CN105566104A - Preparation method of solid superacid catalyst used for esterification of acid type anti-wear agent - Google Patents
Preparation method of solid superacid catalyst used for esterification of acid type anti-wear agent Download PDFInfo
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- CN105566104A CN105566104A CN201510985905.3A CN201510985905A CN105566104A CN 105566104 A CN105566104 A CN 105566104A CN 201510985905 A CN201510985905 A CN 201510985905A CN 105566104 A CN105566104 A CN 105566104A
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- Prior art keywords
- acid
- esterification
- wear agent
- solid super
- type anti
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
Abstract
The present invention discloses a preparation method of an ester type anti-wear agent, relates to the preparation field of fatty acid esterification catalysts, and aims to solve the problems of incomplete reaction, low product purity, many byproducts and deep product color in the process of formation of monoesters from fatty acids. A solid superacid SO4<2-> / TiO2-Al2O3 / La<3 +> prepared by the ways of low temperature aging, rare-earth modification, active carrier loading and the like is used as a catalyst, and when the solid superacid SO4<2-> / TiO2-Al2O3 / La<3 +> is used for esterification of the fatty acids, high purity and high yield fatty acid esters can be obtained. The solid superacid SO4<2-> / TiO2-Al2O3 / La<3 +> has the advantages of being easy in separation after the reaction, reusable, non-pollution to equipment and environmental, and the like. The solid superacid as the catalyst is suitable for mass production of the fatty acid monoesters of different components and contents.
Description
Technical field
The present invention is a kind of production method using solid super-strong acid to synthesize ester type anti-wear agent, relates to fatty acid esterification catalyst field.
Background technology
Along with countries in the world are to the pay attention to day by day of environmental issue, pollute to reduce emission of diesel engine, producing high-quality clean diesel, having become the developing direction of modern petroleum refining industry.This diesel oil generally has the features such as sulphur content is low, and aromaticity content is low, and cetane value is high, and cut is light.Owing to generally have employed harsh hydrodesulfurization in low-sulfur diesel-oil production, polarity in diesel oil also decreases containing the content of oxygen, nitrogenous compound and many rings, double ring arene, thus the natural lubricity of diesel oil is reduced, pump is occurred wearing and tearing, greatly reduce their work-ing life.In low-sulfur diesel-oil, adding oiliness additive and anti-wear agent is the easiest, is also the method for the improvement diesel fuel lubricity extensively adopted at present.For the diesel oil that some acidity is higher, need to use fatty acid ester type anti-wear agent, otherwise it is too high to cause adding agent diesel oil acidity, increases corrosion risk etc.Highly purified ester type anti-wear agent under catalyst action, esterification can be carried out with polyvalent alcohol by fatty acid type anti-wear agent.
When liquid acid as catalyst, very high catalytic activity can be shown at low temperatures, difficult control of reaction conditions is easy to produce side reaction, product colour is comparatively dark, and severe corrosion equipment, also easily causes environmental pollution, compared with liquid acid, solid acid catalyst good reaction selectivity, corrodibility is little, environmental friendliness and the plurality of advantages such as can to reuse.In the research of acid catalyst, usually use Ha Meite (Hammett) Acidity function H
0carry out the strength of acid size of a kind of acid of quantitative description.H
0strength of acid function both can in order to have described the strength of acid of liquid acid, also can in order to describe the strength of acid size of solid acid.H
0less, show that strength of acid is stronger.100%H
2sO
4strength of acid is H
0=-11.94, in acid catalyst, strength of acid H
0the acid of <-11.94 is referred to as super acids.HinoM etc. (MHino, ChemistryLetters, 1979,10,1259-1260) were at 1979 years reported first vitriolization TiO
2, ZrO
2, reactivate obtains catalyst S O
4 2-/ TiO
2, SO
4 2-/ ZrO
2, there is extremely strong strength of acid.SO
4 2-/ TiO
2h
0value is for-14.5, SO
4 2-/ ZrO
2h
0value is for-16.04.
