CN101392185B - White mineral oil for polypropylene - Google Patents
White mineral oil for polypropylene Download PDFInfo
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- CN101392185B CN101392185B CN2007101316158A CN200710131615A CN101392185B CN 101392185 B CN101392185 B CN 101392185B CN 2007101316158 A CN2007101316158 A CN 2007101316158A CN 200710131615 A CN200710131615 A CN 200710131615A CN 101392185 B CN101392185 B CN 101392185B
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- oil
- white mineral
- mineral oil
- polypropylene
- base oil
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- 239000002480 mineral oil Substances 0.000 title claims abstract description 24
- 235000010446 mineral oil Nutrition 0.000 title claims abstract description 24
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 21
- -1 polypropylene Polymers 0.000 title claims abstract description 21
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 21
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 22
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000002199 base oil Substances 0.000 claims description 40
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000010779 crude oil Substances 0.000 claims description 15
- 238000006277 sulfonation reaction Methods 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 13
- 238000000638 solvent extraction Methods 0.000 claims description 12
- 238000005194 fractionation Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 7
- 235000009508 confectionery Nutrition 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 6
- 230000008676 import Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a white mineral oil used for polypropylene. The molecular weight of the white mineral oil is 430 to 500. The white mineral oil consists of 40 percent to 45 percent of naphthenic hydrocarbon and 55 percent to 59.9 percent of paraffinic hydrocarbon and therein, the content of aromatic hydrocarbon is not more than 0.1 percent. The dense of the white mineral oil at 20 DEG C is0.840g/cm<3> to 0.890 g/cm<3>, the refractive index thereof is 1.4700 to 1.4800 at 20 DEG C and the kinetic viscosity thereof is 130mpa.s to 160mpa.s at 20 DEG C. The white mineral oil used for the polypropylene can fully meet the various physical and chemical indexes of a polypropylene catalyst carrier, thereby being capable of completely maintaining the activity of the polypropylene catalyst and keeping the molecule of the catalyst with even granularity during polymerization so as to reduce catalyst poisoning. The product can completely replace the products of import companies, thus changing the layout that the product completely rely on import and providing supporting service for introducing devices from abroad.
Description
Technical field
The present invention the invention belongs to petrochemical industry, be specifically related to a kind of in Vestolen PP 7052 is produced the white mineral oil as support of the catalyst.
Background technology
Vestolen PP 7052 (PP) have good mechanical property, nontoxic, specific density is low, heat-resisting, chemical-resistant resistance, machine-shaping easily, raw material are easy to get, good characteristic such as cheap; Become the kind that rate of growth is the fastest in the five big general synthetic resins, new product development is the most active at present; Be widely used in chemical industry, chemical fibre, building, light industry, automobile making, household electrical appliances, wrapping material etc., and constantly expanding new Application Areas.But compare with PVC, PS, polyacrylic crystallization velocity is slower, and the forming process cycle is long; Low temperature impact properties is poor; Goods gloss is bad with the transparency, and outward appearance lacks aesthetic feeling, and molding shrinkage is bigger; This makes its range of application be restricted to a certain extent again, especially in fields such as transparent container, daily necessities and engineering materialss.
1993, world's Vestolen PP 7052 throughput reached 20.1Mt.To the end of the year 1997, the Vestolen PP 7052 production equipment that China has been constructed and put into operation reaches 135 covers, and overall throughput is 1949.5kt/a.Along with device is gone into operation successively; Also increasing for the polypropylene catalyst demand, but supporting therewith support of the catalyst, domestic development and production do not catch up with the needs of development far away; The high-end whole dependence on import of polypropylene catalyst carrier need a large amount of foreign exchanges of consumption every year at present.Domestic some devices are for reducing cost, thereby adopt the support of the catalyst of technical grade to bring shortcomings such as catalyst activity reduction, easy poisoning.
Summary of the invention
The objective of the invention is provides a kind of support of the catalyst white mineral oil that can satisfy the various physical and chemical indexs of polypropylene catalyst carrier fully in order to overcome the domestic present situation that does not have high-end polypropylene catalyst carrier.
The object of the invention can reach through following measure:
A kind of white mineral oil for polypropylene, this white mineral oil molecular weight is 430～500, and naphthenic hydrocarbon by 40～45% and 55～59.9% paraffinic hydrocarbons are formed, and wherein aromatic hydrocarbon content is not more than 0.1%, and 20 ℃ of density of this white mineral oil are 0.840～0.890g/cm
3, 20 ℃ of specific refractory poweres are 1.4700～1.4800,20 ℃ of kinetic viscosity 130～160mpa.s.Wherein the carbon chain lengths of naphthenic hydrocarbon or paraffinic hydrocarbons is C20～30.
