CN103436290B - Method for producing naphthenic base refrigerating machine oil base oil by using coal tar oil - Google Patents
Method for producing naphthenic base refrigerating machine oil base oil by using coal tar oil Download PDFInfo
- Publication number
- CN103436290B CN103436290B CN201310419444.4A CN201310419444A CN103436290B CN 103436290 B CN103436290 B CN 103436290B CN 201310419444 A CN201310419444 A CN 201310419444A CN 103436290 B CN103436290 B CN 103436290B
- Authority
- CN
- China
- Prior art keywords
- oil
- coal tar
- level
- secondary hydrogenation
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003921 oil Substances 0.000 title claims abstract description 150
- 239000011280 coal tar Substances 0.000 title claims abstract description 50
- 239000002199 base oil Substances 0.000 title claims abstract description 42
- 239000010721 machine oil Substances 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000002283 diesel fuel Substances 0.000 claims abstract description 12
- 238000007670 refining Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 17
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 15
- 238000005194 fractionation Methods 0.000 claims description 14
- 239000011269 tar Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 6
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000003245 coal Substances 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004927 clay Substances 0.000 abstract description 4
- 238000004508 fractional distillation Methods 0.000 abstract 2
- 239000002994 raw material Substances 0.000 description 18
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 235000010446 mineral oil Nutrition 0.000 description 6
- 238000005057 refrigeration Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 239000010687 lubricating oil Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Lubricants (AREA)
Abstract
The invention relates to a method for producing naphthenic base refrigerating machine oil base oil by using coal tar oil. The method comprises the following steps of: (1) carrying out first-stage hydrofining on the coal tar oil; (2) carrying out fractional distillation on a first-stage hydrofining product; (3) carrying out secondary-stage hydrofining on residual oil fractions; (4) carrying out fractional distillation on secondary-stage hydrofining oil; (5) carrying out clay refining on refrigerating machine oil distillate oil, thus obtaining high-additional value products such as the naphthenic base refrigerating machine oil base oil, naphtha oil, diesel oil and refrigerating machine oil base oil. The method has the advantages that the hydrogenation industrial chain of the coal tar oil is extended, the utilization value of the coal tar oil is increased, and the refrigerating machine oil base oil with the high quality is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of cycloalkyl refrigerator oil base oil, is particularly that raw material is to prepare the method for cycloalkyl refrigerator oil base oil with coal tar.
Background technology
Refrigerator oil is the special lube of refrigeration-type compression set, is determine and affect the refrigerating function of refrigeration system and the important component part of effect.In the course of the work, rely on the reduction vaporization of refrigeration agent to obtain low temperature, refrigerator oil then lubricates the working part of refrigeration plant refrigeration compressor.Because refrigerator oil must be in the low temperature environment of refrigeration system for a long time, thus must be allowed a choice for the raw material being used for producing refrigerator oil.According to the difference of raw materials for production, conventional refrigerator oil can be divided into two classes: mineral oil and synthetic oil.The base oil major part of synthesis oil type is polymkeric substance or macromolecular organic compound, and at present, conventional synthetic oil mainly contains alkylbenzene oil, polyolefin oil, polyvalent alcohol lubricating oil, polyvalent alcohol fatty oil.It is good that synthetic oil has oxidation stability, carbon deposit tendency little, the advantages such as long service life, but price comparatively mineral oil is much high.Mineral oil mainly comprises naphthene base crude oil and paraffinic based oil, naphthene base crude oil has lower wax content, viscosity, pour point, feature that low-temperature fluidity is good, be high-quality and the main raw material oil of producing refrigerator oil, in current refrigerator oil market, occupy very consequence.But naphthenic base crude reserves are limited, only account for the 2%-3% of crude oil total reserves.So, open up other refrigerator oil raw materials for production, there is huge realistic meaning.
Kinds of processes method is had to produce refrigerator oil at present both at home and abroad.
