CN107987883B - WSI high-pressure hydrogenation shape-selective isomerization-supplement refining method - Google Patents
WSI high-pressure hydrogenation shape-selective isomerization-supplement refining method Download PDFInfo
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- 238000007670 refining Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 19
- 239000013589 supplement Substances 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 38
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 239000000047 product Substances 0.000 claims abstract description 17
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- 230000000295 complement effect Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 238000007730 finishing process Methods 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000002199 base oil Substances 0.000 description 16
- 239000003921 oil Substances 0.000 description 15
- 239000010687 lubricating oil Substances 0.000 description 13
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000011988 third-generation catalyst Substances 0.000 description 1
- -1 triethylamine chlorohydrate hydrochloride Chemical compound 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Lubricants (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a WSI high-pressure hydrogenation shape-selective isomerization-supplementary refining method, which comprises the steps of mixing raw oil with hydrogen, heating, raising the temperature, and reacting in an isomerization dewaxing reactor filled with a shape-selective isomerization catalyst; after the reaction is finished, adjusting the temperature to be 260-280 ℃, and reacting for 60-80min through triethylamine chloroaluminate hydrochloride; mixing the reaction product of the isomerization dewaxing reactor with thiourea, separating to obtain a complex, feeding the complex into a supplementary refining reactor containing a refining reaction catalyst, and introducing hydrogen for reaction; the reaction effluent is subjected to gas/liquid separation to obtain a product. The product produced by the method has the yield up to 95 percent and the kinematic viscosity at 40 ℃ and 100 ℃ up to 23.8mm2·s‑1、8.1mm2·s‑1The viscosity index reaches 157, the pour point reaches-50 ℃, the sulfur content is as low as 0.20ug/g, the nitrogen content is as low as 0.10ug/g, and the oxidation stability is as high as 50.4 h.
Description
Technical Field
The invention relates to the field of petrochemical processing, in particular to a WSI high-pressure hydrogenation shape-selective isomerization-supplement refining method.
Background
The American Petroleum Institute (API) divides lubricating base oils into API group I, II, III, IV and V base oils. The quality of the produced base oil is different due to different processing technologies of the lubricating oil base oil. The three sets of lube oil processing technologies represented by solvent refining, solvent dewaxing and clay refining (or hydrogenation complementary refining) produce API I base oil which has low viscosity index, high sulfur content and low saturated hydrocarbon content, can only be used as common lube oil and cannot meet the requirements of high-grade lube oil. The production of base oil before the sixties of the last century mainly adopts a physical method to refine and reduce the pour point, and the quality of lubricating oil is mainly improved by additives. The hydrotreating technology appears after sixty years, and the solvent is refined and then is supplemented to play a role in hydrogenating unsaturated hydrocarbons, improving colors and removing sulfur and nitrogen, so that the service life of the lubricating oil is prolonged; the nineties have been followed by Chevron (Chevron) corporation to develop isodewaxing techniques to convert wax molecules to isoparaffins. Isoparaffin has excellent characteristics of high viscosity index, low pour point, low evaporation loss, good additive sensitivity, excellent thermal stability and oxidation stability, and high product yield, and a fourth generation catalyst has been proposed. ExxonMobil (ExxonMobil) also introduced its own isodewaxing process MSDW in 1997, and MWI technology was developed in 2003 to introduce a third generation catalyst. From the late nineties, research on shape selective isomerization hydrogenation technology is also developed domestically, and shape selective isomerization hydrogenation technology developed by the compliant petrochemical institute (FRIPP) and the petroleum chemical institute respectively and independently is successful in succession. The two processes produce the lubricating oil base oil with high viscosity index, low pour point and low aromatic hydrocarbon by performing shape selective isomerization, supplementary hydrorefining and other processes on the raw materials, and the reaction mechanism, the catalyst characteristic and the operation condition of the lubricating oil base oil are basically similar.
However, the yield of base oil is not ideal in the prior art, the product quality is not ideal enough, especially the obtained base oil can only reach API I base oil, and if II and III base oil is obtained, further processing is needed, so that the process is more complicated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a WSI high-pressure hydrogenation shape-selective isomerization-supplement refining method.
The technical scheme adopted by the invention is as follows:
a WSI high-pressure hydrogenation shape-selective isomerization-supplementary refining method comprises the following steps:
s1: mixing raw oil with hydrogen, heating, raising the temperature, and reacting in an isomerization dewaxing reactor filled with a shape-selective isomerization catalyst; after the reaction is finished, adjusting the temperature to be 260-280 ℃, and reacting for 60-80min through triethylamine chloroaluminate hydrochloride;
s2: mixing the reaction product of the isomerization dewaxing reactor with thiourea, separating to obtain a complex, feeding the complex into a supplementary refining reactor containing a refining reaction catalyst, and introducing hydrogen for reaction;
s3: the reaction effluent is subjected to gas/liquid separation to obtain a product.
