CN118047672A - New process for producing isooctanoic acid and matched catalyst - Google Patents
New process for producing isooctanoic acid and matched catalyst Download PDFInfo
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- CN118047672A CN118047672A CN202410017056.1A CN202410017056A CN118047672A CN 118047672 A CN118047672 A CN 118047672A CN 202410017056 A CN202410017056 A CN 202410017056A CN 118047672 A CN118047672 A CN 118047672A
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- isooctanoic acid
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- isooctanol
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- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 78
- 230000008569 process Effects 0.000 title claims abstract description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 159
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 148
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims abstract description 75
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 230000020477 pH reduction Effects 0.000 claims description 41
- 239000002994 raw material Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 28
- 238000011282 treatment Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000012213 gelatinous substance Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 238000010168 coupling process Methods 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000011787 zinc oxide Substances 0.000 description 13
- 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 12
- 239000000047 product Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 238000010924 continuous production Methods 0.000 description 6
- 230000008878 coupling Effects 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000003541 multi-stage reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 150000003752 zinc compounds Chemical class 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000006077 pvc stabilizer Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- -1 sodium lignin sulfonate quaternary ammonium salt Chemical class 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- 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
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A process for producing isooctanoic acid, catalyst Sn/ZnO-Al 2O3 is applied to the process, wherein the process is a reaction kettle-fixed bed coupling process, isooctanol and sodium hydroxide are mixed in a kettle reactor and are put into the fixed bed reactor after heat treatment, catalyst is filled, and isooctanol dehydrogenation is catalyzed to prepare isooctanoic acid until no hydrogen is generated; secondly, a multistage kettle reactor serial connection process is adopted, isooctanol and sodium hydroxide are mixed and preheated in a pretreatment kettle and then are put into a first-stage reaction kettle, the same dehydrogenation catalyst is filled, after a period of reaction, the materials are conveyed to a next-stage reaction kettle for continuous reaction until no hydrogen is generated in a final kettle. And after the reaction is finished, the material is acidified by sulfuric acid, kept stand, separated, rectified and purified to finally obtain the isooctanoic acid product. The process has continuous isooctanoic acid production, short reaction time, high production efficiency, low catalyst cost, high isooctanol conversion rate, good isooctanoic acid selectivity and high stability.
Description
Technical Field
The application belongs to the technical field of chemical catalysis, and particularly relates to an isooctanoic acid production process and a catalyst.
Background
Isooctanoic acid with boiling point of 228 deg.C can be used as intermediate of paint and coating drier, alkyd resin modifier, catalyst for producing peroxide as polymerization reaction, lubricating oil ester and PVC stabilizer, etc. and its application in market is extensive. At present, the main preparation method of isooctanoic acid is an isooctanol catalytic dehydrogenation method, and the method has the advantages of simple process, rich isooctanol sources, low price and the like, and is adopted by most manufacturers at present.
At present, the method is adopted by domestic and Japanese major manufacturers, generally using batch reaction kettles, and cannot be used for continuous production. And the current commonly used isooctanol dehydrogenation catalyst is difficult to realize high conversion rate and selectivity in a fixed bed reactor for a short time, so that the continuous production process of isooctanoic acid is more difficult to appear.
Chinese patent application publication No. CN1817845A discloses a method for preparing isooctanoic acid by a composite catalytic method; the reactants are isooctanol and sodium hydroxide, the catalyst is a composite catalyst formed by combining calcium oxide, vanadium pentoxide and rare earth oxide, and the reaction time is 1.8-2.2h after the isooctanoate is reacted at 240-280 ℃. Then acidifying with sulfuric acid to obtain crude isooctanoic acid, and purifying to obtain isooctanoic acid. The reaction is carried out in a batch reaction kettle, can not be carried out continuously, and the catalyst is not recovered, so that the production cost is increased.
Chinese patent application publication No. CN110878016B discloses that isooctanol and sodium hydroxide are oxidized under inert atmosphere conditions in the presence of TiO 2-CeO2 metal oxide catalyst. The reaction was carried out in a fixed bed, but it was not possible to carry out the reaction with pure sodium hydroxide since the feed had not been pretreated. In the same throughput equipment, the production of finished products per unit time is limited.
Chinese patent application publication No. CN116082140A discloses a sodium lignin sulfonate quaternary ammonium salt catalyst loaded with phosphotungstic acid, which catalyzes isooctanol oxidation under the action of H 2O2, and the process solves the problem of serious environmental pollution of a system for preparing isooctanoic acid by common isooctanol oxidation. But they exhibit limited yields of isooctanoic acid and use of H 2O2, making them difficult to apply to continuous industrial production.
Chinese patent application publication CN115677476B discloses a production process and a system of isooctanoic acid, wherein the system consists of a dehydrogenation kettle, an acidification kettle and a standing kettle, provides a production flow of the system, and solves the problem that a large amount of waste liquid is produced in an isooctanol dehydrogenation system. However, only one dehydrogenation reaction kettle is independently arranged, and only intermittent production can be realized, and the continuous requirement is not met.
