CN115999593A - Catalyst for preparing low-carbon carboxylic acid from low-carbon alcohol and application of catalyst - Google Patents
Catalyst for preparing low-carbon carboxylic acid from low-carbon alcohol and application of catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 229910052799 carbon Inorganic materials 0.000 title claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 13
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims abstract description 58
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical group [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 37
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 claims abstract description 28
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims abstract description 20
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 53
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000011575 calcium Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- HTRVTKUOKQWGMO-UHFFFAOYSA-N 2-ethyloctan-1-ol Chemical compound CCCCCCC(CC)CO HTRVTKUOKQWGMO-UHFFFAOYSA-N 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 9
- 238000011068 loading method Methods 0.000 abstract description 7
- -1 carbon chain fatty alcohol Chemical class 0.000 abstract description 5
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 2
- 239000000194 fatty acid Substances 0.000 abstract description 2
- 229930195729 fatty acid Natural products 0.000 abstract description 2
- 150000004665 fatty acids Chemical class 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000011701 zinc Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
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- 235000011837 pasties Nutrition 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
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- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
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- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
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- 230000020477 pH reduction Effects 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- QNJAZNNWHWYOEO-UHFFFAOYSA-N 2-ethylheptan-1-ol Chemical compound CCCCCC(CC)CO QNJAZNNWHWYOEO-UHFFFAOYSA-N 0.000 description 1
- QZESEQBMSFFHRY-UHFFFAOYSA-N 2-methylheptan-1-ol Chemical compound CCCCCC(C)CO QZESEQBMSFFHRY-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 102100039384 Huntingtin-associated protein 1 Human genes 0.000 description 1
- 101710140977 Huntingtin-associated protein 1 Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000003379 elimination reaction Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000007952 growth promoter Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229910000392 octacalcium phosphate Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
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- 238000011069 regeneration method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- YIGWVOWKHUSYER-UHFFFAOYSA-F tetracalcium;hydrogen phosphate;diphosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].OP([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YIGWVOWKHUSYER-UHFFFAOYSA-F 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalyst for preparing 2-ethylhexanoic acid by catalytic dehydrogenation of 2-ethylhexanol and application thereof. The catalyst of the application is a catalyst for preparing 2-ethylhexanoic acid by catalytic dehydrogenation of 2-ethylhexanol, wherein: the active component of the catalyst is one or more of Mg, ti, mn, cu, zn, zr, ni and Ce; the carrier of the catalyst is Hydroxyapatite (HAP); the mass fraction loading of the active component is 0.5% -50%. Correspondingly, the preparation method of the catalyst and the application of the catalyst in the preparation of fatty acid by dehydrogenation of long carbon chain fatty alcohol are also provided. The catalyst prepared by the method has the advantages of alkali resistance, high temperature resistance, recycling and good catalytic activity.
Description
Technical Field
The application belongs to the technical field of chemical catalysis, and particularly relates to a catalyst for preparing carboxylic acid substances through catalytic dehydrogenation of alcohol substances.
Background
2-ethylhexanoic acid is an important fine chemical raw material and is widely applied to industries such as medical raw materials, lubricants, rubber adhesives, oil additives, rust inhibitors, antifreezes, driers, curing agents, coatings, printing ink, glass fiber reinforced plastics and the like. In addition, the metal salts are upgrading and updating products of naphthenate, are widely applied to the plastic industry, and the esters are excellent plasticizers. In the refrigeration industry, 2-ethylhexanoic acid is used for fluorine-free refrigeration. In the rubber industry, cobalt salts thereof are useful. The said process may be used in petrochemical industry and daily chemical industry to produce various chemical extractants and hydrocarbon gelatinizer. The esters can also be used as food additives, feed additives, fish-farming bactericides and biological growth promoters for the food processing industry, agriculture and fishery, respectively.
The 2-ethylhexanoic acid is prepared by a catalytic dehydrogenation method, and the method has the advantages of simple operation, high selectivity, low equipment investment and the like, so that the method becomes a 2-ethylhexanoic acid production process adopted by a plurality of enterprises. The catalyst of the process is some metal oxides (ZnO, mgO, cuO, etc.). For example, chinese patent publication No. CN106278875A, a process for preparing isooctanoic acid, wherein isooctanol is reacted with a strong base, and a zinc compound is further added to the reaction system. Because of the damage of strong alkalinity and high temperature conditions to the catalyst structure in the reaction process, the existing catalyst is mostly a disposable catalyst, and the subsequent regeneration and recycling are greatly limited.