Preferably, step S1 is: mixing raw oil with hydrogen, heating, raising the temperature, reacting in an isomerization dewaxing reactor filled with a shape-selective isomerization catalyst, controlling the temperature at 330-; wherein, the adding amount of the triethylamine chlorohydrate hydrochloride is 0.8-1.0% by volume ratio.
Preferably, the inlet temperature of the post-purification reactor in step S2 is 240 ℃ to 280 ℃, and the operating pressure is 16MPa to 18 MPa.
Preferably, the thiourea is used in an amount of 0.5 to 1% by volume.
Preferably, the shape selective isomerization catalyst is formed by combining a catalyst a and a catalyst b, wherein the carrier of the catalyst a is H- β molecular sieve and gamma-Al2O3The catalyst a is formed by combining Pd, Pt, Co, Ni and Mo as active components; catalyst b is a commercially available SLD-821 catalyst.
Preferably, the refining reaction catalyst is hollow carbon spheres and gamma-Al2O3The mixture of (A) is a carrier, and the active components of the catalyst are Pd, Fe, Co, Ni and P elements.
Compared with the prior art, the invention has the beneficial effects that:
1. thiourea is added into the supplementary refining reactor and can form complex with isoalkane, and the complex is separated and decomposed at high temperature to obtain high purity isoalkane component.
2. The invention adopts mixed type shape selective isomerization catalyst in the isomerization dewaxing reaction process, and adds ionic liquid catalyst triethylamine chloroaluminate hydrochloride after the reaction is finished, and the composition of oil products can be changed through the synergistic action of various catalysts, so that non-ideal components can form ideal components of lubricating oil, impurities such as sulfur, nitrogen, olefin, aromatic hydrocarbon and the like are removed, and then the lubricating oil base oil is produced through fractionation and cutting.
3. The yield of the base oil of the lubricating oil reaches 95 percent, and the kinematic viscosity of the lubricating oil reaches 23.8mm at 40 ℃ and 100 DEG C2·s-1、8.1mm2·s-1The viscosity index reaches 157 and the pour point reaches-The product has the advantages of 50 ℃, low sulfur content of 0.20ug/g, low nitrogen content of 0.10ug/g and high oxidation stability of 50.4h, and compared with the products in the prior art, the product has excellent quality and is base oil for blending high-grade lubricating oil.
Detailed Description
The invention will be further described with reference to specific examples, the advantages and features of which will become clearer from the following description, but the scope of protection of the invention is not limited to the following examples.
Example 1:
a WSI high-pressure hydrogenation shape-selective isomerization-supplementary refining method comprises the following steps:
s1: mixing raw oil with hydrogen, heating, reacting in an isomerization dewaxing reactor filled with a shape selective isomerization catalyst at 350 deg.C under 17MPa for 200min, adjusting temperature to 270 deg.C, and reacting for 70min with 0.8% (volume ratio) triethylamine chloroaluminate hydrochloride;
s2: mixing the reaction product of the isomerization dewaxing reactor with 0.7 percent (volume ratio) of thiourea, separating to obtain a complex, then feeding the complex into a complementary refining reactor containing a refining reaction catalyst, introducing hydrogen for reaction, wherein the inlet temperature of the complementary refining reactor is 250 ℃, and the operating pressure is 17 MPa;
s3: the reaction effluent is subjected to gas/liquid separation to obtain a product.
The shape selective isomerization catalyst is formed by combining a catalyst a and a catalyst b, wherein the carrier of the catalyst a is H- β molecular sieve and gamma-Al2O3The catalyst a is formed by combining Pd, Pt, Co, Ni and Mo as active components; catalyst b is a commercially available SLD-821 catalyst.
The refined reaction catalyst is prepared from hollow carbon spheres and gamma-Al2O3The mixture of (A) is a carrier, and the active components of the catalyst are Pd, Fe, Co, Ni and P elements.
The properties of the feed oil are shown in Table 1.
