CN100432193C - Paraffin-hydrogenating refining process - Google Patents
Paraffin-hydrogenating refining process Download PDFInfo
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- CN100432193C CN100432193C CNB2005100474742A CN200510047474A CN100432193C CN 100432193 C CN100432193 C CN 100432193C CN B2005100474742 A CNB2005100474742 A CN B2005100474742A CN 200510047474 A CN200510047474 A CN 200510047474A CN 100432193 C CN100432193 C CN 100432193C
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Abstract
The invention disclosed a method of ozocerite hydrogenation refinement, which adopts ozocerite hydrogenation refining catalyst and hydrogenation isomerizing catalyst as the two main catalysts. Under the ozocerite hydrogenation refining conditions, the ozocerite contacts the two catalysts one by one. The invention can not only get refined ozocerite products with low sulphur and nitrogen content, low polycyclic aromatic hydrocarbon content, it can also decrease the content of ortho- diolefine in the ozocerite and overcome the defects of poor tenacity and brittleness. The ozocerite produced according to the invention can be used in food, medicine and cosmetics.
Description
Technical field
The present invention relates to a kind of method for hydrofining paraffin wax, particularly improve paraffin wax product flexible hydrofinishing process.
Background technology
Paraffin is a kind of important chemical material of separating from petroleum fractions, needs in process of production to make with extra care, and to remove wherein a spot of sulfur-nitrogen compound and condensed-nuclei aromatics, guarantees in use harmless.Hydrofining is the process for purification that generally adopts.But comprise common hydrorefined paraffin process for purification, few to the tough property improvement of paraffin wax product, hard paraffin influences its result of use in many fields such as protection against the tide, insulation, sealings owing to have poor toughness, easy deficiency such as cracked.
The hydrorefining paraffin wax process generally need be carried out under lower temperature, and high temperature will cause the obvious rising of oil content in paraffin wax, therefore can not adopt the method that improves temperature of reaction to improve above-mentioned shortcoming.
CN1176296A discloses a kind of hydrorefining paraffin wax method, adopt the two-stage catalytic agent, wherein first section catalyzer be second section 30%～50%, different operational conditions is adopted in the two-stage catalytic agent, catalyzer there are not special requirement, by adjusting the hydrogenation degree of depth that operational condition reaches paraffin.CN1269395A discloses the online benefit sulphur method in a kind of hydrorefining paraffin wax process, can make decaying catalyst recover active, prolongs catalyzer work-ing life.Can not the improve the quality quality of relatively poor hydrorefining paraffin wax product of this technology.The poor toughness that above-mentioned technology exists paraffin wax product, easily problem such as cracked is not improved.
Summary of the invention
At the deficiencies in the prior art, the invention provides the production method of a kind of good toughness, not easily broken paraffin wax product.
Paraffin is the hydrocarbon mixture based on normal paraffin, the in use chipping reason of normal paraffin paraffin is comparatively complicated, one of them may be that normal paraffin matter is hard and exist below melting temperature and change brilliant point, when changeing the concentrated generation of brilliant phenomenon, paraffin can form crackle in crystal edge because of contraction.Isoparaffin does not change brilliant point.Normal paraffin content is higher to be paraffin poor toughness, easy cracked major reason.
The present invention improves paraffin wax product flexible hydrofinishing process, comprises following content, adopts the fixed bed hydrogenation process for purification, under the hydrorefining paraffin wax condition, adopts catalyst for hydrogen refining of paraffin wax and two kinds of catalyzer of hydroisomerization catalyst.The volume ratio of hydroisomerization catalyst and catalyst for hydrogen refining of paraffin wax is 5: 95～50: 50, preferred 10: 90～40: 60.Hydroisomerization catalyst can be contained in before the catalyst for hydrogen refining of paraffin wax and/or afterwards, preferred hydroisomerization catalyst is contained in before the catalyst for hydrogen refining of paraffin wax, and promptly raw material contacts with hydroisomerization catalyst earlier, contacts with Hydrobon catalyst then.Described hydroisomerization catalyst is the hydroisomerization catalyst that contains the β zeolite, and wherein the silicon-dioxide of β zeolite/aluminium sesquioxide weight ratio is 50～90, and average grain size is 0.1～0.5 micron, infrared acidity 0.1～0.4mmol/g.
