CN112852486B - Oxidized wax and preparation method thereof - Google Patents
Oxidized wax and preparation method thereof Download PDFInfo
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- CN112852486B CN112852486B CN202110037904.1A CN202110037904A CN112852486B CN 112852486 B CN112852486 B CN 112852486B CN 202110037904 A CN202110037904 A CN 202110037904A CN 112852486 B CN112852486 B CN 112852486B
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- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 76
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 50
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000001301 oxygen Substances 0.000 claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 43
- 150000002148 esters Chemical class 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 16
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 34
- 229960000583 acetic acid Drugs 0.000 claims description 17
- 239000012362 glacial acetic acid Substances 0.000 claims description 17
- -1 alkyl compound Chemical class 0.000 claims description 8
- FRVCGRDGKAINSV-UHFFFAOYSA-L iron(2+);octadecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRVCGRDGKAINSV-UHFFFAOYSA-L 0.000 claims description 8
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- OCDFTWVGTADYMH-UHFFFAOYSA-N cobalt dodecanoic acid Chemical compound [Co].CCCCCCCCCCCC(O)=O.CCCCCCCCCCCC(O)=O OCDFTWVGTADYMH-UHFFFAOYSA-N 0.000 claims description 2
- SSWSYWBRGQINON-UHFFFAOYSA-L cobalt(2+);hexadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O SSWSYWBRGQINON-UHFFFAOYSA-L 0.000 claims description 2
- ORPKVCOHQRRGSM-UHFFFAOYSA-L cobalt(2+);tetradecanoate Chemical compound [Co+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O ORPKVCOHQRRGSM-UHFFFAOYSA-L 0.000 claims description 2
- VEQVWMIWJMNBTL-UHFFFAOYSA-L dodecanoate;iron(2+) Chemical compound [Fe+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O VEQVWMIWJMNBTL-UHFFFAOYSA-L 0.000 claims description 2
- GIFIIAHOGINLJV-UHFFFAOYSA-K hexadecanoate;iron(3+) Chemical compound [Fe+3].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GIFIIAHOGINLJV-UHFFFAOYSA-K 0.000 claims description 2
- XLDSINOWIMZXDD-UHFFFAOYSA-L iron(2+);tetradecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O XLDSINOWIMZXDD-UHFFFAOYSA-L 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 54
- 230000003647 oxidation Effects 0.000 abstract description 31
- 239000000126 substance Substances 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000001993 wax Substances 0.000 description 147
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 117
- 238000007127 saponification reaction Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000012188 paraffin wax Substances 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 235000021355 Stearic acid Nutrition 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
- 239000008117 stearic acid Substances 0.000 description 8
- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 229940071125 manganese acetate Drugs 0.000 description 5
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 5
- 239000004200 microcrystalline wax Substances 0.000 description 5
- 235000019808 microcrystalline wax Nutrition 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/38—Chemical modification of petroleum
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of oxidized wax preparation, and particularly relates to oxidized wax and a preparation method thereof. The method comprises the following steps: and in the presence of a catalyst and an auxiliary agent, carrying out catalytic oxidation reaction on the molten Fischer-Tropsch wax and an oxygen-containing gas to obtain oxidized wax, wherein the catalyst is an iron catalyst and/or a cobalt catalyst. The method provided by the invention has the advantages that the Fischer-Tropsch wax is subjected to oxidation reaction to realize directional oxidation, so that the product distribution of the oxidized wax product is controlled, the reaction product is carried out towards the target of generating more ester substances, and the ester-acid ratio of the oxidized wax product is improved; meanwhile, the method reduces the production cost and is convenient for industrial production design.
Description
Technical Field
The invention relates to the field of oxidized wax preparation, and in particular relates to oxidized wax and a preparation method thereof.
Background
Before the wax raw material is oxidized, the acid value and the esterification value of the wax raw material are almost zero. The modified wax products have obviously improved properties in the aspects of emulsibility, oil solubility, lubricity, pigment dispersibility and the like.