White mineral oil of the present invention can be prepared by following method:
A, raw material:
After the Karamay oilfield crude oil normal pressure fractionation of Xinjiang, get and wherein subtract three sections hydrogenated base oil A (like Xinjiang naphthene base crude oil K371, KNH4010, KP6010 etc.) that three sections hydrogenation of 350～550 ℃ of fraction sections of four lines obtain,
After the fractionation of Oil of Shanghai Petrochemical Company sweet crude oil normal pressure, get and wherein subtract three or subtract the hydrogenated base oil B (like 300N, 150N etc.) that 320～520 ℃ of fraction sections of four lines two-stage hydrogenation obtains;
The quality consumption of each raw material is: three sections hydrogenated base oil A40～50%, hydrogenated base oil B50～60%;
B, sulfonation reaction: after each raw materials mix, 50～80 ℃ of following gas phase xanthations 10～20 hours, the sulfonation pipeline pressure was 0.025～0.06MPa with sulphur trioxide;
C, neutralization reaction: will pass through the sulfonated hydrogenated base oil and be transferred to pH value to 8～11 with 20～40% aqueous sodium hydroxide solutions (mass content) down at 50～75 ℃;
D, solvent extraction: under 50～75 ℃, carry out solvent extraction with 30～40% alcohol solutions (mass content), wherein the consumption of alcohol solution is 10～40% of a hydrogenated base oil quality;
E, decolouring: after will passing through the thick white oil dehydration of solvent extraction, use activated decoloration, filter.
Wherein three sections hydrogenated base oil A can adopt three sections hydrogenation techniques (hydrogen cracking, Hydrodewaxing, unifining) of various routines to carry out hydrotreatment, preferred hydrogenation pressure 18～20MPa, and the oxide compound that adopts VIB or VIII family element is as catalyzer.After hydrogenated base oil B adopts the fractionation of Oil of Shanghai Petrochemical Company sweet crude oil normal pressure, get and wherein subtract three or subtract 320～520 ℃ of fraction sections of four lines two-stage hydrogenation and obtain.
In the sulfonation reaction, the sulphur trioxide that base oil per ton consumed is 60～100 kilograms.
In the step of wherein decolouring, can adopt vacuum hydro-extraction; Can adopt 5～8% atlapulgite to carry out decolorizing and refining during decolouring; Filter and also can adopt vacuum filtration.
The present invention makes product reach the requirement of polypropylene catalyst carrier aspect thermostability and light stability through adopting the process integration circuit of hydrogenated base oil+sulphur trioxide gas phase sulfonation method.Through processing parameter control, solve this product and guarantee aromatic hydrocarbons structural material complete reaction in process of production, reach 0%.
White mineral oil for polypropylene of the present invention can satisfy the various physical and chemical indexs of polypropylene catalyst carrier fully, and the activity of maintenance polypropylene catalyst that can be intact makes catalyst molecule in polymerization process, keep epigranular, reduces poisoning of catalyst.This product can substitute import firm's product fully, has changed the situation of the complete dependence on import of this product, for external imported unit is done adequate and systematic service.
Description of drawings
Fig. 1 is white mineral oil technological process of production figure.
Embodiment
Embodiment 1
After the Karamay oilfield crude oil normal pressure fractionation of Xinjiang, get and wherein subtract three sections hydrogenated base oil A (like Xinjiang naphthene base crude oil K371) that three sections hydrogenation of 350～550 ℃ of fraction sections of four lines obtain;
After the fractionation of Oil of Shanghai Petrochemical Company sweet crude oil normal pressure, get and wherein subtract three or subtract the hydrogenated base oil B (300N) that 320～520 ℃ of fraction sections of four lines two-stage hydrogenation obtains;
Get three sections hydrogenated base oil A50%, hydrogenated base oil B50% constitutes mixed base oil, adopts sulphur trioxide gas phase sulfonation method that base oil is carried out sulfonation and handles, and wherein, 55 ℃ of following gas phase xanthations 18 hours, the sulfonation pipeline pressure was 0.04MPa; (the sulphur trioxide consumption is 90 kilograms/ton);
To pass through the sulfonated hydrogenated base oil and be transferred to pH value to 8 with 40% aqueous sodium hydroxide solution down at 50 ℃;
Under 65 ℃, carry out solvent extraction with 35% aqueous ethanolic solution, wherein the consumption of ethanolic soln is 40% of a hydrogenated base oil quality;
After will passing through the thick white oil vacuum hydro-extraction of solvent extraction, use 6% activated decoloration, filter and obtain white mineral oil for polypropylene; Total recovery is 93%, and molecular weight is 430～500, naphthenic hydrocarbon 40～45%; Paraffinic hydrocarbons 55～59.9%; Aromatic hydrocarbon content 0.08%, the carbon chain lengths of naphthenic hydrocarbon or paraffinic hydrocarbons are that C20～30,20 ℃ density is 0.845g/cm
3, 20 ℃ of specific refractory poweres are 1.4720,20 ℃ of kinetic viscosity 132mpa.s.
Embodiment 2
After the Karamay oilfield crude oil normal pressure fractionation of Xinjiang, get and wherein subtract three sections hydrogenated base oil A (Xinjiang naphthene base crude oil KNH4010) that three sections hydrogenation of 350～550 ℃ of fraction sections of four lines obtain.
After the fractionation of Oil of Shanghai Petrochemical Company sweet crude oil normal pressure, get and wherein subtract three or subtract the hydrogenated base oil B (150N) that 320～520 ℃ of fraction sections of four lines two-stage hydrogenation obtains;
Get three sections hydrogenated base oil A40%, hydrogenated base oil B60% constitutes mixed base oil, adopts sulphur trioxide gas phase sulfonation method that base oil is carried out sulfonation and handles, and wherein, 60 ℃ of following gas phase xanthations 15 hours, the sulfonation pipeline pressure was 0.025MPa; (the sulphur trioxide consumption is 80 kilograms/ton);
To pass through the sulfonated hydrogenated base oil and be transferred to pH value to 9 with 20% aqueous sodium hydroxide solution down at 65 ℃;
Under 50 ℃, carry out solvent extraction with 40% alcohol mixture (the methyl alcohol 20%+ ethanol 80%) aqueous solution, wherein the consumption of alcohol solution is 30% of a hydrogenated base oil quality;
After will passing through the thick white oil vacuum hydro-extraction of solvent extraction, use 5% activated decoloration, filter and obtain white mineral oil for polypropylene; Total recovery is 94%, and molecular weight is 430～500, naphthenic hydrocarbon 40～45%; Paraffinic hydrocarbons 55～59.9%, aromatic hydrocarbon content 0.06%; The carbon chain lengths of naphthenic hydrocarbon or paraffinic hydrocarbons is that C20～30,20 ℃ density is 0.867g/cm
3, 20 ℃ of specific refractory poweres are 1.4750,20 ℃ of kinetic viscosity 140mpa.s.
Embodiment 3
After the Karamay oilfield crude oil normal pressure fractionation of Xinjiang, get and wherein subtract three sections hydrogenated base oil A (like Xinjiang naphthene base crude oil KP6010) that three sections hydrogenation of 350～550 ℃ of fraction sections of four lines obtain.
After the fractionation of Oil of Shanghai Petrochemical Company sweet crude oil normal pressure, get and wherein subtract three or subtract the hydrogenated base oil B (300N) that 320～520 ℃ of fraction sections of four lines two-stage hydrogenation obtains;
Get three sections hydrogenated base oil A45%, hydrogenated base oil B55% constitutes mixed base oil, adopts sulphur trioxide gas phase sulfonation method that base oil is carried out sulfonation and handles, and wherein, 70 ℃ of following gas phase xanthations 10 hours, the sulfonation pipeline pressure was 0.06MPa; (the sulphur trioxide consumption is 95 kilograms/ton);
To pass through the sulfonated hydrogenated base oil and be transferred to pH value to 10 with 30% aqueous sodium hydroxide solution down at 70 ℃;
Under 70 ℃, carry out solvent extraction with 30% aqueous ethanolic solution, wherein the consumption of ethanolic soln is 30% of a hydrogenated base oil quality;
After will passing through the thick white oil vacuum hydro-extraction of solvent extraction, use 8% activated decoloration, filter and obtain white mineral oil for polypropylene; Total recovery is 95%, and molecular weight is 430～500, naphthenic hydrocarbon 40～45%; Paraffinic hydrocarbons 55～59.9%; Aromatic hydrocarbon content 0.08%, the carbon chain lengths of naphthenic hydrocarbon or paraffinic hydrocarbons are that C20～30,20 ℃ density is 0.887g/cm
3, 20 ℃ of specific refractory poweres are 1.4789,20 ℃ of kinetic viscosity 156mpa.s.