SO
4 2-/ M
xo
ytype solid acid catalyst is simple because preparing; not high and be easy to the study hotspot that the advantages such as regeneration become catalytic field containing corrosive halogen ion, catalytic activity and selectivity, and the processes such as widespread use alkylation, isomerization, esterification, acylations, polymerization and oxidation.At use SO
4 2-/ M
xo
ysolid acid is as SO
4 2-/ TiO
2, SO
4 2-/ ZrO
2, SO
4 2-/ SnO
2, SO
4 2-/ CeO
2etc. do catalyzer esterified fatty acid research in, result show use SO
4 2-/ TiO
2similar with Catalyzed by p-Toluenesulfonic Acid activity, but at use SO
4 2-/ TiO
2solid acid catalyst finds to exist in fatty acid esterification large-scale production process: the problems such as the few and catalyst separating of not high, the repeatable number of times of activity is difficult.Possible reason is: because of esterification dehydration, intrasystem water or water vapour with surperficial as SO
4 2-contact, makes the SO on its surface
4 2-run off, the acid site number of catalyst surface is reduced, causes strength of acid to weaken, catalyst activity reduction; Sterically hindered larger lipid acid, fatty acid ester, in catalyst surface adsorption and desorption and surface reaction, can adsorb, be deposited on catalyst active sites, rear easy formation carbon deposit, and catalyst activity reduction, reusable number of times are declined; In order to improve catalytic activity, increase specific surface area, in preparation process, be generally ground into granularity about 100 orders, after catalyzer mixes with system, create agglomeration, bring difficulty to the later separation of reaction, be unfavorable for the recovery of catalyzer and reuse.In order to SO can be allowed
4 2-/ TiO
2large-scale application, needs to improve activity, the repeatability of solid acid catalyst and improves follow-up separation, by searching document find current work also mainly for activity be separated two aspects and improve.
For catalyst activity aspect, according to SO
4 2-/ TiO
2the acid sites of type solid acid catalyst is only present in catalyst surface characteristic, and therefore, improving specific surface area of catalyst is increase acidic site number, and then improves the important means of surface acidity, introduces nanotechnology, prepares high-specific area nano type SO
4 2-/ TiO
2catalyzer.As (in luxuriant growth, catalysis journal, 2009,30 (3), 265-271) adopts equi-volume impregnating to prepare the mesoporous SO of new type whisker shape
4 2-/ TiO
2solid super-strong acid, can be good at solving high-specific surface area, but with new problem, TiO
2the preparation process of whisker raw material is complicated, wayward.By adding other metals or oxide compound composition multicomponent solid super-strong acid, as SO prepared by (chemical research and application, 2001,290-292) such as Liao Dezhong
4 2-/ TiO
2-MoO
3, Luo Jinyue etc. (Speciality Petrochemicals, 2006,23,10-12) SO
4 2-/ TiO
2-ZrO
2achieve certain effect, but the raw materials such as the use wolframic acid of its larger proportion, zirconyl chloride amount, make the production cost of solid acid higher.Also have the grade (CN1425500) of coca by granular form solid super-strong acid, solid catalyst can be well separated with reaction solution, but its catalytic activity being applied in longer chain fatty acid is not high.
Summary of the invention
The object of the invention is to overcome the problems of the prior art, thus provide the acid anti-wear agent of a kind of solid superacid as catalyst to prepare the method for fatty acid ester, the fatty acid ester anti-wear agent that the method is produced has low-temperature fluidity, good lubricating properties etc., solve in traditional mode of production that the product impurity using liquid acid to bring is complicated, purity is low, color is dark and the problem such as environmental pollution, be that a kind of cost is low, esterification yield is high, product yield be high, aftertreatment is simple, environmental protection, efficiently production method.
The present invention is to the SO of classics
4 2-/ TiO
2solid acid is operated by simple low-temperature ageing and the rare earth modified high-specific surface area that provides that adds a small amount of rare-earth salts is conducive to increasing of catalyst acid position, selects cheap oxide compound to increase the reusable number of times of catalyzer and easily and product separation through modification as active carrier load.These technical schemes can realize that production cost is low, catalyst activity is high, easily after reaction to be separated with system, can be recycled many, that lipid acid carries out that esterification is a kind of is applicable to the feasible method of scale operation, with acid type anti-wear agent for raw material, fatty acid monoester anti-wear agent productive rate prepared by catalytic esterification can reach 72%, product purity more than 95% after aftertreatment, has positive meaning to the development be used in ester type anti-wear agent for finding solid acid catalyst.Step of the present invention comprises:
A. precipitation pickling process is adopted to prepare solid super-strong acid SO
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer, getting a certain amount of soluble titanium solution (titanium tetrachloride or titanium sulfate), is 1/4 ~ 3/4 by Ti/Al atomic ratio, add through roasting, the aluminum oxide pulverized, make it fully flood, drip the weak ammonia precipitation agent of 12%, fully stir hydrolysis, until solution ph is 5 ~ 12, precipitate complete, throw out is filtered after ageing 12 ~ 72h at-10 ~ 20 DEG C of temperature, be precipitated to without chlorion with deionized water wash, dry, by the TiO of drying
2-Al
2o
3grind into powder, soaks 2 ~ 16h in 0.5 ~ 2.0mol/L vitriol oil (wherein chloride containing lanthanum or lanthanum nitrate (wt) 0 ~ 8% is not 0), and suction filtration is dry, then activates in retort furnace 400 ~ 700 DEG C, finally obtains solid super-strong acid SO
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer.
