CN114774164B - Method for preparing oxidized wax - Google Patents
Method for preparing oxidized wax Download PDFInfo
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- CN114774164B CN114774164B CN202210345881.5A CN202210345881A CN114774164B CN 114774164 B CN114774164 B CN 114774164B CN 202210345881 A CN202210345881 A CN 202210345881A CN 114774164 B CN114774164 B CN 114774164B
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 97
- 230000003647 oxidation Effects 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000002808 molecular sieve Substances 0.000 claims abstract description 37
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 48
- 230000005284 excitation Effects 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 17
- 239000012752 auxiliary agent Substances 0.000 claims description 16
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 238000011084 recovery Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000010457 zeolite Substances 0.000 claims description 5
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 235000010338 boric acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000001993 wax Substances 0.000 description 134
- 239000000047 product Substances 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 230000000087 stabilizing effect Effects 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- -1 manganese stearate ethanol Chemical compound 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009418 agronomic effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 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)
Abstract
The invention relates to the technical field of coal-to-liquid chemical industry, in particular to a preparation method of oxidized wax. The method comprises the steps of contacting a wax raw material, an oxidation source, and optionally a catalyst promoter with a catalyst for reaction; the catalyst comprises an active component and a molecular sieve support, the active component comprising elemental manganese and/or elemental cobalt. The method for preparing the oxidized wax can obviously improve the yield of the oxidized wax, improve the product quality (uniform product, light color and high ester-acid ratio) of the oxidized wax, ensure that the product does not contain metal elements such as manganese, cobalt and the like, can be continuously produced, and improve the production efficiency of the oxidized wax.
Description
Technical Field
The invention relates to the technical field of coal-to-liquid chemical industry, in particular to a preparation method of oxidized wax.
Background
Fischer-Tropsch wax is a hydrocarbon product which is synthesized by using synthetic gas under the action of a catalyst and has the molecular weight of 200-2000 and mainly normal hydrocarbon, and has the characteristics of low sulfur, low nitrogen, low aromatic hydrocarbon content and the like. In recent years, with the continuous establishment and realization of long-period full-load operation of Fischer-Tropsch synthesis industrial devices of companies such as Ning coal, yitai, luan, future energy sources and the like, fischer-Tropsch wax productivity is continuously expanded, and the Fischer-Tropsch wax is one of important products in the domestic wax market and also becomes a popular product from a scarce resource.
The oxidation of Fischer-Tropsch wax is the preferred way to study and prepare specialty wax products and to obtain oxidized waxes with high added value. Polar groups such as-OH, -COOH, C=O and COOR are added to the oxidized product of the Fischer-Tropsch wax, and the polar groups endow the oxidized wax product with a plurality of new characteristics such as emulsifying property, lubricating property, oil solubility, flexibility and better pigment dispersibility. When the plastic is processed, a certain amount of oxidized wax is added, so that the plastic has good external lubricity and strong internal lubrication, the production efficiency can be improved, and the production cost can be reduced; wax emulsion products prepared by taking oxidized wax as raw materials are widely used in industries such as petrochemical industry, automobile protection, wood processing, building industry, medical supplies, agronomic industry, papermaking process, explosive industry and the like.
Disclosure of Invention
The invention aims to solve the problems of low production efficiency, poor product quality and low yield of oxidized wax in the prior art, and provides a preparation method of oxidized wax.
In order to achieve the above object, the present invention provides a method for preparing oxidized wax, which comprises the steps of contacting a wax raw material, an oxidation source, and optionally a catalyst auxiliary agent with a catalyst;
the catalyst comprises an active component and a molecular sieve support, the active component comprising elemental manganese and/or elemental cobalt.
Through the technical scheme, the invention has at least the following advantages:
the method for preparing the oxidized wax can obviously improve the yield of the oxidized wax, improve the product quality (uniform product, light color and high ester-acid ratio) of the oxidized wax, and ensure that the product does not contain metal elements such as manganese, cobalt and the like, can realize continuous production of the oxidized wax, and improve the production efficiency of the oxidized wax.
Drawings
FIG. 1 is a flow chart and apparatus corresponding to a preferred method of preparing oxidized waxes according to the present invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, unless otherwise indicated, the term "upper" as used herein generally refers to the portion of the total length of the reaction unit 30% below the top of the reaction unit, and "lower" generally refers to the portion of the total length of the reaction unit 30% above the bottom of the reaction unit.