TABLE 1 Properties of the stock oils
| Item | Raw oil |
| Density (20 ℃ C.)/(g. cm)-3) | 0.851 |
| Distillation range/. degree.C | |
| Initial boiling point/10% | 314/375 |
| 30％/50％ | 395/412 |
| 70％/90％ | 436/475 |
| 95%/end point | 493/502 |
| distillate/mL at 350 ℃ | 2.0 |
| Sulfur/(ug g)-1) | 0.65 |
| Nitrogen/(ug g)-1) | 0.22 |
| Freezing point/. degree.C | 3.1 |
| Kinematic viscosity/(mm)2·s-1) | |
| 40℃ | 24.15 |
| 100℃ | 3.51 |
| Viscosity index | 101 |
Example 2:
a WSI high-pressure hydrogenation shape-selective isomerization-supplementary refining method comprises the following steps:
s1: mixing raw oil with hydrogen, heating, reacting in an isomerization dewaxing reactor filled with a shape selective isomerization catalyst at 330 deg.C under 16MPa for 180min, adjusting temperature to 260 deg.C, and reacting for 60min with triethylamine chloroaluminate hydrochloride of 0.8% (volume ratio);
s2: mixing the reaction product of the isomerization dewaxing reactor with 0.5 percent (volume ratio) of thiourea, separating to obtain a complex, then feeding the complex into a complementary refining reactor containing a refining reaction catalyst, introducing hydrogen for reaction, wherein the inlet temperature of the complementary refining reactor is 240 ℃, and the operating pressure is 16 MPa;
s3: the reaction effluent is subjected to gas/liquid separation to obtain a product.
The shape selective isomerization catalyst is formed by combining a catalyst a and a catalyst b, wherein the carrier of the catalyst a is H- β molecular sieve and gamma-Al2O3The catalyst a is formed by combining Pd, Pt, Co, Ni and Mo as active components; catalyst b is a commercially available SLD-821 catalyst.
The refined reaction catalyst is prepared from hollow carbon spheres and gamma-Al2O3The mixture of (A) and (B) is a carrier, the catalystThe active components of the catalyst are Pd, Fe, Co, Ni and P elements.
The properties of the feed oil are shown in Table 1.
Example 3:
a WSI high-pressure hydrogenation shape-selective isomerization-supplementary refining method comprises the following steps:
s1: mixing raw oil with hydrogen, heating, reacting in an isomerization dewaxing reactor filled with a shape selective isomerization catalyst at 380 deg.C under 18MPa for 240min, adjusting the temperature to 280 deg.C after the reaction, and reacting for 80min with 1.0% (volume ratio) triethylamine chloroaluminate hydrochloride;
s2: mixing the reaction product of the isomerization dewaxing reactor with 1.0 percent (volume ratio) of thiourea, separating to obtain a complex, then feeding the complex into a complementary refining reactor containing a refining reaction catalyst, introducing hydrogen for reaction, wherein the inlet temperature of the complementary refining reactor is 280 ℃, and the operating pressure is 18 MPa;
s3: the reaction effluent is subjected to gas/liquid separation to obtain a product.
The shape selective isomerization catalyst is formed by combining a catalyst a and a catalyst b, wherein the carrier of the catalyst a is H- β molecular sieve and gamma-Al2O3The catalyst a is formed by combining Pd, Pt, Co, Ni and Mo as active components; catalyst b is a commercially available SLD-821 catalyst.
The refined reaction catalyst is prepared from hollow carbon spheres and gamma-Al2O3The mixture of (A) is a carrier, and the active components of the catalyst are Pd, Fe, Co, Ni and P elements.
The properties of the feed oil are shown in Table 1.
Comparative example 1:
a WSI high-pressure hydrogenation shape-selective isomerization-supplementary refining method comprises the following steps:
s1: mixing raw oil with hydrogen, heating, reacting in an isomerization dewaxing reactor filled with a shape selective isomerization catalyst at 300 deg.C under 14MPa for 150min, adjusting temperature to 240 deg.C, and reacting for 50min with 0.6% (volume ratio) triethylamine chloroaluminate hydrochloride;
s2: mixing the reaction product of the isomerization dewaxing reactor with 0.4 percent (volume ratio) of thiourea, separating to obtain a complex, then feeding the complex into a complementary refining reactor containing a refining reaction catalyst, introducing hydrogen for reaction, wherein the inlet temperature of the complementary refining reactor is 200 ℃, and the operating pressure is 15 MPa;
s3: the reaction effluent is subjected to gas/liquid separation to obtain a product.
The shape selective isomerization catalyst is formed by combining a catalyst a and a catalyst b, wherein the carrier of the catalyst a is H- β molecular sieve and gamma-Al2O3The catalyst a is formed by combining Pd, Pt, Co, Ni and Mo as active components; catalyst b is a commercially available SLD-821 catalyst.
The refined reaction catalyst is prepared from hollow carbon spheres and gamma-Al2O3The mixture of (A) is a carrier, and the active components of the catalyst are Pd, Fe, Co, Ni and P elements.