In view of this, the present invention aims to develop a new process capable of continuous and enlarged production, so as to reduce the cost of reaction equipment and improve the reaction efficiency.
Disclosure of Invention
The application aims to provide a process for producing isooctanoic acid, which can realize continuous feeding of isooctanoic acid to produce isooctanoic acid or interval time feeding to produce isooctanoic acid.
It is another object of the present application to provide an improvement in the productivity of isooctanoic acid production.
The third purpose of the application is to provide a process for continuously producing isooctanoic acid by coupling fixed bed reaction equipment with multi-kettle serial reaction equipment.
The fourth object of the application is to provide a catalyst for preparing isooctanoic acid by dehydrogenation of isooctanol, which is used for improving the conversion rate of isooctanol and has high stability suitable for continuous production.
On the one hand, the process for producing the isooctanoic acid comprises a first-stage dehydrogenation reaction kettle and a second reaction kettle, wherein the first-stage dehydrogenation reaction kettle is connected with the second-stage dehydrogenation reaction kettle, a mixture of raw materials isooctanoic acid, sodium hydroxide and a catalyst is introduced into the first-stage reaction kettle, after the reaction in the first-stage dehydrogenation reaction kettle is carried out for a first set time, the mixture in the first-stage dehydrogenation reaction kettle is introduced into the second reaction kettle again for a second set time; and (3) acidizing and purifying the finally obtained product to obtain the isooctanoic acid, wherein the catalyst is Sn/ZnO-Al 2O3.
The method can further comprise a third-stage dehydrogenation reaction kettle, wherein the third-stage dehydrogenation reaction kettle is connected with the second-stage dehydrogenation reaction kettle, and the mixture in the second-stage dehydrogenation reaction kettle enters the third-stage dehydrogenation reaction kettle for reaction.
And the final product enters the acidification kettle for acidification treatment.
According to the isooctanoic acid process, the time period of dehydrogenation reaction in all the reaction kettles is respectively dispersed in the multistage dehydrogenation reaction kettles for reaction, the reaction time in each stage of dehydrogenation reaction kettles can be shortened in multiple, and therefore the interval between two adjacent feeding times can be obviously shortened. Namely, the production efficiency of the isooctanoic acid is improved.
In a second aspect, a process for producing isooctanoic acid comprises a pre-raw material pretreatment kettle, a fixed bed reactor and an acidification kettle, wherein the fixed bed reactor is connected with the acidification kettle, and a catalyst fixed bed is arranged in the fixed bed reactor;
Introducing a mixture of raw materials of isooctanoic acid and sodium hydroxide into a fixed bed reactor, performing dehydrogenation reaction under the action of a catalyst, and introducing the obtained product into an acidification kettle for acidification treatment, and purifying after the acidification treatment to obtain isooctanoic acid, wherein the catalyst is Sn/ZnO-Al 2O3.
According to the isooctanoic acid process, the mixture of the raw materials isooctanoic acid and sodium hydroxide can continuously enter a fixed bed reactor by controlling the airspeed, the sodium isooctanoic acid is prepared by dehydrogenation reaction, the mixture in the fixed bed reactor is continuously discharged from the fixed bed reactor, and the isooctanoic acid is obtained through subsequent treatment.
In a third aspect, a process for producing isooctanoic acid comprises: the first-stage dehydrogenation reaction kettle is connected with the second-stage dehydrogenation reaction kettle, and the last-stage dehydrogenation reaction kettle is connected with the acidification kettle;
The fixed bed reactor is connected with the acidification kettle;
The fixed bed reactor and the first stage dehydrogenation reaction kettle are arranged in parallel;
introducing the mixture of the raw materials of isooctanoic acid, sodium hydroxide and the catalyst into a first-stage dehydrogenation reaction kettle, or introducing the mixture of the raw materials of isooctanoic acid and sodium hydroxide into a fixed bed reactor;
And (3) acidizing and purifying the finally obtained product to obtain the isooctanoic acid, wherein the catalyst is Sn/ZnO-Al 2O3.
The isooctanoic acid is prepared by coupling a fixed bed reactor with a multi-stage reaction kettle, and dehydrogenation reaction can be performed in the fixed bed reactor and the multi-stage reaction kettle in a crossing manner, so that quick feeding and efficient preparation of the isooctanoic acid are realized. In the process that the mixture of the raw material isooctanoic acid, sodium hydroxide and the catalyst reacts in the first-stage dehydrogenation reaction kettle, the mixture of the raw material isooctanoic acid and the sodium hydroxide can be introduced into the fixed bed reactor for dehydrogenation reaction, and the space velocity entering the fixed bed reactor is not required to be reduced. Through the coupling use of the two sets of equipment, the industrialized production of the isooctanoic acid by continuous feeding is realized, and the production efficiency is high.