The catalytic oxidation modification of the wax is an oxidation process which is carried out under certain temperature and time conditions by introducing air after adding a catalyst into the wax raw material. After the catalyst is added, the directional oxidation of the wax can be realized, the generation of fatty acid is inhibited, the generation of ester substances is facilitated, and finally the oxidized wax product with high ester-acid ratio is obtained. The catalyst for wax oxidation reaction mainly comprises manganese catalyst, and the more the catalyst is added, the darker the product color will be correspondingly. The activity of the catalyst cannot be excited due to too low reaction temperature, and the color and luster of the product are deepened due to too high reaction temperature. The reaction time has the most significant effect on the acid number of the oxidized wax, and the acid number of the oxidized wax increases significantly with prolonged reaction time, but the color also deepens correspondingly.
CN103468316A discloses a preparation method of high acid soap oxidized wax, which takes a mixture of molten paraffin and microcrystalline wax as raw materials, manganese acetate or manganese sulfate as a catalyst, stearic acid as an auxiliary agent, and oxygen is introduced during the reaction process to prepare an oxidized wax product with an acid value of 27.95mgKOH/g and a saponification value of 69.78 mgKOH/g. According to the method, manganese acetate or manganese sulfate is used as a catalyst, white granular manganese acetate or manganese sulfate is separated out in the oxidation reaction process, the white granular manganese acetate or manganese sulfate cannot be well melted in wax to participate in catalytic reaction, oxygen is used in the oxidation reaction, the cost is high, the directional oxidation of the reaction is not facilitated, and the color of an oxidized wax product is deepened.
CN105087068A discloses a process for preparing oxidized wax from F-T coal, wherein the wax is prepared from F-T coal, oxygen is introduced during the reaction, one of stearic acid, boric acid or p-toluenesulfonic acid is used as an oxidation catalyst, the acid value of the product of stearic acid as the catalyst is 28.19mgKOH/g, the saponification value is 57.11mgKOH/g, the acid value of the product of boric acid as the catalyst is 28.5mgKOH/g, the saponification value is 61.02mgKOH/g, the acid value of the product of p-toluenesulfonic acid as the catalyst is 27.86mgKOH/g, the saponification value is 62.87mgKOH/g, the ester acid ratio of the prepared oxidized Fischer-Tropsch wax product is about 1:1, comparable to the level of no catalytic oxidation reaction.
CN102921447A discloses a preparation method of a supported Co/SBA-15 catalyst for paraffin oxidation, the catalyst has large pore diameter and specific surface area, but the activity of an active component Co supported on a carrier is low, and the catalyst is beneficial to the generation of acid and is not beneficial to the generation of ester substances. Therefore, the catalyst prepared by the method is not suitable for the preparation process of the oxidized wax with high ester-acid ratio.
CN104593073A discloses a preparation method of oxidized microcrystalline wax, which takes a rotary bed reactor as reaction equipment, takes potassium permanganate loaded on modified activated carbon as a catalyst, performs oxidation reaction at the reaction temperature of 170 ℃ and the reaction pressure of 6MPa in the presence of air containing 50-150mLHCl aqueous solution, and obtains an oxidized wax product with the acid value of 31.45mgKOH/g and the saponification value of 62.75mgKOH/g. The method adopts microcrystalline wax as a raw material, wherein the microcrystalline wax mainly comprises isoparaffin, and paraffin wax and Fischer-Tropsch wax mainly comprise normal paraffin, under the same condition, the isoparaffin is easier to be oxidized than the normal paraffin, and the oxidation induction period of the microcrystalline wax is shorter than that of the paraffin wax, so that if the same oxidation degree is achieved, the reaction time of the paraffin wax and the Fischer-Tropsch wax is longer, the corresponding product color is darker, and the catalyst is not suitable for the oxidation reaction of the paraffin wax and the Fischer-Tropsch wax.
Therefore, a method for preparing oxidized wax with high ester-to-acid ratio is needed.
Disclosure of Invention
The invention aims to overcome the problems of low catalyst activity, long reaction time, incapability of realizing directional oxidation, poor target product selectivity, darker color of an oxidized wax product, low ester-acid ratio and the like in the existing oxidized wax preparation process, and provides oxidized wax and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing an oxidized wax, comprising: in the presence of a catalyst and an auxiliary agent, carrying out catalytic oxidation reaction on the molten Fischer-Tropsch wax and oxygen-containing gas to obtain oxidized wax;
wherein the catalyst is an iron-based catalyst and/or a cobalt-based catalyst.
Preferably, the iron-based catalyst is an iron-containing linear alkyl compound, and the cobalt-based compound is a cobalt-containing linear alkyl compound.