The properties of the feed oil are shown in Table 1.
Comparative example 2:
a WSI high-pressure hydrogenation shape-selective isomerization-supplementary refining method comprises the following steps:
s1: mixing raw oil with hydrogen, heating, reacting in an isomerization dewaxing reactor filled with a shape selective isomerization catalyst at 400 deg.C under 20MPa for 250min, adjusting temperature to 300 deg.C, and reacting for 100min with 1.2% (volume ratio) triethylamine chloroaluminate hydrochloride;
s2: mixing the reaction product of the isomerization dewaxing reactor with 1.2 percent (volume ratio) of thiourea, separating to obtain a complex, then introducing the complex into a complementary refining reactor containing a refining reaction catalyst, introducing hydrogen for reaction, wherein the inlet temperature of the complementary refining reactor is 300 ℃, and the operating pressure is 20 MPa;
s3: the reaction effluent is subjected to gas/liquid separation to obtain a product.
The shape selective isomerization catalyst is formed by combining a catalyst a and a catalyst b, wherein the carrier of the catalyst a is H- β molecular sieve and gamma-Al2O3The catalyst a is formed by combining Pd, Pt, Co, Ni and Mo as active components; catalyst b is a commercially available SLD-821 catalystAn oxidizing agent.
The refined reaction catalyst is prepared from hollow carbon spheres and gamma-Al2O3The mixture of (A) is a carrier, and the active components of the catalyst are Pd, Fe, Co, Ni and P elements.
The properties of the feed oil are shown in Table 1.
Comparative example 3:
a WSI high-pressure hydrogenation shape-selective isomerization-supplementary refining method comprises the following steps: the same as in example 1 except that triethylamine chloroaluminate hydrochloride was not added in step S1 and thiourea was not added in step S2;
comparative example 4:
a WSI high-pressure hydrogenation shape-selective isomerization-supplementary refining method comprises the following steps: the same as in example 1, except that the shape selective isomerization catalyst used catalyst b only.
Product detection: the product properties of the samples of the examples and the comparative examples were measured, and the results are shown in the following table.
The yield of the base oil produced by the method reaches 95 percent, and the kinematic viscosity at 40 ℃ and 100 ℃ reaches 23.8mm2·s-1、8.1mm2·s-1The viscosity index reaches 157, the pour point reaches-50 ℃, the sulfur content is as low as 0.20ug/g, the nitrogen content is as low as 0.10ug/g, and the oxidation stability is as high as 50.4 h.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. A WSI high-pressure hydrogenation shape-selective isomerization-supplement refining method is characterized by comprising the following steps:
s1: mixing the raw oil with hydrogen, heating to raise temperature,entering an isomerization dewaxing reactor filled with a shape-selective isomerization catalyst for reaction, controlling the temperature at 330-2O3The catalyst a is formed by combining Pd, Pt, Co, Ni and Mo as active components; catalyst b is a commercially available SLD-821 catalyst;
s2: mixing the reaction product of the isomerization dewaxing reactor with thiourea, separating to obtain a complex, feeding the complex into a supplementary refining reactor containing a refining reaction catalyst, and introducing hydrogen for reaction;
s3: the reaction effluent is subjected to gas/liquid separation to obtain a product.
2. The WSI high-pressure hydrogenation shape-selective isomerization-complementary refining method as set forth in claim 1, wherein the inlet temperature of the complementary refining reactor in step S2 is 240 ℃ and 280 ℃, and the operating pressure is 16-18 MPa.
3. The WSI high pressure hydroisomerization-finishing process according to claim 1, wherein thiourea is used in an amount of 0.5 to 1% by volume.
4. The WSI high-pressure hydrogenation shape-selective isomerization-supplement refining method as claimed in claim 1, wherein the refining reaction catalyst uses a mixture of hollow carbon spheres and gamma-Al 2O3 as a carrier, and the active components of the catalyst are Pd, Fe, Co, Ni elements.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711180364.2A CN107987883B (en) | 2017-11-23 | 2017-11-23 | WSI high-pressure hydrogenation shape-selective isomerization-supplement refining method |
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| CN1952066A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Hydrogenation process of producing food-level white oil |
| CN103102948A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Production process for lubricant base oil through hydrogenation |
| CN106964401A (en) * | 2017-04-06 | 2017-07-21 | 福州大学 | A kind of light paraffins isomerization ionic-liquid catalyst and preparation method thereof |
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| CN106964401A (en) * | 2017-04-06 | 2017-07-21 | 福州大学 | A kind of light paraffins isomerization ionic-liquid catalyst and preparation method thereof |
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