In any of the processes for producing isooctanoic acid, a Sn/ZnO-Al 2O3 catalyst is used, so that the speed of preparing isooctanoic acid by dehydrogenation and oxidation of isooctanol is improved, and the dehydrogenation reaction can be completed in a short time.
In the fourth aspect, the catalyst for preparing isooctanoic acid by dehydrogenating isooctanol comprises Sn element, znO and Al 2O3, wherein the mass of the Sn element is 0.5-5wt% of the mass of ZnO, and the mass of Al 2O3 is 10-30wt% of the total mass of the catalyst.
The catalyst can improve the efficiency of preparing isooctanoic acid by dehydrogenating isooctanol, and has high conversion rate of isooctanol and high selectivity of isooctanoic acid.
Drawings
FIG. 1 is a schematic diagram of a process flow for producing isooctanoic acid according to the invention.
FIG. 2 is a schematic structural diagram of a multi-pot serial dehydrogenation process for producing isooctanoic acid.
FIG. 3 is a schematic structural diagram of a fixed bed dehydrogenation process for producing isooctanoic acid.
Detailed Description
The novel process for producing isooctanoic acid and the use of the catalyst according to the application are 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 application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative 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.
On the one hand, the process for producing the isooctanoic acid comprises a first-stage dehydrogenation reaction kettle and a second reaction kettle, wherein the first-stage dehydrogenation reaction kettle is connected with the second-stage dehydrogenation reaction kettle, a mixture of raw materials isooctanoic acid, sodium hydroxide and a catalyst is introduced into the first-stage reaction kettle, after the reaction in the first-stage dehydrogenation reaction kettle is carried out for a first set time, the mixture in the first-stage dehydrogenation reaction kettle is introduced into the second reaction kettle again for a second set time; and (3) acidizing and purifying the finally obtained product to obtain the isooctanoic acid, wherein the catalyst is Sn/ZnO-Al 2O3.
The method can further comprise a third-stage dehydrogenation reaction kettle, wherein the third-stage dehydrogenation reaction kettle is connected with the second-stage dehydrogenation reaction kettle, and the mixture in the second-stage dehydrogenation reaction kettle enters the third-stage dehydrogenation reaction kettle for reaction.
And the final product enters the acidification kettle for acidification treatment.
In certain embodiments, more than three stages of dehydrogenation reaction kettles are included, with the multiple stages of dehydrogenation reaction kettles being connected in series.
The number of dehydrogenation reaction kettles can be selected according to the reaction time required by the isooctanol dehydrogenation reaction to prepare isooctanoic acid under the action of a Sn/ZnO-Al 2O3 catalyst and the feeding airspeed of the reaction raw materials set by the process.
Generally, in the process for producing isooctanoic acid, the number of the multistage dehydrogenation reaction kettles may be 3 to 10, and preferably 3 to 5 dehydrogenation reaction kettles are used.
In the reaction process, inert atmosphere is kept in each stage of dehydrogenation reaction kettle. Such as nitrogen protection.
In certain embodiments, the reaction temperature in each stage dehydrogenation reactor is controlled at 200 to 400 ℃, preferably at about 235 to 245 ℃.
In each stage of dehydrogenation reaction kettle, the reaction time is controlled to be 10-40 min.
In the preferred scheme, the reaction time in each stage of dehydrogenation reaction kettle is controlled to be 15-25 min, and five stages of dehydrogenation reaction kettles are arranged together. The scheme comprehensively considers the interval time between feeding and the total reaction duration, ensures the conversion rate of the raw materials, and also considers the processing capacity of the raw materials in unit time. I.e. the scheme can be considered from the aspects of both production quality and production efficiency.
In certain embodiments, the nitrogen pressure in each stage of dehydrogenation reactor is maintained at a reaction initiation gauge pressure of from 0.1 to 0.5MPa. As the reaction proceeds, hydrogen is produced and the pressure increases.
In certain embodiments, the sodium hydroxide, isooctanol, and catalyst are mixed at a temperature in the range of 120 to 180 ℃ prior to entering the first stage dehydrogenation reactor. Preferably, the sodium hydroxide, isooctanol, and catalyst are mixed at a temperature in the range of about 150 ℃.
At 120-180 deg.c, solid sodium hydroxide may be mixed with isooctyl alcohol thoroughly. Particularly, at the temperature of about 150 ℃, the solid sodium hydroxide can be uniformly dissolved in isooctyl alcohol, and the catalyst can be more uniformly dispersed in isooctyl alcohol and enters the first-stage dehydrogenation reaction kettle, so that the catalytic effect is further improved.
The molar ratio of sodium hydroxide to isooctanol is (0.8-1.5): 1, preferably the molar ratio of sodium hydroxide to isooctanol is (1.0-1.1): 1.
In certain embodiments, the Sn/ZnO-Al 2O3 catalyst is used in an amount of 1% to 1.5% by mass of isooctanol.