Preferably, the auxiliary agent is at least one of glacial acetic acid, stearic acid, boric acid and citric acid.
Preferably, the oxygen content in the oxygen-containing gas is from 21 to 50v%.
Preferably, the gas flow rate of the oxygen-containing gas is 1 to 100 mL/min-g.
In a second aspect, the present invention provides an oxidized wax produced by the method provided in the first aspect.
Preferably, the ester value of the oxidized wax is more than or equal to 35mg KOH/g, preferably 35-90mg KOH/g; the acid value is less than or equal to 40mg KOH/g, preferably 10-40mg KOH/g; the ratio of ester to acid is > 1, preferably 1-3.5.
Compared with the prior art, the invention has the following advantages:
(1) The method provided by the invention adopts an iron catalyst and/or a cobalt catalyst, and combines an auxiliary agent and oxygen-containing gas to carry out oxidation reaction on the Fischer-Tropsch wax to realize directional oxidation, thereby controlling the product distribution of the oxidized wax product, leading the reaction product to go towards the target of generating more ester substances, and improving the ester-acid ratio of the oxidized wax product;
(2) The method provided by the invention reduces the using amount of the catalyst, shortens the oxidation reaction time and improves the color index of the oxidized wax product;
(3) Compared with paraffin serving as a raw material, the method provided by the invention has the advantages that the production cost is reduced, and the industrial production design is facilitated;
(4) The oxidized wax prepared by the method provided by the invention has higher ester-acid ratio which is as high as 3.23.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a process for the preparation of an oxidized wax, the process comprising: in the presence of a catalyst and an auxiliary agent, carrying out catalytic oxidation reaction on the molten Fischer-Tropsch wax and oxygen-containing gas to obtain oxidized wax;
wherein the catalyst is an iron-based catalyst and/or a cobalt-based catalyst.
The inventor of the present invention found out that: the controllable shallow catalytic oxidation modification of the existing wax mainly adopts a manganese catalyst, the catalyst has low activity and poor target product selectivity, the ester-acid ratio of the prepared oxidized wax product is about 1, and the catalyst is precipitated and deposited at the bottom of a reactor and cannot completely participate in the reaction; the catalyst-free oxidation modification of the existing wax can not control the distribution of products, can not realize directional oxidation, the reaction is slow, the required time is long, and the ester acid ratio of the prepared oxidized wax product is low; the darker color of the oxidized wax product is mainly due to the use of manganese catalysts and the longer reaction time. Therefore, the inventor adopts an iron catalyst and/or a cobalt catalyst, and combines an auxiliary agent and an oxygen-containing gas to catalyze and oxidize the Fischer-Tropsch wax, so that the oriented oxidation of the oxidized wax product is realized, and the oxidized wax product with high ester value and low acid value is obtained, thereby improving the ester-acid ratio of the oxidized wax product, shortening the oxidation reaction time and improving the color index of the oxidized wax product.
In the present invention, the ratio of ester to acid of the oxidized wax is a ratio of an ester value of the oxidized wax to an acid value of the oxidized wax, unless otherwise specified.
According to the present invention, preferably, the iron-based catalyst is an iron-containing linear alkyl compound, preferably at least one selected from iron stearate, iron palmitate, iron myristate, and iron laurate, more preferably iron stearate.
According to a preferred embodiment of the invention, the catalyst is iron stearate. The ferric stearate is used as a catalyst to realize the directional oxidation of the Fischer-Tropsch wax, the generation of fatty acid in a reaction product can be inhibited, the generation of ester substances in the product is facilitated, the purpose of controlling the product distribution of the oxidized wax product is achieved, and therefore the ester-acid ratio of the oxidized wax product is improved.
According to the present invention, preferably, the cobalt-based catalyst is a cobalt-containing linear alkyl compound, preferably at least one selected from cobalt stearate, cobalt palmitate, cobalt myristate salt, and cobalt laurate, more preferably cobalt stearate.
According to a preferred embodiment of the invention, the catalyst is cobalt stearate. The cobalt stearate is used as a catalyst to realize the directional oxidation of the Fischer-Tropsch wax, the generation of fatty acid in a reaction product can be inhibited, the generation of ester substances in the product is facilitated, the purpose of controlling the product distribution of the oxidized wax product is achieved, and therefore the ester-acid ratio of the oxidized wax product is improved.