Hydrorefining paraffin wax process of the present invention can adopt conventional operational condition, as hydrogen dividing potential drop 4.0～15.0MPa, is preferably 5.0～10.0MPa, and 240～330 ℃ of temperature of reaction are preferably 250～280 ℃, cumulative volume air speed 0.5～3.0h
-1, be preferably 0.5～1.5h
-1, hydrogen wax volume ratio 100～1000 is preferably 200～700.
Hydroisomerization catalyst described in the inventive method contains β zeolite 0.3wt%～20.0wt%, preferred 0.3wt%～10.0wt%, optimum 0.5wt%～7.0wt%.Other carrier component can be one or more in the various inorganic refractory oxides such as mixture of aluminum oxide, silicon oxide, amorphous silicon aluminium, titanium oxide, zirconium white and above several oxide compounds, and commonly used is aluminum oxide.The hydrogenation metal component can be selected from one or more in group vib and the group VIII base metal, one or more that commonly used is among W, Mo, Ni, the Co, be generally 15.0wt%～40.0wt% in the oxide compound metal content, preferred 20.0wt%～35.0wt%.Usually contain group vib metal and group VIII metal simultaneously, as contain W and/or Mo 12.0wt%～30.0wt% in oxide compound, preferred 16.0wt%～28.0wt% contains Ni and/or Co 3.0wt%～10.0wt% in oxide compound, preferred 4.0wt%～7.0wt%.
Hydroisomerization catalyst contains β zeolite character: silicon-dioxide/aluminium sesquioxide weight ratio is 50～90, and average grain size is 0.1～0.5 micron, infrared acidity 0.1～0.4mmol/g.Preferred β zeolite character is: silicon-dioxide/aluminium sesquioxide weight ratio is 60～80, and degree of crystallinity is generally 90～110, preferably 100～110, and average grain size is 0.1～0.3 micron, specific surface area 400～750m
2/ g, preferably 500～600m
2/ g, pore volume 0.25～0.50ml/g, 0.3～0.4ml/g preferably, Na
2O content is less than 0.10wt%, and preferably less than 0.05wt%, infrared acidity is 0.2～0.3mmol/g, and the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume.
Catalyst for hydrogen refining of paraffin wax described in the inventive method is conventional catalyst for hydrogen refining of paraffin wax, and its reactive metal is group vib and group VIII base metal, one or more that commonly used is among W, Mo, Ni, the Co, and carrier is Al
2O
3Or Al
2O
3-SiO
2Deng, can contain auxiliary agents such as P, Ti, B.
Hydroisomerization catalyst and Hydrobon catalyst can be seated in a reactor, also can be seated in two reactors.If two kinds of catalyst loadings then can adopt identical reaction conditions in two reactors, also can adopt different reaction conditionss.All need prevulcanized before described two kinds of catalyzer use, make the activity of such catalysts metal in reaction process, be in sulphided state.
Hydrorefining paraffin wax method of the present invention is in the presence of hydrogen, paraffin enters hydrogenator, contact with two kinds of catalyzer in turn, carry out hydroisomerizing, desulfurization removing nitric and aromatic hydrocarbons saturated reaction, refined products obtains the purpose product that normal paraffin content reduces, virtue is taken off in the deep desulfuration denitrogenation and stability is obviously improved after gas-liquid separation, stripping drying.
The present invention has following advantage:
(1) under the prerequisite that guarantees desulfurization removing nitric and aromatic hydrocarbons saturation effect and hydrogenated products quality, reduces the paraffin normal paraffin content, improved paraffin poor toughness, easy cracked shortcoming;
(2) the hydroisomerization catalyst bed can directly contact with the catalyst for hydrogen refining of paraffin wax bed, and hydrogenation conditions is identical with single hydrorefining paraffin wax reaction conditions, is easy to the operation of catalyst loading and hydrogenation reaction;
(3) be applicable to various wax hydrofining technologies such as existing single reactor single hop and double-reactor one-stage serial, be easy in existing Industrial processes, implement.
The petroleum wax of producing according to the method for the invention can be used for food, medicine and makeup.
Embodiment
The beta-molecular sieve that contains in the beta-molecular sieve catalyzer that technology of the present invention is used is to make by new synthesis modification method, and the key step of modification comprises:
(1) the beta-molecular sieve slurries after the crystallization directly carry out ammonium exchange, filtration, washing, drying and roasting;
(2) beta-molecular sieve that takes off behind the ammonium of roasting carries out acid treatment;
(3) the intact beta-molecular sieve of acid treatment carries out hydrothermal treatment consists again.