Chinese patent CN 1 260 824 discloses a kind of refrigerated machine oil composition that can be excellent with the oilness used containing hydrocarbon coolant, refrigeration agent intermiscibility simultaneously, and containing this refrigerated machine oil composition and the refrigerator fluid composition containing hydrocarbon coolant.Its base oil is hydrocarbon-type oil, adopts desolventizing, solvent extraction, hydrogenative decomposition, solvent dewaxing, contact dewaxing, hydrofinishing, sulfuric acid scrubbing etc.
US Patent No. 3 953 319 and Japanese Patent JP 5 138 305 disclose a kind of method by hydrofining, vitriolization, urea dewaxing, clay finishing production refrigerator oil.Used sulfuric acid in these methods, can produce reluctant acid sludge contaminate environment, and this method can only batch production, treatment capacity is little.
Niu Yu etc. is also had to select xinjiang crude oil normal two wires cut, through benzol-kentone dewaxing, furfural treatment, clay-filtered after obtain MVl60 neutral oil, reduce its pour point by bacterial dewaxing again and prepare refrigerator oil (Niu Yu etc., the development of the totally-enclosed refrigerator oil of L-DRB/A10, refining of petroleum and chemical industry, 7th phase in 2007,55-59).But this method uses " old three cover " technique to prepare refrigerator oil, and its flow process is longer, and there do not have method of hydrotreating to obtain the quality of product to be high.
Chinese patent CN 1 260 824 and Japanese JP 53 136 005 discloses the method for producing refrigerator oil with paraffinic crude, but the low-temperature performance of this paraffinic base product does not have cycloalkyl product good.
In addition, Chinese patent CN 101 177 643 and CN 101 107 503 discloses the refrigerator oil prepared by mixedαolefin polymkeric substance, and is with mineral oil and one or more refrigerator oils prepared for main component becoming hydrocarbon compound, oxygenatedchemicals, polyvinyl ether, synthetic aroma race hydrocarbon etc. disclosed in CN 102 408 938, CN 101 275 099, CN 101 400769, CB 101 305 083, CN 101 024 793, CN 101 248 163, CN 101 233 217 etc.The composition that these methods relate to not only has mineral oil to also have synthetic oil, and its cost is higher than simple mineral oil.CN 102 295 956 is with the naphthenic base oil cut of 300 DEG C ~ 500 DEG C for raw material in addition, carries out hydrotreatment, clay finishing produces refrigerator oil; CN 101 684 416, with being greater than the cut of 360 DEG C in patent ZL02104842.8 hydrogenated oil as raw material, is obtained refrigerator oil base oil be applicable to totally-enclosed air conditioner refrigerating compressor by hydrodewaxing, atmospheric flashing, clay finishing.CN 103 045 303 is with crude oil or cycloalkyl long residuum for raw material, and through thermally splitting, hydrofining, furfural treatment, the method such as clay-filtered produce refrigerator oil;
Xiong Chunzhu etc. with Kelamayi naphthenic base crude Light lube oil for raw material, adopt high-pressure hydrogenation refining-high pressure hydrodewaxing-fractionation cutting technique prepare refrigerator oil (Xiong Chunzhu etc., Production of Refrigerator Oil With High-pressure Hydrogenation Craft is studied, lubricating oil, 2nd phase in 2007,15-17); Yang Weidong etc. with Kelamayi naphthenic base crude Light lube oil for raw material, adopt hydrofining, hydrodewaxing technique prepares refrigerator oil, and (Yang Weidong etc., adopt hydrogenation technique to develop No. 56 refrigerator oils, oil Refining Technologies and engineering, 7th phase in 2010,48-51).The raw material of the Technology of these reports is naphthenic base crude, and the technique still not preparing refrigerator oil with coal tar or its derived product for raw material is reported.
And contriver finds to have in coal tar hydrogenating product a large amount of naphthenic hydrocarbon and aromatic hydrocarbons in further R&D process, can be used as the raw material of preparation cycloalkyl refrigerator oil base oil.
Summary of the invention
Object of the present invention, in order to Appropriate application tar resource, has been widened the raw material sources of refrigerator oil base oil, has been provided a kind of method that coal tar prepares cycloalkyl refrigerator oil base oil.