In the present invention, the aid is intended to accelerate the dissolution of the catalyst without increasing the acid number of the oxidized wax product or causing impurities to be introduced into the oxidized wax product. Preferably, the auxiliary agent is selected from at least one of glacial acetic acid, stearic acid, boric acid and citric acid, preferably glacial acetic acid.
According to a preferred embodiment of the invention, the auxiliary agent is glacial acetic acid. Compared with the prior art that stearic acid is adopted as an auxiliary agent and glacial acetic acid is adopted as the auxiliary agent, the acid value of the final product is lower, and the ester value is higher. Specifically, at the initial stage of the reaction, the acid value of the oxidized Fischer-Tropsch wax sample is higher due to the addition of glacial acetic acid, the glacial acetic acid is volatilized continuously along with the reaction, the acid value of the sample is reduced, the glacial acetic acid is completely volatilized from the sample after about 2 hours, and the fatty acid generated by the reaction can replace the glacial acetic acid to play the role.
According to the invention, the oxygen content in the oxygen-containing gas is preferably 21 to 50v%, preferably 25 to 45v%. Compared with the prior air or pure oxygen, the oxygen-containing gas defined by the invention is beneficial to the directional oxidation of the reaction and the generation of ester substances, thereby controlling the distribution of oxidized wax products; meanwhile, the reaction time and the production cost are reduced, the color index of the oxidized wax product is improved, and the performance of the product is improved.
In the present invention, the oxygen-containing gas has a wide selection range as long as the oxygen content in the oxygen-containing gas is 21 to 50v%. Preferably, the oxygen-containing gas is selected from the group consisting of a mixed gas of air and pure oxygen, and a mixed gas of pure oxygen and an inert gas. In the present invention, the volume ratio of the air and the pure oxygen, and the volume ratio of the pure oxygen and the inert gas are not limited. By controlling the oxygen content in the oxygen-containing gas, the total amount of the oxygen-containing gas introduced into the reaction system achieves the best effect on the premise of ensuring the oxidation degree, color, target product selectivity and ester-acid ratio requirement of the product, the reaction time is shortened, the oxidation degree of the product is improved, and the lowest cost is ensured.
According to the invention, the gas flow rate of the oxygen-containing gas is preferably from 1 to 100mL/min g, preferably from 40 to 70mL/min g. Wherein the gas flow rate means a gas flow rate of an oxygen-containing gas of 1 to 100mL/min relative to 1g of the wax raw material (Fischer-Tropsch wax). By adopting the preferable conditions, under the condition of high oxygen-containing gas flow, water generated after the esterification reaction of the fatty acid in the by-product and the alcohol substance is quickly taken out from the reactor, thus being more beneficial to the esterification reaction and promoting the generation of the ester substance.
According to the invention, preferably the weight ratio of the fischer-tropsch wax, catalyst and promoter is 100:0.01-0.2:1-12, preferably 100:0.02-0.08:1-5. The preferred conditions are adopted to be more beneficial to improving the directional oxidation of the Fischer-Tropsch wax, preparing the oxidized wax product with high ester value, low acid value and high ester-acid ratio and reducing the color of the oxidized wax product.
According to the present invention, preferably, the catalytic oxidation reaction comprises a first stage and a second stage. Specifically, the oxidation reaction of the Fischer-Tropsch wax has an induction period, so that the process of directionally oxidizing the Fischer-Tropsch wax into higher fatty alcohol and fatty acid is hindered, and the temperature of the first stage is higher in order to accelerate the reaction rate, so that the induction period of the reaction is effectively shortened; after the induction period, the oxidation reaction is automatically accelerated, and therefore, the second stage requires a reduction in the reaction temperature to control the selectivity of the oxidized wax product and the quality of the final product.
In some embodiments of the invention, preferably, the temperature of the first stage is 170-200 ℃, preferably 180-190 ℃; the time is 0.1 to 1 hour, preferably 0.5 to 1 hour.
In some embodiments of the invention, it is preferred that the temperature of the second stage is in the range of 140 to 170 ℃, preferably 150 to 160 ℃; the time is 1-8h, preferably 5-6h.
In the invention, the Fischer-Tropsch wax is used as the raw material of the oxidation reaction, and the Fischer-Tropsch wax hardly contains sulfur, nitrogen and oxygen impurities, so that the problem of introducing impurities into an oxidized wax product indirectly due to the raw material is solved, and meanwhile, the commercial price of the Fischer-Tropsch wax is lower than that of paraffin wax, so that the cost is reduced.
