step (A1), the spinel-type ferrite is prepared by a precipitation method, a mechanical mixing method, or a sol-gel method.
4. The method for preparing an iron-based butene oxidative dehydrogenation catalyst according to claim 2, wherein in the step (A1), the compound containing iron, magnesium and zinc comprises one or more of sulfate, nitrate and oxide of iron, magnesium and zinc.
5. The process for producing an iron-based butene oxidative dehydrogenation catalyst according to claim 1 or 2 or 4, wherein the step (1) or (A1) comprises the following step (B1): and uniformly mixing compounds containing iron, magnesium and zinc, adding organic acid, performing sol-gel reaction at a certain temperature, and roasting a product obtained by the sol-gel reaction to obtain spinel type ferrite.
6. The process for preparing an iron-based butene oxidative dehydrogenation catalyst according to claim 1 or 2, wherein in the step (2) or (A3), the iron salt is one or more of sulfate, nitrate and chloride of iron, and the M-containing salt is one or more of sulfate, nitrate and chloride of M.
7. The method for preparing an iron-based butene oxidative dehydrogenation catalyst according to claim 1 or 2, wherein in the step (2) or (A4), the precipitant is one or more of sodium hydroxide, sodium carbonate, ammonia water and sodium bicarbonate.
8. The process for preparing an iron-based butene oxidative dehydrogenation catalyst according to claim 1 or 2, wherein in the step (2) or (A6), the post-treatment comprises aging, washing, activating and molding.
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