The isooctanoic acid process improves the production efficiency of isooctanoic acid, and meets the requirement of high stability of continuous production and isooctanol conversion rate (> 90%).
More specifically, a process for producing isooctanoic acid, comprising:
1) Adding isooctanol and sodium hydroxide into a pretreatment kettle in proportion, adding an Sn/ZnO-Al 2O3 catalyst accounting for 1wt% of the isooctanol mass, continuously stirring at 120-180 ℃ until the isooctanol and the sodium hydroxide are uniformly mixed, and conveying a reaction mixture to a first-stage dehydrogenation reaction kettle through a pipeline;
2) The reaction mixture enters a first-stage dehydrogenation reaction kettle, is stirred in the first-stage dehydrogenation reaction kettle at the temperature of 200-400 ℃ and undergoes dehydrogenation reaction, and hydrogen generated by the reaction is collected; after a period of reaction, the materials in the first stage dehydrogenation reaction kettle are conveyed into the second stage dehydrogenation reaction kettle for a period of reaction, and after no obvious hydrogen is generated in the materials in the last stage dehydrogenation reaction kettle, the generated sodium isooctanoate is conveyed into an acidification kettle and a purification unit, so that isooctanoate is obtained.
More preferably, before entering the acidification kettle, the sodium isooctanoate material enters a buffer kettle and is cooled briefly, and water (the dosage is 15% of the mass of isooctanol) is added for dilution and then the solid catalyst is filtered. And (3) the liquid sodium isooctanoate solution enters an acidification kettle, is acidified by using sulfuric acid with the mass content of about 30%, and is layered and purified after the pH value is regulated to 2-3, so that a high-purity isooctanoate product and a sodium sulfate byproduct are finally obtained.
In a second aspect, a process for producing isooctanoic acid comprises a fixed bed reactor and an acidification tank, wherein the fixed bed reactor is connected with the acidification tank, and a catalyst fixed bed is arranged in the fixed bed reactor;
Introducing a mixture of raw materials of isooctanoic acid and sodium hydroxide into a fixed bed reactor, performing dehydrogenation reaction under the action of a catalyst, and introducing the obtained product into an acidification kettle for acidification treatment, and purifying after the acidification treatment to obtain isooctanoic acid, wherein the catalyst is Sn/ZnO-Al 2O3.
The dehydrogenation reaction is carried out in an inert atmosphere in a fixed bed reactor to prepare the sodium isooctanoate.
In the catalyst fixed bed, a catalyst and an inert carrier are packed. Inert supports include, but are not limited to, quartz sand, silicon carbide, ceramic spheres, inert alumina spheres, and the like, the inert supports comprising 20-50% of the catalyst loading mass. Preferably, 30% quartz sand is used.
In certain embodiments, the temperature of the fixed bed reactor is 200-300 ℃, preferably the reaction temperature is about 250 ℃.
In the fixed bed reactor, the initial gauge pressure of the reaction is 0 to 0.5Mpa, preferably 0.2Mpa. As the reaction proceeds, hydrogen is produced and the corresponding pressure increases.
In order to achieve continuous feeding and ensure sufficient catalytic reaction, the space velocity of the feeding can be controlled.
Generally, the mass space velocity of isooctanol in the fixed bed reactor is in the range of 0.5 to 20h -1, preferably 8h -1.
As in the process for producing isooctanoic acid of the first aspect described above, the sodium hydroxide and isooctanol are mixed at a temperature in the range of 120 to 180℃before they enter the fixed bed reactor. Preferably, the sodium hydroxide is mixed with isooctanol in a range of about 150 ℃.
Particularly, at the temperature of about 150 ℃, the solid sodium hydroxide can be uniformly dissolved in isooctyl alcohol and enters a fixed bed reactor, so that the catalytic effect can be improved.
The molar ratio of sodium hydroxide to isooctanol is (0.8-1.5): 1, preferably the molar ratio of sodium hydroxide to isooctanol is (1.0-1.1): 1.
According to the isooctanoic acid process, the mixture of the raw materials isooctanoic acid and sodium hydroxide can continuously enter a reactor by controlling the airspeed, the sodium isooctanoic acid is prepared by dehydrogenation reaction, the mixture in the reactor is continuously discharged out of a fixed bed reactor, and the isooctanoic acid is obtained through subsequent treatment.
More specifically, a process for producing isooctanoic acid, comprising:
1) Adding isooctyl alcohol and sodium hydroxide into a pretreatment kettle in proportion, continuously stirring at 120-180 ℃ until the isooctyl alcohol and sodium hydroxide are uniformly mixed, and conveying the reaction mixture to a fixed bed reactor through a pipeline;
2) The reaction mixture enters a fixed bed reactor filled with Sn/ZnO-Al 2O3 catalyst, and dehydrogenation reaction is carried out in nitrogen atmosphere at the temperature of 200-300 ℃; and collecting the produced hydrogen and nitrogen, and conveying the reaction product sodium isooctanoate to an acidification kettle and a purification unit to obtain isooctanoic acid.