The technical solution adopted in the present invention is made up of following steps:
(1) coal tar one-level hydrofining
One-level hydrofining is carried out by entering one-level hydrogenator after coal tar and hydrogen mixing, one-level Hydrobon catalyst used is take aluminium sesquioxide as the molybdenum-nickel type catalyzer of carrier, temperature of reaction is 300 ~ 400 DEG C, reaction pressure is 10 ~ 15MPa, hydrogen to oil volume ratio is 800 ~ 1500:1, and liquid volume air speed is 0.3 ~ 0.6h
-1, obtain one-level coal tar hydrorefining product;
(2) fractionation of one-level hydrotreated product
One-level coal tar hydrorefining product is carried out fractionation in separation column, obtains the residue oil fraction being less than the naphtha fraction of 180 DEG C, the diesel oil distillate of 180 ~ 350 DEG C and being greater than 350 DEG C;
(3) secondary hydrogenation of residue oil fraction is refined
In secondary hydrogenation reactor, carry out secondary hydrogenation after being mixed with hydrogen by residue oil fraction refine, secondary hydrogenation catalyst for refining used is take aluminium sesquioxide as the tungsten-ni-type catalyzer of carrier, 280 ~ 380 DEG C, 10 ~ 15MPa, hydrogen to oil volume ratio is 800 ~ 1500:1, and liquid volume air speed is 0.5 ~ 1h
-1, obtain secondary hydrogenation treated oil;
(4) fractionation of secondary hydrogenation treated oil
By the fractionation in separation column of secondary hydrogenation treated oil, obtain the refrigerator oil cut being less than the naphtha fraction of 180 DEG C, the diesel oil distillate of 180 ~ 350 DEG C and being greater than 350 DEG C;
(5) refrigerator oil distillate is clay-filtered
By refrigerator oil cut and carclazyte mix and blend, carclazyte add-on is 5 ~ 10wt%, and 100 ~ 200 DEG C of reaction 20 ~ 50min, cooling, filters, obtain refrigerator oil base oil.
One-level hydrofining is carried out by entering one-level hydrogenator after coal tar and hydrogen mixing in above-mentioned steps (1), one-level Hydrobon catalyst used is take aluminium sesquioxide as the molybdenum-nickel type catalyzer of carrier, temperature of reaction is 350 ~ 380 DEG C, reaction pressure is 13 ~ 15MPa, hydrogen to oil volume ratio is 800 ~ 1200:1, and liquid volume air speed is 0.3 ~ 0.5h
-1, obtain one-level coal tar hydrorefining product.
In secondary hydrogenation reactor, carry out secondary hydrogenation after residue oil fraction mixes with hydrogen by above-mentioned steps (3) refine, secondary hydrogenation catalyst for refining used is take aluminium sesquioxide as the tungsten-ni-type catalyzer of carrier, 300 ~ 360 DEG C, 12 ~ 14MPa, hydrogen to oil volume ratio is 800 ~ 1200:1, and liquid volume air speed is 0.6 ~ 0.8h
-1, obtain secondary hydrogenation treated oil.
Above-mentioned steps (5) is by refrigerator oil cut and carclazyte mix and blend, and carclazyte add-on is 5 ~ 8wt%, and 160 DEG C of reaction 30min, cooling, filters, obtain refrigerator oil base oil.
Above-mentioned steps (1) described coal tar is 500 ~ 700 DEG C of coalite tars or 700 ~ 900 DEG C of coal-tar middle oils that produce in coal pyrolysis process.
In above-mentioned molybdenum-nickel type catalyzer, in catalytically-active metals, molybdic oxide content is at least 20wt%, and nickel oxide content is at least 5wt%, and total pore volume is at least 0.3mL/g, and specific surface area is at least 150m
2/ g.
In the catalytically-active metals of above-mentioned tungsten-ni-type catalyzer, tungstic oxide content is at least 15wt%, and nickel oxide content is at least 2wt%, and total pore volume is at least 0.25mL/g, and specific surface area is at least 140m
2/ g.