The invention provides a preparation method of oxidized wax, which comprises the steps of carrying out contact reaction on wax raw materials, an oxidation source, an optional catalyst auxiliary agent and a catalyst;
the catalyst comprises an active component and a molecular sieve support, the active component comprising and/or elemental cobalt.
The method for preparing the oxidized wax can obviously improve the yield of the oxidized wax, improve the product quality (uniform product, light color and high ester-acid ratio) of the oxidized wax, and ensure that the product does not contain metal elements such as manganese, cobalt and the like, can realize continuous production of the oxidized wax, and improve the production efficiency of the oxidized wax.
In the present invention, the average pore diameter of the molecular sieve carrier is not particularly required as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the average pore diameter of the molecular sieve carrier is not less than 0.5nm. By adopting the foregoing preferred embodiment, the yield and quality of oxidized wax can be further improved.
According to a preferred embodiment of the present invention, the molecular sieve support is selected from at least one of MCM-41 molecular sieves, large pore zeolite molecular sieves, HZSM-5 molecular sieves. By adopting the preferable scheme, the production efficiency, yield and quality of the oxidized wax can be further improved.
According to a preferred embodiment of the invention, the catalyst has an average particle size of 60 to 80 mesh.
In the present invention, the contents of the active component and the molecular sieve carrier in the catalyst are not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the content of the active component in terms of elements in the catalyst is 0.5 to 5wt% and the content of the molecular sieve carrier is 55 to 80wt% based on the total mass of the catalyst. By adopting the preferable scheme, the production efficiency, yield and quality of the oxidized wax can be further improved.
In the present invention, the oxidizing source may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the oxidizing source is an oxygen-containing gas, preferably an oxygen-containing gas having an oxygen content of 20 to 100% by volume, more preferably air and/or oxygen. By adopting the preferable scheme, the production efficiency, yield and quality of the oxidized wax can be further improved.
In the present invention, the catalyst auxiliary may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the catalyst auxiliary is selected from at least one of stearic acid, boric acid, oxalic acid, citric acid, palmitic acid, lauric acid. By adopting the preferable scheme, the production efficiency, yield and quality of the oxidized wax can be further improved.
In the present invention, the wax feed may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the wax feed is a Fischer-Tropsch wax, preferably at least one of a 52# Fischer-Tropsch wax, a 60# Fischer-Tropsch wax, a 70# Fischer-Tropsch wax, an 80# Fischer-Tropsch wax, a 90# Fischer-Tropsch wax, a 100# Fischer-Tropsch wax, a 105# Fischer-Tropsch wax, a 110# Fischer-Tropsch wax. By adopting the preferable scheme, the production efficiency, yield and quality of the oxidized wax can be further improved.
In the present invention, the amount of the catalyst is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the amount of the catalyst is 0.1 to 5 mass% of the amount of the wax raw material. By adopting the preferable scheme, the production efficiency, yield and quality of the oxidized wax can be further improved.
In the present invention, the addition amount of the catalyst auxiliary is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the addition amount of the catalyst auxiliary is 0.5 to 6wt%, preferably 2 to 4wt% of the addition amount of the wax raw material. By adopting the preferable scheme, the production efficiency, yield and quality of the oxidized wax can be further improved.
In the present invention, the amount of the gas flow of the oxidizing source is not particularly limited as long as the object of the present invention can be attained, and according to a preferred embodiment of the present invention, the amount of the gas flow of the oxidizing source is 0.1 to 1.6L/(h.g of wax), preferably 0.2 to 1.2L/(h.g of wax). By adopting the preferable scheme, the production efficiency, yield and quality of the oxidized wax can be further improved.
In the present invention, the method for preparing the catalyst is not particularly limited as long as the object of the present invention can be achieved, and according to a preferred embodiment of the present invention, the method for preparing the catalyst comprises:
a. dissolving a manganese source and/or a cobalt source in a solvent to obtain a manganese solution and/or a cobalt solution;
b. roasting the molecular sieve carrier;
c. and loading a manganese solution and/or a cobalt solution on the molecular sieve carrier after roasting treatment, drying and forming to obtain the catalyst.