Disclosure of Invention
The purpose of the application is to provide a catalyst for preparing low-carbon carboxylic acid by catalytic dehydrogenation of low-carbon alcohol. The catalyst has good catalytic performance, and can effectively improve the conversion rate of 2-ethylhexanol and the selectivity of 2-ethylhexanoic acid in alkaline environment. In particular, in a reaction system for preparing 2-ethylhexanoic acid by catalytic dehydrogenation of 2-ethyl-hexanol, the selectivity of the 2-ethylhexanoic acid is high.
The catalyst for preparing 2-ethylhexanoic acid by catalytic dehydrogenation of 2-ethylhexanol has alkali resistance and high temperature resistance, and can obviously improve the use times and service life of the catalyst.
It is still another object of the present application to provide a method for preparing a catalyst for preparing 2-ethylhexanoic acid by catalytic dehydrogenation of 2-ethylhexanol.
The catalyst for preparing the low carbonic acid by catalytic dehydrogenation of the low carbon alcohol comprises metal elements and hydroxyapatite, wherein the metal elements comprise one or more elements of Mg, ti, mn, cu, zn, zr, ni and Ce, and the content of the metal elements is 0.5-50 wt%.
The low-carbon alcohol is saturated monoalcohol with carbon number lower than 8, and the low-carbon carboxylic acid is saturated monoacid with carbon number lower than 8.
The catalyst is especially used in the reaction system for preparing 2-ethylhexanoic acid by catalytic dehydrogenation of 2-ethylhexanol, and has good catalytic performance. Has the advantages of alkali resistance and high temperature resistance, and can be recycled.
Detailed Description
A catalyst for the catalytic dehydrogenation of 2-ethylhexanol to 2-ethylhexanoic acid is described in further detail below. And do not limit the scope of the application, which is defined by the claims. Certain disclosed specific details provide a thorough understanding of the various disclosed embodiments. However, one skilled in the relevant art will recognize that embodiments can be practiced without one or more of the specific details, with other materials, etc.
In the description and in the claims, the terms "comprising," including, "and" containing "are to be construed as open-ended, meaning" including, but not limited to, unless the context requires otherwise.
Reference in the specification to "an embodiment," "one embodiment," "another embodiment," or "certain embodiments," etc., means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, it is not necessary for an "embodiment," "one embodiment," "another embodiment," or "certain embodiments" to refer to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. The various features disclosed in the specification may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, the disclosed features are merely general examples of equivalent or similar features.
The present application is further illustrated below in conjunction with specific embodiments. It should be understood that these examples are illustrative only of the present application and are not intended to limit the scope of the present application. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages, ratios, proportions, or parts are by weight unless otherwise indicated.
In this application, the concentration unit "M" of a solution means mol/L.
The catalyst for preparing the low-carbon carboxylic acid by catalytic dehydrogenation of the low-carbon alcohol comprises metal elements and hydroxyapatite, wherein the metal elements comprise one or more of Mg, ti, mn, cu, zn, zr, ni and Ce, and the content of the metal elements is 0.5-50 wt%.
The content of the metal element means a ratio of the mass of the metal element to the total mass of the catalyst.
The catalyst passes through metal M-PO x The metal element is doped in the Hydroxyapatite (HAP) structure, and in the reaction process, the contact area of the active site, the reaction substrate and the alkali liquor is high due to the alkali resistance of the catalyst, so that the catalytic activity and the stability of the catalyst are improved. In addition, as active metal sites are dispersed, the atom utilization rate is improved, so that the reaction is independently completed on each dispersed site, and the selectivity is improved. The carrier itself can raise a part of alkaline sites, and has synergistic effect of co-dehydrogenation with active metal, so as to further raise reaction conversion rate.
The metallic elements in the catalyst are all in the form of oxides. The catalytic effect is good.
In certain embodiments, the metallic element comprises one or more of Cu, zn.
In certain embodiments, the metal element is present in an amount of 10wt% to 30wt%.
By regulating and controlling the chemical composition environment of the active metal, the interaction between the carrier and the active metal is enhanced, and the alkali resistance and high temperature resistance of the active metal oxide are greatly improved.