The method that a kind of coal tar provided by the present invention prepares cycloalkyl refrigerator oil base oil is processed the technique of coal tar by two-stage hydrogenation-clay-filtered coupling, and obtain cycloalkyl refrigerator oil base oil, it mainly has the following advantages:
(1) there is for coal tar hydrogenating product the feature of a large amount of naphthenic hydrocarbon and aromatic hydrocarbons, coal tar hydrogenating and clay-filtered technique have been carried out rational coupling by the present invention, obtain the high value added products such as petroleum naphtha, diesel oil and refrigerator oil base oil, extend coal tar hydrogenating industrial chain, improve the utility value of coal tar.
(2) hydrogenation unit of the present invention adopts the processing method of two-section hydrotreating, due to the cycloalkyl characteristic of coal tar, catalyst for hydrogenation de-waxing or the hydroisomerization catalyst of conventional petroleum cut is not used in hydrogenation technique of the present invention, use commercially available business Hydrobon catalyst under certain processing condition, just can ensure to obtain high-quality refrigerator oil base oil.
(3) method of the present invention has widened refrigerator oil base oil raw material sources, and the refrigerator oil base oil quality obtained is high, meets the regulation in standard GB/T/T16630-2012 " refrigerator oil ".
Accompanying drawing explanation
Fig. 1 is the process flow sheet of embodiment 1.
Embodiment
Now in conjunction with the accompanying drawings and embodiments technical scheme of the present invention is further described, but the present invention is not limited only to following enforcement situation.
Embodiment 1
The present embodiment is with coalite tar in producing in coal pyrolysis process for cycloalkyl refrigerator oil base oil prepared by raw material, and the method is realized by following steps:
(1) coal tar one-level hydrofining
Carry out one-level hydrofining by entering one-level hydrogenator after middle coalite tar and hydrogen mixing, temperature of reaction is 370 DEG C, and reaction pressure is 14MPa, and hydrogen to oil volume ratio is 1000:1, and liquid volume air speed is 0.3h
-1, obtain one-level coal tar hydrorefining product;
The present embodiment one-level Hydrobon catalyst used adopts the TK-561 type catalyzer (http://www.topsoe.com/products/CatalystPortfolio.aspx) of TOPSOE company exploitation, it take aluminium sesquioxide as carrier, in catalytically-active metals, molybdic oxide content is at least 20wt%, nickel oxide content is at least 5wt%, total pore volume is at least 0.3mL/g, and specific surface area is at least 150m
2/ g.
In this, the character of coalite tar is as following table 1:
Coalite tar character in table 1
(2) fractionation of one-level hydrotreated product
One-level coal tar hydrorefining product is carried out fractionation in separation column, obtains the residue oil fraction being less than the naphtha fraction of 180 DEG C, the diesel oil distillate of 180 ~ 350 DEG C and being greater than 350 DEG C;
(3) secondary hydrogenation of residue oil fraction is refined
In secondary hydrogenation reactor, carry out secondary hydrogenation after being mixed with hydrogen by residue oil fraction refine, temperature of reaction is 350 DEG C, and reaction pressure is 14MPa, and hydrogen to oil volume ratio is 800:1, and liquid volume air speed is 0.6h
-1.
Secondary hydrogenation catalyst for refining adopts the RN-10 type catalyzer (http://sinopec-catalyst.com/product/detail/id/40.html) of catalyzer branch office of Sinopec Group, it take aluminium sesquioxide as the tungsten-ni-type catalyzer of carrier, in its catalytically-active metals, tungstic oxide content is at least 15wt%, nickel oxide content is at least 2wt%, total pore volume is at least 0.25mL/g, and specific surface area is at least 140m
2/ g.
(4) fractionation of secondary hydrogenation treated oil
By the fractionation in separation column of secondary hydrogenation treated oil, obtain the refrigerator oil cut being less than the naphtha fraction of 180 DEG C, the diesel oil distillate of 180 ~ 350 DEG C and being greater than 350 DEG C;
(5) refrigerator oil distillate is clay-filtered
By refrigerator oil cut and carclazyte mix and blend, carclazyte add-on is 6% of refrigerator oil cut quality, 160 DEG C of stirring reaction 30min, cooling, filters, obtains refrigerator oil base oil, after the petroleum naphtha that the present embodiment step (2) and step (4) fractionation obtain and diesel oil mix, detect its character in table 2 and table 3, gained refrigerator oil base oil yield is in table 4, and refrigerator oil base oil character is in table 5.