The catalyst prepared by the preparation method of the catalyst is particularly suitable for preparing oxidized wax, and can further improve the production efficiency, yield and quality of the oxidized wax.
In the present invention, the manganese source and/or cobalt source may be conventional choices in the art, and according to a preferred embodiment of the present invention, the manganese source is selected from at least one of manganese stearate, manganese naphthenate, manganese sulfate, manganese dioxide, and potassium permanganate, and the cobalt source is selected from at least one of cobalt stearate, cobalt sulfate, and cobalt naphthenate.
In the present invention, the solvent may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the solvent is selected from at least one of ethanol, propanol, toluene, xylene.
In the present invention, the molecular sieve support may be a conventional choice in the art, and according to a preferred embodiment of the present invention, the molecular sieve support is selected from at least one of MCM-41 molecular sieve, large pore zeolite molecular sieve, HZSM-5 molecular sieve.
In the present invention, in the step b, the conditions of the baking treatment may be a conventional choice in the art, and according to a preferred embodiment of the present invention, in the step b, the conditions of the baking treatment include: the roasting temperature is 300-600 ℃, and the roasting time is 1-10 hours, preferably 2-5 hours.
In the present invention, the drying conditions in the step c may be conventional choices in the art, and according to a preferred embodiment of the present invention, the drying conditions in the step c include: the drying temperature is 80-120 ℃, and the drying time is 6-18 h.
According to a preferred embodiment of the present invention, the method is carried out in an apparatus comprising a wax feed unit, an oxidation source feed unit, a material mixing unit, an excitation reaction unit, a first oxidation reaction unit, a second oxidation reaction unit, an oxidized wax collection unit, and an oxidized wax oil recovery unit;
the material mixing unit is provided with a catalytic auxiliary agent feeding hole;
the discharge port of the oxidation source feeding unit is respectively communicated with the lower feed ports of the excitation reaction unit, the first oxidation reaction unit and the second oxidation reaction unit and is used for providing an oxidation source;
the upper feed inlet of the oxidized wax oil recovery unit is respectively communicated with the top discharge outlets of the excitation reaction unit, the first oxidation reaction unit and the second oxidation reaction unit and is used for collecting and recovering oxidized wax oil;
the wax raw material feeding unit is communicated with the material mixing unit, so that the wax raw material and the catalytic auxiliary agent are mixed to obtain slurry; the material mixing unit is communicated with the upper feed inlet of the excitation reaction unit, so that slurry can react with an oxidation source from the lower feed inlet in a countercurrent way from top to bottom; the discharge hole at the bottom of the excitation reaction unit is communicated with the feed hole at the upper part of the first oxidation reaction unit; the bottom discharge port of the first oxidation reaction unit is communicated with the upper feed port of the second oxidation reaction unit; the bottom discharge port of the first oxidation reaction unit is communicated with the feed port of the oxidized wax collecting unit;
the method comprises the following steps:
s1, melting a wax raw material, mixing the melted wax raw material with a catalytic auxiliary agent, and then introducing an excitation reaction unit to perform catalytic excitation reaction with an oxidation source from an oxidation source feeding unit to obtain an excitation material and first oxidized wax oil gas;
s2, introducing the excited material into a first oxidation reaction unit and carrying out a first catalytic reaction on the excited material and an oxidation source from an oxidation source feeding unit to obtain a first reactant material and second oxidized wax oil gas;
s3, introducing the first reaction material into a second oxidation reaction unit to perform a second catalytic reaction with an oxidation source from an oxidation source feeding unit to obtain a second reaction material and third oxidized wax oil gas;
and S4, introducing the second reaction material into an oxidized wax collecting unit to obtain oxidized wax, and introducing the first oxidized wax oil gas, the second oxidized wax oil gas and the third oxidized wax oil gas into an oxidized wax oil recovery unit.
By adopting the preferable scheme, the production efficiency, yield and quality of the oxidized wax can be further improved. According to a preferred embodiment of the invention, the lower feed inlets of the excitation reaction unit, the first oxidation reaction unit and the second oxidation reaction unit are each provided with a gas distributor, preferably a membrane gas distributor and/or a coil distributor, more preferably a membrane gas distributor. By adopting the membrane gas distributor, bubbles with small and uniform size can be obtained, gas-liquid transfer is promoted, and the reaction efficiency is high.