Beta-molecular sieve after the above-mentioned crystallization generally is to be template with organic ammonium (as tetraethyl ammonium hydroxide), uses the hydrothermal crystallization method synthetic.Its SiO
2/ Al
2O
3Weight ratio is generally 25～30, Na
2The content of O is 3.0wt%～4.0wt%.Beta-molecular sieve slurries after the crystallization directly carry out the ammonium salt exchange, and the concentration of ammonium salt in slurries is 0.5～5.0mol/l, and several is carried out in the ammonium exchange, make Na in the molecular sieve of exchange back
2The O weight content is not more than 0.5%, and general ammonium exchange 1～4 time can reach requirement.Beta-molecular sieve after the ammonium salt exchange filters, washes, drying and roasting, and wherein maturing temperature is controlled at 450 ℃～650 ℃, and the time is 5.0～15.0 hours.The beta-molecular sieve that roasting is taken off behind the ammonium carries out acid treatment, filters, and wherein acid treatment condition is for being that the mineral acid of 0.1～5.0mol/l is carrying out acid treatment with concentration under abundant agitation condition, 20 ℃～100 ℃ of treatment temps, and the treatment time is 0.5～5.0 hour.The intact beta-molecular sieve of acid treatment carries out pressurized thermal water to be handled, the hydrothermal treatment consists condition for 100% water vapor at 500 ℃～800 ℃, be preferably 550 ℃～700 ℃, system pressure is 0.05～1.0MPa, be preferably 0.1～0.5MPa, handled preferably 1～2 hour 0.5～5.0 hour.
Three β zeolites of following mask body modification are used for the wax hydrofining heterogeneous catalyst.
β 1 character is: molecular sieve SiO
2/ Al
2O
3Weight ratio 70, relative crystallinity are 107, specific surface 570m
2/ g, infrared acidity 0.25mmol/g, the secondary pore pore volume of 2～10nm accounts for 45% of total pore volume, average crystal grain diameter 0.2 μ m.Concrete modifying process is as follows: get SiO
2/ Al
2O
3Weight ratio 25, Na
2The Na beta-molecular sieve of O 3.65wt% synthesizes slurries 2000ml, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 2.0M ammonium nitrate solution stirred, is warming up to 85 ℃ and constant temperature 2 hours, was cooled to 50 ℃ of filtrations, wet cake carries out the exchange second time again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 550 ℃, constant temperature 10 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 1.2M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 85 ℃, and constant temperature stirred 2 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 600 ℃, control pressure 0.3MPa, and the treatment time is 2 hours.
β 2 character are: molecular sieve SiO
2/ Al
2O
3Weight ratio 60, specific surface 600m
2/ g, relative crystallinity are 105, infrared acidity 0.35mmol/g, and the secondary pore pore volume of 2～10nm accounts for 38% of total pore volume, average crystal grain diameter 0.3 μ m.Concrete modifying process is as follows: get SiO
2/ Al
2O
3Weight ratio 25, Na
2The Na beta-molecular sieve of O 3.65wt% synthesizes slurries 2000ml, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 2.0M ammonium nitrate solution stirred, is warming up to 90 ℃ and constant temperature 3 hours, was cooled to 50 ℃ of filtrations, wet cake carries out second and third time exchange again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 500 ℃, constant temperature 12 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 0.8M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 90 ℃, and constant temperature stirred 4 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 570 ℃, control pressure 0.1MPa, and the treatment time is 3 hours.
β 3 character are: molecular sieve SiO
2/ Al
2O
3Weight ratio 85, specific surface 530m
2/ g, relative crystallinity are 100, infrared acidity 0.15mmol/g, and the secondary pore pore volume of 2～10nm accounts for 52% of total pore volume, average crystal grain diameter 0.2 μ m.Concrete modifying process is as follows: get SiO
2/ Al
2O
3Weight ratio 25, Na
2The Na beta-molecular sieve of O 3.65wt% synthesizes slurries 2000ml, contain solid phase 400g (in butt), with water purification solid-to-liquid ratio is diluted to 1: 10, preparation 3.5M ammonium nitrate solution stirred, is warming up to 90 ℃ and constant temperature 2 hours, was cooled to 50 ℃ of filtrations, wet cake carries out the exchange second time again, condition is with for the first time, and washing then was 110～120 ℃ of dryings 6 hours.Dried beta-molecular sieve is at 600 ℃, constant temperature 10 hours.The beta-molecular sieve that ammonium is taken off in high-temperature roasting adds 2.5M HCl 4000ml through pulverizing weighing 400g, stirs and is warming up to 90 ℃, and constant temperature stirred 3 hours, filter, washing, in 110 ℃ of dryings 6 hours (butt＞80%).Above-mentioned exsiccant sample is carried out hydrothermal treatment consists, and temperature is 650 ℃, control pressure 0.4MPa, and the treatment time is 4 hours.