The naphtha fraction character that table 2 embodiment 1 coal tar hydrorefining obtains
As shown in Table 2, the petroleum naphtha index that hydrogenation obtains all reaches motor spirit GB17930-2006 standard, can be used as gasoline blending component or the reformer feed of high-quality.
Table 3 embodiment 1 coal tar hydrorefining obtains bavin oil properties
As shown in Table 3, gained diesel oil distillate is except cetane value is lower, and all the other indexs all reach the regulation of standard GB/T 252-2000, and diesel oil sulphur, nitrogen content are very low, can be used as fine-quality diesel oil blending component.
Embodiment 2
In the present embodiment, the temperature of reaction of step (1) is 380 DEG C, and reaction pressure is 15MPa, and hydrogen to oil volume ratio is 800:1, and liquid volume air speed is 0.4h
-1, obtain one-level coal tar hydrorefining product; In secondary hydrogenation reactor, carry out secondary hydrogenation after being mixed with hydrogen by residue oil fraction in step (3) refine, temperature of reaction is 360 DEG C, and reaction pressure is 15MPa, and hydrogen to oil volume ratio is 800:1, and liquid volume air speed is 0.8h
-1.Other steps are identical with embodiment 1, obtain refrigerator oil base oil, and its yield is in table 4, and the refrigerator oil base oil character obtained is in table 5.
Embodiment 3
In the present embodiment, the temperature of reaction of step (1) is 370 DEG C, and reaction pressure is 14MPa, and hydrogen to oil volume ratio is 1000:1, and liquid volume air speed is 0.3h
-1, the FZC-41A type catalyzer (http://www.gqcat.com.cn/Chinese/ProductList.asp PID=25) that one-level Hydrobon catalyst used adopts Gong Quan chemical inc, Shandong to produce, obtains one-level coal tar hydrorefining product; In secondary hydrogenation reactor, carry out secondary hydrogenation after being mixed with hydrogen by residue oil fraction in step (3) refine, temperature of reaction is 360 DEG C, and reaction pressure is 13MPa, and hydrogen to oil volume ratio is 800:1, and liquid volume air speed is 0.7h
-1, secondary hydrogenation catalyst for refining used adopts the FV-1 type catalyzer (http://www.sinopec.com/products_services/for_business/catalysts/) of Sinopec Group.Other steps are identical with embodiment 1, obtain refrigerator oil base oil, and its yield is in table 4, and the refrigerator oil base oil character obtained is in table 5.
The yield of table 4 technological condition and each product
The refrigerator oil base oil character that table 5 the present invention obtains
As shown in Table 5, the index of prepared refrigerator oil base oil all meets the regulation of L-DRA46 refrigerator oil in GB/T16630-2012 " refrigerator oil ".
Embodiment 4
In above-described embodiment 1 ~ 3, step (1) carries out one-level hydrofining by entering one-level hydrogenator after middle coalite tar and hydrogen mixing, and temperature of reaction is 300 DEG C, and reaction pressure is 10MPa, and hydrogen to oil volume ratio is 800:1, and liquid volume air speed is 0.3h
-1, obtain one-level coal tar hydrorefining product; In secondary hydrogenation reactor, carry out secondary hydrogenation after residue oil fraction mixes with hydrogen by step (3) refine, temperature of reaction is 280 DEG C, and reaction pressure is 10MPa, and hydrogen to oil volume ratio is 1200:1, and liquid volume air speed is 0.5h
-1.Step (5) is by refrigerator oil cut and carclazyte mix and blend, and carclazyte add-on is 5%, 100 DEG C of stirring reaction 50min of refrigerator oil cut quality, cooling, and filter, other step is identical with corresponding embodiment, obtains refrigerator oil base oil.