In the present invention, there is a wide range of choices for the Fischer-Tropsch wax. Preferably, the fischer-tropsch wax is selected from at least one of a # 60 fischer-tropsch wax, a # 70 fischer-tropsch wax, a # 80 fischer-tropsch wax, a # 95 fischer-tropsch wax, a # 100 fischer-tropsch wax, and a # 105 fischer-tropsch wax. For example, a Fischer-Tropsch wax 60# means that the melting point of the Fischer-Tropsch wax is 60 ℃.
According to the invention, preferably the molten fischer-tropsch wax is obtained by heating the fischer-tropsch wax.
In the present invention, the temperature of the heating is dependent on the melting point of the fischer-tropsch wax. Preferably, the heating temperature is 100 to 130 ℃, preferably 120 to 130 ℃.
According to a particularly preferred embodiment of the present invention, a process for the preparation of an oxidized wax comprises: heating and melting Fischer-Tropsch wax, and then adding a catalyst, an auxiliary agent and oxygen-containing gas for catalytic oxidation to obtain oxidized wax;
wherein the catalyst is ferric stearate, the auxiliary agent is glacial acetic acid, and the oxygen content in the oxygen-containing gas is 21-50v%.
In a second aspect, the present invention provides an oxidized wax produced by the process of the first aspect.
In the present invention, the acid value represents, without particular limitation, the number of milligrams of potassium hydroxide required for neutralizing 1g of a chemical substance in mg. KOH/g; the ester value (in mg. KOH/g) = saponification value-acid value, wherein the saponification value represents the number of milligrams of potassium hydroxide consumed by hydrolysis of 1g of chemical in an alkali, in mg. KOH/g; the ratio of ester acids = ester value/acid value.
The oxidized wax product prepared by the method provided by the invention has the characteristics of high ester value, low acid value and high ester-acid ratio. Preferably, the ester value of the oxidized wax is more than or equal to 35mg KOH/g, preferably 35-90mg KOH/g; the acid value is less than or equal to 40mg KOH/g, preferably 10-40mg KOH/g; the ratio of ester to acid is > 1, preferably 1 to 3.5.
The present invention will be described in detail below by way of examples.
The acid number represents the number of milligrams of potassium hydroxide required to neutralize 1g of chemical, in mg. KOH/g;
the saponification value represents the number of milligrams of potassium hydroxide consumed by 1g of chemical substance hydrolyzed in alkali, in mg. KOH/g;
the ester value = saponification value-acid value in mg · KOH/g;
the ratio of ester acids = ester value/acid value.
Examples 1 to 5
After 100g of No. 70 Fischer-Tropsch wax is gradually heated to 120 ℃ to be completely melted, ferric stearate with different mass (shown in table 1), 3g of glacial acetic acid and oxygen-containing gas (the oxygen content is 25 v%) with the gas flow rate of 50 mL/min. G are respectively added for catalytic oxidation, wherein the temperature of the first stage is 180 ℃, the time is 1h, the temperature of the second stage is 150 ℃, and the time is 6h, so that oxidized wax S1-S5 is obtained.
Wherein the acid value, saponification value, ester value and ester-acid ratio of the oxidized waxes S1-S5 are shown in Table 1; the oxidized waxes S1 to S5 are of comparable color, all lighter and slightly yellowish.
TABLE 1
Examples 6 to 10
After 100g of 70# Fischer-Tropsch wax was gradually heated to 110 ℃ to be completely melted, 0.06g of ferric stearate, glacial acetic acid of different masses (see Table 2) and oxygen-containing gas (oxygen content 25 v%) at a gas flow rate of 50 mL/min. G were added to carry out catalytic oxidation, wherein the temperature in the first stage was 180 ℃ for 1 hour, and the temperature in the second stage was 150 ℃ for 6 hours, to obtain oxidized waxes S6-S10.
Wherein the acid value, saponification value, ester value and ester-acid ratio of the oxidized waxes S6-S10 are shown in Table 2; the oxidized waxes S6 to S10 are of comparable color, all lighter and slightly yellowish.