After the fixed bed reactor enters an acidification kettle, the reactor is cooled briefly, 10 percent (isooctanol mass) of water is added for dilution, sulfuric acid with the mass content of about 30 percent is added for acidification, the PH is regulated to 2-3, and the mixed material is layered and purified, so that a high-purity isooctanoic acid product and a sodium sulfate byproduct are finally obtained.
In a third aspect, a process for producing isooctanoic acid comprises: the first-stage dehydrogenation reaction kettle is connected with the second-stage dehydrogenation reaction kettle, and the last-stage dehydrogenation reaction kettle is connected with the acidification kettle;
The fixed bed reactor is connected with the acidification kettle;
The fixed bed reactor and the first stage dehydrogenation reaction kettle are arranged in parallel;
introducing the mixture of the raw materials of isooctanoic acid, sodium hydroxide and the catalyst into a first-stage dehydrogenation reaction kettle, or introducing the mixture of the raw materials of isooctanoic acid and sodium hydroxide into a fixed bed reactor;
And (3) acidizing and purifying the finally obtained product to obtain the isooctanoic acid, wherein the catalyst is Sn/ZnO-Al 2O3.
In this scheme, the reaction conditions of the dehydrogenation reaction kettles in which different fixed bed reactors and multistage kettles are connected in series, and treatments before and after the reaction kettle are entered, can be referred to the above scheme.
The isooctanoic acid is prepared by coupling a fixed bed reactor with a multi-stage reaction kettle, and dehydrogenation reaction can be performed in the fixed bed reactor and the multi-stage reaction kettle in a crossing manner, so that quick feeding and efficient preparation of the isooctanoic acid are realized. In the process that the mixture of the raw material isooctanoic acid, sodium hydroxide and the catalyst reacts in the first-stage dehydrogenation reaction kettle, the mixture of the raw material isooctanoic acid and the sodium hydroxide can be introduced into the fixed bed reactor for dehydrogenation reaction, and the space velocity entering the fixed bed reactor is not required to be reduced. Through the coupling use of the two sets of equipment, the industrialized production of the isooctanoic acid by continuous feeding is realized, and the production efficiency is high.
In any of the processes for producing isooctanoic acid, a Sn/ZnO-Al 2O3 catalyst is used, so that the speed of preparing isooctanoic acid by dehydrogenation and oxidation of isooctanol is improved, and the dehydrogenation reaction can be completed in a short time. Isooctanol conversion (> 90%) and isooctanoic acid selectivity (> 95%).
The reaction processes involved in the three processes for preparing isooctanoic acid are as follows:
the same catalyst Sn/ZnO-Al 2O3 is adopted in the process for producing the isooctanoic acid. Specifically, the following is described.
In the fourth aspect, the catalyst for preparing isooctanoic acid by dehydrogenating isooctanol comprises Sn element, znO and Al 2O3, wherein the mass of the Sn element is 0.5-5wt% of the mass of ZnO, and the mass of Al 2O3 is 10-30wt% of the mass of ZnO.
Preferably, in the catalyst, the mass of Sn element is 2%, and the mass of Al 2O3 is 20% of the mass of ZnO.
The preparation method of the catalyst comprises the following steps:
1) Adding precursor Sn salt solution to ZnO, stirring to form a gelatinous substance, aging in a closed environment, and drying the aged colloid to obtain solid Sn/ZnO;
2) And mixing Sn/ZnO with PVP solution, adding Al 2O3, uniformly mixing, filtering, and drying and roasting the obtained filter residue to obtain the catalyst Sn/ZnO-Al 2O3.
In certain embodiments, the drying temperatures of steps 1), 2) are each 100-120 ℃.
The drying time is determined according to the actual situation, and preferably, the drying time is 8-12 hours.
In certain embodiments, the aging time is from 5 to 7 hours.
Aging is the standing of the mixture for a certain period of time to allow more complete interaction.
In certain embodiments, the mass of PVP is 4-6% of the mass of ZnO.
Proper PVP (polyvinylpyrrolidone) is added, so that Sn/ZnO and Al 2O3 can be better combined, and subsequent co-heating is facilitated.
In step 2), the calcination is carried out in an air atmosphere at 450-550 ℃.
The roasting time is 3-5h.
The obtained catalyst has good catalytic isooctanol dehydrogenation for preparing isooctanoic acid.
The materials used in the examples below are all chemically pure standard and are all conventional products commercially available.
The process flow for producing isooctanoic acid is explained in further detail with reference to fig. 1-3.