B. under nitrogen protection; acid type anti-wear agent and polyvalent alcohol are pressed 1:1 ~ 5 mixed in molar ratio; add the solid super-strong acid of 0.1-8.0% total amount simultaneously; at temperature 100-200 DEG C; vacuum tightness 10 ~ 1000Pa; reaction 3-8h carries out esterification, and according to unsaturated fatty acids acid constituents and content difference, condition is difference to some extent.SO after using
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer directly can join in esterification system after carrying out suction filtration, oven dry and reuse.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Example 1
This example adopts acid type anti-wear agent to make the preparation method of catalysts conditions esterification at solid super-strong acid
(1) solid super-strong acid SO
4 2-/ TiO
2-Al
2o
3/ La
3+the preparation of catalyzer
In the container of 500L, 9.5kg titanium tetrachloride is placed in still, adds 300kg distilled water diluting, after the aluminum oxide 10kg through roasting, pulverizing is added wherein, fully after dipping, then add 12% (quality) ammoniacal liquor, regulate PH to make it between 8-9.To be precipitatedly no longer increase, ageing at being cooled to 0 DEG C, filters after 48h, with deionized water wash, and the AgNO of 0.1mol/L
3titration detects and is not more than 200us/cm to without chlorion or with conductance measurement.Precipitation 100 DEG C is dried 6h, and grind into powder 100 order sieves, and wherein soak 8h in chloride containing lanthanum 3kg at 300kg containing the vitriol oil of 1.0mol/L, suction filtration is dry, then activates in retort furnace 500 DEG C, finally obtains solid super-strong acid SO
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer.
(2) under nitrogen protection, by 900kg acid type anti-wear agent and the mixing of 300kg glycerine, add 10kg solid super-strong acid, temperature 160 DEG C, vacuum tightness 1000Pa, reaction 5h carries out esterification, and fatty acid monoester content is 71% simultaneously.By the SO after use
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer directly joins in esterification system after carrying out suction filtration, oven dry and reuses, SO
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer use properties is with the increase of multiplicity, and activity declines to some extent, and using and recording fatty acid monoester content when 6 times is 60%.
Example 2
This example adopts acid type anti-wear agent to make the preparation method of catalysts conditions esterification at solid super-strong acid
(1) solid super-strong acid SO
4 2-/ TiO
2-Al
2o
3/ La
3+the preparation of catalyzer
In the container of 500L, by 12kg titanium sulfate solution, add the dilution of 300L ionized water, after the aluminum oxide 8kg through roasting, pulverizing is added wherein, fully after dipping, then add 12% ammoniacal liquor, regulate PH to make it between 8-9.To be precipitatedly no longer increase, ageing at being cooled to 0 DEG C, filters after 48h, and by deionized water wash precipitation, the AgNO3 titration of 0.1mol/L detects and is not more than 200us/cm to without chlorion or with conductance measurement.Precipitation 100 DEG C is dried 6h, and grind into powder 100 order sieves, and the vitriol oil containing 1.25mol/L at 300kg wherein soaks 6h containing in 5kg Lanthanum trichloride, and suction filtration is dry, then activates in retort furnace 500 DEG C, finally obtains solid super-strong acid SO
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer.
(2) under nitrogen protection, by 900kg acid type anti-wear agent and the mixing of 600kg glycerine, add 10kg solid super-strong acid, temperature 150 DEG C, vacuum tightness 1000Pa, reaction 8h carries out esterification, and fatty acid monoester content is 75% simultaneously.By the SO after use
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer directly joins in esterification system after carrying out suction filtration, oven dry and reuses, SO
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer use properties is with the increase of multiplicity, and activity declines to some extent, and using and recording fatty acid monoester content when 6 times is 63%.The content decline recording fatty acid monoester at 9 times still remains on 48%.
Example 3
This example adopts acid type anti-wear agent to make the preparation method of catalysts conditions esterification at solid super-strong acid
(1) solid super-strong acid SO
4 2-/ TiO
2-Al
2o
3/ La
3+the preparation of catalyzer
In the container of 500L, by 9.5kg titanium chloride, add the dilution of 300kg ionized water, after the aluminum oxide 5kg through roasting, pulverizing is added wherein, fully after dipping, then add 12% (quality) ammoniacal liquor, regulate PH to make it between 8-9.To be precipitatedly no longer increase, ageing at being cooled to-5 DEG C, filters after 36h, and by deionized water wash precipitation, the AgNO3 titration of 0.1mol/L detects and is not more than 200us/cm to without chlorion or with conductance measurement.Precipitation 100 DEG C is dried 6h, and grind into powder 100 order sieves, and the vitriol oil containing 1.0mol/L at 300kg wherein soaks 8h containing in 3kg lanthanum nitrate, and suction filtration is dry, then activates in retort furnace 450 DEG C, finally obtains solid super-strong acid SO
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer.
(2) under nitrogen protection, by 900kg acid type anti-wear agent and the mixing of 100kg tetramethylolmethane, add 10kg solid super-strong acid, temperature 150 DEG C, vacuum tightness 1000Pa, reaction 8h carries out esterification, and fatty acid monoester content is 66% simultaneously.By the SO after use
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer directly joins in esterification system after carrying out suction filtration, oven dry and reuses, SO
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer use properties is with the increase of multiplicity, and activity declines to some extent, and using and recording fatty acid monoester content when 6 times is 58%.
Claims (6)
1., for a preparation method for the solid super acid catalyst of acid type anti-wear agent esterification, it is characterized in that comprising the following steps:
A. precipitation pickling process is adopted to prepare solid super-strong acid SO
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer, get a certain amount of soluble titanium solution (titanium tetrachloride or titanium sulfate), add the aluminum oxide after certain proportion process, make it fully flood, drip the weak ammonia precipitation agent of 12%, abundant stirring hydrolysis, until solution ph is 5 ~ 12, precipitates complete, throw out is filtered after ageing 12 ~ 72h under certain temperature, be precipitated to without chlorion with deionized water wash, dry, by the TiO of drying
2-Al
2o
3grind into powder, in 0.5 ~ 2.0mol/L vitriol oil (wherein containing certain density lanthanum salt), soak 2 ~ 16h, suction filtration is dry, then activates in retort furnace 400 ~ 700 DEG C, finally obtains solid super-strong acid SO
4 2-/ TiO
2-Al
2o
3/ La
3+catalyzer;
B. under nitrogen protection, acid type anti-wear agent and polyvalent alcohol are pressed 1:1 ~ 5 mixed in molar ratio, add a certain amount of solid super-strong acid simultaneously; at temperature 100-200 DEG C, vacuum tightness 10 ~ 1000Pa, reaction 3-8h carries out esterification; according to unsaturated fatty acids acid constituents and content difference, condition is difference to some extent.
2. the preparation method of the solid super acid catalyst for the esterification of acid type anti-wear agent according to claim 1, is characterized in that: the aluminum oxide after process described in step a, through roasting and crushing process.
3. the preparation method of the solid super acid catalyst for the esterification of acid type anti-wear agent according to claim 1, is characterized in that: to add a certain proportion of aluminum oxide described in step a be Ti/Al atomic ratio is 1/4 ~ 3/4.
4. the preparation method of the solid super acid catalyst for the esterification of acid type anti-wear agent according to claim 1, it is characterized in that: the scope of Aging Temperature described in step a is-10 ~ 20 DEG C, Optimal Temperature scope is 0 ~ 5 DEG C.
5. the preparation method of the solid super acid catalyst for the esterification of acid type anti-wear agent according to claim 1, it is characterized in that: the salt of lanthanum described in step a is lanthanum nitrate or Lanthanum trichloride, its concentration range is 0 ~ 8% of sulfuric acid quality, and optimal concentration scope is 0 ~ 3%.
6. the preparation method of the solid super acid catalyst for the esterification of acid type anti-wear agent according to claim 1, it is characterized in that: a certain amount of solid super-strong acid consumption described in step b is the 0.1-8.0% of polyvalent alcohol and acid anti-wear agent total amount, and optimum amount scope is 3-5%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126832A (en) * | 2018-08-07 | 2019-01-04 | 陈子清 | A kind of synthetic method of solid super-strong acid |
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| CN102826999A (en) * | 2011-06-15 | 2012-12-19 | 何节玉 | Method for synthesizing neopentyl glycol oleate |
| CN102887825A (en) * | 2012-09-04 | 2013-01-23 | 陕西省石油化工研究设计院 | Method for preparing polyol ester lubricating oil by using composite solid acid catalyst |
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2015
- 2015-12-25 CN CN201510985905.3A patent/CN105566104B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102826999A (en) * | 2011-06-15 | 2012-12-19 | 何节玉 | Method for synthesizing neopentyl glycol oleate |
| CN102311838A (en) * | 2011-08-08 | 2012-01-11 | 华东理工大学 | Low-sulfur diesel oil lubrication additive and preparation method and application thereof |
| CN102887825A (en) * | 2012-09-04 | 2013-01-23 | 陕西省石油化工研究设计院 | Method for preparing polyol ester lubricating oil by using composite solid acid catalyst |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126832A (en) * | 2018-08-07 | 2019-01-04 | 陈子清 | A kind of synthetic method of solid super-strong acid |
| CN109126832B (en) * | 2018-08-07 | 2021-10-26 | 陈子清 | Method for synthesizing solid super acid |
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