TABLE 2
Examples 11 to 15
After 100g of 70# Fischer-Tropsch wax was gradually heated to 130 ℃ to be completely melted, 0.06g of ferric stearate, 3g of glacial acetic acid and oxygen-containing gas (oxygen content is different, see Table 3) with a gas flow rate of 50 mL/min. G were added to carry out catalytic oxidation, wherein the temperature in the first stage was 180 ℃ for 0.5h, and the temperature in the second stage was 150 ℃ for 6h, to obtain oxidized waxes S11-S15.
Wherein the acid value, saponification value, ester value and ester-acid ratio of the oxidized waxes S11-S15 are shown in Table 3; the oxidized waxes S11 to S15 are of comparable color, all lighter and slightly yellowish.
TABLE 3
Examples 16 to 20
After 100g of 70# Fischer-Tropsch wax was gradually heated to 130 ℃ to be completely melted, 0.06g of ferric stearate, 3g of glacial acetic acid and oxygen-containing gas (oxygen content 35 v%) at different gas flow rates (see Table 4) were added to carry out catalytic oxidation, wherein the temperature in the first stage was 180 ℃ for 0.5h, and the temperature in the second stage was 150 ℃ for 6h, to obtain oxidized waxes S16-S20.
Wherein the acid value, saponification value, ester value and ester-acid ratio of the oxidized waxes S16-S20 are shown in Table 4; the oxidized waxes S16 to S20 were comparable in color, all lighter and slightly yellowish.
TABLE 4
Example 21
Following the procedure of example 3, except that the conditions for catalytic oxidation were changed to 160 ℃ for 6 hours in the first stage of excitation temperature, oxidized wax S21 was obtained.
Wherein the acid value of the oxidized wax S21 is 17.9mg KOH/g, the saponification value is 64.4mg KOH/g, the ester value is 46.5mg KOH/g, and the ester-acid ratio is 2.60;
the oxidized wax S21 was darker in color and yellowed than the oxidized wax S3.
Example 22
Oxidized wax S22 was obtained in the same manner as in example 3, except that the conditions for the catalytic oxidation in the second stage were replaced by 140 ℃ for 6 hours.
Wherein the acid value of the oxidized wax S22 is 18.5mg KOH/g, the saponification value is 68.6mg KOH/g, the ester value is 48.8mg KOH/g, and the ester-acid ratio is 2.64;
the oxidized wax S22 was darker in color and yellowed than the oxidized wax S3.
Example 23
Oxidized wax S23 was obtained according to the method of example 3, except that glacial acetic acid was replaced with stearic acid.
Wherein the acid value of the oxidized wax S23 is 27.5mg KOH/g, the saponification value is 77.6mg KOH/g, the ester value is 50.1mg KOH/g, and the ester-acid ratio is 1.80;
the oxidized wax S23 was darker in color and yellowed than the oxidized wax S3.
Example 24
Oxidized wax S24 was obtained by following the procedure of example 3 except that the oxygen content in the oxygen-containing gas was replaced with air (oxygen content: 21 v%).
Wherein the acid value of the oxidized wax S24 is 17.1mg KOH/g, the saponification value is 59.7mg KOH/g, the ester value is 42.6mg KOH/g, and the ester-acid ratio is 2.49;
the oxidized wax S24 was comparable in color to the oxidized wax S3 and slightly yellowed.
Example 25
Following the procedure of example 3, except that iron stearate was replaced with cobalt stearate, oxidized wax S25 was obtained.
Wherein the acid value of the oxidized wax S25 is 22.7mg KOH/g, the saponification value is 72.8mg KOH/g, the ester value is 50.1mg KOH/g, and the ester-acid ratio is 2.21;
the oxidized wax S25 was comparable in color to the oxidized wax S3 and slightly yellowed.
Comparative example 1
Following the procedure of example 3, except that iron stearate was replaced with stearic acid, oxidized wax D1 was obtained.
Wherein the acid value of the oxidized wax D1 is 29.9mg KOH/g, the saponification value is 56.8mg KOH/g, the ester value is 26.9mg KOH/g, and the ester-acid ratio is 0.90;
the oxidized wax D1 was darker in color and pale yellow in color than the oxidized wax S3.
Comparative example 2
Oxidized wax D2 was obtained in the same manner as in example 3, except that iron stearate was replaced with a manganese-based catalyst (manganese acetate).
Wherein the acid value of the oxidized wax D2 is 15.5mg KOH/g, the saponification value is 32.4mg KOH/g, the ester value is 16.9mg KOH/g, and the ester-acid ratio is 1.10;
the oxidized wax D2 was darker in color and yellow in color than the oxidized wax S3.