Specify the solution of the present invention and effect by the following examples.The percentage composition that relates to is a weight percentage.
The paraffin raw material character that the embodiment of the invention and comparative example adopt sees Table 1.
The embodiment of the invention and comparative example adopt A (hydroisomerization catalyst), two kinds of catalyzer of B (Hydrobon catalyst), wherein:
The A1-hydroisomerization catalyst, β 1 zeolite 8wt%, WO
322wt%, NiO 4.8wt%, aluminum oxide surplus, specific surface area 220m
2/ g, pore volume 0.49ml/g;
The A2-hydroisomerization catalyst, β 2 zeolite 1wt%, WO
322wt%, NiO 4.8wt%, aluminum oxide surplus, specific surface area 190m
2/ g, pore volume 0.51ml/g;
The A3-hydroisomerization catalyst, β 3 zeolite 5wt%, WO
322wt%, NiO 4.8wt%, aluminum oxide surplus, specific surface area 195m
2/ g, pore volume 0.50ml/g;
The B1-catalyst for hydrogen refining of paraffin wax, WO
329.8%, NiO 4.5%, specific surface area 232m
2/ g, pore volume 0.48ml/g;
The B2-catalyst for hydrogen refining of paraffin wax, MoO
318.9%, NiO 4.2%, specific surface area 262m
2/ g, pore volume 0.56ml/g.
The embodiment of the invention adopts the type of feed of hydroisomerization catalyst before catalyst for hydrogen refining of paraffin wax.
Table 1 paraffin raw material character
| Project | wax1 | wax2 | wax3 |
| Fusing point, ℃ | 58.35 | 66.80 | 71.20 |
| Oleaginousness, % | 0.37 | 0.49 | 0.82 |
| Penetration degree (25 ℃), 1/10mm | 13 | 14 | 16 |
| Viscosity (100 ℃), mm 2/s | 4.211 | 5.484 | 7.638 |
| Color (Sai Shi), number | 6 | -3 | -16 |
| Light stability, number | 7～8 | ＞9 | ＞9 |
| Readily carbonizable substance | Do not pass through | Do not pass through | Do not pass through |
| Ultraviolet absorptivity (simplified method) 280nm 290nm | 0.408 0.295 | 0.694 0.523 | 1.023 0.812 |
| Normal paraffin, % | 91.2 | 88.0 | 75.3 |
The embodiment of the invention 1, embodiment 2 and comparative example 1, comparative example 2 adopt single reactor one-stage hydrogenation technology.Embodiment 3 and comparative example 3 adopt double-reactor one-stage serial hydrogenation technique, two reactor catalyst equal-volume fillings.Embodiment 4 and comparative example 4 adopt double-reactor one-stage serial hydrogenation technique, and two kinds of catalyzer are seated in respectively in two reactors, and two reactors adopt different temperature of reaction.
The hydrorefined operational condition of the embodiment of the invention and comparative example and the results are shown in Table 2～5 wherein characterizes condensed-nuclei aromatics content with the simplified method ultraviolet absorptivity.