Embodiment 5
In above-described embodiment 1 ~ 3, step (1) carries out one-level hydrofining by entering one-level hydrogenator after middle coalite tar and hydrogen mixing, and temperature of reaction is 400 DEG C, and reaction pressure is 15MPa, and hydrogen to oil volume ratio is 1500:1, and liquid volume air speed is 0.6h
-1, obtain one-level coal tar hydrorefining product; In secondary hydrogenation reactor, carry out secondary hydrogenation after residue oil fraction mixes with hydrogen by step (3) refine, temperature of reaction is 380 DEG C, and reaction pressure is 15MPa, and hydrogen to oil volume ratio is 1500:1, and liquid volume air speed is 1h
-1.Step (5) is by refrigerator oil cut and carclazyte mix and blend, and carclazyte add-on is 10%, 200 DEG C of stirring reaction 20min of refrigerator oil cut quality, cooling, and filter, other step is identical with corresponding embodiment, obtains refrigerator oil base oil.
Embodiment 6
In above-described embodiment 1 ~ 3, step (1) carries out one-level hydrofining by entering one-level hydrogenator after middle coalite tar and hydrogen mixing, and temperature of reaction is 350 DEG C, and reaction pressure is 13MPa, and hydrogen to oil volume ratio is 1200:1, and liquid volume air speed is 0.5h
-1, obtain one-level coal tar hydrorefining product; In secondary hydrogenation reactor, carry out secondary hydrogenation after residue oil fraction mixes with hydrogen by step (3) refine, temperature of reaction is 300 DEG C, and reaction pressure is 12MPa, and hydrogen to oil volume ratio is 1000:1, and liquid volume air speed is 0.7h
-1.Step (5) is by refrigerator oil cut and carclazyte mix and blend, and carclazyte add-on is 8%, 140 DEG C of stirring reaction 40min of refrigerator oil cut quality, cooling, and filter, other step is identical with corresponding embodiment, obtains refrigerator oil base oil.
Embodiment 7
In above-described embodiment 1 ~ 6, the coalite tar being 500 ~ 700 DEG C by temperature by coal tar raw material is replaced, and other step is identical with corresponding embodiment.
Embodiment 8
In above-described embodiment 1 ~ 6, the coal-tar middle oil being 700 ~ 900 DEG C by temperature by coal tar raw material is replaced, and other step is identical with corresponding embodiment.
Claims (4)
1. coal tar prepares a method for cycloalkyl refrigerator oil base oil, it is characterized in that being made up of following steps:
(1) coal tar one-level hydrofining
One-level hydrofining is carried out by entering one-level hydrogenator after coal tar and hydrogen mixing, one-level Hydrobon catalyst used is take aluminium sesquioxide as the molybdenum-nickel type catalyzer of carrier, temperature of reaction is 300 ~ 400 DEG C, reaction pressure is 10 ~ 15MPa, hydrogen to oil volume ratio is 800 ~ 1500:1, and liquid volume air speed is 0.3 ~ 0.6h
-1, obtain one-level coal tar hydrorefining product;
(2) fractionation of one-level hydrotreated product
One-level coal tar hydrorefining product is carried out fractionation in separation column, obtains the residue oil fraction being less than the naphtha fraction of 180 DEG C, the diesel oil distillate of 180 ~ 350 DEG C and being greater than 350 DEG C;
(3) secondary hydrogenation of residue oil fraction is refined
In secondary hydrogenation reactor, carry out secondary hydrogenation after being mixed with hydrogen by residue oil fraction refine, secondary hydrogenation catalyst for refining used is take aluminium sesquioxide as the tungsten-ni-type catalyzer of carrier, 280 ~ 380 DEG C, 10 ~ 15MPa, hydrogen to oil volume ratio is 800 ~ 1500:1, and liquid volume air speed is 0.5 ~ 1h
-1, obtain secondary hydrogenation treated oil;
(4) fractionation of secondary hydrogenation treated oil
By the fractionation in separation column of secondary hydrogenation treated oil, obtain the refrigerator oil cut being less than the naphtha fraction of 180 DEG C, the diesel oil distillate of 180 ~ 350 DEG C and being greater than 350 DEG C;
(5) refrigerator oil distillate is clay-filtered
By refrigerator oil cut and carclazyte mix and blend, carclazyte add-on is 5 ~ 10wt%, 100 ~ 200 DEG C of reaction 20 ~ 50min, and cooling, filters, obtain refrigerator oil base oil;
Above-mentioned coal tar is 500 ~ 700 DEG C of coalite tars or 700 ~ 900 DEG C of coal-tar middle oils that produce in coal pyrolysis process;
In above-mentioned molybdenum-nickel type catalyzer, in catalytically-active metals, molybdic oxide content is at least 20wt%, and nickel oxide content is at least 5wt%, and total pore volume is at least 0.3mL/g, and specific surface area is at least 150m
2/ g;
In the catalytically-active metals of above-mentioned tungsten-ni-type catalyzer, tungstic oxide content is at least 15wt%, and nickel oxide content is at least 2wt%, and total pore volume is at least 0.25mL/g, and specific surface area is at least 140m
2/ g.