As can be seen from the data of examples 1-24 and comparative examples 1-2, the oxidized wax products prepared by the method provided by the present invention have the characteristics of high ester number, low acid number and high ester acid ratio, and particularly, the oxidized wax products with high ester acid ratio are prepared by using ferric stearate as a catalyst and combining glacial acetic acid and oxygen-containing gas to catalyze and oxidize Fischer-Tropsch wax.
Meanwhile, catalytic oxidation is limited to a first stage and a second stage, so that the catalytic oxidation time is effectively shortened while the oriented oxidation of the Fischer-Tropsch wax is realized, and the color index of an oxidized wax product is improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (17)
1. A method of producing an oxidized wax, the method comprising: in the presence of a catalyst and an auxiliary agent, carrying out catalytic oxidation reaction on the molten Fischer-Tropsch wax and oxygen-containing gas to obtain oxidized wax;
wherein the catalyst is an iron catalyst and/or a cobalt catalyst; wherein the iron-based catalyst is an iron-containing linear alkyl compound; the cobalt catalyst is a straight-chain alkyl compound containing cobalt;
wherein the auxiliary agent is selected from glacial acetic acid;
wherein the weight ratio of the Fischer-Tropsch wax to the catalyst to the auxiliary agent is 100:0.01-0.2:1 to 12;
wherein the oxygen content in the oxygen-containing gas is 25-45v%;
wherein the catalytic oxidation reaction comprises a first stage and a second stage; the temperature of the first stage is 170-200 ℃; the time is 0.1-1h; the temperature of the second stage is 140-170 ℃; the time is 1-8h.
2. The method according to claim 1, wherein the iron-based catalyst is selected from at least one of iron stearate, iron palmitate, iron myristate, and iron laurate.
3. The method of claim 2, wherein the iron-based catalyst is iron stearate.
4. The method according to claim 1, wherein the cobalt-based catalyst is at least one selected from the group consisting of cobalt stearate, cobalt palmitate, cobalt myristate, and cobalt laurate.
5. The method of claim 4, wherein the cobalt-based catalyst is cobalt stearate.
6. The method of claim 1, wherein the gas flow rate of the oxygen-containing gas is 1-100 mL/min-g.
7. The method of claim 6, wherein the gas flow rate of the oxygen-containing gas is 40-70 mL/min-g.
8. The process of claim 1, wherein the weight ratio of the fischer-tropsch wax, catalyst and adjunct is 100:0.02-0.08:1-5.
9. The method of claim 1, wherein the temperature of the first stage is 180-190 ℃; the time is 0.5-1h.
10. The method of claim 1, wherein the temperature of the second stage is 150-160 ℃; the time is 5-6h.
11. The process of any one of claims 1-10, wherein the fischer-tropsch wax is selected from at least one of 60# fischer-tropsch wax, 70# fischer-tropsch wax, 80# fischer-tropsch wax, 95# fischer-tropsch wax, 100# fischer-tropsch wax, and 105# fischer-tropsch wax.
12. The process of claim 11, wherein the molten fischer-tropsch wax is obtained by heating fischer-tropsch wax.
13. The method of claim 12, wherein the heating is at a temperature of 100-130 ℃.
14. The method of claim 12, wherein the heating is at a temperature of 120-130 ℃.
15. An oxidized wax produced by the process of any one of claims 1 to 14.
16. The oxidized wax of claim 15, wherein the oxidized wax has an ester number of not less than 35mg KOH/g; the acid value is less than or equal to 40mg KOH/g; the ratio of ester to acid is > 1.
17. The oxidized wax of claim 15, wherein the oxidized wax has an ester number of 35 to 90mg KOH/g; the acid value is 10-40mg KOH/g; the ratio of ester to acid is 1-3.5.
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| CN114774164B (en) * | 2022-03-31 | 2024-02-02 | 国家能源集团宁夏煤业有限责任公司 | Method for preparing oxidized wax |
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| DE1160840B (en) * | 1959-04-25 | 1964-01-09 | Hoechst Ag | Process for the production of hard waxes with a high ester content |
| EP0065704A1 (en) * | 1981-05-12 | 1982-12-01 | Ashland Oil, Inc. | Redox catalyst plus promoter for oxidation of hydrocarbons |
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