The raw material pretreatment kettles are respectively connected with two sets of processes for preparing sodium iso-octoate through dehydrogenation in parallel, the first production process can be called a multi-kettle serial dehydrogenation process, and the second production process is called a fixed bed dehydrogenation process; the end devices of the first production process and the second production process are connected with an acidification kettle, namely, products of the first production process and the second production process are conveyed into the acidification kettle for acidification treatment; the acidification kettle is connected with the crude product tank, and phase separation is carried out in the crude product tank; the crude product tank is respectively connected with the neutralization device and the rectification purification device, the crude product tank is placed in a standing mode to generate phase separation, the lower layer is an inorganic salt water layer, the upper layer is an organic layer, substances on the lower layer enter the neutralization device and the extraction device to be further processed to obtain sodium sulfate, the organic layer on the upper layer enters the rectification purification device, and the products isooctanoic acid are separated through rectification non-separation, so that isooctanoic acid can be reused.
In the multi-kettle serial dehydrogenation process for preparing sodium iso-octoate by dehydrogenation, n-level dehydrogenation reaction kettles are sequentially connected in series, and the last-level dehydrogenation reaction kettle is connected with a buffer kettle. And (3) carrying out solid-liquid separation in a buffer kettle, and separating the solid catalyst from the liquid phase. The fixed bed dehydrogenation process for preparing sodium iso-octoate by dehydrogenation comprises a dehydrogenation fixed bed reactor, wherein a catalyst bed layer is arranged in the reactor.
The use flow is as follows: the raw material pretreatment kettle is connected with a fixed bed dehydrogenation process, the connection with the multi-kettle serial dehydrogenation process is interrupted, the raw material isooctyl alcohol and sodium hydroxide solid are added into the raw material pretreatment kettle, the raw material isooctyl alcohol and the sodium hydroxide solid are mixed at a specific temperature to obtain a first reaction mixture, and the first reaction mixture enters a dehydrogenation fixed bed reactor (the reactor refers to the structural schematic diagram of FIG. 3) to be contacted with a catalyst bed layer, and reacts for a period of time under certain reaction conditions. When the dehydrogenation reaction is carried out by the fixed bed reaction dehydrogenation process, the connection between the raw material pretreatment kettle and the fixed bed dehydrogenation process is disconnected, the connection between the raw material pretreatment kettle and the multi-kettle serial dehydrogenation process is carried out, the raw material isooctanol, sodium hydroxide solid and the catalyst are added into the raw material pretreatment kettle, the raw material isooctanol, the sodium hydroxide solid and the catalyst are mixed at a specific temperature to obtain a second reaction mixture, the second reaction mixture enters the primary dehydrogenation reaction kettle 1 of the multi-kettle serial dehydrogenation process for dehydrogenation reaction under a certain condition, and the mixture in the primary dehydrogenation reaction kettle 1 sequentially enters the secondary multi-stage dehydrogenation reaction kettle 2, the tertiary dehydrogenation reaction kettle 3 and the n dehydrogenation reaction kettle (refer to figure 2) and is reacted in each stage of the dehydrogenation reaction kettle for a set time. In the process of carrying out the multi-kettle serial dehydrogenation process, the mode of connecting the raw material pretreatment kettle and the fixed bed dehydrogenation process can be switched, the switching can be repeated, and the dehydrogenation of isooctanol is carried out in two sets of dehydrogenation processes to prepare sodium isooctanoate. That is, the raw materials are conveyed to one set of process at intervals of high-pressure and high-temperature reaction by utilizing one set of process, and the post-treatment and the front-end treatment of the dehydrogenation reaction device can share the same equipment, so that the whole set of equipment can realize continuous production and improve the effective efficiency.
The multi-kettle serial dehydrogenation process and the fixed bed dehydrogenation process can also be independently used, and devices such as a raw material pretreatment kettle, an acidification kettle at the rear end and the like are respectively configured.
Specific process parameters are specifically illustrated in the examples below.
Example 1
Synthesis of Sn/ZnO-Al 2O3 catalyst
Firstly, 0.220g of stannic chloride is dissolved in 6ml of deionized water, and the mixture is stirred uniformly for later use. While stirring, 5g of technical grade ZnO was added and stirred until a uniform gum-like material formed. And then keeping the container closed, standing and aging for 6 hours. And (3) drying the obtained gelatinous substance for 12 hours at 120 ℃ after ageing, and obtaining Sn/ZnO after drying.
0.25G PVP (relative viscosity K=90) was dissolved in 10mL deionized water and stirred well. Subsequently, the Sn/ZnO was ground into powder, 20mL of deionized water was added, and PVP solution was added dropwise with stirring. Subsequently, 1.5g of Al 2O3 was added and stirring was continued for 30min. The solid obtained by suction filtration was dried at 120℃for 12h. Then roasting for 3 hours at 500 ℃ in an air atmosphere, wherein the temperature rising rate is 4 ℃/min. And grinding the roasted solid into powder to obtain the catalyst Sn/ZnO-Al 2O3. Wherein the load of Sn is 2wt%, and the mass content of Al 2O3 is 30%.