2. coal tar according to claim 1 prepares the method for cycloalkyl refrigerator oil base oil, it is characterized in that carrying out one-level hydrofining by entering one-level hydrogenator after coal tar and hydrogen mixing in step (1), one-level Hydrobon catalyst used is take aluminium sesquioxide as the molybdenum-nickel type catalyzer of carrier, temperature of reaction is 350 ~ 380 DEG C, reaction pressure is 13 ~ 15MPa, hydrogen to oil volume ratio is 800 ~ 1200:1, and liquid volume air speed is 0.3 ~ 0.5h
-1, obtain one-level coal tar hydrorefining product.
3. coal tar according to claim 1 prepares the method for cycloalkyl refrigerator oil base oil, it is characterized in that in secondary hydrogenation reactor, carrying out secondary hydrogenation after residue oil fraction mixes with hydrogen by step (3) refines, secondary hydrogenation catalyst for refining used is take aluminium sesquioxide as the tungsten-ni-type catalyzer of carrier, 300 ~ 360 DEG C, 12 ~ 14MPa, hydrogen to oil volume ratio is 800 ~ 1200:1, and liquid volume air speed is 0.6 ~ 0.8h
-1, obtain secondary hydrogenation treated oil.
4. coal tar according to claim 1 prepares the method for cycloalkyl refrigerator oil base oil, and it is characterized in that step (5) is by refrigerator oil cut and carclazyte mix and blend, carclazyte add-on is 5 ~ 8wt%, 160 DEG C of reaction 30min, cooling, filters, obtains refrigerator oil base oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310419444.4A CN103436290B (en) | 2013-09-13 | 2013-09-13 | Method for producing naphthenic base refrigerating machine oil base oil by using coal tar oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310419444.4A CN103436290B (en) | 2013-09-13 | 2013-09-13 | Method for producing naphthenic base refrigerating machine oil base oil by using coal tar oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103436290A CN103436290A (en) | 2013-12-11 |
| CN103436290B true CN103436290B (en) | 2015-05-27 |
Family
ID=49690010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310419444.4A Active CN103436290B (en) | 2013-09-13 | 2013-09-13 | Method for producing naphthenic base refrigerating machine oil base oil by using coal tar oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103436290B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498090B (en) * | 2014-12-17 | 2017-03-08 | 王树宽 | Perhydro moulded coal tar naphthenic base oils and the system and method for low-coagulation diesel oil |
| CN110499190B (en) * | 2018-05-17 | 2022-02-01 | 中国石油天然气集团有限公司 | Residual oil hydrotreating system and residual oil hydrotreating method |
| CN112280612A (en) * | 2020-11-08 | 2021-01-29 | 盘锦北方沥青股份有限公司 | High-performance transformer oil and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61120896A (en) * | 1984-11-19 | 1986-06-07 | Nippon Steel Chem Co Ltd | Preparation of naphthenic lube base oil |
| EP0251624B1 (en) * | 1986-06-23 | 1990-08-29 | Nippon Mining Company Limited | Process for producing lubricant base oil |
| CN1174225A (en) * | 1996-08-16 | 1998-02-25 | 中国石化安庆石油化工总厂 | Transformer oil and preparation method thereof |
| CN1243814C (en) * | 2004-07-14 | 2006-03-01 | 王守峰 | Medium-high-temperature coal tar hydro cracking process |
| CN101684416A (en) * | 2008-09-27 | 2010-03-31 | 中国石油天然气股份有限公司 | Production method of base oil of air-conditioning refrigerator oil |
| CN102311785A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for hydrogenating naphthenic base distillate to produce lubricating oil basic oil |
| CN103146424A (en) * | 2013-03-28 | 2013-06-12 | 王树宽 | Method for producing fuel oil and lubricant base oil by hydrogenating all fractions of coal tar |