In another aspect, a method for preparing a catalyst for preparing a lower carboxylic acid by catalytic dehydrogenation of a lower alcohol comprises:
1) Mixing a soluble salt containing phosphorus element with a soluble solution containing metal element to obtain solution A, wherein the metal element comprises one or more elements of Mg, ti, mn, cu, zn, zr, ni and Ce;
2) Mixing a soluble salt containing calcium with the solution A, and adjusting the solution to be alkaline to obtain a mixture B;
3) Heating the mixed solution B to precipitate crystals, and washing, drying and roasting the obtained crystals to obtain the catalyst.
In the catalyst, the phosphorus element solution and the active metal element are mixed firstly, and then the mixture is mixed with the calcium element solution, so that the catalyst is formed in one step by a hydrothermal method, HAP is formed in the crystallization process, and the active metal element is uniformly introduced into the HAP, so that the catalyst has good catalytic dehydrogenation performance and higher stability of 2-ethylhexanol.
In the step 1), the mole ratio of the phosphorus element to the metal element in the soluble salt containing the phosphorus element and the soluble solution containing the metal element is 1 (0.28-0.8). The molar ratio of the calcium element of the soluble salt of the calcium element to the phosphorus element of the soluble salt of the phosphorus element in the step 2) is 5 (3.0-3.5). In certain embodiments, in step 2), the soluble salt of the calcium-containing element is mixed with solution a, and the solution is alkaline and the pH of the mixed solution is adjusted to 12.
By controlling the pH of the mixed solution B, the conversion to n (Ca)/n (P) =1.67 of hydroxyapatite is facilitated by the hydrothermal synthesis of hydroxyapatite going through octacalcium phosphate, to amorphous calcium phosphate, to calcium deficient apatite and to hydroxyapatite, the higher the pH, the higher the OH-concentration.
In the preparation process of the catalyst, when the pH is regulated to 12, the metal salt of the active component can be ensured to be uniformly mixed in the hydroxyapatite in the form of hydroxide precipitation, and the metal oxide is formed by post-roasting. In certain embodiments, mixed solution B precipitates crystals at a temperature of 110 ℃ to 150 ℃.
In the crystallization process, the supersaturation degree of the mixed solution B is larger along with the gradual rise of the temperature; when the temperature is raised to 110-150 ℃, the supersaturation degree of the solution is raised to a metastable state, and the solution starts to crystallize attached to the active metal hydroxide particles, and the saturation degree reaches the maximum; in the middle and late stages of the reaction, the supersaturation degree of the solution is reduced, and the crystal growth is slowly ended.
In certain embodiments, the drying temperature is controlled between 75 ℃ and 110 ℃.
In certain embodiments, the firing temperature is controlled at 450 ℃.
The catalyst obtained by in-situ doping not only maintains the activity of the active metal oxide, but also improves the alkali resistance and high temperature resistance of the catalyst, and meanwhile, the active metal oxide is dispersed in the carrier HAP, so that more uniform active sites are provided for the reaction, and the conversion rate and the selectivity of the reaction are improved.
In this application, the solubility of phosphorus-containing elements includes, but is not limited to, (NH) 4 ) 2 HPO 4 、H 3 PO 4 、NaH 2 PO 4 And (CH) 3 O) 3 PO, etc.
Soluble salts of calcium-containing elements include, but are not limited to, ca (NO 3 ) 2 ·4H 2 O、Ca(OH) 2 、CaHPO 4 ·2H 2 O、CaO、CaCl 2 And Ca (OC) 2 H 5 ) 2 Etc.
The soluble solution containing a metal element is usually nitrate or chloride. Nitrate is a preferable substance, has the advantages of no residual elements after decomposition, elimination of interference of anions and low price.
In certain embodiments, the lye comprises an alkali metal hydroxide. Such as sodium hydroxide, or potassium hydroxide, etc.
The catalyst obtained by the method is applied to the reaction of preparing 2-ethylhexanoic acid by catalytic dehydrogenation of 2-ethylhexanol.
In certain embodiments, a process for preparing 2-ethylhexanoic acid by catalytic dehydrogenation of 2-ethylhexanol comprises: the catalyst is placed in 2-ethylhexanol, strong alkali is added, the reaction is carried out in the atmosphere of nitrogen, and the reaction temperature is controlled between 200 ℃ and 250 ℃.
Strong bases include, but are not limited to, sodium hydroxide, or potassium hydroxide, and the like.
In certain embodiments, the mass ratio of catalyst to 2-ethyl octanol is 1:100 to 1:500.
In certain embodiments, the molar ratio of sodium hydroxide to 2-ethylhexanol is from 1:1.3 to 1:0.7.