According to a preferred embodiment of the invention, the top discharge ports of the excitation reaction unit, the first oxidation reaction unit and the second oxidation reaction unit are provided with filter screens, and the size of the filter screens is smaller than 60 meshes.
According to a preferred embodiment of the invention, the excitation reaction unit is provided with baffles.
According to a preferred embodiment of the present invention, the conditions for melting in step S1 include: the temperature is 100-140℃and preferably 110-130 ℃.
According to a preferred embodiment of the present invention, the mixing conditions in step S1 include: the temperature is 110-130 ℃.
According to a preferred embodiment of the present invention, the conditions for the catalytic excitation reaction in the step S1 include: the temperature is 150-190 ℃, preferably 160-180 ℃, the pressure is 0-0.5 Mpa, preferably 0.2-0.4 Mpa, the time is 0.5-3 h, preferably 1-2 h, the oxidation source gas flow is 0.4-1.6L/(h.g of wax), preferably 0.8-1.2L/(h.g of wax), and the space velocity of the mixed liquid raw material is 20-1000 g/1g of catalyst.h. The conditions of the first catalytic reaction in the step S2 include: the temperature is 130-180 ℃, preferably 150-170 ℃, the pressure is 0-0.5 Mpa, preferably 0.1-0.3 Mpa, the time is 1-4 h, preferably 2-3 h, the oxidation source gas flow is 0.4-1.6L/(h.g of wax), preferably 0.8-1.2L/(h.g of wax), and the excited material airspeed is 20-1000 g/(1 g of catalyst.h). According to a preferred embodiment of the present invention, the conditions of the second catalytic reaction in the step S3 include: the temperature is 130-180 ℃, preferably 150-170 ℃, the pressure is 0-0.5 Mpa, preferably 0.1-0.3 Mpa, the time is 1-4 h, preferably 2-3 h, the oxidation source gas flow is 0.4-1.6L/(h.g of wax), preferably 0.6-1.2L/(h.g of wax), the space velocity of the first reaction material is 20-1000 g/(1 g of catalyst.h), wherein the temperature of the excitation reaction is 10-20 ℃ higher than the temperature of the first catalytic reaction and the temperature of the first catalytic reaction.
In the invention, oxidized wax oil gas discharged from the top of the excitation reaction unit, the first oxidation reaction unit and the second oxidation reaction unit is condensed in the recovery tank with substances such as wax oil, water and the like, and noncondensable gas is discharged to the atmosphere or a torch system.
As shown in fig. 1, the wax feed unit includes a feed tank (containing a heating member, not shown) and a feed pump; the material mixing unit comprises a material mixing tank and a material pump; the excitation reaction unit comprises an excitation reactor (containing a heating component, not shown, with an aspect ratio of 5-25:1, preferably 15-20:1); the first oxidation reaction unit comprises a first oxidation reactor (containing a heating component, not shown, with an aspect ratio of 15-30:1, preferably 20-25:1); the second oxidation reaction unit comprises a second oxidation reactor (containing a heating component, not shown, with an aspect ratio of 15-30:1, preferably 20-25:1); the oxidation source feeding unit comprises an air compressor and an air stabilizing tank, a discharge port is respectively communicated with lower feed inlets of the excitation reactor, the first oxidation reactor and the second oxidation reactor, and a flowmeter is arranged to control the feed quantity of the oxidation source; the oxidized wax oil recovery unit comprises an oxidized wax oil recovery tank, and a top feed inlet of the oxidized wax oil recovery tank is communicated with top discharge outlets of the excitation reactor, the first oxidation reactor and the second oxidation reactor; the oxidized wax collecting unit includes a forming device. Specifically, adding a wax raw material to be oxidized into a raw material tank, heating to 100-140 ℃, preferably melting at 110-130 ℃, conveying the raw material to a material mixing tank through a material pump, adding 0.5-6wt%, preferably 2-4wt% of a catalytic auxiliary agent into the material mixing tank, stirring at 110-130 ℃ to uniformly mix the materials, conveying the raw material to an excitation reactor through the material pump, controlling the pressure to be 0-0.5 Mpa, preferably 0.2-0.4 Mpa, adding a catalyst accounting for 