-
2013
- 2013-09-13 CN CN201310419444.4A patent/CN103436290B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61120896A (en) * | 1984-11-19 | 1986-06-07 | Nippon Steel Chem Co Ltd | Preparation of naphthenic lube base oil |
| EP0251624B1 (en) * | 1986-06-23 | 1990-08-29 | Nippon Mining Company Limited | Process for producing lubricant base oil |
| CN1174225A (en) * | 1996-08-16 | 1998-02-25 | 中国石化安庆石油化工总厂 | Transformer oil and preparation method thereof |
| CN1243814C (en) * | 2004-07-14 | 2006-03-01 | 王守峰 | Medium-high-temperature coal tar hydro cracking process |
| CN101684416A (en) * | 2008-09-27 | 2010-03-31 | 中国石油天然气股份有限公司 | Production method of base oil of air-conditioning refrigerator oil |
| CN102311785A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for hydrogenating naphthenic base distillate to produce lubricating oil basic oil |
| CN103146424A (en) * | 2013-03-28 | 2013-06-12 | 王树宽 | Method for producing fuel oil and lubricant base oil by hydrogenating all fractions of coal tar |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103436290A (en) | 2013-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103305267B (en) | A kind of hydrocracking tail oil hydrogenation produces the method for top-grade lubricating oil base oil | |
| CN103289738B (en) | A kind of hydrocracking tail oil hydrogenation produces the combined method of top-grade lubricating oil base oil | |
| SG186734A1 (en) | Process for the preparation of group ii and group iii lube base oils | |
| CN101864327A (en) | Coal tar hydrogenation modification method | |
| CN105462610B (en) | A kind of anthracene oil hydrogenation method | |
| CN102485846B (en) | Preparation method of transformer oil base oil | |
| CN102041029A (en) | Comprehensive utilization method of hydrocracking tail oil | |
| CN103436290B (en) | Method for producing naphthenic base refrigerating machine oil base oil by using coal tar oil | |
| CN114410347A (en) | Method for preparing low-aromatic transformer oil by medium-pressure hydrogenation of naphthenic base distillate oil | |
| CN103436289B (en) | Method for producing naphthenic base transformer oil base oil by using coal tar oil | |
| CN102888243A (en) | Coal tar tail oil fraction and application thereof | |
| CN113663617A (en) | Low-viscosity refrigerator oil base oil and preparation method and application thereof | |
| CN106833740B (en) | Preparation method of transformer oil base oil | |
| CN113088333A (en) | API III lubricating oil base oil and production method thereof | |
| CN102295956B (en) | Preparation method of base oil of refrigerator oil | |
| CN104910959B (en) | A kind of anti-evolving-gas additive of transformer oil and preparation method thereof | |
| CN102021034A (en) | Preparation method of white microcrystalline wax | |
| CN109321273B (en) | Method and device for producing naphthenic base refrigerator oil base oil | |
| CN106047405B (en) | A kind of method that conduction oil is produced using naphthene base crude | |
| CN101684416B (en) | Production method of base oil of air-conditioning refrigerator oil | |
| CN218710201U (en) | System for preparing special oil for cold liquid from naphthenic base distillate oil | |
| CN103789032B (en) | Method for hydrogenation of medium-low temperature coal tar to produce refrigerator oil base oil | |
| CN102465024A (en) | Hydrocracking method for producing lube base oil | |
| CN114085683A (en) | Process for preparing lubricating oil base oil by hydrogenating and regenerating waste lubricating oil | |
| CN104789260B (en) | A kind of method being produced rocket kerosene by coal tar |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |