CN101204645A - Metamorphic carclazyte, preparation method and application thereof - Google Patents
Metamorphic carclazyte, preparation method and application thereof Download PDFInfo
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- CN101204645A CN101204645A CNA2006101695249A CN200610169524A CN101204645A CN 101204645 A CN101204645 A CN 101204645A CN A2006101695249 A CNA2006101695249 A CN A2006101695249A CN 200610169524 A CN200610169524 A CN 200610169524A CN 101204645 A CN101204645 A CN 101204645A
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Abstract
The invention relates to a modified terra alba and a preparation method and application thereof. The preparation method includes the following steps: the terra alba is processed with alkaline solution of mixture of an inorganic alkaline compound and an organic alkaline compound; the terra alba is washed with water till pH value of the washing water is no higher than 12.0; the terra alba is dried. The modified terra alba thus acquired is used as sorbent for deacidification of refined oils, such as base oil of lubricant to absorb and refine dewaxed oil, which can substantially reduce total acid value of oil product without bringing any detrimental effect on other properties of the oil product.
Description
Technical field
The present invention relates to a kind of adsorbent, its method for making and application, more specifically, relate to a kind of as oil product, for example modified argil of lubricating oil basic oil depickling adsorbent, its preparation method and application.
Background technology
In recent years, along with development and national economy, to oil product, for example the demand of lubricating oil is increasing.Yet; be suitable for producing oil product; for example the crude resources of lube base oil is fewer and feweri; cause being used at present producing the quality deterioration day by day of the crude resources of oil product; the crude oil that for example is used for lube base oil production usually can be sneaked into the part crude oil with high acid value, causes the total acid number of lube base oil to exceed standard.Adopt hydrogenation method to carry out post-refining, can solve the problem that the base oil total acid number exceeds standard, but domestic a lot of refinery does not possess hydrofinishing unit, as invests newly-built hydrofinishing unit, and there is the problem of base oil pour reversion in investment than big and hydrofining.
Clay finishing is a back process for refining traditional in the production of lube base oils, can reduce the total acid number of lube base oil, but the amplitude that reduces is very little, and the general range of decrease is not more than 0.03mgKOH/g.
U.S. Pat 6627069 is used the aqueous solution and the consisting of phase-transferring agent of highly basic such as potassium hydroxide, NaOH, ammonium hydroxide, removes the aphthenic acids in crude oil and the distillate thereof, reduces the total acid number of oil product.
U.S. Pat 5389240 has been introduced a kind of method of using the solid solution adsorbent to remove aphthenic acids, solid solution preparation of adsorbent process is: with three aqueous sodium carbonates, magnesium nitrate hexahydrate, nine water aluminum nitrates, six water nickel nitrates stirring reaction at a certain temperature, filtering the back washes solid phase, solid phase after the washing is 100 ℃ of dryings 16 hours, 450 ℃ calcined again 12 hours product.Be mainly used in kerosene and diesel oil removes aphthenic acids.
Some researcher's dialogue land reforms are both at home and abroad studied, mainly be to improve its denitrogenation ability, introduced with complexing agent (copper sulphate, ferric sulfate, titanium sulfate etc.) and acidizer (sulfuric acid, hydrochloric acid, nitric acid etc.) modified argil as Chinese patent CN00130283, prepared the method for high effective and modified argil as denitrifying agent.U.S. Pat 5749955 improves the acid sites on carclazyte surface by loading metal-salt on carclazyte.But the dialogue land reform, the document that improves its depickling ability does not appear in the newspapers.
Existing acid stripping method complicated operation, cost is higher, and perhaps adsorbent depickling ability remains further to be improved, and therefore needs the new depickling technology of exploitation.
Summary of the invention
The object of the present invention is to provide a kind of oil product that is used as, for example modified argil of lubricating oil basic oil depickling adsorbent and preparation method thereof, and this modified argil is reducing oil product, for example application in the lube base total acid number of oil.
The invention provides a kind of preparation method of modified argil, may further comprise the steps:
(a) handle carclazyte with the mixture alkaline solution of a kind of inorganic alkaline compound and a kind of organic basic compound;
(b) wash carclazyte with water, be not higher than 12.0 until the pH of washings value;
(c) dry clay.
The present invention also provides the modified argil that is made by said method.
The invention still further relates to above-mentioned modified argil as oil product, for example the application of the efficient deacidification adsorbent of lube base oil post-refining.
Modified argil of the present invention can significantly reduce oil product, and for example the total acid number of lube base oil makes the oil product total acid number be not more than 0.03mgKOH/g.This acid stripping method of the present invention is easy and simple to handle, with low cost, and other character of oil product are had no adverse effects.
The specific embodiment
The preparation method of modified argil of the present invention may further comprise the steps:
(a) handle carclazyte with the mixture alkaline solution of a kind of inorganic alkaline compound and a kind of organic basic compound;
(b) wash carclazyte with water, be not higher than 12.0 until the pH of washings value;
(c) dry clay.
In the step (a) of the inventive method, carclazyte is handled with alkaline solution.Wherein, the common mode of processing also can adopt other modes simultaneously for soaking, and for example makes the alkaline solution carclazyte bed of flowing through.The alkali compounds of alkaline solution is the mixture of inorganic alkaline compound and organic basic compound, and total alkali concn of alkaline solution is 1-30 weight %, preferred 2-25 weight %, and more preferably 2-20 weight % is a benchmark with the gross weight of solution.Used inorganic alkaline compound for example is selected from the hydroxide of alkali metal and alkaline-earth metal, particularly NaOH, KOH, CaO, MgO and SrO etc., can use one or more inorganic alkaline compounds; Organic basic compound for example is selected from one or more the mixture in diethylenetriamine, triethylene tetramine, TEPA, polyethylene polyamine, monoethanolamine, diethanol amine, triethanolamine, diethylamine, the triethylamine.Inorganic alkaline compound is preferably 1-10 with the ratio of organic basic compound: 1 (weight ratio, down together), preferred 1-6: 1.The weight ratio of alkaline solution and carclazyte is preferably 1.0-10: 1, and preferred 1.5-5: 1.Alkaline solution contacts temperature preferably at 30-100 ℃ with carclazyte.Be 0.2-24 hour time of contact, is preferably 0.3-6 hour.
The basic carclazyte that adopts among the present invention is the general industry carclazyte.
In step (b), carclazyte is separated with alkaline solution, the carclazyte after the separation washes with water, is not higher than 12.0 until the pH of washings value.After the washing carclazyte is separated with solution.
In (c), dry modified argil specifically can adopt oven dry, air drying etc., preferably 105-250 ℃ of temperature oven dry.
Preferably, the dried modified argil that step (c) obtains is pulverized, made its granularity less than 200 orders.
In view of the high adsorption of modified argil of the present invention to acid, it can be used for the post-refining oil product as efficient deacidification adsorbent, for example lube base oil significantly reduces oil product, for example the total acid number of lube base oil.For example, can make the oil product total acid number be not more than 0.03mgKOH/g.Usually, based on oil product weight to be made with extra care, the preferred 0.1-5 weight of adsorbent consumption %, more preferably 0.2-2.5 weight %.Adopt modified argil of the present invention to carry out depickling, easy and simple to handle, with low cost, other character of oil product are had no adverse effects.
Below the invention will be further described with embodiment, but the invention is not restricted to these specific embodiments.
The preparation of No. 11 modified argils of embodiment
With water 80 grams, NaOH 16 grams and TEPA 4 gram preparation alkaline solutions, soak industrial carclazyte (production of Fushun petrochemical Corp., CNPC's oil one factory) 50 grams with alkaline solution at 98 ℃, fully stir after 3 hours, the static room temperature that is cooled to, it is 10.7 that centrifugation under the room temperature, filter cake are washed to cleaning solution pH value.The wet modified argil that obtains is pulverized 250 ℃ of oven dry down, gets granularity and is lower than 200 purpose parts, gets No. 1 modified argil.
The preparation of No. 22 modified argils of embodiment
With water 94 grams, NaOH 2 grams, potassium hydroxide 2 grams and diethylenetriamine 2 gram preparation alkaline solutions, soak industrial carclazyte (production of Fushun petrochemical Corp., CNPC's oil one factory) 29 grams with alkaline solution at 64 ℃, fully stir after 6 hours, the static room temperature that is cooled to, it is 11.5 that centrifugation under the room temperature, filter cake are washed to cleaning solution pH value.The wet modified argil that obtains is pulverized 150 ℃ of oven dry down, gets granularity and is lower than 200 purpose parts, gets No. 2 modified argils.
The preparation of No. 33 modified argils of embodiment
With water 89 grams, potassium hydroxide 9 grams and triethanolamine 2 gram preparation alkaline solutions, soak industrial carclazyte (production of Fushun petrochemical Corp., CNPC's oil one factory) 35 grams with alkaline solution at 85 ℃, fully stir after 1 hour, the static room temperature that is cooled to, it is 11.0 that centrifugation under the room temperature, filter cake are washed to cleaning solution pH value.The wet modified argil that obtains is pulverized 190 ℃ of oven dry down, gets granularity and is lower than 200 purpose parts, gets No. 3 modified argils.
The preparation of No. 44 modified argils of embodiment
With water 90 grams, NaOH 5 grams, diethylenetriamine 1 gram, triethylene tetramine 2 grams and TEPA 2 gram preparation alkaline solutions, soak industrial carclazytes 20 grams (the safe chemical plant of Linzhou City, Zibo China produces) with alkaline solution at 93 ℃, fully stir 0.5 hour after, the static room temperature that is cooled to, it is 11.3 that centrifugation under the room temperature, filter cake are washed to cleaning solution pH value.The wet modified argil that obtains is pulverized 105 ℃ of oven dry down, gets granularity and is lower than 200 purpose parts, gets No. 4 modified argils.
The preparation of No. 55 modified argils of embodiment
With water 98 grams, NaOH 1.5 grams, TEPA 0.5 gram preparation alkaline solution, soak industrial carclazyte 10 grams (the safe chemical plant of Linzhou City, Zibo China produces) with alkaline solution down at 30 ℃, fully stir after 24 hours, centrifugation, it is 11.8 that filter cake is washed to cleaning solution pH value.The wet modified argil that obtains is pulverized 130 ℃ of oven dry down, gets granularity and is lower than 200 purpose parts, gets No. 5 modified argils.
The preparation of No. 66 modified argils of embodiment
With water 70 grams, NaOH 5 grams, potassium hydroxide 10 grams, magnesia 12 grams, TEPA 1.5 grams, polyethylene polyamine 1.5 grams, the preparation alkaline solution, soak industrial carclazyte 65 grams (Huangshan Baiyue Activated Clay Co., Ltd.'s production) with alkaline solution down at 50 ℃, fully stir after 1.5 hours, the static room temperature that is cooled to, centrifugation, it is 10.9 that filter cake is washed to cleaning solution pH value.The wet modified argil that obtains is pulverized 180 ℃ of oven dry down, gets granularity and is lower than 200 purpose parts, gets No. 6 modified argils.
Embodiment 7
The depickling process of the test is as follows:
Get 300 gram feedstock oils and put into 500 milliliters of there-necked flasks, get the industrial carclazyte or the modified argil of a certain amount of (is benchmark with oil product weight), add while stirring in the oil product, at a certain temperature, the absorption certain hour, reaction finishes the back filters, and obtains base oil after the depickling.Feedstock oil character sees Table 1, and experimental condition and result of the test see Table 2, table 3.
By table 2 and table 3 data as seen, modified argil has very high deacidification efficiency.Particularly very difficult to depickling No. 750 dewaxed oils of heavy are no more than at the modified argil consumption under the situation of 2 weight %, and total acid number is reduced to 0.03mgKOH/g by 0.25mgKOH/g.
Table 1 feedstock oil character
| The feedstock oil title | No. 150 dewaxed oils | No. 750 dewaxed oils |
| 40 ℃ of kinematic viscosity, mm 2/s | 32.24 | 154.0 |
| Colourity, number | 0.5 | 4.0 |
| Pour point, ℃ | -12 | -6 |
| Carbon residue, w% | ＜0.05 | 0.12 |
| Flash-point, ℃ | 216 | 286 |
| Total acid number, mgKOH/g | 0.07 | 0.25 |
Table 2 experimental condition and result
Table 3 experimental condition and result
Claims (14)
1. method for preparing modified argil may further comprise the steps:
(a) handle carclazyte with the mixture alkaline solution of a kind of inorganic alkaline compound and a kind of organic basic compound;
(b) wash carclazyte with water, be not higher than 12.0 until the pH of washings value;
(c) dry clay.
2. according to the process of claim 1 wherein that the alkali compounds concentration of described alkaline solution is 1-30 weight %, be benchmark with the total solution weight.
3. according to the process of claim 1 wherein that described inorganic alkaline compound is selected from the hydroxide of alkali metal and alkaline-earth metal.
4. according to the process of claim 1 wherein that described organic basic compound is selected from diethylenetriamine, triethylene tetramine, TEPA, polyethylene polyamine, monoethanolamine, diethanol amine, triethanolamine, diethylamine and triethylamine.
5. according to the process of claim 1 wherein that the ratio of described inorganic alkaline compound with organic basic compound weight is 1-10: 1.
6. according to the process of claim 1 wherein that described processing mode is for soaking.
7. according to the method for claim 6, the time of wherein said immersion is 0.2-24 hour.
8. according to the process of claim 1 wherein that the weight ratio of described alkaline solution and carclazyte is 1.0-10: 1.
9. the temperature when method according to claim 1, wherein said processing is 30-100 ℃.
10. the modified argil that makes of the described method of claim 1.
11. the modified argil of claim 10 is as the application of the deacidification adsorbent of refined oil.
12. according to the application of claim 11, wherein said oil product is a lube base oil.
13. a method that reduces the oil product total acid number comprises and uses the described modified argil of claim 10 to contact with oil product.
14. according to the method for claim 13, wherein said oil product is a lube base oil.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955791A (en) * | 2009-07-17 | 2011-01-26 | 美国Gtc技术有限责任公司 | Be used for removing the method for foreign pigment and sulfur-containing impurities from hydrocarbon stream |
| CN103540339A (en) * | 2013-10-21 | 2014-01-29 | 中国石油化工股份有限公司 | Refining method of lubricating oil stocks capable of effectively reducing acid value of base oil |
| CN104152176A (en) * | 2013-05-14 | 2014-11-19 | 中国石油天然气股份有限公司 | Method for preparing poly-alpha-olefin synthetic oil by adopting coal-based raw materials |
| CN104498086A (en) * | 2014-11-25 | 2015-04-08 | 宁波永润石化科技有限公司 | High acid value marine minus line oil deacidification treatment process |
| CN106883931A (en) * | 2015-12-15 | 2017-06-23 | 中粮集团有限公司 | A kind of method that depickling is carried out to grease |
| CN115041150A (en) * | 2022-06-23 | 2022-09-13 | 烟台齐盛石油化工有限公司 | Preparation method of modified activated clay composite fiber adsorption tube |
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2006
- 2006-12-22 CN CNB2006101695249A patent/CN100569355C/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955791A (en) * | 2009-07-17 | 2011-01-26 | 美国Gtc技术有限责任公司 | Be used for removing the method for foreign pigment and sulfur-containing impurities from hydrocarbon stream |
| CN101955791B (en) * | 2009-07-17 | 2015-04-01 | 美国Gtc技术有限责任公司 | Methods for removal of colored-and sulfur-containing impurities from hydrocarbon streams |
| CN104152176A (en) * | 2013-05-14 | 2014-11-19 | 中国石油天然气股份有限公司 | Method for preparing poly-alpha-olefin synthetic oil by adopting coal-based raw materials |
| CN104152176B (en) * | 2013-05-14 | 2016-03-09 | 中国石油天然气股份有限公司 | Method for preparing poly-alpha-olefin synthetic oil by adopting coal-based raw materials |
| CN103540339A (en) * | 2013-10-21 | 2014-01-29 | 中国石油化工股份有限公司 | Refining method of lubricating oil stocks capable of effectively reducing acid value of base oil |
| CN103540339B (en) * | 2013-10-21 | 2015-10-28 | 中国石油化工股份有限公司 | A kind of lube stock process for purification that effectively can reduce base oil acid number |
| CN104498086A (en) * | 2014-11-25 | 2015-04-08 | 宁波永润石化科技有限公司 | High acid value marine minus line oil deacidification treatment process |
| CN106883931A (en) * | 2015-12-15 | 2017-06-23 | 中粮集团有限公司 | A kind of method that depickling is carried out to grease |
| CN115041150A (en) * | 2022-06-23 | 2022-09-13 | 烟台齐盛石油化工有限公司 | Preparation method of modified activated clay composite fiber adsorption tube |
| CN115041150B (en) * | 2022-06-23 | 2023-06-23 | 烟台齐盛石油化工有限公司 | Preparation method of modified activated clay composite fiber adsorption tube |
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