0.1-5wt% of the dosage of the wax raw material, controlling an air compressor, introducing an oxidation source such as air (0.4-1.6L/(h.g wax), preferably 0.8-1.2L/(h.g wax)) through a stabilizing tank, controlling the temperature of the material to be 150-190 ℃ in the excitation reactor, and controlling the reaction time of the material in the excitation reactor to be 0.5-3 h, preferably 1-2 h, so as to obtain an excitation material and first oxidized wax oil gas; introducing the excited material into a first oxidation reactor, controlling an air compressor, introducing an oxidation source such as air (the air flow rate is 0.4-1.6L/(h.g of wax), preferably 0.8-1.2L/(h.g of wax)) through a stabilizing tank, adding a catalyst accounting for 0.1-5 mass percent of the dosage of the wax raw material, wherein the temperature is 130-180 ℃, preferably 150-170 ℃ and the time is 1-4 h, preferably 2-3 h, and obtaining a first reaction material and second oxidized wax oil gas; the first reaction material is then introduced into a second oxidation reactor, an air compressor is controlled, an oxidation source such as air (0.4-1.6L/(h.g wax), preferably 0.6-1.2L/(h.g wax)) is introduced through a stabilizing tank, the pressure is 0-0.5 Mpa, preferably 0.1-0.3 Mpa, and a catalyst accounting for 0.1-5 mass% of the amount of wax raw material is added, the temperature is 130-180 ℃, preferably 150-170 ℃, the time is 1-4 h, preferably 2-3 h, to obtain a second reaction material and a third oxidized wax oil gas; and the second reactant flow passes through the forming device to obtain an oxidized Fischer-Tropsch wax product, and the first oxidized wax oil gas, the second oxidized wax oil gas and the third oxidized wax oil gas are passed through the oxidized wax oil recovery tank to obtain an oxidized wax oil crude product, and are further separated to obtain an oxidized wax oil product.
The present invention will be described in detail by way of examples (using the apparatus, flow scheme shown in fig. 1). In the following examples, acid value and saponification value were measured by the method of NB/SH/T0809; drop melting point is measured by a drop melting point tester according to the method of GB/T8026; the penetration is measured by a penetration tester according to the method of GB/T4985; chromaticity is measured by a chromaticity measuring instrument according to the method of GB/T6540; the raw materials are all commercial products.
Example 1
Preparation of the catalyst:
a. dissolving 15g of manganese stearate in ethanol, and stirring to uniformly disperse the manganese stearate to obtain manganese stearate ethanol solution;
b. roasting the prepared 20g MCM-41 molecular sieve (average pore diameter is 8 nm) for 5 hours at 450 ℃;
c. dropwise adding a manganese stearate ethanol solution onto the baked MCM-41 molecular sieve, drying in a baking oven at 100 ℃ for 12 hours after dropwise adding, and extruding and forming to obtain the manganese stearate MCM-41 catalyst with the average particle size of 60-80 meshes (the content of active components in terms of elements is 3.8wt% and the content of molecular sieve carrier is 57 wt%);
and adding 60# Fischer-Tropsch wax to be oxidized into a raw material tank, heating to 110 ℃, conveying the sample to a material mixing tank after the sample is completely melted, adding 2wt% of stearic acid catalyst auxiliary agent into the mixture, and stirring the mixture at 110 ℃ to uniformly mix the materials. The pressure of the excitation reactor is controlled to be 0.4Mpa, 1% of the prepared manganese stearate MCM-41 catalyst is added, air (the air flow rate is 1.0L/(h.g wax)) is introduced, the temperature of the material in the excitation reactor is controlled to be 175 ℃, the reaction time of the material in the excitation reactor is controlled to be 2h, the air (the air flow rate is 1.2L/(h.g wax)) is controlled to be introduced into the first oxidation reactor and the second oxidation reactor, the pressure is 0.35Mpa, 1% of the prepared manganese stearate MCM-41 catalyst is added, the temperature is 160 ℃ and the time is 2h, the oxidized wax oil crude product is obtained in the oxidized wax oil recovery tank, and oxidized wax oil is further separated; oxidized Fischer-Tropsch wax products were obtained on a forming apparatus, the properties of which are shown in Table 1.