In certain embodiments, the operating pressure is atmospheric after the nitrogen displacement gas is introduced.
In certain embodiments, the reaction time is from 0.5 to 2 hours.
In the reaction system, the conversion rate of the 2-ethyl Xin Jichun reaches more than 97 percent, and the selectivity is more than 94 percent.
In addition, the catalyst can be repeatedly used for a plurality of times, and can maintain good catalytic performance.
Specifically, the catalytic dehydrogenation of 2-ethylhexanol to prepare 2-ethylhexanoic acid comprises:
placing a catalyst and sodium hydroxide into an intermittent reaction kettle, adding a magneton or magnetic stirring device, sealing, filling nitrogen with certain pressure, evacuating, performing gas replacement, heating to a required temperature, adjusting a proper rotating speed, and reacting for a certain time; and after the reaction is finished, standing and cooling, then reducing the pressure in the kettle to normal pressure, adding distilled water and stirring to obtain the sodium isooctanoate aqueous solution.
Transferring the sodium isooctanoate aqueous solution into a beaker, slowly adding sulfuric acid solution under stirring for acidification, standing for layering, and separating a water phase; washing the oil phase with distilled water to obtain crude isooctanoic acid, distilling under reduced pressure to remove unreacted alcohol, and rectifying to obtain 2-ethylhexanoic acid product.
The catalysts of the present application and their catalytic effects are further described below in conjunction with the specific examples. The substances used in the examples below are all chemically pure standard.
Example 1:
synthesis of Cu in situ supported HAP catalyst
Will 2gNH 4 H 2 PO 4 And 2.51g of Cu (NO) 3 ) 2 Mix in 25 ml deionized water and stir for 12h to give solution a.
6.7g of Ca (NO 3 ) 2 ·4H 2 O was placed in 50 ml deionized water to disperse evenly, and was slowly added dropwise to solution a, then sodium hydroxide was added dropwise to the mixed solution until ph=12, and stirring was continued for 12 hours to obtain solution B.
Solution B was transferred to a polytetrafluoroethylene-lined autoclave and hydrothermally crystallized at 110℃for 24h. The resulting sample was filtered through deionized water, dried at 80℃and calcined in a muffle furnace at 450℃for 2h to give the desired catalyst, designated CuO/HAP. The content of Cu element in the catalyst was 30wt%.
Example 2
Synthesis of Zn in situ supported HAP catalyst
This example method of preparing a catalyst and parameters reference example 1 except that Cu (NO 3 ) 2 2.53g of Zn (NO) 3 ) 2 The catalyst obtained was also designated ZnO/HAP. The Zn content in the catalyst was 30wt%. Example 3
Synthesis of catalyst with Ce in situ supported on HAP
This example method of preparing a catalyst and parameters reference example 1 except that Cu (NO 3 ) 2 Is replaced by 4.36g Ce (NO) 3 ) 2 The resulting catalyst was designated CeO/HAP. The Ce content in the catalyst was 30wt%
Example 4
Synthesis of Cu-Zn bimetallic in-situ supported HAP catalyst
This example method for preparing a catalyst and parameters reference example 1 exceptCu (NO) in example 1 was prepared 3 ) 2 1.26g of Cu (NO) 3 ) 2 And 1.27g Zn (NO) 3 ) 2 The resulting catalyst was designated as CuO-ZnO/HAP. The content of Cu and Zn elements in the catalyst is 15wt% and 15wt% respectively.
Example 5
Synthesis of catalyst carried on HAP by Zn impregnation method
2g NH 4 H 2 PO 4 And 6.7g Ca (NO) 3 ) 2 ·4H 2 Placing O in 75 ml of deionized water, mixing, and stirring for 12h to obtain solution A; then, alkali sodium hydroxide is added dropwise into the solution A until the pH value is=12, and stirring is continued for 12 hours, so as to obtain a solution B. Solution B was transferred to a polytetrafluoroethylene-lined autoclave and hydrothermally crystallized at 110℃for 24h. Filtering the formed sample by deionized water, and drying at 80 ℃ to obtain a required carrier, which is recorded as HAP;
the HAP obtained was combined with 2.53g Zn (NO 3 ) 2 Dissolving in 30ml deionized water, mixing thoroughly, stirring at constant temperature of 60deg.C under 1000rpm to obtain paste, and evaporating to dryness; and (3) standing the obtained pasty substance for 6 hours at normal temperature, putting the pasty substance into a baking oven at 100 ℃, baking the pasty substance for 2 hours at 450 ℃ in a muffle furnace to obtain the required catalyst, namely Zn/HAP-IM, wherein the Zn content is 30wt% of the HAP mass fraction.
Example 6
Synthesis of catalyst loaded on active carbon by Zn impregnation method
2g of Activated Carbon (AC) and 1.74g of Zn (NO) 3 ) 2 Dissolving in 30ml deionized water, mixing thoroughly, stirring at constant temperature of 60deg.C under 1000rpm to obtain paste, and evaporating to dryness; and standing the obtained pasty substance for 6 hours at normal temperature, putting the pasty substance into a baking oven at 100 ℃ for baking, and roasting the pasty substance in a muffle furnace at 450 ℃ for 2 hours to obtain the required catalyst, wherein the catalyst is marked as Zn/AC-IM, and the Zn content is 30wt% of the mass fraction of the activated carbon.
Experimental example 1
The catalysts prepared in examples 1-4 were used in the oxidation of 2-ethylhexanol according to the following protocol: weighing a certain amount of catalyst and sodium hydroxide, adding the catalyst and sodium hydroxide into a 500ml intermittent stirring reaction kettle, adding a certain amount of 2-ethylhexanol, sealing, filling nitrogen with a certain pressure, evacuating, repeating the gas displacement for three times, setting a certain reaction temperature and stirring speed, and starting the reaction. Cooling after stopping the reaction, then reducing the pressure in the kettle to normal pressure, adding distilled water and stirring to obtain the sodium isooctanoate aqueous solution. Transferring the sodium isooctanoate aqueous solution into a beaker, slowly adding sulfuric acid solution under stirring for acidification, standing for layering, and separating a water phase; washing the oil phase with distilled water to obtain crude isooctanoic acid, distilling under reduced pressure to remove unreacted 2-ethylhexanol, and rectifying to obtain 2-ethylhexanoic acid product. The supernatant was subjected to chromatography and the results are shown in Table 1.
TABLE 1
Wherein the subscript number is the active metal loading (mass percent), e.g., cuO 30 HAP, cu loading was 30wt%, and HAP was used as the carrier. Reaction conditions: the reaction substrate is 180g of 2-ethylhexanol, 72g of NaOH and 1g of catalyst are added, the mol ratio of sodium hydroxide to 2-ethylhexanol is 1.3:1, the mass ratio of catalyst to 2-ethylhexanol is 1:180, the reaction temperature is 240 ℃, and the reaction time is 1h.
Experimental example 2
The experimental example is directed to ZnO and ZnO 30 HAP and recycled catalyst catalyze the dehydrogenation of 2-ethylhexanol. Experimental conditions reference experimental example 1, except that different catalysts were used. ZnO and ZnO 30 The HAP and recycled catalyst catalyze the dehydrogenation of 2-ethylhexanol as shown in Table 2.
TABLE 2
Wherein the subscript number is the active metal loading (mass percent) and the suffix is the number of cycles, e.g., znO 30 HAP-1, zn loading of 30wt%, HAP as carrier and 1-cycle catalyst. Reaction stripPiece (2): 180g of 2-ethylhexanol, 72g of NaOH and 1g of catalyst are added, the molar ratio of sodium hydroxide to 2-ethylhexanol is 1.3:1, the mass ratio of catalyst to 2-ethylhexanol is 1:180, the reaction temperature is 240 ℃, and the reaction time is 1h.
Experimental example 3
The catalyst prepared in example 2 was subjected to catalytic dehydrogenation in different reaction raw materials to prepare the catalytic performance of alkyl carboxylic acid, and the results are shown in table 3. See experimental example 1 for additional conditions of the experiment.
TABLE 3 Table 3
| Catalyst | Substrate(s) | Conversion (%) | Corresponding fatty acid selectivity (%) |
| ZnO 30 /HAP | 2-ethylheptanol | 75.2 | 83.1 |
| ZnO 30 /HAP | 2-methyl heptanol | 86.8 | 86.2 |
| ZnO 30 /HAP | Isononol | 54.1 | 80.1 |
| ZnO 30 /HAP | Decyl alcohol | 40.1 | 44.5 |
Wherein the subscript number is the active metal loading (mass percent), e.g., znO 30 HAP, zn loading was 30wt%, and HAP was used as the carrier. Reaction conditions: 180g of reaction substrate, adding sodium hydroxide and a catalyst in a corresponding proportion, wherein the molar ratio of the sodium hydroxide to the alcohol is 1.3:1, the mass ratio of the catalyst to the alcohol is 1:180, the reaction temperature is 240 ℃, and the reaction time is 1h.