No. 58 wax hydrofining operational conditions of table 2 and result
| Project | Embodiment 1 | Comparative example 1 |
| Catalyzer | A1: B1=20: 80 (bodies) | B1 |
| Paraffin | wax1 | wax1 |
| Operational condition | ||
| The hydrogen dividing potential drop, MPa | 5.0 | 5.0 |
| Temperature, ℃ | 260 | 260 |
| The cumulative volume air speed, h -1 | 1.5 | 1.5 |
| Hydrogen wax volume ratio | 300 | 300 |
| Quality product | ||
| Fusing point, ℃ | 58.25 | 58.35 |
| Oleaginousness, % | 0.41 | 0.38 |
| Penetration degree (25 ℃), 1/10mm | 16 | 13 |
| Viscosity (100 ℃), mm 2/s | 4.342 | 4.213 |
| Color (Sai Shi), number | +30 | +30 |
| Light stability, number | 3 | 3 |
| Readily carbonizable substance | By | By |
| Ultraviolet absorptivity (simplified method) 280nm 290nm | 0.034 0.020 | 0.032 0.020 |
| Normal paraffin, % | 76.4 | 90.7 |
No. 66 wax hydrofining operational conditions of table 3 and result
| Project | Embodiment 2 | Comparative example 2 |
| Catalyzer | A2: B2=15: 85 (bodies) | B2 |
| Paraffin | wax2 | wax2 |
| Operational condition | ||
| The hydrogen dividing potential drop, MPa | 7.0 | 7.0 |
| Temperature, ℃ | 280 | 280 |
| The cumulative volume air speed, h -1 | 1.2 | 1.2 |
| Hydrogen wax volume ratio | 500 | 500 |
| Quality product | ||
| Fusing point, ℃ | 66.45 | 66.75 |
| Oleaginousness, % | 0.53 | 0.49 |
| Penetration degree (25 ℃), 1/10mm | 16 | 14 |
| Viscosity (100 ℃), mm 2/s | 5.521 | 5.485 |
| Color (Sai Shi), number | +30 | +30 |
| Light stability, number | 3～4 | 3～4 |
| Readily carbonizable substance | By | By |
| Ultraviolet absorptivity (simplified method) 280nm 290nm | 0.045 0.028 | 0.044 0.026 |
| Normal paraffin, % | 72.3 | 87.2 |
No. 70 wax hydrofining operational conditions of table 4 and result
| Project | Embodiment 3 | Comparative example 3 |
| Catalyzer | A3: B1=10: 90 (bodies) | B1 |
| Paraffin | wax3 | wax3 |
| Operational condition | ||
| The hydrogen dividing potential drop, MPa | 10.0 | 10.0 |
| One anti-temperature, ℃ | 300 | 300 |
| Two anti-temperature, ℃ | 260 | 260 |
| The cumulative volume air speed, h -1 | 0.8 | 0.8 |
| Hydrogen wax volume ratio | 700 | 700 |
| Quality product | ||
| Fusing point, ℃ | 70.45 | 71.00 |
| Oleaginousness, % | 0.91 | 0.84 |
| Penetration degree (25 ℃), 1/10mm | 18 | 16 |
| Viscosity (100 ℃), mm 2/s | 7.823 | 7.639 |
| Color (Sai Shi), number | +30 | +30 |
| Light stability, number | 4 | 4 |
| Readily carbonizable substance | By | By |
| Ultraviolet absorptivity (simplified method) 280nm 290nm | 0.058 0.040 | 0.055 0.039 |
| Normal paraffin, % | 66.7 | 74.9 |
No. 58 wax hydrofining operational conditions of table 5 and result
| Project | Embodiment 4 | Comparative example 4 |
| Catalyzer | A3: B1=40: 60 (bodies) | B1 |
| Paraffin | wax1 | wax1 |
| Operational condition | ||
| The hydrogen dividing potential drop, MPa | 6.0 | 6.0 |
| One anti-hydroisomerizing section temperature, ℃ | 260 | 260 |
| Two anti-hydrofining section temperature, ℃ | 280 | 280 |
| The cumulative volume air speed, h -1 | 1.0 | 1.0 |
| Hydrogen wax volume ratio | 400 | 400 |
| Quality product | ||
| Fusing point, ℃ | 58.15 | 58.30 |
| Oleaginousness, % | 0.42 | 0.38 |
| Penetration degree (25 ℃), 1/10mm | 16 | 13 |
| Viscosity (100 ℃), mm 2/s | 4.345 | 4.214 |
| Color (Sai Shi), number | +30 | +30 |
| Light stability, number | 3 | 3 |
| Readily carbonizable substance | By | By |
| Ultraviolet absorptivity (simplified method) 280nm 290nm | 0.030 0.018 | 0.029 0.018 |
| Normal paraffin, % | 72.3 | 90.6 |
Claims (10)
1, a kind of hydrorefining paraffin wax method, comprise following content, adopt the fixed bed hydrogenation process for purification, under the hydrorefining paraffin wax condition, adopt catalyst for hydrogen refining of paraffin wax and two kinds of catalyzer of hydroisomerization catalyst, the volume ratio of hydroisomerization catalyst and catalyst for hydrogen refining of paraffin wax is 5: 95～50: 50, described hydroisomerization catalyst is the hydroisomerization catalyst that contains the β zeolite, wherein the silicon-dioxide of β zeolite/aluminium sesquioxide weight ratio is 50～90, average grain size is 0.1～0.5 micron, infrared acidity 0.1～0.4mmol/g.