Example 2
The difference from example 1 is that:
in the preparation of the catalyst, the active component is cobalt, the cobalt source is cobalt stearate, the carrier is HZSM-5 molecular sieve (average pore diameter is 0.5 nm), and the catalyst is prepared (the content of the active component is 2wt% based on elements, and the content of the molecular sieve carrier is 77 wt%);
the wax raw material is 90# Fischer-Tropsch wax, the melting temperature is 120 ℃, the addition amount of the auxiliary agent is 3wt%, the addition amount of the catalyst in the excitation reactor, the first oxidation reactor and the second oxidation reactor is 5%, and the oxidation source gas flow is respectively 1.2L/(h.g of wax), 1.0L/(h.g of wax) and 1.0L/(h.g of wax). The temperature of the materials in the excitation reactor is controlled to be 170 ℃; oxidized Fischer-Tropsch wax products were obtained, the properties of which are shown in Table 1.
Example 3
The difference from example 1 is that:
the support was a large pore zeolite (average pore size 11 nm).
The wax raw material is 105# Fischer-Tropsch wax, the melting temperature is 130 ℃, the addition amount of the auxiliary agent is 4wt%, the addition amount of the catalyst in the excitation reactor, the first oxidation reactor and the second oxidation reactor is 2%, and the oxidation source gas flow is respectively 0.8L/(h.g wax), 0.8L/(h.g wax) and 0.6L/(h.g wax); the temperature of the materials in the excitation reactor is controlled to be 180 ℃; oxidized Fischer-Tropsch wax products were obtained, the properties of which are shown in Table 1.
Example 4
The difference from example 1 was that the excitation reactor was controlled to a temperature of 165 ℃. Oxidized Fischer-Tropsch wax products were obtained, the properties of which are shown in Table 1.
Example 5
The difference from example 1 is that the manganese element content is 10%. Oxidized Fischer-Tropsch wax products were obtained, the properties of which are shown in Table 1.
Example 6
The same as in example 1 was found to be different in that the excitation reactor, the first oxidation reactor, and the second oxidation reactor were controlled to have temperatures of 200℃and 190℃and 190℃respectively. The product properties are shown in Table 1
Example 7
The difference from example 1 is that the excitation reactor is controlled to a temperature of 160 ℃ (i.e. no excitation reactor is provided). Oxidized Fischer-Tropsch wax products were obtained, the properties of which are shown in Table 1.
Example 8
The difference from example 1 is that the MCM-41 molecular sieve has an average pore size of 2nm. Oxidized Fischer-Tropsch wax products were obtained, the properties of which are shown in Table 1.
Comparative example 1
The procedure is as in example 1, except that manganese stearate is used directly as catalyst. The product properties are shown in Table 1.
TABLE 1
In conclusion, the method has the advantages of high reaction efficiency, light color, high quality and high ester-acid ratio of the obtained oxidized wax product, which are basically white or light yellow, can realize continuous production, greatly improve the production efficiency and avoid the back and forth loading and unloading of the intermittent kettle production process.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (15)
1. A method for preparing oxidized wax, which is characterized in that the method comprises the steps of contacting and reacting wax raw materials, an oxidation source, and optional catalyst auxiliary agent with a catalyst; the catalyst comprises an active component and a molecular sieve carrier, wherein the active component comprises elemental manganese and/or elemental cobalt;
the content of active components in the catalyst is 0.5-5wt% based on the total mass of the catalyst; the content of the molecular sieve carrier is 55-80wt%;
the molecular sieve carrier is at least one selected from MCM-41 molecular sieve, macroporous zeolite molecular sieve and HZSM-5 molecular sieve;
the preparation method of the catalyst comprises the following steps:
a. dissolving a manganese source and/or a cobalt source in a solvent to obtain a manganese solution and/or a cobalt solution;
b. roasting the molecular sieve carrier;
c. and loading a manganese solution and/or a cobalt solution on the molecular sieve carrier after roasting treatment, drying and forming to obtain the catalyst.
2. The production process according to claim 1, wherein the molecular sieve carrier has an average pore diameter of not less than 0.5nm.
3. The preparation method according to claim 1, wherein,
the oxidation source is an oxygen-containing gas;
the catalyst auxiliary agent is at least one selected from stearic acid, boric acid, oxalic acid, citric acid, palmitic acid and lauric acid; and/or
The wax material is Fischer-Tropsch wax.