It will be evident to those skilled in the art that the present application is not limited to the details of the foregoing illustrative embodiments, and that the present application may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. The catalyst for preparing the low-carbon carboxylic acid by catalytic dehydrogenation of the low-carbon alcohol comprises metal elements and hydroxyapatite, wherein the metal elements comprise one or more of Mg, ti, mn, cu, zn, zr, ni and Ce, and the content of the metal elements is 0.5-50 wt%;
preferably, the lower alcohol is 2-ethylhexanol and the lower carbonic acid is 2-ethylhexanoic acid;
preferably, the content of the metal element is 10wt% to 30wt%.
2. The catalyst according to claim 1, wherein the metal element comprises one or more elements of Cu, zn, ce.
3. A method of preparing the catalyst of claim 1 or 2, comprising:
1) Mixing a soluble salt containing phosphorus element with a soluble solution containing metal element to obtain solution A, wherein the metal element comprises one or more elements of Mg, ti, mn, cu, zn, zr, ni and Ce;
2) Dropwise adding a solution A into soluble salt containing calcium, and regulating the solution A to be alkaline until the pH value is=12 to obtain a mixed solution B;
3) Heating the mixed solution B to precipitate crystals, and washing, drying and roasting the obtained crystals to obtain a catalyst;
preferably, the mixed solution B precipitates crystals at a temperature of 110-150 ℃.
4. A method of preparation according to claim 3, characterized in that:
in the step 1), the mole ratio of the phosphorus element to the metal element in the soluble salt containing the phosphorus element and the soluble solution containing the metal element is 1 (0.28-0.8).
5. The production process according to claim 3 or 4, wherein the molar ratio of the calcium element of the soluble salt of the calcium element to the phosphorus element of the soluble salt of the phosphorus element in step 2) is 5 (3.0 to 3.5).
6. The method of any one of claims 3-5, 4, wherein: the drying temperature is controlled at 75-110 ℃;
preferably, the temperature of the calcination is controlled at 450 ℃.
7. The method of any one of claims 3-6, 4, wherein: the substance for adjusting the pH in the step 2) comprises alkali metal hydroxide; preferably, it is: sodium hydroxide and potassium hydroxide.
A process for the catalytic dehydrogenation of 2-ethylhexanol to produce 2-ethylhexanoic acid comprising: the catalyst of any one of claims 1-2 is placed in 2-ethylhexanol, sodium hydroxide is added, and the reaction is carried out in a nitrogen atmosphere, wherein the reaction temperature is controlled between 200 ℃ and 250 ℃.
9. The method according to claim 8, wherein the mass ratio of the catalyst to the 2-ethyl octanol is 1:100 to 1:500.
10. The process according to claim 8 or 9, characterized in that the molar ratio of sodium hydroxide to 2-ethylhexanol is 1:1.3 to 1:0.7.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1357527A (en) * | 2000-12-15 | 2002-07-10 | 中国石化集团齐鲁石油化工公司 | Production process of 2-ethyl hexanoic acid |
| CN101906027A (en) * | 2009-06-05 | 2010-12-08 | 复旦大学 | Method for preparing aldehydes or ketones by alcohol oxidation reaction |
| CN102989490A (en) * | 2012-12-04 | 2013-03-27 | 复旦大学 | Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof |
| CN111229263A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Hydroxyapatite-based catalyst, preparation and application thereof |
| CN114950505A (en) * | 2022-03-15 | 2022-08-30 | 浙江大学 | Catalyst for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1357527A (en) * | 2000-12-15 | 2002-07-10 | 中国石化集团齐鲁石油化工公司 | Production process of 2-ethyl hexanoic acid |
| CN101906027A (en) * | 2009-06-05 | 2010-12-08 | 复旦大学 | Method for preparing aldehydes or ketones by alcohol oxidation reaction |
| CN102989490A (en) * | 2012-12-04 | 2013-03-27 | 复旦大学 | Copper-hydroxyapatite catalyst for synthesizing methyl glycolate and ethylene glycol and preparation method thereof |
| CN111229263A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Hydroxyapatite-based catalyst, preparation and application thereof |
| CN114950505A (en) * | 2022-03-15 | 2022-08-30 | 浙江大学 | Catalyst for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide and preparation method and application thereof |
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