Example 2
The catalytic performance of the Sn/ZnO-Al 2O3 catalyst of example 1 was compared with that of a zinc compound catalyst having a similar catalytic effect in a short period of time. The reaction is carried out in a single batch kettle reactor, and the dehydrogenation reaction is carried out for 90 minutes under the condition of 0.5MPa nitrogen at the temperature of 240 ℃ and the molar ratio of isooctanol to sodium hydroxide is 1.1:1, and the results are shown in the following table:
TABLE 1 comparison of the catalytic Performance of Sn/ZnO-Al 2O3 catalysts and zinc Compounds
| Catalyst | Catalyst usage/% | Duration/min of reaction | Isooctanol conversion/% | Isooctanoic acid selectivity/% |
| Zinc oxide | 1％ | 90 | 63.22 | 98.96 |
| Zinc acetate | 1％ | 90 | 64.96 | 99.13 |
| Zinc formate | 1％ | 90 | 65.85 | 99.47 |
| Sn/ZnO-Al2O3 | 1％ | 90 | 98.96 | 99.61 |
According to the catalytic reaction results in Table 1, it can be seen that the Sn/ZnO-Al 2O3 catalyst synthesized by the process has catalytic performance obviously superior to that of the traditional zinc compound, and meets the requirements of the isooctanoic acid continuous production process on the catalyst.
Example 3
This example is the dehydrogenation to isooctanoic acid in a fixed bed dehydrogenation reactor.
And (3) putting isooctyl alcohol and sodium hydroxide into a pretreatment reaction kettle in a molar ratio of 1.1:1, heating to 150 ℃ while stirring, and stirring until isooctyl alcohol and sodium hydroxide are uniformly mixed. The mixed material is pumped to a fixed bed dehydrogenation reactor through a pipeline, the flow rate of nitrogen is controlled through a flowmeter, the volume ratio (partial pressure ratio) of isooctyl alcohol to nitrogen is 5:1, the volume ratio is the volume of gas-phase isooctyl alcohol, and the volume ratio of gas-phase isooctyl alcohol to nitrogen is equal in temperature and pressure. The mass ratio of isooctanol feed to the packed Sn/ZnO-Al 2O3 catalyst per hour was 10:1, i.e. the mass space velocity of the fixed bed feed at this time was 8h -1. And regulating the temperature of the fixed bed to 250 ℃, regulating a back pressure valve to enable the back pressure in the fixed bed reaction tube to be 0.2Mpa, and starting a flow pump/meter to start feeding when the temperature and the pressure rise to a set value. The fixed bed reaction tube is connected to an acidification reaction kettle, after being cooled briefly, the reaction kettle is diluted by deionized water with the mass of 10% isooctyl alcohol, then the pH is regulated to 2.5 by sulfuric acid with the mass content of 30%, and the reaction liquid is stood until the reaction liquid is layered. The upper organic phase sample was taken for gas chromatography analysis with an isooctanol conversion of 95.73% and a molar selectivity for isooctanoic acid of 99.79%.
Example 4
In this example, isooctanoic acid is prepared by dehydrogenation in a multi-kettle series dehydrogenation reactor.
Isooctanol and sodium hydroxide are put into a pretreatment reaction kettle in a molar ratio of 1.1:1, and a Sn/ZnO-Al 2O3 catalyst with the mass of 1% isooctanol is put into the pretreatment reaction kettle, and the temperature is raised to 150 ℃ during stirring, and the isooctanol, the sodium hydroxide and the catalyst are stirred until being uniformly mixed. The mixed material is conveyed into a first stage dehydrogenation reaction kettle through a pipeline. The temperature of each stage of reaction kettle is regulated to 240 ℃, the feeding time is controlled to be 20min, and the dehydrogenation reaction time of the materials in each stage of reaction kettle is 20min. The reaction is carried out step by step, materials in a fifth-stage dehydrogenation reaction kettle are conveyed into a buffer kettle, water accounting for 15% of the mass of isooctanol is added for dilution, then a solid catalyst is filtered for drying and roasting for later use, a liquid sodium isooctanoate solution enters an acidification kettle, sulfuric acid with the mass content of about 30% is used for acidification, the pH value is regulated to 2.5, and the reaction solution is stood until the reaction solution is layered. The upper organic phase sample was taken for gas chromatography analysis with an isooctanol conversion of 98.84% and a molar selectivity for isooctanoic acid of 99.71%.