4. The preparation method according to claim 3, wherein,
the oxidation source is an oxygen-containing gas with the oxygen content of 20-100 vol%; and/or
The wax raw material is at least one of 52# Fischer-Tropsch wax, 60# Fischer-Tropsch wax, 70# Fischer-Tropsch wax, 80# Fischer-Tropsch wax, 90# Fischer-Tropsch wax, 100# Fischer-Tropsch wax, 105# Fischer-Tropsch wax and 110# Fischer-Tropsch wax.
5. A production method according to claim 3, wherein the oxidizing source is air and/or oxygen.
6. The preparation method according to claim 1, wherein,
the dosage of the catalyst is 0.1-5 mass% of the dosage of the wax raw material; and/or
The addition amount of the catalyst auxiliary agent is 0.5-6wt% of the addition amount of the wax raw material; and/or
The gas flow of the oxidation source is 0.1-1.6L/(h.g wax).
7. The preparation method according to claim 6, wherein,
the addition amount of the catalyst auxiliary agent is 2-4wt% of the addition amount of the wax raw material; and/or
The air flow rate of the oxidation source is 0.2-1.2L/(h.g wax).
8. The preparation method according to claim 1, wherein,
the manganese source is selected from at least one of manganese stearate, manganese naphthenate, manganese sulfate, manganese dioxide and potassium permanganate; and/or
The cobalt source is at least one selected from cobalt stearate, cobalt sulfate and cobalt naphthenate; and/or
The solvent is at least one selected from ethanol, propanol, toluene and xylene; and/or
The molecular sieve carrier is at least one selected from MCM-41 molecular sieve, macroporous zeolite molecular sieve and HZSM-5 molecular sieve.
9. The preparation method according to claim 1, wherein,
in the step b, the conditions of the roasting treatment include: roasting at 300-600 deg.c for 1-10 hr; and/or
In the step c, the drying conditions include: the drying temperature is 80-120 ℃, and the drying time is 6-18 h.
10. The production method according to claim 9, wherein in the step b, the conditions of the calcination treatment include: the roasting time is 2-5 h.
11. The production method according to any one of claims 1 to 10, wherein the method is carried out in an apparatus comprising a wax raw material feeding unit, an oxidation source feeding unit, a material mixing unit, an excitation reaction unit, a first oxidation reaction unit, a second oxidation reaction unit, an oxidized wax collecting unit, and an oxidized wax oil recovering unit;
the material mixing unit is provided with a catalytic auxiliary agent feeding hole;
the discharge port of the oxidation source feeding unit is respectively communicated with the lower feed ports of the excitation reaction unit, the first oxidation reaction unit and the second oxidation reaction unit and is used for providing an oxidation source;
the upper feed inlet of the oxidized wax oil recovery unit is respectively communicated with the top discharge outlets of the excitation reaction unit, the first oxidation reaction unit and the second oxidation reaction unit and is used for collecting and recovering oxidized wax oil;
the wax raw material feeding unit is communicated with the material mixing unit, so that the wax raw material and the catalytic auxiliary agent are mixed to obtain slurry; the material mixing unit is communicated with the upper feed inlet of the excitation reaction unit, so that slurry can react with an oxidation source from the lower feed inlet in a countercurrent way from top to bottom; the discharge hole at the bottom of the excitation reaction unit is communicated with the feed hole at the upper part of the first oxidation reaction unit; the bottom discharge port of the first oxidation reaction unit is communicated with the upper feed port of the second oxidation reaction unit; the bottom discharge port of the first oxidation reaction unit is communicated with the feed port of the oxidized wax collecting unit;
the method comprises the following steps:
s1, melting a wax raw material, mixing the melted wax raw material with a catalytic auxiliary agent, and then introducing an excitation reaction unit to perform catalytic excitation reaction with an oxidation source from an oxidation source feeding unit to obtain an excitation material and first oxidized wax oil gas;
s2, introducing the excited material into a first oxidation reaction unit and carrying out a first catalytic reaction on the excited material and an oxidation source from an oxidation source feeding unit to obtain a first reactant material and second oxidized wax oil gas;
s3, introducing the first reaction material into a second oxidation reaction unit to perform a second catalytic reaction with an oxidation source from an oxidation source feeding unit to obtain a second reaction material and third oxidized wax oil gas;
and S4, introducing the second reaction material into an oxidized wax collecting unit to obtain oxidized wax, and introducing the first oxidized wax oil gas, the second oxidized wax oil gas and the third oxidized wax oil gas into an oxidized wax oil recovery unit.