2, in accordance with the method for claim 1, the volume ratio that it is characterized in that described hydroisomerization catalyst and catalyst for hydrogen refining of paraffin wax is 10: 90～40: 60.
3, in accordance with the method for claim 1, it is characterized in that described hydroisomerization catalyst is contained in before the catalyst for hydrogen refining of paraffin wax.
4, in accordance with the method for claim 1, it is characterized in that described hydrofining condition is hydrogen dividing potential drop 4.0～15.0MPa, 240～330 ℃ of temperature of reaction, cumulative volume air speed 0.5～3.0h
-1, hydrogen wax volume ratio 100～1000.
5, in accordance with the method for claim 1, it is characterized in that described hydrofining condition is hydrogen dividing potential drop 5.0～10.0MPa, 250～280 ℃ of temperature of reaction, cumulative volume air speed 0.5～1.5h
-1, hydrogen wax volume ratio 200～700.
6, in accordance with the method for claim 1, it is characterized in that described hydroisomerization catalyst contains β zeolite 0.3wt%～20.0wt%.
7, in accordance with the method for claim 1, it is characterized in that described hydroisomerization catalyst contains β zeolite 0.3wt%～10.0wt%.
8, in accordance with the method for claim 1, it is characterized in that described hydroisomerization catalyst contains modified beta zeolite 0.5wt%～7.0wt%.
9, in accordance with the method for claim 1, it is characterized in that the character that described hydroisomerization catalyst contains the β zeolite is, silicon-dioxide/aluminium sesquioxide weight ratio is 60～80, average grain size is 0.1～0.3 micron, infrared acidity is 0.2～0.3mmol/g, and the secondary pore pore volume of 2～10nm accounts for 30%～60% of total pore volume.
10, in accordance with the method for claim 1, it is characterized in that described hydroisomerization catalyst contains one or more among W, Mo, Ni, the Co, is 15.0wt%～40.0wt% in the oxide compound metal content.
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| KR20180096307A (en) * | 2017-02-21 | 2018-08-29 | 현대자동차주식회사 | Connector device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101619241B (en) * | 2008-07-04 | 2013-04-10 | 中国石油化工股份有限公司 | Method for hydrofining paraffin wax |
| CN102453549A (en) * | 2010-10-14 | 2012-05-16 | 中国石油化工股份有限公司 | Production method of vaseline |
| CN101962570B (en) * | 2010-10-22 | 2014-01-15 | 孙雪 | Method for producing high-octane gasoline by hydrocracking distillate oil of low-grade petroleum |
| CN104593074B (en) * | 2013-11-04 | 2016-07-27 | 中国石油化工股份有限公司 | A kind of high melting-point wax hydrogenation method |
| CN109988637B (en) * | 2017-12-29 | 2021-05-04 | 中国石油化工股份有限公司 | Flexible paraffin hydrogenation process |
| CN109988608B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible liquid phase paraffin hydrogenation process |
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| US4992159A (en) * | 1988-12-16 | 1991-02-12 | Exxon Research And Engineering Company | Upgrading waxy distillates and raffinates by the process of hydrotreating and hydroisomerization |
| CN1611581A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Method for producing soft microcrystalline wax |
-
2005
- 2005-10-19 CN CNB2005100474742A patent/CN100432193C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4992159A (en) * | 1988-12-16 | 1991-02-12 | Exxon Research And Engineering Company | Upgrading waxy distillates and raffinates by the process of hydrotreating and hydroisomerization |
| CN1611581A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Method for producing soft microcrystalline wax |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20180096307A (en) * | 2017-02-21 | 2018-08-29 | 현대자동차주식회사 | Connector device |
| KR102244266B1 (en) | 2017-02-21 | 2021-04-26 | 현대자동차주식회사 | Connector device |
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