Example 5
The following test was carried out by using the process parameters of the multistage dehydrogenation reaction kettles in series in example 4, and variously adjusting the reaction time length of each dehydrogenation reaction kettle and the number of dehydrogenation reaction kettles. The materials are sampled and acidified at the end of the reaction of each stage of dehydrogenation reaction kettle, and the conversion rate and the selectivity are recorded, and the results are shown in the following table:
TABLE 2 catalytic reaction results for multistage dehydrogenation reactor series process for isooctanol
It will be evident to those skilled in the art that the 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. A process for producing isooctanoic acid comprises a first-stage dehydrogenation reaction kettle and a second-stage dehydrogenation reaction kettle, wherein the first-stage dehydrogenation reaction kettle is connected with the second-stage dehydrogenation reaction kettle, a mixture of raw materials isooctanoic acid, sodium hydroxide and a catalyst is introduced into the first-stage reaction kettle, after the reaction in the first-stage dehydrogenation reaction kettle is carried out for a first set time, the mixture in the first-stage dehydrogenation reaction kettle is introduced into the second reaction kettle again for a second set time; the finally obtained product is subjected to acidification treatment and purification to obtain isooctanoic acid, wherein the catalyst is Sn/ZnO-Al 2O3;
preferably, the dehydrogenation reaction kettle comprises more than three stages of dehydrogenation reaction kettles, and the multistage dehydrogenation reaction kettles are connected in series;
more preferably, in the process for producing isooctanoic acid, the number of the multistage dehydrogenation reaction kettles may be 3 to 10.
2. The process according to claim 1, wherein the reaction temperature in each stage dehydrogenation reactor is controlled between 200 and 400 ℃, preferably between about 235 and 245 ℃.
More preferably, the reaction time is controlled between 10min and 40min in each stage of dehydrogenation reaction kettle.
3. The process according to claim 1 or 2, wherein the sodium hydroxide, isooctanol and catalyst are mixed in a temperature range of 120-180 ℃ before entering the first stage dehydrogenation reactor;
preferably, sodium hydroxide, isooctanol are mixed with catalyst at a temperature in the range of 150 ℃.
4. A process according to any one of claim 1 to 3, wherein,
The molar ratio of the sodium hydroxide to the isooctanol is (0.8-1.5): 1, preferably the molar ratio of the sodium hydroxide to the isooctanol is (1.0-1.1): 1;
more preferably, the Sn/ZnO-Al 2O3 catalyst is used in an amount of 1 to 1.5% by mass of isooctanol.
5. The process for producing the isooctanoic acid comprises a pre-raw material pretreatment kettle, a fixed bed reactor and an acidification kettle, wherein the fixed bed reactor is connected with the acidification kettle, and a catalyst fixed bed is arranged in the fixed bed reactor;
Introducing a mixture of raw materials of isooctanoic acid and sodium hydroxide into a fixed bed reactor, performing dehydrogenation reaction under the action of a catalyst, introducing the obtained product into an acidification kettle for acidification treatment, and purifying after the acidification treatment to obtain isooctanoic acid, wherein the catalyst is Sn/ZnO-Al 2O3;
Preferably, the sodium hydroxide and isooctanol are mixed in a temperature range of 120-180 ℃ before entering a fixed bed reactor;
More preferably, the sodium hydroxide is mixed with isooctanol at a temperature in the range of 150 ℃.
6. The process of claim 5 wherein the temperature of the fixed bed reactor is 200-300 ℃, preferably the reaction temperature is about 250 ℃;
Preferably, the initial gauge pressure of the reaction is 0 to 0.5Mpa, preferably 0.2Mpa, in a fixed bed reactor.
7. The process according to claim 5 or 6, characterized in that the mass space velocity of isooctanol in the fixed bed reactor is 0.5-20h -1, preferably 8h -1. .
8. A process for producing isooctanoic acid, comprising: the first-stage dehydrogenation reaction kettle is connected with the second-stage dehydrogenation reaction kettle, and the last-stage dehydrogenation reaction kettle is connected with the acidification kettle;
The fixed bed reactor is connected with the acidification kettle;
The fixed bed reactor and the first stage dehydrogenation reaction kettle are arranged in parallel;
introducing the mixture of the raw materials of isooctanoic acid, sodium hydroxide and the catalyst into a first-stage dehydrogenation reaction kettle, or introducing the mixture of the raw materials of isooctanoic acid and sodium hydroxide into a fixed bed reactor;
And (3) acidizing and purifying the finally obtained product to obtain the isooctanoic acid, wherein the catalyst is Sn/ZnO-Al 2O3.
9. A catalyst for preparing isooctanoic acid by dehydrogenation of isooctanol comprises Sn element, znO and Al 2O3, wherein the mass of the Sn element is 0.5-5wt% of the mass of ZnO, and the mass of Al 2O3 is 10-30wt% of the total mass of the catalyst.
Preferably, in the catalyst, the mass of Sn element is 2%, and the mass of Al 2O3 is 20% of the total mass of the catalyst.
10. A method of preparing the catalyst of claim 9, comprising:
1) Adding precursor Sn salt solution to ZnO, stirring to form a gelatinous substance, aging in a closed environment, and drying the aged colloid to obtain solid Sn/ZnO;
2) Mixing Sn/ZnO with PVP solution, adding Al 2O3 powder, uniformly mixing, filtering, and drying and roasting the obtained filter residue to obtain a catalyst Sn/ZnO-Al 2O3;
preferably, the aging time is 5-7 hours;
more preferably, in step 2), the calcination is performed under an air atmosphere at 450-550 ℃.
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