12. The preparation method according to claim 11, wherein,
the lower feed inlets of the excitation reaction unit, the first oxidation reaction unit and the second oxidation reaction unit are respectively provided with a gas distributor; and/or
The top discharge ports of the excitation reaction unit, the first oxidation reaction unit and the second oxidation reaction unit are provided with filter screens, and the size of each filter screen is smaller than 60 meshes; and/or
The excitation reaction unit is provided with a baffle plate.
13. The method of claim 12, wherein the gas distributor is a membrane gas distributor and/or a coil distributor.
14. The method of claim 11, wherein,
the conditions for melting in step S1 include: the temperature is 100-140 ℃; and/or
The mixing conditions in the step S1 include: the temperature is 110-130 ℃; and/or
The conditions for the catalytic excitation reaction in step S1 include: the temperature is 150-190 ℃, the pressure is 0-0.5 MPa, the time is 0.5-3 h, the flow rate of oxidation source gas is 0.4-1.6L/(h.g wax), and the space velocity of the mixed liquid raw material is 20-1000 g/1g catalyst/h; and/or
The conditions of the first catalytic reaction in the step S2 include: the temperature is 130-180 ℃, the pressure is 0-0.5 MPa, the time is 1-4 hours, the flow rate of oxidation source gas is 0.4-1.6L/(h.g wax), and the space velocity of excited materials is 20-1000 g/1g catalyst.h; and/or
The conditions of the second catalytic reaction in the step S3 include: the temperature is 130-180 ℃, the pressure is 0-0.5 MPa, the time is 1-4 hours, the flow rate of oxidation source gas is 0.4-1.6L/(h.g wax), and the space velocity of the first reaction material is 20-1000 g/(1 g catalyst.h);
wherein the temperature of the excitation reaction is 10-20 ℃ higher than the temperature of the first catalytic reaction and the temperature of the first catalytic reaction.
15. The method of claim 14, wherein,
the conditions for melting in step S1 include: the temperature is 110-130 ℃; and/or
The conditions for the catalytic excitation reaction in step S1 include: the temperature is 160-180 ℃, the pressure is 0.2-0.4 MPa, the time is 1-2 h, and the flow rate of oxidation source gas is 0.8-1.2L/(h.g wax); and/or
The conditions of the first catalytic reaction in the step S2 include: the temperature is 150-170 ℃, the pressure is 0.1-0.3 MPa, the time is 2-3 h, and the flow rate of oxidation source gas is 0.8-1.2L/(h.g wax); and/or
The conditions of the second catalytic reaction in the step S3 include: the temperature is 150-170 ℃, the pressure is 0.1-0.3 MPa, the time is 2-3 h, and the flow rate of oxidation source gas is 0.6-1.2L/(h.g of wax).
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| US20040065588A1 (en) * | 2002-10-08 | 2004-04-08 | Genetti William Berlin | Production of fuels and lube oils from fischer-tropsch wax |
| CN102921447A (en) * | 2012-10-30 | 2013-02-13 | 陕西启源科技发展有限责任公司 | Preparation method and using method for paraffin catalyst |
| CN104607115A (en) * | 2015-02-01 | 2015-05-13 | 南京天诗新材料科技有限公司 | Method and device for preparing oxidized wax |
| CN112852486A (en) * | 2021-01-12 | 2021-05-28 | 国家能源集团宁夏煤业有限责任公司 | Oxidized wax and preparation method thereof |
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| US20040065588A1 (en) * | 2002-10-08 | 2004-04-08 | Genetti William Berlin | Production of fuels and lube oils from fischer-tropsch wax |
| CN102921447A (en) * | 2012-10-30 | 2013-02-13 | 陕西启源科技发展有限责任公司 | Preparation method and using method for paraffin catalyst |
| CN104607115A (en) * | 2015-02-01 | 2015-05-13 | 南京天诗新材料科技有限公司 | Method and device for preparing oxidized wax |
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