Claims (3)
1. white mineral oil for polypropylene; It is characterized in that this white mineral oil molecular weight is 430～500; Naphthenic hydrocarbon by 40～45% and 55～59.9% paraffinic hydrocarbons are formed; The carbon chain lengths of described naphthenic hydrocarbon or paraffinic hydrocarbons is C20～30, and wherein aromatic hydrocarbon content is not more than 0.1%, and 20 ℃ of density of this white mineral oil are 0.840～0.890g/cm
3, 20 ℃ of specific refractory poweres are 1.4700～1.4800,20 ℃ of kinetic viscosity 130～160mpa.s.
2. white mineral oil for polypropylene according to claim 1 is characterized in that described white mineral oil is prepared by following method:
A, raw material:
After the Karamay oilfield crude oil normal pressure fractionation of Xinjiang, get and wherein subtract three sections hydrogenated base oil A that three sections hydrogenation of 350～550 ℃ of fraction sections of four lines obtain,
After the fractionation of Oil of Shanghai Petrochemical Company sweet crude oil normal pressure, get and wherein subtract three or subtract the hydrogenated base oil B that 320～520 ℃ of fraction sections of four lines two-stage hydrogenation obtains;
B, sulfonation reaction: after each raw materials mix, 50～80 ℃ of following gas phase xanthations 10～20 hours, the sulfonation pipeline pressure was 0.025～0.06MPa with sulphur trioxide;
C, neutralization reaction: will pass through the sulfonated hydrogenated base oil and be transferred to pH value to 8～11 with 20～40% aqueous sodium hydroxide solutions down at 50～75 ℃;
D, solvent extraction: under 50～75 ℃, carry out solvent extraction with 30～40% alcohol solutions, wherein the consumption of alcohol solution is 10～40% of a hydrogenated base oil quality;
E, decolouring: after will passing through the thick white oil dehydration of solvent extraction, use activated decoloration, filter.
3. white mineral oil for polypropylene according to claim 2 is characterized in that the quality consumption of each raw material is: three sections hydrogenated base oil A 40～50%, hydrogenated base oil B 50～60%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101316158A CN101392185B (en) | 2007-09-17 | 2007-09-17 | White mineral oil for polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101316158A CN101392185B (en) | 2007-09-17 | 2007-09-17 | White mineral oil for polypropylene |
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| Publication Number | Publication Date |
|---|---|
| CN101392185A CN101392185A (en) | 2009-03-25 |
| CN101392185B true CN101392185B (en) | 2012-11-07 |
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| CN2007101316158A Active CN101392185B (en) | 2007-09-17 | 2007-09-17 | White mineral oil for polypropylene |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028798A (en) * | 2019-03-07 | 2019-07-19 | 盐城市恒星石油化学有限公司 | High abrasion resin combination containing ABS |
| CN110028797A (en) * | 2019-03-07 | 2019-07-19 | 盐城市恒星石油化学有限公司 | The polypropylene/polystyrene resin combination of high tensile |
| CN114507304B (en) * | 2022-01-19 | 2023-11-24 | 国家能源集团宁夏煤业有限责任公司 | Dispersing agent, olefin polymerization catalyst slurry, preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044487A (en) * | 1989-12-09 | 1990-08-08 | 茂名石油工业公司研究院 | Method for producing industrial white oil by solvent complexing extraction |
| CN1020919C (en) * | 1988-08-25 | 1993-05-26 | 美国环球油品公司 | Process for production of white oils from heavy alkylate by-product |
| CN1261537C (en) * | 2002-12-24 | 2006-06-28 | 中国石油化工股份有限公司 | Production of high viscosity food grade white oil |
-
2007
- 2007-09-17 CN CN2007101316158A patent/CN101392185B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1020919C (en) * | 1988-08-25 | 1993-05-26 | 美国环球油品公司 | Process for production of white oils from heavy alkylate by-product |
| CN1044487A (en) * | 1989-12-09 | 1990-08-08 | 茂名石油工业公司研究院 | Method for producing industrial white oil by solvent complexing extraction |
| CN1261537C (en) * | 2002-12-24 | 2006-06-28 | 中国石油化工股份有限公司 | Production of high viscosity food grade white oil |
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| CN101392185A (en) | 2009-03-25 |
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Owner name: YANCHENG HENGXING PETROCHEMICAL CO., LTD. Free format text: FORMER OWNER: JIA ZHONGYOU Effective date: 20130530 |
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Effective date of registration: 20130530 Address after: Funing Yancheng City County Road 224421 hailing Jiangsu province Yi Town No. 3 Patentee after: Yancheng Hengxing Petrochemical Co., Ltd. Address before: Funing province Jiangsu County Road 224421 Hailing Yi Town No. 3 Patentee before: Jia Zhongyou |